Acetyl chloride-ethanol brings about a remarkably efficient conversion of allyl acetates into allyl chlorides

Article abstract of DOI:10.1016/j.tet.2003.09.063

AcCl-EtOH transforms primary and secondary allyl acetates into allyl chlorides that retain the olefinic bond in the more stable position. Whereas secondary allyl alcohols also react with almost the same efficacy as the acetates, the reactions of primary allyl alcohols that possess 1, 2-disubstituted alkenes are very slow. The products are isolated in high state of purity simply by removal of the volatiles.

Full text of DOI:10.1016/j.tet.2003.09.063

Tetrahedron 59 (2003) 9111–9116
Acetyl chloride–ethanol brings about a remarkably efficient
conversion of allyl acetates into allyl chlorides
*
Veejendra K. Yadav and K. Ganesh Babu
Department of Chemistry, Indian Institute of Technology, Kanpur 208016, India
Received 11 July 2003; revised 29 August 2003; accepted 18 September 2003
Abstract—AcCl–EtOH transforms primary and secondary allyl acetates into allyl chlorides that retain the olefinic bond in the more stable
position. Whereas secondary allyl alcohols also react with almost the same efficacy as the acetates, the reactions of primary allyl alcohols that
possess 1,2-disubstituted alkenes are very slow. The products are isolated in high state of purity simply by removal of the volatiles.
q 2003 Published by Elsevier Ltd.
1. Introduction
2. The reaction of allyl acetates with AcCl–EtOH
The transformation of an allyl alcohol into its chloride can
be achieved in several ways. The classical method involving
the reaction with SOCl2 generates the rearranged chloride
exclusively from both primary and secondary alcohols.1
MsCl–LiCl,2 Ph3P–CCl4,3 ZnCl2–diethylazodicarboxy-
late–Ph3P,4 N-halosucciniimide–Me2S,5 TsCl–DMAP,6
and tetramethyl-a-haloenamines7 achieve the transform-
ation of primary alcohols containing trisubstituted olefins
An allyl acetate (1 mmol) and EtOH (8 mmol) were mixed
with AcCl (8 mmol) at 238C. The contents were stirred
magnetically until the reaction was complete by TLC. The
volatiles were removed on a rotovap under water aspirator
pressure to obtain the product. Using this simple protocol,
several allyl acetates were transformed into allyl chlorides
in excellent yields. The results are collected in Table 1.
8
into the corresponding primary chlorides. TMSCl–SeO2
9
and BiCl3 are nonspecific reagents that yield both the
The cinnamyl acetate was converted into cinnamyl chloride in
30 min (entry 1). A reaction on 10 mmol scale proceeded just
as well. 2-Acetoxymethyl-2-cyclohexen-1-one gave 2-chloro-
methyl-2-cyclohexen-1-one exclusively in 5 min (entry 2).
Geranyl acetate gave (E)-1,7-dichloro-3,7-dimethyl-2-octene
predominantly (entry 3). Likewise, neryl acetate gave (Z)-1,7-
dichloro-3,7-dimethyl-2-octene predominantly (entry 4). The
geometry of the 2,3-double bond in both the geranyl acetate
and the neryl acetate was retained. Obviously, trisubstituted
alkenes also reacted under the conditions and added the
elements of HCl in Markovnikov fashion.
unrearranged and the rearranged chlorides. Several of these
reagents are expensive, not readily available, toxic and
unfriendly to the environment. Furthermore, they require
aqueous workup and chromatographic purification of the
product. Thus, there is scope for methods that avoid several
or all of the above difficulties.
We report herein a simple, inexpensive, rapid and high
yielding protocol for the conversion of allyl acetates (and
allyl alcohols) into allyl chlorides bearing the p-bond in the
more stable position using reagents as simple as AcCl and
EtOH. To our best information, no method for the direct
transformation of allyl acetates into allyl chlorides has
hitherto been reported in the literature. The products are
isolated in high yields simply by removing the volatiles. The
requisite acetates were prepared very conveniently by
following a known protocol.10
(E)-2-Nonen-1-ol acetate gave a 6.7:1 mixture of (E)-1-
chloro-2-nonene and 3-chloro-1-nonene (entry 5). The
reaction was complete in 150 min. (E)-5-Phenyl-2-penten-
1-ol acetate gave a 6.3:1 mixture of (E)-5-phenyl-1-chloro-
2-pentene and 5-phenyl-3-chloro-1-pentene (entry 6). This
constitutes an efficient preparation of primary allyl chlorides
from the corresponding primary allyl acetates. The
experimental simplicity and the ease of product isolation
easily offset the difficulty arising from the small amount of
the rearranged chloride that is also formed.
The secondary allyl acetates also reacted very well. (E)-4-
Phenyl-3-buten-2-ol acetate gave (E)-2-chloro-4-phenyl-3-
butene exclusively (entry 7). 1-Phenyl-2-propene-1-ol
Keywords: allyl acetate; allyl alcohol; allyl chloride.
*
Corresponding author. Tel.: þ91-512-2597439; fax: þ91-512-2597436;
e-mail: vijendra@iitk.ac.in
0040–4020/$ - see front matter q 2003 Published by Elsevier Ltd.
doi:10.1016/j.tet.2003.09.063

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V. K. Yadav, K. Ganesh Babu / Tetrahedron 59 (2003) 9111–9116
Table 1. Conversion of allyl acetates/alcohols into allyl chlorides.a The values given in the parentheses are for the reactions of the corresponding allyl alcohols
Entry
1
Substrate
Time (min)
30 (30)
Product(s)
Yield (%)
96 (91)
2
5
96
3
15 (15)
95 (93)b,c
4
15 (15)
93 (94)b,d
5
6
7
8
150 (1440)
150 (1440)
30 (30)
94 (2)b,e
95 (2)b,f
95 (93)g
91 (91)
10 (15)
9
5
96
10
11
45 (45)
30 (30)
45 (60)
94 (92)b,h
92 (94)b,h
89 (89)b,i
12
a
The ratio acetate/AcCl/EtOH was 1:8:8.
The ratios were calculated from the relative 1H NMR integrals.
a/b/c¼13.6:5.0:1 (9.4:2.1:1).
The ratio of the normal and the rearranged chlorides was 6.7:1. 1H NMR of the chlorides was identical with reported data.11
The ratio of the normal and the rearranged chloride was 6.3:1.
The 1H NMR of the chloride was identical with reported data.12
1:1 Mixture of chlorides was formed.
The ratio of the rearranged and normal chloride was 2.3:1 (2.1:1).
b
c
d
e
f
a/b/c¼6.1:1.6:1 (5.4:1.2:1).
g
h
i

V. K. Yadav, K. Ganesh Babu / Tetrahedron 59 (2003) 9111–9116
9113
acetate (entry 8) and methyl 3-acetoxy-3-(4-methoxy-
phenyl)-2-methylidenepropionate (entry 9) gave the
rearranged chlorides exclusively. The (E)-geometry of the
p-bond in methyl 3-(4-methoxyphenyl)-2-chloromethyl-
acrylate (entry 9) was determined from nOe studies. The
irradiation of CH2Cl resulted in enhancement of the
absorption for two aromatic protons.
Table 2. Reaction of 2-nonen-1-ol acetate with AcCl–EtOH. A case study
of products distribution (primary vs secondary chlorides) against reaction
time
Entry
Time (min)
Ratio (18:28 chloride)a
% Conversion
1
2
3
4
5
030
060
090
120
150
.20:1
10:1
7.7:1
7.5:1
6.7:1
30
55
80
95
The acetates of 6-phenyl-3-hexene-2-ol (entry 10) and
3-decen-2-ol (entry 11) delivered 1:1 mixtures of the
isomeric chlorides. 1H NMR analysis of aliquots of the
reaction of 3-decen-2-ol acetate that were withdrawn at
intervals of 5 min from the commencement of the reaction
and quenched immediately with water showed the presence
of the corresponding isomeric alcohols in 1:1 ratio, though
in very small amounts, along with a 1:1 mixture of the above
isomeric chlorides. A similar result was obtained from the
reaction of 6-phenyl-3-hexen-2-ol acetate. The formation of
only small amounts of the isomeric alcohols in comparison
to the isomeric chlorides suggests an enormously efficient
capture by the chloride ion of either the allyl cation formed
from ionization of the protonated allyl acetate or the
protonated allyl acetate itself through SN2/SN20 pathways as
shown below. Although we have evidence for both, we
prefer the latter to accommodate the successful reactions of
the acetates of 2-nonen-1-ol and 5-phenyl-2-penten-1-ol
(vide supra) and the failures of the corresponding alcohols
(vide infra).
100
a
The ratio was determined from the 1H integrals of CH2Cl (d 4.04) and
CHCl (d 4.36–4.31) absorptions.
3. The reaction of allyl alcohols with AcCl–EtOH
We have also studied the reactions of allyl alcohols with
AcCl–EtOH to ascertain (a) whether indeed the chloride
formation via the acetate route was necessary, and, if yes,
(b) whether the acetate pathway was any better than the
alcohol pathway. These results are also collected in Table 1.
Several features deserve comment. The primary alcohols
such as 2-nonen-1-ol (entry 5) and 5-phenyl-2-penten-1-ol
(entry 6) that had 1,2-disubstituted olefins reacted extremely
slow as only traces of chlorides were formed even after 24 h.
There was no improvement in the reaction even when
16 equiv. of AcCl and EtOH each were used. In contrast,
cinnamyl alcohol (entry 1), geraniol (entry 3) and nerol
(entry 4) underwent smooth transformation to give cinna-
myl chloride, (E)-1,7-dichloro-3,7-dimethyl-2-octene and
(Z)-1,7-dichloro-3,7-dimethyl-2-octene, respectively, along
with the rearranged chlorides in the last two instances in
high yields.
Secondary alcohols were also conveniently transformed into
isomeric chlorides. As above with the corresponding
acetates, 4-phenyl-3-buten-2-ol (entry 7) reacted without
rearrangement, 1-phenyl-2-propene-1-ol (entry 8) gave
exclusively the rearranged chloride, and 1-phenyl-3-
butene-2-ol (entry 12) gave a 2.1:1 mixture of chlorides
wherein the rearranged isomer predominated. 6-Phenyl-3-
hexen-2-ol (entry 10) and 3-decen-2-ol (entry 11) offered an
almost 1:1 mixture of the isomeric chlorides.
The equal distribution of the two isomeric chlorides
suggests equal propensity of attack by chloride ion on
either terminus of the allyl system. This is due probably to
the secondary nature of both the termini and the energeti-
cally similar disubstituted nature of the p-bond in both the
isomers. The reaction of 1-phenyl-3-butene-2-ol acetate
gave a mixture of the rearranged and the normal chlorides in
the ratio 2.3:1 (entry 12). The larger amount of the
rearranged chloride than that of the normal chloride is
likely to be a consequence of both the (a) faster SN2 attack
on a primary center than that at a secondary center and (b)
higher p-bond stability for its higher substitution.
The rapid reactions of cinnamyl alcohol, geraniol and nerol
in comparison to those of 2-nonen-1-ol and 5-phenyl-2-
penten-1-ol could be attributed to the higher stability and,
hence, faster generation of carbocations in the former
examples. The product-stability controlled the regioselec-
tivity and, thus, predominantly the primary chlorides were
formed from cinnamyl alcohol, geraniol and nerol. The
generation of allyl cations from secondary allyl alcohols
was also smooth and the reaction proceeded with much
facility. These results with 2-nonen-1-ol and 5-phenyl-2-
penten-1-ol are at variance from those obtained from the
corresponding acetates that reacted rapidly and with high
regioselectively.
1H NMR analysis of aliquots, withdrawn at 30 min
intervals, of the reaction of (E)-2-nonen-1-ol acetate was
undertaken to explore the origin of the rearranged chloride.
The results are collected in Table 2. The secondary chloride
is obviously a product of isomerization of the primary
chloride as the concentration of the secondary chloride
increased with the increase in reaction duration. The
primary chloride itself is a product of bimolecular
displacement of the acetate function by chloride ion (vide
infra).
A comparison of the data in Table 1 suggests that in so far as
the transformation of substrates like 2-nonen-1-ol and 5-
phenyl-2-penten-1-ol into the corresponding primary allyl
chlorides is concerned, the reaction via the acetate is the
sole choice. The results for the reactions of other primary
and secondary allyl alcohols and acetates are almost similar.

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V. K. Yadav, K. Ganesh Babu / Tetrahedron 59 (2003) 9111–9116
The acetate route, however, offered cleaner products in
somewhat improved yields.
order. Concentration and filtration through a short silica gel
column gave the desired alcohol; 128 mg, 90% (colorless
liquid).
5.1.3. (E)-6-Phenyl-3-hexen-2-ol. To a suspension of NaH
(1.65 mmol, 40 mg) in THF (2 mL) was added diethyl (2-
oxopropyl)phosphonate (1.65 mmol, 320 mg) in THF
(4 mL) at 08C slowly with stirring. The mixture was
allowed to stir for 5 min. 3-Phenyl-1-propanal (1.5 mmol,
195 mg) in THF (4 mL) was added slowly and the reaction
mixture was stirred overnight. It was diluted with Et2O and
washed with saturated aqueous NH4Cl, water, and brine, in
that order. Concentration and filtration of the residue
through a short silica gel column afforded (E)-6-phenyl-3-
hexen-2-one; 214 mg, 82% (colorless liquid).18
4. Conclusion
We have presented a rapid, operationally simple, inexpen-
sive, and high yield protocol for the transformation of allyl
acetates into allyl chlorides using AcCl–EtOH combination
as a source of in situ HCl. The primary allyl alcohols with
simple 1,2-disubstituted p-bonds such as 2-nonen-1-ol and
5-phenyl-2-penten-1-ol do not react. In contrast, the
corresponding acetates reacted smoothly with high regios-
electivity to furnish the primary chloride almost
exclusively.
(E)-6-Pheyl-3-hexen-2-one (1.23 mmol, 214 mg) was dis-
solved in methanol (2.5 mL) and cooled to 08C. NaBH4
(1.23 mmol, 46 mg) was added to it in one portion under
stirring. A vigorous gas evolution was noticed and the
reaction mixture was allowed to stir for 15 min. MeOH was
evaporated and the residue was taken in Et2O, washed with
saturated aqueous NH4Cl, water, and brine, in that order.
The residue left after solvent removal was filtered through a
short silica gel column to afford (E)-6-phenyl-3-hexen-2-ol;
208 mg, 96% (colorless liquid).19
5. Experimental
5.1. General
IR spectra were recorded on Bruker Vector 22 FTIR
1
spectrophotometer in CH2Cl2 solution. H and 13C NMR
spectra were recorded on JEOL JNM-LA400 in CDCl3. The
1H and 13C positions are reported in d value relative to TMS
(internal standard) and the central line for CDCl3,
respectively. The solvents were removed under reduced
pressure on a rotovap. The chromatographic separations,
whenever required, were performed by silica gel (100–200
mesh) column chromatography using mixtures of EtOAc
and hexanes. 2-Hydroxymethyl-2-cyclohexen-1-one,13 3-
hydroxy-3-(4-methoxyphenyl)-2-methylidenepropionate,14
5-phenyl-3-penten-1-ol15a and 1-phenyl-3-buten-2-ol15b
were prepared using literature protocols.
5.1.4. (E)-3-Decen-2-ol. To
a suspension of NaH
(2.4 mmol, 58 mg) in THF (3 mL) was added diethyl (2-
oxopropyl)phosphonate (2.4 mmol, 464 mg) in THF (5 mL)
at 08C slowly with stirring. The mixture was allowed to stir
for 5 min. Heptanal (2 mmol, 228 mg) in THF (5 mL) was
added slowly and the reaction mixture was stirred overnight.
It was diluted with Et2O and washed with saturated aqueous
NH4Cl, water, and brine, in that order. Concentration and
filtration of the residue through a short silica gel column
afforded (E)-3-decen-2-one; 262 mg, 85% (colorless
liquid).20
5.1.1. (E)-4-Phenyl-3-buten-2-ol. 4-Pheyl-3-buten-2-one
(2 mmol, 292 mg) was dissolved in methanol (5 mL) and
cooled to 08C. NaBH4 (76 mg, 2 mmol) was added to it in
one portion under stirring. A vigorous gas evolution was
noticed and the reaction mixture was allowed to stir for
15 min. MeOH was evaporated and the residue was taken in
Et2O and washed with saturated aqueous NH4Cl, water, and
brine, in that order. The residue left after solvent removal
was filtered through a short silica gel column to afford the
alcohol; 280 mg, 95% (colorless liquid).16
(E)-3-Decen-2-one (1.0 mmol, 154 mg) was dissolved in
methanol (2.5 mL) and cooled to 08C. NaBH4 (1.0 mmol,
38 mg) was added to it in one portion under stirring. A
vigorous gas evolution was noticed and the reaction mixture
was allowed to stir for 15 min. MeOH was evaporated and
the residue was taken in Et2O and washed with saturated
aqueous NH4Cl, water, and brine, in that order. The residue
left after solvent removal was filtered through a short silica
gel column to afford (E)-3-decen-2-ol; 150 mg, 96%
(colorless liquid).
5.1.2. (E)-2-Nonene-1-ol. To a suspension of NaH
(2.4 mmol, 58 mg) in THF (2 mL) was added triethyl
phosphanoacetate (2.4 mmol, 0.48 mL) in THF (2 mL) at
08C slowly with stirring. The mixture was allowed to stir for
30 min. Heptanal (2 mmol, 228 mg) in THF (4 mL) was
added slowly at the same temperature and the reaction
mixture was stirred overnight. It was diluted with Et2O and
washed with saturated aqueous NH4Cl, water, and brine, in
that order. Concentration and filtration of the residue
through a short silica gel column afforded ethyl (E)-2-
nonenate; 294 mg, 80% (colorless liquid).17
5.1.5. Large scale reaction of cinnamyl acetate. AcCl
(80 mmol, 5.7 mL) was added dropwise over 30 min to a
stirred solution of cinnamyl acetate (10 mmol, 1.76 g) in
EtOH (80 mmol, 4.7 mL) that was taken in a round bottom
flask closed with a rubber septum. The stirring was
continued at 308C for 10 min. The volatiles were removed
on a rotovap under reduced pressure to obtain the product,
1.46 g, 96%.
DIBAL-H (2 mmol) was added slowly to a solution of ethyl
2-noneate (1 mmol, 184 mg) in toluene (2 mL) at 08C under
stirring. The mixture was stirred at the same temperature for
1 h and then diluted with Et2O. The ether solution was
washed with 2% cold aqueous HCl, H2O, and brine, in that
5.2. General procedure for the conversion of alcohols
into chlorides
AcCl (8 mmol, 0.57 mL) was added dropwise to a solution

V. K. Yadav, K. Ganesh Babu / Tetrahedron 59 (2003) 9111–9116
9115
of alcohol (1 mmol) in EtOH (8 mmol, 0.47 mL). The
reaction flask was stoppered tightly and the contents were
stirred at 238C. After the reaction was complete to TLC, the
volatiles were removed on a rotovap under reduced pressure
to obtain the product.
1H), 5.68–5.61 (qtd, J¼15.1, 7.1, 0.7 Hz, 1H), 4.02 (d,
J¼7.1 Hz, 2H), 2.38 (q, J¼7.6 Hz, 2H).
1
Characteristic H signals for 5-phenyl-3-chloro-1-pentene
(minor isomer). d 5.96–5.87 (m, 1H), 5.28–5.24 (qd,
J¼17.0, 0.8 Hz, 1H), 5.17–5.14 (dd, J¼10.1, 0.8 Hz, 1H),
4.34–4.29 (dt, J¼7.4, 7.1 Hz, 1H), 2.17–2.08 (m, 2H). 13C
NMR (mixture) d 141.4, 135.0, 128.50, 128.48, 128.4,
128.3, 126.5, 126.1, 125.9, 116.8, 62.2, 45.3, 39.7, 35.2,
33.8, 32.5. Anal. calcd for C11H13Cl: C, 73.13; H, 7.25.
Found: C, 73.00; H, 7.15.
5.2.1. Methyl-3-acetoxy-3-(4-methoxyphenyl)2-methyli-
dinepropionate (colorless liquid). 1H NMR was in
accordance to the reported data.21
5.2.2. 2-Acetoxymethyl-2-cyclohexen-1-one (colorless
liquid). 1H NMR was in accordance to the reported data.22
5.2.9. Mixture of (E)-6-phenyl-2-chloro-3-hexene and
(E)-6-phenyl-4-chloro-2-hexene (1:1) (colorless liquid).
IR cm21 1453, 1374, 1244, 1046, 1028, 740, 700.
5.2.3. (E)-2-Acetoxy-6-phenyl-3-hexene (colorless
liquid). 1H NMR was in accordance to the reported data.23
5.2.4. (E)-2-Acetoxy-3-decene (colorless liquid). IR cm21
1738, 1667, 1460, 1374, 1243, 1025. 1H NMR d 5.73–5.66
(td, J¼15.4, 6.8 Hz, 1H), 5.48–5.42 (qdd, J¼15.4, 6.8,
1.0 Hz, 1H), 5.34–5.28 (quintet, J¼6.8 Hz, 1H), 2.03 (s,
3H), 2.03–2.01 (m, 2H), 1.36–1.28 (m, 8H), 1.29 (d,
J¼6.8 Hz, 3H), 0.88 (t, J¼6.7 Hz, 3H). 13C NMR d 170.3,
133.4, 129.3, 71.2, 32.1, 31.6, 28.9, 28.8, 22.5, 21.4, 20.3,
14.0. Anal. calcd for C12H22O2: C, 72.67; H, 11.19. Found:
C, 72.50; H, 10.94.
Characteristic 1H signals for (E)-6-phenyl-2-chloro-3-
hexene. d 4.55–4.48 (quintet, J¼7.0 Hz, 1H), 2.38–2.33
(m, 2H), 1.56 (d, J¼6.6 Hz, 3H).
Characteristic 1H signals for (E)-6-phenyl-4-chloro-2-
hexene. d 4.34–4.29 (dt, J¼8.2, 6.2 Hz, 1H), 2.18–2.02
(m, 2H), 1.73–1.71 (dd, J¼6.3, 1.5 Hz, 3H). 13C NMR
(mixture) 141.4, 140.9, 132.8, 131.9, 131.4, 128.7, 128.5,
128.44, 128.43, 128.3, 126.0, 125.9, 62.7, 58.3, 40.2, 35.3,
33.6, 32.7, 25.4, 17.5. Anal. calcd for C12H15Cl: C, 74.03;
H, 7.77. Found: C, 73.82; H, 7.62.
5.2.5. Mixture of (E)-1,7-dichloro-3,7-dimethyl-2-
octene,24 (Z)-1,7-dichloro-3,7-dimethyl-2-octene and
3,7-dichloro-3,7-dimethyl-1-octene (colorless liquid). IR
cm21 1661, 1452, 1372, 1255, 1117, 741, 672, 566.
5.2.10. Mixture of (E)-2-chloro-3-decene and (E)-4-
1
chloro-2-decene (1:1) (colorless liquid). H NMR was in
accordance to the reported data.12
Characteristic 1H signals for (Z)-1,7-dichloro-3,7-dimethyl-
2-octene. 1H NMR d 4.08 (d, J¼8.3 Hz, 2H), 2.15 (t,
J¼7.3 Hz, 2H).
5.2.11. Mixture of (E)-1-chloro-4-phenyl-2-butene and 2-
chloro-1-phenyl-3-butene (2.3:1) (colorless liquid). IR
cm21 1665, 1603, 1495, 1452, 1251, 966, 748, 699.
1
Characteristic H signals for 3,7-dichloro-3,7-dimethyl-1-
octene (liquid). 1H NMR d 6.03–5.96 (dd, J¼17.1, 10.7 Hz,
1H), 5.27 (d, J¼17.1 Hz, 1H), 5.12 (d, J¼10.7 Hz, 1H).
Anal. calcd for C10H18Cl2: C, 57.67; H, 8.72. Found: C,
57.54; H, 8.60.
Characteristic 1H signals for (E)-1-chloro-4-phenyl-2-
butene. d 5.72–5.64 (td, J¼15.1, 7.1 Hz, 1H), 4.06 (d,
J¼7.1 Hz, 2H), 3.40 (d, J¼6.8 Hz, 2H).
Characteristic 1H signals for 2-chloro-1-phenyl-3-butene. d
5.23–5.19 (dd, J¼16.8, 0.7 Hz, 1H), 5.14–5.11 (dd,
J¼10.3, 0.7 Hz, 1H), 4.58–4.52 (q, J¼7.4 Hz, 1H), 3.13–
3.11 (dd, J¼7.1, 2.2 Hz, 2H). Anal. calcd for C10H11Cl: C,
72.07; H, 6.65. Found: C, 72.18; H, 6.61.
5.2.6. (E)-Methyl-3-(4-methoxyphenyl)-2-chloromethy-
lacrylate (colorless liquid). IR cm21 1708, 1602, 1512,
1439, 1308, 1259, 1217, 1177, 1091, 1030, 836. 1H NMR d
7.83 (s, 1H), 7.56 (d, J¼8.5 Hz, 2H), 6.98 (d, J¼8.5 Hz,
2H), 4.52 (s, 2H), 3.87 (s, 3H), 3.86 (s, 3H). 13C NMR d
167.0, 160.9, 143.7, 131.8, 126.6, 125.8, 114.4, 55.3, 52.3,
39.6. Anal. calcd for C12H13ClO3: C, 59.99, H, 5.46. Found:
C, 59.80; H, 5.30.
Acknowledgements
Authors thank Council of Scientific and Industrial Research,
Govt. of India, for support of this research. KGB thanks
CSIR for Senior Research Fellowship.
5.2.7. 2-Chloromethyl-2-cyclohexen-1-one (colorless
liquid). IR cm21 1670, 1265, 742. 1H NMR d 7.15 (t,
J¼4.0 Hz, 1H), 4.22 (s, 2H), 2.50–2.44 (m, 4H), 2.07–2.00
(m, 2H). 13C NMR d 197.4, 149.3, 136.0, 40.9, 38.1, 26.0,
22.6. Anal. calcd for C7H9ClO: C, 58.32; H, 6.30. Found: C,
58.20; H, 6.15.
References
5.2.8. Mixture of (E)-5-phenyl-1-chloro-2-pentene and 5-
phenyl-3-chloro-1-pentene (6.3:1) (colorless liquid). IR
cm21 1666, 1603, 1495, 1453, 1251, 967, 748, 699.
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Characteristic 1H signals for (E)-5-phenyl-1-chloro-2-
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