Products and stereochemistry of thermolysis of some diazenes containing the

2-phenyl-2-butyHgroupP
KARLR . MOPECKY.
THOMAS W. MOJELSKY. THOMASGILLAN
.2
JAMESA. BARRY,
A N D JUAN A . LOPEZSASTRE
Depai tinenf oj C h r m l \ t ~ U
~ .n r ~rrsrtj c)jAlbeifn, Edmoi~tonAltii C ~ ~ a i iT6G2G2
ci
Rece~vedOctober 7, 1976
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18

KARLR. KOPECKY, THOMAS W. MOJELSKY, THOMAS GILLAN,JAMES A. BARRY,and JUANA.

LOPEZSASTRE. Can. J. Chem. 55, 1001 (1977).
Thermolysis of (-)-(R)-I-benzyi-2-(2-phenyl-2-butyl)diazene ( - ) - R - 4 , produces (+)-(S)-2-
methyl-1,2-diphenylbutanewith 1297, net retention of configuration at 110 "C in benzene or
pentane containing 1 M butanethiol. The ratio of the rate constant for coupling of the initial
radical pair to that of rotation of the 2-phenyl-2-butyl radical, k,/kr, is calculated to be 0.04-
0.08. Therrnolysis of (+)-(S)-l-(2-phenyl-2-butyl)-2-(2-propyl)diazene at 100 "C in benzene
-
containing 1 M butanethiol produces 2,3-dimethyl-3-phenylpentane with no observable rota-
iion. The product must be less than 15% optically pure. The reaction produces (-)-(R)-2-
phenylbutane, (-)-(R)-IS, with 0.6-1.3% retention of configuration. The ratio of the rate
constant for disproportionation to (-j-(R)-16 to k, is calculated to be 0.02-0.04. Thermolysis of
(-)-(R)-l-(4-nitrophenyl)-2-(2-phenyl-2-butyl-diazene, (-)-(R)-12, at 175 ' C in diphenylether
produced no 2-(4-nitropheny1)-2-phenylbutane. This produci was produced on photolysis of
(+ j-(S)-32 in hexadecane at 15 "Cbut had no rotation. Neither (+)-(S)-7 nor (-)-(R)-12 was
racelnized during thermolysis and (+)-(S)-12 was not racemized during photolysis. Activation
For personal use only.

parameters for thermolysis of ( 1 ) - 4 are A H * = 33 kcal/mol, AS* = 15 eu and for (?)-I&

A H + = 37.3 kcal/mol, AS* = 5.5 eu.

KARLR. KOPECKY, THOMAS W. MOJELSKY, THOMAS GILLAN,JAMESA. BARRYet JUANA.

LOPEZSASTRE. Can. J. Chem. 95, 10Oi (1977).
La therrnolyse du (-)-(R) benzyl-1 (phinyl-2 butyl-2)-2 diazene, ( - ) - R - 4 , conduit au ( + ) - ( S )
methyl-2 diphenyl-1,2 butane avec une retention nette de 12%de la configuration a 110 'Cdans
du benzene ou dans du pentane contenant 1 M de butanethiol. Le rapport des constantes de
vitesse du couplage de la paire de radicaux initiaux et de la rotation du radical phenyl-2 butyle-2,
k,/k,, est d'environ 0.04-0.08. La therrnolysc du (+)-(S) (phenyl-2 butyl-2)-l (propyl-2)-2
diazene a 100 "C dans du benz6ne contenant 1 M de butanethiol conduit au dimethyl-2,3
phenyl-3 pentane pratiquement sans rotation. Le produit doit etre moins que 15% optiquemcnt
pur. La reaction fournit du (-)-(R) phinyl-2 butane, (-)-(R)-16, avec une retention de con-
figuration de 0.6-1.3%. On a calcule que le rapport de la constante de vitesse de disproportiona-
tion en (-)-(R)-16 sur k , est de 0.02-0.04. La thermolyse du (-)-(R) (nitro-4 phtny1)-l (phenyl-2
butyl-2)-2 diazene, (-)-(R)-12, a 175'C dans I'Cther diphenyle ne conduit pas au (nitro-4
pheny1)-2 phenyl-2 butane. Ce compose est obtenu par photolyse du (+)-(Sj-12 dans l'hexa-
dtcane a 15 'C mais il n'y a pas de rotation. I1 11'y a pas de racemisation lors de la thermolyse du
(+)-(S)-7 ou du (-)-(R)-12 et le (+)-(S)-12 n'est pas racernise durant sa photolyse. Les
parametres d'activation pour la thermolyse de (+)-4 sont AH* = 33 kcal,'mol, AS' = 15 ue et
pour (*)-I2 A H * = 37.3 kcal/rnol, AS* = 5.5 ue.
[Traduit par le journal]

The results of the earlier studies of the

thermolysis of the chiral diazenes 1 (I) and 2 (2)
are consistent with the assun~ptionthat in these
compounds both C-N bonds are breaking
simultaneously in the rate determining step, [I].
[I] R-N=N-R' ---t R. N2-R'
There has already been evidence. which is still
'This research was supported by the National Research accumulating, that such a concerted cleavage
Council of Canada. occurs on thermolysis of a number of acyclic (3)
'Holder of a National Research Council of Canada and cyclic (4) diazenes. In most of these com-
Studentship 1966-1968, a Province of Alberta Scholar-
ship, 1966-1967, and a University of Alberta Dissertation pounds R . and R'. are radicals of similar
Fellowship 1968-1969. stability.
 1002 CAN. J. CHEM

At the time that we initiated studies in this
area we began also to examine diazenes that
might provide stereochemical evidence for one-
bond cleavage (5) as indicated by racemization of
optically active starting material, [2], in which R .(R)-9 (13) have been determined. Thus, the ab-
is a much more stable radical than is R'..
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18
tions and absolute configurations of (+)-(R)-(2-
phenyl-2-buty1)diazane ( + ) - ( R ) - 3(1 (-)-(R)-
1,2-diphenyl-2-methyI-2-butanone(-)-(R)-§(12),
and (-)-(R)-2-methyl-2-phenylbutanoicacid (-)-
solute configurations and maximum rotations of
(-)-(R)-4, (+ )-(S)-l,2-diphenyl-2-methylbutane
(+)-(S)-6, (+)-(S)-2,3-dimethyl-3-phenyl-1-pen-
tene (+)-(S)-10, (-)-(S)-2,3-dimethyl-3-phenyl-

Since our work began, stereochemical evidence pentane (-)-(S)-11, and (-)-(R)-12 are es-
for one-bond cleavage during thermolysis of tablished. The absolute configuration and maxi-
several optically active diazenes has appeared (6). mum rotation of (+)-(S)-7 were determined by
Other evidence for one-bond cleavage has been hydrogenolysis to (-)-(S)-2-phenyl-2-butylamine
obtained from kinetic (7), pressure (8), and nmr (-)-(S)-8, of known configuration (11). This
(9) studies of, and the observation of isomeriza- amine was also prepared again in this work from
tion (10) in, the thermolysis of diazenes. (+)-(S)-2-methyl-2-phenylbutanoic acid (+)-(S)-
In this paper the thermolyses of (-)-(R)-1- 9 to check the magnitude of its rotation.
benzyl-2-(2-phenyl-2-buty1)diazene (-)-(R)-4, The magnitude of the rotation of the optically
(+)-(S)-l-(-2-phenyl-2-butyl)-2-(2-propyl)diazene pure coupling product (-)-(S)-11 expected from
(+)-(S)-7, and (-)-(R)- 1-(4-nitropheny1)-2-(2- thermolysis of optically active 7 is smaller than
phenyl-2-buty1)diazene (-)-(R)-12 are described. expected. It was prepared from (-)-(R)-9 by re-
The diazenes each contain a 2-phenyl-2-butyl actions that do not affect the chiral center and the
For personal use only.

group, chosen because it cannot undergo immediate precursor (+)-(S)-10 has a significant
racemization by reversible hydrogen atom ab- rotation. Values of [MI, - 19.2 or -4.4" for the
straction, and constitute a series in which the rotation of (-)-(S)-11 were calculated using
other substituent is varied from benzyl to 2- Brewster's empirical rules (14). By estimat~ngthe
propyl to 4-nitrophenyl. This is in order of density of (-)-(S)-11 to be 0.87 values of a,
decreasing radical stability. It was expected that - 9.5 or -2.2" (neat, l 1 dm) were obtained. The
(-)-(R)-4 would undergo concerted two-bond larger values were obtained using the higher
cleavage and produce a coupling product with polarizabil~tyof the phenyl group which has been
retention of configuration (1, 2), whereas (-)- found to give the more accurate estimate of
(R)-12 would decompose by a one-bond cleavage rotation for many compounds. However, it is
reaction [2] and thus might racemize during known that empirical rules for calculating optical
thermolysis. The mechanism of thermolysis of rotation give erroneous results for con~pounds
(+)-(S)-7 is not so easy to predict and a com- with 2-propyl groups attached to the chiral center
parison of the stereochemistry of the product of (15), presumably because of steric crowding. The
coupling with that from (-)-(R)-4 might be rotation of (-)-(S)-11 did not vary greatly with
informative. In fact, indirect evidence indicates wavelength down to 300 nm, the shortest wave-
that the coupling product from (+)-(S)-7 was length utilizable. The maximum rotation at the
formed with a somewhat smaller amount of position of a low intensity peak was [ ~ 1 ] , , , = ~~
retention of configuration than that from (-)- - 33" (C 1.05, CH,OH).
(R)-4, that (+)-(5')-7 was not racenlized during Results
thermolysis, and that (-)-(R)-12 was not
racemized during either thermolysis or pho- Rates and Products of Thermolysis
tolysis. The rates of thermolysis of (+)-4, (-1)-7, and
(&)-I2 are presented in Table 1. The rate of
Syntheses of Optically Actizje Diazenes and Cou- thermolysis of (+)-4 is about 17 times that of 1
pling Products (1). This is about the effect to be expected on
The syntheses of the optically active diazenes replacing a hydrogen atom of 1 by an alkyl group
and of the coupling products expected from (16). The rate of thermolysis of (-1)-7 is nearly
(-)-(R)-4 and (+)-(S)-7 are outlined in Schemes 1
to 3. Rotations given are those calculated for 3A much more convenient method of resolution of
optically pure compounds. The maximum rota- ( 1 ) - 3 has been found, see Experimental.
 KOPECKY ET A L

(+I-(R)-3
r5,,2'+ 13.6'(neat. I 1 dm)

( I ) LiAIH,
(2) HZ0 t
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18

(3) Na. H
( 4 )C H 3 0 H

( I ) Tartaric
C6H5
1
C2H5CNHNH2
I
' 3 3
( I ) CH,COCH,
(2) LiAIH4
(3) H2O
F
C6H5
I
C2H5CNHNHCH(CH3)2
1
' 3 3
.(3) 0
acid
(2) HO-
2 CH
C6H5
\ C-N=W--CH(CH3)2

C2H5
For personal use only.

(+)-(S)--7
rD25 +42.3" (neat, 1 1 dm)

C6H5 ( I ) soC1, CsH5

\
\CC02H ( 2 ) N3- C-NH2
CH;"~
C2H5
( 3 )H,O, A CH;-'d
C2H5
(+)-(SF9 (-)-(.7)-8
rD25 - 15 7" (neat. 1 1 dm)

(1) SOClz C6H5 CH

F"
,CC02H
(2) CH3Li
(3) H2O
\
,C-C
/jH2H2/Rh +

C2H;"2
fCCH(CH3)2
c~H;''~
CH3 CH3
(5) A
( -)-(R)-9 (+)-(S)-10 (-1-(S)-11
rD2'+ ll.6'(neat, I 1 dm) aD2' -0.4" (neat. I 1 dm)

( I ) Menthyl
C I ~ S chlorocarbonate C6H5 C H
I (2) Recrystalization \ ( 1 ) 4-FC,&N02 C-N=N-(4)-C,H,NO,
CZH5CNIINH2 C-NHNH2
I (3) H O , A CH;*'i' (2) 0 2 ' CH;,'I
CH3 (4) H3O' c2H5 C2H5

(-)-(S)-3
rD2' - 11.6 (neat. 1 1 dm)
 1004 CAN. J. CHEM. VOL. 55, 1977

TABLE1. Rates of thermolysis of diazenes (f)-4, (k)-7, and (*)-I2

Concentration Temperature Moles k x lo4

Diazene Solvent (MI ("c) Nza W1)

(11-4 Cumene 0.16 86.6 0.85 0 . 131b

(i1-4 Cumene 0.16 103.7 0.89F0.04" 1.18+0.05'
(i1-7 Cumene 0.25 122.5 0.85~0.01c-d 1.46f0.02'
(C 1-12 Diphenyl ether 0.35 160.5 O.88&O.0lc 0.213~0.007c3e
( C 1-12 Diphenyl ether 0.35 187.0 0.90C0.02" 2.77k0.03'
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18

OMol N, per mol of diazene.

bAt 103.7'C A H * = 33 kcal/mol, A S * = 15 eu.
'Average of two runs,
*Based on 2 mol of gas (N2 propane or propene) per mol of 7.
eAt 160.5 "C A H * = 37.3 0.6 kcal/mol, AS* = 5.5 2 1.5 eu.

identical to that of I-(2-phenyl-2-propy1)-2-(2- CH, CH,

propy1)diazene 13 (17). Thus, replacement of a I I
methyl group in 13 by an ethyl group has little
effect on the rate of thermolysis.
For personal use only.

The rate of thermolysis of (*)-I2 is very much

slower than that of either (i-)-4 or (+)-7. This
might suggest that (+)-I2 thermolyzes by a
mechanism different from that of the other two
compounds, but the main factor contributing to coupling products were formed. Toluene and
the rate difference between (*)-7 and (f )-I2 is ( 1 ) -16 are formed outside the initial solvent cage
the difference in the entropies of activation, about from benzyl and 2-phenyl-2-butyl radicals by
8 eu (reported for 13 (17) AH' = 36.0 kcal/mol, abstraction of hydrogen atoms from the thiols.
AS* = 14 eu), assuming that the activation An additional source of toluene could be from
parameters of (*)-7 and 13 are nearly the same. disproportionation of the two radicals in the
A larger difference in the enthalpies of activation initial solvent cage. Since the yield of toluene is
than the observed 1.7 kcal/mol might have been only slightly higher than that of (+)-I6 only
expected if 13 were decomposing according to [I] -2% of the radicals undergo disproportionation
and (+)-I2 according to [2]. in the cage. Such a high ratio of coupling to
Thermolysis of a lo-' M solution of ( 1 ) - 4 in disproportionation is common to benzylic
benzene at 110 "C produced toluene, (1)-6, 3,4- radical pairs (1, 18).
dimethyl-3,4-diphenylhexane14, and 1,2-di-
phenylethane 15 in a 12 : 53 : 22 : 13 molar ratio in TABLE 2. Relative yields (%) of products from thermolysis
of ( f )-4 at 110 ' C in rhe presence of scavengers
50% total yield [3]. About a 10% yield of a
mixture, only partially resolved under the gc [Thiol]
conditions used, of 2-phenylbutane (i-)-16, 2- Solvent M Toluene ( f )-I6 ( f )-6
phenyl-1 -butene 17, Z- and possibly E-2-phenyl-
2-butene 2-and E-18 was also formed, as was Pentane-
benzenethiol 1. 2 46 46 8
about a 207, yield of several unidentified com-
pounds. Very similar results were obtained when Benzene-
benzenethiol 0.97 77 23
pentane was used as solvent.
Thermolysis of ( f ) - 4 in the presence of 1 kf Benzene-
butanethiol 0.84 28" 15"
butanethiol or benzenethiol resulted in greatly
increased yields, relative to those of (51-6, Butanethiol 9 . 7 74 26
toluene, and (*)-16, Table 2. No symmetrical
 KOPECKY ET AL.
Numerous other products, most of which were
eluted between ($-)-I6 and (*)-6 under the gc
conditions used, were also formed in the
presence of the thiols. About half the amount of
these products, relative to (*)-6, was formed in
the presence of benzenethiol as was formed in the
presence of butanethiol. Only one of these com-
pounds was identified and it was shown to be
E-1,2-diphenylethene E-19, formed in - 5%
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18
yield in the presence of butanethiol. No E-19 was
formed in the absence of thiol. The formation of
E-19 in low yield has been observed on ther-
molysis of 1,2-dibenzyldiazene in the absence of
scavenger (19). Its origin in these reactions is not
clear. It cannot be formed under the present
conditions by dehydrogenation of 15 because
none of the latter compound is formed. A possible
route to the formation of E-19 is shown in
Scheme 4. Thermolysis of diazenes in the
presence of thiols produces appreciable amounts
of bis(methy1ene)diazanes (azines) (20). Pre-
sumably this occurs by successive hydrogen
For personal use only.
atom abstractions from the diazene by thiyl
1005
radicals [4] (20). This would mean that the
radical generated upon abstraction of the first
hydrogen atom must have enough stability so
that it can survive sufficiently long in the
presence of thiol to undergo a second hydrogen
atom abstraction. The radical 20 generated in
this way from 4 cannot undergo a second
hydrogen atom abstraction.
Dimerization of two such radicals would give
the bis-diazene 21 and subsequent thermolysis of
this compound could produce E-19. The radical
21 also could couple with a thiyl radical to form
the diazene 22 which would give rise to at least
two other products 23 and 24 on therrnolysis. A
search for these compounds was not made.
Thermolysis of 0.5 M ( f ) - 7 in benzene at
100 "C produced (i)-16, 17, 2-18, (f )-11, and
14 in a 23:2:2:59:14 molar ratio in 51% total
yield. Very similar results were obtained at
125 "C. No E-18 was detected. No attempt was
made to detect other products of the 2-propyl
radical. In the presence of 1 M butanethiol a
64: 36 molar ratio of (i-)-16: (&)-I1 was formed
in 57% total yield. No symmetrical coupling
product 14 was detected. A number of un-
identified other products that eluted near
(*)-I1 under the gc conditions used were
formed in both the presence and absence of
thiol. Under both conditions considerable
amounts of hydrazone were formed. A signi-
ficantly larger yield, 30%, of (+)-11 was formed
in the absence of butanethiol than in its presence,
217,. This indicates that a considerable amount
of coupling between 2-phenyl-2-butyl and 2-
propyl radicals must occur outside the initial
solvent cage in benzene. Similar behavior was
observed recently for 2-butyl and diphenyl-
methyl radicals (21).
Products of thermolysis of 0.3 M (k)-12 under
nitrogen in diphenyl ether at 175 "C that were
identified are shown in [5]. Nitrobenzene and
1-phenyl-1-propanone were eluted together under
the gc conditions used. The identified products
accounted for -50% of the 2-phenyl-2-butyl
radicals. Unexpectedly, neither (+)-I16 nor the
coupling product 14 could be detected. The
coupling product 14 was shown to survive heat-
 1006 CAN. J . CHEM. VOL. 55, 1977
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18
ing at 175 ' C in diphenyl ether for a time equal to
several half-lives of decomposition of (f )-12.
None of the unsymmetrical coupling product
2-(4-nitropheny1)-2-phenylbutane 27 was de-
tected either. As in the thermolysis of (f)-7, E-18
predominates greatly over Z-18.
Possible routes to some of the products are
given in Scheme 5. The presence of the ketones
among the products is good evidence that
For personal use only.
2-phenyl-2-butoxy radicals are formed which
then undergo p-sission. The alkoxy radicals must
result from the reaction between 2-phenyl-2-
butyl radicals and a nitro group. The alkenes 17
and Z- and E-18 are not likely to be formed by
disproportionation between two 2-phenyl-2-
butyl radicals since neither the alkane (f )-16,
which would be the other product of dispro-
portionation, nor the coupling product 14 is
formed. The absence of 14 is good evidence that
the radicals never encounter each other since
coupling is an important result of such en-
counters as shown by thermolysis of (f )-4 and
(f)-7 at lower temperatures. The higher tem-
perature in the thermolysis of (+)-I2 should not
be the reason for lack of formation of 14 since in
thermolysis of ( 1 ) - 7 a slightly higher relative
yield of 14 was formed at 125 "C than at 100 ' C .
The alkenes may be formed by disproportiona-
tion of 2-phenyl-2-butyl and 4-nitrophenyl-
diazenyl radicals in the initial solvent cage.
Since 2-phenyl-2-butyl radicals do not couple
under these reaction conditions it is unlikely that
4-nitrophenyi radicals would couple, hence the
suggested route to 25 in Scheme 5. The formation
of 25 in 79% yield on thermolysis of neat
(+)-I2 at 175 "C is consistent with the proposed
route. Higher concentrations of the diazene
-
would favor the addition of the niirophenyl
radical to the diazene. Only 15% total yield of
the products of the 2-phenyl-2-butyl radical were
detected. The reaction was not done in a sealed
tube and these products may have evaporated.
Tl~ernzolyrisof Optically Active D i a z e ~ e s
Thermolysis of (-)-(R)-4 in benzene at 110 "C
produced ( + ) - ( S ) - 6 with 6% net retention of
configuration, Table 3. In the presence of 0.9 M
-
butanethiol (+)-(S)-6 is formed with 12% net
retention of configuration in either benzene or
 KOPECKY ET AL. 1007

TABLE
3. Stereochemistry of (+)-(S)-6from thermolysis of (-)-(R)-4" at 110 ' C

( ( R ) Concentration Butanethiol, (+)-(S)-6b Retentiond

Solvent (mg) (MI (M) (mg) [ ~ r (degIc
l ~ ~ ~ (%)
~ ~

Benzene 3 60 0.1 0 39 C2.67 5.8

Benzene 460 0.04 0.9 40 f5.88 12.8
Pentane 450 0.04 0.9 23 +5.07 11.0
Butanethiol 1170 0.09 9.7 70 + 5.54 12.1
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18

4. Stcreochemistry of thermolysis of (+)-(S)-7at 100 'C in benzene

TABLE

(-)-(R)-16 11
(+)-(S)-7 Concentration Butanethiol, - --
(mg) (M) (MI mg Rotation Retention (Y,) mg 1310~~"

a(c 2.2-2.7, CHIOH).

b z D 2 5t 35.5' (neat, 1 1 dm), 8 4 Z optically pure.
Copticallypure material has ED*^ - 24.3' (neat, I 1 dm) (22a) and [a143623- 55.5 (226).
dz,22 T 14.0' (neat, I 1 dm), 33Z optically pure.
For personal use only.

e ( - ) - ( R ) - 7 \+as actually used, [ r ~ l -

, ~
82.9'
~ ~(c ~
0.567, CCI,). The material uas heated for 22 h, 700 mg recovered material had [ z ] , , , ~ ~
- 81.4" (c 0.631, CCI,).

pentane. In neat butanethiol the degree of
retention is also -12x. These results are very
similar to those obtained on thermolysis of 1
and 2. There is a higher degree of retention in the
presence of butanethiol because no racemic
coupling product is formed outside the initial
solvent cage as in unscavenged runs.
The stereochemistry of the coupling product
obtained from thermolysis of (+)-(S)-7 could not
be determined. Even the isolated product from
scavenged runs had no observable rotation at
3 10 nm, the position of the peak in the ord curve
of optically pure (-)-(S)-11. At the maximum
concentration of coupling product that could be
used without overloading the photomultiplier,
product with an optical purity of 15% would have
given a reading on the ord instrument of -0.05".
This is similar in magnitude to the baseline noise
of the instrument. Thus, the optical purity of the
coupling product is less than 15%.
Fortunately, the 2-phenyl-2-butyl radical pro-
duced in the reaction is also converted to another
product with a chiral center, (-)-(R)-16, which
has an observable rotation. Only in the presence
of scavenger was enough (-)-(R)-16 produced to
be isolated. The optical activity of this product is
due entirely to that fraction of the product that
was formed by disproportionation in the original
solvent cage. Since scavenging of the 2-phenyl-2-
butyl radicals that escape from the original
solvent cage must produce (+)-I6 the amount of
retention of (-)-(R)-16 formed in the cage must
be greater than that indicated in Table 4. The
relative amounts of material formed inside and
outside the solvent cage were not determined but
a reisonable estimate can probably be made. For
the 2-phenyl-2-propyl-cyclohexyl radical pair the
ratio of the rate of disproportionation to 2-
phenylbutane and cyclohexene to the rate of
coupling is estimated to be 0.24 (23). This ratio
for the 2-phenyl-2-butyl-2-propyl radical pair
should be quite similar. From the relative yields
of ( f)-I6 ( 6 4 9 and (+)-I1 (362) formed in the
presence of butanethiol it can be reckoned that
-0.24 x 36/64 = -3 of the total (f)-I6 was
formed in the original solvent cage. Thus, the
(-)-(R)-16 that was formed from (+)-(S)-7 in
-
the original solvent cage was produced with
5-9x net retention of c~nfiguration.~
Recovery of ( - )-(R)-7 after heating at 100 "C
in benzene for one half-life of decomposition
gave product with 1.8x lower rotation than that
of starting material. Since the experimental error
4A radical disproportionation giving product with a
high degree of retention has been observed already. Cage
disproportionation during thermolysis of an optically
active diacyl peroxide produced product with 31-37% net
retention of configuration (24).
 1008 C A N . J. CHEM. VOL. 55, 1977
must be of nearly the same magnitude there is no
evidence that (-)-(R)-7 racemizes during ther-
molysis.
Thermolysis of (*)-I2 produced no coupling
product, 2-(4-nitropheny1)-2-phenylbutane 27 so
the only stereochemical result sought was
whether (-)-(R)-12 racemized during thermoly-
sis. Recovered (-)-(R)-12 showed no loss of
optical activity after heating at 175 "C for 3.5
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18
half-lives of decomposition in cumene. After this
experiment had been performed it was reported
that optically active 28 racemized during pho-
tolysis (6c,d). The photolysis of (+)-(S)-12 was
then carried out. Starting material was recovered
after 4097, decomposition in hexane or 6 0 2
decomposition in hexadecane at 15 "C with no
For personal use only.
loss of optical activity. In hexadecane a 3"7,ield
of coupling product 27 was formed which
showed no optical activity. No attempt was made
to isolate the Z-isomer of (+)-(R)-12.
Discussioii
The main purpose of this study was to deter-
mine whether 7 and 12 underwent thermolysis by
a concerted two-bond [ l ] or a stepwise one-bond
[2] cleavage process. The lack of racemization of
the optically active isomers during thermolysis
provides no support for the stepwise process.
Stereochemical evidence obtained recently indi-
cates that thermolysis of (-)-(S)-29 proceeds by
CH,
F2H5 I
(-)-(5)-29 30
a one-bond cleavage process to give, initially, the
diphenylmethyl-2-butyldiazenyl radical pair (21).
Viewed in this light thermolysis of 12 also would
be expected to proceed in a stepwise manner. The
aryl-N bond of 12 is much stronger than the
2-butyl-N bond of (-)-(S)-29 and the difference
in the strengths of these two bonds probably is
greater than the difference in the strengths of the
other two C-N bonds of the two diazenes.
Evidence in support of one-bond cleavage in the
thermolysis of 12 is the observation that no
coupling product 27 was formed. Had the 2-
phenyl-2-butyl-4-nitro-phenyl radical pair been
formed in the solvent cage some cage recombina-
tion very likely would have occurred as cage
recombination appears to be a reaction common
to all but the most bulky (25) of caged radical
pairs. The observation that the 2-isomers of 28
and 30 decompose thermolytically by a one-bond
cleavage mechanism (6c, 6d, 9) also lends support
to a one-bond cleavage process for thermolysis
of 12.
It is more diificult to determine from circum-
stantial evidence whether 7 undergoes ther-
molysis by a one- or two-bond cleavage process.
The enthalpy of activation for thermolysis of the
structurally analogous compound 13,36 kcal/mol
(17), is within experimental error of that for 12.
Thus, breaking of the 2-propyl-N bond of 7 does
not appear to be important in the rate deter-
mining step. Cage coupling product still could be
formed as a result of a one-bond cleavage
process if the 2-propyldiazenyl radical has a very
short lifetime. It appears that the 2-butyl-
diazenyl radical decomposes within the original
solvent cage (21). Most of the chemistry of 7 can
be accounted for in terms of either a one- or a
two-bond cleavage process. Only the enthalpy of
activation seems to be in favor of a one-bond
cleavage process although arguments in favor of
a concerted cleavage for 13 have been made (17).
The lack of racemization of (+)-(S)-7 and,
especially, of (-)-(R)-12 during thermolysis
contrasts with the reported racemization of
optically active 31 (6a) and 32 (6b). It is clear that
racemization does not necessarily occur during
thermolysis of optically active diazenes that
cleave by a one-bond mechanism.
The lack of racemization of (+)-(S)-12 during
photolysis was also surprising in view of the

racemization of optically active 28 under essen-
tially identical conditions. The latter compound
Is ison~erized on photolysis to the thermally
labile 2-isomer which then decomposes thermally
by a one-bond cleavage process. Recombination
of the 2-phenyl-2-butyl radical pair leads to
partially racernized starting material ( 6 4 . The
reason for the difference in behavior of (+)-(S)-12
is not clear and a discussion of the possible
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18
factors involved would be premature before the
2-isomer is isolated and studied.
The ratio of the rate constant for coupling (or
disproportionation) of the caged radical pair to
that for rotation of the 2-ghenyl-2-butyi radical
with respect to iis caged partner, kc/kr,can be
estimated for the radicals derived from (-)-(19)-4
and (+)-(S)-7[Q] (I),
retention
inversion cage
where F is the fraction of radicals which are
consumed by coupling and disproportionation
For personal use only.
before diffusion froin the original solvent cage
and f is the fraction of radicals consumed in this
way that undergo disproportionation. Accurate
determinations of the cage effects were not
carried out but reasonable estimates for the
range of cage effects can be made. For (-)-(R)-4
the minimum value is 15%, the absolute yield of 6
formed in the presence of scavenger. There is
very little disproportionation. This value is lower
than the values of the cage effect found for 1,
2530% at 110 "C (I), 2, 28% at 105 'C (2, 26),
and 33, 21Y,, extrapolated to 110 "C (27). The
actual cage effect is thus in the range 15-30%.
For (+)-(S)-7 the minimum value is 21%, the
absolute yield of 11 formed in the presence of
scavenger. However, a large amount of dispro-
portionation must also take place. By analogy to
the 2-phenyl-2-propyl-cyclohexyl radical pair
(23) about 1.5 times as much disproportionation
as coupling occurs and the actual cage effect for
(+)-(S)-7 must be -50z. For the radical pair
derived from ( - ) - ( R ) - 4 , kc/k, is in the range
0.04-0.08 at 110°C in benzene and for the
radical pair derived from (+)-(9-7, kcjkr is
0.02-0.04 at 100 "C in benzene. In the latter case
kc actually represents the rate constant for
disproportionation to (-)-(R)-16 and propene.
These values for kc/k,are similar in magnitude to
those, -0.06-0.10, found for the radical pairs
derived from 1 and 2.
Y ET AL. 1009
Experimental
Boiling points and melting points are uncorrected.
Infrared spectra were recorded on Perkin-Elmer model 421
or model 337 recording infrared spectrophotometers.
Ultraviolet spectra were measured on a Bausch and
Lomb Spectronic 600 spectrophotometer. Nuclear mag-
netic resonance spectra wcre recorded on Varian analy-
tical spectrometers, models A-60 and A-56/60, Tetra-
methylsilane was used as internal reference. Neat optical
rotations were taken with a Rudolph polarimeter model
80 and solution optical rotations were taken with a
Perkin-Elmer 141 polarimeter. Optical rotatory dispersion
curves were taken on a Japan Spectroscopic Company
spectropolarimeter model 0RD;UV-5. Gas chroma-
tography was carried out on Aerograph 202 and A90-P3
fractometers with a 6 ft x & in. stainless steel column
packed with 20% SF96 on 6C,'80 Chromosorb P, column
A, or with 10% Carbowax 20 M on 60180 Chromosorb P,
column B.
Chlorobenzene and bromobenzene were purified by
successive shaking with three portions of sulfuric acid,
two of water, and two of sodium bicarbonate. The
materials were dried over magnesium sulfate and distilled
from phosphorus pentoxide through a 4 ft Podbielniak
column or a 24 in. Nester-Faust annular Teflon spinning
band column. Middle fractions were collected and stored
over molecular sieves. Aliquots were distilled from the
stored solutions just before use. Benzene, cumene, and
cyclohexane were purified and stored in the same manner
except that they were distilled from sodiumwire. Diphenyl
ether was recrystallized twice from pentane.
j i/ -I-(I-Meth~~lefkylidene)-2-(2-p/zenyl-2-bcrtyl)diuzc~~ze
A mixture made from 20 g (2-phenyl-2-buty1)diazane
(28), bp 90 "C11.4 torr, nDZ51.5365 (lit. (28) bp 81-84
'C10.4 torr, nD2' 1.5354), 7.5 g magnesium sulfate, and
133 ml acetone was stirred under nitrogen at 45 'C for 2 h
and then at 23 'C for 12 h. The reaction mixture was
-filtered, concentrated, and distilled to yield 21 g (84%) of
a light yellow oil bp 82 "C/0.6 torr; nDZ71.5219; nmr
(CCI,) r 2.75 (m, 5.OH), 5.5 (br, 0.7H), 8.15 (q, J = 7.5
Hz,2H),8.17(~,3H),8.34(s,3H),8.65(~,3.1H)and9.35
(t, J = 7.5 Hz, 3.0H).
( _+ ) - I - (2-Phenyl-2-butylj -2- (2-propj~l)diuzene,( _+ ) - 7
A solution of 2.0 g (0.01 mol) of the above hydrazone
in 20 ml ether was added over 3 h to 0.50 g (0.013 mol) of
lithium aluminum hydride in 100 ml ether. The reaction
mixture was stirred under nitrogen at reflux for 3 days and
then hydrolyzed by successive addition of 0.5 ml water,
1.0 ml 10% potassium hydroxide, and 0.5 ml water. The
mixture was filtered and the filtrate was stirred in an un-
stoppered f ask for 8 h, then washed with water, dried over
sodium carbonate, and concentrated. The residue was ad-
sorbed on a 30 x 1.5 cm column of neutral alumina. A
green band was eluted with 50 n ~ pentane.l Solvent was
removed and the residue kept under vacuum as a thin
film for several hours to leave 1.1 g (55%) of a green oil,
nu2' 1.4932; ir (CCI,) 1580cm-' (N=N, weak); A,,
(ether) 368 nm, log E 1.46; nmr (CCl,) r 2.62 (m, 5.OI-i),
6.25 (septet, J = 6.5 Hz, 1.0H) 8.04 (q, J = 7.5 Hz,
2.2H), 8.62(s, 3.3H), 8 . 7 5 ( d , J = 6.5Hz,6.lH),and9.34
(t, J = 7.5 Hz, 3.lH).
 1010 C A N . J. CHEM. VOL. 5 5 , 1977

distillation apparatus to yield 0.9 g (61%) of a colorless

oil, bp 107-110 "C/23 torr; nDZ51.5103; ir (CCI,) 1635
Reduction of 30 g of (i)-1-(I-methylethy1idene)-2-(2- and 895 cm-' (=CHz); nnir (CCI4) r 2.8 (s, 5.1H), 5.05
phenyl-2-butyljdiazane was carried out as described above (s, 1.9H), 8.12 (q, J = 7 Hz, 2.1H), 8.52 (s, 3.1H), 8.66
except that the reaction mixture (1500 ml), after hydroly- (s, 3.1H), and 9.21 (t, J = 7 Hz, 3.OH). Anal. calcd. for
sis, was filtered into a 2 !flask which contained a cold C13H18:C 89.58, H 10.41; found: C 89.80, H 10.60.
solution of 45 g dibenzoyl tartaric acid (29); mp 89-90 "C;
[rIDz5-115.3' (c 1.03, methanol) (lit. (29) mp 89-91 "C; ( + ) -(S) -2,3-Dimefhyl-3-phenyl-I-pentene, (+)-(S)-10
[rIDz5- 112.5' (30)). Eight grams of precipitate formed A sample of (-)-(R)-2-methyl-2-phenylbutanoic acid
immediately. The remainder of the solution was allowed (31) of [aIDZ5-29.06- (c 4.8, benzene) (lit. (31) [aIDz5
to stand at 5 'C for 48 h to give 20 g of crystals. The two - 30.0" for optically pure material) was converted to the
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18

crops were recrystallized separately twice from 2 : 1 crude 2-acetoxy-2,3-dimethyl-3-phenylpentaneas de-

ethanol-water, 10 ml/g of crystals, to give 1.3 g and 7 g scribed above. This acetate, which was prepared from
of white, slender needles. Both batches had mp 109-110 ketone free alcohol, was pyrolyzed as described above to
"C; [aIDZ5- 65.2' (c 1, chloroform). Further recrystalliza- give the product bp 105-109 "C/21 torr; nDZ91.5101; rDz5
tion did not change the rotation of the salt or that of the + 11.3" (neat, 1 1 dm) whose ir and nmr spectra were
diazene prepared from it. Anal. calcd. for C31H36N,0,: identical to those of the racemic material.
C 65.94, H 6.43, N 4.96; found: C 65.65, H 6.23, N 5.08. ( i.) -2,3-Dirnethyl-3-phei1.v11,e1zfa1ze,( f ) -11
The dibenzoyltartrate salt (3 g) was treated with 20 ml A mixture of 1 g ( f i-10 in 20 ml ethanol and 0.1 g 5%
10% potassium hydroxide solution and the hydrazine was rhodium on alumina was stirred under hydrogen in a
extracted into ether (2 x 20 ml). The csmbined ether microhydrogenation apparatus for 24 h. The theoretical
cxtracts were washed with water, dried, and the hydrazine amount of hydrogen was consumed after 1 h and no
oxidized to the azo compound, which was isolated as more was taken up. The catalyst was filtered, the solvent
described for the preparation of (2)-7, to give 0.65 g oil; removed, and the residue distilled through a micro-
nDZ51.4934; rDZ5 f 35.5' (neat, I 1 dm); ord (c 0.25, dist~llationapparatus to give a colorle~soil, bp 105-107
cyclohexane) [@I,,, +98', + 130U,[@Isoo+230 , 'C 21 torr; nDZ71.5012; nmr (CC1,) r 2.86 (s, 5H), 7.9-
[@I450 +40gC, [@I410 +980°, [@I398 + 111Oo, [@I380
For personal use only.

+506', [@I,,, o', [@I360 -945', [@I346 -127", [@I310
- 620'. Anal. calcd. for Cl,H2,N2 : C 76.42, H 9.87, N
13.71; found: C 76.12, H 9.86, N 13.86.
( t ) -2-Acero.ry-2,3-dimethyl-3-phenllpen/ane
A solution of 13 g (0.066 mol) of 2-methyl-2-phenyi-
butanoyl chloride (31) in 90 ml ether was added to a
rapidly stirred solution of methyllithium, made from 3.7 g
(0.53 mol) lithium and 37.5 g (0.264 molj methyl iodide in
200 ml ether, at -60 'C. The reaction mixture was al-
lowed to warm to 0 'C, 100 ml saturated ammonium
chloride solution was added, and the aaueous solution was
extracted with ether. The combined ether solutions were
successively washed with solutions of sodium bisulfite
and sodium bicarbonate, water, and then dried. The ir
spectrum of the oil obtained on concentration of a
portion of the ether solution showed moderate carbonyl
absorption (1710 cm-') so the entire solution was treated
with excess methyllithiurn and the reaction mixture
worked-up as described above. The ether was removed to
give 12 g of an oil which was acetylated (32) with acetyl
chloride to give 8.5 g (55%) of product, bp 88-89 'C/0.4
torr; nDZ51.5034; nmr (CCl,) r 2.8 (m, 5.1H), 7.75 (m,
2H), 8.14 (s, 3H), 8.55 (s, 3Hj, 8.66 (s, 6K), and 9.33 (t,
J = 7.5 Hz, 3W). Anal. calcd. for C151-12282:C 76.88,
H 9.46; found: C 77.06, H 9.17.
( t) -2,3-Dimethyl-3-p11enyl-l-pentene, ( i.) - l o
A solution of 1.9 g of the above acetate in 10 ml
methanol was pyrolyzed by dropwise addition (33) into a
heated 1 in diameter glass tube filled to 12 in with glass
helices. The optimum conditions were determined by
pyrolyzing small quantities of the solution and analyzing
the pyrolysate by gc. An equal volume of water was
added to the pyrolysate and the resulting mixture shaken
with ether (2 x 20 mi). The combined ether extracts were
shaken with sodium bicarbonate solution, dried, and
concentrated. The residue was distilled through a micro-
8.7 (m, 3H), 8.83 (s, 3H), 9.10 (d, J = 6.5 Hz, 3H), 9.35
(d, J = 6.5 Hz, 3Hj, and 9.31 (t, J = 7 Hz, 3H). Anal.
calcd. for C1SHZO: C 88.57, H 11.43; found: C 88.89, H
11.48.
f -) -(S) -2,3-Dimethyl-3-phenyl-I-penfane,( -) -(S)-I1
+
Hydrogenation of (+)-(S)-10, rDZ511,3",as described
above afforded (-)-(S)-11, bp 108-111 T I 2 3 torr; nDZ6
1.5012; aDZ5-0.4' (neat, I 1 dm); ord (c 1.05, methanol)
-13-, -34-, -58', -42',
[@Iz,, 0". Analys~sby gc showed that the compound was
> 98% pure and contained no starting alkene.
Hj~drogenolysisof ( + ) - (S) - 7 to ( - ) -2-Phenyl-2-bufyi-
amine, (-)-(S)-8
+
A solution of 1.O g (+)-(S)-7, aDZ5 35.gC(neat, I 1 dm),
in 100 ml methanol was stirred over 4.5 g of W-2 Raney
nickel under a hydrogen atmosphere at 22 'C. After 4 h
hydrogen uptake ceased when nearly 1 equiv. was taken
up. The contents of the flask were then held under reflux
for 11 h. The catalyst was filtered, the methanol removed,
and the residue taken up in ether. The ether solution was
extracted with hydrochloric acid and the acid layer made
basic with potassium hydroxide solution. The resulting
mixture was shaken with ether and the ether layer dried
over potassiun~carbonate and concentrated. The product
was collected from the effluent of the gas chromatograph
to give 200 mg of (-)-(S)-8; nDZ5 1.5146; rDZ5 -14.0'
(neat, 1 1 dm) (lit. (29) nDZ51.5148; - 18.2' (neat,
I 1 dm)).
( - )-(S)-2-Phenyl-2-butylan?ine, ( -) -(S) -8
Using the reported procedure (28) (+)-(S)-2-methyl-2-
phenylbutanoic acid [%IDZ5 + 6.60' (c 4.8, benzene) 22%
optically pure was converted to (-)-(3-8, aDZ5 - 3.42"
(neat, 1 1 dm). On this basis optically pure (-)+)-ti
would have aDZ5-15.7- (neat, 1 l dm) (lit. (34) aDz5
+ 16.8"(neat, I 1 dm) for ( + ) - ( R ) - 8obtained by resolution
of the maleate salt).
 KOPECKY ET AL.
( j -1-Benzj~l-2-
(2-phenyl-2-butyl) diazane
A mixture of 2.5 g (0.015 mol) (2-phenyl-2-buty1)di-
azane (28), 0.6 g (0.015 mol) benzaldehyde, 2 g mag-
nesium sulfate, and 20 ml anhydrous ether was stirred for
4 h and then filtered. The filtrate was hydrogenated under
1 atm over 0.4 g 5% palladium-on-charcoal until 1 equiv.
of hydrogen had been taken up. The mixture was filtered
under nitrogen and the residue, after removal of solvent,
was distilled to give 2.7 g (67%) of a colorless viscous oil,
bp 130-132 "C10.2 torr; nDZ51.5582; nmr (CCI,) 7; 2.6-2.9
(ni, 10.1H), 6.20(s, 1.8H), 6.77 (br s, 2.OH, NH), 8.3
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18
(q, J =7.5 Hz)and 8.56 (s) (total 5.2H)and 9.32 (t, J =7.5
Hz, 3.1H). This material was readily oxidized by air and a
satisfactory analysis was not obtained.
( i- )-l-BenzyI-2-(2-p~~enyl-2-bufyl)&zer~e,
( i 1-4
A solution of 0.6 g of the above diazane in 50 ml ether
was allowed to stand under an atmosphere of oxygen for
20 h, then washed uith water and dried over potassium
carbonate. Removal of the ether under reduced pressure
left 0.45 g of a yellow oil, nD" 11.538; nmr (CDCI,) r 2.66
(s, lO.OH),4.97(s, 2H),7.98(q, J = 7.5 Hz,2.1H), 8.57
(s, 3.1H), 9.30 (t, J = 7.5 H L , 3.0H). Anul. calcd. for
C1,HZON2:C 80.91, H 7.99, N 11.10; found: C 80.46,
80.66, H 7.67, 7.68, N 11.06.
I-) -(R) -1-Benzyl-2-(2-yhenJ~I-2-butyl)diazene, (-1 -(R)-4
For personal use only.
This material was prepared as described for the raceinic
compound from (+)-(R)-3 (28), r5,6253.52" (neat, 1 washed several times with water and dried over potassium
1 dm), 26% optically pure (28). The product, nDZ51.5528, carbonate. The crude methyl ether left after removal of
had a n nmr spectrum identical with that of ( i ) - 4 ;
[c(]DZ5 - 12.88", [ ~ ] 5 4 -
6 ~16.6OZ,
~ [X]43625-66.8OC(c2.95,
C6H6);ord (c 32.8, C 6 H 6 ) [@I5,, - 165', [@Iso0-230°,
[@I450 -46OC, [@I400 -I28OC, [@I375 oC, [@I350 1680Ci mixture was added slowly until all the alloy was decom-
[@I300755'.
f +)-(Sl-4
The mother liquor from the first crystallization of the
dibenzoyl tartrate salt of ( i ) - 3 (28) was evaporated and
from the residue was isolated (-)-(S)-3, r546Z5 -2.04"
(neat, I 1 dm), 15% optically pure. This product was con-
verted to the benzyl derivative, as described above, which
was dissolved in a saturated solution of oxalic acid in
ethanol. After several days at 5 'C crystals of the oxalate
salt were filtered, treated with aqueous potassium
hydroxide, and the hydrazine taken up in ether. Oxidation
of the hydrazine with oxygen produced (+)-(S)-4, [nIDz5
$28.0" (c 1.25, C6H,), 56% optically pure. A further
batch of the oxalate salt was obtained after concentration
of the mother liquor and converted to the diazene, [zIDz5 nitrogen at 50 'C for 36 h. The mixture was then cooled
0.00 ( c 1SO, C6H6).Thus, the oxalate salt had undergone
spontaneous resolution,
(-1 - i s ) -(2-P/1enj'l-2-b11tyl)dirrzane,
(-) -(S) -3
A solution of 36.0 g (0.166 mol) nienthyl chlorocar-
bonate (35) in 100 ml ether was added simultaneousiy
with a separate solution of 19.2 g (0.19 mol) triethylamine
to a stirred solution of 27.3 g (0.166 mol) (f)-3 (28) in
150ml ether under nitrogen. The reaction mixture was
stirred overnight and filtered. The filter cake was washed
with ether and the combined ether solutions were eva-
porated to give 58 g of a viscous oil. Five crystallizations
at 0 "C from methanol, containing a little water gave
material of constant rotation [a],,,2"220' (c 1.03, j - ) - ( R )- I-i4-n7ti.o~1/rer~'I)
CC14). Filtration was carried out at 0 ' C and the crystals
were quickly pressed dry. The crystals melted at -- 15 'C.
1011
At 0 "C they turned to syrup after a few minutes exposure
to air. A satisfactory analysis was not obtained.
A solution of 20 g of this resolved product and 20 g
potassium hydroxide in 100 ml methanol was heated
under reflux for 4 h and then evaporated to one half its
volume. The residue was acidified with dilute hydrochloric
acid and the resulting mixture extracted with ether. The
aqueous layer was made basic with dilute sodium hy-
droxide and extracted with ether. The ether layer was
dried under nitrogen with sodium sulfate and concen-
trated to an oil. The oil was distilled to give 3.2 g product,
bp 68-69 'C10.2 torr; nDZ51.5350; xoZ5 - 11.56- (neat, 1
+
1 dm) (lit. (28) for (+)-(R)-3, r546Z511.8" (neat, i 1 dm)
for material 80% optically pure).
( + ) - (S) -1,2-D@henj~i-2-inerhylbutnr2e,( + ) -(S) -6
A sample of (-)-(R)-2-methyl-2-phenylbutanoicacid
(31), [%]Dz5-29.6' (c 4.8, C6H6),98% optically pure, was
converted (13) to (-)-(R)-l,2-diphenyl-2-methyl-l-b~1ta-
none, nDz5 1.5705; [x],'~ -61.1' (C 6, benzene) (lit. (13)
nDZ51.5700, aDZ5-63.7' (neat, 1 ! dm)). The ketone was
reduced to the alcohol with lithium aluniinuni hydride
(13). A mixture of 2.0 g (0.009 mol) of the crude product,
2.5 g (0.017 mol) iodomethane in 100 mi dimethoxy-
ethane, and 0.3 g (0.014 mol) sodium hydride \+as stirred
for 4 h and then heated for 3 h under reflux. Water was
added to the cooled reaction mixture and the resulting
mixture was extracted with ether. The ether layer was
the ether was stirred with 2 ml sodium potassium alloy in
100 ml ether under nitrogen for 24 h at 21 'C. The red
solution was then cooled to 0 "C and a methanol-ether
posed. The reaction mixture was shaken with water and
the ether layer dried over potassium carbonate and con-
centrated. The product was isolated from the effluent of
the gc (column A); nDZ6.51.5584; [c(]DZ5 +78.3"; [c(]546z5
+
+94.7', [s(]43625 178" (C 4.7, C6Hs) (lit. (12) nDZ5
+
1.5550; rDz567" (neat, 1 1 dm)); ord (c 4.7, C 6 H 6 ) [ @ ] 6 0 ~
118", [ Q I S ~ +167",
O [@I500 +224=, [@I450 +326', [@I400
+ +
50OC,[@I350 880C,[@]300 1835^. +
( + ) -1-(4-1Vitrophenyl)-2-(2-yhenyl-2-butyljdiuze~1e,
(+)-I2
A mixture of 1.64 g (0.01 mol) ( 1 ) - 3 , 1.4 g (0.01 mol)
4-fluoronitrobenzene and 1.68 g (0.02mol) sodium
bicarbonate in 6 ml dirnethyl sulfoxide was stirred under
and filtered. The filtrate was stirred under air for 12 h a n d
then diluted with 20 ml ether. The resulting mixture was
shaken several times with water and the ether layer dried
and concentrated. The residue was chromatographed on a
1.5 x 15 cni column of n e ~ ~ t r aalumina.
l Elution with
50 mi ether followed by concentration of the eluate
under vacuum yielded 1.8 g (65%) or a red oil, 1zDZ5
1.5830; nmr (CCI,) T 1.71 (d, J = 8.8 Hz, 2H), 2.21
(d, J = 8.8 Hz, ZH), 2.63 (m, 5H), 7.86 (111, ZH),8.42
(s, 3H), 9.22 (t, J = 7.0 Hz. 3H). Anal. calcd. for C16H17-
N,O,: C67.84, H6.01, N 14.84;found: C67.74, H6.12,
N 14.87.
-2- (2-phenjl-2-bur? lld~azene,
(-)-(R)-12
The procedure used was identical to that for the pre-
 1012 CAN. J. CHEM. VOL. 5 5 , 1977

paration of the racemic compound except that (+)-(R)-3 500 mg (-)-(R)-12 (nDZ51.5910; - 108.8' (C 1.09,
+
(28), [aIDz5 11.6' (c 1.04, CHCI3) was used. The CHCl,)) in 30 ml cumene in a stainless steel bomb which
product had nDZ51.5910; [aIDz5- 109" (C 1.09, CHCI,). was then sealed and heated at 175 "C for 5 h. Cumene was
distilled under reduced pressure and the residue was
+
( ) - (s)-1-(4-Nitrophenfl -2- ( 2 - p h e n ~ > l - 2 - repeatedly chromatographed on activity I alumina using
(+)-(S)-12 benzene-hexane as eluent until pure (tlc, nmr) (-)-(R)-12,
This material was prepared from (-?-(S?-3, aDZ2 31 mg, was eluted, nDZ5 1.5898; [r]D25 - 111.7" (C 1.02,
- 11.6" (neat, 1 1 dm) and had nDZ61.5910; [r1IDz5+ 120" C H C I ~ ) ,
(C 0.582. CHClql.
Photolysis of (+)-(S)-12
( F ) -2-(4-Nitrophenq.1)-2-phenylbutane, ( i:)-27 A solution of 400 mg (+)-(S)-12 (nDZ51.5902; [ciIDz5
A mixture of 1.0 ml concentrated nitric acid, 1.2 ml +
110.2- (c 0.448, CHC13)) in 50 ml hexadecane was
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18

concentrated sulfuric acid and 2.0 g 2,2-diphenylbutane photolyzed at 15 "C under nitrogen in an immersion
(36) was stirred at 6 0 L C for 20 min. The mixture was apparatus fitted with a Pyrex filter using a medium
poured into 200 ml water. The water was extracted twice pressure 200 W Hanovia lamp until 60% of the theo-
with hexane, the combined hexane layers dried and retical amount of nitrogen had been evolved. The reaction
concentrated, and the residual oil chromatographed on a mixture was concentrated under vacuum and the residue
1.5 x 10 crn column of activity 2 alumina using 1 : 1 was chromatographed on 75 g activated alumina which
hexane-benzene as eluent. The first 30 ml of eluent con- had been heated over the full heat of a Bunsen burner for
tained 700 mg starting material; the second 30 ml con-
tained 250 mg of product contaminated (gc) by - 4 h. The column was washed with 1.2 !pentane and then
10% with pentane containing increasing amounts of benzene.
starting material; the third 30 1111 afforded 650 mg of pure Benzene-pentane, 1 : 1, removed pure (tlc, nmr) (+)-(S)-
(gc) product on evaporation; nDZ91.5819; nmr (CCI,) T +
12, 60 mg, nDZ51.5895; [rIDZ5 111" (C 0.130, CHCI3).
1 . 9 6 ( d , J = 8.5Hz,2H),2.71 ( d , J = 8.5Hz,2H),2.87
(n?, 5H), 7.85 (m, 2H), 8.40 (s, 3H), 9.28 (t, J = 7 Hz).
In a similar way 236 mg (+)-(S)-12, [aIDz5 120- (c +
0.400, CHCI,), was recovered from photolysis of 900 mg
Anal. calcd. for C1,HI7NO2: C 75.29, H 6.67, N 5.49; of the diazene, [aIDz5+ 119" (c 0.590, CHCl,), in hexane
found: C 74.97, H 6.67, N 5.69. for 9 h until 40% of the theoretical amount of nitrogen
For personal use only.

Hj,drogenolysis of (+ j -jS)-l-(2-P/~enyl-2-butyl)-2-(2- had been evolved.

propyl)diazene, ( + ) -S-12
A solution of 1.0 g (+)-(9-12, aDZ5435.5" (neat, I from the chromatographies containing impure diazene
1 dm) in 100 ml methanol was hydrogenated using 4.5 g
Raney nickel at 25 "C under 1 atm. Nearly 1 equiv. of
hydrogen was consumed in 4 h when hydrogen uptake
ceased. The mixture was then heated under reflux for 11 h,
cooled, filtered, and the filtrate concentrated to an oil.
The oil was taken up in ether and the resulting solution
shaken with hydrochloric acid. The aqueous layer was
made basic and then extracted with ether. The ether layer
was dried over potassium carbonate, concentrated to a n
oil, and the product isolated from the effluent of the gc
(colun~nA) to give 200 mg (-)-(S)-8, nDZ51.5146; aDZ5
- 14.0" (neat, I 1 dm). Based on the calculated rotation of
aDZ5- 15.7' (neat, 1 1 dm) for optically pure material as
described above the product was 89% optically pure.
Interrupted Tlzern~olysisof ( - j -(R)-7
A solution of 1.4 g (-)-(R)-7, tzDZ2 1.4947, in 300 ml
benzene was divided equally among three 150 ml pressure
bottles. The solutions were boiled for several minutes and
the bottles closed and kept at 100 "C for 22 h. The solu-
The recovered diazenes were combined with fractions
and the resulting mixture photolyzed in hexadecane until
n o more diazene remained (tic). I t was necessary twice to
remove a brown precipitate when nitrogen evolution
ceased before the photolysis was complete. The photo-
lysate was concentrated and the residue chromatographed
on a 100 x 1.2 cm column of silica gel using pentane as
eluent. A sample, 44 mg (373, of pure (tlc) 27 was iso-
lated, [r]36525O.OO(c 0.18, CC14).
Thertnolysis of ( + ) -(S)-4 and (-)-(R)-4
A solution of 0.97 g of (+)-(S)-4, [aIDZ5f 2 8 . 0 ' (c 1.25,
C6H6), and 4.7 g butanethiol in 50 ml benzene in a
stainless steel bomb was flushed with nitrogen. The bomb
was closed and heated at 102 'C for 30 h, then cooled, and
the contcnts evaporated under reduced pressure. The
residue was fractionated by gc using column A. Material
which eluted at the retention time of ( i ) - 6 was collected
and found to consist of a liquid and a white solid. This
mixture was refractionated using column B to two
separate compounds, a small amount of E-19, identified

-
tions were combined and concentrated through a 4 ft
Podbielniak colun~nto 20 ml volume. The residue was
taken up in pentane. Most of the benzene was removed by
a series of crystallizations from this solution at -78 "C,
concentrating the solution after each crystallization. The
final residue was chromatographed on 30 g silica gel at
-30 "C. The hydrocarbon products were eluted with
pentane, and 2% ether in pentane removed pure (tlc,
nmr) (- )-(R)-7,0.70 g, nDZ21.4958. The coupling product
11 was isolated from the concentrated pentane eluent by
gc, column A at 170 'C and 150 ml/min He flow. Rota-
tions are given in Table 4.
Interrupted Thermolysis of (-)-(,?)-I2
Nitrogen was bubbled for 10 mill through a solution of
by its nmr spectrum and gc retention time on both
columns, and ( - ) - ( R ) - 6 , [aIDz5- 4.6' (c 1.8, C6H6),which
was formed with 10.7z retention of configuration.
The same procedure was used for the thermolysis of
(-)-(S)-4. The concentrated reaction mixtures were
fractionated directly with column B. The results arc
presented in Table 3.
Thern~oljsisof (+ )-is) -7
Benzene solutions of (+)-(S)-7 were heated under
nitrogen in a stainless steel bomb as described above.
After 10 half-lives of decomposition the solvent was
distilled slowly through a Vigreaux colun~n.Traces of
alkene were removed by heating the residual oil in a
solution of 10 ml acetic acid containing 2 ml trichloro-
 KOPECKY ET AL. 1013

methylsulfenyl chloride at 85 "C for 60 min. The reaction Kinetic Studies

mixture was taken up in 100 ml pentane and the pentane Rates of evolution of nitrogen from solutions of the
layer shaken 7 times with water, dried, and concentrated diazenes were measured using an apparatus and a pro-
by distillation through a Vigreaux column. The residue cedure similar to that described (39). Rate constants were
was chromatographed on 200 g of activated basic determined from the slopes of plots of log (V, - Vo/
alumina at 0 'C using pentane as eluent. The hydrocarbons V, - V,). The results are presented in Table 1.
11 and (-)-(R)-16 were isolated from the effluent of the gc
using column A. The results are presented in Table 4.
1. K. R. KOPECKY and T. GILLAX.Can. J. Chem. 47,
Pvoduct Studies
-
Solutions of 35 mg ( k ) - 7 in 0.4 ml benzene or 1 M
2371 (1969).
2. F. D. G R E E ~ M. E . A. BERWICK. and J. C. STOWELL.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 47.15.234.20 on 03/29/18

butanethiol in benzene were placed in glass tubes and J. Am. Chem. Soc. 92,867 (1970).
degassed by three freeze-thaw cycles under torr. 3. ((1) H. C. RAMSPERGER. J . Am. Chem. Soc. 51, 2134
The tubes were sealed and heated at 100 ' C for 130 h or at (1929); (0) S. G. C O H Eand ~ C. H. WAX. J . Am.
125 "C for 14 h. The reaction mixtures were then ad- Chem. Soc. 77, 3628 (1955); ( c ) C. G. OVERBERGER
sorbed on 5 g of neutral activity I alumina and the and A. V. DIGUILIO. J . Am. Chem. Soc. 81, 2154
alumina was washed with 15 ml pentane. Furthrr elution (1959); (cl) S. SELTZER. J . Am. Chem. Soc. 83. 2625
with pentane removed another material, presumably (1961): (r) S. SELTZER.J. Am. Chem. Soc. 85. 15
hydrazone, which interfered with subsequent analysis. (1963); ( f ) S. SELTZER and S. G. MYLONAKIS. J . Am.
The eluent was concentrated by distillation through a Chem. Soc. 89,6584 (1967); ( g ) J. HINZ,R. OBERLIN-
Vigreaux column, a known amount of bromobenzene was N E R . and C. RC'CHARDT. Tetrahedron Lett. 1975
added to the residue which was then analyzed by gc using (1973); ( h ) T. R . LYNCH.F . N. MACLACHLAN, and J.
column A (temperature programmed; initial temperature L . SUSCHITZKY. Can. J. Chem. 51, 1378 (1973).
90 "C, rate of increase 1.S0C/min, initial H e 90 ml/min). 4. (a) R. J . CRAWFORD and R. MISHRA. J . Am. Chem.
Calibrations were made using mixtures of known con- Soc. 87, 3768 (1965): ( h ) R . J . CRAWFORD and D. M.
centration in benzene. The products were identified on the c . 4 ~ ~ ~ Can.0 3 .J . Chem. 45. 691 (1967); (c) B. H.
basis of their retention times. Authentic samples of 17, Can. J. Chem. 46.
For personal use only.

AL-SADER and R. J. CR-\WFORD.

Z- and E-18 were prepared (37) as were ~neso-and dl-14 3301 (1968): (ci) K . R. KOPECKY and J . SOLER. Can. J .
(38), which were not separated under the gc conditions Chem. 52,2111 (1974).
used. In the decompositions at 125 'C the relative yield of 5. S. SELTZER and F. T . D U N N EJ.. Am. Chem. Soc. 87.
(*)-I6 was 2% lower and that of 14 was 3% higher than 2628 (1965).
in the decon:positions at 100 "C. The relative yields of the 6. ((I)A. TSOLIS.S. MYLONAKIS. M. NIEH.and S. SELT-
other products were the same at the two temperatures. ZER.J . Am. Chem. Soc. 94. 829 (1972); (0) R. A.
Solutions of (+)-4 in the various solvents were placed JOHNSON and S. SELTZER. J. Am. Chem. Soc. 95.938
in a stainless steel bomb and flushed for several minutes (1973); ((,) N . A. PORTER.M. E. L A N D I Sand . L. J .
with nitrogen. The bomb was closed and heated at 110 'C M..\RXETT.J. Am. Chem. Soc. 93.795(1971);(ci)N. A.
for 20 h. The reaction mixtures were analyzed directly by PORTERand L. J. MARZETT. J. Am. Chem. Soc. 95,
gc using column B (temperature progran~nled; initial 4361 (1973).
temperature 100 'C, rate of increase 3 'C/min, initial H e 7 . ((1) W. A. PRYORand K . SMITH.J . Am. Chem. Soc.
85 ml/min). The compounds were identified on the basis 92, 5403 (1973); ( b ) K. TAKACI and R. J. CRAWFORD.
of their retenrion times. In one case a known amount of J . Am. Chem. Soc. 94,7406 (1972); (c) A. W. G,ARNER,
bromobenzene was added just before analysis. Calibra- J. W. TIMBERLAKE. P. S . ENGEL, and R. A.
tions were made using mixtures of known concentration MELAUGH. J . Am. Chem. Soc. 97,7377 (1975).
in benzene. 8. R. C. N E U M N . JR.. G. D. LOCKYER. JR.. and M. J.
A solution of 700 mg ( & ) - I 2 in 7 g diphenylether was AMRICH. Tetrahedron Lett. 1221 (1972).
heated under nitrogen in a stainless steel bomb at 175 - C 9. (a) N. A. PORTER, L . J. MARNETT. C . H. LOCKMUL-
for 18 h. A known amount of dimethylaniline was added L E R . G. L . CLOSS,and M. SHOBATAKI. J. Am. Chem.
to the reaction mixture and this was analyzed by gc Soc. 94,3664 (1972): (O)N . PORTER, J. G. G R E E Nand
,
using colunln B (120 'C, H e 50 ml/min). Calibrations G. R . D U B ~ Y Tetrahedron
. Lett. 3363 (1975).
were made using mixtures of known concentration in 10. N. A. PORTER and M. 0 . F U N KChem. . Commun. 263
benzene. The volatile compounds were identified by mass (1973).
spectral analysis as they emerged from the gc. The mass 11. D. J . CRAMand J. S. BK.ADSHAW. J. Am. Chem. Soc.
spectral cracking patterns were conlpared to those of the 85. 1108 (1963).
authentic compounds. The amount of 25 formed was 12. D. J . CRAMand J . A L L I N G EJR. .Am. Chem. Soc. 79,
found by adding an aliquot of the reaction mixture to 2858 (1957).
hexane, collecting, and comparing (mp, ir) the precipitate 13. D. J . CRAMand J. AI-LINGER. J . Am. Chem. Soc. 76.
with an authentic sample of 65. 4516 (1954).
A 2 g sample of ( + ) - I 2 was heated at 175 ^C for 18 h 14. J. H. BREWSTER. J. Am. Chem. Soc. 81,5475 (1954).
under nitrogen in a 5 ml flask fitted with a condenser. 15. T . R. THOMPSOV. J . Am. Chem. Soc. 75,6070 (1953).
After cooling the residue was stirred several times with 16. P. S. EXGELand D. J. BISHOP.J . Am. Ghem. Soc. 97,
small amounts of hexane. The insoluble material, 0.67 g 6754 (1975).
(79%) was nearly pure 25. Dimethylaniline was added to 17. C. G. OVERBERGER and A. V. DIGUILIO.J . Am.
the combined hexane washings and the solution analyzed Chem. Soc. 81,2154 (1959).
by gc. 18. ((I)S. F. NELSONand P. D. BARTLETT. J. Am. Chem.
 1014 CAN. J. CHEM. VOL. 5 5 . 1977

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Chim. Pays-Bas 69, 312 (1950); ( b ) B. K. BANDLISH. Soc. 55,2605 (1933).
A. W. GARNER. M. L. HODGES.and J. W. TIMBER- 30. G. loss^. Chem. Ber. 87. 1279 (1954).
LAKE. J. Am. Chem. Soc. 97,5856 (1975). 31. D. J. CRAMand J . D. KSIGHT.J. Am. Chem. Soc. 74,
20. A. F. BICKEL and E. C. K O O Y X ~ ANature.
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For personal use only.
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