Rhodium-catalyzed reaction of aroyl chlorides with alkynes

Article abstract of DOI:10.1021/jo960915p

Aroyl chlorides react with terminal alkynes accompanied by decarbonylation in the presence of a catalytic amount of [RhCl(cod)]₂ and PPh₃ to give the corresponding vinyl chloride derivatives regioand stereoselectively in good yields.

Full text of DOI:10.1021/jo960915p

J . Org. Chem. 1996, 61, 6941-6946
6941
Rh od iu m -Ca ta lyzed Rea ction of Ar oyl Ch lor id es w ith Alk yn es
Ken Kokubo, Kenji Matsumasa, Masahiro Miura,* and Masakatsu Nomura
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565, J apan
Received May 17, 1996X
Aroyl chlorides react with terminal alkynes accompanied by decarbonylation in the presence of a
catalytic amount of [RhCl(cod)]2 and PPh3 to give the corresponding vinyl chloride derivatives regio-
and stereoselectively in good yields. The catalyst efficiency is a marked function of the ratio of
PPh3 to the rhodium species; satisfactory results are obtained by employing a PPh3/Rh ratio of 1.0.
The reaction may involve chlororhodation to the alkynes by the intermediary arylchlororhodium-
(III) species generated in situ followed by reductive elimination of the products, which are suggested
by the results of some control experiments. In contrast to the reaction with terminal alkynes, that
with some internal ones proceeds without decarbonylation to produce 2,3-disubstituted-1-indenones
as the predominant products. The product structures suggest that, while the arylchlororhodium
intermediate is also involved, arylrhodation to the alkynes, reinsertion of CO (coordinated to the
metal), and intramolecular cyclization sequentially take place to give the indenones.
In tr od u ction
catalysis,7 we observed that aroyl chlorides can effectively
react with terminal alkynes accompanied by decarbony-
lation in the presence of [RhCl(cod)]2 and PPh3 to give
the corresponding vinyl chloride derivatives regio- and
stereoselectively with good product yields (eq 2). More-
over, the reaction of aroyl chlorides with some internal
alkynes in place of terminal ones has been found to
proceed without decarbonylation to produce 2,3-disub-
stituted-1-indenones (eq 3).8
Aroyl chlorides are known to smoothly react with low-
valent transition-metal species, including rhodium and
palladium complexes, to produce the corresponding aroyl-
chlorometal complexes which may be further transformed
into arylchlorometal complexes by decarbonylation at
somewhat elevated temperatures.1 The aroyl- and aryl-
metal species may be expected to be synthetically ver-
satile, and indeed, catalytic aroylation of alkenes2 and
alkynes3 and arylation of alkenes4 and dienes5 with aroyl
chlorides using palladium complexes have been success-
fully developed. While such catalytic reactions could also
be realized by using rhodium species, they have been so
far unexplored.
On the other hand, we have recently reported that
benzoic anhydride smoothly reacts with styrene under a
normal pressure of hydrogen in the presence of a tertiary
amine and catalytic amounts of [RhCl(cod)]2 and a
phosphorus ligand to give 1,2-diphenyl-1-propanone to-
gether with its 1,3-diphenyl isomer (eq 1);6 however,
benzoyl chloride is ineffective for this reaction.
In the context of our study of arylation and aroylation
of unsaturated compounds by means of homogeneous
X Abstract published in Advance ACS Abstracts, September 1, 1996.
(1) (a) Collman, J . P.; Hegedus, L. S.; Norton, J . R.; Finke, R. G.
Principles and Applications of Organotransition Metal Chemistry;
University Science Books: Mill Valley, 1987. (b) Colquhoun, H. M.;
Thompson, D. J .; Twigg, M. V. Carbonylation; Plenum Press: New
York, 1991.
Consequently, a detailed investigation has been carried
(2) (a) Anderson, C.-M.; Hallberg, A. J . Org. Chem. 1988, 53, 4257.
(b) Daves, G. D., J r.; Hallberg, A. Chem. Rev. 1989, 89, 1433.
(3) Tohda, Y.; Sonogashira, K.; Hagihara, N. Synthesis 1977, 777.
(4) (a) Blaser, H.-U.; Spencer, A. J . Organomet. Chem. 1982, 233,
267. (b) Spencer, A. J . Organomet. Chem. 1982, 240, 209. (c) Spencer,
A. J . Organomet. Chem. 1983, 247, 117. (d) Spencer, A. J . Organomet.
Chem. 1984, 265, 323.
(5) (a) Obora, Y.; Tsuji, Y.; Kawamura, T. J . Am. Chem. Soc. 1993,
115, 10414. (b) Obora, Y.; Tsuji, Y.; Kawamura, T. J . Am. Chem. Soc.
1995, 117, 9814.
(7) (a) Miura, M.; Hashimoto, H.; Itoh, K.; Nomura, M. J . Chem.
Soc., Perkin Trans. 1 1990, 2207. (b) Okuro, K.; Furuune, M.; Miura,
M.; Nomura, M. J . Org. Chem. 1992, 57, 4754. (c) Okuro, K.; Furuune,
M.; Enna, M.; Miura, M.; Nomura, M J . Org. Chem. 1993, 58, 4716.
(d) Okuro, K.; Inokawa, N.; Miura, M.; Nomura, M. J . Chem. Res.,
Synop. 1994, 372. (e) Satoh, T.; Itaya, T.; Okuro, K.; Miura, M.;
Nomura, M. J . Org. Chem. 1995, 60, 7267.
(8) The relevant transition metal-mediated synthesis of indenones
using aryl halides and alkynes: (a) Liebeskind, L. S.; South, M. S. J .
Org. Chem., 1980, 45, 5426. (b) Larock, R. C.; Doty, M. J .; Cacchi, S.
J . Org. Chem., 1993, 58, 4579 and references therein.
(6) Kokubo, K.; Miura, M.; Nomura, M. Organometallics 1995, 14,
4521.
S0022-3263(96)00915-2 CCC: $12.00 © 1996 American Chemical Society

6942 J . Org. Chem., Vol. 61, No. 20, 1996
Kokubo et al.
Ta ble 1. Effect of Liga n d s on th e Rea ction of Ben zoyl
Ch lor id e (1a ) w ith P h en yla cetylen e (2a )a
Ta ble 2. Rea ction of Va r iou s Acid Ch lor id es 1 w ith
Ter m in a l Alk yn es 2a
entry
ligand (equiv)b
% yieldc
1
2d
3
4
5
6
7
8
9
10
11e
12f
13g
14h
15i
PPh3 (1)
PPh3 (1)
PPh3 (0)
PPh3 (2)
PPh3 (6)
PBu3 (1)
P(OPh)3 (1)
dppb (1)
dppb (0.5)
dppp (0.5)
PPh3 (1)
PPh3 (1)
PPh3 (1)
PPh3 (1)
PPh3 (1)
71
92
2
7
1
17
21
5
10
23
23
57
68
47
33
a
The reaction was carried out in octane at 140 °C for 20 h under
N2. [[RhCl(cod)]2]:[ligand]:[1a ]:[2a ] ) 0.01:0.02:2:2 (in mmol).
b
d
Relative to Rh metal. c GC yield based on 1a used. [2a ] ) 3
mmol. e Reaction at 100 °C. f Reaction at 120 °C. Reaction in
o-xylene. Reaction in 2-methoxyethyl ether. [[RhCl(cod)]2] )
0.001 mmol, [2a ] ) 3 mmol.
g
h
i
out to elucidate the factors affecting these reactions. The
results are described herein.
Resu lts a n d Discu ssion
Rea ction of Ben zoyl Ch lor id e (1a ) w ith P h en yl-
a cetylen e (2a ). When the reaction of 1a (2 mmol) with
2a (2 mmol) in the presence of [RhCl(cod)]2 (0.01 mmol,
1 mol %) and PPh3 (0.02 mmol; P/Rh ) 1.0) was carried
out in octane at 140 °C (bath temperature) for 20 h under
nitrogen, (Z)-1-chloro-1,2-diphenylethene (3a ) was ob-
tained in a yield of 71% (Table 1 and eq 1; Ar ) R ) Ph).
The product yield was increased up to 92% (based on
amount of 1a used) by using 3 mmol of 2a . Analysis of
1
the reaction mixture by H NMR and GC-MS confirmed
that no (E)-1-chloro-1,2-diphenylethene was formed. The
reaction was found to be very sensitive to the amount of
the ligand added; the product yield was very low, when
the PPh3/Rh ratio was g2 or 0. Other phosphorus
compounds, PBu3, P(OPh)3, dppb (Ph2P(CH2)4PPh2), and
dppp (Ph2P(CH2)3PPh2) were examined as ligands; how-
ever, none of them was superior to PPh3. At a lower
reaction temperature of 100 or 120 °C, the product yield
was considerably decreased. While o-xylene could be
used as well as octane as solvent, (CHCl2)2, 2-methoxy-
ethyl ether, and PhCN were less effective.
Rea ction of Va r iou s Acid Ch lor id es w ith Ter m i-
n a l Alk yn es. The reactions of 4-chloro- and 4-methyl-
benzoyl chlorides (1b and 1c) with 2a gave the corre-
sponding vinyl chloride derivatives 3b and 3c in good
yields, as did that of 1a (Table 2). Cinnamoyl chloride
(1d ) and crotonoyl chloride (1e) also reacted with 2a
smoothly to afford chlorodienes 3d and 3e. 1-Octyne
(2b), 1-ethynylcyclohexene (2c), and butyl propargyl
ether (2d ) could be used in place of 2a , giving compounds
3f-h . Reaction of 1a (6 mmol) with 1,7-octadiyne (2e; 2
mmol) gave compound 3i.
isomers, respectively, were contaminated. Reaction of
benzoyl bromide (1g) with 2a gave (Z)-1-bromo-1,2-
diphenylethene (3j) (73%) along with its (E)-isomer 3j′
(3%) (Table 3).
The configuration of each product was determined by
1H NMR with the aid of NOE experiments. For example,
NOE peak enhancements observed for products 3f and
3g were as follows. It should be noted that each product,
with the exception of 3h and 3i, did not accompany other
regio- and stereoisomers, which was confirmed by 1H
NMR and GC-MS. In the case of 3h and 3i, small
amounts (e5%) of the corresponding (E) and (Z,E)
Rea ction Sch em e for th e F or m a tion of 3.
A
plausible reaction mechanism, which may rationalize the
regio- and stereoselective formation of 3 from 1 and 2, is
illustrated in Scheme 1.
The reaction may be considered to involve initial
oxidative addition of aroyl chloride to a catalytically
active rhodium(I) species A generated from [RhCl(cod)]2
in the presence of PPh3 and a terminal alkyne to form

Rhodium-Catalyzed Reaction of Aroyl Chlorides with Alkynes
J . Org. Chem., Vol. 61, No. 20, 1996 6943
Sch em e 1
Sch em e 2
treatment of cinnamoyl chloride (1d ) and its R-phenyl
derivative 1f under the present catalytic conditions gave
no trace of â-chlorostyrenes (eq 4). In the light of these
results, the reaction sequence C f D f F seems to be
unlikely involved.
While chlororhodation to alkynes is less common, a
number of reactions, which involve chloropalladation to
them, are known.13,14 It has been recently reported that
stereochemistry of alkyne chloropalladation is dependent
on chloride ion concentration; at a low chloride concen-
tration, cis-chloropalladation predominates, whereas at
a high chloride concentration, trans-chloropalladation
becomes to be favorable.14 Consequently, we examined
effect of addition of a quaternary ammonium chloride or
bromide on the present reaction. When PhCH2NEt3Cl
(2 mmol) was added to the reaction of 1a (2 mmol) with
2a (3 mmol), a mixture of 3a and its (E)-isomer 3a ′ in a
ratio of 19:13 was formed (eq 5 and Table 3). This is in
marked contrast to the fact that without the chloride,
the (Z)-isomer 3a is exclusively produced. Addition of
Bu3NMeBr to the reaction of 1g with 2a also increased
the product (E)/(Z) ratio. These results led us to deduce
that the present haloarylation of terminal alkynes pre-
dominantly involves halorhodation reaction. The forma-
tion of the (E)-isomers 3a ′ and 3f′ is attributable to the
anti-addition of chloride and bromide added in interme-
diate C as shown in Scheme 2.
an aroylrhodium complex B. The subsequent decarbon-
ylation gives intermediate C. Then, there may exist two
possible pathways; the one is arylrhodation where the
aryl moiety migrates to the coordinated alkyne in C to
give complex D, and the other is chlororhodation where
the chlorine migrates to the alkyne to give complex E.
Whichever arylrhodation or chlororhodation, reductive
elimination affords product 3 along with carbonylrhod-
ium(I) species F . While the catalytic cycle proceeds,
ligand L′ is possibly CO, since it is known that complete
removal of CO from rhodium(I) species is rather dif-
ficult.1,9 However, the second CO seems to be capable of
being replaced by alkyne 2. It should be noted that
carbon monoxide exchange reaction in benzoyl chloride
with 13CO has been reported to occur in the presence of
RhCl(CO)(PPh3)2 even at 90 °C.10
If the reaction proceeds via arylrhodation, it has to
involve reductive elimination of the vinyl moiety with
chlorine from D. Generally, reductive elimination of
organic halides from haloorganometals usually requires
high temperatures over 200 °C.1,9,11 It is noted that
decarbonylation of R,â-unsaturated acyl chlorides with
a stoichiometric amount of RhCl(PPh3)3 has been re-
ported to produce vinyl triphenylphosphonium salts,
giving no vinyl chlorides.12 It was also confirmed that
R ea ct ion of Ar oyl Ch lor id es w it h In t er n a l
Alk yn es. In order to examine applicability of internal
alkynes to the present reaction, reaction of 1a with
4-octyne (2f) was first carried out as the representative
in o-xylene under the same conditions with those em-
ployed for the reactions with terminal alkynes. It was
somewhat surprising that 2,3-dipropyl-1-indenone (4a )
(12) Kampmeier, J . A.; Harris, S. H.; Rodehorst, R. M. J . Am. Chem.
Soc. 1981, 103, 1478.
(13) (a) Wiger, G.; Albelo, G.; Rettig, M. F. J . Chem. Soc., Dalton
Trans. 1974, 2242. (b) Wipke, W. T.; Goeke, G. L. J . Am. Chem. Soc.
1974, 96, 4244. (c) Mann, B. E.; Bailey, P. M.; Maitlis, P. M. J . Am.
Chem. Soc. 1975, 97, 1275. (d) Kaneda, K.; Uchiyama, T.; Fujiwara,
Y.; Imanaka, T.; Teranishi, S. J . Org. Chem. 1979, 44, 55. (e)
Yamaguchi, R.; Kawasaki, H.; Yoshitome, T.; Kawanisi, M. Chem. Lett.
1982, 1485. (f) Ma, S.; Lu, X. J . Chem. Soc., Chem. Commun. 1990,
733. (g) Ma, S.; Lu, X. J . Org. Chem. 1991, 56, 5120. (h) Ma, S.; Zhu,
G.; Lu, X. J . Org. Chem. 1993, 58, 3692. (i) Ba¨ckvall, J .-E.; Nilsson, Y.
I. M.; Andersson, P. G.; Gatti, R. G. P.; Wu, J . Tetrahedron Lett. 1994,
35, 5713. (j) J i, J .; Zhang, C.; Lu, X. J . Org. Chem. 1995, 60, 1060. (k)
Wang, Z.; Lu, X. J . Chem. Soc., Chem. Commun. 1996, 535.
(14) Ba¨ckvall, J .-E.; Nilsson, Y. I. M.; Gatti, R. G. P. Organometallics
1995, 14, 4242.
(9) Ohno, K.; Tsuji, J . J . Am. Chem. Soc. 1968, 90, 99.
(10) (a) Kampmeier, J . A.; Mahalingam, S. Organometallics 1984,
3, 489. (b) Kampmeier, J . A.; Mahalingam, S.; Liu, T.-Z. Organome-
tallics 1986, 5, 823.
(11) Blum, J .; Scharf, G. J . Org. Chem. 1970, 35, 1895.

6944 J . Org. Chem., Vol. 61, No. 20, 1996
Kokubo et al.
Ta ble 3. Effect of Ad d ition of Am m on iu m Ha lid e on th e
Rea ction of 1a or 1g w ith 2a a
Ta ble 4. Rea ction of Ar oyl Ch lor id es 1 w ith In ter n a l
Alk yn es 2f-k a
3, % yield
1
additive
none
PhCH2NEt3Cl
none
(Z)
(E)
1a
1a
1g
1g
92
19
73
41
0
13
3
Bu3NMeBr
12
a
Reaction was carried out in octane at 140 °C for 20 h under
N2. [[RhCl(cod)]2]:[ligand]:[1]:[2a ]:[additive] ) 0.01:0.02:2:3:2 (in
mmol).
was produced in 34% yield (14% in octane) as the single
major product, no vinyl chloride derivative being detected
(eq 3; X ) H, R ) Pr). By adding Na2CO3 as base to trap
hydrogen chloride evolved and some modifications of the
reaction conditions using 2 mol % of [RhCl(cod)]2, the
yield of 4a was increased up to 76% based on amount of
2f used (Table 4). The reactions of 4-substituted benzoyl
chlorides 1b, 1c, and 3-methylbenzoyl chloride (1h ) with
2f also gave indenones 4b-d . It was of quite interest
that the carbonyl moiety in these products was found to
be shifted to the neighboring position in the starting aroyl
chlorides. The reaction of 2-naphthoyl chloride (1i) with
2f predominantly gave 2,3-fused compound 4e along with
its 1,2-fused isomer 4e′. Alkynes 2g-k could react with
1a to give the corresponding indenones, while the product
yields were moderate to low. In the reactions using the
unsymmetrical alkynes 2i-k , two possible regioisomers
were formed in each case. In contrast to the reactions
with 2i-k , treatment of 1a with ethyl 2-heptynoate (2l)
gave ethyl (E)-3-chloro-2-phenylheptenoate (3k ) in a yield
of 41% (eq 6), no indenone product being detected.
Reaction of cinnamoyl chloride (1d ) with 2f afforded a
mixture of chlorodienes 3l and 3l′ in a ratio of 77:23, the
combined yield being 36% (eq 7). These results suggest
that the precedence of the reaction courses leading to
tetrasubstituted naphthalenes as byproducts in very low
yields (e4%). One of them produced from 1a and 2f was
isolated and determined to be 1,2,3,4-tetrapropylnaph-
thalene (5). It was also obtained in 18% yield from the
reaction in octane at a bath-temperature of 150 °C.
Rea ction Sch em e for th e F or m a tion of 4. A most
plausible mechanism to account for the formation of
indenones 4 based on the observed results is illustrated
in Scheme 3. The key intermediate leading to 4 may be
arylchlororhodium(III) species I, which is the equivalent
to C in Scheme 1, formed via complexes G and H.
Arylrhodation in I followed by reinsertion of carbon
monoxide coordinated to the metal center affords complex
K. The subsequent cyclization reaction accompanied by
vinyl chlorides and indenones depends on the structure
of acid chlorides as well as that of alkynes.
It is noted that elaborated analysis of the reaction
mixtures with 2f-k by GC-MS suggested formation of

Rhodium-Catalyzed Reaction of Aroyl Chlorides with Alkynes
Sch em e 3
J . Org. Chem., Vol. 61, No. 20, 1996 6945
regeneration of G and evolution of HCl gives product 4.
While aroylrhodation in H would lead to 4, the route may
be ruled out, since the structure of 4b-d and 4e′ is not
consistent with it. The structures of 4d and 4e may
suggest that each final cyclization step of K to 4 is
sterically controlled; steric hindrance by the methyl group
and the peri-hydrogen on the benzene and the naphtha-
lene rings, respectively, may be the major reason for the
selective formation of these products. The byproduct 5
may be formed via insertion of another alkyne molecule
in complex J (L′ ) 2).
Sch em e 4
Thus, it may be reasonable to consider that the present
rhodium-catalyzed reaction of 1 with 2 involve arylchlo-
rorhodium(III)-alkyne complexes such as C and I as the
common intermediates; chlororhodation and arylrhoda-
tion in them lead to vinyl chlorides 3 and indenones 4,
respectively. One of the major factors determining the
reaction routes and the product structures may be steric
repulsion in the vinylrhodium intermediates from C and
I (Scheme 4). Of the two possible intermediates J and
J ′ from I, there seems to be considerable steric repulsion
between the R group and the rhodium moiety in J ′ and
hence, arylrhodation to give J predominates. The steric
interaction in E from C appears to be small and therefore,
in the case of terminal alkynes, chlororhodation may be
the favorable path. The repulsion in J ′ in the reactions
of 1a with 2l (Ar ) Ph, R ) COOEt) and of 1d with 2f
(Ar ) PhCHdCH-, R ) Pr) may be relatively small to
produce vinyl chlorides 3k and 3l. Consequently, chlo-
rorhodation may be considered to be the energetically
favorable route relative to arylrhodation, when steric
hindrance dose not intervene.
carried out using a silicone OV-17 glass column (L 2.6 mm ×
1.5 m) or a CBP-1 capillary column (L 0.5 mm × 25 m). (E)-
1,2-Diphenyl-2-propenoyl chloride15 (1f), 3-butoxy-1-propyne16
(2e), and ethyl 2-heptynoate17 (2l) were prepared by the
methods reported previously. Other starting materials were
commercially available. The following experimental details
given below may be regarded as typical in methodology and
scale.
Rea ction of Ben zoyl Ch lor id e (1a ) w ith P h en yla cety-
len e (2a ). To a flask containing [RhCl(cod)]2 (4.9 mg, 0.01
mmol) and PPh3 (5.2 mg, 0.02 mmol) under nitrogen (with a
balloon) was added a solution of 1a (281 mg, 2 mmol), 2a (306
mg, 3 mmol), and 1-methylnaphthalene (ca. 100 mg) as an
(15) Fieser, L. F.; Williamson, K. L. Organic Experiments; D. C.
Heath and Company: Lexington, 1987.
(16) Vartanyan, R. S.; Kazaryan, Z. V.; Kucherov, V. F. Arm. Khim.
Zh. 1974, 27, 295; Chem. Abstr. 1974, 81, 77405r.
(17) Tsuji, J .; Takahashi, M.; Takahashi, T. Tetrahedron Lett. 1980,
21, 849.
Exp er im en ta l Section
1H NMR spectra were recorded at 400 MHz for CDCl3
solutions. MS data were obtained by EI. GC analysis was

6946 J . Org. Chem., Vol. 61, No. 20, 1996
Kokubo et al.
internal standard in octane (5 mL), and the resulting mixture
was stirred at 140 °C for 20 h. GC and GC-MS analyses of
the mixture confirmed formation of 3a (439 mg, 92%). Product
3a (434 mg, 91%) was also isolated by column chromatography
on silica gel using hexane as eluent.
1.49-1.69 (m, 4H), 2.38-2.63 (m, 4H), 6.59 (d, 1H, J ) 15.8
Hz; 3l′), 6.60 (d, 1H, J ) 15.8 Hz; 3l), 7.00 (d, 2H, J ) 15.8
Hz), 7.21-7.48 (m, 10H); MS m/ z 248, 250 (M+). HRMS m/ z
(M+) Calcd for C15H19O2Cl: 248.1332. Found: 3l; 248.1332,
3l′; 248.1329.
Rea ction of Ben zoyl Ch lor id e (1a ) w ith 4-Octyn e (2f).
To a flask containing [RhCl(cod)]2 (9.8 mg, 0.02 mmol), PPh3
(10.4 mg, 0.04 mmol) and Na2CO3 (212 mg, 2 mmol) under
nitrogen (with a balloon) was added a solution of 1a (422 mg,
3 mmol), 2f (220 mg, 2 mmol), and 1-methylnaphthalene (ca.
100 mg) as an internal standard in o-xylene (5 mL), and the
resulting mixture was stirred at 145 °C for 24 h. GC and GC-
MS analyses of the mixture confirmed formation of 4a (325
mg, 76%). Product 4a (312 mg, 73%) was also isolated by
column chromatography on silica gel using hexane-dichlo-
romethane (9:1, v/v) as eluent.
6-Ch lor o-2,3-d ip r op yl-1-in d en on e (4b): yellow solid, mp
50.5-50.7 °C; 1H NMR δ 0.93 (t, 3H, J ) 7.3 Hz), 1.03 (t, 3H,
J ) 7.3 Hz), 1.49 (sextet, 2H, J ) 7.5 Hz), 1.63 (sextet, 2H, J
) 7.7 Hz), 2.23 (t, 2H, J ) 7.6 Hz), 2.51 (t, 2H, J ) 7.8 Hz),
6.96 (d, 1H, J ) 7.7 Hz), 7.28 (dd, 1H, J ) 7.7, 2.0 Hz), 7.32
(d, 1H, J ) 2.0 Hz); MS m/ z 248, 250 (M+); IR (KBr): 1707.2
(CdO) cm-1. Anal. Calcd for C15H17ClO: C, 72.43; H, 6.89;
Cl, 14.25. Found: C, 72.26; H, 6.93; Cl, 14.10.
2,3-Dip r op yl-6-m et h yl-1-in d en on e (4c): yellow oil; 1H
NMR δ 0.92 (t, 3H, J ) 7.3 Hz), 1.01 (t, 3H, J ) 7.3 Hz), 1.47
(sextet, 2H, J ) 7.4 Hz), 1.63 (sextet, 2H, J ) 7.5 Hz), 2.21 (t,
2H, J ) 7.6 Hz), 2.30 (s, 3H), 2.49 (t, 2H, J ) 7.8 Hz), 6.90 (d,
1H, J ) 7.3 Hz), 7.08 (dt, 1H, J ) 7.3, 1.0 Hz), 7.18 (d, 1H, J
P r od u cts. Compounds 3a ,18 3a ′,19 3e,20 3j,21 3j′,21 4a ,8b 4f,8a
4g,8a 4h ,8a 4h ′,8a and 4j′8b are known and were compared with
those authentic specimens. The analytical data of other
products 3, 4, and 5 are as follows.
) 1.0 Hz); MS m/ z 228 (M+); IR (neat): 1707.2 (CdO) cm-1
.
HRMS m/ z (M+) Calcd for C16H20O: 228.1514. Found:
228.1512.
(Z)-1-Ch lor o-2-(4-ch lor op h en yl)-1-p h en yleth en e (3b):
mp 60.0-60.5 °C; 1H NMR δ 7.00 (s, 1H), 7.35-7.43 (m, 5H),
7.67-7.70 (m, 4H); MS m/ z 248, 250, 252 (M+). Anal. Calcd
for C14H10Cl2: C, 67.49; H, 4.05; Cl, 28.46. Found: C, 67.69;
H, 4.05; Cl, 28.36.
2,3-Dip r op yl-5-m eth yl-1-in d en on e (4d ): yellow oil; 1H
NMR δ 0.93 (t, 3H, J ) 7.3 Hz), 1.03 (t, 3H, J ) 7.3 Hz), 1.48
(sextet, 2H, J ) 7.3 Hz), 1.63 (sextet, 2H, J ) 7.3 Hz), 2.22 (t,
2H, J ) 7.8 Hz), 2.38 (s, 3H), 2.50 (t, 2H, J ) 7.8 Hz), 6.83 (s,
1H), 6.93 (d, 1H, J ) 7.3 Hz), 7.26 (d, 1H, J ) 7.3 Hz); MS
m/ z 228 (M+); IR (neat): 1705.3 (CdO) cm-1. HRMS m/ z (M+)
Calcd for C16H20O: 228.1514. Found: 228.1529.
(Z)-1-C h lo r o -2-(4-m e t h y lp h e n y l)-1-p h e n y le t h e n e
1
(3c): mp 45.5-46.0 °C; H NMR δ 2.38 (s, 3H), 7.04 (s, 1H),
7.21 (d, 2H, J ) 8.1 Hz), 7.33-7.42 (m, 3H), 7.64-7.71 (m,
4H); MS m/ z 228, 230 (M+). Anal. Calcd for C15H13Cl: C,
78.77; H, 5.73; Cl, 15.50. Found: C, 78.81; H, 5.92; Cl, 15.45.
(Z,E)-2-Ch lor o-1,4-diph en yl-1,3-bu tadien e (3d): mp 111-
2,3-Dip r op ylben z[d ]-1-in d en on e (4e): yellow solid, mp
46.0-46.5 °C; 1H NMR δ 0.97 (t, 3H, J ) 7.3 Hz), 1.08 (t, 3H,
J ) 7.3 Hz), 1.54 (sextet, 2H, J ) 7.3 Hz), 1.73 (sextet, 2H, J
) 7.3 Hz), 2.32 (t, 2H, J ) 7.8 Hz), 2.63 (t, 2H, J ) 7.8 Hz),
7.32 (s, 1H), 7.41 (t, 1H, J ) 7.8 Hz), 7.48 (t, 1H, J ) 7.8 Hz),
7.73 (d, 1H, J ) 7.8 Hz), 7.80 (d, 1H, J ) 7.8 Hz), 7.81 (s, 1H);
MS m/ z 264 (M+); IR (KBr): 1699.5 (CdO) cm-1. Anal. Calcd
for C19H20O: C, 86.32; H, 7.63. Found: C, 86.23; H, 7.62.
2,3-Dip r op ylben z[e]-1-in d en on e (4e′): red solid, mp
43.5-44.5 °C; 1H NMR δ 0.96 (t, 3H, J ) 7.3 Hz), 1.06 (t, 3H,
J ) 7.3 Hz), 1.54 (sextet, 2H, J ) 7.6 Hz), 1.69 (sextet, 2H, J
) 7.3 Hz), 2.25 (t, 2H, J ) 7.6 Hz), 2.56 (t, 2H, J ) 7.6 Hz),
7.26 (d, 1H, J ) 8.3 Hz), 7.31 (t, 1H, J ) 8.3 Hz), 7.47 (t, 1H,
J ) 8.3 Hz), 7.69 (d, 1H, J ) 8.3 Hz), 7.85 (d, 1H, J ) 8.3 Hz),
8.69 (d, 1H, J ) 8.3 Hz); MS m/ z 264 (M+); IR (KBr): 1693.7
(CdO) cm-1. HRMS m/ z (M+) Calcd for C19H20O: 264.1514.
Found: 264.1516.
1
112 °C; H NMR δ 6.80 (d, 1H, J ) 7.9 Hz), 6.94 (d, 1H, J )
5.3 Hz), 7.25-7.40 (m, 7H), 7.49-7.52 (m, 2H), 7.67-7.69 (m,
2H); MS m/ z 240, 242 (M+). Anal. Calcd for C16H13Cl: C,
79.83; H, 5.44; Cl, 14.73. Found: C, 79.52; H, 5.70; Cl, 14.38.
(Z)-2-Ch lor o-1-p h en yl-1-octen e (3f): oil; 1H NMR δ 0.90
(t, 3H, J ) 6.8 Hz), 1.30-1.37 (m, 6H), 1.65 (quintet, 2H, J )
7.3 Hz), 2.48 (t, 2H, J ) 7.3 Hz), 6.46 (s, 1H), 7.23-7.27 (m,
1H), 7.32-7.36 (m, 2H), 7.58-7.59 (m, 2H); MS m/ z 222, 224
(M+). Anal. Calcd for C14H19Cl: C, 75.49; H, 8.60; Cl, 15.92.
Found: C, 75.69; H, 8.73; Cl, 15.84.
(Z)-1-Ch lor o-1-(1-cycloh exen yl)-2-p h en ylet h en e (3g):
1
oil; H NMR δ 1.60-1.68 (m, 2H), 1.72-1.78 (m, 2H), 2.22-
2.27 (m, 2H), 2.34-2.39 (m, 2H), 6.50-6.52 (m, 1H), 6.69 (s,
3-7.37 (m, 2H), 7.63 (d, 2H, J ) 7.3 Hz); MS m/ z 218, 220
(M+). Anal. Calcd for C14H15Cl: C, 76.88; H, 6.91; Cl, 16.21.
Found: C, 76.63; H, 6.96; Cl, 16.09.
3 (or 2)-Bu tyl-2 (or 3)-m eth yl-1-in d en on e (4i a n d 4i′;
1:1): yellow oil; 1H NMR δ 0.89-0.98 (m, 6H), 1.30-1.46 (m,
6H), 1.56-1.60 (m, 2H; 4i), 1.80 (s, 3H; 4i′), 2.11 (s, 3H; 4i),
2.27 (t, 2H, J ) 7.5 Hz; 4i′), 2.53 (t, 2H, J ) 7.5 Hz), 7.00-
7.02 (m, 2H), 7.13-7.17 (m, 2H), 7.26-7.37 (m, 4H); MS m/ z
(Z)- a n d (E)-3-Bu toxy-2-ch lor o-1-p h en yl-1-p r op en e (3h
a n d 3h ′; 85:15): oil; 1H NMR δ 0.93 (t, 3H, J ) 7.6 Hz), 1.38-
1.44 (m, 2H), 1.57-1.65 (m, 2H), 3.45 (t, 2H, J ) 6.6 Hz; 3h ′),
3.52 (t, 2H, J ) 6.6 Hz; 3h ), 4.17 (s, 2H; 3h ), 4.21 (s, 2H; 3h ′),
6.74 (s, 1H; 3h ), 6.94 (s, 1H; 3h ′), 7.24-7.29 (m, 1H), 7.32-
7.37 (m, 2H), 7.63 (d, 2H, J ) 7.3 Hz); MS m/ z 224, 226 (M+).
HRMS m/ z (M+) Calcd for C13H17OCl: 224.0968. Found:
224.0960.
(Z,Z)-2,7-Dich lor o-1,8-d ip h en yl-1,7-octa d ien e (3i): mp
58.5-59.5 °C; 1H NMR δ 1.71-1.75 (m, 4H), 2.51-2.55 (m,
4H), 6.49 (s, 2H), 7.23-7.27 (m, 2H), 7.32-7.36 (m, 4H), 7.58-
7.60 (m, 4H); MS m/ z 330, 332, 334 (M+). Anal. Calcd for
C20H20Cl2: C, 72.51; H, 6.09; Cl, 21.40. Found: C, 72.47; H,
6.11; Cl, 21.32.
Eth yl (Z)-3-ch lor o-2-p h en yl-2-h ep ten oa te (3k ): oil; 1H
NMR δ 0.96 (t, 3H, J ) 7.3 Hz), 1.23 (t, 3H, J ) 7.1 Hz), 1.42
(sextet, 2H, J ) 7.3 Hz), 1.67-1.75 (m, 2H), 2.79 (t, 2H, J )
7.7 Hz), 4.19 (q, 2H, J ) 7.1 Hz), 7.25-7.38 (m, 5H); MS m/ z
266, 268 (M+). HRMS m/ z (M+) Calcd for C15H19O2Cl:
266.1073. Found: 266.1077.
200 (M+); IR (neat): 1709.1 (CdO) cm-1
.
HRMS m/ z (M+)
Calcd for C14H16O: 200.1201. Found: 200.1203.
2-P h en yl-3-(tr im eth ylsilyl)-1-in den on e (4j): yellow solid,
mp 111.5-112.0 °C; 1H NMR δ 0.08 (s, 9H), 7.10-7.42 (m, 9H);
MS m/ z 278 (M+); IR (KBr): 1705.3 (CdO) cm-1. Anal. Calcd
for C18H18OSi: C, 77.65; H, 6.52. Found: C, 77.75; H, 6.56.
1,2,3,4-Tetr a p r op yln a p h th a len e (5): oil; 1H NMR δ
1.08-1.13 (m, 12H), 1.56-1.71 (m, 8H), 2.71-2.75 (m, 4H),
2.98-3.03 (m, 4H), 7.38-7.41 (m, 2H), 7.97-8.00 (m, 2H); MS
m/ z 296 (M+); HRMS m/ z (M+) Calcd for C22H32: 296.2504.
Found: 296.2501.
Ack n ow led gm en t. The present work was partly
supported by a Grant-in-Aid for Scientific Research from
the Ministry of Education, Science and Culture of
J apan.
(E,Z)- a n d (E,E)-4-Ch lor o-1-p h en yl-3-p r op yl-1,3-h ep -
ta d ien e (3l a n d 3l′; 3:1): oil; H NMR δ 0.93-1.01 (m, 6H),
Su p p or tin g In for m a tion Ava ila ble: 1H NMR spectra for
3h (+3h ′), 3k , 3l (+3l′), 4c, 4d , 4e′, 4i (+4i′), and 5 (8 pages).
This material is contained in libraries on microfiche, im-
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journal, and can be ordered from the ACS; see any current
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1
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