'I
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I}

I 4'
\
iH‘

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quW
H H“
s7 Ly M H K

M
H

w '.
'\

‘t'

777: 7 i , —
;,7»

l

K

1

‘ ['1‘] h‘

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THE LITHEUMcAMINE REDUCEON
OF THEANAPHTHENE AN!) SQME
01‘ £75 DERWATW‘ES

Thais iar fha Dogma a! M. S.
MECHESAN STARE ENWERSITY
{fay P. O‘Brien
€962

l'THEsxs

6.5L

 

  
  

  
 

“DIARY

M'CH’CW ST “.75 U‘J.‘VFFS:'TY

LAST LAmeb,Mthu/m

THE LITkIUM~A£INE BLDUCTIOR
0F TEIANAPBTHhRE AED SGEE
OF ITS DERIVATIVES

3!

JAY P. O'BRILK

submitted to the College of Scionco and Art-

of Michigan Stat. Univorsity 9f Agriculture

and Applied Scions. in partial fulfill-eat
o! the requircnontl for the degree of

MASTER OF SCIENCE

Department of Chemistry

1962

ACILN 02': LbDGl-nui‘x‘ '1‘

The author wishes to express his appreciation to
Professor Robert D. Schuetz for his guidance and counsel

throughout the course of this investigation.

ii

VITA
Jay P. O'Brien

Date and Place of dirtn: Feoruary la, 195?, in Dayton, Ohio

Education: Rutgers, The State university, hewark, hew Jersey
ly5y-lyOJ. Bachelor of arts, lyod.

hichigan State University, East Lansing, hichigan
lyéo-lyéa.

ProfeSsional Affiliations: American Chemical Society.

iii

THE LITHIUMeifilfli REDUCTION
OF THIANAPHTHENE AND SOME
OF ITS DERIVATIVES

3!

JAY P. O'BRIEN

AR iBSTRACT

Submitted to the College of Science and Attl
of Michigan state Univereity of Agriculture
and Applied Science in partial fulfillment

of the requirements for the degree 0!

MASTER OF SCIENCE

Department of Chemistry

Year 1962

Approved

AdSTRaC

The reduction of thianaphthene using a lithium-aliphatic
amine system was investigated as fossiole synthetic route to
partially reduced thianaphtnenes. The reduction was found to
involve cleavage of the Garcon-sulfur bond in the heterocyclic
ring to yield o-ethylthiofhenol and E-ethylcyclohexanone, in

the Case of tnianaghtnene.

O
11 C.H-
I ”a a 9 02H5
CHE Nn , +
c 5 2 SE

The o-ethylthioPhenol was established as an intermediate in the
process by its isolation and reduction with lithium-ethylamine

to a-ethylcyclohexanone. Attempts to isolate adaitional
intermediates by using various diluting agents, ethanol,
piperidine, and morpholine or by lowering the reaction temperature
(-od) and reducing the reacting time (three hours and one hour)
only increased the yield of o-etnylthioyhenol at the expense

of Z-ethylcyclohexanone. These observations suggest the

following reasonaole mecnanism for the reduction.

Li C B.

 

____..————7 3 b
- e
CZESNHZ 8 Li
L/ \d
C H
2 5 <’ 02h5 0‘35
8 Li SH
320
02H5
0

To alter the nature of the heterocyclic carbon-sulfur
bond, methyl groups were placed in various positions in the
thienayhthene nucleus. The 2-methy1. 3emethyl and 3,5eeimethyl
thianaphthene derivatives were prepared. inch yielded the
corresponding nerceptan ind Ketone by reductive cleavage with
the metal-amine system. It was noted that as the +1 effect of
the ring substituente increased the amount of ketone was decreased
very procnbly due to an increase in the electron density of the
benzenoid ring.

The 2-fluerothinnaphthene was preyared by fluorinating
Z-lithiunthianaphthene with perchloryl fluoride (-10 to 0°).
The compound was characterized by nuclear nagneticepectra and

analytical data. Reduction of thin fluoroheterocyclic yielded

o-ctdylthiophe1ol and B-ethylcyclohexanone as the sole
reduction products in very low yields.

The lithium-amtne reduution of the garent heterocyclie,
thinpheno, yieliei a Bfllll emaunt or an unidentified high
coiling neutral product which possibly contained a carbonyl

group. The aciiic fraction W18 not investigated further due to

the extreme odor of the possible product, n-nutylmercantnn.

TABLE OF C CN '1 241‘; 1‘8

Pat.

lliprUUUTIUHooooooo-ooooooooooooooooooooocoo-0.000.000.0000 1

HISTiJRICALO0.0.0....OCOOOOOOOOODOOOOOOOOOOO0.00000000000... 2

DISCUSLSI‘JNOOIOOOOOOOOOOOOOOOOOOOOOQOOIOOIOOOOIOOQOOOIOIOOO. 13

£XPLI€IM§§NTQLOIOOOOOOOOOIOOUIOOOOOOOOOOOOOOOQOOOOOOOIOOOOQOQ 26

SU1‘.;I'L£'ABYOOO0.0.0....OOOOOOOOQOQCOOODOOOOOOOOOOOOOOOOOIOOQOOO k5

hLFELE;EiiCIIASOIOOOOOOOOOOOOQOOOOOOOOOOOOOOOOOOOOOCOOOOOOCQOOOO “6

viii

LLST OF TKBLLS

T115124};

I neduction of Thianaphthnne with the Lithium-
Lthylamina System and the Effect of Various

Cosolventa on $1.40 FQduCEIOnooo00000000000000.0000... 15

II Reductlon of Alkyl Sulatltuted Thianaphtneneso...ooo l9

ix

FIGUQL Pago

I Infra-red Speotrn Of ThiandphtheIIOcuooocoo-0.0.000.o. 21

II Infra-red Spectra of E-Fluorotnianaphtheno.......... 22

III Nuclelr Eagnetic Resonance Sgactra of

ThiafiapRChQBCocooocooaooouooooa000ococoooooooooooooo 23

IV Nuclear Magnetic Resonance Spectra of

Z'F‘lUOTOthianaphthGHCOOo000000000.0000000000000000... 2“

Iil'L'L' QDUCTL ON

The present investigation was undertaken to determine
the effect of the lithium-aliphatic amine reductive system
on thianaphthene an a possible synthetic route to partially
reduced heterocyelice. To elter the nature of the hetero-
eyelic carbon-sulfur bond, nethyl substituted thianaphthenea
and the Entluorothianaphthene were also reduced using the

lithium-amine system.

HISTORICAL

The partial reduction of aromatic compounds using motel-
liquid ammonia, end alcohol combinations has been known for some
tise as the Birch reduction. Metals usually employed are the
alkaline and alkaline earths.

Liquid ammonia is very similar to the low molecular weight
alcohols as e solvent for organic substances. The metals dissolve
in the liquid ennonis to give deep blue colored solutions.

The alcohol functions as a diluent or cosolvent and alters the
solubility and rate of the reaction. In addition to alcohols,
enlonius chloride. sorpholine. piperidine, tetrahydrofnran, and
ether have been used as cosolvents‘1)o

The essential step in the metal ammonia reduction is the
addition of the two electrons to the arosatic compound in e
stepwise sanner. It is rather difficult to determine wether
the addition of the first electron or the second is the rate
determining step. The negatively charged molecule is associated
with positive ions derived tron the setal supplying the electrons.
The charged specie say possibly be as intermediate. This
charged specie then reacts with the cosolvent to pick up

two protons and give the partially reduced compound.

Ln;-

An acidic ernton is needed which prohanly comes from

H H

the alcohol. (2)
Such reduction mixtures have seen known to ole-vs aliphatic
others to alcohols and elkanes. In tne cleavfige an alkoxide
ion and carbanion are formed. If the anions are intermediates
then the R group containing the less electron donating grouys
or more electron attracting groans should ag,ear as the alxane.
The Clfifivagfi of unisole with sodium, awnonin, and alcohol

leads to a vinyl other which is cleaved to give u ketone.

OCH} 0 U
~©Q©~©

Adding two electrons to o—ncthylanicolo will yleld two sgstons;

OMe

one in which the electron is equally distributed to the 1,3,5
positions and the other to the a,h,6 positions. The hydroficns
will add to the 3 and 5 positions first since theme are of
greatest electron density. Then hydrOgens will add °‘ , J to

the 5 and 5 positions giving two isomeric products.

OCH" 1" 3
J .rC‘i3 OCH}
ca} cu- N,
—____.) J+ wt 3
0633 OCH3
Ch:5 01135 (2)

in 19); erkuflul (g) oaseTVed that n b'rtrifi quAuLLtJ of
lloulum Ha; uQuUJQcJ ad un urouotlc Liarocurbon 4nd in lyyfi (5)
he reyo;tel Lao algh aolootivlLJ of tic litzium~uuine reduction
ayatom. Lituiun metal Jiusolvefl in low moleculur weight amino.
such an uotuyl and otnyl amines to give tse caaructorlatle do.)
alas colorod BOiHCLQlS- £16 uramatlo ayatomo are reduced to

I
aoaoolafins b; Buéh relualn; systems. An o:g4no-llthiun
intarmeJlAta is postulated alloo a definite ratio of licuium
is aeooraod per fiQld of aromatic congoond roduoed.

Otuor «lined whluh navo aaccea.fully 0294 use} lu than.
redlotiana include n-gragyl, lamprouyl, and n~3nnyl. However,
due to the aaluoil;ty of LLthiAN metal decreaaing in ties.
amines ma the nolaoullr weight of the aainoo increase, the rcdlfltiol
was slofldr tnd a ulxtura of interldl¢43d gradlots wore Ldol4tod.

23a dlifcrance )ecween taa lltniaa~qalue an! saaluw-aamonia
Bystcmu 13 cousldo;anlu. «niaale snen roiucad alto Litlium,

mothylamino, and ethanol as oJJolveat yields 95m of :,;~1~¢;dro-

aainole ehile sodiun, anaonia, and ethanol yields the fission
produotx , G ocyclohoxenone. However, use of Just a lithium
and ethyl-amine results in a mixture of oyolohexanol and cyclo-
hexanone. (k) Biphenyl yields cyclohexylbonzene on reduction
with sodium and ammonia shile a 49% yield of l-cyolohexyl-
oyclohexeno is obtained with lithiun and methylanine, and a
92% yield of l-cyolohexylcyclohexone is observed using morpholine
an a cosolvent. Naphthalene when reduced with lithiun and amnonia
gives only tetralin, but with lithius and ethylanine a 90% yield
at A 9'10 octalia and 10% A 9'1 octalin is observed (It).
Beakeses (5) reduced a series of mono alkyl substituted
bensenes using the lithiusaanine systen. Using methyl. ethyl,
isoPropyl. and t-butyl benzenes he found that the most stable
olefin was turned in all canes. However as the bulk of the
alkyl group and its +1 effect increased the yield of reduction

product decreased.

R
______Ii___)
ENKZ

The sane reduction systen was found to reduce phenyl ketones

to oyclohexenyl alcohols.
COCH CHOHCH

3
u __A
RN32

3

 

Phenol is reduced with tue lithium-amino syston in yields
of 96} of cyclohexanono using only a slight excess of lithium
and rapid hydrolysis. The mechanism is probably reduction of the
V‘ '_
arUMatio ring to a cyclic monooleiln, Vlnjl alcohol, WhiCh
tautouerizes to toe ketouo. Using a VCPJ ldrmo excess of lithium
a mixture of CJQlOucdanUl and uJolohoxanouo la OuLained (a).
drouutlo uitrileu are reduced to a naturoted amino using

tho l.lthiuxa-~4.J.Lxm uyst-cm.

0.4 on an:
L1 ‘ "
_._—«9
mug
1* 7’32;

'0
denaonitrlle is nae only oasa, as yet, in wnich a nonoolefin
was not JrJJUCOde Hula guy poeoibly so due to the electron with-
drd in; offecu of tLo nitrilo which roluccd tic electron density
in tin aPOQJSLG ring, tLua, Iavorin; comylote reduction. “he
”- -o - § , n
HDHJOieiln 11 yroduced could po;3uorino and account LOP the

turrJ og~producto. However, if the nitrilo gran; is rcaovod

n
fffld ;;o rid; bj a single owrfion a mongolofin is aroiuced.

Nitrooonzeneo anon reduced with litnlum and nothylamine
yield anilines. However, with ethyluminc a mixcure of anilinea

and cyclohexyl amines are formed.

n02 2
I" @
—___fl——<>
[::::] CEBNHZ
ca3 033
no N82 “”2
2
L1 { + (5}
czxsnnz .
CH3 3} . bn3

Tho toiloro of tho ring to undergo further roduction io duo to
tho fact thot ohon tho nitro group io reduood thoro io an

incroasing amount of. ENE- Li’. onido icno coin; fornod which

arc in oqnilibrinn with tho onilido iono. _
CB} NH o

Sinoo tho onido ion io o otroogor baoo than tho anilido ion,

tho oquilibriul will 11o to tho right.

- _____;> . ~
+ ENE NB
V‘“
’[::::L + RN32
CH

033 3

N32

Formation of the onilido ion is analOgono to tho onno at

bcnzyl alcohol which in roducod to toluono whilo tho salt of
the alcohol io not. duo to tho doVelOPoont of o negativo chargo
on tho oxygen in a basic media. 'Tho amino alcno io roducod to

cyclohoxylaming,

332 nae

O ”
~—————-—>
mun
. 2
ca ‘
3 ca}
50%

oiooo thoro 1o no olkyl onido iono tormcd initially. Howovor.
no amide iono oro torood tho rodnction stapo, Accounting to:
tho loo :iold o! roduotion product. E.fl-dinothylonilino.
hooovor. io roducod to cyclohoxanono ohich can ho onploinoo a;
tho Iornoticn of o vinyl onino and ito hydrolyoio to tho vinyl
alcohol folloood by tnncooorio roorrongcoont to tho kotooo (7).

R(Cn3) fiCCfl5)

Hfla hfia
L1
____,~,,_—;

Thuo. it to cloar that tho formation of o nogativo chargo on
o group octochod to an aromatic ring will inhibit roductxcn of

tho ring by tho lithiuo-omino combination.

Ii
————————9

HRH“
¢
The reduction of the alkyl halides with sodium and

ammonia yielda prhmarily tho hydrocarbon, in addition to somo

Amino and tho oxyoctod wurtn coupling product.

la
CH. Cl NH.’ CH. o camnfl + can,
c’ J 5:. .J l— L. b
YUfi dU% traco
Na '
c‘._njm- 77—, 97% + czafiwnz + ca;5(cn2)2cnj
5 70% 40% traco

Tho reduction of aromatic unlidco likauiso aivoa tho hydrocarbon
and tho oorrooponding amino. ?ho «mine being yroducod by a
oenzyno intermediate {0).

01 NH

TJ

1‘ *1 , 131-1. 1'

#4
I

Orgwnio sulfur canoounda are extremely difficult to reduoo
with hydrOgen aul a platinum or palladium catalyst due to tho
poisoning cfzeot of sulfur on these cutalynbn. 3hLOphenc no:
icon reduced (9) to tetrnhygrotniOphene uoing molyodsuum
oulfido on tho catalyst. Uutano, hydrogen sulfide and n-butyl-
ncrooptan woro also isolated from the hnyU£KNASiJu uroducts.
Using a large cxcoas of walladium catalyat, the reductive
hydrogenation of thioyhene yielded only tetrnhydrottionhcne.

In 1951 Riroh and Mcifildn (10) troated thiopheno with a

10
oodinn. ammonia. alcohol mixture yielded 40% of n mixture of
tho 2,} and 2.5 dihydrothioyhono.

5‘. RE
3 § h
I I \3‘ I
0.2 on [ .l [ ]
“5 '5

d 5
Inc 2.) dihydro compound was very cucoptiole to polymerization.

Upon further reduction of the 2.3 dihydro compound only polymeric

natorial one obtained. which can be explained b y the following

ncchanicn aasuning ring cleavage.

“\j —9 ca 3cm 20330333] —» [cznficaacnacnfl ——9 polymer

The 2 5-dihydrothi0phonc on further reduction wan converted to

n nixturo of unsaturated mercaptnnco

~----—

2o‘~—s. CH ~Cfi-GH-032 -S

[——-'l * ‘ 2
s ¢://;B’

+ CHE ICHCH CH SH

CH 03-0303 83 2 2

a 2
In 1951 Birch (ll) elco reduced 3-nothylthiophene to
Janethyl-Z,S-dihydrothiophcno which conld be further reduced

to n mixture of uncaturatod norcaptano.

‘ on) on}
-—- ca ac(cs )cu ca.sn
[L‘ l —9 l I a 3 e 2 a

C33C(CHB)aCBCHZSH

 

 

The reduction of 2.5-dincthylthioPhencn using sodium, almonia.

11

and methanol yielded only 2-hexanone. proonbly oy hydrolycio

of the intornediato thiokotone.

“fin £333 a; 0
“flfifl ca on

Using just sodium and amnonia or sodium and ethanol. nwbutyl

CB

‘41
“Q

nercaptan in the sole product.

There in n single reduction up system that will reduce
thinnnghthene to a yartioISy reduced compound. Fricko and
Syilkcr in 1923 (12) reduced thicnnphthene with sodium and alcohol
to obtain 2.}~dihydrotmiannphtheno and o-othylthiOphonol.

a Fancy Nickel reduction in nethanol will deeulfurino'
thianaphthenc to othylbonzeno (755). Frionc and Spilkor clco
reduced thinnephthcno with hydroxen (ll otn.. #380) in the aboenco
of a catnlyct to obtain a mixture of yrodnctc. o-othylthiOPhenol.
toluene. ethylbonnono. end benzene.

The 2.3-dihydrothianephthone has also been progared (1})
by a ring clocuro procedure ucing o-eninc-Z-chloroetnylbenccnc3
the amino following diocotisation nae treated with potaeeinn ethyl

nantnato.

5532 lo KONG

 

7

.N or! o‘ -. (:l'a ‘e‘lr- '
“Edi-”“201 of o Kuvb £235

The only other partially reduced thianaphtheno reported one
#,5.6,7-tetrnhydrothianaphtheno.' Ito synthesis started with
thiophono. (14. 15)

1o Succinic anhydride, SnClh

 

 

 

[I:j]] 2. Clcmnenaon reduction
‘8 3. 80012
h' SnCl“ Clenmenaonlgcduction

 

In 1959 (16) thionnyhthene one reduced with nodiun and
ammonia. treated tirct with chlorine. then with acetic acid,
and finally with nmnonin to convert the reduction product, a
nercaptnn. to o oultonanido. In addition to the nulfonamido,

unroducod thinnaphtheno one aloe recovered.

 

2. n" sown
l ,__ ¥i% a 2
3. c1 "
s 2
h. u
H 3

The S-nethyl derivative of thianaphthene can also reduced and
yielded an the only reduction product reported. 2-othyl-h-nethyl-

thicphontl.

1}

DISCUSsICN

The reduction of thianaphthcne using the lithium-ethylamine
systes of Benkeser was (5) investigated to determine whether
this procedure was applicable to the synthesis of partially
reduced thianaphthcnes, and in particular to ootainine those
not previously described. However, in every case studied,
during the course of this work, one of the carbon-sulfur bonds
underwent fission.

Due to the increased reducing power of the lithium-ethyl-
amine system over the sodiun-anmonia one, reduction of the
benzenoid ring was also sccosplished. rhc reduction of
thianaphthenc when treated with lithius-ethylamine for ten hours
at roos temperature gave two fractions. The neutral fraction
was identified as Z-cthylcyclohexanone. being obtained in #?.§%
yield. Acidification of the aqueous phase of the reaction
sixture with concentrated sulfuric acid yielded 29% of onethyl-

thioPhenol.

0 en
1. L1. 6.3 NH
.2 5 :2 0235 02115

‘ ”r -+

2. H20

ho unredueed thianaphthene was obtained.
The identity of the ketone was established by preparation
of its known semicarbazide derivative. The cyclic ketone was

also reduced with Fancy Nickel in methanol to the corresponding

14

known alcohol. The o-ethylthioPhenol identity was established
by converting it to its known lead salt derivative and also

by desulfurisinz the nercaptan with Haney nickel in methanol
to obtain ethylbensene.

It was shown that one of the intermediates in the reduction
of thianaphthene is the sereaptan. o-ethylthioyhenol, which
then could be reduced to the corresponding mercnptan followed
by its hydrolysis to yield the ketone. The o-ethylthiOphenol
was synthesized by an unequivical method involving the
chlorosulfonation of ethylbensene with chlorosulfonie acid,
and reduction of the acid chloride to the mercaptan with zinc
and dilute sulfuric acid.

0 H

C H 2 5

2 5 .
. (3130 H __., 502"1

023

50201 - Zn ‘9 SH
dil. Hasoh

The sercaptan, o-ethylthiOphenol. was then reduced to 2-ethyl-

cyclohexanone with lithius-ethylamiae is a 15.9% yield.
Attempts to isolate additional intermediates in the

reduction of thianaphthene by adding various diluting reagents,

ethanol, norpholine. and piperidine only decreased the yield

of ketone and increased the yield of aercaptan (Table I).

The thianaphthene reduction was also conducted at a lower

temperature (-60) and the riaction tine was reduced to periods

15

TABLE I

Reduction of Thianaphthene with the Lithium-hthylamine
System and the Effects of Various Cosolvents

on the Reduction

 

Reaction Yield %

Cosolvents Time hr.

 

C H 0,3
2

 

2 ‘ a 5

0 SH
none 8 47.5 29.0
causes 3 20.0 75.0
N(CHZ)5 3 trace 59.5

0(CH2)#N 3 41.5 5H.O

16

of three hours and one hour. In each case o-ethylthioPhenol
was the only najor product isolated. A trace of impure
2-ethylcyclohexanone was also isolated. The reasonable
aechanisn.oiashd on these observations. for the lithiusu

amine reduction of the sulfur heterocyclie can he suggested.

 

 

_ L1 > 235
C 3 NH
2 5 2 B- Li+
u’// \h
C H- E.
2 b ( 2 b 0235
8 8 L1 SH
320

0235
O

The negative charge associated with the mercaptan sulfur
would probably increase the electron density of the sing,
siailarily to the case of the anilide ion in the reduction of
nitrobensene (7). Such an increase in the liectron density would
probably prohibit complete reduction to the thioenolate anion.

In an effort to increase the strength of the carbon-sulfur
bond an electron donating group, methyl. was substituted in the
various positions of the thianaphthene nucleus.

The Zesethylthianaphthene was obtained folIOwing the procedure

or Heyd (18’s

17

n-hutyl lithiun
ethyr ~10°

fi?

   

/// methyl tosylate
k
CH
lhe isomeric 3-methyltnianaphthene was prepared by a ring

closure reaction of acetonyl phenyl sulfide with phosphorous

pentoxide.

as
on ~g-CH Cl ““03 9
" 3 a —-—-"" CH-.ccn.,s
520 5’ "
Egg-CE} P205 . CH3
-s-cfia __.__—~9

The dialkylthianaphthsne. 3.Svdimethylthianaphthene, was
synthesized employing the above procedure and using p-methyl-
thiophenol as the initial starting material.

The three alhyl derivatives of thianaphthene were subjected

to the reduction procedure. of treatment with lithium-amine.

18

identical to the reduction procedure of thianaphthene itself.
The results are sussarized in Table 11.

Examination of this data indicates clearly that there
is s decrease in the yield of the ketone an the +1 effect or
the number of electron donating groups present on the arene
nucleus inereaees. Such a result can be accounted for the
fact that as the +1 effect increases. the electron density of
the ring is increased, which in turn makes it more difficult
to reduce the ring.

The effect of an electron withdrawing group on the carbon-
sulfur bond was studied. The Z-Fluorothianayhthene was synthesised
by the direct fluorinstlon of Z-lithiusthianaththene with
perchloreyl fluoride. This new yroeedure for the introduetion
of fluorine into erenes and is partieular into heteroeyelie
systems use developed partially during the course of the present

investigation.

' n-butyllithius
ether «~10i I Li

 

Due to the sisilsrity of the boiling point and refractive
index of the 2-f1uorothianaphthene, an organic qualitative
test for fluorine was attempted on this material using

zirconium-alisarin test gaper. (26). This failed to give a

13

TABLE II

Reduction of Alkyl Substituted Thianaphthenes

R2 R1
U R

 

 

 

Yield %
Substituent
CH-QH 03-03
R ‘ 2 R l I 2
2 R1 R 2 R1 R
0 53
R = CH3
53-0 33-0
R1 = R2 = H
R = R2 = H
17.5 60.5
R1 = 633
R = E
9'0 5900
R R = CH

20

positive result. The infra-red spectra of thianaphthene

.

and aefln.rothlnnu3htnsnz were dctdlmifiei dad ore fiJQnd in
figures I and 11 resuactlvoly. Tue nonstrn :re sidiihr out
not lJfiuiiodle foe nuclear mnguctlo resonnnoe or ctru of
thisnlputuene and its é-Iluo-o dsrivltive were niao determined
end are shown in Figure» I11 and 1V. Integration of the areas
under toe two acts of cents of taixnlpntguue are. a to l. Ilr
tne [our OCHbQJDuQ hydrogens nd tau tau buiuyflflhfl hydrogena

respucoivelj. fine integra.-en oi Lee «.314 under CJQ bio soil

\

0.... gatinfi of; our .;~£_-.u<..u‘uolu'i.l “hurl-ucrxu w.:-‘<:, r to .L. l u." but:
four oennmuud hydrogenu .1. .d ,.5:'...;.:g}.u t...:..3;,~mmu hydrogen mo_;_..eetively.
The single hydrogen on toe tuioghene ring of nailuoro.hiaunuhthene
is solit into a doualet by tne fluorine.
fine negative "u.l;tnuile iinoriuo tout ans oasaiolj due to
the dl£€ioulty in or:nxin; the sarong—fluorine nun} :o yield
sodium flaooide. and an; aloe no due to tie nnlli nuount of fluorine
greddflb in tue compound. rue quantitative a logon anglysiu for
tne Hind-fldJPLuAted clidnngncncne was in agrgwmnnt with the
tutor-I2 31.).) .17. .arumnt.
5331.2 l:i*:1\1\.)f(’t-l.i.1n..;):Ititfiile '.‘.".~.’-.-‘5 redwood in the 2.:i.t!:.:':.':;sz~
(«Mina groueddre is}. .’1":1..;.';t‘l it.) that ref-MG 1.40;. 03. ch: g‘wll'ent
title-Luighmsélifie Che red-.56 L..i.J‘l “mum“: J3 Ubuntillud any?» isvrgl'uit’tal
to than: idolatui in the: reduction «1' '....:...:1.4..:L.t..-m2. “T‘scevu'z‘o
tuc yieluu of the reduoeu 3:0iuvtu oatuluuu were u4t:uucly low;
7.5w fiur E—etnjicyoloatnanonc “Ma ; .95 £3: Owethyltniouhcnel.

Thene were the only organic oomyouuns iuolutod from the reduetiOl

mixture. who infra-red upectrn, nuclear magnetic resonance speetse.

2‘).

ma

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

8H

now-mi

22

385 8233825.“ no 58% 2.55 H .5

28.2 5 533...:
on m o i. o m

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

#-

 

 

OOH

23

 

Solvent: 0C1,4

Filter Bandwidth: # c.p.s.
H.F. Field: 0.0330.

Sweep Tine: 250 sec.

Sweep Width: 500 c.p.s.
Sweep Offset: 0.000
Spectrum Anp.: 1.0

Internal Reference: 81(0H5)“

 

 

 

 

 

 

 

 

 

 

 

1 ppm

T

8 7

 

Fig. 111 Nuclear Magnetic Resonance

Spectra of Thianaphthene

2:.

 

Solvent: 0014

Filter Bandwidth: 2 Cp.8.
P.F. Field: 0.05sG.

q Sweep Time: 250 sec.
Sweep Width: 500 c.p.s.
Sweep Offset: 0.000

W Spectrum Amp.: 6.0

 

 

Internal Reference: Si(CH

3’t+

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

J. ML

l
' ; PM“
7.5 6.5

 

 

 

L

 

Fig. IV Nuclear Magnetic Resonance

Spectra of 2-Fluorothianaphthene

..‘.: ‘ 3 ‘fl ‘ 3" '3, .‘ s" r. ‘$.‘E‘\H *« ’5‘ \»~
and tea retnn._0n time. a. the vapor Ph4u@ ch.uaatog.a Ly of

3 from zafluorotnianaphthene were

0
(I
a
v
t;
0

tne reduction products 3"
identical to the products of the thianaehthene reduction.
Ho unrcduced waluurothinnnjhthnnn was recovered from the
reduction media nor Has any am'ne from a possible Jenzyns
intzrsejiate observed to be present in the reduction products.
The reduction of thicphene using lithium~ethylaeine
yielded a small amount of a neutral product which could not
be obtained in a sufficient degree of purity for prayer
identification. in infra-red spectra of the crude prodrct
indicated the possibility of a carbonyl group (5.85 t\ ), which
could as accounted for it ring o,onin; had steered giving rise
to a thioaluouyue which on hjirolgnis unuld yiuli fin Iliehyde.
The acidic fraction ohtained on acidification of the reduction

product was not investigated further due to the extreme odor of

the possible product, n-hutyluerCantnn.

26

EXPERIMENTAL
Redeetioe of Thienephtheee

To e 500 .1. three neck fleet equipped with e eeehenieel
etirrer, dropping tueeel. dry iee ooedeeeer fitted with e eeleie-
chloride drying tube, end e eitrozee inlet tube wee edded
250 :1. of ethyleliee ( whieh hed been predried over Iodid-
hydroxide pellete) end 8.} 3. (1.2 a. et.) of lithiee ehipe.

To the derk blue eolered eoletioe. keyt et 0., wee edded
drogwiee 13.# 3. (0.10 eOle) or thiehephtheee during e period

of an hoer. The reeetioe eixture undereeet e eoler eheece tro-
blee to tan to pale green. during e reeetioe period of eight
hoere. it thie point eereeeted pieeee or lithiue were

reeoved fro: the dreduetioe eixtere with toreepe. Deeoepoeition
o: the eeiee wee eeeoepliehed by eentioeely eddies eeeoeiee
ehloride. until the eolutioe beoeee eolorleee. The reeetioe
eixtere wee thee eet eeide overnight to yer-it eveyoretioe of
the eoleeet.

The fleet containing the eolid reeidee wee cooled in en
iee-weter beth end eater wee edded dropwiee until the eolid
dieeolved. The eqeeoee eolntioe wee extreeted three tieee with
100 .1. of ether. The eoebieed ether extreote were waehed
with 100 ll. of weter, dried over eehydroue eegneeiue eulfete,
treeted with lorit and filtered. The dried eolwtion wee

eoeeeetreted on e eteen bath, end the reeidee wee Ireetionated

27
through e eie inch Vigreux eolunn, b.p.,75-79/25nn..

180-1547760R1He. “$6.5 I le‘t520, yiOId 6.0 ‘e (0e048 5010' 47e5%)e
The reported boiling point of 2-ethylcyolohexenoee ie

182-1oj?760 an. end .g‘ . 1.4528 (20).

To the etirred equeoue freetion, etter eooling it in en
iee~weter beth. wee added dropwiee )0 n1. eoncentreted eulfutie
eeid. The eeidie solution wee eetreeted three tieee with ether.
end the ether extraete were eoeoined, washed with 100 ll.
of water, dried over nnhydroue eagneeiee eulfete. treated

with Norit. filtered. end eoeoentreted on e eteae bath.

The residue wee treetioeeted ueing e eir ieeh Vigreux

26
D

h to (0.029 I010; 29%). The litereture waleee reported for

eolnen, b.,.. 90°/25ee.. n . 1.565h. The 11.14 wee

o-ethylthioPhenol are b.p., 210/760 am. and u§° . 1.5700 (17).
The Reduction of Thihnaphthene with Varioue Diletin; Reegente

The generel experieentel epperatue heed wee the name
ee that described in the previous reduction reeetion.
To 160 el. of ethylaeine, predried over eodiue hydroxide
pellets, wee edded e eolution eonteieing 9.0 g. (0.067 mole)
of thienephthene dieeolved ie 20 ll. e! 95% etheeol. A 7.0 3.
(1.0 3. et.) queetity of lithiee ehipe wee edded pieee by
pieee to the leter eolntioe durin; e period of en hoer.
When ell the lithiuw had been edded the reeetioh eixture had
taken on e blue eoloretioe. Thie pereieted for en hour end
e helf etter whieh it ohenged to e derh grey. At thie
juneture 100 ll. of weter wee onutiouely end elowly edded

to the redeetion eixture. ddditioeel weter wee then edded

28

to diecolwe the remaining eolide. The reeultieg pale green co
colored eolutioe wee extracted with ether and the product
wee ieoleted in the nanner described ebove. The reeidue
wee dietilled using a six inch Vigreux column. to obtain

1.? g. (0.01} nolet 20%) of e colorleee product boiling

2%
D 3 lekfisoe

The equeouc fraction wee acidified and inolathdn of the

at 1800/76Omm. end n

organic product wee accomplished in a nanner identicel to
that deecribed ebove, to obtain e colorlecc product
boiling fro: 91—929/25em. end n33'5 a 1.5682. yield of
7.2 g. (0.052 hole; 78%).

To 160 ml. of ethylanine. predricd over codiue hydroxide,
wan added a colution containing 9.0 g. (0.06? nole) of
thienaphthene dieoolced in 20 eh. of morpholine. To thin
solution we. added slowly 7.0 g. (1.0 g.et.) of lithiun
piece by piece during e period of en hour. Product

icolation wee conducted in n manner identicel to thet described

ebowc. The basic extract gewe e product with the following

22
D

hole). The ecid extract gave a cecond product with these

prepertiee; b.). 7k°/25nn.. e e l.k5621 yield 3.5 g. (0.028

propertiee. b.p. 89/20nn.. n23

D I 1.5685. inld 5.0 Kc

(0.036 holes 5#%).
The above ceperinent wee repeated cubetitnting 20 ll.
of piperidine for the norpholine. The heeic extrect gave
only e trece of oil which wee not obtained in sufficient quantity
to dictill. The acid extract yielded 5.5 g. (0.039 eole:

59.5%) of e product having a boiling point of 950/25nn. end

1.

ng . 1.5682.

29

Proof of Structure of Z-ethylcyclohexanoae
Reduction of the Ketone Group

To 25 a. of Haney Nickel suspended in methanol wae
added #.55 I. (0.055 eclc) ot the kctoae dieeolvcd in aethenol.
The total voluae ot the reaction eolation wae 250 el. Thin
wee allowed to reflux for three houre. cooled and the catalyet
wae reaovcd by filtration and cached with methanol. The
eethanol eolution wee diluted with a liter of dietillcd water
and extracted three tiece eith 100 el. of chlorofore.
The chlorotcre extracte were coebined. dried over anhydroue
calciua chloride, filtered. and concentrated on a eteea
bath. The residue wee dietillcd uein; a eix inch Vigreux

coluea to obtain a product boiling at 180°/760na. and

26
D

literature valuee reported for z-ethylcyclohcxanol are

n a l.t642. and yield 4.5 x. (0.03% eole: 96%). The

..p. 799/12... and nil . 1.u6uo (an).

Preparation of the Seeicarbazone

The derivative eae prepared by dieeolvinz 0.2 c.
(0.002 eole) of eeaiearhenide hydrochloride and 0.5 3.
(0.00fi eole) ct eodiee acetate in a few drope of water.

To the eolutica wee added 0.2 c. (0.00; aolc) of the
ketone. Ethanol (95%) wee added until the eolntice becaee
clear, after which it can heated on a etcae bath for
15 ainutce. cooled. and filtered to obtain the cryetalline

product. The dried crystalline eateriel wae recryetalliecd

Iron a eeall amount of ethyl acetate. The product melted
at 150° (uncorr.). The literature value reported for the

eelting point of this material in 157° (20).
Proof of Structure of o-zthylthioPhenol

To a eaturated solution of lead acetate in ethanol (95%)
wee added 0.5 al. of the aercaptan. n characterietic yellow
colored lead ealt precipitated inetantaneouely. After three
recryetallinatioae (roe ethyl acetate a char, aelting
point of 1&7-lh80 (uncorr.) wee obtained. The neltin:
point reported in the literature for thie aaterial ie
1h?.5. (21).

in atteept to prepare a 2,0cdinitr0phcnyleulfide

derivative of thie aercaetan wee uneucceaful.

in Attempt to Deeulfuriec the Mercaptan

To 10.0 ;. (0.0725 eolc) of the nercaptan wae added
11.62 3. (0.069b ecle) of frechly redietilled triethyl
phoephitc. The reaction aixture wee eet aeide at roon
teepereture for a day and then elowly dietillcd. Two

fractione were obtained; (a) b.p. 57°/25en.. n25

0
literature valuee for triethyl phoephite, b.). l559/760en..

. 1e~1283

literature valuee for o-ethylthiophenol b.p. 210/760an.,

‘ 105692.

a: - 1.5700 (17).

31

To 25 g. of Raecy Nickel euepcnded in methanol wae
added #.h g. (0.031 eole) of the nercaptan dieeolvcd in
methanol. The total volume of the reaction eixture can
300 el. It wae heated at ite reflux tceperature for three
honre, cooled and the catalyct wee removed by filtration
and waehcd with ecthanol. The nethenol eolution wee diluted
with a liter of dietilled water and extracted with three
100 nl. portiona of chlorofore. The chloroform cxtraete
were coebincd, dried with anhydroue calciue chloride. filtered,
and concentrated on a etean hath. The rceidue wae dietillcd
ueinz a air inch Vizrcux coluan, to obtain a product boiling

at 35-37° /25nn. and n27 a 1.h9}0, and yield 2.8 t. (0.026 aele:

D
85%). The literature valaeefor ethyl benncne are b.). 130-

136° /760na.. .if" . 1.1.9828 (23).

Preparation of o-ethylthiOphenol

To 192.5 3. (1.65 aolee) of well etirred chloroeulfenic
acid. precooled to aero dezrcee in a dry ice-acetone hath.
wee added 5# 3. (0.51 eole) cf ethylbennene during a period
of #5 ninutce, while holding the temperature of the acid
between .5 and 0.. Following the addition of acid the reaction
aixture wae eet aeide in a refrigerator for 18 houre at 0°.
The product wee then poured with vigoroue etirrinz onto
700 ll. of crushed ice and the oily layer wae eeparated.

In a two liter three ncch flash equipped with a

nechenical etirrer. thernoecter, coadeneer. and droppin;

32

funnel wee placed 1000 ll. of crushed ice and 325 ll. of
concentrated eulfuric acid. The acid mixture wee cooled in
a dry ice-acetone bath to 0°. The eulfonyl chloride product
fron the above chloroeulfonation wee added by aeano of a
drapping funnel into the rapidly etirrcd acid mixture
followed by addition of 163 g. (2.5 nolee) of zinc. Following
the addition of the nine the eixture wae allowed to were to
room temperature and then heated at ite reflux temperature
for five houre. It wae then cooled. filtered. and the eolid
waehed with ether. The filtrate wae extracted three tieee
with 100 el. portione of ether. Thcec were coabincd. dried
with anhydroue nagnceiun eulfatc. filtered, and concentrated
on a etean bath. The residue was dictilled using a six inch

Vigreux colunn, to obtain a product, h.p. 95~96° /25en.,

age a 1.5628 in n yield of 5h.2 g. (0.592 nole; 76.5%).
The literature valuee for o-cthylthiophenol are b.p. 210/760ne.,
I20 8 1e5700e (i7)e-

D

Proof of an Intermediate in the Reduction

Reduction of o-cthylthiOphenol

The general experimental approach won the none as
that utilized in the reduction involving thianaphthone.
To 250 nl. of cthylanine, predried over codiun hydroxide,
woe added 7.25 3. (1.05 5. at.) of lithiue eetal chips.

To the dark blue colored solution. externally cooled.

33

«ac added droniee. 20.5 g. (0.15 mole) of o-ethylthioyhenol
during a period of an hour and a quarter. The total reduction
tine eae ten houre. The reaction producte were isolated in
the aaaaer already deecribed. Basic fraction; b.p. 80-

29 . 1.k523. 11.1a, 3.0 g. (0.02h nole: 15.9%).

D
Acidic traction; h.p. 9k-95° [ZS-a., a

03° /29IIe . n
g9 . 1.5621. Yield,

10.0 fie (0.072 I010} 50%’e
Reduction of thianaphthene at ~60°

The experieeetal procedure used wae that employed for
the reduction deecrihed above. To 250 el. of dried ethylanine,
precooled to -60° with a dry ice—acetone hath, wee added
8.3 c. (1.2 g. at.) of lithiue natal chips. To the dark
blue colored solution was elowly added 1}.“ g. (0.10 aole)
.: thianauhthene during a period of an hour. The total
reaction tine wae 3.5 houre and the reduction producte were
ieolated in the manner preVicuely dcecrihed. Baeic fractionl
c.p. 76° /25ea.. a35 a 1.3521. Iield wee 1.0 3.(0.0079 aelc;

7.9%) of 2-ethylcyclohexanone. Acidic traction; b.p.9k.,/25ea..

‘26
D

thiOPKOIOIe

a 1.5655. licld wae 10.0 5. (0.072 .9103 72%0 cl o-ethyl-

Preparation of 2-Hethylthiannphthene

To a 1 liter three neeh rcaad hottoe flack equipped with

a aechanical etirrcr; dropping fennel. condeneer with attached

calcite chloride tube. and a nitrogen inlet tube can placed

9 g. (1.3 g. at.) of lithiun netal chips and 200 ml. of
anhydrous other. A solution containing 82.2 g. (0.60 mole)
of n~butyl bromide dieeolved in 120 ml. of anhydroue other
can added during a period of one hour to the stirred, cooled
(-100) metal-ether euepeneion. To complete the reaction.
etirring wan continued for an additional 1.5 houre at ~100.

The purple colored nnhutyl lithium eolution wan filtered through
glean wool by nitrogen preeaare into a previouely cooled (-100)
1000 ml. three neck round button flack. a 55.6 g. (0.“0 mole)
quantity of thianaphthenc diaaolved in 100 ml. of anhydroue
ether can added during a 20 minute period to tho stirred,
cooled alhyl-aetal nixturc. The reaction wae completed by stirring
for an additional 1.5 hours at elOOC. To force the reaction
to completion at thin point the ether was removed by a water
aepirator until eolid material began to precipitate tron
coletion. Thea 100 nl. of anhydroue ether eae added and
evaporated again via the cater acpirator. Thie procedure nae
repeated a third tine to remove an etch butane with the ether ae
poeaible.

A eolution containing 7h.4 g. (0.#O mole) of nethyl-p-
tolueaeeultonate dieeolved in 100 nl. of anhydroue ether cae
added drepwiee to the Zalithiun thiaaaphtheae during a period
of a half hour while keeping the reaction tcnperature at 2°

by euepeneioa in an ice-eater hath. Following the addition

of the organic aulfonate the reaction mixture nae etirred at
ite reflux tenperature for a half hour. The mixture was then

allowed to were to roon tenperature and the hroeninh-red

)5

colored solution you goured OVor 3 liter of ice chips.
The etncr Sugar you §€?Z.”t”d aid t?» figuefine phase was
extracted three times with 300 hi. EJJfiiphfl of other.
the other extracto were coueinod. dried w.th curydrwus fit5fi£51hfi
onlfnte, filtered, and canoeuErated on a steam mitt.
The roeid o one dietilled vein; a nix inch ~i¢16nr culnrn,
to obtain a liquid grv not, h.p. 103-1100/i3on. The oiiy
orodwet on cooling nolidi ind. It was r%CljfitfllliaE§ t;
dissolving it in % small amount 01 ligroiu and cooling.
The orgntullino ,roivct Vd$ recordr'd by filtration Aid
oir dried. to ootain az.o 3. (4.15o “air; }?A) of n pure

eh -.o
prodtct, w.p. )i‘bd . ?;c literature VolUt for tie writing

. . _. . , , . no“
point at hunfiihyithi~na.fitnenu in blob-34 u. (16}.
Preparation of icetonylphenyl Sulfide

In a l litor three hock round cotton {leak equipped
with a mechanical dii;r6r. reflux ooa.¢wnor. Aern.motu:,
and dfiigping funnel were 3'addd 40.0 g. (1.0 mole) of no;iua
hydroxide discoqud in lid nl. of distiiioi water. The alxuline
,Po

solution can GJOlaJ to d) an] 110 g. (1.3 male) 03 thloghcnol

«an added quicxly. To to

(F

stirred aodlun thiophenolote solution.
9” g. (1.0 mole) of chlorOuoetano was tron added during a h;1£

.. .. _ . , “,0
hour Whli. hsldlag the reaction temperature at LJ"¢) .
To complete the roaotion tho mixture was etirred at roan
teaporaiure I): an hour following the addition of the

onlorgheuono. ?ne product one extrxcted lot? 300 file of

 

other. eaehed with 100 al. of eater, dried over anhydroue
ealeiua chloride, filtered and concentrated on a eteaa
bath. The erude product was distilled ueinz a air inch
Vizreux column to ootain 150 g. (0.755 3010; 78.5%) of a
pure liquid product, o.,. lj7o/l5aa. The literature value

reported for thie sulfide ie, b.p. 139-1H00/16an. (18).
Preparation of Acutouyl-p-tolyl éulfidc

The general experineetal proeedure need in the eyatheeie
of thie eulfide eae the eaae ae that need in the preparation
of aeetonylphenyl eulfide. A 52.2 x. (0.805 aole) quanti’y
of eodiua hydroxide was dissolved in 80.5 ml. of dietilled water
and placed in a flask. To the cooled (25°) alkaline eolution
was added 100 a. (0.u05 tale) of p-toluenetniol. To the
thielate eolutioa eae added 7h.2 c. (0.805 sole) or ehloroaeetoae
during a half hour period. The iaolation of the pure eulfide
eae accomplished in a manner identical to that deeoribed in the
previone eyatheeie. Physical prOpertiee of the product.
b.p. 1650/19 ne.. yield 117.0 g. (0.65 .010; 80.7%). The
literature value reported for the boiling point ie 160-1629/1713.

(18).
Preparation of B-Nethylthiauaphthene

la a 5J0 e1. round bottom three neek flask equipped

with a nechanieal etirrer. reflux condeneer, thermometer, and

37

drorping funnel were ylaced 22 a. (U.l§ molt) of ghosphoroue

gentixile. In the drag.;n; annel Vale placed 65.5 g. (0.39

3
hole) of acetJnyl‘houyl Sulfide. AerOiiuutoly One quurtor of
the sulfide was added initially to the reaction flask and
the reaction mixture Wflb cautiously heated with u Bunben
Juroo- to initiate the reaction, which ocuurei ”han tLu reaction

: _ u 1 ~ + ‘ . p-—\0-. me .. -
mixture ha; reacuud a temperature of loo 0. inc exothermic
.‘ouctiun canned to rent tic)” Lem;:era.tn1-e to rise to about
Halo . . . . ,_,_, ., q.
LOU C. and resulted in acne decomposition. titer aiiOuing the

- _ e e A Q '0 - e -. . ‘--. : 1

reuot-ou tcmpcxiturc to drug to i7U , hue ruuuiiuu; u; the
sulfide to» added drofigise to the reaction mixture a-tcr

: s. ’ i V- 5 ': v ' '- J "' "O o .1‘ l . 1 7.‘ ‘ .
“1113.0... 1.. was stirred wzo “Cited at. luv-luv .LOX‘ an. dualthBal
three quarters of an hour. The dark colored reaction mixture
was cooled to room temuerature and 200 ml. of water were added.
Tie reaction was extracted with 100 ml. of other. an emuleion
formed which hid to be filtered, mashed wits other and -he aqueou-
luyer extxdcted three tints "it; other. The other extracte
were oomoinod, taghed vita 100 ll. of water. dried with
anhydrous calcium chloride. iiltored, and concentrated on a
steam bgtho The crude groduct wan dietilled using a six inch
Vi‘ro.x column to obtain the pure liquid product, b.p. llé/LSut..
yield 23.5 g. (0.16 mole; 40.5L). The re,orced literature value

- e 9 .q\ o A r
for this comgouno 16. o.p. 75-;6 4mm. (13).

Preparation of j,5-Dimetny1thianaphthene

The gencral GXECiiKuntal procedure caployed in tho

preparation of this material was the eame as that used in

the pre.«ration of 3-naet31y vlt lLfid‘)q nsne. Tne quantities of

rewctants 133! were, 55.3 ' (3.575 Wale) of phneyhoroua
weatoxiie and 117.0 g. (3.55 J01Q) of 13024131~p~tfilyl sulfide.
‘ ‘. . - I . . - >' ' ~ g. ")0 6'.- -~ "1‘

Tfi“ pure proi"ct Hfid a Doiulng yOLflb o. 1}” /L) mm. .50
litsratnre Value reported :0“ tue hailing paint of this rat rial

is 1 5'3-135°/1;3:m . (13) .
Reduction of Z-Metnylthieuaghthene

The gencral exyerimental proccd4.e is two aume us trgt
u ed :3“ the rriuction of thi‘xuyhthene. Tao q. ntifieb of reactants

r' ' . o » ‘ I j ' ’1 1
used wars, 250 ml. of dry athglunine, 6.} g. (1.u . at.) of

“I

675$]. CALI-‘5. aJ-‘rf‘ 1.1.8 ‘. {0.1. Mule) {ff (3—; c135 ‘utlfianuphthenc.

ELJ
‘J.
do
2‘

The total reduction time was ten hours. The :rdnction {ruducte
were isolated in the nannor fireviously deneribed. Basic fraction.
. - .no . 26 m., ._ , .

u-p. 96";‘3 /‘I5Meg 11;) 8 10421.03 yield {.0 cc (0.053 E010353%).

The literature values for 2-n-gr01310yclohoxanoue are h.p. 1999/760nn;

N

n b 2 1.h510 (rh). ¢Le SCLicurhanfde derivrtive Of the

C

cyclic I:ctone v 7&9 prcrmred in thy Manner descriheé ‘revioualy
. . ,,o ,
and recrystallized iron ethyl acetate. m.p. 3¢~lgd . Tne
. 0
literature value reported for the mel_ting ktJth is 133-.5
n - r a..0
lot {If E (cmicorbazide (2%). inc acidic fraction; b.p. ¢¢¢
‘ 26
at atmospheric pressure and the refractive index was, “D s 1.55k53

yield 5.0 a. (0.033 mole; 3}%). The Litarature value reported

for tne boiling {Oiflt of this naterial is 219-2z1°/730mc. (17).

Reduction of metnylthianaghthene

The gel-'81 exPerincntal method used in this reduction was

39

iueutieal to that uueu tor the zeduction involviag thbhayhthGICQ
The quantitieu of reacthutr umkluyeu wcxe £99 &1. of at:
eihylanine, b.) g. (1.1 g. at.) or lithium chips, and

14.9 x.(0.l mnle) or B-netnylthiauapnthtub. inc total

rouuctiun tile was tau houra. ihe reduction products wexc
isolated in the manner a4xeady deaczibea. Labia tract;on§

b.}&. {filo/lamb“. n26 I loleSG‘ yield 213 E. (Gobi? 5012; 17.5%).

D
Ebe literature values ior the physical cbhhihhtb of £~1wopr0py10

12

D

derivative Of the cyclic kctono wan preyarou in the usual

. .o . . , r.

cyclonexwuoue are, b.p. 9cllpmm.. n a $.k50b(¢khhe somioarbaaido
. , _ a

manner, and rocryntu¢llzeu tram ethyl acetate, &.p. ¢bb .

J . A ‘ . . r “who 5

fine ¢1teraturc value rep-rtod 10r the moltllg poxnt is Lur ior

5 n n l' r \ l v~~ ; v» ,‘ O for ~
this fiemlcurpuzlue (Ll). The aclulu llhctlnn; n.y. ¢u7 [cbmm..

26 _

0 1.556%; yield D.& g. ( 0.061 rule; CD.L%). The literature

I)
. . , - . . . . ,,. . ,0
value reportoa tor c-lBOprOPylthloyhenol 10 hop. ccj—(c( /?60mn.

‘17).
Reduction of 5,S-Dimethylthianayhthenc

The general experimental prucouuro was the same as Luau
used for the reduction of thianaphtneno. The quantitius of
reactants used were 2:0 :1. of dry ethylamine. b.) g. (1.2 g. at.)
of lithiun metal chipu, and 1b.} a. (0.1 mole) of 5.5-dinothyl-
thianaphthono. The total reduction time was ten hours. The reduc-

tion products were isolated in the manner previously doacrlbed;

15
Basic fraction; b.p. 909/25:m., up: 1.5??9; yiold 1.7 g.

#0

(d.009 male; 3%). The UeAJ éa£ll qudut;tj of yIO¢LC‘

iSOIJtfid was finsufiio¢aut to ohcaLA an dualyt¢cai¢1 puxc sumplo

'3‘
L

D a 1.5472.

. 4 s ., , . a ,p
;)r auaiyfi;flo A3$QLC graot¢0u5 o.y. l;J /;3 mm., a

Jiold o.5 g. (J.Q)9 moles 53$). Galen. for ”lunlfis'
J. ?Jo&9‘ J, 30%); J. 11.23. Found: U. 7(0)?! 3, d.uy‘

J, l)ol_io
Preparation of Z-Fluorothianaphthono

The a-;;cn;uu thiuu‘yatnwne Cvuyouna waa yregareu as
cebcrLOud gn .fie oxyegimunbal Jruucuure for obtaining c-Hethyl-
t‘£;;33;a1.1'—..ltus.t3, exooft that in win Game one-nah the
gaunLiLleu of reactants welc used.

Fezch;or;l fluoride has Uflfi pubbcu lxto {LL otheral
thutivl at 00L. thrhuhh u dihyL1L¢ou tune. The reactlon was
emoLLcluic and tho temperutule nan oontrollen by immersion in
a ax) ice-acetone Bath and hue rate of the aduition or the gas.
h whit; precigitato IOImeo in the orango coloroa reaction
solution biving it a yellow uppoorauoo. A blue glow was
viaiole arouna the uinporslon tube which brightened with
an incxeased rot. of $19: of the gasooan perchloryl fluoride.
aha addition of can no: continROd until the blue slow stappod.
at which Quint nitr03en ‘1. was paoood through the reaction
solution for about ten minute: to {luau out oxen-s perchloryl

{Juarido gas. in. roaotion aixturc was then transforod to :

two liter boaser and water was addod to dissolvo tho precipitato.

The solution was then wade basic with sodiun carbonate. Tho rod

#1

colored other layer nae eeparnted and the aqueous phase
eae extracted with three 100 nl. yortione of ether. The ether
fractxona were combined, washed vith water until neutral,

dried with anhydrous ragneaiun sulfate, filtered, and confientrnted
on a steam bvth. The residue was distilled using a six inch
Vigreux column to obtwin a liqu1i oraduct, 0.9. 95-940/P§~m.,

2? ( ‘ 01 '- ‘ V
no 2 1.5110. m.g. 20 C. inal. baled for bOHJSF: C. 53.16%

a. 3.29; 3, 21.05; F, 12.50. Founi: c. 65.19; H. 1.51:

3, 21.20; F, 12.57.

Reduction of a-Fluorothianoyhthene

The general experimental procedure employed in this rednetion
was the sane an that used for the reduction of thianaphthene.
The quantities of reactantu used were Bio 91. of dry
ethylanine, 3.) g. (1.2 a. at.) of lithium metal chipl, and
15.2 c. (0.1 mole) of 2. fluorothianaphthene. The total
reaction tine was ten nonre. The reduction prodnete were
inolnted in the manner already deaeribed. Basie traction;
b.). 879/30an.. n36 e 1.#527. yield 2.5 3. (0.02 nole:
20%). The infrn‘red npeetra enn found to be identical to
that of Z-ethyloyelohexanone. Aoidie fraction; b.p. 879/24nn.,
n36 e 1.5668. A aanjle eubnitted to vapor phase chromatography
gave the eane retention tine an oaethylthiOphenol. The yield
of product eae 2.5 x. (0.018 mole; 18%). The nuclear nagnetie

reeonanee and infra-red absorption spectra of the reduction

product were identical with those of o-ethylthiophenol.

#2

Reduction of ThiOphene

The general exyeriuental grocedure noel in this reduction
was the same no tnat used for the previously deoorioed reduction-
ot thianapnthene. To 250 ml. of anhydrouo ethylnmino was
added 7.“ g. (1.05 g. at.) of lithium natal chips. To the dark
blue colored metal-amine solution was added ld.0 g. (0.15 male)
a! telephone dropwine during a period of two hours. The total
reduction tine was ten hours. At tho end of thin goriod no lithiun
netnl remained. Tue reaction produotn were isolated in the manner

previously deeeribed. Basie fraction: o.p. range 66-77é/13nn.

.21.

D I 1e4625)e

The yield of product nae approximately 0.5 g. (n
An infra-red oyectra of tho product was determined and

contained the following yanks (in microns) 3.4 (Ci strecn),

6.0 (enroonyl), 6.9 (CH2 deformation), [.65 (an; deformation).
The product did not contain 8. 8. or halogen. The eomgound gave
a small amount of precipitate with 2.hadinitroPhenylhydrazine.
Unfortunately, insufficient emanate o! the derivative or the
original produet eonld not be ootained for further identification
and characterization dork. Acidie fraction; a small QUnntit’

of the aqueous phase nae eoidified with dilute acetic acid and

a solution of lead tetraacetate was added. An instant black
precipitate was observed, which indicated the presence of

enlfur. possibly in too form of a meroaptan. Further work

wan not onrried out with the aqueous phase due to the

possibility of isolating n~butylmeroaptmn.

“3

Attempt to Desulfurize Aromatic Mercaptane with Triethyl Phosphite

denoonobhlol

To 11.62 g. {0.069% mole) of gurlfled triecnyl pLOthite
was added 7.6j 5. (o.o0y+ mole) oi benzenethiol. Tao reaction
mixture was set aside for u coy at room tugberutuxo. inc
mixture was tucu traualored to a fractionul liooiildoion

_. . . . .‘0 . , .-‘ . .-

apyéel‘eloda fluid “alum to IJU ob. at Hulfl-‘JJ oexuyrnuure {10
Volatile material was obtained. iuo uiotiliuolon temyorature

. - -= ,VO 3 . - r . x . 9
and Buun roioca to ljU-l/J iur Locuo] m¢HUUUS and then to coo

e . ._ .- . i ‘o . ‘
et union yulai a uiosiliauo. u.9. ljj“$U) . was cocainoo.
It wag identified an a mixture of trietuyl ynoouuice and
oeuaenethiol.
poaihlorutwiuyuenol

The uauomyced dosuliuriaatinu reaction wag regoated using
ll.uz 5. {0.069% mole) of triuciyl phasyhite and 10.09 g.
(0.0694 male) of p-oulquuniogheuol. Tue initial fraction
Obtained oy distillation of tulo mixture was li.0 g. of a

, _ . . H. ” n.,o , , l. ‘
compound nHVia‘ I flailing goinb. 1))‘iod //0Jmu.. luenLlChi to
that of trietnyl puospuite.
Qantauhlorothiuyhenul

£0 a ).Ol g. (U.U§#d mole) quauoity o1 triocuyl ghUdfihlt.
was aouod 10.0 a. (0.0340 uoie) or ywdt&6hldr0tuioghvnul
diesulveo in 1:) ml. of caroun tetrdonloriue. Hue relation
solution duo refluxed on a steam out: for a day mud tuen cooled

to room temperature. a oryubnlline prouuot «aw outlined

. . # ~ w 9 n '
whicu mm ted at fizy-dgz e a mixture oelting yoint of
.a

tale ontoriol and pontchflurofihioyhenol did not dogrona

the Rolling goint below timt of yuro ieutaohlorooaioyhxnul.

u.

1.

I‘d

3.

h.

5.

'+5

3 UNNA l-L‘. I

Thiunaphthene was reduced using the lithium—amine

system to Z-ethylcyelohexnnone end o-ethylthiogheuol.

he o-ethylthioyhonol was established to be an intermediate

in the reduction of thiannphtheue by this procedure.

The Z-Methyl, B-nethyl. and 3.5-dimethylthianayhthene
derivatives were redueed to yield the eorresgonding

netonee and mercaptune.

The z-fluorothianughthene was pregnred and reduced to
o-ethylthiophenol and 2-ethyleyclohexnnone no the
sole reduction produete indicating reductive cleaVage

of the cornea-fluorine bond.

ThicPhene on reduction with lithium-amine yielded a small

quantity of unidentified high boiling neutral product.

l.

2.

10.

'1
-1...

12.
13.
1%.
15.

16.

17.
13.

19.

.5

PLFIFrbCES

a. w. watt, Chen. Fev., fig, 317 (1950).

n. J. Birch, Quart. Rev., 2, 69 (1950).

R. A. Benkeser, J. Am. Chem. Soc.,'zg, 5699 (1952).

R. A. Benkeser, J. Am. dhe». Soo.,{ZZ, 60h2 (1959).

R. A. Beukeeer, J. 5m. Ghem. 806.3‘22, )830 11935).

R. k. Bonkeoer, J. Am. Chou. 800.,‘QQ, 65?} (1958).

R. A. Beakeser, J. Org. Chen., £3, 85% (1959).

G. F. white. J. in. Chou. 306., h", 779 (1925).

Holdnvski and PrOpOpchuk, J. Gen. Chen. nussia, 3, 293 (193“);
Chen. Abatr.,l§2, 1314 (1935}.

S. F. Birch and D. T. Kc llan, J. Chem. 300., 2:96 (1951).

8. F. Birch and D. T. EcAlan, J. Chem. 506., 5411 (1951).

R. Friche and G. Soilker, Bnr., 2Q, 1589 (1925).

Bennett and fllfoz, J. Chem. Soc., 852 (thl).

Fieozr ani Kennellj, J. Am. Chem. Soc., 22, 1511 (1955).
Cougniaat, Canpt. reu1., £12, 100 (1950}.

K. Nakauaki, flipgon Angwkoi Jaoehi,‘gg, 687 (1959);

Case. «ostr., 22, 5553 (1951}.

C. Hanazh and W. Blondon, J. Au. Chem. 306., 22, 1&51 (1948).
C. E. Boyd, Ph. D. Thesia, Richigan State University, 1996.

E. G. Earner, Rec. trav. :him., ii, 5J9 (1949).

N

N
0‘. \Ji
0

27.

28.

“'7

1

E. K. Sen and K. Mondul, J. Inuian Chem. $00.,‘2, 809.

k. Fricke and 3. Syilker, ior.,‘2§, an (1925).

F. j. Sohuetz 131 P. L. Jacobs, J. Org. Cnem., :2, 1799 (1958).
V. Meningo, ”Organic Syntheses," John 'iley & bone, Inc.

how York, ljhl, Vol. al, p. 13.

Vuvon and Hitchovitch, jull. eoc. Cain. Yranco, :3, J61 (1929).
i. J. Birch, J. Chem. 3.... 53} (1-46).

3. L. Shriner, R. C. Fuson, and D. Y..Curtin, "The Syntunatic
Identification of firbanic Compounds," ch ed., John Wiley &
Sons, Inc., New York, 1956.

Vavon and Collier, Bull. aoc. chin. France, 3;, 360 (1927).

C. D. Eodgnan,"Hnndbook of Chemistry and Physics," 58th ed.,

Chemical Eubber rublinhing 00., Cleveland, Ohio, 1956.

.r

cums?“ UBKN“;
tar-“fig

.goyof ur-“f 3' ‘3'
d...~..‘,.gn3-v:é - -

 

 

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