Preparation and reactivity of 1,3-bis(alkylthio)allenes and tetrathiacyclic bisallenes

Article abstract of DOI:10.1021/jo9915675

Reactions of Ph₂C₃ dianion, prepared from 1,3-diphenylpropyne and n- butyllithium, with alkyl thiocyanates or alkane dithiocyanates gave 1,3- bis(alkylthio)allenes 1 or tetrathiacyclic bisallenes 2, respectively. Thermal reactions of 1 gave thiophenes 4 and 7, benzothiepin 5, 1,2- bis(benzylidene)cyclobutane 6, thiete 8, and α,β-unsaturated ketone 9, and the reactions of tetrathiacyclic bisallenes 2a gave a cyclic dimer, 1,2- bis(benzylidene)cyclobutane derivative 10, quantitatively. Irradiation of 1,3-bis(alkylthio)allenes 1 and tetrathiacyclic bisallenes 2a caused rearrangement to give alkynes 18, 20, and 21. In the irradiation of the cyclic bisallenes 2a, isomerizations from dl to meso and meso to dl isomers were also found. In the reactions of allenes 1 and cyclic bisallenes 2a with diphenyl diazomethane, the diazomethane reacted selectively with the double bond rather than with the sulfur atom.

Full text of DOI:10.1021/jo9915675

J . Org. Chem. 2000, 65, 1721-1728
1721
P r ep a r a tion a n d Rea ctivity of 1,3-Bis(a lk ylth io)a llen es a n d
Tetr a th ia cyclic Bisa llen es
Toshio Shimizu, Kensuke Sakamaki, Daisuke Miyasaka, and Nobumasa Kamigata*
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University,
Minami-ohsawa, Hachioji, Tokyo 192-0397, J apan
Received October 7, 1999
Reactions of Ph2C3 dianion, prepared from 1,3-diphenylpropyne and n-butyllithium, with alkyl
thiocyanates or alkane dithiocyanates gave 1,3-bis(alkylthio)allenes 1 or tetrathiacyclic bisallenes
2, respectively. Thermal reactions of 1 gave thiophenes 4 and 7, benzothiepin 5, 1,2-bis(benzylidene)-
cyclobutane 6, thiete 8, and R,â-unsaturated ketone 9, and the reactions of tetrathiacyclic bisallenes
2a gave a cyclic dimer, 1,2-bis(benzylidene)cyclobutane derivative 10, quantitatively. Irradiation
of 1,3-bis(alkylthio)allenes 1 and tetrathiacyclic bisallenes 2a caused rearrangement to give alkynes
18, 20, and 21. In the irradiation of the cyclic bisallenes 2a , isomerizations from dl to meso and
meso to dl isomers were also found. In the reactions of allenes 1 and cyclic bisallenes 2a with
diphenyl diazomethane, the diazomethane reacted selectively with the double bond rather than
with the sulfur atom.
Sch em e 1
In tr od u ction
Allenes are reactive species with cumulated double
bonds and are useful intermediates for organic synthesis.
Many studies have been performed on their preparation
and reactivity.1-3 Allenes substituted by heteroatoms,
such as silicon, phosphorus, and sulfur atoms, have also
received attention.3 Among the sulfur-substituted allenes,
mono-,4,5 1,1-bis-,6 tris-,7 and tetrakis(alkylthio)allenes7
were synthesized in the 1960s. However, few of their
reactivities have been clarified, except for isomerization
between the allenes and acetylenes. We succeeded in
preparing 1,3-bis(alkylthio)allenes by reacting Ph2C3 di-
anion with the corresponding alkyl thiocyanates, and the
introduction of alkylthio groups to the 1- and 3-positions
of allenes was found to strongly influence their reactivi-
ties. It has also been found that the thermal reactions of
1,3-bis(alkylthio)allenes gave thiophene, benzothiepin,
cyclobutane, thiete, and R,â-unsaturated ketone deriva-
tives. In this paper, we report the preparation and some
reactivities, such as the thermal reaction, photochemical
* To whom correspondence should be addressed. Tel: +81 (426) 77-
2556. Fax: +81 (426) 77-2525. E-mail: kamigata-nobumasa@c.metro-
u.ac.jp.
(1) For reviews, see: (a) Smadja, W. Chem. Rev. 1983, 83, 263. (b)
The Chemistry of the Allenes; Landor, S. R., Ed.; Academic Press: New
York, 1982; Vols. 1-3. (c) Brandsma, L.; Verkruijsee, H. D. Synthesis
of Acetylenes, Allenes and Cumulenes; Elsevier: New York, 1980. (d)
The Chemistry of Ketenes, Allenes and Related Compounds; Patai, S.,
Ed.; Wiley: New York, 1980; Vols. 1 and 2. (e) Huche´, M. Tetrahedron
1980, 36, 331. (f) Mavrov, M. V.; Kucherov, V. F. Russ. Chem. Rev.
1967, 36, 233.
(2) For reviews, see: (a) Pasto, D. J . Tetrahedron 1984, 40, 2805.
(b) Baldwin, J . E.; Fleming, R. H. Fortschr. Chem. Forsch. 1970, 15,
281. (c) Taylor, D. R. Chem. Rev. 1967, 67, 317.
(3) For reviews, see: (a) Bruneau, C.; Dixneuf, P. H. Compr. Org.
Funct. Group Transform. 1995, 1, 953. (b) Marshall, J . A. Chem. Rev.
1996, 96, 31. (c) Schuster, H. F.; Coppola, G. M. Allenes in Organic
Synthesis; Wiley: New York, 1984; and references therein.
(4) (a) Pourcelot, G.; Cadiot, P.; Willemart, A. Compt. Rend. Acad.
Sci. 1961, 252, 1630. (b) Pourcelot, G.; Le Quan, M.; Simonnin, M.-P.;
Cadiot, P. Bull. Soc. Chim. Fr. 1962, 1278.
reaction, and reaction with diphenyl diazomethane, of
1,3-bis(alkylthio)allenes and tetrathiacyclic bisallenes.8
Resu lts a n d Discu ssion
P r epar ation of 1,3-Bis(alkylth io)allen es an d Tetr a-
th ia cyclic Bisa llen es. When a THF solution of 2 equiv
of methyl thiocyanate was added dropwise to Ph2C3
dianion (1,3-dilithiated allene), prepared from 1,3-diphen-
ylpropyne and n-butyllithium in ether/THF solution,9 at
-80 °C and allowed to warm to room temperature, 1,3-
bis(methylthio)-1,3-diphenylpropadiene (1a ) was ob-
tained in 62% yield (Scheme 1). A similar reaction of the
(5) Brandsma, L.; Wijers, H. E.; Arens, J . F. Rec. Trav. Chim. Pays-
Bas 1963, 82, 1040.
(6) Wildschut, G. A.; van Boom, J . H.; Brandsma, L.; Arens, J . F.
Rec. Trav. Chim. Pays-Bas 1968, 87, 1447.
(7) Wildschut, G. A.; Brandsma, L.; Arens, J . F. Rec. Trav. Chim.
Pays-Bas 1969, 88, 1132.
(8) For a preliminary communication, see: Shimizu, T.; Sakamaki,
K.; Kamigata, N. Tetrahedron Lett. 1997, 38, 8529.
(9) (a) Klein, J .; Backer, J . Y. J . Chem. Soc., Chem. Commun. 1973,
576. (b) Leroux, Y.; Mantione, R. Tetrahedron Lett. 1971, 591.
10.1021/jo9915675 CCC: $19.00 © 2000 American Chemical Society
Published on Web 03/02/2000

1722 J . Org. Chem., Vol. 65, No. 6, 2000
Shimizu et al.
Th er m al Reaction of 1,3-Bis(alkylth io)allen es an d
Tetr a th ia cyclic Bisa llen es. Cyclodimerization reac-
tions of allenes are well-known,2,10,11 and tetrakis(meth-
ylthio)allene7 and 1,1-bis(alkylthio)allene12 have also
been reported to undergo dimerization even at room
temperature to give cyclic dimers. However, 1,3-bis-
(methylthio)allene 1a and 1,3-bis(benzylthio)allene 1b
were stable at room temperature. When a p-xylene
solution of 1a was refluxed for 3 days, 68% of 1a was
consumed and 2,4-diphenyl thiophene (4),13 1,3-dihydro-
2-benzothiepin 5, and 1,2-bis(methylthiobenzylidene)-
cyclobutane 6 were obtained in 30, 18, and 8% yields,
respectively (Scheme 2). The position of the double bond
for the thiepin ring of 5 was determined by HMBC NMR
measurements. A stereoisomer of 6 was also obtained in
this reaction in 8% yield, which showed C2 or Cs sym-
1
metry on H and 13C NMR spectra, although the stereo-
F igu r e 1. Crystal structure of meso-2a showing 50% prob-
ability displacement ellipsoids with hydrogen atoms removed
for clarity; selected bond lengths (Å) and bond angles (deg):
S(1)-C(1), 1.7753(7); C(1)-C(2), 1.3095(8); C(2)-C(3*), 1.3162-
(8); S(2*)-C(3*), 1.7873(7); S(1)-C(1)-C(2), 122.26(6); C(1)-
C(2)-C(3*), 175.73(9); S(2*)-C(3*)-C(2), 117.85(6).
chemistry could not be clarified. The stereochemistry of
6 was determined by X-ray crystallographic analysis, as
shown in Figure 2, which showed a trans geometry for
the two methylthio groups on the cyclobutane ring and
a cis geometry for the olefins. In addition, the crystal was
found to be racemic and the cyclobutane ring was nearly
planar; dihedral angles in the ring were 4.2-4.6°. 1,3-
Bis(benzylthio)allene 1b also readily underwent a ther-
mal reaction to give 2,3,5-triphenylthiophene (7),14 thiete
8, and R,â-unsaturated ketone 9 in 63, 5, and 11% yields,
respectively, under reflux in p-xylene for 1 h. It is clear
that the thermal reaction of 1,3-bis(alkylthio)allenes is
affected by the substituents on the sulfur atoms.
dianion with benzyl thiocyanate gave 1,3-bis(benzylthio)-
1,3-diphenylpropadiene (1b) in 88% yield. 3,3-Bis(alkyl-
thio)-1,3-diphenylpropyne, the formation of which is also
anticipated from the reaction, was not obtained in either
reaction, whereas reaction of the Ph2C3 dianion with ethyl
bromide under similar conditions yielded 3,3-diethyl-1,3-
diphenylpropyne in 63% yield together with 14% of the
1,3-diethyl-1,3-diphenylpropadiene.
The thermal reaction of cyclic bisallene dl-2a caused
intramolecular cyclization, rather than other reactions
found in the case of compounds 1, to give tricyclic
compound 10 in quantitative yield. The isomer meso-2a
also gave an identical compound stereoselectively and
quantitatively under similar conditions. In both cases,
head-to-head cycloadduct 10 was obtained with the same
Reaction of the Ph2C3 dianion with ethane 1,2-dithio-
cyanate formed 14-membered cyclic bisallene 2a in 21%
yield (dl/ meso ) 41/59), although the reaction with
methylene dithiocyanate did not give the corresponding
cyclic bisallene. The stereochemistry of one isomer of the
cyclic bisallenes, meso-2a , was determined by X-ray
crystallographic analysis, as shown in Figure 1.8 The
bond lengths are almost normal, and the bond angle
C(1)-C(2)-C(3*) and torsion angle S(1)-C(1)-C(3*)-
S(2*) are 176 and 94°, respectively, indicating a strain-
free geometry. Similarly, larger sulfur-substituted cyclic
bisallenes 2b-e were also obtained in yields of 25% (dl/
meso ) 64/36), 20% (dl/ meso ) 75/25), 14% (dl/ meso )
24/76), and 13% (dl/ meso ) 67/33), respectively, by
reacting the dianion with corresponding alkane dithio-
cyanates. The structures and the ratios of the dl- and
meso-isomers of 2b-e were estimated by comparison of
their 13C NMR spectra with those of dl- and meso-2a .
Cyclic monoallenes, which were expected to be formed
when using longer alkane dithiocyanates, were not
obtained in any of the reactions, whereas the reaction of
the dianion with 1,8-dibromooctane gave 1,3-diphenyl-
undeca-1,2-diene although the yield was low (7% yield).
The lack of formation of the cyclic monoallene is perhaps
due to the conformation in the ring-closure reaction
because the reaction of the dianion with 0.5 equiv of
methyl thiocyanate gave a ca. 1:1 mixture of the mono-
(methylthio)allene and the bis(methylthio)allene, and this
result indicates that the reactivity of the anion 3 is not
low.
(10) For examples, see: (a) Lebedev, S. V. J . Russ. Phys. Chem. Soc.
1913, 45, 1249; Chem. Abstr. 1914, 8, 320. (b) Blomquist, A. T.; Verdol,
J . A. J . Am. Chem. Soc. 1956, 78, 109. (c) Williams, J . K.; Sharkey, W.
H. J . Am. Chem. Soc. 1959, 81, 4269. (d) Pilgram, K.; Korte, F.
Tetrahedron Lett. 1962, 883. (e) Roedig, A.; Bischoff, F.; Heinrich, B.;
Markl, G. Ann. Chem. 1963, 670, 8. (f) Slobodin, Y. M.; Khitrov, A. P.
J . Gen. Chem. USSR 1963, 33, 146. (g) Slobodin, Y. M.; Khitrov, A. P.
J . Gen. Chem. USSR 1963, 33, 2748. (h) Roedig, A.; Detzer, N.;
Friedrich, H. J . Angew. Chem. 1964, 76, 379. (i) Fischer, H.; Fischer,
H. Chem. Ber. 1964, 97, 2975. (j) Banks, R. E.; Haszeldine, R. N.;
Taylor, D. R. J . Chem. Soc. 1965, 978. (k) Skattebøl, L.; Solomon, S.
J . Am. Chem. Soc. 1965, 87, 4506. (l) Gajewski, J . J .; Shih, C. N. J .
Am. Chem. Soc. 1969, 91, 5900. (m) J acobs, T. L.; McClenon, J . R.;
Muscio, O. J ., J r. J . Am. Chem. Soc. 1969, 91, 6038. (n) Gajewski, J .
J .; Black, W. A. Tetrahedron Lett. 1970, 899. (o) J acobs, T. L.; Muscio,
O. J ., J r. Tetrahedron Lett. 1970, 4829. (p) Dolbier, W. R., J r.; Dai,
S.-H. J . Am. Chem. Soc. 1970, 92, 1774. (q) Gajewski, J . J .; Shih, C.
N. J . Org. Chem. 1972, 37, 64. (r) Dai, S.-H.; Dolbier, W. R., J r. J . Am.
Chem. Soc. 1972, 94, 3946.
(11) (a) Roberts, J . D.; Sharts, C. M. Org. React. 1962, 12, 1. (b)
Moore, W. R.; Mogolesko, P. D.; Traficante, D. D. J . Am. Chem. Soc.
1972, 94, 4753. (c) Levek, T. J .; Kiefer, E. F. J . Am. Chem. Soc. 1976,
98, 1875. (d) Becher, G.; Skattebøl, L. Tetrahedron Lett. 1979, 1261.
(12) Minami, T.; Okauchi, T.; Matsuki, H.; Nakamura, M.; Ichikawa,
J .; Ishida, M. J . Org. Chem. 1996, 61, 8132.
(13) Wynberg, H.; van Driel, H.; Kellogg, R. M.; Buter, J . J . Am.
Chem. Soc. 1967, 89, 3487.
(14) (a) Smith, A. J . Chem. Soc. 1890, 57, 647. (b) Mitra, S. K. J .
Indian Chem. Soc. 1938, 15, 59. (c) Karakasa, T.; Takeda, S.; Saito,
T.; Motoki, S. Bull. Chem. Soc. J pn. 1986, 59, 3279.

1,3-Bis(alkylthio)allenes and Tetrathiacyclic Bisallenes
J . Org. Chem., Vol. 65, No. 6, 2000 1723
F igu r e 2. Crystal structure of 6 showing 50% probability
displacement ellipsoids with hydrogen atoms removed for
clarity; selected bond lengths (Å), bond angles (deg) and
dihedral angles (deg): C(1)-C(1*), 1.620(4); C(1)-C(2), 1.533(4);
C(2)-C(2*), 1.467(4); C(1)-S(1), 1.851(4); C(1)-C(3), 1.520(5);
C(2)-C(4), 1.356(4); C(1*)-C(1)-C(2), 87.1(2); C(1)-C(2)-
C(2*), 92.8(2); C(1*)-C(1)-C(3), 115.5(3); C(2)-C(1)-C(3),
119.2(3); C(2)-C(1)-S(1), 114.7(3); C(1)-C(2)-C(4), 129.1(3);
C(2*)-C(2)-C(4), 137.6(3); C(2)-C(1)-C(1*)-C(2*), 4.2(3);
C(1*)-C(1)-C(2)-C(2*), -4.3(3); C(1)-C(2)-C(2*)-C(1*), 4.6(3);
C(3)-C(1)-C(1*)-C(3*), 121.9(3); S(1)-C(1)-C(1*)-S(1*),
-123.4(2); C(4)-C(2)-C(2*)-C(4*), 21.2 (9).
F igu r e 3. Crystal structure of 10 showing 50% probability
displacement ellipsoids with hydrogen atoms removed for
clarity; selected bond lengths (Å), bond angles (deg), and
dihedral angles (deg): C(1)-C(2), 1.535(9); C(1)-C(4), 1.63(1);
C(2)-C(3), 1.46(1); C(3)-C(4), 1.544(9); C(1)-S(1), 1.852(7);
C(2)-C(5), 1.33(1); C(3)-C(6), 1.34(1); C(4)-S(2), 1.812(8);
C(2)-C(1)-C(4), 85.4(5); C(1)-C(2)-C(3), 92.9(5); C(2)-C(3)-
C(4), 91.0(5); C(1)-C(4)-C(3), 86.4(5); C(4)-C(1)-C(2)-C(3),
15.5(5); C(2)-C(1)-C(4)-C(3), -14.7(5); C(1)-C(2)-C(3)-
C(4), -16.4(6); C(2)-C(3)-C(4)-C(1), 15.4(5); S(1)-C(1)-
C(4)-S(2), -21.2(6); C(5)-C(2)-C(3)-C(6), -36(1).
Sch em e 2
To examine the reaction mechanism, the thermal
reaction of 1a was carried out in the presence of 1.5 equiv
of 1,1-diphenyl-2-picryl hydrazyl (DPPH). After refluxing
for 3 days, compounds 4, 5, and 6, which were obtained
by the thermal reaction of 1a , were not detected. In the
case of 1b, addition of 2.5 equiv of DPPH also inhibited
the formation of 8 (<1%) and 9 (trace); however, thiophene
7 was obtained in 38% yield. Using 10 equiv of DPPH,
thiophene 7 was still formed in 35% yield, although
compounds 8 and 9 were not detected. The formation of
thiophene 7 can be explained by a fast intramolecular
ring-closure reaction in the solvent cage. Thus, the
thermal reactions of 1 may proceed via a radical path.
One possible mechanism for the formation of thiophene
derivatives 4 and 7 is shown in Scheme 3, though the
existence of a biradical intermediate could not be clari-
fied. The intramolecular coupling reaction of biradical 11,
generated from 1 by intramolecular hydrogen abstrac-
tion, gives dihydrothiophene 12, and elimination of a thiol
gives thiophene 4 or 7. In the case of 1a (R ) H), a carbon
radical of 11 also attacks the ortho position of the phenyl
group to yield 13. Finally, a hydrogen shift of 13 forms
1,3-dihydro-2-benzothiepin 5. In the case of 1,3-bis-
(benzylthio)allene 1b (R ) Ph), homolytic cleavage of the
carbon-sulfur bond occurs competitively to give thiyl
radical 14, maybe due to the small bonding energy of the
sulfur-carbon bond and the stability of the resulting
benzyl radical. Intramolecular cyclization of 15 followed
by hydrogen abstraction yields thiete 8. Hydrogen ab-
stereochemistry, and the crystal structure of tricyclic
compound 10 is given in Figure 3. The crystal structure
showed that the ethane dithiolate was fused to the
cyclobutane ring with cis geometry, in contrast to that
of 6. The cyclobutane ring had a nonplanar geometry;
dihedral angles in the ring were 14.7-16.4°. The geom-
etries of olefin moieties were trans, and the two double
bonds were not conjugated; dihedral angle C(5)-C(2)-
C(3)-C(6) ) -36°.

1724 J . Org. Chem., Vol. 65, No. 6, 2000
Shimizu et al.
Sch em e 3
straction of 15 followed by hydrolysis gives R,â-unsatur-
ated ketone 9. On the other hand, intramolecular cy-
clization of dl-2a and meso-2a yielded the same compound
10 as a sole product. Therefore, this reaction did not
proceed through a concerted path. Tricyclic compound 10
is considered to be formed via 2,2′-bisallyl biradical 16.11
Biradical 16 is formed from both the dl- and meso-isomers
2a ; thus, the tricyclic compound 10 is obtained as a sole
product from both isomers. The formation of bismeth-
ylidene cyclobutane 6 in the reaction of 1a can also be
explained by a similar mechanism involving the biradical
17. In this case, two stereoisomers were obtained.
Sch em e 4
P h otoch em ica l Rea ction of 1,3-Bis(a lk ylth io)a l-
len es a n d Tetr a th ia cyclic Bisa llen es. Irradiation of
a benzene solution of allene 1a through a Pyrex filter
gave 3,3-bis(methylthio)-1,3-diphenylpropyne (18a ) and
3-methylthio-1,3-diphenylpropyne (19a ) in 13 and 29%
yields, as shown in Scheme 4. Similarly, irradiation of
allene 1b yielded bis(methylthio)acetylene 18b and ben-
zylthioacetylene 19b in 22 and 23% yields, respectively.
Compounds 19 were found to be secondary products from
18 because irradiation of a benzene-d6 solution of acety-
lene 18a yielded compound 19a (18a /19a ) 3/1 after
irradiation for 1 h). Photochemical reaction of cyclic
bisallenes dl- and meso-2a also gave rearranged products
20 and 21 from both isomers, and the syn/anti ratios of
21 were ca. 1/1 in both reactions. In these reactions, meso-
2a was also formed from dl-2a , and dl-2a was formed
from meso-2a . Cyclopropane derivative,15,16 which was
expected to be formed by the reaction, was not obtained.
Two possible mechanisms can be considered for this
photochemical reaction, as shown in Scheme 5. However,
mechanism B involving [1,3]sigmatropic rearrangement
via transition state 22 seems to be disadvantageous
because the photoisomerization between dl-2a and meso-
2a cannot be explained since irradiation of 18a did not
give the allene 1a . Thus, an alternative explanation may
be needed for the photorearrangement of 1 (mechanism
A). A photoinduced 1,2-rearrangement of the alkylthio
group of 1 forms carbene 24 via biradical 23. Further
rearrangement of the alkylthio group of 24 yields acety-
lene derivative 18. Photochemical rearrangement of 2a
may also proceed through a similar stepwise mechanism,
and photoisomerization of 2a can be explained as a result
of a reverse reaction from the carbene or the biradical.16
Rea ction of 1,3-Bis(a lk ylth io)a llen es a n d Tetr a -
th ia cyclic Bisa llen es w ith Dip h en yl Dia zom eth a n e.
When a benzene solution of 1,3-bis(methylthio)allene 1a
and diphenyl diazomethane was refluxed for 14 h, 65%
of 1a was consumed and cis-butadiene derivative 25 was
obtained in 79% yield (Scheme 6). The cis geometry of
(15) For examples, see: (a) Stierman, T. J .; J ohnson, R. P. J . Am.
Chem. Soc. 1983, 105, 2492. (b) Murray, R. I.; Sligar, S. G. J . Am.
Chem. Soc. 1985, 107, 2186. (c) Klett, M. W.; J ohnson, R. P. J . Am.
Chem. Soc. 1985, 107, 3963. (d) Price, J . D.; J ohnson, R. P. J . Org.
Chem. 1991, 56, 6372.
(16) (a) Steinmetz, M. G.; Mayes, R. T. J . Am. Chem. Soc. 1985,
107, 2111. (b) Stierman, T. J .; J ohnson, R. P. J . Am. Chem. Soc. 1985,
107, 3971. (c) Stierman, T. J .; Shakespeare, W. C.; J ohnson, R. P. J .
Org. Chem. 1990, 55, 1043.

1,3-Bis(alkylthio)allenes and Tetrathiacyclic Bisallenes
J . Org. Chem., Vol. 65, No. 6, 2000 1725
Sch em e 5
Sch em e 7
Sch em e 6
The first step in this reaction is 1,3-dipolar addition
of diphenyl diazomethane to the double bond of 1 to give
benzylidene cyclopropane derivatives 30 via a five-
membered cycloadduct and the subsequent elimination
of nitrogen (Scheme 7). In the case of 1a , the ring-opening
reaction of 30a proceeds with migration of the methylthio
group on the cyclopropane ring to give butadiene deriva-
tive 25. On the other hand, in the case of 1b, the ring-
opening reaction of 30b with elimination of the benzylthio
radical followed by hydrogen abstraction yielded acety-
lene derivative 26. This behavior may be due to the
stability of the benzylthio radical. The product 28 in the
reaction of tricyclic compound 10 with diphenyl diazo-
methane may be accounted for by formation of ylide 31
as an intermediate. In compound 10, the carbon-carbon
double bond may be less reactive than the sulfur atom
toward diphenyl diazomethane. The subsequent intramo-
lecular rearrangement of ylide 31 will give products 28
and 29. Episulfide 27 may be obtained by the further
reaction of diphenyl diazomethane and thiobenzophe-
none, formed by the addition of diphenyl diazomethane
and sulfur generated by side reactions from the sub-
strates.20
25 was confirmed by X-ray crystallographic analysis. In
the case of allene 1b, the corresponding butadiene did
not form, but 3-benzylthio-1,3,4,4-tetraphenyl-1-butyne
(26) and episulfide 27 were obtained in 11 and 87%
yields, respectively. The alkylidenecyclopropane deriva-
tive was not obtained in either reaction, whereas carbon-
substituted allenes are known to react with diphenyl
diazomethane to give alkylidenecyclopropane deriva-
tives.18,19 Heating a benzene solution of cyclic bisallene
meso-2a with diphenyl diazomethane gave episulfide 27,
bicyclic compound 28, and 1,3-dithiolane 2917 in 12, 17,
and 13% yields, respectively, together with intramolecu-
lar cyclization product 10 (48%). In this reaction, the
thermal cyclization reaction must occurred in preference
to the reaction with diphenyl diazomethane, and products
28 and 29 are considered to be formed as secondary
products. In fact, heating a benzene solution of tricyclic
compound 10 with diphenyl diazomethane yielded com-
pounds 28 and 29 in 41 and 29% yields, respectively,
together with 20% yield of 27.
Con clu sion
1,3-Bis(alkylthio)allenes and tetrathiacyclic bisallenes
could be obtained by the reaction of Ph2C3 dianion with
the corresponding alkyl thiocyanates and alkane dithio-
cyanates, respectively. The thermal reaction of 1,3-bis-
(alkylthio)allenes mainly afforded thiophene derivatives,
and the reaction of tetrathiacyclic bisallenes gave a cyclic
dimer, 1,2-bis(benzylidene)cyclobutane derivative, quan-
titatively. Irradiation of 1,3-bis(alkylthio)allenes and
tetrathiacyclic bisallenes caused intramolecular rear-
rangement to give alkynes. Irradiation of the tetrathia-
cyclic bisallenes also yielded dl- and meso-isomerized
products. Furthermore, the diphenyl diazomethane re-
acted with the double bonds rather than the sulfur atoms
of sulfur-substituted allenes.
(17) Sondej, S. C.; Katzenellenbogen, J . A. J . Org. Chem. 1986, 51,
3508.
(18) Brandi, A.; Goti, A. Chem. Rev. 1998, 98, 589.
Exp er im en ta l Section
(19) For examples, see: (a) Blomquist, A. T.; Connolly, D. J . Chem.
Ind. 1962, 310. (b) Heinrich, F.; Lu¨ttke, W. Angew. Chem., Int. Ed.
Engl. 1972, 11, 234. (c) Fitjer, L.; Conia, J . M. Angew. Chem., Int. Ed.
Engl. 1973, 12, 332. (d) Creary, X. J . Am. Chem. Soc. 1980, 102, 1611.
(e) Kaufmann, D.; de Meijere, A. Chem. Ber. 1984, 117, 1128.
Gen er a l Meth od s. TLC was performed with Merck Art.
5554 DC-Alufolien Kieselgel 60 F254. Column chromatography
(20) Scho¨nberg, A.; Frese, E. Ber. 1962, 95, 2810.

1726 J . Org. Chem., Vol. 65, No. 6, 2000
Shimizu et al.
was performed with Merck silica gel 60. Gel-permeation
chromatography (GPC) was performed using J AI LC-08 and
J AI LC-908 recycling liquid chromatographs with two J AI-
GEL-1H columns (20 mm × 600 mm) with chloroform as
eluent. All solvents were distilled and stored under nitrogen.
Reactions in benzene solution were carried out in a hood.
Gen er a l P r oced u r e for P r ep a r a tion of 1,3-Bis(a lk yl-
th io)a llen es a n d Tetr a th ia cyclic Bisa llen es. To an ether-
THF solution (20 mL/20 mL) of 1,3-diphenylpropyne (1.00 g,
5.21 mmol)21 was added dropwise at -80 °C n-butyllithium
(1.59 mol/L, 6.4 mL, 10.2 mmol) under nitrogen, and the
solution was stirred for 2 h. A THF solution (20 mL) of alkyl
thiocyanate (12.0 mmol) or alkane dithiocyanate (5.70 mmol)
was added dropwise to the solution and allowed to warm to
room temperature. Water (100 mL) was added to the solution,
and products were extracted with ether. The combined organic
extracts were washed with brine and dried over anhydrous
magnesium sulfate. After removal of solvent in vacuo, the
residue was subjected to gel-peameation chromatography
(GPC). 1a : 62%; 1b: 88%; 2a : 21%; 2b: 25%; 2c: 20%; 2d :
14%; 2e: 13%.
1,3,10,12-Tetr aph en yl-4,9,13,18-tetr ath iacyclooctadeca-
1,2,10,11-tetr a en e (2c). As a dl/meso (75/25) mixture: color-
less solid; 1H NMR (500 MHz, CDCl3) δ 1.81-1.92 (m, 8H),
2.72-2.78 (m, 8H), 7.25-7.55 (m, 20H); 13C NMR (125 MHz,
CDCl3) δ 27.2, 27.6, 31.8, 32.0, 113.4, 114.0, 126.45, 126.53,
128.3, 128.4, 128.6 (duplicate), 134.77, 134.81, 196.4, 197.1;
IR (KBr) νmax 3025, 2920, 1900, 1595, 1585, 1490, 1445, 1310,
1290, 1210, 1150, 1075, 1030, 895, 760, 690 cm-1; MS m/z 620
(M+, 11), 532 (5), 500 (15), 444 (28), 412 (49), 380 (9), 255 (74),
190 (100); HRMS calcd for C38H36S4 620.1700, found 620.1675.
1,3,11,13-Tetr a p h en yl-4,10,14,20-tetr a th ia cycloeicosa -
1,2,11,12-tetr a en e (2d ). As a dl/meso (24/76) mixture: yellow
liquid; 1H NMR (500 MHz, CDCl3) δ 1.39-1.53 (m, 4H), 1.57-
1.73 (m, 8H), 2.64-2.75 (m, 8H), 7.23-7.58 (m, 20H); 13C NMR
(125 MHz, CDCl3) δ 28.0, 28.2, 28.75, 28.82, 32.4, 32.6, 112.5,
113.8, 126.6, 126.7, 128.2, 128.3, 128.49, 128.50, 134.8, 134.9,
196.7, 198.2; IR (KBr) νmax 3060, 2925, 1900, 1595, 1585, 1490,
1445, 1305, 1280, 1210, 1150, 1080, 1030, 890, 760, 690 cm-1
;
MS m/z 648 (M+, 19), 546 (3), 514 (6), 444 (11), 412 (13), 380
(3), 255 (100), 190 (52). Anal. Calcd for C40H40S4: C, 74.03; H,
6.21. Found: C, 74.12; H, 6.48.
1,3-Bis(m eth ylth io)-1,3-d ip h en ylp r op a d ien e (1a ): yel-
1,3,12,14-Tetr a p h en yl-4,11,15,22-tetr a th ia cyclod ocosa -
1,2,12,13-tetr a en e (2e). As a dl/meso (67/33) mixture: yellow
liquid; 1H NMR (500 MHz, CDCl3) δ 1.39-1.46 (m, 8H), 1.65-
1.72 (m, 8H), 2.68-2.71 (m, 8H), 7.25-7.58 (m, 20H); 13C NMR
(125 MHz, CDCl3) δ 28.4, 28.5, 28.6, 28.7, 32.65, 32.66, 113.7,
113.9, 126.5 (duplicate), 128.3 (duplicate), 128.5 (duplicate),
134.98, 135.02, 196.7, 197.0; IR (KBr) νmax 3075, 2960, 2875,
1915, 1605, 1585, 1500, 1470, 1455, 1275, 1220, 1155, 1040,
900, 775, 755, 705 cm-1; MS m/z 676 (M+, 27), 528 (10), 445
(13), 412 (30), 380 (8), 339 (19), 255 (100), 191 (46), 116 (35),
84 (12); HRMS calcd for C42H44S4 676.2326, found 676.2395.
Gen er a l P r oced u r e for Th er m a l Rea ction of 1,3-Bis-
(a lk ylth io)a llen es a n d Tetr a th ia cyclic Bisa llen es. A p-
xylene solution (2 mL) of 1,3-bis(alkylthio)allene (0.4 mmol)
or tetrathiacyclic bisallene (0.2 mmol) was refluxed for the
desired period under nitrogen. After removal of solvent in
vacuo, the residue was subjected to gel-peameation chroma-
tography (GPC). 1a : 68% conversion, 4 (30%), 5 (18%), 6 (8%),
stereoisomer of 6 (8%); 1b: 100% conversion, 7 (63%), 8 (5%),
9 (11%); dl-2a : 100% conversion, 10 (100%); meso-2a : 100%
conversion, 10 (100%).
1
low liquid; H NMR (400 MHz, CDCl3) δ 2.24 (s, 6H), 7.26-
7.59 (m, 10H); 13C NMR (100 MHz, CDCl3) δ 15.6, 116.9, 126.4,
128.4, 128.5, 135.0, 194.7; IR (neat) νmax 3050, 3025, 2980,
2910, 1905, 1650, 1630, 1595, 1575, 1550, 1490, 1445, 1310,
1225, 1175, 1075, 1025, 960, 885, 755, 685 cm-1; UV (cyclo-
hexane) λmax 229 (ꢀ 2.9 × 104), 286 (ꢀ 2.3 × 104) nm; MS m/z
284 (M+, 20), 237 (100), 222 (40), 191 (27). Anal. Calcd for
C
17H16S2: C, 71.78; H, 5.67. Found: C, 71.92; H, 5.42.
1,3-Bis(ben zylth io)-1,3-d ip h en ylp r op a d ien e (1b): pale
1
yellow liquid; H NMR (400 MHz, CDCl3) δ 3.65 (d, 2H, J )
13.2 Hz), 3.74 (d, 2H, J ) 13.2 Hz), 7.13-7.47 (m, 20H); 13C
NMR (100 MHz, CDCl3) δ 36.9, 113.7, 126.5, 127.1, 128.3,
128.4, 128.5, 129.0, 134.6, 137.1, 197.3; IR (neat) νmax 3055,
3030, 2955, 2930, 1910, 1600, 1495, 1450, 1070, 1030, 860
cm-1; UV (cyclohexane) λmax 228 (ꢀ 2.8 × 104), 289 (ꢀ 1.6 ×
104) nm; MS m/z 345 (M+ - CH2Ph, 45), 313 (100), 255 (21),
222 (13), 190 (7), 123 (5), 91 (56). Anal. Calcd for C29H24S2: C,
79.77; H, 5.54. Found: C, 79.94; H, 5.40.
d l-1,3,8,10-Tet r a p h en yl-4,7,11,14-t et r a t h ia cyclot et r a -
d eca -1,2,8,9-tetr a en e (d l-2a ): mp 144-145 °C (colorless
1
powder from dichloromethane-hexane); H NMR (500 MHz,
2,4-Dip h en ylth iop h en e (4): mp 115-116 °C (colorless
plates from benzene-hexane) (lit.13 mp 121-121.5 °C); 1H NMR
(400 MHz, CDCl3) δ 7.28-7.31 (m, 2H), 7.38 (d, 1H, J ) 1.5
Hz), 7.39-7.42 (m, 4H), 7.58 (d, 1H, J ) 1.5 Hz), 7.60-7.66
(m, 4H); 13C NMR (100 MHz, CDCl3) δ 118.7, 121.3, 124.9,
125.3, 126.2, 126.7, 127.8, 127.9, 133.3, 134.8, 142.1, 144.0;
IR (KBr) νmax 1595, 1485, 1445, 750, 730, 685 cm-1; MS m/z
236 (M+, 100), 202 (9), 191 (10), 165 (5), 121 (5), 77 (5).
CDCl3) δ 3.07 (s, 8H), 7.27 (tt, 4H, J ) 1.5, 7.3 Hz), 7.32 (ddd,
8H, J ) 1.5, 7.3, 7.3 Hz), 7.53 (dd, 8H, J ) 1.5, 7.3 Hz); 13C
NMR (125 MHz, CDCl3) δ 31.4, 112.4, 126.7, 128.5, 128.6,
134.2, 197.7; IR (KBr) νmax 3060, 3030, 2950, 2920, 2850, 1960,
1910, 1595, 1580, 1485, 1440, 1265, 1210, 1145, 910, 885, 760,
690 cm-1; UV (cyclohexane) λmax 234 (ꢀ 4.2 × 104), 287 (ꢀ 2.7 ×
104) nm; MS m/z 564 (M+, 7), 536 (19), 508 (8), 476 (32), 472
(10), 444 (100), 412 (10), 387 (27), 282 (6). Anal. Calcd for
1,3-Dih yd r o-5-m eth ylth io-3-p h en yl-2-ben zoth iep in (5):
C
34H28S4: C, 72.34; H, 4.96. Found: C, 72.59; H, 5.00.
1
brown liquid; H NMR (400 MHz, CDCl3) δ 2.28 (s, 3H), 3.32
m eso-1,3,8,10-Tetr a p h en yl-4,7,11,14-tetr a th ia cyclotet-
(d, 1H, J ) 12.2 Hz), 4.06 (d, 1H, J ) 12.2 Hz), 4.42 (d, 1H, J
) 7.8 Hz), 5.90 (d, 1H, J ) 7.8 Hz), 7.21-7.49 (m, 9H); 13C
NMR (100 MHz, CDCl3) δ 15.8, 33.8, 46.1, 122.0, 127.7, 127.8,
128.4, 128.6, 128.8, 129.0, 129.3, 137.4, 137.8, 138.1, 139.0;
IR (neat) νmax 3050, 3005, 2900, 1590, 1485, 1435, 1305, 1235,
1200, 1170, 1065, 1025, 950, 760, 690 cm-1; MS m/z 284 (M+,
8), 269 (2), 252 (2), 237 (100), 203 (18), 191 (5), 135 (4), 91
r a d eca -1,2,8,9-tetr a en e (m eso-2a ): mp 162-163 °C (colorless
1
needles from dichloromethane-hexane); H NMR (400 MHz,
CDCl3) δ 3.09-3.23 (m, 8H), 7.25-7.54 (m, 20H); 13C NMR
(100 MHz, CDCl3) δ 31.7, 110.3, 126.9, 128.5, 128.7, 134.0,
200.5; IR (KBr) νmax 3060, 2430, 2175, 1900, 1595, 1580, 1485,
1440, 1425, 1420, 1335, 1310, 890, 760 cm-1; UV (cyclohexane)
λmax 238 (ꢀ 3.1 × 104), 277 (sh, ꢀ 2.4 × 104) nm; MS m/z 564
(M+, 5), 536 (17), 508 (6), 476 (30), 472 (12), 444 (100), 412
(14), 387 (30), 282 (5). Anal. Calcd for C34H28S4: C, 72.34; H,
4.96. Found: C, 72.39; H, 5.05.
1,3,9,11-Tetr a p h en yl-4,8,12,16-tetr a th ia cycloh exa d eca -
1,2,9,10-tetr a en e (2b). As a dl/meso (64/36) mixture: colorless
solid; 1H NMR (400 MHz, CDCl3) δ 2.02-2.08 (m, 4H), 2.73-
2.94 (m, 8H), 7.24-7.54 (m, 20H); 13C NMR (100 MHz, CDCl3)
δ 29.4, 29.7, 31.3, 31.6, 109.8, 112.5, 126.9, 127.1, 128.3, 128.4,
128.55, 128.60, 134.3, 134.6, 198.6, 200.5; IR (KBr) νmax 3050,
3020, 2910, 1900, 1595, 1485, 1445, 1070, 1025, 880, 755, 685
cm-1; MS m/z 592 (M+, 17), 518 (4), 486 (14), 444 (100), 412
(8), 313 (53), 190 (33); HRMS calcd for C36H32S4 592.1387,
found 592.1403.
(10), 77 (35); HRMS calcd for
284.0713.
C17H16S2 284.0693, found
1,2-Bis(m et h ylt h io)-(Z)-3,4-b is(1-m et h ylt h iob en zyli-
d en e)-1,2-d ip h en ylcyclobu ta n e (6): mp 196-197 °C dec
(yellow needles from dichloromethane-hexane); 1H NMR (500
MHz, CDCl3) δ 1.19 (s, 6H), 1.58 (s, 6H), 7.01-7.78 (m, 20H);
13C NMR (125 MHz, CDCl3) δ 15.0, 15.9, 72.2, 127.4, 127.7,
127.8, 128.3, 128.6, 129.5, 134.3, 136.9, 137.3, 139.1; IR (KBr)
νmax 3050, 3020, 2985, 2920, 1595, 1575, 1555, 1535, 1485,
1445, 1305, 1215, 1175, 1150, 1100, 1075, 1025, 960, 760, 690
cm-1; MS m/z 568 (M+, 97), 553 (8), 521 (9), 506 (9), 491 (29),
474 (100), 459 (18), 444 (41), 427 (25), 412 (19), 380 (16), 237
(26); HRMS calcd for C34H32S4 568.1387, found 568.1419.
Ster eoisom er of 6. As a mixture with 6: 1H NMR (500
MHz, CDCl3) δ 1.53 (s, 6H), 2.26 (s, 6H), 7.01-7.78 (m, 20H);
(21) J acobs, T. L.; Dankner, D. J . Org. Chem. 1957, 22, 1424.

1,3-Bis(alkylthio)allenes and Tetrathiacyclic Bisallenes
J . Org. Chem., Vol. 65, No. 6, 2000 1727
13C NMR (125 MHz, CDCl3) δ 15.4, 17.9, 74.1, 126.4, 127.0,
1,3-Dip h en yl-3-m eth ylth iop r op yn e (19a ): pale yellow
liquid; 1H NMR (500 MHz, CDCl3) δ 2.21 (s, 3H), 4.94 (s, 1H),
7.27-7.58 (m, 10H); 13C NMR (125 MHz, CDCl3) δ 14.2, 40.5,
86.0, 86.7, 122.9, 127.7, 127.9, 128.27, 128.31, 128.5, 131.8,
138.3; IR (neat) νmax 3070, 3040, 2925, 1670, 1605, 1585, 1495,
1455, 1250, 1180, 1080, 1035, 960, 920, 760 cm-1; MS m/z 238
128.3, 129.4, 129.6, 134.2, 135.2, 138.0, 139.4.
2,3,5-Tr ip h en ylth iop h en e (7): mp 136-137 °C (colorless
needles from dichloromethane-hexane) (lit.14a mp 127 °C;
1
lit.14b mp 157 °C; lit.14c mp 132-134 °C); H NMR (400 MHz,
CDCl3) δ 7.14-7.58 (m, 15H), 7.28 (s, 1H); 13C NMR (100 MHz,
CDCl3) δ 125.6, 126.5, 127.0, 127.4, 127.6, 128.4, 128.5, 128.9,
129.06, 129.14, 134.1, 134.2, 136.6, 138.0, 139.0, 142.6; IR
(KBr) νmax 1600, 1495, 1480, 755, 690 cm-1; MS m/z 312 (M+,
100), 278 (6), 235 (3), 192 (3), 121 (3).
(M+, 24), 223 (22), 191 (100), 77 (21); HRMS calcd for C16H14
238.0816, found 238.0784.
S
3-Ben zylth io-1,3-d ip h en ylp r op yn e (19b): yellow liquid;
1H NMR (500 MHz, CDCl3) δ 3.81 (d, 1H, J ) 13.4 Hz), 4.05
(d, 1H, J ) 13.4 Hz), 4.80 (s, 1H), 7.23-7.53 (m, 15H); 13C
NMR (125 MHz, CDCl3) δ 36.6, 39.0, 86.3, 87.1, 122.9, 127.1,
127.8, 128.1, 128.3, 128.4, 128.55, 128.57, 129.0, 131.8, 137.7,
137.9; IR (neat) νmax 3075, 3055, 3025, 2925, 2360, 2330, 1600,
4-Ben zylth io-2,4-d ip h en ylth iete (8): yellow liquid; 1H
NMR (500 MHz, CDCl3) δ 3.60 (d, 1H, J ) 13.1 Hz), 3.83 (d,
1H, J ) 13.1 Hz), 6.18 (s, 1H), 6.92-7.58 (m, 15H); 13C NMR
(125 MHz, CDCl3) δ 46.7, 75.8, 123.9, 126.7, 127.1, 127.4,
127.7, 127.8, 128.6, 128.7, 129.2, 130.6, 133.3, 136.2, 142.3,
144.1; IR (neat) νmax 3050, 3020, 2900, 1595, 1570, 1485, 1440,
1255, 1070, 1030, 750, 690 cm-1; MS m/z 346 (M+, 2), 313 (21),
256 (100), 224 (5), 192 (5), 91 (3), 77 (2); HRMS calcd for
C22H18S2 346.0850, found 346.0816.
1490, 1455, 1440, 1335, 1240, 1070, 1025, 915, 755, 690 cm-1
;
MS m/z 314 (M+, 13), 237 (2), 223 (9), 191 (100), 123 (5), 91
(12), 77 (4); HRMS calcd for C22H18S 314.1129, found 314.1132.
8-P h en eth yn yl-1,3,8-tr ip h en yl-4,7,9,12-tetr a th ia cyclo-
d od eca -1,2-d ien e (20): mp 116-117 °C dec (colorless solid);
1H NMR (500 MHz, CDCl3) δ 2.83 (ddd, 1H, J ) 5.5, 6.7, 12.2
Hz), 3.01 (ddd, 1H, J ) 7.4, 7.4, 14.0 Hz), 3.06-3.15 (m, 2H),
3.22-3.31 (m, 3H), 3.37 (ddd, 1H, J ) 8.0, 9.8, 12.2 Hz), 7.24-
7.87 (m, 20H); 13C NMR (125 MHz, CDCl3) δ 30.3, 30.5, 32.2,
32.9, 58.1, 87.6, 88.8, 109.1, 109.2, 122.1, 126.2, 127.3, 127.4,
128.30, 128.31, 128.46, 128.50, 128.51, 128.70, 128.72, 128.8,
131.9, 133.9, 134.0, 141.0, 202.5; IR (KBr) νmax 3050, 3025,
2910, 2350, 2325, 1900, 1590, 1575, 1485, 1440, 1425, 1410,
1260, 1200, 1180, 1140, 1110, 1070, 1025, 995, 925, 880, 860,
750, 710, 680 cm-1; MS m/z 564 (M+, 100), 536 (23), 504 (21),
476 (32), 472 (55), 444 (98), 412 (72); HRMS calcd for C34H28S4
564.1074, found 564.1068.
3-Ben zylth io-1,3-diph en yl-2-pr open e-1-on e (9). The ster-
eochemistry has not been clarified: mp 122-123 °C (yellow
1
needles from dichloromethane-hexane); H NMR (500 MHz,
CDCl3) δ 3.66 (s, 2H), 7.04 (s, 1H), 7.01-7.96 (m, 15H); 13C
NMR (125 MHz, CDCl3) δ 37.7, 119.9, 127.1, 128.07, 128.11,
128.3, 128.47, 128.54, 128.9, 129.0, 132.2, 136.7, 138.4, 139.0,
162.9, 188.4; IR (KBr) νmax 3060, 3030, 2940, 1630, 1600, 1575,
1525, 1485, 1245, 1230, 1045, 1020, 955, 705, 660 cm-1; MS
m/z 239 (M+ - CH2Ph, 100), 105 (28), 91 (29), 77 (26). Anal.
Calcd for C22H18OS: C, 80.00; H, 5.45. Found: C, 79.65; H,
5.46.
1,3,8,10-Tetr aph en yl-4,7,11,14-tetr ath iatr icyclo[8.4.0.02,9]-
tetr a d eca -(E,E)-2,8-d ien e (10): mp 234-235 °C dec (yellow
plates from dichloromethane-hexane); 1H NMR (500 MHz,
C6D6, 60 °C) δ 2.54-2.57 (m, 4H), 2.80-2.85 (m, 2H), 3.41 (br
s, 2H), 6.73-7.80 (m, 20H); 13C NMR (125 MHz, C6D6, 60 °C)
δ 28.2, 29.3, 66.1, 127.0, 127.1, 127.6, 128.4, 128.7, 129.6
(duplicate), 130.6, 138.9, 139.7; IR (KBr) νmax 3050, 2925, 1590,
1555, 1485, 1440, 1400, 1270, 1215, 1175, 1080, 1025, 915, 880,
840, 820, 770, 755, 685 cm-1; MS m/z 564 (M+, 9), 536 (28),
508 (11), 476 (51), 472 (98), 444 (100), 412 (76), 387 (43), 366
(51), 334 (51), 302 (51), 221 (16), 189 (15), 145 (20), 121 (72),
77 (14). Anal. Calcd for C34H28S4: C, 72.23; H, 4.96. Found:
C, 72.56; H, 5.15.
2,7-Dip h en eth yn yl-2,7-d ip h en yl-1,3,6,8-tetr a th ia cyclo-
d eca n e (21). As a syn/anti (ca. 1/1) mixture: colorless solid;
1H NMR (500 MHz, CDCl3) δ 3.54 (br s, 8H), 7.25-7.88 (m,
20H); 13C NMR (125 MHz, CDCl3) δ 31.8, 31.9, 59.07, 59.13,
87.35, 87.42, 89.27, 89.31, 122.19, 122.22, 126.04, 126.06,
128.29, 128.30, 128.34, 128.4, 128.5 (duplicate), 128.81, 128.82,
131.9 (duplicate), 141.26, 141.30; IR (KBr) νmax 3050, 3025,
2910, 2345, 1595, 1575, 1490, 1445, 1420, 1400, 1285, 1270,
1180, 1070, 1030, 1000, 920, 855, 840, 755, 715, 685 cm-1; MS
m/z 564 (M+, 100), 536 (33), 504 (28), 476 (32), 472 (17), 444
(77), 412 (46). Anal. Calcd for C34H28S4: C, 72.34; H, 4.96.
Found: C, 72.85; H, 5.17.
Gen er a l P r oced u r e for Rea ction of 1,3-Bis(a lk ylth io)-
a llen es a n d Tetr a th ia cyclic Bisa llen es w ith Dip h en yl
Dia zom eth a n e. A benzene solution (10 mL) of diphenyl
diazomethane22 (1.2 mmol) and 1,3-bis(alkylthio)allene (0.6
mmol) or tetrathiacyclic bisallene (0.3 mmol) was refluxed for
14 h under nitrogen. After removal of solvent in vacuo, the
residue was subjected to silica gel column chromatography
(dichloromethane) followed by gel-peameation chromatography
(GPC). 1a : 65% conversion, 25 (79%); 1b: 38% conversion,
26 (11%), 27 (87%); meso-2a : 100% conversion, 10 (48%), 27
(12%), 28 (17%), 29 (13%); 10: 54% conversion, 27 (20%), 28
(41%), 29 (29%).
1,2-Bis(m eth ylth io)-1,3,4,4-tetr a p h en yl-(Z)-1,3-bu ta d i-
en e (25): mp 169-169.5 °C (yellow prisms from dichlo-
romethane-hexane); 1H NMR (500 MHz, CDCl3) δ 1.87 (s, 3H),
2.14 (s, 3H), 6.75-7.41 (m, 20H); 13C NMR (125 MHz, CDCl3)
δ 15.4, 16.1, 126.79, 126.81, 127.0, 127.2, 127.5, 127.6 (dupli-
cate), 127.7, 128.8, 130.0, 130.97, 131.01, 133.9, 135.1, 137.1,
138.1, 140.2, 142.95, 143.01, 143.5; IR (KBr) νmax 3050, 2930,
1595, 1575, 1540, 1495, 1440, 1320, 1280, 1185, 1075, 1035,
765, 695 cm-1; MS m/z 451 (M+ + 1, 100), 436 (7), 403 (6), 388
(10), 356 (30), 279 (15). Anal. Calcd for C30H26S2: C, 79.95; H,
5.82. Found: C, 79.89; H, 5.82.
Gen er a l P r oced u r e for P h otoch em ica l Rea ction of 1,3-
Bis(a lk ylth io)a llen es a n d Tetr a th ia cyclic Bisa llen es. A
benzene solution (100 mL) of 1,3-bis(alkylthio)allene (0.4
mmol) or tetrathiacyclic bisallene (0.2 mmol) was irradiated
with a 450 W medium-presure mercury lamp through a Pyrex
filter under argon for the desired period. After removal of
solvent in vacuo, the residue was subjected to gel-peameation
chromatography (GPC). 1a : 80% conversion, 18a (13%), 19a
(29%); 1b: 89% conversion, 18b (22%), 19b (23%); dl-2a : 94%
conversion, 20 (24%), 21 (20%), meso-2a (5%); meso-2a : 94%
conversion, 20 (22%), 21 (23%), dl-2a (6%).
3,3-Bis(m eth ylth io)-1,3-diph en ylpr opyn e (18a): mp 93.5-
1
94 °C (pale yellow solid); H NMR (500 MHz, CDCl3) δ 2.27
(s, 6H), 7.29-7.91 (m, 10H); 13C NMR (125 MHz, CDCl3) δ 15.8,
55.5, 86.5, 89.1, 122.4, 127.2, 128.2, 128.3, 128.4, 128.7, 131.9,
139.9; IR (KBr) νmax 3060, 3025, 3000, 2925, 2370, 2340, 1600,
1495, 1485, 1445, 1430, 1415, 1315, 1265, 1175, 1075, 1030,
965, 915, 860, 760, 725, 705, 685 cm-1; UV (cyclohexane) λmax
248 (ꢀ 1.9 × 104) nm; MS m/z 284 (M+, 28), 237 (100), 190 (40),
77 (21). Anal. Calcd for C17H16S2: C, 71.78; H, 5.67. Found:
C, 71.67; H, 5.50.
3,3-Bis(ben zylth io)-1,3-d ip h en ylp r op yn e (18b): yellow
liquid; 1H NMR (500 MHz, CDCl3) δ 3.98 (d, 2H, J ) 11.9 Hz),
4.10 (d, 2H, J ) 11.9 Hz), 7.09-7.95 (m, 20H); 13C NMR (125
MHz, CDCl3) δ 38.0, 56.3, 87.2, 89.5, 122.4, 127.1, 127.31,
127.32, 128.30, 128.33, 128.4, 128.8, 129.4, 131.9, 136.4, 139.9;
IR (neat) νmax 3075, 3050, 3025, 2920, 2350, 2320, 1660, 1595,
1490, 1450, 1445, 1310, 1235, 1175, 1160, 1070, 1025, 915, 840,
755, 740, 685 cm-1; MS m/z 435 (M+ - 1, 6), 413 (22), 345 (6),
313 (15), 222 (6), 190 (10), 91 (100); HRMS calcd for C29H24S2
436.1319, found 436.1269.
3-Ben zylth io-1,3,4,4-tetr a p h en yl-1-bu tyn e (26): yellow
liquid; 1H NMR (500 MHz, CDCl3) δ 3.33 (d, 1H, J ) 11.6 Hz),
3.62 (d, 1H, J ) 11.6 Hz), 4.67 (s, 1H), 6.98-7.83 (m, 25H);
13C NMR (125 MHz, CDCl3) δ 36.4, 56.9, 63.3, 89.6, 90.4, 123.2,
126.4, 126.8, 127.18, 127.23, 127.5, 127.9 (duplicate), 128.0,
(22) (a) Smith, L. I.; Howard, K. L. Organic Syntheses; Wiley: New
York, 1955; Collect. Vol. III, p 351. (b) Staudinger, H.; Anthes, E.;
Pfenninger, F. Ber. 1916, 49, 1928.

1728 J . Org. Chem., Vol. 65, No. 6, 2000
Shimizu et al.
128.1, 128.2, 128.5, 129.3, 129.6, 130.4, 131.5, 137.0, 140.4,
140.5, 141.4; IR (neat) νmax 3060, 3025, 2920, 1595, 1490, 1450,
1265, 1070, 1030, 915, 760, 690 cm-1; MS m/z 479 (M+ - 1),
389, 357, 313, 279, 191, 165, 121, 91, 77; HRMS calcd for
Com p ou n d m eso-2a . A colorless prism of C34H28S4 having
approximate dimension of 0.30 × 0.30 × 0.20 mm3. Triclinic
space group P1 with a ) 5.733(1) Å, b ) 11.069(3) Å, c )
12.306(3) Å, R ) 113.05(2)°, â ) 91.25(2)°, γ ) 99.24(2)°, V )
706.2(3) Å3, Z ) 1, and F(calcd) ) 1.328 g cm-3. Of the 3512
unique data, the 2575 with I > 3σ(I) were used in the least-
squares refinement to yield R ) 0.037 and Rw ) 0.039.
Com p ou n d 6. A yellow needle of C34H32S4 having approximate
dimension of 0.50 × 0.40 × 0.40 mm3. Monoclinic space group
P2/a with a ) 18.064(5) Å, b ) 11.274(2) Å, c ) 16.359(3) Å,
â ) 116.62(2)°, V ) 2978(1) Å3, Z ) 4, and F(calcd) ) 1.266 g
cm-3. Of the 6278 unique data, the 4624 with I > 3σ(I) were
used in the least-squares refinement to yield R ) 0.052 and
Rw ) 0.053. Com p ou n d 10. A yellow plate of C34H28S4 having
approximate dimension of 0.40 × 0.30 × 0.15 mm3. Ortho-
rhombic space group P212121 with a ) 9.803(2) Å, b ) 32.311(8)
Å, c ) 8.859(2) Å, V ) 2806(1) Å3, Z ) 4, and F(calcd) ) 1.336
g cm-3. Of the 3351 unique data, the 2412 with I > 3σ(I) were
used in the least-squares refinement to yield R ) 0.057 and
Rw ) 0.063. Com p ou n d 25. A yellow prism of C30H26S2 having
approximate dimension of 0.60 × 0.30 × 0.25 mm3. Monoclinic
space group P21/n with a ) 12.994(3) Å, b ) 18.214(3) Å, c )
10.907(2) Å, â ) 107.68(1)°, V ) 2459.5(7) Å3, Z ) 4, and
F(calcd) ) 1.217 g cm-3. Of the 2679 unique data, the 2481
with I > 3σ(I) were used in the least-squares refinement to
yield R ) 0.060 and Rw ) 0.108.
C
35H28S 480.1912, found 480.1940.
Tetr a p h en ylep isu lfid e (27): mp 171-172 °C (colorless
needles from dichloromethane-hexane) (lit.20 mp 177-179 °C);
1H NMR (500 MHz, CDCl3) δ 7.01-7.20 (m, 20H); 13C NMR
(125 MHz, CDCl3) δ 66.7, 126.6, 127.1, 130.9, 140.2; IR (KBr)
νmax 3060, 3025, 1595, 1490, 1440, 1315, 1220, 1180, 1075,
1030, 900, 840, 780, 750, 690 cm-1; MS m/z 365 (M+ + 1, 58),
333 (100), 288 (8), 165 (58), 77 (11).
2,7,9,10-Tetr aph en yl-3,6-dith iabicyclo[6.2.0]deca-(Z,Z,Z)-
1,7,9-tr ien e (28): mp 208-209 °C (yellow solid); 1H NMR (500
MHz, CDCl3) δ 3.22 (s, 4H), 6.54-7.32 (m, 20H); 13C NMR (125
MHz, CDCl3) δ 35.5, 120.6, 127.0, 127.1, 127.3, 127.8, 128.0,
130.8, 131.7, 139.4, 143.8, 152.1; IR (KBr) νmax 2900, 1590,
1570, 1440, 1400, 1260, 1090, 1070, 1025, 800, 770, 750, 690
cm-1; MS m/z 472 (M+, 91), 444 (37), 412 (100), 380 (9), 302
(23), 77 (11). Anal. Calcd for C32H24S2: C, 81.31; H, 5.12.
Found: C, 81.23; H, 5.08.
2,2-Dip h en yl-1,3-d ith iola n e (29): mp 95.5-96 °C (lit.17 mp
105 °C); 1H NMR (500 MHz, C6D6) δ 2.81 (s, 4H), 6.98 (t, 2H,
J ) 7.4 Hz), 7.06 (dd, 4H, J ) 7.4, 7.4 Hz), 7.77 (d, 4H, J )
7.4 Hz); 13C NMR (125 MHz, C6D6) δ 40.1, 77.5, 127.4, 128.3,
128.9, 145.2; MS m/z 258 (M+, 53), 229 (100), 198 (24), 181
(14), 165 (71), 77 (15).
X-r a y An a lysis: Gen er a l. Each crystal was mounted on a
glass fiber in a random orientation. Preliminary examination
and data collection were performed with Mo KR radiation (λ
Ack n ow led gm en t. This work was financially sup-
ported in part by a Grant-in-Aid for Scientific Research
on Priority Area and General Scientific Research from
the Ministry of Education, Science, Sports, and Culture,
J apan.
) 0.710 69 Å) on
a Mac Science MXC18 diffractometer
equipped with a graphite crystal, incident beam monochro-
mator. Cell constants and an orientation matrix for data
collection were obtained from least-squares refinement. The
data were collected at a temperature of 25 ( 1 °C using the
ω-2θ scan technique. The scan rate varied from 0 to 5 °/min
(in omega). Lorentz and polarization corrections were applied
to the data. No absorption correction was made. An extinction
correction was not necessary. Hydrogen atoms were included
in the refinement but restrained to ride on the atom to which
they are bonded. The structure was refined in full-matrix least-
squares where the function minimized was Σw(|Fo|-|Fc|)2, and
the weight w is defined as 1.0 for all observed reflections.
Su p p or tin g In for m a tion Ava ila ble: Detailed informa-
tion of the X-ray crystallographic analysis of 6, 10, and 25
including structure diagrams, details of data collection and
reduction and structure solution and refinement, tables of
positional and thermal parameters, and bond lengths, angles,
and torsional angles. This material is available free of charge
via the Internet at http://pubs.acs.org.
J O9915675