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6, 5-D5MEI'HYLFULVENE

Thesis for the Degree of M. S.

MECHEGAN STATE UNIVERSWY

0N EREFE

1971

VERN

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, LIBRARY

" Michigan Sm:
University

 

ABSTRACT

COPPER(I) CATALYZED DECOMPOSITION OF ETHYL DIAZOACETATE
IN THE PRESENCE OF 6,6-DIMETHYLFULVENE

by

Vernon E. Rife

Ethyl diazoacetate (l) was decomposed to the carbene (g) with cuprous

bromide in the presence of 6,6-dimethylfulvene (Z). When the ratio of

NZCHCOZEt :CHCOzEt O

I % Z

1:1 was l.5:l.0, two mono-adducts of g to the double bonds of z and at
least three di-adducts were obtained.

The epimeric mono-adducts ethyl (lfif, 5§f, 6§f)-4-isopropylidene-
bicyclo[3.l.0]hex-2-ene-6-carboxylate (g) and ethyl {lg}, 5§f, 63f)-4-
isopropylidenebicyclo[3.l.OJhex-Z-ene-G-carboxylate (2) accounted for

39% of the volatile product material.
I OzEt

‘f H C02Et ./H

H H
8
’b

80

Two isomeric di-adducts which accounted for another 28% of the
product were isolated but their structures could not be definitely
assigned. The major di-adduct (25% of the product) was shown by nmr
to be either diethyl (le, 23f, 3§f, 4§f, 6§f, 7§f)-5-isopropylidene-
tricyclo[4.l.0.02’4]heptane-3,7-dicarboxylate (11) or diethyl (13f, 2§f,
33?, 43?, 6§f, 7§f)-5-isopropylidenetricyclo[4.l.0.02’4]heptane-3,7-
dicarboxylate (lg).

 

The other isolated di-adduct (3% of the product) was shown by
nmr to be either diethyl (lgf, 23f, 33f, 4§f, 6§f, 7§f)-5-isopropylidene-
tricyclo[4.l.0.02’4]heptane-3,7-dicarboxylate (lg) or diethyl (13}, 2§r,

2,4

33f, 43f, 6§f, 7Bf)-5-i50propylidenetricyclo[4.l.0.0 ]heptane-3,7—

dicarboxylate (l$)°

      

0 Et

Although at least one other di-adduct (approximately l0% of the
product) was present in the reaction mixture, it was not obtained in
a pure form. The nmr spectrum of the impure material showed peaks in
the vinyl region suggesting the presence of a di-adduct in which the

carbene, g, had added to the egg: double bond of Z;

Both diethyl fumarate and diethyl maleate as well as an apparent
carbene trimer were also present in the reaction mixture and account
for ll% of the volatile product material. A mono-adduct of the carbene
(g) to dicyclopentadiene (present as an impurity in the starting

fulvene (1)) was also isolated and identified.

COPPER(I) CATALYZED DECOMPOSITION OF ETHYL DIAZOACETATE
IN THE PRESENCE OF 6,6-DIMETHYLFULVENE

By

‘\,r'
‘T.
‘5

Vernon E: Rife

A THESIS

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

MASTER OF SCIENCE

Department of Chemistry

1971

To My Wife,

Karen

ACKNOWLEDGMENT

The author wishes to express his appreciation to
Professor Harold Hart for his enthusiasm, encouragement,
and guidance throughout the course of this study.
Appreciation is extended to Michigan State University
for a Graduate Teaching Assistantship from September, 1969
to June, 1970, and from September, T970 to March, l97l.
Appreciation is also extended to the National Institutes
of Health for financial support from June, 1970 to August,
1970, and from March, l97l to August, l97l.

TABLE OF CONTENTS

Page
INTRODUCTION .......................... l
NOMENCLATURE .......................... 5
RESULTS AND DISCUSSION ..................... ll
EXPERIMENTAL .......................... 24
A. General Procedures .................. 24
B. Preparation of Ethyl Glycinate Hydrochloride ..... 24
C. Preparation of Ethyl Diazoacetate (l) ......... 25
D. Preparation of 6,6-Dimethylfulvene (Z) ........ 25

E. Reaction of 6,6-Dimethylfulvene (Z) with Ethyl
Diazoacetate (l) in the Presence of Cuprous Bromide. . 26

F. Method of Separation of Products ........... 27
G. Identification of Products .............. 28
SUMMARY ............................ 3l
LITERATURE CITED ........................ 32

APPENDIX ............................ 34

TABLE

II
III
IV

LIST OF TABLES

Distribution of Products from the Copper(I) Catalyzed
Decomposition of l in the Presence of l and Their
Retention Times .....................
Proton Assignments for the Major Mono-adduct (g) . . . .
Proton Assignments for the Major Di-adduct (ll or lg). .

Relative Shifts of Ethyl and CycloprOpyl Protons of
Compounds g, ll (or lg), and lg (or ll) .........

Page

13
14
18

21

FIGURE

Chm-boom

10

11

12

13

14

15

LIST OF FIGURES

Mass spectrum of c], a mixture of 8 and its epimer 9
(87:13 ratio) ......................

Mass spectrum of pure j2, either ll or l2 ........
Mass spectrum of pure j], either ll or ll ........
Mass spectrum of combined peaks 9 and h, may contain ll .
Mass spectrum of d, carbene trimer (28) .........

Mass spectrum of f, mono-adduct of carbene (2) to
dicyclopentadiene ....................

Nmr spectrum of c , a mixture of 8 and 9 (87:13 ratio),
before adding shiIt reagent ...............

Nmr spectrum of c], a mixture of 8 and g (87:13 ratio),
after adding shift reagent ................

Nmr spectrum of c], a mixture of and 9, after adding
shift reagent. Sweep offset = 20 ; sweep width = 250.
Integration showing ratio ................

Nmr spectrum of pure jz, either ll or l2, before adding
shift reagent ......................

Nmr spectrum of pure j2, either ll or 2, after adding
shift reagent ......................

Nmr spectrum of pure j], either ll or ll, before adding
shift reagent ......................

Nmr spectrum of pure j , either ll or
shift reagent. Sweep width = 255 ............

Nmr spectrum of pure j , either ll or ll, after further
addition of shift reagAnt ................

Nmr spectrum of the combined peaks 9 and h, may contain

11 ............................

Page

35
36
37
38

39

41

42

43

44

45

INTRODUCTION

Copper powder and various compounds of copper, including cupric
sulfate, cuprous bromide, and bis(acetylacetonato)copper(II), have been
shown to catalyze the thermal decomposition of ethyl diazoacetate (l)
to the carboalkoxycarbene (2) or some carbenoid intermediate (equation

”.1234

(l) NZCHCOZCHZCH3 ———> N2+ + :chochZCH3

1, 2,

Other methods of production of 2 include photolytic and thermal
(uncatalyzed) decomposition of the diazo ester. According to Kirmse,
temperatures above 150° are required for the thermal decomposition of l;
whereas, 90°-100° is sufficient with copper powder? , Dull and Abend
found that using cuprous bromide catalyst in refluxing n-hexane (68°),
the evolution of nitrogen from l was vigorous and quantitative}

The decomposition of l in the presence of olefins can give rise to
cyclopropane derivatives; furthermore, when two isomers are possible, the
less hindered product is preferred? D'yakonov and co-workers have shown
vthat the cupric sulfate catalyzed decomposition of l in the presence of

1,3-cyclohexadiene yields compounds 3 and l in a ratio of 8.5:1.2

COZEt
H H
02Et
i\H \\ \H
H H
% i

Skell and Etter independently obtained a ratio of 17:1 for the same cupric
suflate catalyzed reaction and further showed that greater selectivity is
obtained by the copper catalyzed route than by photolytic decomposition?
Warkentin extended the generality of this result? Photolytic
decomposition of l in the presence of cyclopentadiene produced epimers

5 and Q in a ratio of 3:1.
C02Et

H H

COzEt

\\H \\H

H
Q 9

In contrast the copper powder catalyzed route yielded a ratio of 5:1.
Copper chelate compounds such as bis(acetylacetonato)copper(II) have also
shown similar selectivity in the presence of olefins“ Recent work has
shown that stereoselectivity is also dependent upon the olefin concentration?
Schlosser and Heinz show that the more dilute the olefin (in petroleum ether
'solvent for example), the greater the stereoselectivity of the carbene (or
carbenoid) intermediate.

In this study the decomposition of l in the presence of 6,6-dimethy1-
fulvene (l) was examined using cuprous bromide as the catalyst (equations

1 and 2).

 

(1) N CHCO CH CH CUB? > :CHCO

2 2 2 3 2CH2CH3

Q

(2) O + g > products

g-a

 

Hart and co-workers have shown that reactions of simple alkylfulvenes
with dichlorocarbene produced meta—chlorostyrene derivatives presumably
via a homofulvene intermediate (i.e. equation 3); however, attempts to

isolate the reactive homofulvene intermediates were unsuccessful?

T (:1

C1
-HC1
0 + __> o —————> O .

 

 

A carboethoxycarbene was chosen for reaction with 1 because the homo-
fulvene mono—adducts were predicted to be much more stable than the
dichlorocarbene analogs. Although methyl diazoacetate would have given
simpler nmr data, ethyl diazoacetate was the carbene precursor of choice
because it was readily available and much less likely to detonate
thermally than its methyl analog. Cuprous bromide was chosen as the
catalyst because of its ability to efficiently decompose l at moderate

temperatures.

Thus, if stable homofulvene products (i.e. Q and 3) could be obtained,
various aspects of their reactivity could be examined under different
conditions. The photoisomerization of homofulvenes to aromatic compounds

has been studied by Tabata and Hart9 and also by Rey,10

,/ CO Et

2

2 \H
\H H
§ “ 2
The acid-catalyzed rearrangements of pentamethylhomofulvene has been
studied by Criegee.11 The thermal rearrangement of a homofulvene to a
cyclopentadiene was studied by Hart and DeVrieze}2
The main purpose of the present study was to examine in detail the
products of the decomposition of l in the presence of Z and to identify
the structures and stereochemistry of the various mono- and di-adducts.

Further reactions of the homofulvene products were not carried out in

this study.

NOMENCLATURE

The number of possible mono- and di-adducts oflg to the double
bonds of’Z is large. Since products were obtained which represent
several of the possible ring systems and since others are likely to be
obtained at a later date, I have included the following section to
clarify the nomenclature of the possible compounds. The possible

isomers of adducts (mono- and di-) to double bonds are as follows:
H
5:4 c025t

 

 

 

C02Et

 

 

 

The fundamental ring systems involved in these products are:

A. Bicyclo[3.1.0]hex-2-ene

 

 

 

H H
C—— C
6//// 1 2\\3
HZC H
\C u
5H H2
B. Spiro[2.4]hepta-4,6-diene
g H 1
:==C CH
6 7
\.$// I 2
C
11/ \
CS:C CHZ
H H 2
. 2,4
C. Tr1cyclo[4.1.0.0 ]heptane
H
6 2 ”
H C H
7 C/5\C\3
H c/ 1 CH
2 \| 1/«2
C C
H1 2 H

D. Spiro[bicyclo[3.l.0]hex-3-ene—2,l'-cyclopropane]

H
H / 2'
\\ :1 C
CL} 3 \ /"CH2
*5 §C\cL
C 1
.c \H
H

Thus, disregarding stereochemistry for the moment, the names
of the compounds are:

$2"

Ethyl 4-isopropylidenebicyclo[3.1.0]hex-2-ene-6-carboxylate

10 —-
'Vb
Ethyl 2,2-dimethylspiro[2.4]hepta-4,6-diene-l-carboxylate

111’ R, 13a 15b 12’ 12 "

Diethyl 5-isopropylidenetricyclo[4.l.0.02’4]heptane-3,7-dicarboxy1ate

ll, 1%, .12. 22 "

Diethyl 3',3'-dimethylspiro[bicyclo[3.1.0]hex-3-ene-2,1'-cyclopropane]-
2'-6-dicarboxylate

Regarding the stereochemistry involved in these compounds, one
could use prefixes to assign the absolute configuration for each
asymmetric carbon atom in each enantiomer (each of the above compounds,
with the exception of 1% and 1Q which are mgsgf compounds, has an
enantiomer). However, since no attempt was made to separate enantiomers,
it would be cumbersome if not useless to assign the absolute configurations.
The most simple system which can be used unambiguously and unifOrmly to
describe the relative stereochemical relationships involved in all of
the compounds referred to in this paper is probably the Rf, Sf (spoken
R star, S star) system described in Rule E-5.lO of the "IUPAC Tentative
Rules for the Nomenclature of Organic Chemistry. Section E. Fundamental

Stereochemistry".l3

According to this system the compound is always oriented so that
3* is assigned arbitrarily to the lowest numbered asymmetric center.
For cases in which synmetry permits numbering in either direction around
the ring (i.e. 1%), the preferred direction is the one which assigns 3*
at the first point of difference.

Using this sytem, one finds that only one set of stereodescriptors
is necessary for each pair of enantiomers.

Thus, the stereodescriptors for these compounds, to be cited in

front of the names given above, are as follows:

Q: (13*, 5§*, 68*)-

2: (13*, 58*, 63*)-

lg: none is needed in this case, but 3* — may be used
rlvlb: (13*, 23*, 33*, 43*, 63*, 73*)-

«111%: (13*, 221:, 33*, 43*, 6§_*, 7_S*)-

lg: (13*, 23*, 33*, 48*, 68*, 78*)-
14: (13*, 28*, 33*, 43*, 68*, 73*)-

15: (lR*, 2R*, 3R*, 48*, 68*, 3*)
m _ _. _ — __

1 : (13*, 28*, 38*, 43*, 68*, 73*)-

(13*, 23*, 2'§*, 55*, 6R*

)-
(133, 2§f5 2'53, 5§f W*)
(13f: 233, 2'§f: 5§f @*)_

)-

$$$S

(13*, 2§*, 2 R*, 55*, 68*

10

The stereodescriptors g39:, endg; and 515;, 53335; will also
be used to describe the above compounds but, in each case, the group
which is eggg; (g39;, §j§;, trans;) and the group it is £399; with
respect to will be specified (i.e. the carboethoxy group is egggy

with respect to the five-membered ring in g).

RESULTS AND DISCUSSION

Both ethyl diazoacetate (l) and 6,6-dimethy1fu1vene (1) were
prepared from readily available starting materials. An Organic Synthesis
preparation was used to make 1 from ethyl glycinate hydrochloride}“

Ethyl glycinate hydrochloride was prepared quantitatively by bubbling

dry hydrochloric acid into a solution of glycine in hot absolute ethanol.
The fulvene (1) was prepared by mixing acetone with a basic solution of
freshly distilled cyclopentadiene at 0° and then vacuum distilling the
product.

Equations 1 and 2 illustrate the reaction of l with 1 via the

 

carbene, g.
CuBr .
(1) N2CHC02CHZCH3 T56“? N2 + .CHCOZCHZCH3
l, 2.
(2) \ / + g :>» products

After a so1ution of Z and a catalytic amount of cuprous bromide in hexane
was initially warmed to 45° (it was discovered that reflux temperatures
were not necessary), the temperature of the solution was maintained by

the exothermic decomposition of l which was slowly added to the solution.

11

12

Five minutes after the addition of 1.5 mole equivalents of l to the solution
of Z’ an ir spectrum showed that the strong peak from 1 at 2150 cm'1
(N=N stretch) was no longer present indicating that the diazo ester had
completely decomposed. Analytical gas-liquid chromatography (glc) of this
crude reaction mixture indicated the distribution of volatile products to
be as listed in Table I. Then, following fractional vacuum distillation
of the product mixture, preparative glc on a ten-foot (1/4" diameter)
8E 30 column was used to obtain the major products (major product being
defined as at least 4% of the total product material) in a pure or (in
two cases) a semi-pure state.

Compounds b1 and b2 (purified) were shown to be diethyl fumarate

(21) and diethyl maleate (22) respectively by comparison of glc retention

times, ir spectra, and nmr spectra with authentic material.

H\\C —6//C02 Et EtO 2C\\t_ 6/,C02 Et
EtO2 C///= C\\tl H//C —\\\H

22 23
’VL

’L’b

Mass spectrum of c1 (free of c2) showed the parent peak at m/e 192
(Figure l, appendix) suggesting the presence of a mono-adduct. First
inspection of the nmr spectrum of this peak suggested that c1 was pure g
(new compound) and proton assignments were made as shown in Table II.
The Hd' ally1ic protons were assigned the position downfield from the Hd
protons because the a11ylic protons of the starting fulvene, 1, appear

at r 7.9 whereas the ally1ic methyls of the symmetric di-adduct (peak j2 -

13

TABLE I. Distribution of Products from the Copper(I)
Catalyzed Decomposition of I in the Presence
of Z and Their Retention Times.*

Peak % of Total Retention Time (min.)
Label Product FFAP, 177°

 

 

a (hexane)

a1 (fulvene decomposition products)

b1 4 1.2
b2 7 1.6
c1 39 2.8
c2 < l 3.4
d 4 5.2
e 3 6.8
f 8.6
g 3 11.0
h 9 12.6
i < 1 15.2
J 28 19 2
k < 1 24.0

*Relative amounts of products were determined using relative peak areas
obtained by analytical gas-liquid chromatography (5' x 1/8" FFAP, 177°,
on a Varian Aerograph Series 1400 instrument with a f1ame ionization
detector using nitrogen carrier gas).

14

 

8
*8

TABLE II. Proton Assignments for the Major Mono-Adduct (8).

 

 

Proton(s Appearance Chemical Shift (T) Coupling Constants (Hz)
Ha = Ha' triplet 3.9 Jaa' = 1.2

Hb broad doublet* 7.4 Jbb' = 7.2*

Hb' broad doublet* 7.4 Jbb' = 7.2*

HC triplet* 8 9 Jcb = J cb' = 2.7*

Hd singlet 8.2

Hd' singlet 8.1

He quartet 5.9 Jef = 7.6

Hf triplet 8.8 def = 7.6

 

*Coupling could be clearly observed only after addition of Eu(DPM)3
shift reagent.

15

not yet discussed, but see Figure 10, appendix) occur at r 8.2. Addition
of 2 to cyclopentadiene produced the epimeric mono-adducts 5 and 63 which
can be compared with 8. The proton which is endo- with respect to the

five-member ring in 3 appears at r 9.17 whereas the Q39; proton of 6 occurs

OEt
C02Et
\H . \H

H
8 8

2

somewhere between T 6.89 and T 8.36.3 Thus, as Warkentin suggests for g,
the upfie1d position of the ggggfproton (HC of 8, Table II) is probab1y
due to shielding by the n-electrons of the carbon-carbon double bonds}5

In an attempt to better observe the coup1ing of the cyclopropyl
protons of 8, a shift reagent was added. The shift reagent, tris-(2,2,6,6-
tetramethylhepta-3,5—dionato)europium(1II) (the abbreviation EuflPM)3 will
be used throughout the rest of this discussion), was used because it was
known that this reagent coordinates with the carbonyl oxygen of esters}6
It was expected, therefore, that the cyclopropyl protons of 8 (Hb, Hb"
and Hc’ Table II) would be shifted more than the ally1ic methyls (Hd and
Hd.) or the methyl triplet (Hf). According to expectations, the triplet
of HC was shifted so that its coupling could be clearly observed and
measured (compare Figures 7 and 8, appendix). One of two ally1ic cyclo-
propyl protons (arbitrarily assigned Hb) was shifted somewhat less than
the other (Hb') so that coupling between these two protons could also be
observed (Figure 8). The general ranges for coupling constants for cyclo-

propyl hydrogens have been reported by Zimmerman as 7.3-11.2 Hz for gig;

1.6

and 3.9-8.0 Hz for Ergg§;.17 The coupling constants measured for the
cyclopropyl protons of 8 were 7.2 Hz for £13: (Jbb" Table II) and 2.7 Hz
for Eggggf (JCb = Jcb" Table II). The fact that these values do not
fall within Zimmerman's general ranges does not negate their validity
since none of the cyclopropyl compounds cited in that report is fused

to a five-member ring. This steric perturbation could easily account

for the discrepancy.

Unexpectedly, the addition of Eu(DPM)3 shift reagent to c1 (which
was assumed to be pure 8) revealed the presence of an impurity which was
assigned structure 8 (new compound) by nmr even though the peaks of the
ethyl protons and cyclopropyl protons were the only peaks that could be
clearly observed (Figure 8, appendix). The fact that the ethyl protons
of 8 were shifted further downfield than the ethyl protons of 8 suggest
that the shift reagent coordinates more strongly with the carboethoxy group
that is $39; with respect to the five-member ring than with the Eggp-
carboethoxy group. Integration of the methylene quartets of 8 and 8
revealed that the mixture of epimers consisted of approximately 13% 8
(Figure 9, appendix). Thus, since "compound" c1 contained 39% of the total
product material, compounds 8 and 8 contribute 34% and 5% respectively.
Attempts to further separate 8 and 8 were unsuccessful.

Preparative glc with an SE 30 column (10' x 1/4") effectively
. separated two pure compounds which had identical retention times on the
analytical FFAP (5' x 1/8") column (peak j, Table I). The two compounds,
relabeled j1 and j2 for the SE 30 column, had nearly identical mass

spectra with a parent peak at m/e 278 (Figures 2 and 3) which indicated

17

that j1 and jz were both di-adducts. Since the amount of j2 available
(approximately 25% of the total product) was large compared to j1
(approximately 3% of the total product), j2 was analyzed first.

The major di-adduct, j2 (new compound), was shown by nmr to be the
pair of enantiomers 88 or else the @389: compound 88. Proton assignments

are listed in Table III. The gig; (J = 6.5 Hz, Table III) and

bb'
jggg§; (Jab = Jab' = 2.9 Hz) coupling constants could be very clearly
observed without adding shift reagent (Figure 10, appendix); furthermore,
they correspond well with those obtained for the mono-adduct 8. The
equivalent ally1ic methyls (HC, Table III) and the two-protons (Ha) at
r 8.6 with trgg§f cyclopropyl coup1ing suggest a symmetric structure in
which both of the carboethoxy groups are £39; with respect to the
five-member ring (either 88 or 88). Addition of Eu(DPM)3 shift reagent
made it possible to observe the two-proton triplet (Ha) more clearly
and further confirmed the symnetry (Figure 88).

Deciding experimentally between structure 88 and 88 is difficult.
One would need to add something to the remaining double bond which
would effect the protons of the product in some way. Thus, addition
of diphenyl carbene to 18 would give 88 for which the nmr spectrum
would no longer be symmetric; whereas, addition of diphenyl carbene to
88 would give 88 or more likely 88 since attack from the least hindered
side is expected to be more favorable. Both 88 and 88 would continue
to give a symmetric nmr, and one could further determine the stereo-

chemistry by noting which protons are shielded by the phenyl groups.

An attempt to obtain an adduct of 88 (or 88) by slowly adding diphenyl-

18

d e

COZCHZCH3

3 2

 

 

TABLE III.

Proton(s) 3ppearance

Ha triplet

Hb two doublets

Hbl two doublets

HC singlet

Hd quartet

He triplet

 

2
m

1
m

Proton Assignments for the Major Di-Adduct.

Chemical Shift (1) Coupling Constants (Hz)

 

 

8.6 Jab = Jab' = 2.9
7.8 Jab ‘ 2.9, Jbb' 6.5
8.0 Jab' ' 2.9, Jbb' - 6.5
8.2

5.9 def = 7.8

8.8 J = 7.8

   

CH3CH202C~.
H~- ,cH3
CH3
CH3CH202

 

diazomethane to a solution of j2 in refluxing methylcyclohexane (100°)
with cuprous bromide catalyst was unsuccessful.

The second di-adduct isolated (j1, new compound) was shown by nmr
to be either 88 or 88. Proton assignments could not be made completely
(Figure 12, appendix); however, addition of shift reagent elucidated a
high-field one-proton triplet with Eggggf cyclopropyl coup1ing (J =
2.8 Hz; see Figure 13, appendix). Because of its coupling, this proton
(Ha) must be assigned the position which is gggg; to the five-member
ring; since there is only one cyclopropyl proton at this position, the

other corresponding cyclopropyl proton, Ha" must be 939;. The asymmetry

20

of the molecule is further shown by the fact that the shift reagent
shifted one set of ethyl protons much more than the other set (Figures
13 and 14, appendix). This effect (similar to the effect observed when
shift reagent was added to the mixture of epimers 8 and 8) further
proves that the shift reagent coordinates more strongly to carboethoxy
groups which are 9597 rather than gggg; to the five-member ring.

In order to definitely assign either 1 or 88 as the structure
of j], the relative shifts (using Eu(DPM)3 shift reagent) of the ethyl
and cyclopropyl protons of compounds 8, 88 (or 88), and 88 (or 88)
were compared. The results are listed in Table IV. One would predict
that fbr compound 88, protons HD and Hc would be shifted more than for
compounds 8 and 88 (or 88) since the protons of 88 would be affected
by the shift reagent through association with both of the carboethoxy
groups. In contrast, one would predict that proton Ha of compound 88
would be shifted more than proton Ha of 8 and 88 (or 88). The fact
that Ha is shifted somewhat more in compound j1 suggests that 88 is
the correct structure; however, since the shift reagent is coordinated
much less strongly to the Eggg; carboethoxy group, the effect is small
and the result is not conclusive.

As Kirmse explains, when two isomers are possible, the less
hindered product is generally obtained in higher yield? This argument
is consistent with the fact that 8 is obtained in higher yield than
8 and j2 (88 or 88) in higher yield than j1 (88 or 88). Using the
same argument one would expect 88 to be formed in excess of 88, and

88 in excess of 88 (88 and 88 being the less hindered products).

21

TABLE IV. Relative Shifts* of Ethyl and Cyclopropyl
Protons of Compounds 8, 88 (or 88), and 88 (or 88).

 

d e
COZCHZCH3
Q it (or 1%) 1% (or l&)**
Ha 8.1 8.0 9.3
Hb*** 7.2 8.7 9.2
HC*** 9.3 9.8 9.2
Hd* 10.0 10.0 10.0
He 3.5 3.1 3.4

 

*Relative shifts were measured as relative changes in chemical shift
after addition of Eu(DPM)3 shift reagent. For comparative purposes,
the shifts of the methylene protons of the g3gfcarboethoxy group (with
respect to the five-member ring) were assumed to be constant for these
compounds and was arbitrarily set at 10.0.

**The relative shifts of the endo-ethyl protons were 3.1 for the methylene
protons and 1.3 for the methyl protons.

***It was difficult in the case of 8 and 88 (or 88) to determine whether
Hb or Hc was shifted more; thus, they may be reversed.

22

In an attempt to isolate other di-adducts peak d and peak f were
isolated, and peaks 9 and h were collected as one fraction. The mass
spectrum of d (Figure 5, appendix) showed a parent peak at 258 and a
base peak at 112 (1055 of two carboethoxy groups) suggesting a carbene
trimer (i.e. adduct of 8 to diethyl fumarate or diethyl maleate). The

structure of the trimer was not analyzed further, but was thought to

be 88.
C02Et
H H
EtO C H
2 0 Et
26 2
’VL

The mass spectrum of f (Figure 6, appendix) showed a parent peak
at 118 and a base peak at 66. The fragmentation pattern clearly shows
that f must be a mono-adduct of the carboethoxy carbene (8) to dicyclo-
pentadiene. The strong peak at m/e 152 indicates loss of cyclopentadiene,
the strong peak at m/e 79 indicates loss of cyc10pentadiene plus a
carboethoxy group, and the base peak indicates the loss of a mono-adduct
of 8 to cyclopentadiene. The stereochemistry of f was not analyzed
further.

The mass spectrum of the combined g and h peaks showed a parent
peak at 278. The fragmentation was similar to that of j] and j2 but
the ratios were considerably different. The nmr spectrum showed protons
in the vinyl region suggesting the presence of a di-adduct in which one
carbene has added to the gggr double bond. Further separation by

preparative glc was attempted, but the nmr spectrum remained essentially

23

the same (Figure 15) and analytical glc indicated the presence of at
least two conpounds. The singlets at r 8.6 and r 8.8 were predicted
for the cycloprOpyl methyls of 88 or 88 (compared with gem-dimethyl
cyclopropane).18 The one proton singlet at r 8.2 corresponds with
the lone hydrogen on the spiro cyclopropyl ring (compared with
carbomethoxy cyclopropane).19 The ally1ic cyclopropyl proton, Hd"
was expected at r 7.5. The ethyl protons at r 5.9 and r 8.8 were
also predicted. Proton Hc’ if gflgg; with respect to the five-member
ring, should be observed at approximately I 8.6; whereas, the Hd and
Hc (if g397) cyclopropyl protons should be observed between I 7.9 and
T 8.3. Finally the vinyl peaks at r 4.0 and r 4.7 correspond to the
vinyl protons; however, the integration did not show the proper ratio
of protons compared to the rest of the spectrum. Nevertheless, the
data indicate that at least one di-adduct such as 88 or 88 is probably

present in the mixture.

EXPERIMENTAL

A. General Procedures

 

Melting points were determined using a 6406-K Thomas-Hoover Unimelt
apparatus and are uncorrected. Infrared (ir) spectra were recorded
with a Unicam SP 200 spectrophotometer. All ir spectra were taken
in CCl4 using 0.1 mm cells. All nuclear magnetic resonance (nmr)
spectra were taken in CCl4 using a Varian T-6O spectrometer. Chemical
shifts are reported in Egg_values from internal tetramethylsilane
standard. The shift reagent used in all cases was tris-(2,2,6,6-tetra-
methylhepta-3,5—dionato)eur0pium(III) hereafter called Eu(DPM)3. Mass
spectra were recorded on a Hitachi Perkin Elmer RMU-6 mass spectrometer.

Analytical gas-liquid chromatography (glc) was conducted on
a Varian Aerograph Series 1400 instrument with a flame ionization
detector using nitrogen carrier gas. Preparative glc was perfOrmed

using a Varian Aerograph model 90—P instrument.

B. Preparation of Ethyl Glycinate Hydrochloride2O

 

Glycine (100 g) was mechanically stirred in 250 ml of absolute
ethanol with heating in a l 1., 3-necked round-bottomed flask fitted
with a condenser and a gas inlet tube. Dry HCl (54 g) was bubbled
into the solution. Then 50 ml of benzene was added and a glass packed
column was used to fractionally distill the benzene, ethanol, water

azeotrope. The remainder of the solvent was evaporated on the rotary

24

25

evaporator. Drying of the white powder was completed by evacuation
to constant weight using the vacuum pump (5.0 Torr) at room temperature.

Yie1d 181.1 g (97.0%).

C. Preparation of Ethyl Diazoacetate (8)

 

This was prepared according to the method of N. E. Searlel“ using
the ethyl glycinate hydrochloride prepared previously. When the
product was slightly basic (pH indicator paper) it was steam distilled,
extracted with CHZClZ, dried over anhydrous sodium sulfate and most of
the CH2C12 was evaporated (because of the explosive nature of the
product, all of the CH2C12 was not evaporated). Yield 137.5 g (purity
was determined by nmr to be 73.1% by weight ethyl diazoacetate in
CHZClz) 67.9% yield. Nmr data: triplet r 8.70 (3H) J = 7.0 Hz; quartet
T 5.74 (2H) J = 7.0 Hz; singlet T 5.11 (1H). Ir: 2150 cm" (N=N stretch).

D. Preparation of 6,6-Dimethylfulvene (8)

 

In a 500-ml round-bottomed flask equipped with magnetic stirring
bar, 132.2 g (2 mole) of freshly distilled cyclopentadiene was combined
with 3.4 g KOH in 50 m1 absolute ethanol and the mixture was cooled
in an ice-salt bath. Acetone (73.5 ml, 1 mole) was added slowly with
stirring; the reddish-brown colored solution was stirred for an
additional hour under N2. The reaction mixture was then poured into
100 ml ice water and 200 ml ether. The ether layer was separated and
extracted with 50 m1 aliquots of H20 until the ether layer was neutral

(pH paper). Solvent was evaporated <40° using the rotary evaporator.

26

The remaining oil was vacuum distilled (25°C, 1.0 Torr). Total yield:

54.2 g (51.1%). Nmr data: singlet r 7.86 (6H); singlet 1 3.60 (4H).

E. Reaction of 6,6-Dimethy1fulvene (1) with Ethyl Diazoacetate (l)

 

in the Presence of Cuprous Bromide

Cuprous bromide (0.5 g) and 6,6-dimethy1fulvene (38.6 g, 0.363 mole)
were mixed with 80 ml of hexane (dried over molecular sieves) with
magnetic stirring in a 250-ml, 3-necked round-bottomed flask fitted
with a nitrogen inlet tube, a condenser, and a pressure equalizing

dropping funnel. After the system was flushed with N 62.3 g (0.546

2,
mole) of ethyl diazoacetate (73.1% solution in CH2C12) was placed in
the dropping funnel with 80 ml of dry hexane. After the flask was
initially heated to 45°, the ethyl diazoacetate mixture was added by
drops over a period of 2 hr. so that the heat of reaction kept the
reaction mixture at 30-50°. The mixture was then stirred until no more
evolution of N2 was observed and ir indicated the complete absence of
the band at 2150 cm'1 (about 5 min.). Analytical glc of the crude

mixture indicated the presence of the following products (analytical

5' x 1/8" FFAP, 177°):

 

 

Peak % of Total Retention Time (min.)
Labe1 Product FFAP, 177°
a (hexane)

a1 (fulvene decomposition products)

b1 4 1.2
b2 7 1.6
c1 39 2.8

27

 

 

Peak % of Total Retention Time (min.)
Label Product FFAP, 177°
c2 < l 3.4

d 4 5.2

e 3 6.8

f 4 8.6

g 3 11.0

h 9 12.6

1 < 1 15.2

3' 28 19.2

k < 1 24.0

F. Method of Separation of the Products

 

After evaporating the solvent using the rotary evaporator, the
mixture was vacuum distilled. Fraction 0 which distilled at 44-45°
(0.2 Torr) was rich in compounds b1 and b2. The large fraction
(Fraction E) which distilled at 77-80° (0.2 Torr) was rich in c1 and
contained very little of the compounds with longer retention times.
Fraction F (BO-100°, 0.2 Torr) contained large amounts of d and f.
Another large fraction (Fraction H) distilled at 127-140° (0.2 Torr)
and contained primarily compounds g, h, and j.

Final purification was obtained using a 10' x l/4" SE 30 column.
At 152° and 40 p.s.i. (300 ml/min, compounds b] (retention time, 4 min.)
and b2 (7 min.) were isolated from fraction 0. At the same temperature,

c1 (ret. time 14 min.) was isolated from fraction E.

28

At 180° compounds d (ret. time 15 min. 30 sec.) and f (ret. time
23 min.) were isolated from fraction F. At 200°, compounds g and h
were collected as one peak (ret. time, 20 min.) while j separated into
two peaks which were isolated as 3'1 (31 min.) and j2 (36 min.). The

ratio of j] to 32 was approximately 1:8.

G. Identification of Products

 

Compounds b1 and b2 were found to be diethyl fumarate and
diethyl maleate respectively by comparison of their glc retention
times and their ir and nmr spectra with authentic material.

Mass spectrum of c] (Figure l, appendix) showed the parent
peak at m/e 192, the base peak at m/e 119 (loss of COZEt), and a

strong peak (72% of base) at m/e 91. Ir spectrum showed strong

1 1 1

absorption at 1713 cm'1 (C=0), 1278 cm- , 1178 cm' and 1168 cm' .
Nmr spectrum (Figure 7) showed; triplet at r 3.9 (2H) (J = 1.2 Hz),
quartet at r 5.9 (2H) (JAB = 7.6 Hz), broad multiplet at r 7.2-7.6
(2H), singlets at r 8.1 and r 8.2 (3H each), triplet at r 8.8 (3H)
(JAB = 7.6 Hz), and a one-proton triplet at about r 8.8 (1H) covered
up by the three proton triplet. Addition of Eu(DPM)3 shift reagent
(Figure 8) shifted the one proton triplet so that the splitting could
be clearly observed and measured (J = 2.7 Hz). The two proton
multiplet was then observed as an AB multiplet (J = 7.2 Hz). These
data indicate that the structure of the product must be 8. After
addition of the shift reagent, an additional quartet and corresponding

triplet were also visible since they were not shifted as much as the

ethyl protons in 8. These peaks and other peaks not attributed to 8

29

suggested the presence of its epimer 9. Expansion of the quartets
and integration (Figure 9) showed that 9 accounts for approximately
13% of c].

Pure j2 was a white crystalline solid (mp 59-62°). Mass spectrum

of 32 showed the parent peak at 278, base peak at 131 (loss of 2—C0 Et

2
and 1H) with strong peaks at 232, 205, 204, 159, and 91 (Figure 2). Ir

showed strong peaks at 1712 cm'] (C=0), 1419 cm.1 1

, 1281 cm' , and 1177
cm']. Nmr spectrum (Figure 10) showed a triplet at r 8.8 (6H), J = 7.8
Hz, two doublets at r 7.7-7.9, J = 2.9 Hz and J = 6.5 Hz, and two
doublets at r 7.9-8.1, J = 2.9 Hz and J = 6.5 Hz. Addition of shift
reagent (Figure 11) caused the four sets of doublets to eventually
merge into one set of doublets (J = 2.9 Hz). The allylic methyl
protons remained equivalent and the two proton triplet (J = 2.9 Hz)
was seen clearly. 0n the basis of these data, it was determined that
jz must be either 11 or the me§9;isomer 12.

Mass spectrum of j1 (Figure 3) was almost superimposable on that
of j2 except for minor peak ratio differences. Ir showed strong peaks

1 1 1

at 1717 cm" (C=0), 1421 cm' , 1287 cm‘ , and 1167 cm” .

1

A sharp peak

in the ir is present at 1145 cm' for 3'1 but is absent for j2. In

contrast j2 has a sharp peak in the ir at 1040 cm-1

which is not present
in j]. The nmr spectrum (Figure 12) showed triplets (J = 7.5 Hz) at

r 8.8 and r 8.7 (3H each), singlets at r 8.3 and r 8.2 (3H each), a
quartet at r 5.9 (J = 7.5 Hz) (4H), an apparent doublet at r 7.9 (2H),

a multiplet at T 8.1-8.0 (2H), a one proton triplet at r 8.6, and one

proton apparently hidden under the singlet at T 8.2. Addition of shift

30

reagent (Figure 13) shifted the one proton triplet downfield from the
other triplets so that it could be clearly seen (J = 2.8 Hz) and
separated two quartets (Figure 14) and the corresponding triplets of
the obviously non-equivalent ethyl groups. On the basis of these data,
j1 was determined to be either 13 or 14.

Mass spectrum of d (Figure 5) showed a parent peak at 258 and
a base peak at 112 (loss of two carboethoxy groups) indicating the
presence of a carbene trimer. The nmr spectrum showed sets of peaks
at r 8.5-8.9 and r 5.5-6.1, a singlet at T 6.1, and vinyl singlet at
T 3.1 with an integrated ratio of 66:37:8z3. It was concluded that

the sample was impure, and d was assigned structure 26.

C02Et
H
Et02 H
26 OzEt
’VL

Mass spectrum of f (Figure 6) showed a parent peak at 218, a base
peak at 66, and strong peaks at 152 and 79. The mass spectrum clearly
shows that f must be a mono-adduct of carbene 2 to dicyclopentadiene.

Mass spectrum of the g and h combined peaks (Figure 4) showed a
parent peak at 278, a base peak at 91, and a strong peak (98% of base)
at 131. The fragmentation was similar to that of 3'1 and 3'2 but the
ratios were considerable different. The nmr spectrum (Figure 15) showed
protons in the vinyl region, suggesting the possibility of a di-adduct
in which the carbene has added to the £597 double bond. Although further
attempts at purification were unsuccessful, analysis of the nmr of the

mixture indicated that one of the products could be 17.

 

SUMMARY

1. The copper(I) catalyzed decomposition of ethyl diazoacetate in the
presence of 6,6-dimethylfulvene yielded two mono—adducts and at least

three di-adducts.

2. The major product of the reaction was the mono-adduct ethyl (13f,
SSf, 65f)-4-isopropy1idenebicyclo[3.l.0]hex-2-ene-6-carboxylate (8)

and accounted for 34% of the volatile product material.

3. The other mono-adduct, ethyl (13f, 55f, 6Rf)—4-isopropy1idene-
bicyclo[3.1.0]hex-2-ene-6-carboxy1ate (9) accounted for 5% of the

product material but could not be isolated from a mixture of 8 and 2.

4. The structures of the di-adducts were not definitely determined;
however, the major di-adduct was shown to be either 11 or 12 while
another di-adduct was shown to be either 11 or 11. Yields were

approximately 25% and 3% respectively.

5. At least one other di-adduct is present, but it has not yet been
isolated in pure form. The nmr spectrum of the impure material
contains peaks in the vinyl region, suggesting the possibility of a

di-adduct in which the carbene has added to the e597 double bond

(i.e. 11).

31

10.
11.

12.
13.
14.

LITERATURE CITED

M. F. Dull and P. G. Abend, J. Amer. Chem. Soc., 61, 2588 (1959).

 

I. A. D'yakonov, T. V. Domareva-Mandel'shtam, and V. V. Razin,

 

Zh. Obshch. Khim., 66 (10), 3434-8 (1963); Chem. Abstr., 66, 4023g
(1964).

 

J. Narkentin, E. Singleton, and J. F. Edgar, Can. J. Chem., 16

 

(12), 3456-8 (1965).

H. Nozaki, H. Takaya, S. Moriuti, and R. Noyori, Tetrahedron,

 

61, 3655-69 (1968).

N. Kirmse, "Carbene Chemistry", Academic Press, New York, N. Y.,
1964, pp 95-98.

P. S. Skell and R. M. Etter, Proc. Chem. Soc., 443 (1961).

 

M. Schlosser and G. Heinz, Chem. Ber., 161, 3543-52 (1970).
H. Hart, R. L. Holloway, C. Landry and T. Tabata, Tet. Lett.,
66, 4933 (1969).

T. Tabata and H. Hart, 1619,, 66, 4929-32 (1969).

M. Rey, U. A. Huber, and A. S. Dreiding, ibid,, 11, 3583-88 (1968).
R. Criegee, H. Gruner, D. Schonleber, and R. Huber, Chem. Ber.,
161, 3696-704 (1970).

H. Hart and J. D. DeVrieze, Chem. Comm., 61, 1651 (1968).

 

J. Org. Chem., 66 (9), 2849-67 (1970).

 

N. E. Searle, Orgg Syntheses, 16, 25 (1956).

 

32

15.

16.

17.

18.

19.

20.

33

L. M. Jackman and S. Sternhell, ”Applications of Nuclear Magnetic
Resonance Spectroscopy in Organic Chemistry", 2nd edition,
Pergamon Press, New York, N. Y., 1969, p. 83.

H. Hart and G. M. Love, Tet. Lett., 1, 625 (1971).

H. E. Zimmerman, S. S. Hixson, and E. F. McBride, J. Amer. Chem. Soc.,

 

gg, 2000 (1970).
J. Org. Chem., 61, 2720 (1962).

 

N. S. Bhacca, D. P. Hollis, L. F. Johnson, E. A. Pier, and
J. N. Shoolery, "High Resolution NMR Spectra Catalog", The
National Press for Varian Associates, 1963, spectrum 112.

Curtius and Goebel, J. Prakt. Chem., 11 (2), 159 (1888);

 

C. S. Marvel, Org. Syntheses, Coll. Vol. 6, 310 (1943).

 

APPENDIX

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