The Pyrolysis of some Neopentyl Xanthates: a Competitive Formation

of Olefins and Dithiolcarbonates

K. G. RUTHERFORD,
B. K. TANG,L. K. M. LAM,AND D. P. C. FUNG'
Deparrmer~r(:/' C / r e t ~ ~ i s / rUtriuersity
y, o/' Windsor, Windsor, Otrrario
Received April 28. 1972

A study of the pyrolysis of a series of neopentyl-type xanthate esters was carried out at 250 "C. The forma-
tion of olefins and dithiolcarbonates were found to be two competing processes. The olefin formation process
became more important when the number of b-phenyl groups increased and when there was an electron
donating group substituted at the para-position of the b-phenyl ring. Kinetics studies supported the proposal
that the transition state of the olefin formation process involved a stabilized phenonium ion. However the
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22

dithiolcarbonate formation became more important when there was the least number of P-phenyl substituents
and this rearrangement appeared to proceed through a concerted four-membered cyclic transition state.

Nous avons entrepris une etude de pyrolyse sur une serie d'esters xanthates de type neopentyl i 250 'C.
Nous trouvons que la formation d'olefines et de dithiolcarbonates s'effectue selon deux processus compe-
titifs. Le processus dc [ormation d'olefines prend de I'importance lorsque le nombre de groupe /I-phenyl
augmente et qu'un groupe donneur d'electrons est substitue en position para du cycle P-phknyl. Les Ctudes
cinitiques appuient la proposition quc I'itat de transition du procede de formation d'olifines implique un
ion phenonium stabilise. La formation de dithiolcarbonate predomine lorsqu'il y a un nombre minimum de
substituants b-phenyl et ce rearrangement se produit en passant par un Ctat de transition cyclique concerte
impliquant quatre membres. [Traduit par le journal]
Canadian Journal of Chemistry, 50, 3288 (1972)
For personal use only.

Introduction propylethyl dithiolcarbonate. A concerted four-

The formation of olefin(s) by the pyrolysis of
xanthate esters is called the Chugaev reaction
(for reviews, see ref. 1). The mechanism of this
reaction has generally been agreed to involve a
concerted six-membered cyclic transition state
(2-5). However, other mechanisms have been
proposed (6, 7).
A rather interesting side reaction observed in
the pyrolysis of some S-methyl xanthate esters
involves the formation of dithiolcarbonates.
For example, in the pyrolysis of the xanthate
ester of 1-cyclopropylethanol, Overberger and
Borchert (8) reported yields of 45% of the ole-
fins and 35% of the dithiolcarbonates, of which
the major component was identified as l-cyclo-
SCHEMEI. A cyclic transition state proposed for the
dithiolcarbonate formation from pyrolysis of I-cyclo-
propylethyl xanthate.
--
'Present address: Eastern Forest Products Laboratory,
Canada Department of the Environment, Ottawa 7,
Canada.
membered cyclic transition state was suggested
(Scheme 1).
Recently, this rearrangement reaction was
studied by Taguchi and co-workers (9- 1 1 ) who
found that the pyrolysis of trans-2-dimethyl-
aminocyclohexyl xanthate gave only the cor-
responding dithiolcarbonate while the cis
isomer underwent the expected elimination.
Participation by the neighboring amino group
was suggested in an ion-pair transition state
(Scheme 2).
In a study of the pyrolysis of some neopentyl
xanthate esters, Laakso (12) reported no olefin
formation whatsoever (Scheme 3).
The corresponding dithiolcarbonates were
found in 70-80% yield. These results would
appear to indicate that xanthate-dithiolcar-
bonate rearrangement is a true case of the
classic cyclic S,i mechanism since one would
surely expect in a neopentyl-type system a t
least some olefin formation would be observed
from Wagner-Meerwein rearrangement (13) if
an ion-pair intermediate was involved. A study
was carried out to pyrolyze a series of neopentyl-
type xanthates in order to investigate if
Laakso's result was a general phenomenon.
 RUTHERFORD ET AL.: PYROLYSIS OF NEOPENTYL XANTHATES 3289

CH-
I
C I H,CS-C-s S-C-SCH,
II

SCH, SCH,
SCHEME 2. A proposed ion-pair transition state for the dithiolcarbonate formation from the pyrolysis of ircirrs-2-
dimethylaminocyclohexyl xanthate.
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22

0
II
SCSCH,

OCSCH, - SCSCH,
For personal use only.

II
S 0
II
SCHEME
3. Pyrolysis of some neopentyl xanthate esters

Results and Discussion
Synthesis of' Xan tha tes
A series of S-methyl xanthate esters of neo-
pentyl-type alcohols were synthesized. All
xanthates prepared shown in Table 1, were
relatively stable. Thus these xanthates could be
purified by distillation and/or recrystallization.
They were synthesized according to procedures
developed in this laboratory (14).
As shown in Table 1 boiling points and melt-
ing points of this series increase as the formula
weight increases and as the number of P-phenyl
substituents increases. It is interesting to note
that neopentyl xanthate did not decompose
even at reflux temperature for 24 h. Again while
an electron-withdrawing group at the para-
position of the P-phenyl group raises the de-
composition temperature, an electron-donating
group decreases it. The increasing number of
P-phenyl groups also reduces the decomposition
temperature of a xanthate ester.

TABLE1. Xanthate derivative

Deconlposition
Xan thate* M.p. ("C) B.p. ( C) temperature ("C)
-
(CH3)3CCH20X 217 (760 mm) t
p-BrC6H4(CH3),CCH,OX 135 ( 0 . I mm) 300
C~HS(CH~)~CCH~OX 105 ( 0 . 2 mm) 280
II-CH,C~H,(CH~)~CCH,OX 122 (0.3 mm) 270
(C,H j)2(CH3)CCH20X 52-53 245
(C6Hs),CCH,OX 97-98 210

I1
*X = -CSCH,.
tNo decomposition at boiling temperature
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22
For personal use only.

CANADIAN JOURNAL OF CHEMISTRY. VOL. 50. 1972

 RUTHERFORD ET AL.: PYROLYSIS OF NEOPENTYL XANTHATES
It was decided to study the pyrolytic products
in detail because the decom~ositionof these
xanthates suggested that Wagner-Meerwein
rearrangement may be occurring. The pyrolytic
temDerature was chosen to be 250 "C which
represents a median decomposition temperature
for this series.
Product Studies
Weighed amounts of xanthate were heated at
250 "C for 30 min and/or several hours when
required. Olefins were separated by g.1.c. and
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22
were identified by standard procedures. The
relative amounts of olefinic products were
determined by the use of g.1.c. and by n.m.r.
spectroscopy. The residues were analyzed by
similar methods. A summary of product
distributions is shown in Table 2.
To summarize the results of Table 2 the
following salient points should be noted :
(I) Neopentyl xanthate undergoes only
rearrangement to the dithiolcarbonate. No
evidence of methyl group participation was
For personal use only.
observed.
(2) Increasing P-phenyl substitution leads to
increasing amounts of olefin formation. The
olefinic products are derived only from phenyl
migration. No xanthate-dithiolcarbonate re-
arrangement was observed at all in the pyrolysis
of 2,2,2-triphenylethyl xanthate and only a
small amount ( < 4%) of dithiolcarbonate was
observed in the diphenylpropyl system.
(3) There is a predominance of terminal
olefins.
(4) No skeletally rearranged dithiolcarbonate
was observed.
These observations prompted a further study
into the course and nature of the pyrolysis of
the xanthates under investigation.
TABLE3. Pyrolys~sof neopentyl-type xanthate at 250 "C
- - . --
Xanthate
*k,= Rate constant of disappearance of xanthate.
tk,= Rate constant of formation of dithiolcarbonate.
$Not available.
§Calculated value.
3291
k~
(0) Xanthate + Dithiolcarbonate
+
-o
a'
- -
Olefins
k, k2
-
(b) Xanthate Dithiolcarbonate Olefins
k,
( r ) Xanthate Dithiolcarbonate
Olefins
SCHEME4. The probable courses of reaction for the
pyrolysis of neopentyl-type xanthates.
There are three probable ways to account for
the products: (a) two competing processes to
afford both olefin(s) and dithiolcarbonate; (b)
a consecutive process, and (c) a competing-
consecutive process (Scheme 4). A kinetic
study of the pyrolysis of these xanthates was
undertaken in the hope that the results would
help to differentiate between the above pro-
cesses.
Kinetic Studies
Small samples of the xanthates placed in
loosely-corked test tubes or sealed tubes (under
a nitrogen atmosphere) were suspended in a
constant temperature silicone oil bath. At set
intervals, reaction was quenched in ice and
samples were analyzed by n.m.r. spectroscopy.
Using methyl benzoate as an internal standard,
the S-methyl groups of both the xanthate and
the dithiolcarbonate were compared with the
methyl group of methyl benzoate and the per-
cent of reaction was calculated.
The rate constants of disappearance of the
xanthates (k,) were determined from the first
order rate equation and are listed in Table 3.
If a given reaction occurs by two first-order
--
k , (s-')* k ~ (s- ')f
 3292 CANADIAN J O U R N A L OF CHEMISTRY. VOL. 50. 1972

formation; [XI = concentration of xanthate at

time t ; [X,] = concentration of xanthate at
1.20 - time zero; [Dl =concentration of dithiolcar-
bonate; [O] = concentration of olefin(s). Thus
for two competing processes the plot of [Dl us.
[X - X,] should be a straight line as predicted
by eq. 2. If so, eq. 4 is also satisfied.
Figure 1 confirms the linear relationship
0.80 - between [Dl and [X, - XI for both neophyl
and p-bromoneophyl xanthates. The rates of
[in - XI dithiolcarbonate formation (kD)were calculated
1s I from the slopes of these lines and are shown in
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22

Table 3. Thus the production of olefin and

0.1~0 - dithiolcarbonate are two competitive processes
in the pyrolysis of these two compounds. This
result indicates that the relationship in eq. 4 is
also true.
Further studies showed that there was no
olefin formation from the pyrolysis of neopentyl
I I I I
and neophyl dithiolcarbonates under similar
0.1 0.2 0.3 0.4
experimental conditions. On this basis, the con-
Iol/[s 1
secutive process and the competing-consecutive
FIG.1. The rate of disappearance of p-bromoneophyl can be eliminated.
For personal use only.

( 0 )and neophyl (A)xanthates against the rate of formation

of the corresbinding dithiolcarbonates: [S] = concentration
of the internal standard. Wagner-Meerwein Rearrangement Leading to
OleJn Formation
competing processes as shown in (a) in Scheme The rate constants of olefin formation (k,)
4, then were calculated according to eq. 4. For 2,2-
diphenylpropyl, p-methylneophyl and 2,2,2-tri-
[I] [XI = [x,] e -"(I)
phenylethyl xanthates, it was assumed that
k, = k, because less than 5% of dithiolcarbon-
ate was observed after 70% completion of
pyrolysis.
[0] = -h[x-x,] Table 4 shows that the rate of olefin for-
k, mation increases with increasing number of
P-phenyl substituents. ~urthermore, the rate
[41 k,=k~+ko was also increased by electron-donating groups
where k, = rate constant of disappearance of substituted at the para-position of the benzene
xanthate; k, = rate constant of dithiolcarbon- ring. A similar observation was obtained in the
ate formation; k, = rate constant of olefin acetolysis of neopentyl-type brosylates (15).

TABLE4. Rates of acetolysis of neopentyl-type brosylates (k,) at 75 "C and calculated rates of
olefin formation in the pyrolysis of neopentyl-type xanthates (ko) at 250 "C
--

Pyrolysis of xanthates Acetolysis of brosylates

ko (s- ') -log ko k, (s-') -log k,

 RUTHERFORD ET AL.: PYROLYSIS OF NEOPENTYL XANTHATES
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22
FIG. 2. The linear free energy plot of the rates of
For personal use only.
pyrolysis of neopentyl-type xanthates (k,) and the rates of
acetolysis of neopentyl-type brosylates (k,).
Figure 2 shows a linear free energy relationship
between the two reactions. The straight line
relationship suggests that there is a considerable
parallelism between mechanisms of the two
reactions (16). It has been demonstrated that
the rates of acetolysis of neophyl brosylates
were moderately sensitive to substituent effects.
A Hammett plot of log k, us. a+ values gave a
p-value of -2.96 for the reaction. Based on
these observations, it was concluded that
ionization with phenyl participation was the
rate determining step in the acetolysis of neo-
phyl brosylates. This author further proposed
that acetolysis of 2,2-diphenylethyl brosylate
and 2,2,2-triphenylethyl brosylate should also
proceed with the same mechanism (15).
SCHEME
5. Proposed transition state for the olefin(s) formation process.
3293
FIG. 3. Plot of log k, for the pyrolysis of para-sub-
stituted neophyl xanthates at 250 "C against u+ values:
-0.306 for p-CH,; 0.00 for p-H; f0.148 for p-Br.
In our studies, the decomposition rates of the
substituted neophyl xanthates were also found
to be moderately sensitive to the nature of
substituents. This observation, coupled with
the apparent similarity between the two sys-
tems, suggests that a phenonium ion transition
state is also involved in the olefin formation
during the neophyl-type xanthate pyrolysis
process as shown in Scheme 5.
Figure 3 shows a Hammett-Taft plot of cal-
culated rate constants of olefin formation of
three substituted neophyl xanthates us. the
corresponding a+ values of the substituents. A
reasonably good straight line relationship was
obtained. The p-value for the reaction was cal-
culated to be -2.42. This further supports the
proposed involvement of the phenonium ion
transition state.
It is interesting to note that there is a pre-
dominance of the Hofmann-type olefins in the
product. In the acetolysis of neophyl brosylate,
the 2-benzylpropene to 2,2-dimethylstyrene
 3294 CANADIAN JOURNAL OF CHEMISTRY. VOL. 50. 1972

tally rearranged dithiolcarbonates indicates

that the reaction might have proceeded through
a non-assisted tight ion-pair or a cyclic SNi
mechanism as shown in Scheme 7. In case of an
ion-pair, electron-donating groups at the ter-
tiary carbon should stabilize the ion-pair while
electron-withdrawing groups should destabilize
it. Thus it is expected that the rate of rearrange-
SCH, \ ment would be faster when R = CH, than
SCH, when R = aryl. The rate of formation of
SCHEME 6. The proposed transition state of the pyro- neophyl dithiolcarbonate was almost nine
lysis of diphenylpropyl xanthate. times faster than that of the neopentyl dithiol-
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22

carbonate as shown in Table 3. Therefore a

ratio was 1 :1 (15). Kwart and co-workers (17, mechanism involving the formation of a non-
18) reported a ratio of 2.2 :1 of 2-benzylpropene assisted tight ion-pair intermediate during the
to 2,2-dimethylstyrene in the pyrolysis of xanthate-dithiolcarbonate rearrangement ap-
neophyl acetate in the gas phase at 575 "C. pears to be in contradiction to the observed
Statistically speaking, the ratio of the two ole- results. On the other hand, a concerted SNi
fins should be 3 : l . Since in the pyrolysis of mechanism involves little charge development
neophyl xanthate the observed ratio is 2:1, the in the cyclic transition state. The presence of
larger than statistically predicted amount of electron-withdrawing groups at the tertiary
conjugated olefin formed in the reaction sug- carbon atom will enhance the electrophilicity
gests that both statistical and thermodynamic of the methylene carbon, and this increases the
For personal use only.

effects are important. rate of dithiolcarbonate formation. This ex-

The 1-benzylstyrene (1) to methylstilbene (2) plains the observed faster rate of neophyl di-
ratio should be 3:2 in the pyrolysis of 2,2- thiolcarbonate formation over that of neopentyl
diphenylpropyl xanthate if statistics were the dithiolcarbonate. Moreover, the smaller rate of
only controlling factor. Experimentally, the formation ofp-bromoneophyl dithiolcarbonate
ratio was found to be 1 : 1. If isomerization of than that of neophyl dithiolcarbonate also sup-
1 to 2 was unimportant under the reaction ports this argument. Thus, the mechanism of
condition^,^ the larger than statistically pre- the dithiolcarbonate formation may involve a
dicted amount of fully conjugated olefin, 2, concerted four-membered cyclic transition state.
again indicated that both statistic and thermo-
dynamic effects are important during the olefin Summary and Conclusions
formation process. On the other hand, if all the The olefin formation and the dithiolcarbon-
methyl-trans-stilbene formed were considered ate formation in the pyrolysis of neophyl
to come from the isomerization of l-benzyl- xanthates are found to be two competing pro-
styrene, the 1 to 2 ratio is 3.2, exactly as pre- cesses. The Wagner-Meerwein rearrangement
dicted by the statistical consideration. The becomes more important when the number of
reasons for a predominant formation of methyl- P-phenyl groups increases and when there is an
cis-stilbene over that of the fr-ans isomer electron-donating group substituted at the para-
(3.5: 1) is not entirely clear (Scheme 6). position of the P-phenyl ring. The transition
state of the olefin formation process is best
Dithiolcarbonate Formation represented by a stabilized phenonium ion. The
In the dithiolcarbonate formation process, driving force of the rearrangement appears to
both neopentyl and neophyl xanthate gave con- be mainly electronic in nature, however, release
siderable yields of dithiolcarbonates without of steric crowding at the ground state could
skeletal rearrangement. The absence of skele- also play an importante role. The dithiolcar-
bonate is thermally more stable than the cor-
'Under the reaction conditions, it was found that I -
benzylstyrene isomerized u p to 48% to methyl-trut~s-stilbene
responding xanthate and its formation becomes
but gave no methyl-cis-stilbene. N o cis- runs isomerization more important when the number of P-phenyl
of stilbenes was observed. substituents is the least. This rearrangement
 RUTHERFORD ET AL.: PYROLYSIS OF NEOPENTYL XANTHATES
7. The possible transition state of the xanthate-dithiolcarbonate rearrangement. (R = CH3, aryl).
SCHEME
TABLE5. Element of analysis of xanthates
Theoretical (%)
Xanthate Carbon Hydrogen
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22
appears to proceed through a concerted four-
membered cyclic transition state.
For personal use only.
Experimental
Syntllesis of' Xatitl~ates
All Xanthates were synthesized according to procedures
developed in this laboratory (14)., Elemental analyses of
these xanthates are summarized in Table 5. The i.r. and
n.m.r. spectral data of these compounds all supported the
desired xanthate structures.
Pyrolysis of Neopentyl Xatithnte
Neopentyl xanthate (5 g) was refluxed under nitrogen for
48 h. No decomposition was observed as the i.r. spectrum
of the product was identical with that of neopentyl xanthate.
Another attempted decomposition was carried out in
sealed tube at higher temperature. The xanthate, 1 g, was
sealed in a 4 ml micro test tube under nitrogen and was kept
at 270 "C for 5 h. The product was analyzed by g.1.c. (8 ft
Lac-728 column, 120 "C! 60 cc heliumlmin) and gave two
peaks. The first peak (retention time, 32 min; 60%) was
identified as unreacted neopentyl xanthate. The second
FIG.4. An N-tube for pyrolysis.
31n the synthesis of para-bromoneophyl xanthate, sodium
hydride was used instead of potassium metal to generate
the sodium salt from the corresponding alcohol.
-
-- --
Found (%)
Bromine Carbon Hydrogen Bromine
peak (retention time, 38 min; 40%) was identified as
neopentyl dithiolcarbonate: i.r. (lo%, CCI,) 2960 and 2870
(s, C-H), 1650 (s, C=O), 1365 (m, C-H), 860 (s, S-CO-
S): n.m.r. (lo%, CDCI,) 0.97 (s, 9, C(CH3),), 2.48 (s, 3,
SCH,), 3.07 (s, 2, SCH2).
In an attempt to detect olefin formation, this xanthate
(200 mg) was sealed in an n.m.r. tube and heated in a silicone
oil bath at 250 "C. A spectrum was run every 4 h. After 40 h
no olefin was observed and the corresponding dithiolcar-
bonate was the only product in 42% yield.
Pj~rolysisof Neopentyl Ditliiolcarbotrate
The dithiolcarbonate (200 mg) in a sealed n.m.r. tube was
kept in a silicone oil bath at 250 "C. An n.m.r. spectrum
was run every 10 h. After a duration of 40 h, no decomposi-
tion was observed. The i.r. spectrum of the resultant liquid
was identical to that of the starting dithiolcarbonate.
Pyrolysis o f Neoplzyl Xanthate
Decomposition of a small amount of the xanthate (0.5 g,
2.1 mmol) was carried out in an N-tube (Fig. 4) in a silicone
oil bath at 250 "C. The xanthate was pipetted into a straight
tube A D 12 cm x 7 mm which was bent to an N-shape as
shown in Fig. 4. Part A of the tube was immersed in a n oil
bath while part C was cooled. The advantage of this N-tube
is to allow easy separation of olefin from the residue and
also only small amounts of xanthate are required by this
method. After heating for 2 h, part A was cooled and was
separated from part C. The olefins in part C weighed 127
(9.5 mmol, 45%) while the residue in part A weighed 270
mg. The loss of material was due to escape of gaseous
products.
Analysis of the Olefils
The olefins were separated by g.1.c. (8 ft Lac-728 column,
125 "C, 60 cc helium/min). On the chromatogram two peaks
appeared with retention times of 5.5 (67%) and 7.5 min
(33%). The first peak was identified as 2-benzylpropene:
11L5 1.5050 (lit. (30) 1.5057); i.r. (lo%, CCI,) 3080 (s,
C=CH), 3020 (s, Ar-H), 2980 and 2970 (s, C-H), 1645
 3296 CANADIAN JOURNAL OF CHEMISTRY. VOL. 50, 1972
(m, C=C), 1600 and 1490 (w, Ar), 884 (s, C=CH,), 690 (s,
Ar-H): n.m.r. (lo%, CDCI,) 1.65 (s, 3, C=C-CH,). 3.24
(s, 2, C=C-CH2-Ar), 4.62 (s, 2, C=CH2), 7.00 (bs, 5,
C6Hs). The second peak was identified as 2-methyl-l-
phenylpropene: nk5 1.5367 (lit. (34) nh0 1.5400): i.r. (10%
CCI,) 3060 (s, C=CH), 3020 (s, Ar-H), 2970 and 2920
(s, C-H), 1659 (m, C=C), 1600 and 1490 (w, Ar), 825 (m,
C=CH), 690 (s, Ar-H); n.m.r. (10%. CDCI,) 1.85 (m, 6,
C=C(CH,),), 6.10 (m, I, C=CH), 7.07 (bs, 5, C6H,).
Analysis of the olefinic mixture by n.m.r. integration
showed a similar product distribution.
Isomerizarion Sludy of//le Olefins
A 30 mg sample of each of the two olefins was heated
separately in an N-tube at 250 "C for 30 min. The n.m.r.
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22
spectrum showed that no isomerization occurred for both
2-benzylpropene and 2-methyl-I-phenylpropene.
Ar~a1j~si.s
of fhe Residue
The residue was separated by g.1.c. (6 ft Lac-728 column,
200 "C, 60 cc heliumlmin). On the chromatogram only two
peaks appeared at 130 (60%) and 138 min (40%). The com-
pound corresponding to the first peak was identical to the
unreacted xanthate. The second component of the residue
was identified as the neophyl dithiolcarbonate: nk6 1.5757:
i.r. (lo%, CCI,) 3020 (w, Ar-H), 2950 and 2920 (s, C-H),
I640 (s, C=O), 860 (s, S-CO-S), 690 (s, Ar-H): n.m.r.
(lo%, CDCI,) 1.34 (s, 6, C(CH,),), 2.28 (s, 3, SCH,), 3.20
(s, 2, SCH,), 7.00 (bs, 5, C,H5).
For personal use only.
Analysis of the residue by n.m.r. integration showed a
similar product distribution.
Hydrolysis and Reduction of Neophyl Di/hiolcarbonafe
Neophyl dithiolcarbonate (I g) was hydrolyzed by
sodium hydroxide according to the method of Taguchi and
Makao (9) followed by Ra-Ni reduction according to the
method of Sondheimer and Rosenthal (19). The resultant
reaction mixture was extracted with ether. The organic
layer was concentrated and analyzed by g.l.c., i.r., and
n.m.r. 1-Butylbenzene was the only observed product.
Another neophyl xanthate sample (500 mg) was charged
to an N-tube which was heated for 30 min. The olefins
weighed 42 mg (17%). Analysis by n.m.r. integration showed
that 2-benzylpropene and 2-methyl-I-phenylpropene were
present in the ratio 67:33. The residue weighed 412 mg and
the n.m.r. integration showed that the xanthate to the
dithiolcarbonate ratio was 90: 10. The loss of material was
due to escape of gaseous products.
Pyrolysis of Neoplzyl Dif/ziolcarbonafe
The dithiolcarbonate (22 mg) was heated in an N-tube at
250 "C for 2 h. No olefin was found. The residue was
analyzed by g.l.c., i.r., and n.m.r. and was found to be the
starting dithiolcarbonate.
Pyrol~lsisof p-Bromoneoplzyl Xarzfhafe
Decomposition of this xanthate (41 mg, 0.13 mmol) was
carried out in a 75 x 10 mm test tube at 250 "C for 2 h. The
composition of products was analyzed by n.m.r. integration
without further purification (methyl benzoate was used as
internal standard). The mixture contained 50% of the un-
reacted xanthate and 17% of the dithiolcarbonate. The ole-
fin portion was not analyzed.
Pyrolysis of p-Meflzyh~eophylXanflzafe
Decomposition of this xanthate (33 mg, 0.13 mmol) was
carried out in a 75 x 10 mm test tube at 250 "C for 30 min.
The composition of products was determined by n.m.r.
integration without further purification (methyl benzoate
was used as internal standard). The mixture contained 27%
of the unreacted xanthate and less than 4% of the dithiol-
carbonate. The olefin portion was not analyzed.
Pyrolysis 01'2.2-Diplze~lylpropyIXo~zr/ttl/e
Decomposition o f this xanthate (500 mg. 1.65 mmol) was
carried out in an N-tube in a silicone oil bath at 250 "C for
30 min. No olefin was found in part C of the tube. The
product was analyzed in the following manner.
Analysis of Olefins
The olefins were separated from the reaction mixture by
liquid column chromatography (silica gel, petroleum ether
(b.p. 30-60 T ) ) and weighed 280 mg (88%). Olefins were
further separated by g.1.c. (6 ft 10% SE-30, 170 "C, 6 0 c c
helium/min). On the chromatogram three peaks appeared
with retention times of 6.4 (3973, 7.4 (4973, and 10.8 min
(12%). Analysis of the olefinic mixture by n.m.r. integration
showed a similar product distribution. The first peak was
identified as methyl-cis-stilbene: m.p. 46-47 'C (lit. (20)
m.p. 48 "C): i.r. (lo%, CCI,) 3060 (s, C=CH), 3020 (s,
Ar-H), 2970 and 2920 (w, C-H), 1600 and 1490 (m. Ar),
849 (m, C=CH), 690 (s, Ar-H); n.m.r. (lo%, CCI,) 2.1 1
(d, 3, J = 2 Hz, C=CCH,), 6.21 (m, I, C=CH), 6.70-7.10
(bd, 10, C(C6H5),). The second peak was identified as
I -benzylstyrene: 1.5893 (11t.(21) nA5 1.5891): i.r. (lo%,
CCI,) 3060 (s. C=CH), 3020 (s, Ar-H), 2910 (m. C-H),
1625 (m, C=C), 1600 and 1490 (m, Ar). 890 (s, C=CH,),
690 (s, Ar-H); n.m.r. (lo%, CCI,) 3.65 (s, 2, C=CCH,Ar),
4.80 (bd, 1, C=CH), 5.25 (bd, 1. C=CH), 6.90-7.10
(bs, 10, C(C,H,),). The third peak was identified as methyl
trans-stilbene: m.p. 81-82 "C (lit. (20) m.p. 82°C); i.r.
(lo%, CCI,) 3060 (s, C=CH), 3020 (s, Ar-H). 2980 and
2940 (w, C-H). 1600 and 1490 (m, Ar), 849 (m. C=CH),
690 (s, Ar-H): n.m.r. (lo%, CCI,) 2.17 (d, 3, J = 2 Hz,
C=CCH,), 6.65 (m, I, C-CH), 6.90-7.20(m, 10, C(C,H,),).
Olefin Isomerizafion Sfudy
A 30 mg sample of each of the three olefin products was
heated separately in three micro test tubes at 250 "C for 30
min. The n.m.r. analysis showed that no isomerization
occurred between trans- and cis-stilbenes. However, 48% of
benzylstyrene was isomerized to methyl-frcijzs-stilbene.
At7alysis of Oflzer Protlucfs
The remaining material on the chromatography column
weighed 60 mg. The i.r. spectrum showed characteristic
xanthate bands and dithiolcarbonate bands at 1645 and
860 c m - ' . The n.m.r. spectrum showed that the mixture
contained 66% of the unreacted xanthate. Attempts to
isolate the dithiolcarbonate were unsuccessful.
Pyrolysis of 2,2,-7-Triphetlylefhyl Xatzfhafe
Decomposition of this xanthate (Ig, 2.7 mmol) was
carried out in a micro test tube in a silicone oil bath at
250 "C for 30 min. The product weighed 700 mg (2.7 mmol).
The t.1.c. analysis (silica gel, pentane) showed only one spot
corresponding to triphenylethylene: m.p. 88-89 "C. The i.r.
spectrum was identical to an authentic sample.
An Affempf fo Defect Diflziolcarbo~~are
Formafiotl
The S-methyl xanthate ester of 2,2,2-triphenylethanol
 R U T H E R F O R D ET AL.: PYROLYSIS O F NEOPENTYL XANTHATES 3297

(0.5 g) in an n.m.r. tube was heated in a silicone oil bath at 6. C. DJERASS~ and W. S. BRIGGS. J . Org. Chem. 33,
200 "C. An n.m.r. spectrum was run every 30 min for a 1625 ( 1 968).
period of 2 h. No dithiolcarbonate formation was observed. 7. R. E. G I L M A NJ., D. HENION, S. SHAKSHOSKI. J. I. H.
Another sample was heated in an oil bath at 160 "C. An PATTERSON, M. J . BOGDANOWICZ. R. J. GRIFFITH, D. E.
n.m.r. spectrum was run every 6 h for a period of 36 h. HARRINGTON, R. K. RANDALL, and K. T. FINLEY.
Again, no dithiolcarbonate formation was observed. Can. J . Chem. 48, 970 (1970).
8. C. G . OVERBERGER and A. E. BORCHERT.J. Am.
Kittetic Studies Chem. Soc. 82, 4896 (1960).
Kinetic studies of the pyrolysis of xanthate esters were 9. T. TAGUCHIand M. MAKAO. Tetrahedron, 18, 245
carried out on neat samples. An accurately weighed sample ( 1962).
(30 mg) o r the solid xanthate ester to be studied was placed 10. T. T A G U C I -Y.~ I , KAWAZOE,and M. MAKAO. Tetra-
in a 75 x 10 mm test tube. For liquid xanthate esters, a 30 i11 hedron Lett. 131 (1963).
sample was introduced into the test tubes by means of a I I. T. TAGUCHI, Y. KAWAZOE. K. YOSHIHIRA, H. KANA-
constant volume addition syringe and then it was weighed Y A M A . M. MORI.K. TABATA, and K. HARANO.Tetra-
accurately. The test tubes were loosely corked or sealed
Can. J. Chem. Downloaded from cdnsciencepub.com by 47.15.2.191 on 02/12/22

hedron Lett. 2717 (1965).

under a nitrogen atmosphere and were suspended in a 12. P. V. LAAKSO. Suomen Kemi, 13B, 8 (1940): C h e n ~ .
constant temperature silicone oil bath a t the desired Abstr. 34, 5059 (1940).
temperature. Samples were removed at set intervals and 13. P. DE MAYO. In Molecular rearrangements. Vol. I.
were immediately cooled in ice-water. The samples were Interscience, New York, N.Y. 1963. pp. 6-15.
analyzed by n.m.r. using methyl benzoate as an internal 14. K. G. RUTHERIZORD, R. M. OTTENBRITE, and B. K.
standard. The relative amounts of xanthate left unreacted TANG. J. Chem. Soc. C. 582 (1971).
and the relative amounts o r products formed at each 15. S. WINSTEIN and R. HECK. J. Am. Chem. Soc. 79,
interval were estimated by n.m.r. integrations. The maxi- 3432 (1957).
mum error in integration was estimated to be about 5%. 16. H. C. BROWN,R. BERNHEIMER, and K. J. MORGAN.
J. Am. Chem. Soc. 87, 1280 (1965).
1. C . H. DEPUYand R. W. KING. Chem. Revs. 60. 431 17. H. KWARTand D. HOSTER. Chem. Commun. 1155
(1960): H. R. N ~ c e . Irr Organic reactions. Vol. XII. (1967).
John Wiley and Sons, Inc., New York, N.Y. 1962. p. 58. 18. H. KWARTand H. G . LING. Chem. Commun. 302
For personal use only.

2. 5. MARCH. It1 Advances in organic chemistry. (1969).

McGraw-Hill, Inc., New York, N.Y. 1968. p. 757. 19. F. SONDHEIMER and D. ROSENTHAL.J. Am. Chem.
3. F. F. BORDWELL and P. S. LANDIS.J. Am. Chem. Soc. SOC.80. 3995 (1958).
80, 6379 (1958). 20. E. ELLINGUOE and R. C. F u s o ~ . J . An]. Chem. Soc.
4. D. J. CRAM. J. Am. Chem. Soc. 71, 3883 (1949). 55, 2964 i1933).
5. R. F. W. BADERand A. N. BOURNS. Can. J . Chem. 21. D. H. HUNTERand D. J. CRAM. J . Am. Chem. Soc.
39, 348 (1961). 88, 5499 (1966).