lllllllllllllllllljljl\llllllllll   z. R‘ Y

Micbigan State
Tnams LhfiYCflfiQV

 

This is to certify that the

thesis entitled

Part I The Synthesis of Porphyrins
Part II The Synthesis and Reactions
of Pyrroles

presented by

Kim Steven Chamberlin

has been accepted towards fulfillment
of the requirements for

Ph. D. _ Organic Chemistry
degree1n______________

gag/W

Major professor

 

June 7, 1979
I)ate

 

0-7 639

 

 

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this checkout from your record.

 

 

 

 

PART I

THE SYNTHESIS OF PORPHYRINS

PART II

THE SYNTHESIS AND REACTIONS OF PYRROLES

By

Kim Steven Chamberlin

A DISSERTATION

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

DOCTOR OF PHILOSOPHY

Department of Chemistry

1979

 

N______ .

ABSTRACT
PART I
THE SYNTHESIS CH“ PORPHYRINS
PART II
THE SYNTHESIS AND REACTIONS OF PYRROLES
By

Kim S. Chamberlin

PART I

The most widely used models for the study of porphyrin
chemistry is the sparingly soluble 2,3,7,8,12,13,l7,18—
octaethylporphyrin. Thus, a general synthetic route to
more soluble higher homologues was developed. Condensation
Of 3,4—dialkylpyrroles with formaldehyde in the presence of
hYdrobromic acid in a large volume of ethanol gave 2,3,7,8,—
l2,13,l7,l8—octaalkylporphyrins.

Tetra(polymethylene)porphyrins were synthesized in one

Step from ethyl 2—methy1—3,4-polymethylenepyrrole—S—

’7//O'//j"

carboxylates. The 2—methylpyrroles were transformed into
their monoacetoxymethyl derivatives when treated with one
equivalent of lead tetraacetate in acetic acid. The result—
ing diesters were hydrolyzed with potassium hydroxide fol-

lowed by cyclization to porphyrin in refluxing acetic acid.

PART II
Various acylmethylenetriphenylphosphoranes were syn—

thesized by alkylation of lithiotriphenylphosphinioacetonide

 

Kim S. Chamberlin

d,B—Unsaturated ketones were efficiently produced by reflux—
ing these ylides with the appropriate aldehyde in methylene
chloride. 3,4—Disubstituted pyrroles were prepared by the
reaction of p-toluene—sulfonyl methyl isocyanide with the
a,B—unsaturated ketones in the presence of base. Reduction
of these acylpyrroles with lithium aluminum hydride led to
six new 3,4—dialkylpyrroles.

Two pyrrole molecules were directly coupled or connected
by one, three, or five carbon bridges to give bipyrroles, di—
pyrromethanes, dipyrrotrimethines, or dipyrropentadienones

respectively.

To Marian

ii

 

 

ACKNOWLEDGMENTS

I would like to thank the Department of Chemistry at
Michigan State University for providing financial support
in the form of teaching assistantship for the past five
years. I would also like to express my appreciation to
Professor Eugene LeGoff for his guidance, enthusiasm, and

for arranging financial support.

 

”Like all young men I set out to be a genius, but

mercifully laughter intervened."

Clea Lawrence Durrell

 

iv

 

TABLE Cfi‘ CONTENTS

PART I
INTRODUCTION
RESULTS AND DISCUSSION
EXPERIMENTAL

General procedure

Tetrapropyltetrapropyrylporphyrin (12)

Tetrabutyltetrabutyrylporphyrin (13)

Tetrapentyltetrapentyrylporphyrin (14)

Tetrahexyltetrahexyrylporphyrin (l5)

Tetraheptyltetraheptyrylporphyrin (16)

Tetraoctyltetraoctyrylporphyrin (17) . .

Tetrabutyltetraarhydroxy)butylporphyrin (18)

Octapropylporphyrin (19) .

Octabutylporphyrin (20) .

Octapentylporphyrin (21)

Octahexylporphyrin (22)

Octaheptylporphyrin (23)

Octaoctylporphyrin (24) .

l ,2 3, 4— 5, 6— 7, 8— Tetra(trimethylene)porphyrin (25)

l ,2— 3, 4— 5, 6— 7, 8— Tetra(tetramethylene)—
porphyrin (26) . . .

1 ,2— 3, 4— 5, 6— 7, 8— Tetra(decamethylene)—
porphyrin (27)

APPENDIX

PART II
INTRODUCTION
RESULTS AND DISCUSSION
EXPERIMENTAL

General .

l— (2— Thienyl)- -hex— l- ene (36)

6— —Hydroxy— 4- ~decyne (38) . .
Propyrylmethylenetriphenylphosphorane (4la)
Butyrylmethylenetriphenylphosphorane (41b)
Pentyrylmethylenetriphenylphosphorane (410)
Hexyrylmethylenetriphenylphosphorane (41d)
Heptyrylmethylenetriphenylphosphorane (4le)

V

Page

66
7O
87

87
87

89
89

90
90

TABLE OF CONTENTS (continued)

Octyrylmethylenetriphenylphosphorane (41f) .

l, 3— —Diacety1methylenetriphenylphosphorane (41g)

4- Octene— 3— —one (39a)

5— Decene— 4— —one (39b)

6— Dodecene— 5— —one (390) .

7— Tetradecene— 6— —one (39d)

8— Hexadecene— 7— —one (39s)

9- Octadecene— 8— —one (39f)

3, 11— Tridecadiene— 4, 10— dione (39g)

3— —Propyl— —4- —propyry1pyrrole (42)

3—Butyl—4-butyrylpyrrole (43)

3—Pentyl-4—pentyrylpyrrole (44)

3—Hexyl—4—hexyrylpyrrole (45)

3— —Heptyl— 4— —heptyry1pyrrole (46)

3— —Octyl— —4— —octyrylpyrrole (47) .

l, 7— bis[— 3— (4— —methy1pyrro)]— —l, 7— —heptanedione (48)

1H——pyrro— [3, 4 ,a]- y— butyrolactone (49) . .

3— ~Butyryl- -4— (2— thienyl) —pyrr01e (11)

2——Carbethoxy— 3, 4, 5—tr1methylpyrrole (50)

2— Carbethoxy— 3, 4— diethyl— —5— —methylpyrrole (51)

2—Carbethoxy—3, 4—trimethy1ene—5-methylpyrrole
(52) . .

2-Carbethoxy— 3, 4—tetramethy1ene- 5—methylpyrrole
(53

2-Carbethoxy—3, 4—decamethylene—5—methylpyrrole
(54) .

2—Carbo- -t- butoxy— 3, 4, 5— —trimethylpyrrole (55 ).

2- Carbo— t— butoxy— 3, 4- tetramethylene— 5— —methyl—
pyrrole (56) . .

2— —Carbobenzyloxyl- 3, 4, 5— —trimethy1pyrrole (57)

3, 4, 5— —Trimethyl- -2— —pyrrole carbonitrile (58) .

Diethyl 2— —methyl— —4— phenylpyrrole 3— carboxamide
(59) . .

3, 4— —Dipropylpyrrole (60)

3, 4—Dibuty1pyrrole (61)

3, 4— —Dipentylpyrrole (62)

3, 4—Dihexy1pyrrole (63) .

3, 4— —Diheptylpyrrole (64)

3, 4— —Dioctylpyrrole (65)

2——Formyl— 3, 4, 5—trimethy1pyrr01e (67) .

5— —Acetoxymethyl— 2— carbethoxy— -3, 4— —decamethylene—
pyrrole (68) . .

2— —Carbethoxy- -5— formyl— 3, 4— decamethylenepyrrole
(69) . . . ,

4—Acety1—3——ethyl—2—iodopyrrole (70)

4— —Carbethoxy— 3— —methyl— 2- -iodopyrrole (71) .

3——Acetyl— 5——methy1——4——pheny1——2— iodopyrrole (72)

3 ,4— —Dimethyl— —5— formyl— 2— iodopyrrole (73)

2 ,5——Dimethy1——3,4—diiodopyrrole (77) .

5, 5'—Diiodo— 2, 2' —dipyrroketone (78)

Vi

101
101

102
102
102

103
104
104
105
105
105
105
106

107

107
109

.‘ 109

109
110
110
110

 

TABLE OF CONTENTS (continued)

Page
Ethyl 3, 4—dimethy1—5—iodopyrro1e—2-carboxy1ate
(74) . . . 111
Diethyl 3-methy1— —5— iodopyrro1e- -2, 4— —dicarboxy1ate
(75) . . 111
2— —Benzy1 4— ethyl 5— iodo— 3—methy1pyrrole- 2 ,4—
dicarboxylate (76) . . . . 112
Diethyl 3, 3', 4, 4'—tetramethy1— 2, 2' —bipyrro1e—
5,5'— —dicarboxy1ate (79) . . . . . 112
Tetraethyl 4, 4'— —dimethy1— 2 ,2'— —bipyrrole—3, 3',
5, 5‘—tetracarboxy1ate (81) . . . . 113
5,5'—Dibenzy1 3, 3‘ —diethy1 4 ,4 —dimethy1— 2, 2'—
bipyrrole—3,3', 5, 5' —tetracarboxy1ate (99) . . 113
3,3 ,4 ,4'— Tetramethy1~ ~2, 2' ~bipyrrole—5, 5'—
dicarboxylic acid (80) . . . . 113
3,3'—Diethy1——4, 4'— dimethyl— 2, 2'—bipyrrole— 3, 3'—
dicarboxylate— 5, 5'— —dicarboxylic acid (99) . . 114
3—Acety1—4-pheny1-2,2'—bipyrrole (92) . . . . . . 115
3—Acety1—3',4'—dimethy1—4—pheny1—2,2‘-
bipyrrole (99) . . . . . . . . . . . . . . . . 116
2-Methy1—4—pheny1—3,2'—dipyrroketone (99) . . . . 116
2, 3', 4' —Trimethy1-4—pheny1—3,2'—dipyrroketone
(91) . . . . . . . . . . . . . . . . 116
5, 5'—Dicarbethoxy— 3, 3' ,4 4'—tetramethy1-2,2'—
dipyrromethane (93) . . . . . . . . . . . 117
3,3' ,5 5' —Tetracarbethoxy- —4, 4'— —dimethy1—2, 2'—
dipyrromethane (94) . . . 117
5,5'— —Carbobenzy10xy— 3, 3' ,4 ,4' —tetramethy1— —2 ,2'—
dipyrromethane (95) . . . 118
3,3', 4, 4' -Tetramethy1— —2, 2' ~dipyrromethane, 5, 5'—
dicarboxylic acid (96) . . . . 119
Diethyl 4 ,4' -dimethy1— —2, 2'— —dipyrromethane— —5, 5'—
dicarboxylic acid— 3, 3' —dicarboxy1ate (97) . . 119
5,5'-D1ethoxycarbony1— 3, 3' ,4 ,4'— —tetramethy1-
2, 2' —dipyrroketone (98) . . . . . . . 119
3, 3' ,4 4' 5, 5'-Hexamethy1dipyrro— 2 ,2'—
trimethme hydrobromide (100) . . _ 121
1 ,5— Di— (5— carbo— t— butoxy— 3, 4— dimethy1— 2— —pyrro)—
1 ,4— —pentadiene— 3— —one (103) . . , , 122
2 ,5— Di— (5— —carbo— t- butoxy— 3, 4— —dimethy1- pyrr- 2—
y1methy1ene)- cyclopentanone ($94) . . . . . . 122
APPENDIX . . . . . . . . . . . . . . . . . . . . . . . 123
BIBLIOGRAPHY . . . . . . . . . . . . . . . . . . . . . 231

Table

[0

\‘lQCfibbCO

 

 

LIST OF TABLES

PART I
Acylporphorphyrins
Symmetrical octaalkylporphyrins
13CMR chemical shifts of octaalkylporphyrins

Cyclomethylene porphyrins

PART II
a,B-Unsaturated ketones
3,4—Disubstituted pyrroles
Tetrasubstituted pyrroles
3,4—Dia1ky1 pyrroles
Iodopyrroles
Bipyrroles and dipyrroketones

Dipyrromethanes

viii

Page

16
25
26

28

73
74
75
77
79
81

83

Figure
PART I
1. Porphyrin isomers
2. PMR of meso protons of porphyrin isomers
3. Infrared spectrum of tetrapropyltetra—
propyrylporphyrin (12 ) . . .
4. Infrared spectrum of tetrabutyltetra—
butyrylporphyrin (13) . .
5. Infrared spectrum of tetrapentyltetra—
pentyrylporphyrin (l4) . .
6. Infrared spectrum of tetrahexyltetra-
hexyrylporphyrin (15) . . .
7. Infrared spectrum of tetraheptyltetra—
heptyrylporphyrin (16) . . . .
8. Infrared spectrum of tetraoctyltetra-
octyrylporphyrin (l7) . . . .
9. Infrared spectrum of tetrabutyltetra(d—
hydroxy)butylporphyrin (18) .
10. Infrared spectrum of octapropylporphyrin (I?)
ll. Infrared spectrum of octabutylporphyrin (g9)
12. Infrared spectrum of octapentylporphyrin (a1).
13. Infrared spectrum of octahexylporphyrin (EE)
14. Infrared spectrum of octaheptylporphyrin (%§)'
15. Infrared spectrum of octaoctylporphyrin (24)
16. PMR spectrum of tetrapropyltetrapropyryl—
porphyrin (12) . -
l7. PMR spectrum of tetrabutyltetrabutyryl-

LIST OF FIGURES

porphyrin (13)

ix

Page

17

18

44

45

46

47

48

49

57

57

 

Figure
18.

19.

20.

21.

22.
23.
24.
25.
26.
27.
28.
29.

30.

 

LIST OF FIGURES (continued)

PMR spectrum

PMR

PMR

PMR

PMR
PMR
PMR
PMR
PMR

PMR

porphyrin

spectrum

porphyrin

spectrum

pOrphyrin

spectrum

porphyrin

spectrum
spectrum
spectrum
spectrum
spectrum

spectrum

Mass spectra

PMR

spectrum

of

(1:1)

of
(15

of

(lg)

of

<13)

of
of
of
of
of
of
of

of

(tetramethyle

tetrapentyltetrapentyryl—

tetrahexyltetrahexyryl—
) . . . . . . . . . . .
tetraheptyltetraheptyryl—
tetraoctyltetraoctyryl—
octapropylporphyrin (19)
octabutylporphyrin (20)
octapentylporphyrin (21)
octahexylporphyrin (22)
octaheptylporphyrin (23)
octaoctylporphyrin (24)
octaalkylporphyrins

l,2—3,4—5,6—7,8—tetra—
ne)porphyrin (26)

PMR spectrum of 1,2—3,4—5,6—7,8—tetra—

Infrared spec
(36) . .

(decamethylene)porphyrin (23)

PART II

trum of 1—(2—thienyl)—heX—l-ene

Infrared spectrum of 6—hydroxy—4—decyne (§§).

Infrared spectrum of propyrylmethylenetri—
phenylphosphorane (41a) . . . . . . . .

Infrared spectrum of butyrylmethylenetri—
phenylphosphorane (41b) . . . . . . .

Infrared spectrum of pentyrylme
phenylphosphorane (419) . .

thylenetri-

Page

58

58

59

59
6O
6O
61
61
62
62

63

64

64

123

123

124

125

 

Figure

6.

10.
11.
12.

13.

14.
15.

16.

17.

18.

19.

20.

21.

22.

23.

LIST OF FIGURES (continued)

Infrared spectrum of
phenylphosphorane

Infrared spectrum of
phenylphosphorane

Infrared spectrum of
phenylphosphorane

Infrared spectrum of
triphenylphosphorane (41g)

Infrared
Infrared
Infrared

Infrared
(39d)

Infrared
Infrared

Infrared
dione

Infrared

spectrum
spectrum
spectrum

spectrum

spectrum
spectrum

spectrum
<§g§>

spectrum

pyrrole (42)

Infrared

spectrum

pyrrole (43)

Infrared

spectrum

pyrrole (44)

Infrared spectrum
pyrrole (45)

Infrared spectrum
pyrrole (46)

Infrared spectrum
pyrrole (47)

of

of

of

of

of

hexyrylmethylenetri—
(41d) .

heptyrylmethylenetri—
(41e)

octyrylmethylenetri—
(41f) . . . .

1, 3— —diacety1methy1ene—

4—octene-3—one (39a)
5—decene—4-one (39b)
6—dodecene—5-one (390).

7—tetradecene—6—one

8—hexadecene-7—one (39e).
9—octadecene—8—one (39f).

3,11—tridecadiene—4,10,—

3—propy1—4—propyry1—
3—buty1—4—butyryl—
3-penty1—4—pentyry1-
3—hexy1—4—hexyry1—
3—heptyl—4—heptyry1—

3—octy1—4—octyry1—

Infrared spectrum of 1, 7- -bis[— —3- (4— methyl—
pyrro)]1, 7— —heptanedione (48) . . .

xi

Page

127

128

129

130
131
132

133

135

136

137

139

140

141

143

144

 

 

LIST OF FIGURES (continued)

Figure

24.

25.

26.

27.

28.

29.

30.

31.

32.

33.

34.

35.

36.
37.
38.
39.
40.
41.

42.

Infrared spectrum of lH—pyrro— [3, 4 ,a]— y-
butyrolactone (49) .

Infrared spectrum of 3——butyry1-—4—(2-
thieny1)— pyrrole (11) . .

Infrared spectrum of 2-carbethoxy—3,4,5—
trimethylpyrrole (50) . . . . . .

Infrared spectrum of 2-carbethoxy-3,4—
diethyl—5-methy1pyrr01e (51) . .

Infrared spectrum of 2—carbethoxy-3,4—
trimethy1ene-5—methy1pyrr01e (52)

Infrared spectrum of 2—carbethoxy—3,4—
tetramethylene-5—methy1pyrrole (53)

Infrared spectrum of 2—carbethoxy—3,4—deca—
methylene—5—methy1pyrrole (54) .

Infrared spectrum of 2—carbo—t—butoxy-
3,4,5—trimethy1pyrrole (55)

Infrared spectrum of 2— carbo- t-butoxy—
3, 4- -tetramethy1ene- 5—methy1pyrrole (56)

Infrared spectrum of 2—carbobenzyloxy1-
3,4,5—trimethy1pyrrole (57) . . .

Infrared spectrum of 3, 4, 5- trimethy1-2—
pyrrole carbonitrile (58) .

Infrared spectrum of diethyl 2—methy1—4—
phenylpyrrole 3—carboxamide (59)

Infrared spectrum of 3,4—dipropy1pyrrole (60).

Infrared spectrum of 3,4—dibuty1pyrrole (61)

Infrared spectrum of 3,4—dipentylpyrrole (62).

Infrared spectrum of 3,4—dihexy1pyrrole (63)

Infrared spectrum of 3,4—dihepty1pyrrole (64).

Infrared spectrum of 3,4—diocty1pyrrole (65)

Infrared spectrum of 2— —formy1— 3, 4, 5—
trimethylpyrrole (67)

xii

Page

145

146

147

148

149

150

151

152

153

154

 

LIST OF FIGURES (continued)

Figure

43. Infrared spectrum of 5-acetoxymethy1-2—
carbethoxy—B,4—decamethy1enepyrrole (68).

44. Infrared spectrum of 2—carbethoxy—5—formy1—
3,4—decamethy1enepyrrole (69) . . . .

45. Infrared spectrum of 4— acetyl— 3— .ethy1——2—
iodopyrrole (70) . .

46. Infrared spectrum of 4- -carbethoxy— 3-methy1—
2— iodopyrrole (71) . . . . . .

47. Infrared spectrum of 3— acety1—5—methy1——4—
pheny1—2——iodopyrrole (72) .

48. Infrared spectrum of 3, 4—dimethy1—5—formy1—
2— iodopyrrole (73) . . . .

49. Infrared spectrum of ethyl 3,4—dimethy1—5—
iodopyrrole—Z—carboxylate (74) .

5O Infrared spectrum of diethyl 3—methy1—5-
iodopyrrole—2,4—dicarboxylate (75)

51 Infrared spectrum of 2—benzy1 4—ethy1 5—
iodo—3—methy1pyrrole—2,4—dicarboxy1ate(76)

52. Infrared spectrum of 2 ,5— dimethyl— 3, 4—
diiodopyrrole (77) .

53 Infrared spectrum of 5,5'—diiodo—2,2'—
dipyrroketone (78) . . . . . .

54. Infrared spectrum of diethyl 3, 3' ,4 ,4'—
tetramethyl— —2, 2' -bipyrrole— 5, 5'—
dicarboxylate (79)

5. Infrared spectrum of 3,3',4,4'—tetramethy1-
2,2'-bipyrr01e—5,5'—dicarboxy1ic acid (80).

6. Infrared spectrum of tetraethyl 4,4'—dimethy1—
2,2'—bipyrrole—3,3',5,5'—tetracarboxy1ate
(81) . . . . . . . . . . . . . . .

7. Infrared spectrum of 5,5'—dibenzy1 3,3'—
diethyl 4,4'—dimethy1—2,2'—bipyrrole—
3,3',5,5'—tetracarboxy1ate (82)

8. Infrared spectrum of 3,3'—diethy1 4,4'-di—

methyl—2,2'—bipyrrole—3,3'-dicarboxylate—
5,5'—dicarboxy1ic acid (83) . . . .

xiii

Page

164

165

166

167

168

169

170

171

172

174

175

176

177

178

 

 

LIST OF FIGURES (continued)

‘igure

59.

60.

61.

62.

63.

35.

 

Infrared spectrum of 3— acety1——4- -phenyl-
2, 2'—bipyrrole (87) .

Infrared spectrum of 3—acety1—3',4'—dimethy1—

4—pheny1-2,2‘-bipyrrole (88)

Infrared spectrum of 2— —methyl— 4-pheny1-
3, 2' -d1pyrroketone (90) . .

Infrared spectrum of 2,3',4'-trimethy1-4—
pheny1—3,2'—dipyrroketone (91) .

Infrared spectrum of 5,5'-dicarbethoxy-3,3',—
4,4'—tetramethy1—2,2'—dipyrromethane (93)

Infrared spectrum of 3, 3', 5, 5'—tetra-
carbethoxy— —4, 4' —dimethy1— 2, 2'— —dipyrro—
methane (94) . . . . . . . .

Infrared spectrum of 5, 5'-carbobenzyloxy-
3, 3', 4 ,4'—tetramethy1— 2, 2'— —dipyrro—
methane (95) . . . .

Infrared spectrum of 3, 3' ,4 ,4 —tetramethy1—
2, 2' —dipyrromethane— 5, 5' —dicarboxylic
acid (96) . . . . . ..

Infrared spectrum of diethyl 4,4'—dimethy1—
2,2'—dipyrromethane—5,5'-dicarboxylic
acid—3,3'—dicarboxy1ate (97)

Infrared spectrum of 5, 5'- -diethoxycarbony1—
3, 3' 4, 4'—tetramethy1— 2, 2' —dipyrro-
ketone (98)

Infrared spectrum of 3, 3' ,4 ,4‘ ,5 5' —hexa~
methyldipyrro— 2, 2'—trimethine hydro—
bromide (100) . .

Infrared spectrum of 3, 3', 4 4' ,5 5' —hexa—
methyldipyrro— 2, 2‘ -hexacyclotrimethine
hydrobromide (101) .

Infrared spectrum of 1 ,5— di- (5— carbo— t—
butoxy— 3, 4— dimethyl— 2— pyrro)— 1, 4-
pentadiene— 3— —one (103) . . .

Infrared spectrum of 2, 5— di— (5— carbo— t—

butoxy- 3, 4—dimethy1pyrr—2—y1methy1ene)-
cyclopentanone (104)

xiv

Page

180

181

182

183

184

185

186

187

188

190

191

193

 

 

 

——'———

Figure
73.

74.

75.

76.

77.

78.

79.

80.

81.

82.
83.

84.

 

85.
86.
87.

88.

LIST OF FIGURES (continued)

PMR spectrum of 1— (2— thienyl)— —hex- 1— —ene
(36) .

PMR spectrum of 6—hydroxy—4-decyne (38)

PMR spectrum of propyry1methy1enetripheny1—
phosphorane (41a) .

PMR spectrum of butyrylmethylenetriphenyl—
phosphorane (41b) .

PMR spectrum of pentyrylmethylenetri—
phenylphosphorane (410) . . .

PMR spectrum of hexyrylmethylenetriphenyl—
phosphorane (41d) . .

PMR spectrum of heptyrylmethylenetri—
phenylphosphorane (41e) .

PMR spectrum of octyrylmethylenetri—
phenylphosphorane (41f) . . .

PMR spectrum of 1, 3— —diacety1methylenetri—
phenylphosphorane (41g) . .

PMR spectrum of 4—octene—3-one (39a)

PMR spectrum of 5—decene-4—one (39b)

PMR spectrum of 6-dodecene—5—one (399)

PMR spectrum of 7—tetradecene—6—one (399)
PMR spectrum of 8—hexadecene—7—one (39g)
PMR spectrum of 9—octadecene—8—one (393)

PMR spectrum of 3,11—tridecadiene—4,10,—
dione (39g) . . . . . . . . . . . . .

PMR spectrum of 3—propy1—4—propyry1pyrrole

(42)
PMR spectrum of 3—buty1—4—butyry1pyrrole
(43) . . . . . . . . . . . . .

PMR spectrum of 3—pentyl—4—pentyry1pyrrole

(:13)............

XV

Page

194

194

195

196

197

197

198

199

199
200
200

201

201

202

203

Figure
92.

93.

94.

95.

96.

97.

98.

99.

O4.

35.

LIST OF FIGURES (continued)

PMR spectrum of 3— —hexyl— —4— —hexyry1pyrrole

(45)

PMR spectrum of 3— —hepty1— —4— —heptyry1pyrr01e
(46)

PMR spectrum of 3— octy1— —4- -octyry1pyrrole
(47)

PMR spectrum of 1, 7— bis[— 3— (4—methylpyrro)]—

l, 7- -heptanedione (48)
PMR spectrum of 1H—pyrro-[3,4,a]—y—butyro-
lactone (49) . . . . . . . . . . . . . .

PMR spectrum of

3-butyryl—4-(2—thieny1)—
pyrrole (11) . . . . . . . . . . . .

PMR spectrum of 2— carbethoxy— 3, 4, 5— tri—

methylpyrrole (50)

PMR spectrum of 2— —carbethoxy— 3, 4— —diethy1—
5— —methy1pyrrole (51) . .

PMR spectrum of 2—carbethoxy—3,4—tri—
methylene—5—methy1pyrr01e (52) . .

PMR spectrum of 2—carbethoxy—3,4—tetra—
methylene—5—methylpyrrole (53) . . .

PMR spectrum of 2—carbethoxy—3,4—deca—
methylene-5—methy1pyrrole (54) . .

PMR spectrum of 2— carbo- t- —butoxy— 3, 4 ,5—
trimethylpyrrole (55) . . . .

PMR spectrum of 2- carbo— t— —butoxy— 3, 4— tetra—
methylene- 5— —methy1pyrrole (56) . . .

PMR spectrum of 2— carbobenzyloxyl- 3, 4 ,5-
trimethylpyrrole (57) . . ,

PMR spectrum of 3, 4, 5-trimethy1——2-—pyrrole
carbonitrile (58) .

PMR spectrum of diethyl 2- -methyl- 4— —pheny1—
pyrrole 3— carboxamide (59) . _

PMR spectrum of 3,4—dipropy1pyrrole (69)

xvi

Page

203

204

204

205

205

206

206

207

208

209

210

211

 

gure

10.
11.

L3.

LIST OF FIGURES (continued)

PMR spectrum of 3,4-dibutylpyrrole (61)

PMR spectrum of 3,4-dipenty1pyrrole (Q2)

PMR spectrum of 3,4—dihexy1pyrrole (g3)

PMR spectrum of 3,4—diheptylpyrrole (64)

PMR spectrum of 3,4-dioctylpyrrole (g5)

PMR spectrum of

2-formyl-3,4,5—trimethyl—
pyrrole (67) . . . . . . . . . . . .

PMR spectrum of 5—acetoxymethyl—2—
carbethoxy—B,4—decamethy1enepyrrole (§§)

PMR spectrum of 2— carbethoxy— 5— formyl— 3, 4—
decamethylenepyrrole (69) ,
PMR spectrum of 4—acety1—3——ethyl——2-iodo—
pyrrole (70) . . . . .
PMR spectrum of 4— carbethoxy— 3— —methy1— 2—
iodopyrrole (71) . . .
PMR spectrum of 3— acetyl— 5—methy1- -4— ~pheny1—
2— iodopyrrole (72) . ,
PMR spectrum of 3, 4— —dimethyl— 5— formyl— 2—
iodopyrrole (73) . . . . .

PMR spectrum of ethyl 3,4—dimethy1—5-
iodopyrrole—Z—carboxylate (74) . .

PMR spectrum of diethyl 3—methy1—5—iodo—
pyrrole-2,4—dicarboxy1ate (Z5) . . . .

PMR spectrum of 2—benzy1 4—ethy1 5-iodo—3—
methylpyrrole-2,4—dicarboxylate (76) . .

PMR spectrum of 2, 5— —dimethyl- 3, 4— diiodo-
pyrrole (77) . .

PMR spectrum of 5, 5‘ —diiodo— 2 ,2 —dipyrro—
ketone (78) . . . .

PMR spectrum of diethyl 3, 3' ,4,4'—tetra—
methyl——2, 2' —bipyrr01e—5, 5'——dicarboxylate
(79) . . . . . . . . .. .

xvii

Page
212

212
213
213
214

214

215

215

216

216

217

217

218

218

220

 

 

 

 

LIST OF FIGURES (continued)

PMR spectrum of 3,3',4,4'—tetramethyl—2,2'—
bipyrrole-5,5'—dicarboxylic acid (89)

PMR spectrum of tetraethyl 4 ,4'— —dimethyl-
2, 2' -bipyrrole— 3, 3' ,5 5'—tetra—
carboxylate (81) . . .

PMR spectrum of 5, 5' —dibenzy1 3, 3' —diethyl
4 4' —dimethy1——2 2' -bipyrrole— 3, 3' ,5,5'—
tetracarboxylate (82) . . .

PMR spectrum of 3— —acety1- -4- -pheny1— 2, 2'—
bipyrrole (87) . .

PMR spectrum of 3— acety1——3',

—d1methy1—
4— —pheny1— 2, 2' —bipyrrole (88) . .

PMR spectrum of 2— ~methy1— —4— —pheny1— —3, 2'—
dipyrroketone (90) . . .

PMR spectrum of 2, 3' 4' —trimethy1—4——pheny1—
3, 2' —dipyrroketone (91) . ,

PMR spectrum of 5,5'—dicarbethoxy—3,3',—

4,4'—tetramethy1-2,2'—dipyrromethane (93).

5,5’—tetracarbethoxy-

PMR spectrum of 3,3',
-dipyrromethane (94)

4,4'—dimethy1—2,2'
PMR spectrum of 5,5'—carbobenzyloxy—3,3',—

4,4'-tetramethyl—2,2'—dipyrromethane (g§).

4,4'—tetramethy1—2,2'—

PMR spectrum of 3,3',
—dicarboxylic acid

dipyrromethane-5,5'
(9g) . . .
PMR spectrum of diethyl 4, 4'——dimethy1—2,2'—
dipyrromethane— 5, 5' —dicarboxy1ic acid—
3, 3'—dicarboxy1ate (97) . . . . .
PMR spectrum of 5, 5'— —diethoxycarbony1—

3, 3', 4, 4'- tetramethy1——2, 2'— dipyrro—
ketone (98) . . . . . .
PMR spectrum of 3,3',4,4',5,5'—hexamethy1—
dipyrro—2,2'—trimethine hydrobromide
(100) . . . . . .
PMR spectrum of 3,3',4,4',5,5'—hexamethy1—
dipyrro-2,2'-hexacyclotrimethine hydro—
bromide (101) . . . . . . . . . .

xviii

Page

221

221

222

222

223

223

224

224

225

225

226

226

227

227

228

 

 

LIST OF FIGURES (continued)

Figure
142. PMR spectrum of 1, 5— di— (5— carbo- t— —butoxy—

3,4-dimethy1——2——pyrro)——1,4——pentadiene—
3—one (103) .

143. PMR spectrum of 2, 5— di— (5— —carbo— t—butoxy—
3, 4- dimethyl— pyrr- 2— —y1methy1ene)—
cyclopentanone (104) . . . .

Page

228

229

 

 

PART I

THE SYNTHESIS OF PORPHYRINS

- £33.

 

 

INTRODUCTION

-ergy mediators of life. Chlorophylls a and b trap energy

a reductive process while porphyrins release the energy

the controlled oxidative processes of metabolism. Since

2

./

classic studies of Hans Fischerl—s, culminating in the

1thesis of chlorophyll4, a great deal of knowledge of the

rmistry and structure of porphyrins has been accumulated.
Various strategies for the synthesis of the pigments

8 been developed from pyrroles (a), pyrrole aldehyde (b),
ilomethylpyrrole (c), dipyrromethanes (d), dipyrro—
lenes (e and f), dipyrroketones (g), (oxy—)bilanes (h),

enes (i), or biladienes (j), Scheme 1. The relative
t of each route, which is largely dependent on symmetry
the nature of the substituent has been discussed in

5

11 previously

The synthesis of porphyrins from pyrroles (routes a,

Id 0) has often been used in the formation of symmetri—

Orphyrins. In 1935, Fischer6 condensed pyrrole alde—

in refluxing formic acid to yield the parent compound
in.

In the same year Rothemund7 obtained porphin from

aerobic reaction of pyrrole and formaldehyde. Neither

:ed yields of greater than 0.026%. A third approach

2

 

me 1

NH

RICHO

_ NH...

 

8:!» "I Owl
II:
Bu : 23.: r

NH N
2HBr

NHN

 

4
porphin was reported by Krol8 who obtained a 5% yield
an 2—hydroxymethylpyrrole was refluxed in acetic acid
[taining benzoyl peroxide as an oxidizing agent. The
lZOYl peroxide irreversibly oxidized the porphyrinogens
,ch formed as intermediates to porphyrins. Beitchman9
lified this procedure by using atmospheric oxygen as the
.dizing agent. Although only a slightly higher yield of
'phin was obtained, Beitchman found it considerably easier
purify his product. Longo and Adler10 discovered that a
.0% yield of porphin was formed when a total volume of
11 of Z—hydroxymethylpyrrole was added to 3 liters of
Lacidified, chromatographed ethylbenzene at 1000C. They
>orted that efforts to increase the reaction rate caused
.ecrease in yield. The above reactions are shown in

eme 2.

eme 2

3‘ HcozH HOAc / \

I CHO ‘—"' ’ p] {‘4‘ H
I
p.
H2CO MeOH f.
CSHSN
/ \
[/ \5 N

N
H

I
I

 

 

 

e higher yields which are generally obtained are the re—
lt of decreased side reactions involving electrophilic

tack at the 8 positions and increased nucleophilicity

the a position. Steric effects enhance the formation of

)yrryomethene (1) over its geometric isomer (2) which

le require isomerization before cyclization to porphyrin

ld be possible.

2,3,7,8,12,13,l7,l8—Octamethylporphyrin (0MP) was first

'rted by Fischerll who prepared it in 12% yield by heat—

3,4—dimethylpyrrole in formic acid. Siedel and

lerlz synthesized 0MP in 47% yield by decarboxylation

yrrole (3) in refluxing formic acid with concomitant

ansation. An amazing 77%

13 when they refluxed 3,4—dimethylpyrrole with

yield was obtained by Treibs
Iaberele

.ldehyde in acetic acid and pyridine. A similar yield

14 .
P was described by Cheng and LeGoff us1ng the same
ants in acidified ethanol. The change of solvents
rise to a far simpler work—up in the latter case,

3 3.
)Ctaethylporphyrin (OEP) is one of the most widely used

: for the study of porphyrin chemistry. In addition to

 

6
Scheme 3
CH3 CH3 H
2/ \S C02” HCOZH / \
N CC>H
H OH 3' 2
3
HOAc/CSHSN
H2CO r
HBr /EtOH
CH3 CH3
2/ \S
N
H
ts ”natural” substitution pattern, OEP is highly symmetri-
tl, stable,

and lacks extraneous functional groups. These

asirable properties have prompted numerous syntheses of
iP. Any discussion of OEP must include the synthesis and
ansformations of its pyrrole precursors since these reac—
Ons represent the major hurdle to its formation. Thus the
iginal preparation of OEP by Fischer and Baumler (Scheme 4)
ve poor yields and the product was invariably contaminated
:h bromine.
Modern routes to OEP take advantage of its symmetry by

ng condensations of monopyrroles. 2—Carboethoxy—3,4—

thyl—S—methyl pyrrole (4) is the usual intermediate in

se Syntheses owing to its stability and well established

 

Scheme 4

/\n’

O

«gs-2v sew—we 4p
HOzAcW

H . ,F H350,
H H u c025:
' Br

ansformations. Inhoffen, Furhop, Voight, and Brockmanl6

ported the first high yield preparation of OEP, shown in
heme 5. The acetoxymethylpyrrole (§) was isolated in

% yield when 4 was treated with one equivalent of lead
traacetate. This was then converted to the air—sensitive
l-diethyl—5—hydroxymethylpyrrole 2—carboxylic acid in 96%
31d. Cyclization in the presence of potassium ferri—
.nide in hot acetic acid gave, after chromatography, 44%

OEP. Unfortunately, this last step was reported to have

en a disappointingly low yield when scaled up.

 

8
eme 5
/ \ PHOAc). /
a C02” N com
4 2‘
JKOH

PK)“: HC1\~:§r-j§:
(—___
K3Fe(CN), N COQH
H

Until recently the most widely used synthesis of OEP
based on the improvements Whitlock and Hanauer14 de—
ped for the Eisner and Linstead18 approach, Scheme 6.
titative diborane reduction eliminated the need for

pressure hydrogenation of 4—acetylpyrrole and subse—

t chromatography of the product.

 

/ c / \
‘BZHL" N\ ”28$an an 02E?
H

1)NaOAm
NaOH
—CO2
FKJAc Jflggflfl ““"'HC¥C N CCQH

 

9

In 1976, Dolphin et al.19 developed an efficient syn—

thesis of OEP on a large scale using inexpensive starting

materials as shown in Scheme 7. Hydrolysis of (6) gave

ethyl propionylacetate contaminated by regenerated start-

ing material. This impurity was carried through the Knorr

reaction, Since even pure ethyl propionylacetate gives rise

to some undesired ethyl—3,5—diethylpyrrole 2—carboxylate
f7) via the Fischer—Fink side reaction. After reduction
)f the mixture, the undesired pyrrole (7) was easily removed

»y conversion to the Mannich base (§) followed by acid ex—
raction. The large scale conversion of 4 to OEP owed its
uccess to the avoidance of the often unreliable trichlori—
ation of the d—methylpyrrole and lack of isolation of any
ensitive intermediates.

In the year following Dolphin's OEP synthesis,
1d LeGoff14

Cheng
published an even more efficient preparation
‘ the porphyrin, Scheme 8. Quantitative reduction of the
omeric porphyrins led to a 55% overall yield for the four—
ep sequence in which no overly sensitive intermediates
re formed.

Only two syntheses of octapropylporphyrin (OPP) have
in reported. Both routes start from 2—methyl—3,4—dipropyl—
'role (9) which was prepared20 by a long reaction sequence,
-gued by poor yields and sensitive intermediates, Scheme 9.
cher2O chose to make OPP through the dipyrromethene route
le Siedel and Winklerlz used the milder but longer method

n monopyrrole (10), as shown in Scheme 10.

11

me8

‘5)3PZCHCOCH3 L CH3CH2CHZCHCOCH3

CH,QSO,CH,N:C: NaH

HZCO
EtOH

 

RI

 

me 9
a» gram
5' HOAc 5'

 

H E
g A Dill—g H2505 -
1 C02Et N c025:

NH2NH2

EtONCI / \

\cozm N

 

CZ:

Zn
HOAc

 

\

I

12

1e 10
g R
IN _B_ra__,k H \R COQH
B HBr [55
r Br R R
R R
RZanyopyl’
V EH“ Br
MeOH
Pb(OA . g
()4, KOH / \

/ \
com \9/0 N com A N
H H

lctaarylporphyrinsz1 have been
11. This method worked well
ed derivatives, but extension

aliphatic d—diketones failed

:ondensation of these compounds under basic conditions.

prepared as outlined in
with benzil and its sub—
of this pyrrole synthe—

due to a facile self—

A A

 

13

ell

 

 

 

RESULTS AND DISCUSSION

>rder to provide a general synthetic route to meso—
lmetrical octasubstituted porphyrins a number of 3,4—
,uted pyrroles (preparation in Part II) were required.
'roles were effective intermediates, not only because
reactive d—positions but because the substituents in
ition prevent reaction at those sites. The relatively
nthesis of porphyrins devised by Cheng and LeGoff14

n because of the high yields and ease of work—up.
ategies to the target compounds (Scheme 12) seemed

y well suited. The most direct route to these por—

s by condensation of 3,4—dialkylpyrrole with formalde—
Wever, 3,4-dialkylpyrroles must be synthesized from
roles and thus the number of steps in each path would
3e. In addition the electron-rich 3,4—dialkylpyrroles
Lir sensitive. Therefore, condensation of B-acyl—

'ith formaldehyde to give acylporphyrins followed by
was attempted first.

ituted thiophenes can be reduced to alkanes and

as a source of butyl or higher alkyl substituentsgz
E B-thienylpyrrole (ll, R'=H) with formaldehyde and
>nly trace amounts of the porphyrin. Indeed a pure

he product was never obtained. This is probably

tivation of the pyrrole by the electron withdrawing

l4

 

15

3:2

/ \ H2CO

:IZ

 

 

 

 

l6

,tuent. Consequently, electrophilic attack occurs at the
ositions on the thiophene moiety. Even if a modest yield
phyrin could have been isolated from the resulting black
r, nickel would probably have been incorporated into the
from the reactions normally employed in reducing the
-containing heterocycle. This would have required an
>nal step to obtain the metal—free product.

tention was next turned to porphyrin synthesis via the
—4—acylpyrrole condensation with acidified formaldehyde.

ults are tabulated in Table l.

 

 

 

 

 

 

R’ R
RI
R R' HBr R
</ \3 HZCO
, -————————>
N EtOH
H
R R
R’ R’
role R R' % yield porphyrin
12
; CH3(CH2)2 CH3CH2CO 17 M
7 13
F CH3(CH2)3 CH3(CH2)2CO 5 ”W
4 l4
CH3(CH2)4 CH3(CH2)3CO 3 MW
CH3(CH2)5 CH3(CH2)4CO 42 l5
l6
CH3(CH2)6 CH3(CH2)5CO 40 W
17
CH3(CH2)7 CH3(CH2)6CO 36 N

isomeric porphyrins are possible in the condensation

Insymmetrical pyrroles, Figure l. Tetraacetyltetra—

yrin which had been separated by high pressure liquid

 

 

 

17

l
R' R R R
R R' R’ R’
R' R R’ R’
R R’ R R
Type1 Type 2
R R' R R
R' R R, R’
R' R' R R
R R R’ R'
Type 3 Type 4 :

)graphy, was obtained as a 2:4 1 mixture of Type II,

f, and Type IV isomers respectively23. Comparison of

» region in the PMR of the new porphyrins with the
mixture of tetraacetyltetraethylporphyrin shows that
probably a statistical l 1 4:2 mixture of isomers
gure 2. This is consistent with the distribution re—
from the condensation of 3—tert—butylpyrrole with
1yde.

:e results suggest that steric and electronic factors
1e effect on the formation of porphyrin isomers

conditions used. A possible mechanism is shown in

 

 

.mHmEowH ETTEQHOQ Mo meowosm omoE wo MES .N ohswfim

 

 

 

Own
oomflmmoommo go .lvfimmovmmo u .m.m
oomfimmovmmo no .umfimmocmmo u .m.m
commommo he .lmxmmocmmo u .m.m
oommo he .«mmommo u .m.m

 

 

 

19

 

 

 

 

 

20

 

 

All! I I . .m
AME? .~_ /.~_ riuv :2
8 + U

\z a b «qu117.

AU.HQOU¢ 04. D~3D3))

 

 

21

 

l Ji|rj

MOQ}F

an>h men»;

—0Q>P

 

+£u 3 ~— .1 IV

36 n . .
z: :z E .m a z
.x L LI/ 3 a . MIN \l._._ :2

 

 

 

22

 

 

 

u
:2

a, + .
A‘fu 17:. ..I-.

 

 

 

l Jill.

   

V 0&3.

i

m 0Q>h

 

 

23

 

I: :2
+/ .
3 ~— /1V

Z: 22‘:

V
K
II

 

24

One possible route to symmetrical porphyrin was to

duce the tetraalkyltetraacylporphyrin to octaalkyl—
rphyrin. Diborane reduction resulted in a product which
ssessed a visible spectrum similar to OEP but required
re polar solvents to elute it from silica columns. The
1e result was obtained for 1) commercial diborane in

Lrahydrofuran, 2) freshly prepared diborane in tetrahydro—
‘an, 3) diborane in methylene chloride, 4) diborane gen—
ted in situ, 5) tetrabutylammonium borohydride, and

diborane stored over sodium borohydride. The major band

lated from chromatography was identical in every respect
:he sole product obtained through the use of sodium

>hydride. Infrared and mass spectroscopy confirmed that

product was a mixture of isomers of tetraalkyltetra—

oxyalkylporphyrins (18). More vigorous conditions gave

to visible spectra which indicated proportionately

3r concentrations of chlorin, formed by hydroboration

1e porphyrin ring.

 

 

 

25

Reduction of acylporphyrins with lithium aluminum
[ride resulted in the formation of aluminum—containing
'phyrins. Aluminum can not be removed easily from the
'and and thus represents a poor route to the metal—free
phyrins. Other reduction methods, such as Clemmensen

Wolff—Kishner reactions, resulted in the destruction
the porphyrin moiety.

Since the various methods of reducing ketones to hydro—
Jons proved to be unsuitable for ketoporphyrins lg—lz,
)rts were directed to forming the target compounds from
Ietrical pyrroles. The 3,4—dia1kylpyrroles were con—

:ed with formaldehyde in acidified ethanol under nitrogen.
r refluxing for one day, the cooled solution was exposed
ir for one week to permit oxidation to the porphyrin.

results of these reactions are shown in Table 2.

 

 

R
a 2 R R R R
/Z \S H2CO EtOH _
N HBr
H
R R
R R
)yrrole R % yield porphyrin
69 CH3(CH2)2— 32 lg
61 CH3(CH2)3— 33 29
62 CH3(CH2)4— 40 a}
§§ CH3(CH2)5— ll 23
gg CH3(CH2)6— 11 a3

@115 CH3(CH2)7— 22 24

«M,

.L

. . _ L L. .r but K. v .1 (C HKKQKRQVKPM\KRNNNNRR

 

—i—

26

The 13

CMR of these alkyl porphyrins are shown in

‘able 3. As expected, the chemical shifts of the ring
arbons are unaffected by different alkyl groups. The meso,
6”, and ”a“ carbons appear at 96.8, 140.2, and 144.1 f

.1 ppm respectively. The assignment of the alkyl carbons
see experimental) is based on the Grant and Paul equation25
sing a predetermined pentylporphyrin as the modelze. The

Llculated chemical shifts are within i 0.5 ppm of the

:tual values.

.ble 3

 

 

27

A new class of symmetrical porphyrins was synthesized
.sing alkyl 2-methyl—3,4—polymethylenepyrrole 5—carboxylate
s an intermediate. This approach was preferable to the
se of 3,4—disubstituted pyrroles, since the tetrasubsti—
uted pyrroles are simpler to synthesize and less air
ensitive.

The usually near quantitative monohalogenation of the
zrrole methyl group did not proceed as expected with these
7rroles. When ethyl 2—methyl—3,4—trimethylenepyrrole
-carboxylate (52) was treated with one equivalent of bromine,
greenish solution developed. This is in stark contrast to
e light orange to red hue normally obtained at the end of
e reaction. Upon treatment with diethylamine and work—up,
st of the starting pyrrole was recovered. The greenish
Lution may have been a charge—transfer complex since
‘role—halogen complexes of this type are known27. Since
:ochlorination of 52 with sulfuryl chloride also gave back
arge amount of starting material, monoacetoxymethyl—
roles were synthesized using one equivalent of lead
raacetate. Due to difficulties in the purification of
;e diesters, they were often hydrolyzed to the corre—
Lding hydroxy acids which were then transformed into
hyrins without isolation. The reactions and results
summarized in Table 4.

Another variation in the synthesis of 21 was to use
L 2—formyl—3,4-decamethylenepyrrole 5-carboxylate (69).

pyrrole, which was synthesized from 54 using two

28

ble 4

 

 

   
 

 

 

KOH
C ,
( H9. *9. CH)”
HOAc / \
If: fl CIHK
/, H
% yield from
pyrrole n methylpyrrole porphyrin
52 3 12 25
53 4 27 26
54 10 12 21

W

'alents of lead tetraacetate, gave only a 1% yield of

yrin when treated with potassium hydroxide followed

fluxing in acetic acid.

The addition of a second

ron withdrawing group to the pyrrole ring apparently

Lses the acidity of the nitrogen hydrogen to such an

that it is removed by base at a much faster rate

he ester is hydrolyzed.

 

29

A third approach to these systems involved the ”one—
at” reaction of tert-butyl 2-methyl—3,4-trimethy1enepyrrole
-carboxylate (56) with bromine. Tert—butylpyrrole esters
re rapidly hydrolyzed by acids. Addition of bromine to
'rrole (56) in cold acetic acid under nitrogen gave an
’ange solution which rapidly turned dark red when refluxed
d exposed to air. The bromine reacted to give 2—bromo—
thylpyrrole and hydrobromic acid. This acid hydrolyzed
e ester which decarboxylated to give 27% of porphyrin 26,

heme 14.

1eme 14

/ \ __§;.,__, \ +HBr
N
u HOAc H
56

O O

HOAc

O O

26

In an attempt to synthesize an isomerically pure
II porphyrin, B—bridged pyrrole (48) was condensed

formaldehyde in acidified ethanol, Scheme 15. The

Scheme 15

\ /

’\ NHHN /

48

 

30

 

HBr
PBCO

 

 

 

"i .. .

31

v

sible spectrum showed that the reaction stopped at the

pyrromethene or porphodimethene stage. This indicates

at the reaction failed either because the formaldehyde

uld not find its way inside the cavity of the initially

rmed dipyrromethene, or more likely, the attack of the

ectrophile was not selective. The d—position adjacent

the methyl is more nucleophilic than a—position next

the ketone. This should lead to the formation of the

metrical dipyrromethene. If on the other hand the re—

ion lacked sufficient regioselectivity, then formation

the unsymmetrical dipyrromethene could occur and prevent

)hyrin formation due to steric strain.

It was envisioned that a symmetrical.porphyrin bear—
functionalized substituents could be formed via the
ensation of pyrrole (49) by the usual conditions. Un-

unately the lactone ring proved labile and provided an

11y effective electrophile in the B—position. A red

luble polymer was the sole product obtained. This is
.ned in Scheme 16.

 

 

32
;heme 16

2:2

 

 

I2
HBr
[fat H,co
N
H
O
jg—ggja pdynwr
N
H

 

 

 

 

 

EXPERIMENTAL

neral Procedure

The melting points were determined on a Thomas Hoover
i—melt melting point apparatus and are uncorrected.

The infrared spectra were recorded on a Perkin—Elmer
lel 237B or 137 spectrometer. The PMR spectra were ob—
ned on a Varian T—60 spectrometer with chemical shifts
orted in 6—units measured from tetramethylsilane as the
ernal standard. The 13CMR were obtained on a Varian
-20 spectrometer with chemical shifts reported in é—units

n CDCl as the internal standard. The UV and Visible

3
:tra were reporded on a Unicam SP—SOO spectrometer using
1 quartz cells. A Hitachi Perkin—Elmer EMU-6 mass
;trometer was used to obtain the mass spectra.
Microanalyses were performed by Spang Microanalysis
ratory, Eagle Harbor, Michigan. Although not all of
analyses are within the generally accepted limits, they
included for completeness. The tendency of porphyrins

)mplex metals and the difficulty in crystallizing these

:ules frequently causes such deviations.

33

 

34
Tetrapropyltetrapropyrylporphyrin (12), tetrabutyltetra—
butyryrlporphyrin (13), tetrapentyltetrapentyrylporphyrin
(14), tetrahexyltetrahexyrylporphyrin (15), tetraheptyl-
tetraheptyrylporphyrin (16), and tetraoctyltetraoctyryl—
porphyrin (II)

General Procedure:

A solution of pyrrole (42:47) (1.5 mmol), 37% aqueous
formaldehyde (6 ml), 48% hydrobromic acid (1 ml), in abso—
Lute ethanol was refluxed for 24 hours. The reaction mix—
:ure was then allowed to stand at room temperature for one
'eek. The ethanol was removed under reduced pressure.
fter neutralizing the residue with aqueous sodium carbo—
ate it was extracted with methylene chloride. The
ethylene chloride was removed and the residue chromato—
raphed on silica gel (methylene chloride/1% methanol
Luent). The yields are listed in Table 1 on page 16.
)ectral characteristics of 12, 13, 14, 15, 16, and 17

'e summarized below.

trapropyltetrapropyrylporphyrin (12)

Amax (CHC13): 428 nm, 523, 555, 594, 648; IR (CHClB):

l

90 cm‘ (N—H), 1660 (c=0); PMR (CDC13): 5—3.44 (broad s,

, N—H), 1.25 (m, 12H, CHZCH2CH3), 1.52 (m, 12H, COCHZCHs),

35 (m, 8H, CH CHZCHB), 3.59 (m, 8H, cocg ), 4.12 (m, 8H,

2
,—porphyrin), 10.00 (s, 1H, meso—H), 10.40 (s, 2H, meso—H),

61 (s, 1H, meso—H); MS (70 eV): m/e = 702 (parent).

Anal. Calcd for C44H54N4O4: C, 75.18; H, 7.79; N, 7.97

Found: C, 74.90; H, 7.58; N, 8.22.

 

35

Tetrabutyltetrabutyrylporphyrin (13)

Amax (CHC13): 427 nm (e = 240,000), 522 (16,000),
556 (8,900), 594 (7,100), 648 (3,100); IR (CHC13): 3400 cm—1
(N-H), 1655 (C=O); PMR (CDC13): 5—3.39 (broad s, 2H, N—H),
1.03—1.07 (m, 24H, CH ), 1.75—2.25 (m, 24H, CHZCHZCH2CH3
and COCH2CH2CH3), 3.59 (m, 8H, COCHZ), 4.20 (m, 8H, CH2—
porphyrin), 10.09 (s, 1H, meso—H), 10.45 (s, 2H, meso—H),

L0.60 (s, 1H, meso—H); MS (70 eV): m/e = 814 (parent).

Anal. Calcd for C52H7ON4O4: C, 76.62; H, 8.66; N, 6.87
Found: C, 76.28; H, 8.36; N, 6.93.

etrapentyltetrapentyrylporphyrin (14)

Amax (CHCls): 427 nm, 521, 556, 593, 647; IR (CHC13):
300 cm~l (N-H), 1665 (C=O); PMR (CDC13):6—3.60 (broad s,
1, N-H), O 98—l.20 (m, 24H, CH3), 1.43—2.34 (m, 40H,
12(CH2)3CH3 and COCH2(CH2)ZCH3), 3.60 (m, 8H, C0CH2), 4.05
1, 8H, CHZ—porphyrin), 9.70 (s, 1H, meso—H), 10.18 (s, 2H,
eso—H), 10.39 (s, 1H, meso—H); MS (70 eV): m/e = 926

arent).

Anal. Calcd for C6OH86N404: C, 77.71; H, 9.35; N, 6.04
Found: C, 77.05; H, 9.20; N, 6.36.

trahexyltetrahexyrylporphyrin (15)
Amax (CHC13): 426 nm, 520, 556, 592, 647; IR (CHClB):
)0 cm—1 (N-H), 1670 (C=O); PMR (CDC13): 6-3.34 (broad s,
N-fi), 0.70—1.06 (m, 24H, CH3), 1.10—2.50 (m, 56H,
(CH2)4CH3 and COCH2(CH2)3CH3), 3.53 (m, 8H, COCH2), 4.10

8H, CHZ—porphyrin), 10.00 (s, 1H, meso—H), 10.30 (s,

 

 

36
2H, meso—H), 10.45 (s, 1H, meso-H); MS (70 eV): m/e = 1038

(parent).

Tetraheptyltetraheptyrylporphyrin (16)

Amax (CHC13): 427 nm, 522, 558, 594, 650; IR (CHC13):
3300 cm_1 (N—H), 1665 (C=O); PMR (CD013): 6-4.03 (broad s,
2H, N—H), 0.80-1.13 (m, 24H, CH3), 1.15—2.50 (m, 72H,
CH2(C_H2)5CH3 and COCH2(CH2)4CH3), 3.57 (m, 8H, COCHZ), 4.08
(m, 8H, CHZ—porphyrin), 9.50 (s, 1H, meso—H), 10.15 (s, 2H,
meso—H), 10.42 (s, 1H, meso—H); MS (70 eV): m/e = 1150

(parent).

Tetraoctyltetraoctyrylporphyrin (12)

Amax (CHC13): 427 nm, 520, 555, 594, 650; IR (CHClB):
3290 cm"1 (N—H), 1665 (C=O); PMR (CDC13): 6—4.17 (broad s,
2H, N—H), 0.70—0.97 (m, 24H, CH3), 1.00—2.44 (m, 88H,
3H2(CH2)6CH3 and COCH2(CHZ)5CH3), 3.50 (m, 8H, COCHZ), 3.90
'm, 8H, CHZ—porphyrin), 9.35 (s, 1H, meso—H), 10.10 (s, 2H,
leso-H), 10.37 (s, 1H, meso—H); MS (70 eV): m/e = 1262

parent).

etrabutyltetra(d—hydroxy)butylporphyrin (18)
Tetrabutyltetrabutyrylporphyrin (0.32 mmol) was dis—

)lved in 150 ml of tetrahydrofuran and cooled in an ice

1th under nitrogen. Diborane (4 m1 of a 1N tetrahydrofuran

>1ution) was added and the reaction mixture was stirred at

’ for one hour and at room temperature for four hours. The

action was quenched with hydrochloric acid (45 ml of a 5%

ueous solution). The mixture was poured into 100 m1 of an

 

 

37
aqueous 1M sodium carbonate solution and the product ex—
tracted into methylene chloride. After removal of the
solvent, the residue was chromatographed on alumina using
8% methanol in chloroform as eluent. Removal of the solvent
yielded 0.278 mmol (87%) of 18: Amax (CHC13): 408 nm, 508,
540, 575, 626; IR (CHC13): 3425 cm_1 (O—H), 3210 (N—H); MS
(70 eV): m/e = 750 (parent — 4H20).

Octapropylporphyrin (19), octabutylporphyrin (29), octa—
pentylporphyrin (21), octahexylporphyrin (22), octaheptyl—
porphyrin (23), and octaoctylporphyrin (24)

General Procedure:

A solution of pyrrole (69—65) (2.5 mmol), 37% aqueous
formaldehyde (12 m1), and 48% hydrobromic acid (0.5 ml) in
100 ml of absolute alcohol was refluxed for 24 hours under
nitrogen and for an additional 24 hours exposed to the at—
mosphere. The resulting solution was allowed to stand at
700m temperature for seven days. The ethanol was removed
Lnder reduced pressure. After neutralizing the residue with
.queous sodium carbonate, the organics were extracted into
ethylene chloride. The methylene chloride was removed and
he residue chromatographed on silica gel (1:1 hexane/toluene
luent). The yields are listed in Table 2 on page 25. Spec-
cal characteristics of 19, 29, 21, 22, 23, and 24 are

Immarized below.

 

38

Octapropylporphyrin (19)

20’21 sintered 2760);A

mp. sintered 275—278O (lit. max

(CHC13)Z 399 nm, 499, 535, 569, 622; IR (CHClS): 3310 cm—1
(N—H); PMR (CDC13): 0—3.44 (broad s, 2H, N—H), 1.40 (t,
24H, CH3), 2.42 (hextet, 16H, CHZCHS), 4.03 (t, 16H, CH2-

porphyrin), 9.97 (s, 4H, meso—H); l3

CMR (CDC13): 014.72
(9H3), 26.87 (QHZCHB), 28.62 (QHZ—porphyrin), 96.90 (meso
carbons), 140.17 (“8” carbons), 144.35 (”d” carbons); MS

(70 eV): m/e = 646 (parent).

Anal. Calcd for C44H62N4: C, 81.68; H, 9.66; N, 8.66

Found: C, 81.35; H, 9.44; N, 8.53.

Octabutylporphyrin (2Q)

 

mp. sintered 266—2670; Amax (03013): 400 nm, 500, 535,
569, 622; IR (CHC13): 3310 em‘l (N—H); PMR (CDC13): 6—3.65
{broad s, 2H, N—H), 1.12 (t, 24H, 023), 1.77 (m, 16H, CHZCHBL

3-20 (m, 16H, cg CH2CH3), 3.95 (t, 16H, CHZ—porphyrin), 9.85

2
s, 4H, meso-H); 13CMR (CDC13): 614.20 (9H3), 23.42 (QHZCHB),
6-32 (QHZ-porphyrin), 36.10 §H24H§CH3), 96.70 (meso carbonsL
40.17 (”8” carbons), 144.07 (”9” carbons); MS (70 eV):

/e = 758 (parent).

Anal. Calcd for C52H78N4: C, 82.26; H, 10.36; N, 7.38

Found: C, 82.93; H, 9.57; N, 7.18.

:tapentylporphyrin (21)

 

mp. sintered 222—2270; Amax (CHC13): 401 nm, 500, 535,

‘9, 594, 621; IR (CHC13): 3370 cm"1 (N—H); PMR (CDC13)=

 

39
6-3.58 (broad s, 2H, N—H), 1.08 (t, 24H, CH3), 1.75 (m, 32H,
CHZCHZCHB), 2.36 (m, 16H, CHZCH2CH
porphyrin), 10.00 (s, 4H, meso—H);

CH3), 4.03 (t, 16H, CH2-
13

2
CMR (CDC13): 014.06

[CH3), 22.74 (CHZCHB), 26.61 (CH2-porphyrin), 32.56

:QHZCHZCHB), 33.56 (QHZCHZCHZCHB), 96.79 (meso carbons),

.40.22 (”8” carbons), 144.19 (”3” carbons); MS (70 eV):

n/e = 870 (parent).

Anal. Calcd for C H N C, 82.70; H, 10.88; N, 6.43

94 4:
Found: c, 82.88; H, 10.74; N, 6.40.

60

ctahexylporphyrin (22)

 

mp. sintered 173.5—175.50; A (CHC13): 399 nm, 500,

max
34, 569, 622; IR (CHC13): 3295 cm’1 (N—H); PMR (CDC13):

-3 45 (broad s, 2H, N—g), 1.08 (t, 24H, C23), 1.70 (m, 48H,
[2CH2CH2CH8), 2.45 (m, 16H, cg CH2 2
Lz'Porphyrin), 10.08 (s, 4H, meso—H);

CH CH2CH3), 4.15 (t, 16H,

136MB (CDC13): 614.03
H3), 22.64 (9H2CH3), 26.67 (QHZ—porphyrin), 30.01
H2(CH2)2CH3), 31.90 (QHZCHZCHB), 33.80 (CH2(CH2)3CH3),

.78 (meso carbons), 140.31 (”8” carbons), 144.08 (”d”

rbons); MS (70 eV): m/e = 982 (parent).

:aheptylporphyrin (23)

 

mp. 151—1520; A (CHC13); 400 nm, 501, 535, 569, 622;

max
(CHC13): 3310 om‘l (N—H); PMR (CD013): 61.05 (t, 24H,
.): 1.57 (m, 64H, (CH2)4CH3), 2.47 (m, 16H, CH2(CH2)4CH3),
5 (t, 16H, CHZ—porphyrin), 10.05 (s, 4H, meso—H), N—H not
erved; 13CMR (cnc13): 614.01 (9H3), 22.66 (QHZCHS), 26.63

Z‘porphyrin), 29.42 (CHZCHZCH4CH3), 30.34 (CH2(CH2)3CH3),

 

40

31.90 (QHZCHZCHS), 33.91 (9H2(CH CH3), 96.78 (meso carbonSL

2)4
140.22 (”8” carbons), 144.08 (”0” carbons); MS (70 eV):

m/e = 1094 (parent).

Anal. Calcd for C76H126N4: C, 83.30; H, 11.59; N, 5.11

Found: C, 83.61; H, 11.48; N, 4.91.

)ctaoctylporphyrin (24)

 

mp. 140.5—1410; Amax (CHC13): 400 nm, 500, 536, 568,

:21; IR (CDC13): 3310 cm‘1

(N—H); PMR (00013): 6—3.53 (broad
, 2H, N-H), 1.00 (t, 24H, CH3), 1.48 (m, 80H, (c32)5cn3),

.42 (m, 16H, CH2(CH2)5CH3), 4.10 (t, 16H, CH
13

Z—porphyrin),

0.03 (s, 4H, meso—H); CMR (CDC13): 614.01 (CH3), 22.63
zHZCHB), 26.63 (QHZ—porphyrin), 29.39 (9H2(CHZ)ZCH3), 29.74
:H

_ 2(CH2)3CH3), 30.41 (9H2(CH2)4CH3), 31.93 (QHZCHZCH3),

3°93 (QHZ(CH CH3), 96.79 (meso carbons), 140.21 (”8” car—

2)5
)nS), 144.19 (”3” carbons); MS (70 eV): m/e = 1206 (parent).

A . . . .
nal Calcd for C84Hl42N4. C, 83.51, H, 11.85, N, 4.64

Found: C, 83.25; H, 11.71; N, 4.70.

2-3,4—5,6—7,8—Tetra(trimethylene)porphyrin (25)

Ethyl 2—methy1—3,4—trimethy1enepyrrole 5—carboxylate
3) (0.24, 1.3 mmol) was dissolved in 10 ml of acetic acid.
1d tetraacetate (0.6g) was added and the mixture was
.rred at room temperature for 10 min. Water (50 ml) was
led and the product was extracted into methylene chloride.
er removal of the methylene chloride, 0.25 g of potassium
roxide in 5 m1 of water and 5 m1 of ethanol was added to

residual oil. This solution was refluxed for 2 hours,

41

cooled, and diluted with 20 m1 of acetic acid. This acidic
solution was refluxed for 1 hour while air was blown over
the surface. After sitting one day, the black solution was
poured into water and extracted into methylene chloride.

the methylene chloride was removed under reduced pressure
Lnd the residue chromatographed on alumina using 1% methanol
.n methylene chloride as the eluent. Removal of the solvent
"ave 0.017 g (12%) of 25: A (CHC13): 419 nm, 516, 552,

max
88, 638; MS (70 eV): m/e = 470 (parent).

,2-3,4—5,6—7,8—Tetra(tetramethylene)porphyrin (26)

 

) Ethyl 2—methyl-3,4—tetramethylenepyrrole 5—carboxylate
[.78 g, 8.6 mmol) was dissolved in 10 ml of acetic acid.
sad tetraacetate (4.2 g) was added over a 15 min period.
Lter (100 ml) was added and the product extracted into
‘thylene chloride. The methylene chloride was removed

der reduced pressure and 2 g of potassium hydroxide in

m1 of water and 10 ml of ethanol was added to the re—
dual oil. This solution was refluxed for 2 hours, cooled,
i diluted with 20 ml of acetic acid. The acidic solution
5 refluxed for one hour while air was blown over the sur—
:e. After evaporation of the solvent, the porphyrin was
'omatographed on alumina using 1% methanol in methylene

oride as an eluent to yield 0.3 g (27%) of 26.

2-Carbo-t—butoxy—3,4-tetramethy1ene—5—methylpyrrole
) (1.17 g, 5 mmol) was dissolved in 10 ml of acetic acid

cooled to 00 under nitrogen. Sulfuryl chloride (5 mmol)

 

 

42
in 20 m1 of acetic acid was added dropwise to the pyrrole
solution over 15 min. The initially light yellow solution

turned green. After stirring for one hour at room tempera—

ture, the nitrogen was removed and the solution was refluxed.
Heating was continued for three hours and the solution was
allowed to sit for a week at room temperature. After re—
moval of the solvent the residue was chromatographed on
silica gel using 1% methanol in methylene chloride as eluent
to yield 0.02 g (1%) of 26: Amax (CHCl3): 419 nm, 518 nm,
553, 589, 638; PMR (CDC13): 62.58 (m, 16H, porphyrin—
2CHZCHZCHZ—porphyrin), 4.17 (m, 16H, porphyrin—CH2CH2CH2CHZ—
porphyrin), 10.00 (s, 4H, meso—H); MS (70 eV): m/e = 526

CH

(parent).

.,2-3,4—5,6—7,8—Tetra(decamethylene)porphyrin (22)
.) 2—Carbethoxy—5—formyl—3,4—decamethy1enepyrrole (2.95,
.7 mmol) and 3 g of potassium hydroxide were refluxed for
hours in 80 ml of 50% aqueous ethanol. After cooling to
oom temperature, the solution was neutralized with acetic
:id. The solvent was removed under reduced pressure.
:etic acid (60 ml) was added to the residue and the solu—
.on was refluxed for 3 hours while air was blown over the
erace. After sitting one week, the solvent was removed
d the mixture was chromatographed on silica gel using
The product was recrys—

thylene chloride as the eluent.

lized from toluene to yield 0.02 g (1%) of 27.

 

 

IIIIIIIIIIlIll"::::7____________——i

43
B) 2—Carbethoxy—5—acetoxymethy1—3,4—decamethylene-pyrrole
(1.0 g, 2.9 mmol) was dissolved in 20 m1 of 50% aqueous
ethanol. Potassium hydroxide (l g) was added and the solu—
tion was refluxed for two hours. Acetic acid (50 ml) was
deed to the cooled solution and this was refluxed for one
[our while air was passed over the surface. After sitting
‘ne week, the solvent was removed and the residue was
hromatographed on silica gel using 1:1 toluene/methylene
hloride as eluent. Recrystalization from toluene yielded
.07 (12%) of 23: Amax (CHC13): 400 nm, 502, 535, 520, 622;
AR (CDC13/DMSO—d6): 01.3—2.0 (m, 48H, -CH2CH2(CH2)6(3H2CH2—L
2CH2‘
CHZCH2-), 10.42 (m, 4H, meso—H); MS (70 eV): m/e =

.43 (m, 16H, —CH2CH2(CH2)6CH2CH2—), 4.13 (m, 16H, —CH

’H2)6
12 (parent).

 

 

APPENDIX

 

 
 
 

TRANSMHTANCE(%)

5.0

I2

Lgure 3.

 

44

MICRONS

Rtrztmmm
Of

n

2500 2000

FREQUENCY kM

on 70 80 MKRONS 100 1L0120

¢ R! : (“EEC")

1800 1600 I400

VRECIIEN,V (v

Infrared spectrum of tetrapropyltetra—
propyrylporphyrin (12).

160

 

 

 

 

 

45

MICRONS

 
     
 
 

TRANSMITTANCE (%)

3500 3000 2500 2000
FREQUENCV cw

MICRONS ‘0‘0

(D
O

u <v1vuIIHIVLC [70}

R ; R, : (047)3013‘ A

0
l3 cdmmmr.

1800 1600 1400 1200 1000 800

FREQUENCY CM ‘

gure 4. Infrared spectrum of tetrabutyltetra—
butyrylporphyrin (16).

 

 

 

46

! MKRONS

 
   

lKANbMHIANLt(%)

FREQUENCY [Mi

7.0 8.0 M'CRONS 10.0 11.0120

 

100

«a--\,v,

wazcmmm
Or

14

1800 1600 1400 1200

FREOUE NC V th‘

Iure 5. Infrared spectrum of tetrapentyltetra—
pentyrylporphyrin (14).

 

 

 

 

    

 

 

47
25 . ‘30 35 40 MKMER 50 60 80
'00 "“iiiigfi'j'fg“"', " " ' 'f‘ "‘ '“ ' ' ’ ' ' ”' '00
H V I “ ”—7—“. JNW
l J 1
80-r———v‘r*--* - ; ‘* 80
E 1 1‘77 '
Lu __ 1 1 1 .' .
(2)60 . R’ R 1
< ' IR R.
E _“"’ ' ' ‘ “ '
5 l
m ,
Z 40 E— _ A ’7 R ‘i
< R '
I:E ' ' R. j
_* ‘ ' ‘ ' ‘ R ¢ R':(CH,)5CH,‘ ‘ ‘ r” " ' -_+
j . m ;]
20——_4m .. . . . . ,, . - . l5 co(cn,),cn,. ,. f] . 20
0 1. ‘ 0
4000 3500 3000 2500 2000 I500
w*”“R9”5100 H0120 160
I“ ‘ "—."_T“—.___;.—.T.._.—ljr_-f_l]00
, _ __1_1

 

’20

    

.1 R '7 R'
R ¢ RI : (CHQLCH:
07

i 15 co(cu,),CH,

 

igure 6. Infrared spectrum of tetrahexyltetra—

hexyrylporphyrin (16).

 

48

25 30 35 4o MWRONS 50 60 80
00 - ,_, - w 7.. 1n.~. 77”. .0... » - - 1 - ~1oo

80

60

  

 

40 40
20 ' ‘ ' ‘ " ‘ ’ ' ' ‘ R ¢ R’= tu,kCHa'i “‘ ‘ ’ , 20
. . V 0 . . o' . .“ . N . V , L
16 co(cu,),c1-1J . TEEN
O ' T
4000 3500 3000 2500 2000 1500
50 60 70 8O MKRONS 100 110120 160

‘ “' ‘ " < mo

3
E. R ¢ R' : (CH1)bCHJ
or

16 co(c1-1,),c11J
1 800

     

000 1600 1400
Infrared spectrum of tetraheptyltetra—

ure 7. .
heptyrylporphyrln (£§)'

 

49

W 35 4.0 MICRONS 50 50 80

 

~~ 'f—‘HTIOO

A? -A~~~ 8O

 

 

 

   
 
 
   

 

  
 

 

 

 

\J I t
Z l} _ 60
: n IJ
2 *1 U'
kl)
2 .1 ~ ~ -_ ——4o
5 . R' » 1' 1' , _ A 0
~ Rf. R’: (C11,),CH; ‘ -. “W ' A%_“
m — ~ .7 . g ,
'7 C°(<Ha).CHJ- +——~ ~ — ~ ~~'———;’ 2o
_-‘: _ ,7--- "a W -._.__:r I
. 1 1 7 —»
oL———- ‘ ‘ o
4000 3500 3000 2500 2000 1500
50 50 70 80 MICRONS100 1Lo1zo 160

unI‘LLK'/o)

R ;t 11' : (cH,),cH,-
or

‘7 co(cu,)‘,cr1J

 
 

   

1600

2000 1800 1400 1000

ml. ‘

Igure 8. Infrared spectrum of tetraoctyltetra—
octyrylporphyrin (I1).

LL‘

 

 

 

50

 

0
O

TRANSMHTANCE(%)
A
O

20

 

 

 

 

 

0 a
4000 3500 3000 2500 2000 1500
*REQUFN’ ‘ \
50 ‘ do 70 00 MmRONS 100 110120 150
mo~r—‘ ' - » -v 1 ~ ¢-— V mo

80

 

 

 

 

 

2000 1800”__"—_M1500" 1400 1200 1000 800

LRLCUKNL‘ ( “

gure 9. Infrared spectrum of tetrabutyltetra(d—
hydroxy)butylporphyr1n (I§).

 

 

 

51

2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0

    

0 1 .
4000 3 500 3000 7500 2000 1500

5.0 6.0 7.0 30 WHO“ 10.0 11.0120 15.0

.7;__,_

   

     
 

 

80

 

1

19 5:001:11. . “J“ """“ ‘70

 

C1

300 1800 1600 1400 1200 1000 817"

gure 10. Infrared spectrum of octapropylporphyrin (If).

 

 

 

52

 

 

 

 

 

 

 

2.5 3.0 3.5 4.0 M'CRONS 5.0 5.0 8.0
100 100
80 '7 80

550 5 60
Z
<(
E 7
2
V)
Z 40 5 40
<2
0:
’—
20 W m 20

0 .

4000 3500 3000 2500 2000 1500

5.0 5.0 / 0 8.0 M'CRONS 10.0 11.0 12.0 15.0
100:—‘ M“ ' _—"'" E" E' I * " " " “ 1"“ —_j100
80 WW 80

1
$60 1 R R 50
Z 1 ' R
5 J R
'1.
27:40 R / R 40
3" R R
20 R : (CH1)JCHJ
21 20
i
. , ~ "Jo

2110’; 7711} 7 117;“ g "‘1 1.3 1‘." 300

gure 11. Infrared spectrum of octabutylporphyrin (39).

2.5
100

TRANSMITTANCE 17.11

 

  

 

30 15 40 MKKNB 50 50 80

 

‘ .‘ 7V. 4 Rwy. 7 v .WVV~_.*‘_¥._J‘.

 

 

 

 

 

 

 

 

 

4000 3500 3000 2500 2000 1500
HatQJkNiv (M
50 50 70 00 MKRONS 100 110120 150
H”. ~77 ~——400

 

 

 

21 R : «119.01,

 

----- ~———2o

 

 

0%
2000

1800

gure 12.

1400 1200 1000 800

1:1c1:'.4v n

1600

Infrared spectrum of octapentylporphyrin (El)-

 

54

MKRONS 50

J
p

TRANSMITTANCE (

 

2000

FREQUENCY CM

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

50 ' 60 70 00 MIRONS 100 110120 100
1 ' ‘ 1 1 1
we r ’ 2 2 ‘ . 1 mo
1 f I 3 1 1.
80
fl
3 60
z
5
1
) 1
2 ‘ *rr40
: R I ' : 1‘ 1 3 ‘ j
—+*~~' 22 ‘12 :(04.15%:"h’r’rfim" : 1 j- i 1
20 ——— 7 — — A _, ‘ W- ~ v- a 20
1
0 V ‘ ‘ ‘ ' us‘ 0
2000 1800 1500 1400 1200 1000 800

VREOUENCY FM

 

Lgure 13. Infrared spectrum of octahexylporphyrin (g2).

 

 

55

25 ‘ . 4.0 MICRONS 570
m0

 

IKANDMII IANLt 170)

3500 2500

FREQUtNCY CM

7.0 50 ”(FONS 100 110 12.0 16.0

 

 

 

 

 

 

:ure l4. Infrared spectrum of octaheptylporphyrin (3:3,).

56

MICRONS 5:0

  
 
 

 

TRANSMITTANCE (%)

2,4 R :‘ “HQFH:

3500 3000 2500 2000 1500
FREQUENCY (M

5.0 1 6.0 7.0 8.0 M'CRONS 10.0 11012.0 16.0

 

 

 

 

 

 

O
O

 

 

 

 

”\HIVQIVUI IANLE 1‘70)

 

 

 

 

40___-__-_,-,-_ n —R R — j ~ ~ 40
”'_":*"" ’4 ' T“ "5‘ ' '7 ' 24 R :(CH,),CH; " ”f " ' " "" 'I"——§ "‘
20 —7~—~r .,- i ...., - , é' ~ , 4A 74 -~ --—---—— i 20
0 ‘ ‘ o

2000 1800 1600 1400 1200 1000 800

FNOUE’»CY ('1‘

gure 15. Infrared spectrum of octaoctylporphyrin (gé).

 

 

57

 

3:11}—

    

 

 

 

 

 

R p R
. V R' I
M R7fn':(cn,),cu,‘
12 co(cn,)ic11,

1 . l . l l . l l
441.41.444.41. 4 1. 44 7.
gure 16. PMR spectrum of tetrapropyltetrapropyry1—

porphyrin (12).
.A

I 1 1 1 1 1 .L. 1 I"; 1 1

 

 

R¢W=cmmm
Of

'1. 13 co(c11,),cu,
L1 .11 1 .111.'.)1. .1" .1. 1.
.PMR Spectrum of tetrabutyltetrabutyryl—

are 17.
porphyrin (l§)'

 

 

58

 

 

R p / R
. . R R'
R i R' : (01,104,
of

14 1:0(c1-1,)Jc11J

   
 

 

 

‘ Ln
"I" "' I rr ”1 ‘w| 1 “run

 

 

 

Figure 18. PMR spectrum of tetrapentyltetrapentyry1—
porphyrin (14).

 

 

  

. R'
R ¢ 11' : (01.11211.
or

 

 

1s co(cr1,).cu, 1 1 l
.— 1 ’ “‘ 1

so 70 so 5.0 ppm 111 4.0 so

”igure 19. PMR spectrum of tetrahexyltetrahexyryl-
porphyrin (l5).

 

 

59

R¢R':(CH,)HCH

'6 co(CH,),CH

 

 

 

 

Figure 20. PMR spectrum of tetraheptyltetraheptyry1-
porphyrin (16).

 

 

    

m R : R, : (CH1)7CHJ
0'
co(c1-1,).CH 1 1 1

:L—f‘—:£=r-” 1 1. 1 . .1. 1 1 .44

 

'igure 21. PMR spectrum of tetraoctyltetraoctyryl—
porphyrin (If).

 

 

60

 

 

A
r I I \ I I 1 I v r . I jfi—[fi
* $ 0 I 1 M

 

 

 

 

R
R
~‘R
R
19
. l l l 1 J
._.__L. . I I . . . . 1 J . 1 l . 1
so 70 50 5‘0 pm I31 40 :10 2.0 1.0 o

 

Figure 22. PMR spectrum of octapropylporphyrin (19).

 

erT‘vfi’rYIIvvIIYIIIIIvalvva

 

 

 

 

ID I I 70 so 5.0 ”4.47"” to 30

igure 23. PMR spectrum of octabutylporphyrin (g9).

61

 

 

 

 

 

 

A
1 1 ' 1 : I - - - 1 . 1 I .f
am 2:10 1A0 on:
H}
_ 1‘
h
\
R R
R R
Iva R
R R
m R : «”vLCHM I l J, l
._u l . I . l J . .7 l I 14 . . . I
80 70 so 6.0 pm'!‘ 40 30 20 10 0

Figure 24. PMR spectrum of octapentylporphyrin (21).

 

 

 

 

 

 

 

A
.11....1...y1...v1v..'Ivvvvl'.v‘luvvvl....lV
n t k m k 1m

”9
l
R R
R R
R , R .
R R
22R:(CH)CH I 1 I 1
7f“.... . l...l.. l I..A.l
so ‘70 so 5,0 PPM‘E’ ‘0 30 70 In 0

'igure 25. PMR spectrum of octahexylporphyrin (gg).

 

 

 

62

 

 

 

 

 

 

 

A
' ' ' I I I I I ' ' ' I ' ' I I
I I k I I on
I
— I
I
R R
R R
R R
R R
23 R :(cmmu, I I I I
A I ..I..II‘L.I...I .II I I...F
an 70 so 5.0 MM 1.0 no 2:: l0 0

Figure 26. PMR spectrum of octaheptylporphyrin (23).

 

 

 

 

A
"'I' I I I I I 1I 'I' '1'
T II, I, II I IL, II
R R w
I
L

 

 

 

l
Wm . I I .991;
50 PPM'I“ ‘0 3°

20 l0 0
so 70 60 I

 

igure 27. PMR spectrum of octaoctylporphyrin (E3).

 

 

 

63

Porphyrin mfe I
19 707 100
“fl 693 36

679 10

646 4

354 18

20 818 100
MW 812 74
758 59

409 17

406 15

21 932 100
“W 871 9
465 19

22 1044 100
M” 984 14
962 19

522 28

23 1155 100
M” 1150 43
1096 100

577 39

548 38

24 1269 20
W 1208 100
1166 19

604 36

Figure 28.

Mass spectra of octaalkylporphyrins.

64

 

 

 

 

 

 

1 A
I I «1 I I I 1 I 1 1 T 1 I
I
IT I1 I I I II I I AJ_,
igure 29. PMR spectrum of 1,2—3,4—5,6—7,8—tetra—
(tetramethylene)porphyrin (26).
A

 

 

 

 

gure 30. PMR spectrum of 1,2—3,4—5,6—7,8-tetra-
(decamethylene)porphyrin (23).

 

 

PART I I

THE SYNTHESIS AND REACTIONS OF PYRROLES

65

 

 

INTRODUCTION

The introduction of a new synthetic route to 3,4—
;ubstituted pyrroles by van Leusen et al.28 in 1972 has
7mitted the direct synthesis of many pyrroles which had
aviously been available only through multistep reac—

1,29,30,31
)ns .

In this procedure the acidic proton

:a = 11) of p-toluenesulfonylmethyl isocyanide (TosMIC)
readily removed by base, and the resulting nucleophile
an adds to Michael acceptors followed by closure of the

Ig. Loss of p—toluenesulfinic acid and tautomerization

Ipletes the reaction, Scheme 1.

,eme l

30502CH2N2C: I—flai—a CHa-Q-song-mc:

RCH2CHZCHCOR
R R R RCH2CH-QHCOR
‘______ <—-——-'Tos C“
"~ Tos N /
N

‘ ___———>
. N
H

66

 

 

 

67
Ten new pyrroles were prepared by this reaction and
arved as precursors to the porphyrins described in Part I.

The reductive condensation of oximes with B—diketones

LS reported by Kleinspehn32 in 1955. The oxime is reduced

, situ and always condenses with the least hindered car—

nyl function. An internal aldol condensation then forms

five—membered ring, which after ester cleavage and tauto—

rization gives the pyrrole (Scheme 2). This modified

)rr reaction led to the synthesis of several novel pyrroles

I several well—known, synthetically useful pyrroles.

eme 2

g kw R
NQH Zn NH I

B’Lk HOAC Wklz? H
RI .‘fl N

  

 

R R H
I 9‘
g A 1;}?
I
I
02B or CN

Several potentially useful dipyrrolic intermediates

synthesized for use in the synthesis of ring expanded

yrins (223)33’34’35. These included dipyrroles of the

wing kind:

68

28

n1+nIEil_
m:n_1_

porphyfin

1) Two pyrrole units are directly connected to form

)yrrole (29).

/\II
”\/
29

2) Two pyrrole units are connected by a one carbon
dge to form dipyrromethane (30), dipyrromethene (31),

dipyrroketone (32).

C)
.\\ ,/
IH HN H \/NH HN
30 3] 32
3) Two pyrrole units are connected by a three carbon

ge to form dipyrrotrimethine (33).
\x ‘\
<\ Mm
33

4) Two pyrrole units are connected by a five carbon

:e to form dipyrropentadienones (34, 35).

 

69

 

 

35

 

 

 

 

RESULTS AND DISCUSSION

nthesis of pyrroles

 

In order to prepare the 3,4-disubstituted pyrroles
ad in Part I, a general synthesis of a,B-unsaturated
;ones was required. Four possible routes were explored

shown in Schemes 3 and 4.

eme 3
U m.» H ___+ co
R
s A103 5 NHzNHz R s
’OH ‘
Cg
MF

\A w ' m RvflvH
s CH:CHCO(CH2)4R NaOH 5 n
O

36 '

NaH CHa-QSOZCHzNZC:

~s \ MR kw
Ni
/N\ Jr a
43

H
II

70

 

71

:heme 4
:(CH,)2 cacu RCHZCECH (C6H5)3P:CHCOCH3
- ,7 40
I I EfMgBr .
R2'3“ 2IR'(CH,)2CH0 3 "‘332“
H
CH2I2CH=CH3R2 RCH2CECCHICH2I2R (C6H5)3P:CHCOCH2R
38 41
Hg+2
H9C|2 “30+ RICH2)2CHO

2H2)2CH:CHHgCI R(CH2)2CH:CHCO.CH2R

I37 AICL, I 39

RC H2COCI

a. ' b ' c

Thiophene-Z—carboxaldehyde was condensed with 2—
:anone in the presence of base to give l—(2—thienyl)-
-l—ene (36). Unlike furfural, which is known to give
.1 amounts of the wrong isomer36, no competing condensa—
, at the methylene group was observed. This d,B-
turated ketone reacted with TosMIC under basic condi—
s to give 3—butyryl—4—(2—thieny1)pyrrole (11). At—
ted reduction of the thiophene moiety using Raney nickel
ed unpromising, but nickel boride was effective under
30nditions described by C. A. Brown37, giving pyrrole
which was contaminated with small amounts of 3—(2—

Lyl)-4—butyry1pyrrole. This route to the target compound

 

72
I
I

as discontinued for the following reasons: 1) It is not
Litable for preparing octapropylporphyrin; 2) 5—alkyl thio—
iene—2—carboxaldehyde would have to be prepared in three
:eps—Friedel—Crafts acylation of thiophene followed by
alff-Kishner reduction of the ketone and formylation-for
is route to be applicable to the higher homologues;

high regioselectivity of the aldol condensation is re—
ired; 4) better routes to pyrrole (39) were found.

Another synthesis of d,B—unsaturated ketones involved

3 use of vinyl mercuric chloride (33), as shown in
leme 4 path a. This reagent was prepared in the manner

38 Thus treatment of vinyl boranes

scribed by H. C. Brown
:h mercuric acetate gave 33, along with large quantities
elemental mercury. This mixture defied purification de—
te repeated washing of the precipitate. Although crude
reacted smoothly with acid chlorides to give 39, the
te was marred by modest yields, toxic compounds, and a
iously unpleasant odor associated with the vinyl mercuric
Jride.

A different approach to d;B—unsaturated ketones was de-
led to use the Meyer—Schuster rearrangement of acetylenic

Iinols prepared by addition of acetylenic Grignard re—

.ts to appropriate aldehydes, as shown in Scheme 4 path b.

e a large number of terminal alkynes and aldehydes can
btained from chemical supply houses, path b would pro-
an easy access to the a,B—unsaturated ketones. How—

, yields of the isomerized product were only modest,

 

 

 

|IIIIIIIIIIII::::_________________——_

73
Ind the development of an improved synthesis led to dis—
pntinuation of this route.
I The best synthesis of a,B-unsaturated ketones proved
3 be via a Wittig reaction. Alkylation of the deep red
'Lthiotriphenylphosphinoacetonide4O gave the substituted
-ketophosphorane (41) as shown in Scheme 4 path 0. The
asired d,B-unsaturated ketone (39) was efficiently produced

' refluxing the new ylide with a suitable aldehyde in

thylene chloride (Table l).

1) n-BuLi
———————v-+

 

ble 1. (C6H5)3P = CHCOCH3 2) RX (C6H5)3P==CHCOCH2R
4O 41
R(CH2)2CHO
———————*——-+ R(CH ) CH = CHCOCH R
2 2 2
% yield
R d,B-unsaturated ketone from $9 §9
I— CH3(CH2)2CH=CHCOCH2CH3 . 85 a
ICHZ— CH3(CH2)3CH=CHCO(CH2)2CH3 92 b
(CH2)2- CHBCCH2)4CH=CHCO(CH2)3CH3 64 C
(CH2)3— CH3(CH2)5CH=CHCO(CH2)4CH3 56 d
(CH2)4- CH3(CH2)6CH=CHCO(CH2)5CH3 62 e
(CH2)5— CH3(CH2)7CH=CHC0(CH2)6CH3 62 f
2CHZCHZ— CHBCH=CHCO(CH2)SCOCH=CHCH3 68 g

It was found that removal of lithium salts from the
.methylenetriphenylphosphorane prior to its reaction with
aldehyde resulted in higher yields. Apparently the
ium cation complexes the ylide and decreases the charge

arbon by creating a more enolate—like species, which is

 

 

 

IIIIIIIIIIIT___________________——_V
74

is likely to react with aldehydes to form a betaine inter—
Iiate. The alkylated Wittig reagents were invariably con—
ninated with starting material. Separation at this stage

not possible, so the impurity was carried through the
ction and the resulting methyl ketone separated from the
ger chain ketone by distillation.

3,4—Disubstituted pyrroles were synthesized by reacting
MIC under basic conditions with d,B—unsaturated carbonyls

shown in Scheme 1. Results are summarized in Table 2.

I

 

R R
Le 2 U
N
H
R R' % yield pyrrole
COCH2CH3 CHZCHZCH3 74 42
CO(CH2)2CH3 CH2(CH2)2CH3 69 43
CO(CH2)3CH3 CH2(CH2)3CH3 34 43:1
CO(CH2)4CH3 CH2(CH2)4CH3 28 45
CO(CH2)5CH3 CH2(CH2)5CH3 31 46
CO(CH2 )6CH3 CH2(CH2 ) 6CH3 42 4:1
-CO(CH2)5CO— 2 CH3 53 48
—COOCH2CH2— ll 49
CO(CH2)2CH3 2—thienyl 35 11

This provides a simple method for preparing 2,5—
stituted pyrroles which were previously inaccessible.

the C C and nitrogen atoms of the pyrrole ring

2’ 5’
arived from TosMIC, a large variety of pyrroles can

75
I obtained by varying the structure of the Michael
ceptor.
A different pyrrole synthesis gave various 2,3,4,5—
trasubstituted pyrroles by reductive condensation of

imes with B—diketones, Scheme 2. Results are summarized

 

Table 3.
)le 3 I / \
N H,
H
R R' pyrrole % yield ref
CH3 C02Et 59 65 32
CHZCH3 COZEt 51 _ 64 43
-CH2CH2CH2— COZEt 52 7 -—
—CH2(CH2)2CH2— COZEt 53 56‘ ~—
—CH2(CH2)8CH2— C02Et 54 50 ——
CH3 C02C(CH3)3 55 50 43
—CH2(CH2)2CH2— C02C(CH3)3 56 43 -—
CH3 COZCH2C6H5 57 76 43
CH3 CN 58 46 32

This modified Knorr synthesis led to extremely useful
ole intermediates since mono—, di— or trihalogenation
he d—methyl group yielded reactive alkyl halides, alde—
s, or carboxylic acids respectively.

A convenient one pot synthesis of a B-pyrrole car—

nide (59) was conducted as shown in Scheme 5. Reaction

Lethylamine with diketene gave N,N—diethyl acetoacetamide

76
,heme 5
+ Ni(a¢:c1c)2 h ,A

H . N
J H
59
Lch was reacted without isolation with 2—phenylazirine

give 59 in 61% yield.

 

Variation of the nucleophile
le lead to different acetoacetic acid derivatives which

.ld also be converted to pyrroles. The functionalized

roles could serve as useful intermediates in the syne

sis of porphyrins and other pyrrolic annulenes.

ctions of pyrroles

Transformation of functional groups:

Following a reported synthesis of 3,4-dipropylpyrrole4l,

reduction of B-ketopyrroles with lithium aluminum hy—

le was investigated. The reduction of amides to amines
lithium aluminum hydride is well known and extension

his reaction to these vinylogous amides proved to be an

edingly clean, high—yield method for reducing the

nes (Table 4). The crude, spectroscopically pure

ales, were extremely air sensitive. It proved necessary

)nvert them to the octaalkylporphyrins, as shown in

I.

Another useful reduction procedure for the transforma—

of functional groups on pyrroles utilizes the rela—

y recent discovery that reduction of nitriles can be

 

77

 

 

 

 

 

 

 

le 4
R R R R
N [N3
H H
R % yield pyrrole

CH3(CH2)2— 7O 99
CH3(CH2)3— 76 g}
CH3(CH2)7— 85 51.5

Jed at aldehydes using one equivalent of diisobutyl
Lnum hydride (66)42. Cyanopyrrole (§§) was reduced
.dehyde (63) using DiBAl in 66% yield. This reagent
fly simplifies the lengthy procedure43 previously used

eparing 67.

)xidation of d—alkylpyrroles can also be used to pro—
:he necessary functionalization for synthetic inter—
:es. Thus when ethyl 2—methyl-3,4-decamethylenepyrrole
toxylate (54) was treated with one equivalent of lead

,cetate, it yielded 82% of monoacetoxymethylpyrrole (6§).

     
  
  
  

78
equivalents of lead tetraacetate gave a-formylpyrrole
) in 55% yield. These new functionalized pyrroles were

d in the preparation of porphyrins described in Part I.

Preparation and derivatization of dipyrrolic intermedi—.
ates:

Much of the synthetic effort in this part of the re—
ch was directed toward the preparation of dipyrrolic

rmediates (29)—(35). They are divided into four

gories.
(i) Zero carbon bridge:

Bipyrroles have been prepared by the Ullman reaction

44

)dopyrroles. In an earlier study of bipyrroles, it

poted that the iodopyrroles must contain at least one
\

' for the coupling to succeed. Various new iodopyrroles
synthesized to test this statement and to provide syn—
cally useful intermediates (Table 5).

t was found that the Ullman coupling succeeded only

he 2—iodopyrrole bore an ester function at the 5—

on and that yields improved if an ester was also

d at the 3—position. Other electron—withdrawing

onality in 70, 72, and 78 failed to activate the

 

 

 

79

 

 

1e 5
R: R”
N R
H
I R' R" R"' 2 yield pyrrole method ref
CH3CO CH2 CH3 I 7 l 19 A -—
COZEt CH3 I 54 Z} A —-
CH3CO C6H5 I 84 Z3 A -——
CH3 CH3 I 21 73 A —-
CH3 CH3 I 95 Zé B 44
CH3 C02Et I 88 Z? B 44
1C6H5 CH3 002Et I 78 29 B 44
I I CH3 99 ZZ A ——
H H CO 15 78 A —— I
A = pyrrole-H + KI + H202. Method B = pyrrol;:C02H + 12.

a and an ester at the 4-position proved equally

though no new bipyrroles resulted from this study, a

of improvements were found. Iodopyrrole (34) led to

pected product when the reaction was run in dimethyl—

de as described44, see page 84. However, bipyrrole

3 formed in 38% yield when dimethylacetamide was used

ent.

mew method of coupling iodopyrroles gave improved
Bis(triphenylphosphine)nickel(II) dichloride was

with zinc in the presence of triphenylphosphine to

F tris(triphenylphosphine)nickel(O) in situ. Yields

 

 

 

8O

nging from 50—100% were obtained when this homogeneous
ckel reagent45 was used in place of copper as the coupling
agent. The lower yields occurred when the extremely air—
nsitive nickel coupling reaction was scaled—up. The
oduct had to be isolated as the bipyrrole diacid (39) due
difficulty in separating the very insoluble bipyrrole
m the triphenylphosphine used in the reaction. Hydrolysis
the esters gave a base soluble product which could be
Eily isolated by basic extraction of the reaction mixture
Llowed by neutralization.
Synthetically useful bipyrroles could be produced by
lification of the functionality on the existing bi—
‘roles. Since difficulties were encountered in the pref—
ntial hydrolysis of tetraester (3}), mixed bipyrrole
raester (§§) was synthesized by coupling iodopyrrole (26),
lowed by removal of the benzyl groups by catalytic hy—
genation43. In contradiction to an earlier report46
3h claimed ”benzilic compounds are not significantly
?ogenolyzed” by nickel boride, it was found that diacid
could be conveniently produced by nickel boride reduc—
of the mixed tetraester (§2)' The reagent is readily
ared by the reduction of nickel(II) dichloride hexa—
ate with sodium borohydride while hydrogen is provided
gh the reaction of water with the reducing reagent.
method of reducing pyrrole benzyl esters eliminates

eed for an external hydrogen source and specialized

ment.

 

 

81

 

 

H
R
N
H R/

R R' . bipyrrole
COZEt CH3 Z?
COZH CH3 é?
COZEt C02Et §l
COZCHZC6H5 C02Et 33
COZH C02Et 33

A new method for synthesizing bipyrroles was developed

.zing pyrroles (§Q), (§l), and (§g) bearing substitu—
which are suitable for pyrrole syntheses. These pyr—
were synthesized by known methods47’48. Thus a

‘ate conversion to bipyrroles g] and §§ was obtained

2—phenylazirine was stirred with pyrroles ag and §§

ight in acetone. Two isomeric products were isolated,

own in Table 6.

 

6
R R
/
N
H
lvkxndz

rrole R. R' bipyrrole yield dipyrroketone 4¥yield
§3 H CH3 §Z 17.4 29 40.0
fl; CH CH §§ 37.4 2; 59.3

3
86 CH3 OEt 89 0 23 0

W4

 

 

82
The minor component, which eluted first during chroma—
raphy, was tentatively assigned the bipyrrole structure.
extreme insolubility of both isomers made spectroscopic
;urements difficult. Supportive evidence for the assign—

‘ was found in the beautiful blue fluorescence of the

 

r component, which is characteristic of bipyrroles, and
xtreme air-sensitivity which would be expected of its
{tron—rich half. A possible mechanism is shown in

me 6. Dipyrroketone is formed predominantly in this

tion because it results from the kinetically preferred

eophilic attack at the ketone rather than the vinylogous

 

83

A small amount of uncharacterized solid was obtained
n a corresponding reaction of B—ketoester (86). NO
Irrole could be isolated from the modified Knorr reac—

1 with any of these pyrroles.

(ii) Single carbon bridge:
As possible precursors to porphyrins and platyrinsBS,
mber of dipyrromethanes were prepared in the manner

ribed by Paine43, Table 7.

e 7

R R
R 33’ \ NOH
(3A: ” a
3* ' \ NHHN / -' \ NHHN /

 

 

R' R'
R R' R" % yield dipyrromethane ‘
CH3 COZEt -- 40 9E
COzEt COZEt -- 54 Q4
CH3 COZCH2C6H5 -- 42 2?
CH3 -- COZH 55 a?
C02Et -- COZH 84 g3

In contrast to Paine's report, the d—ethyl esters

be preferentially hydrolyzed when treated with base,
5 it unnecessary to synthesize the mixed tetraesters,
ved by catalytic reduction of the benzyl esters.

LS mentioned on page 79, ethyl 2—iodo—3,4—dimethyl-
.e—5—carboxylate led to an unexpected product when

lman reaction was run in dimethylformamide. Although

84

product had a PMR spectrum identical to that expected

bipyrrole, it was identified as dipyrroketone (98) on

basis of its melting point49’ 50 and mass spectrum. Re—

tion with sodium borohydride yielded dipyrromethene (99)

:h verified the existence of the inserted carbon.

Cu
DMF

 

 

Since the product might have incorporated carbon

:ide, formed by decomposition of dimethylformamide, as

. in Scheme 7, the reaction was repeated under a carbon
ide atmosphere. The resulting product was bipyrrole
and these proved to be the only conditions under which
oheues formed using dimethylformamide as the solvent.
er investigation is necessary to provide a plausible
iism and explain the change of products under carbon

ide.

:iii) Three carbon bridge:

lipyrrotrimethine has proven useful in the synthesis
landed porphyrin systems35. Dipyrrotrimethines (£99)
01) were synthesized by reacting tert—butyl ester

ith the appropriate B—dicarbonyl compound under acidic

ions, Scheme 8.

 

85

 

 

 

 

 

eme 8
Me Me
e
\ HBr
~N
H
55 cgk

 

 

86

(iv) Five carbon bridge:

As a possible precursor to a 26 pi annulene, both 1,5—
(5—carbo—t—butoxy-3,4—dimethyl—2—pyrro)—l,4—pentadiene-
ne (l98) and 2,5—di—(5—carbo-t—butoxy—3,4—dimethyl—pyrr—
lmethylene)-cyclopentanone (lgg) were synthesized by
sting pyrrole aldehyde (l9?) under aldol condensation
iitions with acetone and cyclopentanone respectively

leme 9).

eme 9

>1:

NaOH

.[ .
8.1

102

C)
NaOH

OED-t0

 

 

  

 

EXPERIMENTAL

ineral

Instruments used are described in Part I.

(2—Thienyl)—hex—l—ene (36)

 

Thiophene 2—carboxaldehyde (7 g, 62.5 mmol) and 2—
ntanone (13 g, 150 mmol) was stirred in 150 ml of water
700 for four hours along with l g of sodium hydroxide.
a resulting oil was separated and the aqueous layer was
:racted twice with ether (50 ml). The organic layers
'e combined and dried over magnesium sulfate. The vola—
.es were removed under reduced pressure to yield 9.7 g

%) of 36: IR (Neat): 1670 cm"1

(C=O); PMR (CDC13): 60.97
3H, CH3), 1.67 (hextet, 2H, CHZCH3), 2.54 (t, 2H,

a2),
7.50 (d, 1H, CH=CHCO); MS (70 eV): m/e = 180 (parent).

6.43 (d, 1H, CH=CHCO), 6.85—7.33 (m, 3H, thiophene—

ydroxy—4—decyne (38)

 

Magnesium turnings (1.2 g, 49.3 mmol) was added to
11 of tetrahydrofuran under nitrogen along with a crystal
.odine. Bromoethane (6 g, 54.9 mmol) was added at such
,te that the exothermic reaction remained mildly vigor—
After one hour no more magnesium was visible. 1—
yne (25 mmol) in 20 ml of tetrahydrofuran was added
wise over three hours, followed by the dropwise addi—
of n—pentanal (25 mmol). After sitting overnight the

87

 

 

 

 

88

ution was added to 500 ml of saturated ammonium chloride

water. This was extracted with ether (2 X 100 ml) and
ed over magnesium sulfate. The volatiles were removed
er reduced pressure to yield 3.6 g (93%) of 38: IR
at): 3400 cm“1 (N—H), 2375 (CEC); PMR (CDC13): 60.93
erlapping t, 6H, CH ), 1.43 (m, 6H, CHBCHZCHZCECCH(OH)—
in

ZCH3), 2.20 (t, 2H, chCEC), 3.47 (broad s, 1H, OH);

:70 eV): m/e = 154 (parent).

tyrylmethylenetriphenylphosphorane (41a), butyrylmethyl—

 

riphenylphosphorane (419), pentyrylmethylenetriphenyl—

 

phorane (419), hexyrylmethylenetriphenylphosphorane

 

), heptyrylmethylenetriphenylphosphorane (gle), and

 

rylmethylenetriphenylphosphorane (41f)

 

ral Procedure:
To a solution of acetylmethylenetriphenylphosphorane
3 g, 85 mmol) in dry tetrahydrofuran (700 ml) was added
ution of n—butyllithium (40 ml of a 2.2 N hexane solu—
85 mmol) was added. After stirring the dark red
ion for 15 min at —780 alkyl halide (85 mmol) was
The solution was stirred overnight at room tempera—

(red color of ylide anion was discharged). The tetra-
furan was removed under reduced pressure. The residual
is dissolved in methylene chloride. This solution was
1 with water followed by removal of the methylene
.de. Yields, spectral characteristics, and purifica—

lethods (if any) are summarized below.

 

89

‘pyrylmethylenetripheny1phosphorane (41a)

 

The residual oil was taken up into 50 ml of methylene
oride and filtered into 400 m1 of ether. The white solid
collected by filtration and vacuum dried to give 27.8 g

1

95% pure 41a: mp 193—1950; IR (Nujol): 1535 cm’ (C=O);

(CDC13): 61.17 (t, 3H, CH ), 2.30 (q, 2H, CEZCHs), 3.64

1H, p=cg), 7 o—7.7 (m, 15H, c6g5); 130MB (CDC13):

.79 (2H3), 35.84 (d, cogHZ, JP_C 15.6 Hz), 51.09 (d,
I, JP—C 106 Hz), 126.50—134.57 (seven signals, 96H5),
23 (C=O).

rylmethylenetriphenylphosphorane (41b)

 

The residual oil was taken up into 50 ml of methylene
ride and filtered into 400 m1 of ether. The white solid

collected by filtration and vacuum dried to give 29.4 g

1

0% pure 419: mp 132—1340; IR (Nujol): 1535 cm- (C=O);

\
l
J
1
(CDC13): 60.95 (t, 3H, CH3), 1.58 (sextet, 2H, CHZCHS), I
(m, 2H, COCHZ), 3.57 (d, 1H, P=CH), 7.0—7.7 (m, 15H,
); 13CMR (CDC13): 613.40 (9H3), 19.60 (QHZCHB), 42.45
IOCH2, JP—C 1513 Hz), 50.22 (d, P=QH, JP—C
:5—132.32 (seven signals, Q6H5), 192.76 (C=O).

106 Hz),

rylmethylenetriphenylphosphorane (41c)

 

The resulting ylide was 89% pure and was used without

1

er purification. IR (Nujol): 1535 cm" (C=O); PMR

60.90 (t, 3H, CH3), 1.50 (m, 4H, CH CHZCH3), 2.27

3)‘
1, cocgz), 3.66 (d, 1H, p=cg), 7 o-7.7 (m, 15H, c6g5);

(CDC13): 613.38 (9H3), 22.05 (QHZCHs), 28.05

 

 

 

90

: CH2CH3), 40.66 (d, cocgg, JP_C 15.4 Hz), 50.16 (d,

108 Hz), 124.43—132.50 (seven signals, 96H5)’

2

H, JP—C

.16 (9:0).

yrylmethylenetriphenylphosphorane (41d)

 

The resulting ylide which was 88% pure was used without
:her purification. IR (CHC13): 1535 cm“1 (C=O); PMR

:13): 60.85 (t, 3H, ch), 1.0—1.8 (m, 6H, CHZCHZCHZCH3),

: (m, 2H, coch), 3.60 (d, 1H, P=CH), 7.047.7 (m, 15H,
);13CMR (09013): 612.86 (9H3), 21.31 (QHZCHs), 25.58

(CH CH3), 30.65 (QHZCHZCHB), 40.35 (d, COCH J

— 2’ P—C
107 HZ), 124.46—132.54

2)2
Hz), 50.29 (d, P=gH, JP_C

en signals, Q6H5), 192.45 (g=0).

Vrylmethylenetripheny1phosphorane (41g)

 

The resulting ylide which was 73% pure was used without

1

1er purification. IR (Nujol): 1535 cm- (C=O); PMR

.3): 60.83 (t, 3H, 033), 1.1—l.8 (m, 8H, (CH2)4
(q, 2H, Cocgz), 3.61 (d, 1H, P=CH), 7.0—7.7 (m, 15H,
13

CH3),

CMR (CDC13): 613.52 (9H3), 22.05 (QHZCHB), 26.60

CH2)3CH3), 28.76 (9H2(CH2)2CH3), 31.24 (QHZCHchB),
(d, cogHZ, JP_C 14.6 Hz), 50.33 (d, P=§H, Jp_C 107

124.63—132.66 (seven signals, 96H5)’ 193.45 (9:0).

Ilmethylenetriphenylphosphorane (41f)

 

The resulting ylide was 73% pure and was used without
2r purification. IR (Nujol): 1535 cm"1 (C=O); PMR

t): 60.83 (t, 3H, CH3), 1.1-1.8 (m, 10H, (CH2)5
q, 2H, COCHZ), 3.63 (d, 1H, P=CH), 7.0—7.7 (m, 15H,

CH3),

 

 

 

 

 

91
, 13
, CMR (CDC13): 611.76 (9H3), 20.13 (QHZCHB), 24.70

CH2)4CH3), 26.76 (9H2(CH2)2CH3), 27.13 (9H2(CH2)3CH3),

(9H2CH2CH3), 39.12 (d, COQH2, JP—C 15.2 Hz), 49.21 (d,

JP—C 108 Hz, 122.86-132.04 (seven signals, 96H5)’

6 (9:0).

iacetylmethylenetriphenylphosphorylpropane (41g)

To a solution of acetylmethylenetriphenylphosphorane
g, 21.3 mmol) in dry tetrahydrofuran (150 ml) was added
ution of n-butyllithium (10 m1 of a 2.2 N hexane solu—

21.3 mmol). After stirring the solution for 15 min at

1,3—diiodopropane (1.23 ml, 10.7 mmol) was added. The
ion was stirred overnight at room temperature (red

of ylide anion was discharged). The tetrahydrofuran
emoved under reduced pressure. The resulting solid was
Lved in methylene chloride and filtered into 100 ml
ler. The white solid which precipitated was collected
.tration and vacuum dried to yield 7.2 g (100% yield)

, bis—Wittig reagent: IR (Nujol): 1535 cm_1 (C=O);
'DClB): 61.50 (m, 6H, COCH2(CH2)3CH2CO), 2.21 (m, 4H,

, 3.59 (d, 2H, p=cg), 7 0—7.7 (m, 30H, 0635); 130MB
): 626.08 (CHZQHZCHZQHZCHZ), 27.34 (CHZCHZQHZCHZCHZ),
(d, COQHZ, JP—C
23.68—132.00 (seven signals, Q6H5), 192.59 (2:0).

14.8 Hz), 49.78 (d, P=§H, JP-C 107

II

 

92
tene—3—one (999), 5—decene—4—one (99p), 6-dodecene—5—
(99g), 7—tetradecene—6—one (99g), 8—hexadecene-7—one

), and 9—octadecene—8—one (39f)

ral Procedure:

A solution of ylide (gig—f) (60 mmol) and the appro—
:e aldehyde (12 mmol) in 250 m1 of methylene chloride
'efluxed under nitrogen for 24 hours. Pentane was added
:he precipitate of triphenylphosphine oxide filtered
the solution. Distillation gave the d,B—unsaturated
e. The yields are listed in Table l on page 73. Spec—
characteristics of 999, 99E, 99g, 99g, 999, and 99f are

rized below.

ene—3—0ne (999)
IR (Neat): 1685 cm_1 (C=O); PMR (CDC13): 60.8—1.1

Lapping t, 6H, C93), 1.47 (hextet, 2H, CHZCHB), 2.0—2.7

.apping t, 4H, CHZCH=CH and COCH2), 5.8—7.0 (AB quartet,

[=CH); MS (70 eV): m/e = 126 (parent).

ne~4—one (999)

6—Hydroxy—4—decyne (l g, 6.5 mmol) and mercuric oxide
, 0.48 mmol) were refluxed in 25 ml of 85% formic acid
6 hour. The cooled solution was diluted with 200 ml
sodium carbonate in water. The product was extracted
ther (3 X 50 ml). The ether was removed under reduced

7e and the brownish liquid (60%) was suitable for con—

l to pyrrole (43).

 

 

 

 

 

93
b) From Wittig reaction: IR (Neat): 1680 cm‘1 (C=O);

{R (CDC13): 60.93 (t, 6H, CH3), 1.2-1.7 (m, 6H, CHBCHZCH2

2CH2 CH3), 2.0-2.6 (overlapping t, 4H, CHZCH=CH and

CH2), 5.7—6.9 (AB quartet, 2H, CH=CH); MS (70 eV): m/e =

d COCH

4 (parent).

Dodecene—5—one (99g)

 

IR (Neat): 1700 cm‘1 (C=O); PMR (09013): 60.90 (t, 6H,
3), 1.1—1.8 (m, 10H, CH 3(CH2)3 and COCH 2(CH2)2CH3), 2.0-
s (m, 4H, CHZCH=CH and 00092), 5.7—7 0 (AB quartet, 2H,

=CH); MS (70 eV): m/e = 182 (parent).
‘etradecene—6-one (99g)

IR (Neat): 1710 cm‘1 (C=O); PMR (CDC13): 60.90 (t, 6H,

 

), 1.1—1.8 (m, 14H, CH 3(CH and COCH2(CH2)3CH3), 2.0—2.6

2)4
CH=CH and 00092), 5.8—7.0 (AB quartet, 2H, cg=cg); 5

 

4H, C92

(70 eV): m/e = 210 (parent).

axadecene—7—one (39e)

W

 

 

IR (Neat): 1710 0111—1 (C=O); PMR (CDC13): 60.87 (t, 6H,

, 1.0—1.5 (m, 18H, CH3(CH_2)5 and COCH2(CH2)4CH3), 2.1—2.6

4H, cg CH=CH and 00692), 5.8—7.0 (AB quartet, 2H, 09:03):

2
70 eV): m/e = 238 (parent).

tadecene—S—one (39f)

 

IR (Neat): 1700 cm"1 (C=O); PMR (CDC13): 60.90 (t, 6H,

, 1. 1— l. 5 (m, 22H, CH3 (CH and COCH2 (CH CH3), 2.1—2.6

—2)6 —2)5
1H, CH2CH=CH and 60092), 5.8—7.0 (AB quartet, 2H, cg=cg);

70 eV): m/e = 266 (parent).

 

 

 

94

 

11—Tridecadiene-4,10—dione (99g)

A solution of ylide (41g) (7.4 g, 11 mmol) and acetal—
hyde (44 mmol) in 50 ml of methylene chloride was stirred
room temperature for 84 hours. The solvent and remaining
iehyde was removed under reduced pressure. Pentane was
led and the precipitate of triphenylphosphine oxide
Ltered from the solution. The pentane was removed under
luced pressure to give 1.7 g (68%) of Egg : IR (Neat):
’0 and 1640 cm—1 (C=O); PMR (CD013): 61.43 (m, 6H, COCHZ—
:2)3CH2CO), 1.82 (two 8, 6H, Cfls), 2.50 (overlapping t,

COCHZ), 5.8—7.0 (AB quartet, 2H, CH=CH).

ropyl—4—propyrylpyrrole (42), 3—buty1—4—butyrylpyrrole

 

), 3—pentyl—4—pentyry1pyrrole (44), 3—hexy1—4—hexyryl-

 

role (46), 3—heptyl—4-heptyrylpyrrole (46), 3—octyl—4—

 

Irylpyrrole (4]), l.7—bisfi3—(4—methylpyrro)]—1,7-heptane—

 

te(4§), lH—pyrro—[3,4,a]— butyrolactone (42), and 3—

 

ryLA—(Z—thienyl)—pyrrole (11)

 

Iral Procedure:

A solution of p—toluenesulfonyl methyl isocyanide (20
) and d,B—unsaturated ketone (89) (20 mmol) in 100 m1
ther—dimethyl sulfoxide (2:1) was added dropwise to a
red solution of sodium hydride (40 mmol) in 40 m1 of
r. The mixture was stirred for 15—30 min after comple—
of addition. Water (100 ml) was added to the stirred
Ire and the product was extracted with ether (3 X 100 ml)

ether was removed under reduced pressure and the product

 

 

 

 

95
ecrystalized from methylene chloride/pentane. Yields are
isted in Table 2 on page 75. Spectral characteristics of

2, 43, 44, 45, 4g, 47, 4g, 49, and g9.

-Propyl—4—propyry1pyrrole (42)

 

mp. 96—980; IR (Nujol): 3200 cm'1 (NvH), 1535 (C=O);
[R (CDC13): 01.13 (overlapping t, 6H, CH ), 1.58 (hextet,

?, CH CHZCHZ), 2.72 (m, 4H, COCH and CHZ—pyrrole), 6.45

3 2
, 1H, 2—pyrrole—H), 7.23 (m, 1H, 5—pyrrole-H), 9.22

13

road 8, 1H, N—H); CMR (CDC13): 07.85 (QHBCHZCO), 13.00

HBCHZCHZ)’ 22.11 (CHBQHZCHZ), 27.55 (CHBCHZQHZ), 31.40
HZCO), 116.39 (CS—pyrrole carbon), 121.09 (CB—pyrrole
rbon), 123.81 (CZ—pyrrole carbon), 124.01 (C4-pyrrole

ébon), 195.85 (9:0); MS (70 eV): m/e = 164 (parent).

 

3utyl—4—butyrylpyrrole (43)

 

a) 3-Butyryl-4—(2—thienyl)—pyrr01e (0.6 g, 2.7 mmol) 1
. nickel (II) dichloride hexahydrate (6.45 g, 27 mmol)

e dissolved in 300 m1 of ethanol. The solution was

led to 00 and refluxed under nitrogen while sodium boro—
ride (81.5 mmol) in 80 ml of water was added dropwise.
er completion of addition the solution was refluxed for
hour. The precipitated nickel was filtered from the
Led solution and the solvent removed under reduced pres—

e. The crude product was eluted from an alumina column

 

'ield 80% of 43 after removal of the solvent.
)) From TosMIC reaction: mp. 70—720; IR (Nujol): 3200

(N—H), 1665 (C=O); PMR (CDC13): 00.97 (overlapping t,

 

 

 

 

 

96

H, CH3), 1.2—1.9 (m, 6H, CHBCHZCHZCHZ and COCHZCHZCHB),

.70 (overlapping t, 4H, COCH2 and CEZ—pyrrol), 6.48 (m,
, CZ—pyrrole—H), 7.27 (m, 1H, C5—pyrrole—fl), 9.28 (broad

13

, 1H, N—fl); CMR (CDC13): 512.93 (QHB's), 17.41 (CHSQH —

2
2CO), 21.50 (CH39H2(CH2)2), 25.18 (CH3(CH2)29H2), 31.28
H3CH2§H2CH2), 40.58 (QHZCO), 116.39 (Cs—pyrrole carbon—H),
1.67 (CB—pyrrole carbon—E), 124.03 (CZ-pyrrole carbon—H),
4.39 (C4—pyrrole carbon—H), 195.51 (C=O); MS (70 eV):

e = 192 (parent).

Penty1—4-pentyrylpyrrole (44)

 

mp. 63—650; IR (Nujol): 3210 cm—1 (N—H), 1640 cm—

1
‘=O); PMR (CDC13): 00.88 (overlapping t, 6H, CH3), 1.1—
9 (m, 10H, CH3(CHZ)3CH2 and COCH2(CHZ)2CH3), 2.70 (over—

pping t, 4H, CH —pyrrole and COCH2), 6.45 (m, 1H, C —

2
—pyrrole—g), 9.00 (broad s, 1H,

2
rrole—H), 7.25 (m, 1H, C
13

5
i); CMR (CDC13): 013.81 and 13.93 (QHB'S), 22.46 (CH3—

,'s), 26.43 (CH3(CH 9H2), 27.24 (CH3CH 9H CHZCO), 29.66

2)3 2 2
{3(CH2)29H2CH2), 31.75 (CHBCHZQHZCHZCHZ), 39.63 (QHZCO),
7.33 (C5—pyrrole carbon), 123.04 (CB—pyrrole carbon),
2.87 (C2-pyrrole carbon), 126.23 (C4—pyrrole carbon),

:.44 (C=O); MS (70 eV): m/e = 220 (parent).

exyl—4—hexyry1pyrrole (45)

 

mp. 65.5—670; IR (Nujol): 3200 cm’1

(N-H), 1625 (C=O);
(CDC13): 00.90 (overlapping t, 6H, CH3), 1.1—1.9 (m, 14H,

(C32)4CH2 and COCH2(CH2)3CH3), 2.70 (overlapping t, 4H,

 

 

 

 

 

 

97

—pyrrole and COCHZ), 6.42 (m, 1H, CZ—pyrrole—H), 7.23

13
1H, c5

.82 and 14.19 (QHB's), 22.48 (CHBCHZ'S), 24.79 (CH3(CH2)2—

‘CH2CO), 26.46 (CH3(CH2)4CH2), 29.19 (CH3(CH2)22H2(CH2)2),

2)3_ 2)3 and CHBCHZ-

(CH2)2CO), 39.90 (CH3(CH2)39H2c0), 117.33 (Cs—pyrrole

$96 (CH3(CH CH 2CH2), 31.65 (CHBCH CH2(CH

bon), 123.08 (CB—pyrrole carbon), 124.84 (CZ-pyrrole
Don), 126.23 (C4—pyrrole carbon), 197.47 (C=O); MS (70

m/e = 248 (parent).

aptyl—4-heptyrylpyrrole (46)

 

mp. 64.5—670; IR (Nujol): 3195 cm“1 (N—H), 1610 (C=O);

(CDC13): 00.85 (overlapping t, 6H, C33), 1.34 (m, 18H,
CH2)2CH2 and COCH2(CH2)4CH3), 2.71 (overlapping t, 4H,

pyrrole and COCHz), 6.45 (m, 1H, C2—pyrrole—H), 7.27

1H, C5-pYrrole-fl), 9.13 (broad S,_1H, N‘E); 13CMR

13): 013.84 (QHB'S), 22.37 and 22.48 (CH39H2's), 25.20
(CH2)3 CH2 CH 2c0), 26.53 (CH 3(CH2) 59H2), 29.06 and 29.49

CH2 (CH CO and CH3(CH CH2 (CH 31.56 and

2)3— 2)2)’
CH2§H2(CH2)3CO), 39.96 (CH3—

CH2)2 2)2
5 (CH 3CH29H2(CH2)4 and CH3

14C HZCO) 117.49 (CS-pyrrole carbon), 122.79 (Cs—pyrrole
an), 125.20 (CZ—pyrrole carbon), 126.02 (C4—pyrrole car—

197.80 (9:0); MS (70 eV): m/e = 266 (parent).

iyl-4—octyry1pyrrole (41)
F

 

hp. 42—440; IR (Nujol): 3200 cm—1 (N—H), 1620 (C=O);
1
DC13): 00.90 (overlapping t, 6H, CH3), 1.27 (m, 22H,

2)6CH2 and COCH 2(CH2)50H3), 2.67 (overlapping t, 4H,

—pyrrole—H), 8.32 (broad s, 1H, N—H); CMR (CDClSM

 

 

 

98

2H2

5—pyrrole—H), 9.73 (broad s, 1H, N—H); MS (70 eV): m/e =

—pyrrole and COCHZ), 6.42 (CZ—pyrrole—H), 7.25 (m, 1H,

94 (parent).

,7-Bis[~3—(4—methylpyrro)]—1,7—heptanedione (48)

 

Same procedure as other 3,4—disubstituted pyrroles ex—
pt two equivalents of p—toluenesulfonyl methyl isocyanide

d four equivalents of sodium hydride were used to give a

1

% yield of 48: mp. 78—800; IR (Nujol): 3290 em’ (N—H),

50 cm—1

(C=O); PMR (CDCIB/DMSO-de): 01.53 (m, 6H, COCHZ—
132)3CH2CO), 2.23 (s, 6H, C33), 2.65 (t, 4H, COCHZ), 6.40
1, 1H, CZ—pyrrole—H), 7.22 (m, 1H, C5—pyrrole—H), 10.04

13

Iroad s, 1H, N-H), CMR (DMSO—ds): 012.81 (9H3), 25.32

OCH2CH CH CH CHZCO), 29.53 (COCH CH CH CH CHZCO), 39.49

2 2— 2 2 2— 2 2
QQHZ), 118.94 (C2—pyrrole carbon), 119.35 (C4—pyrrole
rbon), 123.46 (CB—pyrrole carbon), 126.03 (C5—pyrrole

rbon), 196.52 (C=O); MS (70 eV): m/e = 286 (parent).

-pyrro—[3,4,a]—y—butyrolactone (49)

 

mp. 163—1660 (decomp.); IR (Nujol): 3300 cm"1 (N—H),

:0 (C=O); PMR (CDC13): 05.15 (s, 2H, CH2), 6.60 (m, 1H,

pyrrole-H), 7.10 (m, 1H, C —pyrrole—H), 9.83 (broad s,

5
N—H); MS (70 eV): m/e = 123 (parent).

utyryl—4—(2-thienyl)—pyrr01e (ll)

 

mp. 136-1370; PMR (CDC13): 00.95 (5, 3H, CH3), 1.70
(tet, 2H, CHZCHB), 2.67 (t, 2H, COCHZ), 6.8—7.4 (m, 5H,
'ole and thiophene protons), 10.07 (broad s, 1H, N—H);

[R (CDC13): 012.91 (9H3), 17.34 (QHZCH3), 40.95 (COQH2),

 

 

 

 

99
116.61, 118.88, 121.01, 122.34, 124.77, 125.23, 125.81,
and 136.17 (eight signals, pyrrole and thiophene carbons),

195.08 (C=O); MS (70 eV): m/e = 219 (parent).

2—Carbethoxy—3,4,5—trimethylpyrrole (59), 2—carbethoxy—

 

3,4—diethyl—S—methylpyrrole (51), 2—carbethoxy—3,4—

 

trimethylene—5-methylpyrrole (52), 2—carbethoxy—3,4—

 

tetramethylene—S-methylpyrrole (53), 2—carbethoxy-3,4—

 

decamethylene—5—methy1pyrrole (54), 2—carbo—t—butoxy—

 

3,4,5—trimethy1pyrrole (55), 2—carbo—t—butoxy—3,4—

 

trimethylene—5—methylpyrrole (26), 2—carbobenzyloxyl—3,4,5-

 

trimethylpyrrole (57), and 3,4,5-trimethy1—2—pyrrole

 

carbonitrile (58)

 

General Procedure:

 

The appropriate B—diketone (1 mole) and zinc dust
(265 g) in 500 ml of acetic acid were stirred rapidly while
diethyl oximinomalonate (or ethyl oximinocyanoacetate)
(1 mole) in 250 m1 of acetic acid was added dropwise. The
exothermic reaction was kept at 950 by adjusting the rate
)f addition. Towards the end of the addition a steam bath
'as required to maintain the temperature. After being
tirred and heated for an additional hour, the solution was
oured into 2 kg of ice. The product was collected by fil—
ration and recrystalized from 95% ethanol. Yields and

pectral characteristics are summarized below.

 

 

 

100

2—Carbethoxy—3,4,5—trimethylpyrrole (59)
1

 

IR (Nujol): 3380 cm_ (N—H), 1665 (C=O); PMR (CDC13):

01.40 (t, 3H, CH CH3), 1.92, 2.18, and 2.28 (three 5, 9H,

13

2
CH3), 4.28 (q, 2H, CH2CH3), 8.97 (broad s, 1H, N—H); CMR
(CDC13): 08.50 (C4—QH3), 10.50 (Cs—9H3), 11.10 (CS—QHS),

14.38 (OCH2QH3), 59.38 (OQHZCHB), 116.45 and 116.79 (C2 and

C4 pyrrole carbons), 127.18 and 129.66 (C3 and C5 pyrrole

carbons), 161.91 (C=O); MO (70 eV): m/e = 181 (parent).

2—Carbethoxy-3,4—diethyl—S—methylpyrrole (51)

IR (Nujol): 3280 cm“1 (N-H), 1650 (C=O); PMR (CDC13): m

 

0O.9—1.4 (overlapping t, 9H, CHZCHB), 1.95 (S, 3H, CH3),
2.28 (q, 2H, C —CH2CH3), 2.61 (q, 2H, C4—CH2CH3), 4.17 (q,

13

3
2H, OCHZCHB), 8.83 (broad s, 1H, N-H); CMR (CDC13): 011.11
(CS-9H3), 14.32 (OCHZQHB), 15.78 (C3 and C4—QH3), 16.90

_ _ 1
(C4 QHZCHB), 18.24 (C3 QHZCHS), 59.36 (OQHZCHB), 116.50 '
(C2—pyrrole carbon), 122.89 (C4—pyrrole carbon), 129.46 (C5—
pyrrole carbon), 133.34 (CB—pyrrole carbon), 161.56 (C=O);

AS (70 eV): m/e = 209 (parent).

é—Carbethoxy—B,4—trimethy1ene—5—methy1pyrrole (52)
l

 

. mp. 139—1410; IR (Nujol): 3270 cm‘

TMR (CD013): 01.33 (t, 3H, CHZCHB), 2.13 (S, 3H, CH3), 2.0—

(N—H), 1645 (C=O);

.9 (m, 6H, —cg2cH2cH2—), 4.23 (q, 2H, OCHZCHB), 8.67 (broad

,, 1H, N-H); 13CMR (cnc13): 611.89 (c5-9H3), 14.38 (0CH29H3),

 

.4.1O (—CH29H2CH2—), 26.50 (C4—9H2), 30.74 (CB—9H2), 59.38

QQHZCHB), 112.54 (CZ—pyrrole carbon), 125.53 (C4-pyrrole

 

 

 

101
carbon), 129.36 (C5-pyrrole carbon), 138.95 (CB-pyrrole
carbon), 161.56 (C=O); MS (70 eV): m/e = 193 (parent).

2-Carbethoxy—3,4—tetramethy1ene—5—methy1pyrrole (53)
1

 

mp. 132—1330; IR (Nujol): 3290 em‘ (N—H), 1635 (C=O);

PMR (CDC13): 01.30 (t, 3H, CHZCH3), 1.72 (overlapping p,

4H, —CH CH CHZCH2—), 2.12-2.67 (m, 4H, —CH CH CH CH —), 2.20

2 2 2 2 2 —2
(s, 3H, CH3), 4.18 (q, 2H, CHZCHS), 8.83 (broad s, 1H, N—H);

13CMR (CDC13): 010.01 (CS—9H3), 14.27 (OCHZQHB), 20.81

(CB—9H2), 22.66 (—CH29H29H2CH2-),
(OQHZCHB), 116.83 (CZ—pyrrole carbon), 119.21 (C4—pyrrole

23.06 (C4—QH2), 59.30
carbon), 125.54 (C5~pyrrole carbon), 132.50 (CB—pyrrole
carbon), 162.14 (C=O); MS (70 eV): m/e = 207 (parent).

2-Carbethoxy-3,4—decamethy1ene—5—methy1pyrrole (54)
mp. 142-1430; IR (Nujol): 3275 cm-1 (N—H), 1630 (C=O);

 

PMR (CDClS): 01.30 (t, 3H, CHZCH3), 1.42 (m, 16H, -CH2(CH2)—

CH2—), 2.17 (s, 3H, CH3), 2.27 (q, 2H, c —CH2), 2.73 (q, 2H,

4
CS—CHZ), 4.23 (q, 2H, CHZCHB), 8.83 (broad s, 1H, N—fi);
13 ,
CMR (CDC13). 011.47 (C5—9H3), 14.27 (OCHZ—QHB), 21.10,
22.58, 25.52, 25.63, 26.13, 26.44, 28.50 (—(§H2)1O—), 59.25
:QQHZCHB), 116.21 (CZ—pyrrole carbon), 122.02 (C4—pyrrole
:arbon), 130.03 (C5—pyrrole carbon), 132.49 (Cs—pyrrole

:arbon), 161.43 (C=O); MS (70 eV): m/e = 291 (parent).

—Carbo—t—but0xy-3,4,5—trimethylpyrrole (55)

IR (Nujol): 3310 cm_1 (N—H), 1660 (C=O); PMR (CDC13):
1.57 (s, 9H, C(CH3)3), 1.87, 2.13, 2.20 (three s, 9H, C33),
.07 (broad s, 1H, N—H); 13CMR (CDC13): 08.51 (C4—QH3),

 

3.59 (CB—CH3), 11.12 (cs—9H3), 28.36 (C(CH3)3), 79.67

 

 

 

102
(9(CH3)3), 116.49 (C2-pyrrole carbon), 117.76 (C4-pyrrole
carbon), 126.18 (CB—pyrrole carbon), 129.05 (CS—pyrrole car—
bon), 161.60 (C=O); MS (70 eV): m/e = 209 (parent).

2—Carbo—t-butoxy—3,4—tetramethy1ene—5—methy1pyrrole (56)
1

 

IR (Nujol): 3310 cm— (N—H), 1650 (C=O); PMR (CDC13):

61.57 (s, 9H, C(CH3)3), 1.73 (m, 4H, ~CH2(CH2)2CH2—), 2.18
(s, 3H, CH3), 2.53 (m, 4H, —CH2(CH2)CH2—), 9.20 (broad s,
1H, N-H); 13CMR (CDC13): 610.17 (Cs—9H3), 20.92, 22.85,

23.15, 26.59 (~(QH2)4—), 28.32 (C(CH3)3), 79.59 (C(CH3)3),
118.26 (CZ—pyrrole carbon), 119.00 (C4-pyrrole carbon),
124.55 (CB—pyrrole carbon), 132.28, (CB—pyrrole carbon),

161.77 (C=O); MS (70 eV): m/e = 235 (parent).

2—Carbobenzyloxyl—3,4,5—trimethy1pyrrole (57)
1

 

IR (Nujol): 3300 cm” (N—H), 1655 (C=O); PMR (CDC13):

51.83, 2.12, 2.20 (three 8, 9H, CH3), 5.15 (S, 2H, OCHZ),

13

7.15 (s, 5H, C6E5)’ 8.92 (broad s, 1H, N—H); CMR (CDC13):

68.52 (C4-QH3), 10.62 (CS—QH3), 11.18 (Cs—9H3), 65.16
*OQHZ)’ 116.08, (CZ-pyrrole carbon), 117.06 (C4—pyrrole
,arbon), 127.77 (ortho and para phenyl carbons), 128.33

,

ICB—pyrrole carbon), 129.76 (meta phenyl carbons), 130.01

bs—pyrrole carbon), 136.62 (quaternary phenyl carbon),

61.41 (9:0); MS (70 eV): m/e = 243 (parent).
1 1
L4,5—Trimethy1—2-pyrrole carbonitrile (58)

? IR (Nujol): 3265 cm'1 (N—H), 2210 (CN); PMR (CDC13):

 

..83, 2.05, 2.10 (three 8, 9H, CH3), 8.60 (broad s, 1H,
13

JH); CMR (CDC13): 08.41 (C4—9H3), 9.88 (cs—9H3), 11.17

 

$1

 

 

 

103
(C5-QH3), 96.06 (9N), 115.63, 130.83, 131.36 (pyrrole car—

bons); MS (70 eV): m/e = 134 (parent).

Diethyl 2—methy1-4—phenylpyrrole 3—carboxamide (59)

 

Diethylamine (2 m1, 19.3 mmol) was stirred in 40 m1 of
dry acetone under nitrogen. Diketene (19.3 mmol) was added
dropwise and the solution was stirred for three hours at
room temperature. 2-Phenylazirine (2.0 m1) and 0.1 g of
nickel acetylacetonate was added and the solution was stirred
overnight. Water (120 ml) was added and the beige crystals
were collected by filtration to yield 3.0 g (61%) of 59:

mp 162-1630; IR (Nujol): 3125 and 3180 cm_1

(N—H), 1580
(C=O); PMR (CDC13): 00.72 and 1.12 (two t, 6H, CH2CH3), 1.98
(s, 3H, CH3), 3.00 and 3.47 (two q, 4H, NCHZCHB), 6.50 (d,

1H, C —pyrrole-H), 7.28 (m, 5H, C635), 9.78 (broad s, 1H,

13

2
N—HO); CMR (CDC13): 09.35 (C2—QH3), 10.78 and 11.74
(QHZCHB'S), 41.00 (NQHZCHB'S), 111.82, 112.84, 119.76, 123.29
pyrrole carbons), 124.09 (ortho phenyl carbons), 124.83

para phenyl carbon), 126.37 (meta phenyl carbons), 134.02
quaternary phenyl carbon), 166.68 (C=O); MS (70 eV): m/e =

56 (parent).

,4—Dipropylpyrrole (69), 3,4—dibuty1pyrrole (61), 3,4—

 

 

ipentylpyrrole (62), 3,4-dihexylpyrrole (63), 3,4—diheptyl—

brrole (64), and 3,4-diocty1pyrrole (g5)

 

eneral Procedure:

Lithium aluminum hydride (50 m1 of a 0.67 M ether solu—

ion, 33.4 mmol), was added to a stirred solution of pyrrole

 

 

104
(42-42) (8.3 mmol) in 150 m1 of tetrahydrofuran under
nitrogen. The mixture was refluxed for three hours. To
the cooled solution was added cautiously and in order
water (1.3 m1), sodium hydroxide (1.3 m1 of 15% w/w aqueous
solution), and water (3.9 ml). The inorganic precipitate
was filtered by suction and washed with tetrahydrofuran.
The tetrahydrofuran was removed under reduced pressure.
Yields are given in Table 4 on page 77. Spectral charac—

teristics of 60, 61, 62, 63, 64, and 65 are summarized below.

3,4—Dipropy1pyrrole (60)

 

1

IR (Neat): 3380 cm— (N-H); PMR (CDC13): 50.93 (t, 6H,

CH. 1.58 (hextet, 4H, CEQCH3)» 2.37 (t, 4H, GHQ—pyrrole),

13

3),

6.23 (d, 2H, pyrrole—H), 7.42 (broad s, 1H, N—H); CMR
(CDC13): 013.98 (CH3), 23.47 (QHZCHB), 27.30 (QHZCHZCH3),

114.73 (C2— and C —pyrrole carbons), 122.53 (C3— and C4—

5

yrrole carbons).

,4—Dibuty1pyrrole (g1)

 

1

IR (Neat): 3380 cm' (N—H); PMR (CDC13): 60.95 (t, 6H,

I13),
.41 (d, 2H, pyrrole—H), 7.67 (broad s, 1H, N—H);

1.52 (m, 8H, CH2CHZCH3), 2.43 (5, 4H, CHZ-pyrrole),
13CMR
CDC13): 013.90 (9H3), 22.65 (QHZCH3), 24.86 (9H2(CH2)2CH3),
2.59 (QHZCHZCHB), 114.70 (C2- and C5—pyrrole carbons),

22.95 (C3— and C —pyrrole carbons).

4

 

 

 

 

105

3,4-Dipenty1pyrrole (62)

 

1

IR (Neat): 3375 cm- (N-H); PMR (CD013): 00.88 (t, 6H,
CH3), 1.40 (m, 12H, (CH2)3CH3), 2.38 (t, 4H, CHZ-pyrrole),
6.35 (d, 2H, pyrrole-H), 7.56 (broad s, 1H, N-H); 13CMR

(CDC13): 613.90 (9H3), 22.47 (QHZCH3), 25.16 (9H2(CH2)3CH3),
30.10 (CH2(CH2)ZCH3), 31.84 (QHZCHZCHs), 114.70 (02— and

05-pyrrole carbons), 122.94 (C3- and C4—pyrrole carbons).

3,4—Dihexy1pyrrole (63)
IR (Neat): 3380 cm”1 (N—H); PMR (CD013): 00.87 (t, 6H,

CH 1.35 (m, 16H, (CH2)4CH3), 2.36 (t, 4H, CHZ-pyrrole),

13

3),
6.27 (d, 2H, pyrroleffl), 7.50 (broad s, 1H, Neg); CMR
(CDC13): 013.87 (CH3), 22.50 (QHZCHB), 25.15 (9H2(CH2)4CH3),
29.26 (9H2(CH2)2CH3), 30.34 (9H2(CH2)3CH3), 31.65 (QHZCHZCHBL
114.62 (CZ— and C5—pyrrole carbons), 122.72 (C3— and C4—

:pyrrole carbons).

3,4-Dihepty1pyrrole (64)

 

IR (Neat): 3380 cm"1 (N-H); PMR (CDC13)I 60.95 (t. 6H,
H3), 1.58 (m, 20H, (CH2)5CH3), 2.46 (t, 4H, CHZ—pyrrole),

13CMR

.45 (d, 2H, pyrrole—H), 7.73 (broad s, 1H, Nfifi);
CDC13): 013.90 (9H3), 22.54 (QHZCHB), 25.18 (QHZ(CH2)5CH3),
.9.13 (9H2(CH2)ZCH3), 29.58 (QH2(CH2)3CH3), 30.41 (9H2(CH2)4—
3H3), 31.77 (QHZCHZCHs), 114.65 (C2— and C5—pyrrolecarbons),

.22.81 (03— and C4—pyrrole carbons).

.,4—Dioctylpyrrole (65)
IR (Neat): 3380 om‘l (N—H); PMR (CDC13): 60.85 (t, 6H,

 

H 1.28 (m, 24H, (CH2)6CH3). 2.38 (t, 4H. CEZ-pyrrole),

3).

 

 

 

106

13

6.33 (d, 2H, pyrrole—H), 7.57 (broad s, 1H, N—H); CMR

(CDC13): 613.84 (9H 22.51 (QHZCHB), 25.14 (9H2(CH2)6CH3),

3),
29 19 (9H2(CH2)2CH3), 29.40 (QH2(CH2)3CH3), 29.59 (9H2-

(CH CH3), 30.39 (QHZ(CH2)5CH3), 31.77 (CHZCHZCHS), 114.61

2)4
(C2— and 05-pyrrole carbons), 122.66 (03— and C4-pyrrole

carbons).

2—Formyl—3,4,5—trimethy1pyrrole (67)

 

2—Cyano—3,4,5—trimethy1pyrrole (6.7 g, 50 mmol) was
stirred in 50 m1 of benzene. Diisobutyl aluminum hydride
(50 ml of a 1N hexane solution) was added slowly at room
temperature under nitrogen. The initially colorless solu—
tion turned orange and warmed slightly as the reducing
agent was added. After one hour 3 ml of methanol was added
and the solution was stirred for 15 min. Water (5 ml) was

added and the solution turned warm and gelatinous. The

   
  
  
  
  
  
   
  
  

inorganics were removed by suction filtration and washed
ith methylene chloride. The solvent was removed from the
iltrate under reduced pressure and the crude product re—

rystalized from methanol/water to yield 4.5 g (66%) of 67.

1

R (Nujol): 3245 cm‘ (N—H), 1635 (C=O); PMR (CDCl 01.85

3)‘

s, 3H, C —CH3), 2.19 (s, 6H,(3-and(thH 9.20 (s, 1H,

3 3),
13CMR (CDCl 68.05 (C4—QH

5
H0), 10.04 (s, 1H, N—H); 3): 3),
.60(C3—QH3), 11.13 (CS—9H3), 117.54 (C4—pyrrole carbon),
753 (C2—pyrrole carbon), 132.86 (C5—pyrrole carbon),

.71 (CB—pyrrole carbon), 175.06 (9&0); MS (70 eV): m/e =

7(parent).

 

 

 

 

 

 

107

5—Acetoxymethyl—2—carbethoxy—3,4—decamethy1enepyrrole (68)

 

2—Carbethoxy—3,4—decamethylene—5-methy1pyrrole (5.82
g, 20 mmol) was dissolved in 200 m1 of acetic acid. Lead
tetraacetate (9.8 g) was added in small portions over one—
half hour. The slurry was stirred for 15 min after comple—
tion of addition. Water (100 ml) was added and the crude
product which precipitated was collected by filtration,
washed with water and recrystalized from hexane to yield
5.7 g (82%) of 68: mp. 152—1530; IR (Nujol): 3285 cm-1
(N—H), 1710 (C=O); PMR (CDC13): 01.32 (t, 3H, CHZCH3), 1.43
(m, 16H, —CH2(CHZ)CH2—), 2.05 (s, 3H, CH ), 2.65 (m, 4H,
—CH2(CH2)8CH2—), 4.20 (q, 2H, CHZCHB), 6.57 (s, 2H, CH3—
COCHZ—), 9.05 (broad s, 1H, N—H); 13CMR (CDC13): 014.31
(OCHZQHB), 20.84, 22.39, 22.76, 25.51, 25.79, 26.34, 26.41,
28.42 (—(gH2)lO—), 29.72 (COCHB), 57.28 (QHZOCOCHS), 118.80
(CZ—pyrrole carbon), 125.34, 127.01 (C4— and 05—pyrrole
carbons), 131.74 (CB—pyrrole carbon), 161.00 (EtOQ=O),

171.45 (CH3Q=O); MS (70 eV): m/e = 349 (parent).

3—Carbethoxy—5—formyl—3,4—decamethy1enepyrrole (69)

 

2—Carbethoxy—3,4—decamethylene—5—methylpyrrole (5.82
, 20 mmol) was dissolved in 200 m1 of acetic acid. Lead
etraacetate (19.6 g) was added over 15 min at room tem-
erature. The solution was heated on a steam bath for one

ur after completion of addition and then diluted with

 

0 m1 of water. The product was extracted into methylene

loride. The methylene chloride was stripped off and the

 

 

 

IIIIIIIIIIIIT_______________________h_—_-________________—__—____—-='7T7‘

108

product recrystalized from hexane to yield 3.35 g (55%) of

69: IR (Nujol): 3270 om‘l (N—H), 1675 (C=O); PMR (CDC13):
01.33 (t, 3H, CHZCHB), 1.47 (m, 16H, —CH2(CH2)8CH2-), 2.67
(t, 4H, —C§2(CH2)8CH2-), 4.28 (q, 2H, CHZCHB), 8.67 (broad

s, 1H, N—H), 9.62 (s, 1H, CH0); 13

CMR (CDC13): 014.05
(OCHZQHB), 20.69, 21.63, 22.18, 22.72, 25.09, 26.05, 26.31,

28.31, 31.05 (—(9H 60.69 (OQHZCHB), 124.38 (C2—

2)10‘)’
pyrrole carbon), 129.88, 131.79 (C4— and C5—pyrrole carbons),
135.50 (CB—pyrrole carbon), 160.51 (EtOg=O), 179.46 (HC=O);

MS (70 eV): m/e = 305 (parent).

4—Acety1—3—ethy1—2—iodopyrrole (ZQ), 4—carbethoxy—3—methyl—

 

2—iodopyrrole (71), 3-acetyl—5—methy1-4—pheny1—2—iodopyrrole

 

(72), 3,4—dimethy1—5—formy1-2—iodopyrrole (73), 2,5—dimethyl—

 

‘3,4—diiodopyrrole (7]), and 5,5'—diiodo—2,2'-dipyrroketone

(Z§)

 

General Procedure:

 

To a refluxing solution containing 12.5 mmol each of
the appropriate pyrrole, acetic acid and 30% hydrogen per—
oxide in 15 m1 of ethanol, there was added 12.5 mmol of
potassium iodide in 10 ml of water. The rate of addition

as adjusted so that the dark red color which immediately
formed with each drop, rapidly disappeared. The solution

as refluxed for one hour after completion of addition and

llowed to sit at room temperature overnight. The white

rystals were collected by suction filtration, washed with

 

 

 

 

 

109
95% ethanol, and allowed to dry. Spectral characteristics

of 70, 71, 72, 73, 77, and 78 are summarized below.

M

4-Acety1—3—ethyl—2—iodopyrrole (ZQ)

 

mp. 146-147.50; IR (Nujol): 3125 cm"1 (N—H), 1620 (C=O);

PMR (CDC13): 01.07 (t, 3H, CHZCH3),

2.67 (q, 2H, CHZCHs), 7.30 (d, 1H, C5-pyrrole-fi), 8.83
13

2.37 (s, 3H, COCHB),
(broad s, 1H, N—H); CMR (CDC13): 013.89 (CHZQHB), 19.91
(QHZCH3), 26.09 (COQH3), 68.82 (CZ—pyrrole carbon), 122.72
(Cs—pyrrole carbon), 128.15 (C5—pyrrole carbon), 130.15
(C4—pyrrole carbon), 191.34 (C4—pyrrole carbon); MS (70 eV):

m/e = 263 (parent).

 

4-Carbethoxy—3—methy1—2—iodopyrrole (11)

IR (Nujol): 3235 om’1 (N-H), 1660 (C=O); PMR (CDC13):
201.30 (t, 3H, CH2CH3), 2.20 (s, 3H, CH3), 4.17 (q, 2H,

QHZCH3), 7.28 (d, 1H, c5
N-H);13CMR (CDC13): 612.20 (Cs-CH3), 13.37 (CH29H3), 58.08

—pyrrole—H), 8.37 (broad s, 1H,

 

(OQHZ), 67.35 (CZ—pyrrole carbon), 114.02 (CS-pyrrole carbonL

I W! ' .‘..' '—

126.76 (03— and C —pyrrole carbons), 161.29 (C=O); MS (70

4
eV): m/e = 279 (parent).

B-Acetyl-5—methyl-4-pheny1-2-iodopyrrole (12)

 

mp. 158—1590; IR (Nujol): 3145 om‘l (N-H), 1615 (C=O);

’MR (CDC13): 61.81 (s, 3H, C -CH3), 2.45 (s, 3H, COCH3),

5 ._
13

'.17 (S, 5H, C6E5)’ 10.95 (broad S, 1H, N—H); CMR (CDCl

3)‘
12.48 (CS-CH3), 28.75 (COQH3), 64.84 (CZ—pyrrole carbon),

20.95, 125.51, 129.26, 135.46, 137.34 (C3-, C4—, Cs—pyrrole

 

 

110
.carbons and quaternary and para phenyl carbons), 126.53
(ortho phenyl carbons), 128.90 (meta phenyl carbons), 192.66

(C=O); MS (70 eV): m/e = 325 (parent).

3,4—Dimethyl’5—formy1-2-iodopyrrole (73)
1

 

IR (Nujol): 3195 cm‘ (N-H), 1620 (C=O); PMR (CDC13/

DMSO-d6): 01.92 and 2.23 (two S, 6H, CH3), 9.18 (S, 1H, CHO),

13

10.98 (broad S, 1H, N-H); CMR (CDClB/DMSO-d6): 08.11, 10.00

(9H3), 80.36 (CZ—pyrrole carbon), 124.28, 128.09, 132.38

(C3—, C and C —pyrrole carbons), 174.86 (C=O); MS (70 eV):

4" 5
m/e = 249 (parent).

2,5-Dimethy1—3,4—diiodopyrrole (77)

 

mp. 113-114.50; IR (Nujol): 3345 (N—H); PMR (CDC13/
DMSO-da): 02.23 (s, 6H, C33), 10.10 (broad s, 1H, N—H);
, 120MB (CDCl /DMSO—d ): 013.65 (CH ), 70.78 (C - and C —
3 6 —-3 3 4
. pyrrole carbons), 128.68 (C2— and C5—pyrrole carbons);

EMS (70 eV): m/e = 347 (parent).

5,5'—Diiodo-2,2'—dipyrroketone (78)
1

 

IR (Nujol): 3165 cm‘ (N—H); PMR (Ruse—66): 67.22 (m,

4H, —pyrrole—H); MS (70 eV): m/e = 412 (parent).

Ethyl 3,4-dimethy1—5—iodopyrrole—2—carboxylate (14), diethyl

 

3-methyl—5—iod0pyrrole—2,4—dicarboxy1ate (Z5), and 2-Benzy1

 

4-ethy1 5-iodo—3—methy1pyrrole 2,4-dicarboxy1ate (16)

 

General Procedure:

 

The appropriate pyrrole-Z-carboxylic acid43 (200 mmol)

was dissolved in 250 m1 of ethanol and 365 m1 of water

 

 

111
containing 43.6 g of sodium bicarbonate. The solution was
warmed to 650 and a mixture of iodine (47.1 g) and potassium
iodide (69 g) in 550 m1 of water was added dropwise as fast
as it was decolorized. After being stirred for an addi—
tional 10 min, the hot solution was filtered and allowed
to cool. The product was collected by suction filtration.
Spectral characteristics of 74, Z5, and 76 are summarized

below.

Ethyl 3,4—dimethyl—5—iodopyrrole—2—carboxylate (74)

IR (Nujol): 3250 cm‘1 (N—H), 1670 (C=O); PMR (CDC13):

01.33 (t, 3H, CH2CH3), 1.93, 2.27 (two S, 6H, CH3), 4.25

13

(q, 2H, CHZCHB), 9.00 (broad s, 1H, N—H); CMR (CDC13):

4—QH3), 14.34 (CH2CH3), 60.08
(OCHZ), 73.36 (Cs—pyrrole carbon), 123.56, 126.68, 128.68

610.92, 11.66 (c3- and c

(C3-, C4—, and C2—pyrrole carbons), 160.82 (C=O); MS (70

eV): m/e = 293 (parent).

Diethyl 3—methy1—5—iodopyrrole—2,4-dicarboxy1ate (Z5)

IR (Nujol); 3240 cm_1 (N-H), 1665 and 1690 (C=O);
PMR (CDC13): 01.33 (t, 6H, CHZCHB), 2.50 (s, 3H, C3—CH3),
4.20 (q, 4H, CH2CH3), 11.83 (broad s, 1H, N—H); 13CMR
(CDCIB): 010.30 (CB-CH3), 12.62, 12.70 (CHZQHB), 57.88,
58.26 (QHZCHS), 77.67 (C5—pyrrole carbon), 118.08, 123.20,

128.48 (C3—, C4—, and C2—pyrrole carbons), 158.46, 161.73

(C=O); MS (70 eV): m/e = 351 (parent).

 

 

112

4—Benzyl 2—ethyl 5—iodo—3—methylpyrrole—2g4—dicarboxylate (76)

IR (Nujol): 3230 cm”1 (N—H), 1670 and 1685 (C=O); PMR

 

(CDC13): 61.50 (t, 3H, CHZCHB), 2.68 (CB—CH3), 4.38 (q, 2H,

CHZCHB), 5.37 (S, 2H, CH C6H5), 7.35 (S, 5H, C6H 9.48

_. _5)7
(broad s, 1H, N—H); MS (70 eV): m/e = 412 (parent).

Diethyl 3,3',4,4'-tetramethy1—2,2'—bipyrrole—5,5'-

 

dicarboxylate (19), tetraethyl 4,4'—dimethy1—2,2'—bipyrrole-

 

3,3',5,5'—tetracarboxy1ate (81), and 5,5'—dibenzy1 3,3'—
diethyl 4,4'—dimethyl—2,2'—bipyrrole—3,3',5,5'—tetra—

carboxylate (82)

General Procedure:

 

The iodopyrrole (10 g) was dissolved in N,N—dimethy1—
formamide (5 m1) and 1 g of copper bronze was added. The
mixture was stirred at 1000 for three hours. The copper
was then filtered and washed with hot chloroform (4 X 501n1)
The filtrate and washings were extracted with 1N hydro—
chloric acid (2 X 100 m1) and with water (2 X 100 m1) and
dried over magnesium sulfate. After removal of the solvent,
the product was recrystalized from chloroform/hexane. The

spectral characteristics of 79, 81, and 82 are summarized

below.

Diethyl 3,3',4,4'-tetramethyl—2,2'—bipyrrole—5,5'-
iicarboxylate (19)
—1 _ . .
IR (Nujol): 3240 cm (N—H), 1655 (C—O), PMR (CDC13).

51.28 (t, 6H, CHZCHS), 1.95, 2.23 (two S, 12H, CH3), 4.17

 

 

 

 

 

113
(q, 4H, CHQCHS), 11.00 (broad s, 2H, N-H); MS (70 eV):

m/e = 332 (parent).

Tetraethyl 4,4'—dimethyl—2,2'—bipyrrole—3,3',5,5'-

tetracarboxylate (81)

 

IR (Nujol): 1690 and 1615 (C=O); PMR (CDC13): 01.55
(t, 12H, CHZCH3), 2.55 (s, 6H, C4-CH3), 4.28 (overlapping
q, 4H, CHZCHs), 13.98 (broad s, 2h, N—fi); MS (70 eV):

m/e = 448 (parent).

_§L5'—Dibenzy1 3,3'—diethyl 4,4'-dimethy1-2,2'-bipyrrole—
3,3',5,5'-tetracarboxy1ate (82)

IR (Nujol): 1720 and 1625 (C=O); PMR (CDC13): 01.38
(t, 6H, CHZCHB'S), 2.57 (s, 6H, C4-CH3), 4.30 (q, 4H,
CHZCH3), 5.25 (s, 4H, CH C6H5), 7.20 (m, 10H, Gags), 14.13

(broad s, 2H, N—H); MS (70 eV): m/e = 572 (parent).

3,3',4,4'—Tetramethy1-2,2'—bipyrrole—5,5'—dicarboxylic

acid (§9)

 

In an oven—dried 100 m1 flask, bis(triphenylphosphine)—
nicke1(II)dichloride (4.0 mmol), triphenylphosphine (8.0
mmol), and zinc dust (4.0 mmol) were stirred in 20 m1 of
oxygen—free N,N-dimethy1formamide. The system was evacu-
ated by a pump and flushed with nitrogen. This was repeated
twice before the flask was immersed in an oil bath at 500
and stirred for an hour. The deep blue solution turned
green and then brown. Ethyl 3,4-dimethy1-5—iodopyrrole—2—

carboxylate (3.0 mmol) in 20 m1 of oxygen-free N,N-dimethy1-

formamide was added and the solution was stirred overnight.

 

 

 

114
The cooled solution was poured into 80 m1 of 2% aqueous
hydrochloric acid. The product was extracted into 120 m1
of chloroform and diluted with 120 m1 of ether. This
solution was washed with water, then brine, and dried over
magnesium sulfate. The solvent was removed under reduced
pressure and the residual solid and 1.0 g of potassium
hydroxide was refluxed overnight in 50 m1 of 1:1 ethanol/
water. The cooled solution was extracted twice with ether.
Acetic acid (1 ml) was added to the aqueous layer to pre—
cipitate a quantitative yield (contaminated by a small
amount of triphenylphosphine) of 89: IR (Nujol): 3280 cm—1
(N-H), 1700 (C=O); PMR (CDC13/DMSO-d6): 01.93, 2.25 (two s,
12H, CH3), 10.62 (broad s, 2H, N—H); MS (70 eV): m/e = 188

(parent).

3,3'—Diethyl—4,4'—dimethyl—2,2'-dipyrrole—3,3'-dicarboxy-
late—5,5'—dicarboxylic acid (83)

5,5'-Dibenzyl 3,3'—diethyl 4,4'-dimethy1—2,2'—
bipyrrole-3,3',5,5'-tetracarboxylate (1.4 mmol) and
nicke1(II)dichloride hexahydrate (27.2 mmol) were dissolved
in 300 ml of absolute ethanol under nitrogen and cooled to
00. Sodium borohydride (81.5 mmol) in 80 m1 of water was
added dropwise. The black mixture was refluxed for one
Iour after completion of addition. The black precipitate
vas removed by suction filtration and the solvent removed
Inder reduced pressure. The residue was dissolved in ether

1nd extracted with 10% aqueous sodium hydroxide. The basic

 

 

115
aqueous layer was neutralized to precipitate 1.1 mmol (78%)

1

of §§‘ IR (Nujol): 3200-3400 om‘ (N4H) and OH), 1635

(C=O); MS (70 eV): m/e = 348 (parent —2C02).

3-Acety1-4-phenyl-2,2'-bipyrrole (81), 3-acety1-3',4'—

 

dimethyl—4-phenyl—2,2'-bipyrrole (88), 2—methyl-4-phenyl—
3,2'-dipyrroketone (90), and 2,3',4'-trimethy1-4—pheny1—

3,2'-dipyrroketone (91)

 

General Procedure:

 

2-Acetoacetylpyrrole (84 or 85) (12 mmol) and nickel
acetylacetonate (0.1 g) were dissolved in 20 m1 of acetone
-under nitrogen. 2—Pheny1azirine (12 mmol) was added and
the solution was stirred overnight. Water (75 ml) was
added and the product collected by suction filtration. The
Acrude product was chromatographed on silica gel using
.methylene chloride to elute bipyrrole (87 or 88) and 2%
‘methanol in methylene chloride to elute dipyrroketone (90
or 91). Yields are given in Table 6 (page 81) and spectral

characteristics are summarized below.

3—Acetyl-4—phenyl—2,2'-bipyrrole (8])
IR (Nujol): 3400 and 3200 cm—1 (N—H), 1600 (C=O); PMR
(CDC13): 02.02 (COCHB), 6.19-6.75 (four m, 4H, pyrrole—g),
7.20 (s, 5H, CGHS), 8.50 and 11.70 (two broad s, 2H, N-g);
l3CMR (CDC13): 631.02 (cogHB), 105.78, 109.49 (03,— and
—pyrrole carbons), 118.57, 116.95, 118.81, 124.03, 126.93,
C

C4,
127.66, 130.98 (C2,-, C5,-, C2—, C3-, C4—, 5-pyrrole and

116
para phenyl carbons), 128.24 (ortho phenyl carbons), 129.36
(meta phenyl carbons), 136.06 (quaternary phenyl carbon),

193.42 (C=O); MS (70 eV): m/e = 250 (parent).

3—Acety1-3‘,4'-dimethy1-4—phenyl-2,2'—bipyrrole (88)

IR (Nujol): 3330 and 3190 cm"1 (N—H), 1615 (C=O); PMR
(CDC13): 62.08 (s, 3H, C0053), 2.13, 2.35 (c3- and C4—
CH3), 6.63 (m, 2H, pyrrole—H), 7.30 (s, 5H, C6H5), 8.53,
11.22 (two broad s, 2H, N—H); 13CMR (CDC13): 610.10, 10.85
(CH3), 31.10 (COQHB), 116—136 (aromatic carbons), g=0 not

observed; MS (70 eV): m/e = 278 (parent).

2-Methy1—4-phenyl—3,2'-dipyrroketone (99)

IR (Nujol): 3260 and 3185 cm"1 (N-H), 1570 (C=O); PMR
(CDC13): 02.40 (s, 3H, pyrrole-CH3), 6.00-6.80 (four m, 4H,
pyrrole—H), 7.17 (m, 5H, C6H5), 8.43, 9.53 (two broad s,
2H, N—H): 13CMR (CDC13): 612.56 (CZ-9H3), 105-136 (aromatic

carbons), 9:0 not observed; MS (70 eV): m/3 = 250 (parent).

2,3',4'—Trimethy1-4-phenyl-3,2'dipyrroketone (91)

IR (Nujol): 3355 and 3150 om"l (N-H), PMR (CDC13):
02.02, 2.05, 2.30 (three s, 9H, pyrrole-CH3), 6.60, 6.73
(two m, 2H, pyrrole—H), 7.13 (m, 6H, C655 and pyrrole-H),
9.83, 10 42 (two broad s, 2H, N-H); 13CMR (CDClS/DMSO—da):
58.82, 9.02, 10.87 (pyrrole-9H3), 113—136 (aromatic carbons),

2=O not observed; MS (70 eV): m/e = 278 (parent).

 

 

117
5,5'-Dicarbethoxy-3,3'L4,4'-tetramethyl—2,2'—dipyrromethane
(93), 3,3',5,5'-tetracarbethoxy-4,4'-dimethy1-2,2'—dipyrro—
methane (94), and 5,5'—carbobenzyloxy—3,3',4,4'-tetra-

methyl-2,2'-dipyrromethane (95)

General Procedure:

The appropriate 2—methylpyrrole (300 mmol) was dis—
solved in 550 ml of acetic acid and warmed to 50°. Sulfuryl
chloride (300 mmol) in 30 m1 of acetic acid was added drop—
wise over an hour. The crude chloromethylpyrrole was col—
lected by suction filtration and used without further
purification. The chloromethylpyrrole was refluxed in
acetic acid (90 m1) and water (60 ml) for two hours. Water
(30 ml) was added and the dipyrromethane was collected by
filtration. Yields are given in Table 7 (page 83) and

spectral characteristics are summarized below.

5,5'-Dicarbethoxy—3,3',4,4'—tetramethyl—2L2'—dipyrromethane
(93)

IR (Nujol): 3320 cm“1 (N-H), 1670 and 1625 (C=O); PMR
(CD013): 01.25 (t, 6H, CHZCHB), 1.92, 2.20 (two s, 12H,
pyrrole—CH3), 3.77 (s, 2H, pyrrole—CHZ—pyrrole), 4.13 (q,

4H, OCH CH3), 9.15 (broad s, 2H, N—H); MS (70 eV): m/e =

2
346 (parent).

3L3',5,5'—Tetracarbeth0§y74,4'-dimethy1—2,2'—dipyrro—

nethane (94)
IR (Nujol): 3410 om"l (N—H), 1725 and 1695 (C=O); PMR

 

[CDC13): 01.58 (overlapping q, 12H, CHZCHB), 2.50 (s, 6H,

 

 

118
pyrrole-CH3), 4.20 (s, 2H, pyrrole—CHZ-pyrrole), 4.37
(overlapping q, 8H, CH CH3), 10.00 (broad s, 2H, N—H);
l3CMR (CDC13): 611.76 (C4-9H3), 14.20 (0CH29H3), 24.39
(pyrrole—QHZ—pyrrole), 60.02 (QQHZ), 112.98, 118.59, 129.58,
138.77 (pyrrole carbons), 160.93, 166.33 (9:0); MS (70 eV):

m/e = 462 (parent).

5,5'—Carbobenzyloxy—3,3',4J4'-tetramethyl—2,2'-

dipyrromethane (95)

 

IR (Nujol): 3315 om‘l (N—H), 1670 and 1640 (C=O); PMR
(CD013): 01.93, 2.20 (two s, 12H, CH3), 3.70 (s, 2H,
pyrrole-CHZ—pyrrole), 5.13 (s, 4H, OCH C6H5), 7.15 (s, 10H,
C6H5), 9.17 (broad s, 2H, N-H); 13CMR (CDC13): 68.70 (C4—
QHB), 10.71 (CB-9H3), 22.70 (pyrrole—QHZ—pyrrole), 65.49
(QQHZ), 116.99 (CS-pyrrole carbons), 117.09 (CB—pyrrole
carbons), 127.52 (ortho phenyl carbons), 127.67, 127.88
(C4-pyrrole and para phenyl carbons), 128.23 (meta phenyl

carbons), 130.63 (CZ—pyrrole carbons), 136.19 (quaternary
phenyl carbon), 161.89 (§f=0); MS (70 eV):

m/e = 470 (parent).

3,3',4,4'—Tetramethyl—2,2'-dipyrromethane-5,5'—dicarboxylic
acid (96) and diethyl 4,4'-dimethy1—2,2'—dipyrromethane—

5,5'-dicarboxylic acid-3,3'—dicarboxylate (97)

general Procedure:

Dipyrromethane (93 or 94) (78.8 mmol) was heated to

boiling in 350 m1 of ethanol. Sodium hydroxide (20 m1 of

119
a 4.1M aqueous solution, 82 mmol) was added and the solu-
tion was refluxed for three hours. Hydrochloric acid (20
ml) was diluted with 100 m1 of ethanol and added to the
cooled basic solution. The product was collected by suc—
tion filtration and washed with ethanol. Yields are given

in Table 7 (page 83) and spectral characteristics of 96

and 97 are summarized below.

3,3',4,4'—Tetramethy1—2,2'—dipyrromethane-5,5'—
dicarboxylic acid (96)

IR (Nujol): 3325 (N-H and O-H), 1670 (C=O); PMR
(CDCls/DMSO—de): 02.00, 2.23 (two s, 12H, CH3), 3.73 (s,
2H, pyrrole—CHZ—pyrrole), 9.07 (broad s, 2H, N—H);

MS (70 eV): m/e = 290 (parent).

Diethyl 4,4'—dimethy1—2,2'—dipyrromethane—5,5'-
dicarboxylic acid—3,3'-carboxylate (92)
1

IR (Nujol); 3420, 3365, and 3215 om’ (N-H and o—H),

1710 and 1650 (C=O); PMR (CDC13/DMSO—d6): 01.32 (t, 6H,
CH2
pyrrole), 8.70 (broad s, 2H, N—H); MS (70 eV): m/e = 406

CH3), 2.43 (s, 6H, CH3), 4.20 (q, 2H, pyrrole-CH2—

(parent).

5,5'—Diethoxycarbonyl-3,3',4J4'—tetramethy1—2,2'-

dipyrroketone (98)

 

Ethyl 3,4—dimethy1—5—iodopyrrole—Z—carboxylate (7 g,
23.9 mmol) and copper bronze (7 g) were stirred in 35 m1 of
N,N—dimethylformamide at 1000 for three hours. The hot

solution was filtered by gravity. The copper was washed

 

 

120
with chloroform (4 X 50 ml). The filtrate and combined
washings were extracted with 1N hydrochloric acid (2 X
100 m1) and water (2 X 100 ml). The solvent was remoVed
under reduced pressure and the crude product was recrys-
talized from chloroform/hexane to give 1.2 g (27%) of 98:
mp. 210-2110 (Iit.50 212-2140); IR (Nujol); 3255 cm‘1
(N-H), 1665 and 1625 (C=O); PMR (CD013): 01.38 (t, 6H,
CHZCHs), 2.23, 2.28 (two s, 12H, CH3), 3.98 (q, 8H,
CHZCH3), 8.97 (broad s, 2H, N—H); 13CMR (CDC13): 69.71,
10.04 (C3— and C4—QH3), 14.04 (CHZQHB), 60.65 (OQHZ),
121.78 (CS—pyrrole carbon), 126.64, 126.80 (C3— and C4—
pyrrole carbons), 131.59 (CZ-pyrrole carbon), pyrrole-

§=O—pyrrole not observed; MS (70 eV): m/e = 360 (parent).

3,3',444’,5,5'-Hexamethy1dipyrro—2,2’—trimethiH§
hydrobromide (190) and 3,3',4,4',5,5'—hexamethy1dipyrro—

2,2'—hexacyclotrimethine hydrobromide ($01)

General Procedure:
2—Carbo—t-butoxy-3,4,5-trimethy1pyrrole (10 mmol) and
5 mmol of malonaldehyde bis-(dimethyl acetal) or 1,3-cyclo—
hexadione were brought to a reflux in 40 ml of ethanol.
Hydrobromic acid (1 ml) was added to the refluxing solution
which immediately turned ink—blue. After refluxing for one—
half hour, the solution was allowed to cool overnight. The
product was collected by suction filtration and washed with

ether. Yields and spectral characteristics of 100 and 101

are summarized below.

121
3,3',4,4',5,5'-HexametHyldipyrro-2,2'—trimethine
hydrobromide (1gp)

65%; IR (Nujol): 3125 om‘l (N—H), 1560 (C=C); PMR
(CDC13): 01.98 (s, 6H, C3— and C3rCH3), 2.17 (s, 6H,
C4— and C4,—CH3), 2.50 (s, 6H, C5— and C5,—CH3), 7.17
(m, 3H, vinyl-H); MS (70 eV): m/e = 254 (parent—HBr).

3,3‘,4L4',5,5'-Hexamethy1dipyrro—2,2'—hexacyclo—
trimethine hydrobromide (191)

33% yield; IR (Nujol): 3125 mm1 (N—H), 1555 and
1510 (C=O); PMR (CDC13): 01.97 (s, and m, 8H, C3- and
C3,—CH3and C=CH—CH2CH2), 2.28 (s, 6H, C4- and C4,—CH3),
2.55 (s, 6H, C5— and C5,-CH3), 2.88 (t, 4H, C=CH-CH2),
7.95 (s, 1H, C=CH), 11.88 (broad s, 2H, N—H);13CMR
(CD013): 08.74 (C4—QH3), 12.31(CB-QH3), 13.77 (C5—CH3),
27.15 (C=CH-QH2), 35.89 (C=CH-CH2—QH2), 115.88, 123.98,
130.17, 134.47 (pyrrole carbons), 146.34 (Q=CH), 153.71

(C=QH); MS (70 eV): m/e = 292 (parent—HBr).

1,5—Di—(5-carbo—t-butoxy—3J4—dimethyl—2—pyrro)—1L4—
pentadiene-B—one (193) and 2,5-di-(5—carbo—t—butoxy—

3,4—dimethy1—pyrr—2-y1methylene)-cyclopentanone (igg)

General Procedure:

To a stirred mixture of 5—carbo-t—butoxy—3,4—
dimethylpyrrole—Z-carboxaldehyde43 (10 mmol), 4 m1 of 15%
NaOH, 10 m1 of water and 14 m1 of ethanol was added 5 mmol
of acetone or cyclopentanone at room temperature. The

mixture was stirred for two hours and then allowed to stand

122

overnight. The orange precipitate was collected by suction

filtration to yield 1.5 g (65%) of 103 or 0.8 g (33%) of

104. Spectral characteristics are summarized below.

1,5—Di-(5-carbo-t—butoxy—3,4-dimethyl-2—pyrro)—l,4—

pentadiene—B—one (103)

IR (Nujol): 3350 and 3225 cm—1 (N-H), 1655 (C=O),

1595 (C=C); PMR (CDC13/DMSO—d6): 01.57 (s, 18H, C(CH3)3),
2.10, 2.17 (two s, 12H, CH3), 6.88—7.67 (AB q, 4H, J =
18 Hz, vinylic protons), 10.72 (broad s, 2H, N—H); MS

(70 eV): m/e = 468 (parent).

2,5—Di-(5-carbo-t-but0xy—3,4—dimethy1epyrr72-ylmethylene)—

cyclopentanone (lgg)

 

IR (Nujol): 3460 om‘1 (N—H), 1655 (C=O), 1580 (C=O);

PMR (CDC13/DMSO—d6): 61.58, 1.63 (two s, 18H, C(CH3)3),
2.07, 2.12, 2.22 (three s, 12H, CH3), 2.95 (s, 4H,
-CH2CH2—), 6.63, 7.35 (two 8, 2H, vinylic protons), 8.67

(broad s, 2H, N—H); MS (70 eV): m/e = 494 (parent).

APPENDIX

123

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WAVELENGTH (MICRONS)

Figure 2. Infrared spectrum of 6-hydroxy—4-decyne (H8).

4000 3000 2000 1500 (Jw* 1000 900 800 /00
0.0 .. 1‘ : :, ...T.‘1'T.“...‘... . ‘ . ‘, 0

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WAVELENGTH (MICRONS)

       

    

    

        

11 12 13‘ 14 m

Figure 1. Infrared spectrum of 1—(2—thienylfhex—1—ene
(36).

124

2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
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phosphorane (413).

 

125

3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
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Figure 4. Infrared spectrum of butyrylmethylenetriphenyl—
phosphorane (419)..

 

 

126

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2000 CM
Infrared spectrum of pentyrylmethylenetri-

'igure 5.
phenylphosphorane (419).

 

 

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Infrared spectrum of hexyrylmethylenetriphenyl-
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1800 1600

128

    

 

 

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100 ‘ ' N ' ‘ ' 100
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Figure 7. Infrared spectrum of heptyrylmethylenetriphenyl-
phosphorane (4&9).

 

 

129

 

    

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2000 1800 1600

Infrared spectrum of octyrylmethylenetriphenyl—

Fi ure 8.
g ,phosphorane (41f).

 

 

130

2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0

 

 

     

   

  
     

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2000 1800 1600 1400 1200 1000 800
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phenylphosphorane (4lg).

 

 

131

 

 

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20

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2000 1800 1600 1400

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1200 1000 800

Figure 10. Infrared spectrum of 4—octene—3—one (§2§)°

 

 

132

2.5 370 3.5 4.0 M'CRONS 5.0 6.0 8.0

  
 
  

  

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Figure 11. Infrared spectrum of 5-decene-4-one (§22)‘

 

 

133

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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1800 1600 1400 1200 1000 800

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Figure 12. Infrared spectrum of 6—dodecene-5—one (§29)°

 

 

 

134

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2000 1800 1600 1400 1200 1000 800

FREQUENCY (CM" )

zigure 13. Infrared spectrum cf 7—tetradecene-6—one (39d).

 

 

1135

 

 

 

 

 

         

 

 

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100 100
80 80
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4000 3500 3000 2500 2000 1500

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2000 1800 1600 1400 1200 1000 800

FREQUENCY (CM ‘

will-Jill (f

igure 14. Infrared spectrum of 8-hexadecene-7—one (39e).

 

 

136

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'Figure 15. Infrared spectrum of 9—octadecene—8—one (323).

 

 

 

137

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3500 3000 2500 2000 1500

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MKRONS

   
 
  
   
 

     

   
  

1400 1200 1000 800
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16. Infrared spectrum of 3,11—tridecadiene—4,10,

dione (gag).

1800 1600

 

 

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Figure 17. Infrared spectrum of 3—propy1-4—propyry1-
pyrrole (42).

139

1
3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
m0

 

 

80

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18. Infrared spectrum of 3—butyl-4—butyrylpyrrole

Figure
(:18).

 

 

140'

 

 

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”igure 19. Infrared spectrum of 3—pentyl—4-pentyry1-
pyrrole (44).

141

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100 ‘ ' ' ' 'if' I

 

 

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7000 1800 1600 1400 1200 1000 800

Figure 20. Infrared spectrum of 3—hexy1—4-hexyry1pyrrole
(45).

2.5 3.0 3.5 4.0 M'CRONS 5.0 670 8.0
‘00 _ 1 100
80 80

E

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'Figure 21. Infrared spectrum of 3—hepty1-4—heptyry1pyrrole.

142

 

 

 

             

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7 60

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20 20

          

2000 1800 1600 1400 1200 1000 800

Infrared spectrum of 3-octy1-4-octyry1pyrrole.

Figure 22.
(47).

 

 

144

5.
2

8 0
100
80
60
40
20

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4.0 MICRONS 50

   

3.5

     

     

                    

      

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Infrared spectrum of 1

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7—bis[—3—(4—

)

heptanedione (38)

1,7:

Figure 23.

 

 

 

 

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igure 24.

1600

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1200

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800

Infrared spectrum of lH—pyrro-[3,4,a]-y_
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100 A . . . , . _ . . .

   
   

100

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2000 1800 1600 1400 1200 1000 800

Figure 25. Infrared spectrum of 3-butyry1-4-(2—thieny1)—
pyrrole (11).

 

 

 

 

147

 

 

 

 

 

 

 

 

 

 

 

 

 

  
  

 

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4000 3500 3000 2500 2000 1500
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2000 1800 1600 I400 1200 1000 800

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'igure 26. Infrared spectrum of 2—carbethoxy—3,4,5-
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148

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100 100

80 80 .

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Figure 27. Infrared spectrum of 2—carbethoxy-3,4—diethy1—
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2000 I 800 1600

 

 

 

 

 

149

 

 

 

 

 

 

 

 

 

 

 

 

          

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4000 3500 3000 2500 2000 1500

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2000 1800 1600 1400 1200 1000 800

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Figure 28. Infrared spectrum of 2—carbethoxy-3,4—
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150

 

 

 

 

 

 

 

 

 

 

 

   

 

 

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4000 3500 3000 2500 2000 1500

mueucv (cw) .

5.0 6.0 7.0 3.0 M'CRONS 10.0 11.0 12.0 16.0
100: - - - ' ‘ 100
80: 80
60: 60
4o 40

2o

20

    

o “ ‘
2000 1800 1600 . 1400 1200 1000 300

Figure 29. Infrared spectrum of 2—carbethoxy-3,4—tetra-
methylene-S-methylpyrrole (53).

 

 

151

 

 

 

 

 

 

 

 

 

     

 

    

 

I
2.5 . l l 3.0 3.5 4.0 MICRONS 50 6.0 8.0
‘00 JlI111111-111111111111...I.l‘.,,,
100
80 80
$5
360 60
E
E
2
U)
240
é ‘.»"a w 40
h 24

20 20

° 0
4000 3500 3000 2500 2000 1500

mourncv (cu-I)

5.0 - 6.0 7.0 8.0 M'CRONS 10.0 11.0 12.0 16.0
100 ' ' 3100
80 80

a? _L _._,__
E’
U
260 60
<
p—
’:
E
3 40
<40
0:
*—
20—~w§—- 20

OL____ ' __-__.._-.- ___—_._- ' ' ‘ ' 0

2000 1800 1000 1400 1200 1000 800
Figure.30. Infrared spectrum of 2—carbethoxy—3,4—deca-

" methYlene¥5>methylpyrrole'(EE).

 

 

152

2.5 . 3.0 . 3.5 4.0 M'CRONS 5.0 6.0 8.0
100 I 100

 

80 80
$5
5’
U60
2 60
<
.—
’2
5,
240 40
<
a:
1..
20 20
0 ' ' ‘ ‘ ' 0
4000 2500 2000
FREQUENCY CM I
6.0 7.0 8.0 M'CRONS 10.0 11.0120 16.0
' 100
80
03
3
260 60
<
.—
L".
E
<(40 40
a:
.—
20

2O

.....

 

 

.....

     

_ .. ,

   

I400 1200 1000 800

at 1 ,ft.‘

0 ' '
2000 1800 1600

Infrared spectrum of 2—carbo-tebutoxy—3,4,5—

Figure 31.
trimethylpyrrole (§§).

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

I .
2.5 3.0 3.5 4.0 M'CRONS 5.0 00 80
. l I IllllllllAllllllllllllljlilllA‘Jl.
'mo um
80 80
E;
{360 60
z
<
E
g
24
< 0 40
a:
.-
20 20
0 II I o
4000 3500 so? 2500 2000 1500
~ ”QUINCY (0“)
5.0 6.0 7.0 8.0 M'CRONS 10.0 11.0120 16.0

100

  
     

 

100;f;

"*80

§‘

3'

U

2: 60
<

p—

t

E

‘2 40
<49

0:

p.

20 20

          

           

1400 1200 1000 800

FREQUENCY (CM 'I

0 i V : '
2000 1800 1600

Infrared spectrum of 2-carbo—t—butoxy—3,4—

Figure 32. I —
teffamethy1ene-5—methylpyrrole (§§)°

'154

2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
100 ' ' ‘ - ‘K - - ' ' ' 100

 

 

g?

E .
060

z 60
f.‘

t

E,

z 40 40
<

a:

p...

20

N)
O

     

o L ' ‘ I . . ’ i .
4000 3500 3000 2500 2000 I 500

FREOJENCV CM
5.0 6.0 7.0 8.0 M'CRONS 10.0 11.0120 16.0

100 *+—-~ 100

 

  

80 80
Q?
E’
U
2 60 60
<
p—
L’.
2
$2 40
< 40
a:
p,—

O

 

 

£500 1800 — 1600 1400 1200 1000 800
Infrared spectrum of 2—carbobenzyloxy1-3,4,5_

Figure 33.
trimethylpyrrole (éZ).

 

 

155

 

 

 

 

 

 

 

 

 

 

 

 

2.5 3.0 3 5 4.0 M'CRONS 5.0 6.0 8.0
l l l J l I I l l l l l l l l l l I l l I l . . l l a n 1 . 1 . .
100 1m)
80 HF 30 '
E
560 60
E
E
5, 11
240 0': CN 40
§ a
,-
20 20
1
1%00 3500 3000 2500 2000 1500
FREQUENCY (CAN)
8.0 M'CRONS 10.0 11.0120 16.0

 

(‘70)

IRHNOMIHIUVLC
5‘
O

20

0
2000

Figure 34.

6.0 7.0

  

100

80

60

 

 

1800 1600 1400 1200 1000 800

FREQUENCY CM

Infrared spectrum of 3,4,5—trimethy1_2_
.pyrrole carbonitrile (§§).

156

2.5 w . 3.0 3.5 4.0 MICRONS 5.0 6.0 8.0
100 ' - d 'I' I

 

 

100

 

 

 

 

80 80
§
I .
L“’60
Z 60
<
i
Z40 40
<
Z
20 20
0 ‘ i f 1 3. 5 E 3 3 3, § 3 :* 3 ; _:.. : E : : : : : : ' 0
4000 3500 3000 2500 2000 1500
FREQUENCY (CM‘)
5.0 6.0 7.0 8.0 M'CRONS 10.0 11.0 12.0 16.0
100 I I ' l 100
80 80
a3
K
J
Z 60 60
<
E
0
Z 40
I 40
:
20-~ 20
0' ' ' ' ‘ 1 ‘ 0

“H .‘E\'

Figure 35. Infrared spectrum of diethyl 2—methy1-4—
phenylpyrrole3—carboxam1de (£2).

 

 

 

 

157

 

 

 

 

2.5 3.0 3.5 4.0 MICRONS 5.0 6.0 8.0
100 100
8° 3:};§9§0? E‘Qné 3": '2 ‘ ' 80

§
K
J
z 60 60
<
E
z 40 4o
(
Z
20t 20

0 T '. '_' L ‘ ,7. 4 , ' ' ' 7 o

4000 3500 3000 2500 2000 1500
FREQUENCY (CM')

5.0 6.0 7.0 8.0 M'CRONS 10.0 11.0120 16.0

100 :- ., -7 -7 - . . . . . . . I . . . . . . . __7100
80

§

3

J

zoo 60

t

E

E40 40

20 20

0 : 5 ' 0
2000 1800 1600 1400 1200 1000 800

FRLOUENCY ICM‘

Figure 36. Infrared spectrum of 3,4-dipropy1pyrrole (g9).

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

2.5 ' 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
. I I I I I I I I I I I . I I I I I I l I I I I I 1 1 1 I l n 1 . n A 1
1m) 1m)
p-u.
80 80
33:
560 60-
5
E f““” ’ W ‘
2 i z 2 S
240 y ' u ‘ 40
»°-‘ 13:95?
20 20
o . o
4000 3500 3000 2500 2000 1500
unwaxv(av) ' . .
' 6.0 7.0 8.0 M'CRONS 10.0 11.0120 16.0

 

‘ 100

.. .

 

* 80
$3
33’
U .
z 60
<
.—
2:
2
‘2 * 40
< 40
M
.—

2O

     

     

       

   

      

1400 I 200 1000 800

FREQUENCY ICM 'l

O 2 a 3 : ;
2000 1800 1600

Figure 37. Infrared spectrum of 3,4—dibutylpyrrole (g3).

 

159

2.5 3.0 3.5 4.0 MICRONS 5.0 6.0 8.0
100 100

      

      

80 80
E
“J ,
U 60
z ,- _ 60
< .
C
E
z 40 _ 40
< . "I
E 3 :-
20 .20
O : I ‘ ' .' ' . . . ' f .: '— 1' 4* * 0
4000 3500 3000 2500 2000 1500
FRFOUEN(Y oCM‘
6.0 7.0 870 M'CRONS 10.0 11.0 12.0 16.0
100
80 80
§
5’
U
260 60
<
p—
t
E
‘2 4o
<(40
(z
.—

20 20

      

$500 1800 1600 1400 1200 1000 800

Flag 1 IN '

Figure 38. Infrared spectrum of 3,4—dipentylpyrrole (fig).

 

 

100

TRANSMITTANCE(°/o)

100

 

 

 

160

2.5 3.0 3.5 4.0 MICRONS 5.0 6.0 8.0
. , _ , , n . . 100

60 7 50
40 z s 4o
2:] Z CH,),CH,T " ' a ‘ ’

20

N
O

       

,,., _.
-- -. ‘.._

2000 I 500

2500

     
 

3000

0 ' V “ ‘
4000 3500
FREQUENCY (CM ‘)
5.0 ' _ 6.0 7.0 3.0 M'CRONS 10.0 11.0120 16.0

  
    

100

            

80
o3
E’
U
2 60 60
<
y...
':.
2
‘2 40
< 40
a:
.—
20 20
O z ‘ . : - ‘ I ' f ‘ 0
2000 1800 1600 1400 1200 1000 800

FPEOUIN' v' (.M

Figure 39. Infrared spectrum of 3,4-dihexy1pyrrole (§§).

I

161

25 10 as 40 MKRONS 50 60 80
00 ' ' 100

 

                       

  
  

 

   

    

80 80
03
E’
U
2 60 60
<
.—
’2
5
240 40
<
a:
y—
20 ;"_2o
0 3 t : . : f .f i 37 Z 1. :: :'_ ‘-
4000 3500 3000 2500 2000 _ 1500
FREQUENCY (CM ’1
5.0 ' 6.0 7.0 8.0 M'CRONS 10.0 11012.0 16.0
100
80 80
a?
E’
U
Zoo 60
<
.—
L:
E
‘2 4o
<49
CZ
.—
20 20
i
O I I ‘ ' ' 3 I ' - 0
2000 1800 1600 1400 1200 1000 800

Figure 40.

FREO'ifM - C"

Infrared spectrum of 3,4—dihepty1pyrrolef(§§).

 

 

 

 

 

 

 

 

 

 

 

 

 

      

2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
. I I I I IIIIIII Illllllllllllllllll-Jll
100 , 100
80 80
E .
86° '60
5 2 I
E N '
3, a = «men.
240 65 40
<
a:
.—
20 2o
0
4000 3500 3000 2500 2000 1500
neauencv (cu-u
5.0 ' . 6.0 7.0 8.0 M'CRONS 10.0 11012.0 16.0
100 ' ' 100
80
a?
E’
U
260 60
<
y...
:
S
‘2 4o
<(40
(z
.—
20 2°
0 - T ; ; ‘ O
2000 1800 1600 1400 1200 1000 300

fREOIJINC Y CM

Figure 41. Infrared spectrum of 3,4—diocty1pyrr01e (fig).

 

 

 

 

 

163

2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
100

80 80
o3
I .
“’6
21 O , 60
E
’2
3,
2240 40
<
a:
.—

20 20

 

o : ' z : s z . - , ;

4000 3500 3000 2500 2000 1500
FREO-JENCY (M

5.0 . 6.0 7.0 8.0 M'CRONS 10.0 110120 16.0

100 100

 

80 80
§
If
U
2:60 60
<
y.-
:I
'2
U) 40
Z
<4O
a:
p—

20

 

1600 1400 1200 1000 800

2000 1800

Infrared spectrum of 2-formyl- 3, 4, 5— —trimethy1-

Fi urc 42.
g pyrrole (67).

 

 

 

.164

 

 

 

 

 

 

 

 

 

 

 

 

2.5 ' 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
. I I I I I I lllll ILIIJIIIIIII .111411-...
100 100
80 q 80
'? f LAW
:5
560 I 60
z
<
E
3,
540 4o
95 : fl ”1"
63
20 20
o L
4000 3500 3000 2500 2000 1500
FREQUENCY (CM" ) .
6.0 7.0 8.0 M'CRONS 10.0 110120 16.0

100

    

 

80

 

(%)

 

   

u.)

U

2 60 60

<

p...

':

2

‘2

< 40 40

a:

'—
20 ' 20

0 ' : ' . . ' E O

2000 1800 1600 1400 1200 1000 800

Figure 43. Infrared spectrum of 5—acetoxymethy142-
carbethoxy-B,4-decamethylenepyrrole (§§).

 

 

 

165

l
2.5 3.0 3.5 4.0 M'CRONS 50 6.0 3.0

 

 

 

 

 

 

 

 

 

 

 

100 I 1 I11J111111-.|J|11111|11I.141...-...'oo

80 80
E
860 60
Z
E
— r"
3,
54° - 40
E : fl CQF

09
2o ’ 4 W 20
0 W
4000 3500 3000 2500 2000 1500
mousscv (cm)

6.0 7.0 8.0 M'CRONS 10.0 11012.0 16.0
. . .. I , w . . 100

    

 

 
  
  

        

‘ 80

§
5'
U
2 60 60
<
p—
’:
2
Q 40
< 40
z

20 2o

0 .7 1 I , i . ‘ ; . ‘ o
2000 1800 1600 1400 1200 1000 800
FREQUENCY ICM I
Figure 44. Infrared spectrum of 2-carbethoxy—5-formy1—

3,4-decamethy1enepyrrole (62).

 

 

 

166

3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
mo

    

 

180

 

::::::

60

0
O

'40

TRANSMITTANCE (%)
A
o

.....

20

M
O

.....

  

0 E 5 5 5 - ' Q ' ‘ E ' F . - : _ I ' r : ' : ; : .
4000 3500 3000 2500 2000 1500
_ FREQUENCY ICM" ,
I
50 00 70 ao‘mmgNsldo melao

”00
mo 4‘ 3‘ ' 7‘ 1 ‘7 ; ; ; I ; 4‘3? mo

 

 

I
I
.

 

 

 

 

(I)
O
I.
I

‘ I
I .
-I
I
I .
I .
co
0

 

 

60

 

 

 

 

 

 

 

 

 

 

 

A
O
I
|..
J
I
I
I

TRANSMITTANCE (Zn)
8
In
..1
“ I
H I
I
I
I
"—0“ 'I
I I
I;
I L
I m

 

 

 

I ‘ ' I. . J. . . . V I . . - .... . I -I—— 4 I1, _-_-.
. . - ~ , . . . .
I I . . n l ,
' ‘ ‘ I . . . . . .
I ' ' .. . . ~ I - ,
. . u -
1 ~ ~~~ . .. . .20
l I I ' I I ' '
. . .

M
O
I
I
I
I
I
I
I
I
I
I
_J

 

 

 

 

 

 

 

 

 

 

 

 

1800 1600 1400 1200 1000 800

FREQUENCY 'CM "

O
2000

Figure 45. Infrared spectrum of 4—acety1-3—ethyl-2-
iodopyrrole (39).

 

 

167

 

100

80-

 

 

 

60

 

 

 

 

 

 

 

 

 

 

 

 

40 ?

 

 

 

TRANSMITTANCE(°/o)

 

 

 

2O

 

 

   
   

I . . I |
._.* _._..V _‘ . -'IP"“—_.“_——.—
, . . a

 

 

 

 

 

 

2500 2000 1500

8.0 MICRONS 10.0 11.0120 16.0

80

 

(%)

60

0
O

TRANSMITTANCE
A
' o

20

      

$000 1800 1600 1400 I200 1000 800
WEO~IINQ v I'. 5‘
Infrared spectrum of 4-carbethoxy-3-methyl—

Figure 46.
2-iodopyrr01e (11).

 

 

 

168

2.5 3.0 3.5 4.0 MICRONS 5.0 6.0 8.0
Ioo;‘;;;,w; '100

  
 
 
 

80
$5
E _.
U
z . 60
<
.—
I:
5
Z 40 40
<
a:
p...

20

N
O

         
  

   

 

 

0 ‘ . A . A , f : ‘.
4000 3500 3000 2500 2000 1500
FREQUENCY ICM'I
6.0 7.0 8.0 M'CRONS 10.0 11.0120 16.0
' 100

80

§

5'

U " ' ; v I 1 I E . i ,

260 : . 3 . I ; g , i 60

< : ' 2 ~ 2 _I‘ _ ‘ _ 1 .

H _ __u- _., . . , . , . , .

I:

2

W

2

<(40 40

O!

p...
20

 

2O

 

 

 

o ‘ ' _ _
2000 1800 1600 I400 1200 1000 85

Q

Figure 47. Infrared spectrum of 3—acety1—5-methyl—4—
phenyl—2-iodopyrrole (23).

 

169

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

   

z :0 3s 40 ‘NCRONS 50 60 80
I """“" - —— ~—-»---» T7100
80
E
{‘3
Z
<(
E
Z -4! ~'—I 40
< 3 ‘ '
(I . _kfl - “1-“...—
20- ~ 1 —« é— *~—~«2o
I I
0a —- , ~ ~ ~ —~-~ 1-. ',
4000 350: 3000 2500 2000 1500
6.0 7.0 8.0 M'CRONS 10.0 11.0120 16.0
' ' ' ' 100
80 80
§
E
U
260 60
<
’—
’2
E
‘2
< 40 40
o:
I'—

 

2000 1800 1600 1400 I 200 1000 800

$9!) IIN v

Figure 48. Infrared spectrum of 3,4—dimethyl-5-formyl-
2—iodopyrrole (Z§)'

 

 

 

170

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

  
       

2.5 3.0 3.5 4.0 MICRONS 5.0 6.0 8.0
I I I IIIIIIIIIAIIIIIIIIIIII.IIIIIPILII
m0 mo
80 80
3%
I360 / “I“: 60
z
<
t u cqa
% n
240 40
<
a:
..—
20 2o
4%00 3500 3006' 2500 2000 1500
REQUENCY (CM“)
6.0 7.0 8.0 M'CRONS 10.0 110120 16.0
' ' ' ' 100
80
§‘
I
U
260 60
<
.—
’2
z
3 40
<40
c:
y—
20 20
o I ' I l ' 0
2000 1800 1600 I400 I200 1000 800

“I; ”:N'v ‘2

Figure 49. Infrared spectrum of ethyl 3,4-dimethyl—5—
' ,iodopyrrole—Z—carboxylate (33).

 

171

 

    

25 30 as 40 MKFONS 50 60 00

    
   

100

O
O

401'

IKHIVOMII IANLt("’Ol

'. ,, ,v , ._ . , _ , I 0
40000 3500 3000 2 500 2000 1500

 

50 00 70 80 MICRON5100 110120 160

‘100

O___

 

 

b-
O

vunmuuu- IMIVgC‘V’O‘}
0

N
O
__,47__.__ _ 7‘ v

 

 

 

og—vfiii - 7 Vii—J W- W” V V ‘\ V V 11' l"~‘”
2000 1800 ‘03:? IAN ‘.

gure 50. Infrared spectrum of diethyl 3-methy1~5—iodo—
pyrrole—2,4-dicarboxy1ate (Zé).

 

172

60

lk’ANlel IANLt “m
1:.
O

 

 

 

m
r.» , , , «um ~ . ,_ "W —— ,

4000 3500 3000 2500 2000 1500

50 60 70 a0 MKRONS 100 1L012D Iao

100

 
  

IKANDMII lANLt(”/o)

O A
2000 1800 1600 1400 1200 1000 800

FMDUENZ" (N

'igure 51. Infrared spectrum of 2—benzy1 4—ethyl 5—iodo—
,3—methy1pyrrole—2,4-dicarboxylate (Z§)'

 

 

173

2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 8

 

O
4000 3500 3000 2500 2000 1500

FREQUENfiY VCM U

 

50 a0 70 80 MICRONS100 1L0120 160

100_———»+~A-<————+——w~<47s¢~ -r~7. 7 ‘ ”A-w7*_“

 

 

 

 
 

 

 

 

80
3
I
)
for
I i7
E f”'
'3 I
:40: * - ----- I
‘ x
I I
1 . —~ ———
20' a A -,
o ,, ,4 __, . , , , , 7* _,, ,,,,__ W _.ffin,‘
2000 1850 (~(‘w 1400 2'30 1000 800

igure 52. Infrared spectrum of 2,5—dimethyl-3,4—di-
iodopyrrole (23).

.0

100

’40

2O

 

 

 

 

 

  

174
25 30 35 40 MWM”5 50 00 80
100 ' 100
80 30
i, 60 60
:40 40
20 20
0 f . ' r I ‘ ; ' :
4000 3500 3000 2500 2000 1500
5.0 6.0 7.0 3.0 M'CRONS 10.0 11012.0 16.0
I00 ' 100
80 80
60 60
40 40
20 20
0

   

2000 1800 1600 1400 1200 1000 800

FREQUENCY vCM

igure 53. Infrared spectrum of 5,5'—diiodo—2,2'-di—
pyrroketone (78).

175

 

 

 

 

 

25 3.0 3.5 4.0 M'CRONS 5.0 6.0 so
I I I I I I I I I I I I I | I I I I I I I I I I I | I J 1 n
100 - 100
80 80
160 H 60
E I ~ .
g H
:40 40
2o 20
c c
4000 3500 3000 2500 2000 1500
FREQUENCY (CM")
50 ‘ 60 10 80 MKRON5100 1L0120 160

 

1800 1600 1400 1200 1000 800
igure 54. Infrared spectrum of diethyl 3,3',4,4'—
tetramethyl—2,2'—bipyrrole—5,5'—
dicarboxylate (79).

176

   
 
    

 

100
80
60

. v 7 . _ : _'_ _._ ~ - . _ ,_ _ _ -
. I . ._ . '_ - _- ~
40 " ' ’ ' ‘ ‘ ' ; ”w W " ' ‘ '
a ‘ " u -— . ,
,. . . . . . . . . . ,_ . _ _ , . - 4o
- I . I ’ ‘ 1 -' 7- . _ , ‘ .7 --> - _‘ , — _-
- . . . ' ‘ 0 - . _ _ ‘ _ , _ , .
- . .1 . ~ . _ _ __ ____ :,- _ _ A 4
-- ‘ . I _ ‘ - r V“

  
  

 

O: , *3 ‘ z ; ‘ ‘ ‘ — a'5:.--‘
4000 2500 2000 1500
FREQUENCY ICM I I
510 ' 6.0 7.0 8.0 M'CRONS 10.0 11.0 12.0 16.0 7

 

100

 

60

_._ ,_.,

         

  

   

I400 I200 1000 800

FREQUENCY lCM")

000 1800 1600‘

ure 55. Infrared spectrum of 3,3',4,4'—tetramethy1_
2,2'—bipyrrole-5,5'—dicarboxylic acid (80).

177

H ”N 5 0 Ll 8.0

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

r 80
t h ‘ 00
H 7 I
. / N . .fi
[I E'OIC N I I
H .
no L“
I a] I 40
I "4 2O
‘ " ?%‘W 2000 1500
50 00 7. 50 * ‘ 00 wt 00 w“
00 ‘”—'—‘ *7 — _._ — * A ‘ .> 100

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

7:" f”! I? '2 I : 4 I 20'" 1036’ I ;, gf.
.gure 56. Infrared spectrum of tetraethyl 4,4'—dimethyl—

2,2'—bipyrrole—3,3',5,5'—tetracarboxylate (§}).

 

178

15 I 30 4.0 MKRONS 50
mo ‘

 
 
 

TRANSMHTANCE(%I

3500 3000 2500 2000 1500
FREQUENCV (MI
50 00 70 a0 MKRONS 100 1L0120 100

(D
O

. l\r\l VQIVII I IHIVLE I70}

I800 I600 I400 I200 IOOO 800

rnsouchv cu‘

Lgure 57. Infrared spectrum of 5,5‘—dibenzyl 3,3'-diethy1
4,4'—dimethy1—2,2'—bipyrrole—3,3‘,5,5'—tetra—
.carboxylate (§E)'

179

2.5 30 3.5 4.0 M'CRONS 5.0 60

 

 

 

 

 

I I 1 I111 I I IIIIIIIJIIIIIII... ”80
I00 I00
80 80
6° ' [I
/ I ”I fl 60
I w
H
Ho,c N 04" I,
7 H II
20 . 50 20
C 0
4000 3500 3000 2500 2000 1500

Intouzucv Icn')
8.0 M'CRONS 10.0 11012.0
I 100

 

 

, . _ . . 0
I 1800 I600 1400 1700 1000 800

gure 58. Infrared spectrum of 3,3'—diethyl 4,4'—dimethy1-
2,2'-bipyrrole—3,3'—dicarboxylate—5,5'-
dicarboxylic acid (§§)'

 

180

4 MIL RONS 5 L; 0.0 8.0

80

~ e ~~60

 

 

 

 

 

 

40LI 39“' 3000 2500 2000 1500

5.0 6.0 7.0 8.0 M'CRONS 10.0 I'I.0 12.0 16.0
00 ’ f ; j ——+~‘ ~w~+—a-m-v+———e~ %— j I 100

 

 

 

, , - - - - < 4 - o - . - v - - - v - , - - . -
I . I , - I .

I . I l . I

. . . |

 

“___ _...__.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

2699 ’0' I500“ ‘ 7‘100C- I400 I200 I000 800

igure 59. Infrared spectrum of 3-acety1—4-pheny1-2,2'—
' bipyrrole (87).

/

181

      
  

_3 ,k' NIICRONS 50 60 8 0
_" 100
80
I
‘i’
. I ..
:c‘ 20
T,._
O‘—- ‘_- _. 7 .u_ _- . ' . . f I
4000 5. 3:90 2500 2000 1500
5.0 6.0 7.0 8.0 M'CRONS 10.0 11.0 12.0 16.0
00 100
80
60
IO 40
20

IO

  

I.-.
I

  

I400 I200 IOOO 800

[m :0” N .

2%00 I 800 1600
I /
sure 60. Infrared spectrum of 3—acety1—3',4'-dimethy1-
4-phenyl—2,2'-bipyrrole (§§).

182

 

 

 

 

 

 

 

 

    

  

 

3 5 4 O MICRONS 5 (I 6 0 8 C
H N IMHH- *' ‘_'*—“~‘ A m-" I” - ___h-‘H -— IUQ
30
Z 60
E
g «40
<
E!
20
O __ ._- ,_ - .-__ I-.. __ a-
4000 3500 3000 2500 2000 I500
50 6.0 7.0 8.0 MICRONS I0.0 II.0 I20 16.0
I00 ------ a I00
80 80
z
D
J I
Z 60- 60
i I
€40 40
20
0

I 800 I600 I400 I 200 IOOO 800

I'd '

"igure 61. Infrared spectrum of 2-methy1— —4- -phenyl- 3, 2'—
dipyrroketcne (90).

183

8.0
I00

80

60

4O

 

50 00 10 80 "“CRONS I00 III)IZO 150
)0 ' ' ' m0

- - g a - ___

80

-----

'0 60

4O

OI_ ..... . .‘ _-g.-.; . . . .__ .---_j_________ -__: . 20

 

         

I000. I400 I200 I000 800

3,_ , n, ___,_____ __
000 I800

gure 62. Infrared spectrum of 2,3',4'-trimethy1—4—
phenyl—3,2'-dipyrroketone (2}).

184

 

 

 

 

 

 

 

 

 

 

 

 

(VI
ISL‘II’
5.0 6.0 7.0 8.0 M'CRONS I0.0 II.0 I2.0 16.0
I00; . - ~~~ r : uI——~—:-uw—j———~_+——~-+~—~~I—--a --~~%~-I00
I . I I ' , I ‘
If
1 - +4 _«___‘.__.__.: _ _-._I_.-_+‘.- _4.--..__ -..__.__.

80

'.‘I

 

 

 

40

TRAMS/VIIITANCEI0

 

 

 

 

 

?5,{ 1856 1600 I400 1200 I000 800

Infrared spectrum of 5,5'-dicarbethoxy-3,3g-

Fi ure 63. ,
g 4,4I_tetramethy1-2,2'—d1pyrromethane (29).

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

185
2.5 3.0 3.5 4.0 MICRONS 5.0 6.0 8.0
I00 IOO
80 80
’ 60 60
40 40
20 20
0 ' ' ' 3 ' ' ‘ : 2 t
4000 3500 3000 2500 2000 1500
50 60 70 80 M'CRONSI00 II0I20 I60
100 ; . % I-—---~~——v-- —r— ~---‘~- - - 4 - - ~~ ~ 1,- - -' A- t-wIOO
, _'4 _ I I - . . . .
by“; I- ‘._- 4 — ._---_-._-.--._- -——-~--
80 fl; _ .- .80
i
60 f '160
.I ‘ I .
40 , ~ 540
I
I ,
20 I '20
_fi—‘fifi _. - - - .. - .. ..
0 I ' ' ““ht'O
2000 I800 I600 I400 I200 I000 800
gure 64. Infrared spectrum of 3,3',5,5'-tetracarbethoxy—

4,4'-dimethy1—2,2'-dipyrromethane (23).

 

186

 

 

     

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

35 40 MKRONS 50 60 80
fi'"“ "' -~~—TII00
760 I
z "'“’“ fi“” I
:‘ Q_ nu _Q ~—
m . _ . ..... .0. . .
2, 40 - - « ~ . - + —---—~- “"‘, ; 4o
2; ' t "
20 —~ v#~—~~2o
0 -— ~ ~ , ~-- — ——-—— .N-_._- ' I
4000 3600 3000 2500 2000 I500
5.0 6.0 7.0 8.0 M'CRONS I0.0 II.0 I20 I60

100

80 80
3
Lu
U
2:60
< 60
.—
t:
.2
3
<14O
CZ
’—
2O

 

.
_ ‘ ,

  

O

2000 1800 1600 1400 1200 1000 800

FREQUENCY -CM I

Infrared spectrum of 5,5'-carbobenzyloxy-

?igure 65.
3,3',4,4'-tetramethyl—2,2'-dipyrromethane (95).

187

2.5 3.0 3.5 4.0 M'CRONS 5.0 60 8.0
. . . . .- I00

 

 

........................

......

80

60 60

40

40

2O 20

 

O . ' ‘ ' f I I I . i '
4000 3500 3000 2500 2000 I500
‘DEOUFN(V CM
5.0 - 6.0 7.0 8.0 M'CRONS I00 I10 I20 I60
- ‘ ' ‘ I00

  
  

 

80

60

40

20

      

)

000 1800 1600 1400 1200 1000 800

FREQUENCY CM -

gure 66. Infrared spectrum of 3,3',4,4'—tetrameth¥1_
2,2'—dipyrromethane-5,5'-dicarboxy11c ac1d

<93).

188

25 30 35 60 MKRONS 50 60 so
100 , - W‘r- ‘7 77 —r~ . -~. ‘7 ---NA- I r§m0

0 (I)
O O

TRANSMITTANCE(°/o)
a.
o

 
 
     

0 . .
4000 3500 2500 2000

50 60 70 80 MICRON5100 II0I20 I60
A , . < v - - I00

TRANSMITTANCE(%)

    

  

04———~—«—_—— r~m~~a-n 7 _
2000 1800 I600 I400 I200 IOWC aw

 

Infrared spectrum of diethyl 4,4’—dimethy1—
2,2'—dipyrromethane-5,5'-dicarboxylic acid—
3,3'—dicarboxylate (g3).

igure 67.

 

 

 

 

 

189
2.5 ' 3.0 3.5 4.0 M'CRONS 5.0 6i0 8.0
I | I | I I I I I | I l I I I I I I I I
mo mo
80 80
E
,3 60 60
E
I: NHHN
5 no ” 03
z 40 40
<
QC
’—
20 20
0 0
4000 3500 3000 2500 2000 1500
FlEOUENCY 1044]
00 "“CRONS I00 110 120 I60

   

 

 

 

 

 

  

 

 

 

 

 

 

 

 

 

§60£_:I
II
In I I

 

 

 

 

£000 I800 I600 1400 I200 1000 800

Lgure 68. Infrared spectrum of 5,5'—diethoxycarbonyl—
3,3',4,4'—tetramethyl—2,2'-dipyrroketone (g§).

190

25 30 36 60 MKRONS 50 60 80

II\I"'\IVIJIV\II IHIVLEI‘VOI

 

0 . ,
4000 3500 3000 2500 2000 1500

60 60 70 60 MKRONS 100 IL0120 I60
I 100

I~I

 

Hi

jmgo I800 I600 I400 1200 1000 800
gure 69. Infrared spectrum of 3,3',4,4',5,5'-hexa—
methyldipyrro-Z,2'—trimethine hydrobromide

(299-

191

25 30 35 40 MKRONS 50 60 80

  

 

0 .
4000 3500 3000 2500 2000 1500

50 6o 70 60 MKRONS 100 IL0I20 I60

 

1800 1600 1400 1200 1000 800

FREQUENCV CM

0
2000

gure 70. Infrared spectrum of 3,3',4,4',5,5'—hexa—
methyldipyrro-2,2’—hexacyclotrimethine

hydrobromide (101).

192

 

 

 

 

 

 

 

25 3.0 3.5 4.0 M'CRONS 5.0 6.0 so
I | I I I I I I I I l I I I | I I I I I I l I I I I I I I | . I

mo mo
80 30
60 60
4o 40
20 20
c

4000 3500 3000 2500 2000 1500

FREQUENCY (cu-I)
50 60 70 80 MICRONSI00 H0I20 I60

 

3 ' ; . r~47v~»u»-n-r~-w-A - - - - - . «~~—r——II00

 

 

Im q+

 

000 1800 _VAI60077 I400 I200 :000 800

gure 71. Infrared spectrum of l,5—di—(5-carbo-t—butoxy—
3,4-dimethy1-2-pyrro)—l,4—pentad1ene—3—one
(103).

 

 

193
2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 8.0
I I I I I I I I I I I I . I I I I I I I I I I I I I I I I I I I I I I I
30 I00
30 —/ ~ I 80
" ‘ I
50 I 60

 

 

 

 

 

 

 

 

I0 I 40
I0 20
3300 3500 3000 2500 2000 1500
FREQUENCY (cu-I)
5.0 6.0 7.0 8.0 M‘CRONS I0.0 II.0 I20 I60
' ' ' I00
80
) 60
40
- -—»- ~ 20

     

 

IOO I800 I600 I400 I200 I000 800

3'ure 72. Infrared spectrum of 2,5-di—(5-carbo—t—butoxy-

D 3,4—dimethylpyrr-2-ylmethylene)—cyclopentanone
(104).

194

 

 

 

 

 

I. II I I l 41 I l
.IA.I_I I .II IIIIL. I

20 7C 60 )I am | ‘0 3‘» In :0 0

Figure 73. PMR spectrum of l—(2—thienyl)—hex—l-ene
(36).

 

 

 

 

 

 

 

 

 

Figure 74. PMR spectrum of 6—hydroxy-4—decyne (§§).

 

195

 

 

 

 

 

 

 

A
I ' ' I I I ' ' I I ' ' ' l j—‘
l
5L) ‘& 300 2& ‘40 DH
)H’
(C‘HSIJPZSECO(CH2)ICH:
_—/’/—
J I I I l I
I I]...III...IAI I I I I .
an 70 60 5‘0 pm“) w 30 70 10 0

Figure 75. PMR spectrum of propyrylmethylenetripheny1—

phosphorane (41a).

‘ v

 

rvrv-IIIII

K—

_I
0—
o_I_

'LI' .I.

§—._

5

(CbHSIJPZSECOKHIIfiH,

 

 

I I I | I l I
.2.44***r . I . . . I . . 30 PPM I.) . Io . . In . II II . . I I
Iigure 76.. PMR spectrum of butyrylmethylenetripheny1—

phosphorane (41b).

196

 

  

(chsIavzcncotchqu
4k

  
  

 

 

 

‘ , I , I
I .IIIIIIJIIIIT I . I l I ILII
0

8.0 70 6.0 5,0 pm I}! 4.0 10 20 1.0

Figure 77. PMR spectrum of pentyrylmethylenetriphenyl—
phosphorane (41c).

 

 

A
jin L I I I I I VI 1 r 1 I rj—.
550 ML) £0 filo 130 I'M-n

I}.

(C H I PZCHCOICH )CH
6 5 J 41d 2 4 J

  

 

 

an ‘ ‘ ‘ 70 A 60 5.0 ”M‘II ‘0

“igure 78.I PMR spectrum of hexyrylmethylenetripheny1—
phosphorane (gig).

 

 

 

 

 

 

 

 

 

 

 

 

197
A
I I ' ' I ' ' ‘I I ' ' ' I I I Ifi
' r v
5&) ‘& MO 2&3 1J0 0H1
)HD
(CoHsIJPZSII-lCOICHz)SCH3
. I . . I . . . I I . . I . . . I
._II ,I II..II...II.,..I....I....I...I.
8.0 7.0 5.0 5,0 pm I,” 0.0 3.0 20 1.0 o

 

Figure 79. PMR spectrum of heptyrylmethylenetriphenyl-
phosphorane (41e).

 

 

A
'l fl 'I' I 'I' I I I rs
5L) 4& 31'!) 2& ‘40 0H:
”-0

F f— (CbHSIJPZSII-‘ICOKHch H3

 

/
L

. I . I . . . . I . I . I I . . I
n..I.‘.j.I.l...I. ...I I. ...I. ...I. ...I.

A A A I A A A
so 70 6.0 5.0 pm '3’ 4.0 so 2.0 III 0

 

 

 

Figure 80. PMR spectrum of octyrylmethylenetripheny1—
phosphorane (Elf).

 

 

‘ _fl#‘g£?p

-' _"a..‘.'.;- «I. . - .

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

198
IA
' ] ‘ r' ' .‘ w 1 I v . 7 .
I ' * .I ! I 1 .I I l I T
E
I
[COHQJPZSIZCOKI-‘lzgcm
A I figk
I . I I I I I I . I I I; I
.j I. .7 IIE‘I.I .LIJII IlguII
Figure 81. PMR spectrum of 1,3—diacetylmethy1ene—
triphenylphosphorane (41g).
A
l' I I} A! ‘ Ile I I I~ j T'I :TIY I YI ' fir ; I I T 'l I II LI IVIV lf 1' I I
530 4& k 2& 130 III-Ix
i CH3(CH2I2CH§,§°HCO(CH,),CHJ /
i W
I . . III I I i I . I I i I
iJ‘I I I.{ .1.. .1.... . .II ..IiI .I I II.
9.0 7.0 so 5p pm ‘3’ to 3.0 10 1.0 o

 

Figure 82. PMR spectrum of 4—octene—3—one (§2E)-

 

 

 

III I, 'L' ,I, ‘10 J g

CHJ(CH,)3CH:3.9CbI-ICO(CH,)1CHJ

 

 

 

 

 

J I I A I I
I I I I I I . u I I l I I I I I I I I I I I I I I
so 70 so 5,0 ”’L‘I) do JO :0 1,0 I)

Figure 83. PMR spectrum of 5—decene—4—one (39b).

 

 

    
 

CHJ(CH,).CH:CHCO(CH,)3CH,
39c.

 

 

 

I I I I . I 0
MI 40 30 20 to
no 70 5° 5:0 "LI

Figure 84. PMR spectrum of 6—dodecene—5—one (§EE)-

200

 

 

 

CH3(CH,)5CH§§§ICOICH,)4CH3

 

 

L

WI] I
IAJIIJAAIALIIIIJII A

3.0 2.0 1.0

 

 

4.0

 

 

l A l A I l J ‘ A l l l I l l ‘ l I
60 5.0 pm "I

Figure 85. PMR spectrum of 7—tetradecene—6-one (39d)

 

 

A
far I rvjjr V. "y'r L 1 1 I r T I I '1 1 v I T I I I ‘l'fi
bk AL Ill!) 2&3 110 OH:
HO

  
 

CH3(CH2)6CH:CHCOICH,)5CHJ
39o

 

 

 

I I I I A u I I I I I I u
A I A A j A I A J A I A A l A I A A A A A A l
8.0 7.0 e o 5.0 pm I,”

86. PMR spectrum of 8—hexadecene-7—one (§2§)‘

4.0

 

 

Figure

201

-A—_yu‘ .. -- , ”a“ .'

 

 

 

 

 

 

 

 

 

 

 

A
$' 1 1 f I‘’ I I V " fl } ‘7 l Iii I 'l I T I I I '1 ‘l 1 '4 ‘
& m A .& I
)
CH,(CH,I,CH:CHCO(CH,)6CH3
39f
MW
[-
i I I I I J J , .1
L A A I A A A A ]L J 4L# 1 L A A A A A A I A A 1 A AL 14 A I A
3.0 70 so 5,0 pm_I}T 4.0 3.0 2.0 to 0

Figure 87.

PMR spectrum of 9—octadecene—8—one (39f).

 

4H

 

 

 

EHJCH: CHco(CH,I‘LCH,

JHL J

 

 

 

‘ I I
A I A A A A I A A A A I A A A A I A A A

|

Figure 88.
dione (§2§)°

l

I

l

L

PMR spectrum of 3,11—tridecadiene—4,10,

 

 

_""= .... .I P '_ _. -

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

A
I I! g I l I Y I ! I' l I . l 1' I I l I I I I l I T—"l
5&0 ‘L, “I,0 2&3 v v'JO ......... om
)I-D
CHJICHzIz/ \COICH,),CH3
N
H
_ 42
4f-
I I I I I I I , I I I I l I I I I l I ..... I
_mI I I I I I I I I I I I I I I I I I
8.0 70 6.0 5,0 mn_‘:’ 4.0 3.0 2.0 1.0 0
Figure 89. PMR spectrum of 3—propyl-4-propyry1pyrrole
(42).
A
Y Y I 7‘ fr r T Y Y r T 'I V Y— T I: I I T Y I," T Y V' I Y ' 'rvi V V Tr VI Y ' ‘f' T'j'fi
I "' *" " I I I Im
)I-D
043(03): COICH2I2CH3
K \
N
H
43
W
I I I . l
I I I I l I l . I I I l I I I I
QIJI II ImLIIIImI IIIIIIIIIIII 1I°III
8.0 70 6.0 5.0 pm 3 4.0 3.0 2.0

Figure 90.
(39>.

PMR spectrum of 3—butyl-4—butyrylpyrrole

 

 

 

 

203

 

 

 

 

 

 

 

 

 

 

A
I I I! T r I I 'I I I l I 1 I‘l l r I I I IA I I I V T'
I I I I I '1;
H9
CH3(CH,)I COICH,)3CH3
(/ \5
N
H
_ 44
1f
1
I I
II I I . I.JII{IIII4 I I 1.4 III I.1II I IIIII
PIIIIIIIIIIILIIIIAIIIIIIIIIIIIIIALIIIIIII.TI
0.0 7.0 60 5.0 "M (9) 4.0 3.0 2.0 L0 0
Figure 91. PMR spectrum of 3—pentyl—4—pentyry1pyrrole
(44).
A
'.LI . '.'.J .' 1L ‘.TITL' '.1. fl 1*.1. ...ilfi
k k 2% 1& ([301:
NO
CH,(CH,)s COICH2LCHJ
/\
N
H
45

 

 

 

 

 

A I A A A A I I 4 A I l l A I A A . J I A A A A_]_ I
l i “‘;II{ II1III IIIIII IIIIII .II II IIIIII III.
‘ ‘ 0.0 7.0 5.0 5.0 pm (9) 4.0 30 2.0 1.0 0
Figure 92.
(45).

PMR spectrum of 3—hexy1—4—hexyry1pyrrole

204

 

 

 

 

 

I . ' | I I I I I I I I
soc .97 I .1; I I
CHJICH,)6 C0(CH,)§CH,
[/ \3 '
N
H
46
M
I l . l I | 4 I
.4_L l L I I I I I J I I
so ab 5' ,

 

igure 93. PMR spectrum of 3-heptyl—4—heptyrylpyrrole

 

 

 

 

 

(46).
I I I I I 1 fi] fl 1 I
I I I I | I
500 406 )0“ 20(. IDC 0 m
CHJ(CH,), co(CH,),,CH,
[/ \I
N
H
47
vumwnwfkwfiflA“*n. Tt‘ r }h
L I I | I L

 

gure 94. PMR spectrum of 3-octyl—4—octyry1pyrrole
(47).

 

 

 

\ NHHN
48

f

M

29%

Figure 95. PMR spectrum of 1,7—bis[—3—(4—methylpyrro)]—
1,7—heptanedione (48).

 

 

 

 

I1 . I
1 | .1.

 

 

 

 

 

 

 

 

A
I I | I I ' I I I
I I l T | I
I
I
N
H
49 u] n- u - “7“" "' Li .
1.3:; .- ‘u‘w—v "1""! l V' ' "VW‘VW
' WL
I I . I . I I I I
I I I . A I J . I I I L | I

 

 

Figure 96. PMR spectrum of lH—pyrro-[3,4,a]—y—
butyrolactone (£9).

 

206

 

 

 

 

 

 

 

 

 

o __I—

I ‘ l A A L ‘ I A l I A l
g A I A l A I l A A A A I l A A _A I l A A A I A l A A I l A A A 1 A A A l I

80 70 00 50 ppm ‘ 40 39 70 7;

Figure 97. PMR spectrum of 3-butyryl-4—(2-thienyl-
pyrrole (ll).

 

<u
d
I-fi
.1

.1

Ad
1—
q
_I
q

—

 

' V V V V I ' V I
, r . —. r I I r I r . 7 v I . I .
‘k 300 2& 1&

§_'I

T V I V T I T l T V " I ! I 'Iyi' V I I
0H:
”-9

 

 

 

 

 

 

 

 

 

 

 

 

   

 

 

 

 

_ I
1;:COZEI ' v
H ' I
50 j! .
W
m .1 '
I I I
‘ I
I I .
I
R A __k __A ‘
i J , - A . l . i A I I I . I . I . .
L A A I A A A A I A 4 A A l A A A A J L A l A I A A A A I A A A A I A A L A I A
8.0 7.0 6.0 5,0 pm ‘3’ 4.0 3.0 2,0 1.0 o

 

Figure 98. PMR spectrum of 2—carbethoxy-3,4,5—tri-
methylpyrrole (50).

 

207'

 

 

 

 

 

 

 

 

 

 

 

 

 

 

' I I l I I ' l
I I I ' l
500 400 300 700
X
H
5]
h i7 ‘ ‘w—v
I A . , I . . . I . . . . I . A .
A__A_ l A I A I A I I l J l A l A l I A l I A A A J A A A A I A A
80 60 5L PPM ‘ 40 30 70 IO

Figure 99.

PMR spectrum of 2—carbethoxy—3,4—diethyl—
5—methylpyrrole (51).

 

 

 

 

'igure 100.

 

 

A A ‘l A A A A A A A
AIAAAAIIIA AIAIAIIIAAAIAA I'll]

‘
p“.- ‘ I ._ 3'. P ‘3 ‘ f

PMR spectrum of 2—carbethoxy—3,4—tri—
methylene-5—methylpyrrole (§3)-

 

 

 

 

208

 

 

 

 

 

 

 

II A j l A A A l A A l J

A A
L A I l j A A J l A L IL L I A¥J L A I I 4 AL 4L I A _l_ _L .1 l l L A I
66 7: 50 50 pp» | 4r 3f

 

Figure 101. PMR spectrum of 2—carbethoxy-3,4—tetra—
methy1ene-5—methylpyrrole (53).

 

 

 

 

 

 

 

 

 

1 1 *r1’ * I 1 '£" 1 1 ev wIa
T fl r I I I v 1 I
\
/
H
54
___V
W
m4.— _, i "_._A .. W.
I I I I I I I I I I I
III I..1 ....I ...II II II IIIII IIIII. IIII. I.III

 

,..:

Figure 102. PMR spectrum of 2—carbethoxy-3,4-deca—
methylene—5-methylpyrrole (54).

_. ‘.. ‘_. _

209

 

 

. . , , 1
5m AI): 3‘ .. J I ,_

 

 

 

 

 

 

55
J
_._—I‘M
l Lub-— L}
J I I I . I I I I I I I I I
A_A A T A A A 4 I A A A A LA I A A T A J A A I A l A A I l A A A I A A A A I A AA A l A
8( 7". s" 5. 99.-u ‘ 4? 3C .- I.

Figure 103. PMR spectrum of 2—carbo—t—butoxy—3,4,5-
trimethylpyrrole (55).

 

 

A
#TI
1
0

I I Y I I I I ' I I
I I I r I ' I
500 100 30c 2o voc I,

IN.

 

 

 

 

A A l l l A i i A i
I A A I A A A A l A A A A l A A A A l l A A A I A l A A I 1 A A A A A A A ‘ A A A A J
, 4

MI 90m ‘ Au II: M

Figure 104. PMR spectrum of 2— carbo- t- -butoxy— 3, 4—
tetramethy1ene—5—methylpyrrole (56).

 

210

 

 

 

 

 

 

 

 

 

 

 

 

 

ITVJ VLlr'Vr'IIVIY IV I ff] [III IT I
I I k I I ' 'Iom
NO
/ 1153 '
fiCO2
57
P—

___) __J U
liiliii.i..‘.li.IAI...‘.1II....
HA.I.AA.IILA.JAI..1.,A.IIA..T.A..I...AIAIA.I.

3.0 7.0 6.0 5,0 "M ‘3) ‘.0 3.0 2.0 10 0

Figure 105. PMR spectrum of 2—carbobenzyloxyl—3,4,5—
trimethylpyrrole (57).

 

 

 

 

 

 

 

 

 

A
livr T ITrTivr I g Y YYVV 7 I ' " " 7' I V' '7 'r 1 1 ' Y: Y I 1‘ 7 V'fiY' TI! 1" V 1' V Lfit '.'v' " I‘v‘
{ 5L; ‘L k 2&) 1& (I)!!!
no
2:101
___/’.— '.'
58
A
\— _Lr_ I Y M M
I A i . A I . i I . I . . J . I A . A i I . i A A I
l I A L A A I A A I I l A A I l 1 l l A L I A L J A —I l I A ‘ I A I A l I J A ‘ A l ‘
3.0 70 so 5.0 pm ‘0 4.0 3.0 20 1.0 o

 

Figure 106. PMR spectrum of 3,4,5-trimethy1—2-pyrrole
carbonitrile (58).

 

... , ~— _ .
...- ‘..._.- --.—... -. .-..

211

 

fifi >

 

§-
.‘
§_
ga
:3

)H’

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

59
FL
1 . - . 1 A i J - A . 1 . . - 1 - - . i 1
-. .1.. A.1.- ..1..,..1.. .-1-- ..1.. ..1.. ..J.. ..1.
9.0 70 so 5,0 mm ‘97 4.0 3.0 2.0 1.0 0
Figure 107. PMR spectrum of diethyl 2—methyl—4—
phenylpyrrole 3-carboxamide (59).
.A
rfi7! firvl 'Y'LYY‘IT‘IVfiI vrvl'rv‘rrvluvu VYYT"'YTL1VYV'Y'['
I L I I I I;
_ R R
R : (CH,),CH3
60
1
. - . 1 . . 1 . . - - 1 - A - 1
.'.1.1.‘.1.{. .1... .1... . ... .1... .1... .1.i.iir.
5,0 pm ‘H to 3.0 20 1.0 o

 

8.0 70 60

Figure 108. PMR spectrum of 3,4—dipropylpyrrole (g9).

 

 

 

 

 

 

 

 

 

A
f £7 V I V 1' Tfil’ T 7 l U T I V V I IV 7 I Y T I I
6L lb 1'30 2& 1L) """" Er
H.
R R
R:(CH2)3CH3
61
-l ..... l s i i - i i l ...... i J . ..... l
s I 14 ..Js.. JL.. I I iirli. .1 .. I
so 10 so 5.0 mg? 40 - so 20 1o 0

Figure 109. PMR spectrum of 3,4—dibutylpyrrole (61).

 

 

 

 

 

 

 

 

 

 

A
I fi' I ! VT 'T Ur T I VI I r '7 ‘r' 17 '7 '71 '17 ‘.‘ I 'I 1' Y I7 7 'l Ifi: I I L Y vrfi 1' Yr 1 V I V' V ! YY YI 1 1' ijfi
5L) 4L) III!) E ‘10 3H:
”-9
d ' 2f§
R : (mafiaJ / i
62 g
!
. . l . . . l . . . . l . i . 4 J . i i J
11‘ 1....1....1........1..i.1...1 .1.
l 0.0 ‘ A A ‘ 7.0 60 5,0 mm ‘9) to 3.0 2.0 1.0 0

Figure 110. PMR spectrum of 3,4—dipenty1pyrrole (g2).

 

213

 

H

R : (CH2)5CH3
63

 

 

 

 

 

 

I . s i i u . i J A I i A i i l . . .
I I I I I L L i 4 J I I l I I I I I I I I I I I l I I I I l J I J
6 o 5.0 pm ‘.' ’ 4.0 3.0 2.0 1.0 o

 

Figure 111. PMR spectrum of 3,4—dihexy1pyrrole (63).

 

T I 1 I II t rr V l v I v r v r I t ! 1 1 r v I 'l I I v rfi
& & m & r '1:
)I'D

 

H

R I (01960-13

 

 

 

 

 

 

 

64
l L A A A l A A l A AL A A l J 1 1 A J 1 . 4 J
I A A A A I A A A A I A A A A l A A A L L A A A A l A L A A I A A A A T A A A A l A
7 o 6.0 5.0 mm W 4.0 3.0 2.0 1.0 o

 

Figure 112. PMR spectrum of 3,4—diheptylpyrrole (gfi).

214

 

 

 

 

 

 

 

 

 

A
l I v I I I I II I g l I I Ir l ' l I
5& ‘k 2!!) 2k 1&3 (I) H:
H.
— R R
R : (cs-1,),CH,
65
/—‘
. . . . l . . . . l - . . . . . I . . l . J . l
A—A_ A I A A A A I A l A A l A A A A A A A A A A A I A A ' A A l A A A A I A A A I A
0.0 7.0 5.0 6.0 pm ‘9) 4.0 3.0 2.0 m

 

 

 

 

 

 

 

 

3
67
1AA
A
l
l . 1 l . l i
L #414 A L A I A A A A I A A A A I 1 A ; A A l

 

 

 

Figure 114. PMR spectrum of 2—formy1-3,4,5—trimethyl—
pyrrole (g2).

215

 

— N (025'

m a J
g V

l . A J l A A I I

 

 

 

 

 

 

 

.T..I.7IA...:IK..A.:II.W;;.‘ICAI..1....JI....'ICJ...I.
Figure 115. PMR spectrum of 5—acetoxymethyl—2—
carbethoxy-B,4-decamethylenepyrrole (68).

 

 

 

 

 

 

 

 

 

ffi I I L jfr’ I I I I I I Ifi
I I V I I T f r I
/\
o H ‘
1 69 .
I
wl‘fir-“ ‘ :: _.‘W MN
A A I A l A A l A J
fri... .I.{. I ...Al... .1....I ....I.A. .1.A‘41,

 

I

Figure 116. PMR spectrum of 2—carbethoxy-5-formyl—
3,4edecamethylenepyrrole (g2).

 

 

 

 

216

 

 

 

 

 

 

 

 

 

 

 

 

A.
I I ..
' l I I I l I I I I r
WI
I . . l . I . I . . I . I I I
_A.I. ...I‘ ‘..}; ..AII 1;.1. ,..IJ ...I. ...1
Figure 117. PMR spectrum of 4—acety1~3—ethy1—2—
iodopyrrole (70).
IA
‘ ' ’ IF ’fifi 'j ' I I I f ijfi
r I I I I I I [I ..l _

 

 

 

l A 4L A A J A l
l 1 i A I A A A i A A A A I I A A 4 I A I A I l L A A A I A A A A T A A A A I

 

I

Figure 118. PMR spectrum of 4—carbethoxy—3-methy1—2—
iodopyrrole (2}).

217

 

 

 

 

 

 

 

 

 

 

 

I I I T
5L0! IIIJIII 'I'YWJ ,I‘.t..!, It..r‘
$0 2& 1& 0H:
no

_ /_—‘ n

f .

.‘.—AM I

I
A A 4 g A J I A A A A l; A A A I A-l A A I A A 1A A A AAAAA J A
A—J¥L l A LJ‘A I A A l 1 I L A l A I L A l 1 l A L A A l A A l l I l A L A I LA L L l l

8.0 7.0 6.0 5,0 pm I}! 4.0 3.0 2.0 1.0 o

 

Figure 119. PMR spectrum of 3-acetyl—S-methyl—4—phenyl—
2-iodopyrrole (72). '

 

FY rIV I I l I I TV '11 I ' '4' I 1 lil l I '1' I V TII I I V I ‘l I I I‘lfi
I vv Iv v fi‘v T '.' Y r u IlI1rv I

 

 

 

 

 

 

 

 

 

 

I

I . , . . I . . . . I i . L I . . . I I _ I I I A

I. A A I L A A A I A A A A I A l A l I A A A A I l A A A l A A A A I A A A A I A A J A_ 1 I
8.0 7.0 5.0 5,0 pm_‘ 3’ 4.0 3.0 2.0 1.0 o

Iigure 120. PMR spectrum of 3,4—dimethy1—5—formyl—2-
iodopyrrole (Z§)°

 

 

 

 

 

 

 

 

 

 

 

 

IA
1' l fiffw'uv ’1 [fit I 1
I t A "m """"" I j {m
‘ . i ,
M
NC02E3
H I
74 .
ILL A . . 1‘. I . I 1 . A A A J . A A . J I - . s 1
LAIII...LA.III....I.,.11.,..T....l....II.JAI.
0.0 7.0 6.0 5,0 m (3T 4.0 3.0 2.0 1.0 0
Figure 121. PMR spectrum of ethyl 3,4-dimethyl—5-
iodopyrrole-Z-carboxylate (74).
IA

 

 

_ A ‘ _ AAA - A h A
V v- 7" fly 'v—v "V v ’

80%: I
N C025: ; I
H .
75 I
'.L- A A .A - 4 W f h “A“AM r

 

 

_A.‘ A A _“_A AA- ———‘ A A “_A A

 

 

 

vw—V 1w

 

 

 

 

 

1 I . I
J I I I I l . . . A I . . I I l I . I I . A

I A A A A I A A A A l A A A A l A A A A I A A A A I A A A A l A A A A I A A A A I
A ‘ 3.0 7.0 so 5,0 mm '3) 4.0 3.0 2.0 1.0 0

Figure 122. PMR spectrum of diethyl 3—methy1—5—iodo—
' pyrrole—2,4—dicarboxy1ate (2?).

 

 

219

 

 

 

 

 

 

 

 

 

III! 1.1 ! llY 1" ! I I ‘E I I I l I rTfi
500 I ‘00 300 [OI (I) (EH1
I E'Oz HO
I
I _:;>
I N C02
I H
¥ 76 I
l W I
1
' i
l .
I.
l
I
l
I
WWJ I
l
I A A . I l . I A I l . . . l . . . J I I . I
.1....1....II..III...T....I.IIII....T....I.
80 70 so so am I 40 3c 20 10 o

 

Figure 123. PMR spectrum of 2—benzy1 4—ethyl 5-iodo—
3-methylpyrrole—2,4—dicarboxylate (76).

 

 

 

 

 

 

 

 

 

 

 

A
‘I_‘I L ff er 1 I 1' Ir 1' Y fliTT Ifi'TVI I Tr ILLfYYfier‘Tv! Ti I y ‘r—[fi
&I ’I I m I 3m
NO
fir
I
Il
A i
ff.— N
H
77
I . A , I . I . J . . A I I A A A I I I I A A; I
A A I A A A A l A A A A l A A A A I A A A A I A A A A l A A A A I A A A A I A A A l J
8.0 7.0 so 5‘0 pm I.” ‘0 3.0 2.0 1.0 o

 

PMR spectrum of 2,5-dimethy1—3,4-diiodo-

Figure 124.
pyrrole (77).

 

 

220

 

 

 

 

 

 

 

I I I I I I I I I ' T
I I l l T
500 400 300 200 00 o n:
O
\ NH HN
78
I . . I I I . . I I . I . I I I I . I I I
P; A I A A A_ A I A A J A I A A A A I I A A A I A I A l I l A A A I A A 1 A I A I
so 70 oo 50 Dmv | 40 30 70 IO 0

Figure 125. PMR spectrum of 5,5'—diiodo—2,2'-dipyrro—
ketone (78).

 

 

 

 

 

 

 

 

 

 

A
"L I‘L' [171' l r ' WI'jfi
6k 4k 31; 2% IL) (IN!
H.
p, i
«M‘- H / I I
79
I
V*.. ... A-‘r—v v"* A .7 _V Awfw “ ‘v
, J I I I I I . I I . I _I I I A I I I I A A I I . I I I
L A I A_A L A I A A A A I A A A A I A A A A I A A A A1 A J J A I L L A A I A A L A I
an 7.0 6.0 6‘0 "’L‘I’ 4.0 an 10 1.0 o

 

Figure 126. PMR spectrum of diethyl 3,3',4,4'—tetra-
- methyl-2,2'—bipyrrole—5,5'—dicarboxylate

(353).

 

 

221

 

 

 

‘A
i l f. ! I. 'Y" I 1 .T I l T V I I I I V 1 fl
5 k k & , f & 3m
H
\ N
HOfi N CO?‘ .
H / .
w i

 

 

 

 

 

l J A A 4 4‘ J llllllll l J J J l
80 70 6.0 5‘0 pm (H 40 30 2.0 10 o

 

Figure 127. PMR spectrum of 3,3',4,4'-tetramethy1—
2,2'-bipyrrole—5,5'—dicarboxylic acid

 

 

(80).
W A
'fflffoll'.'T'.T.".','.'T.r:'v',!I"".!.'.' '1 ..... T7
Ob IE JD 2& ‘ (IJHz
)l!’

f

_ ,/\m

 

IV
O,Et l

H i

N ‘ ;

aqc N \ cqa ~ K
H

H2] ‘ “_J: _J;

 

 

 

 

 

 

 

 

 

A A l . A . . L l ‘4 A ‘ . A . I 4 A . . . J A J 4 . J
J T A A l A A I A I A L A A l L I I A l l I A A A A 1 A A A A I J l L 1 L4
. ‘ A 8.0 I 7.0 6,0 5,0 ""1. (g) 4.0 3.0 2.0 1.0 0

'Figure 128. PMR spectrum of tetraethyl 4,4'-dimethyl—
2,2'-bipyrrole—3,3',5,5'-tetracarboxylate
(81).

 

- h -——r—-- ._~—_~—_1,-,

222

 

 

 

 

 

 

 

 

 

 

 

e . ‘_i4...NI..:1i.,.l.i.‘...i.'...i11..J
Figure 129. PMR spectrum of 5,5'—dibenzy1 3,3'—diethyl

4,4'—dimethy1-2,2'-bipyrrole-3,3',5,5'—
tetracarboxylate (82).

 

 

 

 

 

 

 

 

 

 

 

 

 

I I I I I ' I f I r ' I ' ' ' ' lfi
I I I I 7 , I , Y
500 40C 300 200 '00 OH:
H
N
H
87
——I"—" —" I
. .'. “—2.: “‘ A u M
i
, I I J I A J I 4‘ I
.‘.—_‘l I I A I I l A A A I A l A A I l A A A II 4 g A I I
a L o v a k' pm. ' u .5 20 o

 

Figure 130. PMR spectrum of 3—acety1-4—phenyl—2,2'—

bipyrrole (§Z).

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

223

 

 

 

 

 

 

 

 

 

 

500 ‘00 300 2‘10 ”I“ O H:
3 H
.? N
.’ H 1
j 88 t
3! ,1
I;
4 I
I_.L I J I
80 7 O 0

 

 

Figure 131. PMR spectrum of 3—acetyl—3',4'-dimethyl—
4-phenyl—2,2'-bipyrrole (88).

 

 

 

 

 

 

 

 

 

I 1 I I ’ l I I I ' 7“
I I I I I
500 £00 300 200 |00 OH:
I.
\ i.
H N
90 H
J I . . I l A , A A I A I I A l . . . , l
A A I A A A L I A A A A I A A A A I I A A A I A I A A I l A A A I A A A A I A A A A I A
so 70 oo 50 pm I 40 30 20 no 0

 

Figure 132. PMR spectrum of 2—methyl-4—phenyl—3,2'—
dipyrroketone (29).

 

 

224’

‘-“‘_-.—‘.r ~—

 

 

 

A

r v Ir ! 7 I Y' I I, ‘ ! .... I ! I l I """ , v v I ' h
5& ‘& J” ’g 7‘& ' (II-l:

)H’

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

\
NH N’
91 H
. J I I I . I I . I I I I II . . . I
mr.I A...I ....I I...I .... ....I A .I I ... .
3.0 7.0 6.0 5.0 pm I!) 4.0 3.0 2.0 to 0
Figure 133. PMR spectrum of 2,3',4'—trimethy1-4—pheny1—
3,2'-dipyrroketone (91).
IA
I I I I I ' I '* ' Tr
' ' ' ' ' I, ' A ' .I 3m
I
I
. I I . l . l
}.T. I I I r ILA I I ‘II I I I

 

tetramethyl-2,2'—dipyrromethane (93).

Figure 134. PMR Spectrum Of 5,5'-dicarbethoxy-3,3',4,4'—

225

 

 

A
I ‘ I , ! - I v ' l’ j! I V V I 1 l I v I v 1 v I I u I I v I 1 v . v 1—‘
53° 40 ago 2;) ' ‘10 ' t ' ‘ arm
”-0
5'02 0,5:

 

 

 

 

 

 

 

I....JI.A...II.A....J..JI.I,4
glilll‘ll‘llll‘l‘l

. . . I
I J I I I A I A A l I l A A l A A A 1 I 1 I A A T j
so 5'0 ”M—(I I 4.0 3.0 2.0 1.0 o

 

Figure 135. PMR Spectrum of 3,3',5,5'-tetracarbethoxy—

4,4'—dimethyl—2,2'—dipyrromethane (94).

 

 

 

 

 

 

 

 

 

 

 

IA
. [WHIP
!T II? I I I l, ,1 Y I..
I f ;
i W
JI _J .f__/
/
NN
QM p
7 95 lo2 I J
..‘IIIHIINLHIHI.I....II_immIHHJUHI.

Figure 136. PMR spectrum of 5,5’—carbobenzyloxy-3,3',—
4,4'—tetramethy1—2,2'-dipyrromethane (g§).

 

226

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LA A‘
v‘

 

“‘ J “_‘A-AA“ A

‘A
I ‘1 *' .1 . r fa v
530 T «10 1 i, I 250 I l I l I
~ I
l
x ’ l
N N i ‘i
H H i . .
HO: 96 02“ 1
I
l . l
L L l I
Figure 137. PMR spectrum of 3,3',4,4'-tetramethyl—
2,2'—dipyrromethane—5,5'-dicarboxylic
acid (96).
‘A
‘j IF I ' I I ‘ T I ' ' I ' ‘4 ' ‘ I I I
I ' .I I ;I ' I F k
T?;j/E:§f' I
N / 5
H H 1
H0 97 O,H I

V'V’VVV'V‘V'VWV—W 7.7.7...

 

 

 

Ki.“Ii.l...i.1..I....i..,l.i...‘l‘i.l...fri.”1.
Figure 138. PMR spectrum of diethyl 4,4'-dimethyl—2,2'—
dipyrromethane-5,5'—dicarboxy11c a01d—

3,3'~dicarboxylate (32).

 

 

"227

 

 

A
1T!‘T'1'Y‘x! I T'l‘.!'7‘r vI'r 7] TI ' l ‘
5L ‘b J” ’& f '5":

no
0

 

 

AJ

 

 

 

 

 

A A A A 4* A_ A A ALA #n—L 4 AA A L A J A #4 J A A J A J A A A A A 4 J I A J A A - I A A A l
A I A A J A I A A A L I A A A AA T J A A A I A A A A l A l A A A A J A A A J l A
3.0 7.0 6.0 5.0 pm GI 4.0 3.0 2.0 1.0 o

PMR spectrum of 5,5'-diethoxycarbonyl—3,3',—

Figure 139.
4,4'—tetramethyl-2,2'—dipyrroketone (98).

IA

 

 

 

 

 

 

I I I ' I I I l ' I Ff fl f ‘ F I
T I I Y i I ' I T I
500 400 300 200 I00 0H:
m
\ NH HN
Br
100
A . A l ‘ A A A l ‘ 4 A A l A A A A l A A A l
A1 l A A A A I A A A A I A A A A I l A A A I A I A A I l A A A I A A A A l A A A A l
(:0 7w oo 50 pm I 40 JD 70 I0 0

PMR spectrum of 3,3',4,4',5,5'—hexa—
methyldipyrro—2,2'—trimethine hydrobromide

($92» -

Figure 140.

 

 

 

228

 

 

I I ' ' I I f ' L' J I ' I I
I_ I I ' ' I f I I
50'.) IOC 300 200 IU‘ \ -
I

I

I

\ NH HN "

Br

I .

“_A AA AA “AA“ _AAA AAA AA—‘A AAAAA‘ ‘AflA‘
'F—w‘v'v'wv'v w-vv- W uw-v‘v vv-‘V " ' W

I . . I . . l I

A A A A A
A A A A A A A A l A A A I A I A A T4 AL AL A I A A A A
BO 7U 00 50 pm; I 40 3C 20

 

 

 

 

 

 

 

Figure 141. PMR spectrum of 3,3',4,4',5,5',-hexa—

methyldipyrro-2,2'—hexacyclotrimethine
hydrobromide (101).

 

 

 

 

 

 

 

Y I 1 r I 1 1 I 1 I 1 T I v w I v v 1 *v I v v v 1*!
I T f T I I f I ' Y I
500 “1 30c n IOO W— U m
I
" o
J /
NH H
W 7 ___. P
. . I . A l . l I A I . l
L; A I A L A A I A A A A I A A A A I A A A A I A I A A I I A A A I A A A A I A A A A L A
L ‘ ‘ 3' pp ‘ .1 I' ; I

 

Figure 142. PMR spectrum of 1, 5- di— (5— carbo— t- -butoxy—

3, 4— dimethyl- -2- pyrro)- -l 4- pentadiene- 3—
one (£99)‘

 

 

229,

 

 

 

 

 

 

 

 

f I | ' I 'l‘ I ' L I T I ‘ * I T I 'Ifi
I I I
soc- 400 300 700 no 10m
"<0
1!!
I
I
I
,I
I
\
l A ; L L l 1 l A 1 I - ‘ A J I A A A l L l A I
A A l j A A L J I A l l l L J A L l l A L J T A l l l I l 4 L L l A A L L I 1 A A A I 1
80 7c 00 50 pa» * 4o 30 70 lo 0

 

Figure 143. PMR spectrum of 2,5-di-(5-carbo—g—butoxy—
3,4—dimethyl—pyrr-2-ylmethylene)—
cyclopentanone (104).

10.

11.

12.

13.

14.

15.

BIBLIOGRAPHY

H. Fischer and H. Orth, "Die Chemie des Pyrrols”,
Vol. 1, Akademische Verlag, Liepzig, 1934.

H. Fischer and H. Orth, ”Die Chemie des Pyrrols”,
Vol. IIi, Akademische Verlag, Liepzig, 1937.

H. Fischer and H. Stern, "Die Chemie des Pyrrols”,
Vol. 1111, Akademische Verlag, Liepzig, 1940.

R. B. Woodward, W. A. Ayer, J. M. Beaton, F. Bickel—
haupt, R. Bonnett, P. Buchschacher, G. L. Closs,

H. Dutler, J. Hannah, F. P. Hauck, S. It6, A Langemann,
E. LeGoff, W. Leimgruber, W. Lwowski, J. Sauer,
Z. Valenta, and H. Volz, J. Amer. Chem. Soc., 82
3800 (1960). M”

 

K. M. Smith, ”Porphyrins and Metalloporphyrins”,
Elsevier Scientific Publishing Company, 1975,
pp. 29— 55.

H. Fischer and W. Gleim, Justus Liebigs Ann. Chem.,
521, 157 (1935).

 

P. Rothemund, J. Amer. Chem. Soc., 57, 2010 (1935).

 

S. Krol, J. Org. Chem., 24, 2065 (1959).

S. Beitchman, Ph.D. thesis, University of Pennsyl—
vania, 1966.

F. R. Longo, E. J. Thorne, A. D. Adler, and S. Dym,
J. Heterogycl. Chem., 12, 1305 (1975).

H. Fischer and B. Walach, Justus Liebigs Ann. Chem.,
450, 164 (1926).

 

W. Siedel and F. Winkler, Justus Liebigs Ann. Chem.,

 

554, 162 (1943).

A. Treibs and N. Haberle, Justus Liebigs Ann. Chem.,
718, 183 (1968).

 

D. 0. Cheng and E. LeGoff, Tetrahedron Lett., 1469
(1977).

H. Fischer and R. Baumler, Justus Liebigs Ann. Chem.,
468, 58 (1929).

230

 

 

 

17.

18.

19.

20.

21.

22.

23.

24.

25.

26.
27.

28.

29.

30.
31.
32.
33.

34.

231

H. H. Inhoffen, JrH. Fuhrhop, H. Voigt, and H.
Brockman, Jr., Justus Liebigs Ann. Chem., 695, 133
(1965). "w“

 

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