Polychlorobutanoic and polychlorobutenoic acids in the synthesis of polyfunctional derivatives

Article abstract of DOI:10.1023/A:1020980921916

From 3,4,4-trichloro-3-butenoic acid 3,3,4,4,4-pentachlorobutanoic, 3,4,4,4-tetrachloro-2-butenoic, and 2,3,4,4-tetrachloro-3-butenoic acids were synthesized. By Friedel - Krafts reaction from 3,4,4-trichloro-3-butenoyl and 3,3,4,4,4-pentachlorobutanoyl c

Full text of DOI:10.1023/A:1020980921916

Russian Journal of Organic Chemistry, Vol. 38, No. 8, 2002, pp. 1099 1104. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 8, 2002,
pp. 1150 1155.
Original Russian Text Copyright
2002 by Potkin, Kaberdin, Petkevich, Kurman.
Polychlorobutanoic and Polychlorobutenoic Acids
in the Synthesis of Polyfunctional Derivatives
V. I. Potkin, R. V. Kaberdin, S. K. Petkevich, and P. V. Kurman
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, 220072 Belarus
Received November 7, 2001
Abstract From 3,4,4-trichloro-3-butenoic acid 3,3,4,4,4-pentachlorobutanoic, 3,4,4,4-tetrachloro-2-
butenoic, and 2,3,4,4-tetrachloro-3-butenoic acids were synthesized. By Friedel Krafts reaction from
3,4,4-trichloro-3-butenoyl and 3,3,4,4,4-pentachlorobutanoyl chlorides with aromatic hydrocarbons the
corresponding aryl chloroalkyl ketones were prepared. It was established that dehydrochlorination of
2,2,3,3,3-pentachloropropyl phenyl ketone with aqueous alkali under conditions of the phase-transfer
catalysis at the molar ratio of reagents ketone: KOH: triethylbenzylammonium chloride equal to 1: 4: 0.05
involved the cleavage of two HCl molecules and resulted in 3,3,3-trichloro-1-propynyl phenyl ketone.
Chloro-substituted carboxylic acids possess
versatile useful properties and find application as
extractants for rare-earth elements, as promotors of
Ziegler Natta catalysts, fire inhibitors, and biolo-
gically active compounds [1]. We formerly developed
a convenient preparation method for 3,4,4-trichloro-
3-butenoic acid (I) [2], a promising compound for the
synthesis of various polyfunctional substances. The
initial compound for the preparation of acid I is the
dehydrochlorination product of an available trichloro-
ethylene dimer, 2-H-pentachloro-1,3-butadiene (II).
The reaction of diene II with a methanol solution of
alkali or sodium methylate results in methyl 3,4,4-tri-
chloro-3-butenoate (III), and its acid hydrolysis
furnished the target acid I.
according to patent data [3] carboxylic acids contain-
ing no less than 4 carbon and 5 chlorine atoms
possess high biological activity. The chlorination was
carried out with gaseous chlorine in a carbon tetra-
chloride solution at room temperature in the sunlight.
Under these conditions reaction was complete within
30 min affording in 90% yield product of chlorine
molecule addition across the double carbon carbon
bond in the trichlorovinyl group, 3,3,4,4,4-penta-
chlorobutanoic acid (IV). No hydrogen substitution
in the CH2 group was observed. By boiling acid IV in
methanol in the presence of catalytic quantity of
H2SO4 its methyl ester V was obtained in 92% yield.
The composition and structure of acid IV and its
ester V were confirmed by elemental analysis and
1
We carried out chlorination of acid I aiming at
IR, H, and mass spectra, and also by measuring
preparation of more chlorinated derivatives since
equivalent weight of acid IV by titration. In the IR
1070-4280/02/3808-1099$27.00 2002 MAIK Nauka/Interperiodica

1100
POTKIN et al.
spectra of compounds IV, V the absorption bands of
chlorinated crotonic acids appear in stronger field, in
130 ppm region, whereas the corresponding signals
for the Z-isomers are present at 140 148 ppm [7].
C=O bond vibrations appear respectively at 1721 and
1
1744 cm . To the OH group of acid IV corresponds
1
a broad band in the region 2500 3200 cm , to the
The treatment of ester VII with sodium methylate
solution in methanol provided in 60% yield a product
of internal chlorine substitution by a methoxy group,
the corresponding methyl 3-methoxy-4,4,4-trichloro-
2-butenoate (VIII) whose structure was proved by
spectral data (see EXPERIMENTAL). The character-
istic signal in the 13C NMR spectrum of compound
VIII at 94.73 ppm belonging to the trichloromethyl
group [8] indicated, that the group remained intact,
and the substitution occurred at C3 atom.
vibrations of C Cl bonds in both compounds belong
1
the absorption bands in the 736 823 cm range. In
1
the H NMR spectrum of acid I the signals of CH2
and COOH groups were found as a singlet at
3.72 ppm and a broadened singlet at 10.10 ppm
1
respectively. In the H NMR spectrum of ester V the
signal of methoxy group appears as a singlet at
3.74 ppm, and a singlet of methylene group is
observed at 3.54 ppm. In the mass spectrum of ester
V in the group of molecular ion peaks the ratio of
intensities of the main isotope components (61: 100:
65: 21) corresponds to the presence of five chlorine
atoms in the molecule [4, 5].
The hydrolysis of esters VII, VIII with 20%
hydrochloric acid took an uncommon course, and
instead of the corresponding crotonic acids gave rise
to 2,3,4,4-tetrachloro-3-butenoic acid that formed by
isomerization of the 3,4,4,4-tetrachloro-2-butene
skeleton. Therewith in ester VIII occurred also a
formal substitution of chlorine for methoxy group in
position 3 of the molecule. Presumably first an enol
structure VIIIa formed followed by substitution of
the hydroxy group by chlorine and rearrangement
into 2,3,4,4-tetrachloro-3-butenoic acid (IX). By a
special experiment we demonstrated that boiling of
acid VI in 20% hydrochloric acid for 8 h resulted in
its complete isomerization into acid IX.
The dehydrochlorination of acid IV and ester V
was studied under various conditions. It was found
that dehydrochlorination with aqueous KOH in the
presence of triethylbenzylammonium chloride as
phase-transfer catalyst and also dehydrochlorination
with triethylamine in methanol is accompanied by
tarring, and the yield of target products does not
exceed 5 15%. Reactions with water solutions of
sodium hydrogen carbonate and potassium carbonate
failed to occur. The optimum procedure consisted in
the use of pyridine in methanol solution at heating to
60 C. Under these conditions acid IV underwent
more selective dehydrochlorination furnishing in 55%
yield 3,4,4,4-tetrachloro-2-butenoic acid (VI). The
dehydrochlorination of compound V gave rise to
methyl 3,4,4,4-tetrachloro-2-butenoate (VII) in 38%
yield. In the reactions an appreciable amount of tar
was formed.
The composition and structure of products VI and
VII were confirmed by elemental analysis and IR,
1H, and mass spectra, and also by comparison of the
physical characteristics with the published data [6].
The presence of the central C=C bond is proved by
the appearance in the IR spectra of compounds VI,
VII of a characteristic absorption band at 1629 and
In the IR spectrum of acid IX to the vibrations of
the terminal C=C bond corresponds an absorption
1
band at 1593 cm , to those of C Cl bond the bands
1
1
at 752, 848, and 923 cm . In the H NMR spectrum
the proton of the CHCl group appears as a singlet
with the chemical shift of 5.85 ppm, and to the
COOH group corresponds a broadened singlet at
10.41 ppm. The 13C NMR spectrum of acid IX lacks
the signals of trichloromethyl group in the region
85 95 ppm and of =CH group that are characteristic
of the crotonic acid VI; instead signals appear from
CHCl group at 57.88 ppm (JC H 150.5 Hz) and from
carbon atoms of trichlorovinyl moiety at 125.72 and
127.02 ppm.
1
1634 cm respectively. In the 13C NMR spectra the
signals of trichloromethyl groups are observed at
95.29 ppm for acid VI and 95.28 ppm for ester VII.
The appearance of signals from carbons in = C 3Cl
moiety in the 13C NMR spectra of compounds VI and
VII at 147.36 and 144.82 ppm respectively evidence
that both the acid VI and ester VII form as Z-iso-
mers: Preliminary detailed studies of 13C NMR
spectra from a series of chlorobutenoic acids and their
esters has demonstrated that the signals of carbon
atoms of = C 3Cl moieties in the E-isomers of
The available trichlorobutenoic (I) and penta-
chlorobutanoic (IV) acids can serve as convenient
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

POLYCHLOROBUTANOIC AND POLYCHLOROBUTENOIC ACIDS
1101
initial compounds for preparation of chlorine-sub-
stituted alkyl aryl ketones. Chlorine-substituted
ketones are interesting substances applied to prepar-
ation of helminthicides, insecticides, and the other
biologically active compounds [9]. Some among them
are more active than penicillin and streptomycin.
By treating acids I, IV with solution of thionyl
chloride in carbon tetrachloride the corresponding
acyl chlorides X, XI were obtained in 95 and 74%
yield respectively. Then we used compounds X, XI
for acylation of aromatic hydrocarbons along Friedel
Krafts method to prepare ketones XII XVII.
R = H (XII), 4-CH3 (XIII), 4-Br (XIV), 4-OCH3 (XV), 2,5-(CH3)2 (XVI).
The acylation took 3 4 h and afforded ketones
with trichloroallyl (XII XVI) or pentachloropropyl
(XVII) group and with different substituents in the
aromatic ring in 48 75% yields.
products of hydrogen substitution by chlorine in the
methylene group or aromatic ring was detected.
A reaction of dehydrochlorination of 2,2,3,3,3-
pentachloropropyl phenyl ketone XVII with aqueous
alkali was studied under conditions of phase-transfer
catalysis. It was established that under optimal con-
ditions [at the molar ratio of reagents ketone: KOH
The composition and structure of ketones
XII XVII obtained were confirmed by elemental
1
analysis and IR, H, and mass spectra. The relevant
data are given in a table. In the IR spectra are ob-
served the absorption bands from vibrations of the
(20%
water
solution): triethylbenzylammonium
chloride equal to 1: 4: 0.05] the reaction at room
temperature took 3 h and resulted in a cleavage of two
HCl molecules furnishing 3,3,3-trichloro-1-propynyl
phenyl ketone XVIII in 46% yield. At reduced
relative amount of alkali or at its lower concentration
a mixture of products formed, and some of initial
ketone XVII remained unreacted. The raising of
temperature in this case did not provide positive
result and favored decomposition of the initial com-
pounds and reaction products.
1
following bonds: C=O, at 1677 1700 cm ; C=C, at
1
1
1555 1617 cm ; C Cl, at 726 841 cm . In the
1H NMR spectra of compounds XII XVII the singlet
in the region 4.19 4.28 ppm is assigned to the
protons of CH2 group, and multiplets at
6.90
8.00 ppm to the protons of aromatic ring. In the
spectra were also observed the signals from the
substituents attached to the aromatic ring with an
appropriate integral intensity. In the mass spectra of
ketones the groups of molecular ion peaks are present
where the relative intensity of the main isotope
components equal to 100: 98: 32: 3.5 for compounds
XII XVI and 61: 100: 65: 21 for compound XVII
indicating the presence in the molecule of three and
five chlorine atoms respectively [4, 5].
The structure of 3,3,3-trichloropropynyl phenyl
ketone (XVIII) was confirmed by elemental analysis,
IR, 1H and 13C NMR spectra, and by GC-MS
method. In the IR spectrum of compound XVIII
appear the absorption bands of carbonyl group vibr-
ations at 1644 cm , of C=C bonds from the benzene
ring at 1583 and 1598 cm , of acetylene C C bond
at 2218 cm , of C Cl bond at 763 cm .
1
1
The chlorination of 2,3,3-trichloroallyl phenyl
ketone (XII) with gaseous chlorine in CCl4 under
sunlight was investigated. It was shown that the reac-
tion occurred exclusively at the double bond if the tri-
chlorovinyl group of compound XII giving rise to
2,2,3,3,3-pentachloropropyl phenyl ketone (XVII)
in preparative yield of 92%. The compound was
identical by its physical characteristics and spectra to
the product of benzene alkylation with acyl chloride
XI; this fact additionally supports its structure. No
1
1
1
In the H NMR spectrum of compound XVIII to
the protons of aromatic ring belong multiplets with
the chemical shifts of 7.63 ppm (3H arom) and 8.09
(2H arom). In the 13C NMR spectrum registered with
decoupling from protons appear signals at 76.7 and
83.8 ppm characteristic of acetylene carbons, and
a signal at 86.0 ppm corresponding to the trichloro-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

1102
POTKIN et al.
1
Yields, melting points, IR, H NMR spectra, and elemental analyses of ketones XII XVII
1
Compd. Yield, mp,
no.
IR spectrum, , cm
1H NMR spectrum, , ppm
%
C
XII
75 45 46 1690(C=O), 1584, 1600, 1617(C=C), 749, 784 4.28 s (2H, CH2), 7.55 m (3H arom),
(C Cl) 7.95 m (2H arom)
XIII
XIV
XV
71 75 76 1683 (C=O), 1568, 1608 (C=C), 758, 823 (C Cl) 2.42 s (3H, CH3), 4.25 s (2H, CH2),
7.28 d(2Harom), 7.83 d(2Harom, J 7.7 Hz)
48 82 83 1686 (C=O), 1571, 1590, 1614 (C=C), 767, 830 4.24 s (2H, CH2), 7.64 d (2Harom), 7.28 d
(C Cl)
7.80 d (2H arom, J 8 Hz)
55 66 67 1679 (C=O), 1592, 1614 (C=C), 766, 785, 841 3.85 s (3H, OCH3), 4.22 s (2H, CH2),
(C Cl)
6.93 d (2H arom), 7.91 d (2H arom,
J 9 Hz)
XVI
70 48 49 1677 (C=O), 1555, 1571, 1607 (C=C), 761, 2.36
s
(3H, CH3), 2.46
s
(3H,
CH3), 4.19 s (2H, CH2), 7.13 d and
7.23 d (2H arom, J 8 Hz), 7.41 br.s
(1H arom)
830 (C Cl)
XVII
58 91 92 1700 (C=O), 1578, 1595 (C=C), 726, 764, 793 4.27 s (2H, CH2), 7.55 m (3H arom),
(C Cl) 7.98 m (2H arom)
Found, %
Calculated, %
H
M
Compd.
no.
Formula
C
H
Cl
C
Hlg
founda
calc.
XII
48.77 2.80 42.41
50.46 3.22 40.13
36.70 2.08 56.43
46.89 3.50 38.16
52.10 4.34 38.59
37.22 2.45 54.51
C10H7Cl3O
C11H9Cl3O
C10H6Cl3BrO
C11H9Cl3O2
C12H11Cl3O
C10H7Cl5O
48.13 2.83
50.13 3.44
36.57 1.84
47.26 3.25
51.92 4.00
37.48 2.20
42.63
40.36
56.72
38.05
38.32
55.32
248
262
326
278
276
318
249.55
263.55
328.43
279.55
277.58
320.44
XIII
XIV
XV
XVI
XVII
a
Molecular weight determined from mass spectra (values listed in table are for ions M+ containing 35Cl isotope).
methyl group [8]. It follows from the spectrum
registered in the DEPT mode that to the aromatic ring
carbons correspond the signals with the chemical
shifts 129.4, (C3H, C5H), 130.1 (C2H, C6H), 135.6
(C4H) and 136.2 (C1) ppm. The signal from the
carbonyl group is located at 175.9 ppm. The mass
spectrum of ketone contained the isotope peaks of
molecular ion of m/z 246 (calculated for 35Cl isotope).
to TMS. Mass spectra were measured on mass
spectrometer MKh-1320 at ionizing electrons energy
50 eV. GC-MS analysis was performed on Hewlett-
Packard GC/MS 5890/5972 instrument.
The reaction progress was monitored and the
products were analyzed by GLC on chromatograph
Chrom-41 equipped with glass columns 1500 3 mm,
stationary phase 5% SE-30 on Chromaton N-AW-
DMCS (0.160 0.200 ). detector katharometer, oven
temperature 160 C, carrier gas helium.
The ketones obtained are convenient synthons for
further application to the organic synthesis of poly-
functional compounds.
3,4,4-Trichloro-3-butenoic acid (I) was prepared
by procedure [3] from 2-H-pentachloro-1,3-butadiene
(II).
EXPERIMENTAL
IR spectra were recorded on Fourier spectro-
photometer Protege-460 from KBr pellets (com-
pounds IV VI, IX, XI XVIII) or from thin film
(compounds VII, VIII, X, XI). NMR spectra were
registered on spectrometer Tesla -567A (100 MHz) in
CDCl3 solutions, chemical shifts measured relative
3,3,4,4,4-Pentachlorobutanoic
acid
(IV).
Through a solution of 5.7 g (0.03 mol) of 3,4,4-tri-
chloro-3-butenoic acid (I) in 25 ml of carbon tetra-
chloride under sunlight was passed a stream of
chlorine for 30 min. The separated colorless crystal-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

POLYCHLOROBUTANOIC AND POLYCHLOROBUTENOIC ACIDS
1103
line precipitate was filtered off and washed with cold
CCl4. We obtained 7.05 g (90%) of 3,3,4,4,4-penta-
chlorobutanoic acid IV, mp 132 134 C (from CCl4).
Found, %: C 18.70; H 1.41; Cl 67.88. Meq 260.
C4H3Cl5O2. Calculated, %: C 18.45; H 1.16; Cl
68.09. M 260.34.
3,4,4,4-tetrachloro-2-butenoate (VII) in 5 ml of
MeOH at 25 C while vigorous stirring was added
dropwise 0.68 g of sodium methylete in 5 ml of
methanol. The mixture was stirred for 2 h, the
precipitate was filtered off, the filtrate was poured
into water, and the product was extracted with ether.
The extract was dried with CaCl2, the solvent was
removed. The vacuum distillation of the residue
afforded 1.18 g (60%) of ester VIII. bp 80 81 C
( 4 mm Hg). d240 1.427. n2D0 1.5031. IR spectrum,
Methyl 3,3,4,4,4-pentachlorobutanoate (V). In
30 ml of anhydrous methanol was dissolved 1.3 g
(5 mmol) of acid IV, 3 drops of concn. H2SO4 was
added, and the mixture was boiled for 8 h. Then the
mixture was poured into water, the precipitate was
filtered off, washed with water, dried in a vacuum,
and recrystallized from hexane. We obtained 1.26 g
(92%) of ester V, mp 50 51 C. Found, %: C 22.29;
H 2.15; Cl 64.20. [M]+ 272 (for 35Cl). C5H5Cl5O2.
Calculated, %: C 21.89; H 1.84; Cl 64.61. M 274.37.
1
cm : 780, 827 (C Cl), 1646 (C=C), 1730 (C=O),
1
3088 (=C H). H NMR spectrum, , ppm: 3.78 s
(3H, COOCH3), 4.12 s (3H, OCH3), 6.28 s (1H,
=CH). 13C NMR spectrum, , ppm: 52.34 (OCH3,
JC H 147.6 Hz), 65.67 (OCH3, JC H 147.8 Hz), 94.73
(CCl3), 101.20 (=CH, JC H 165.5 Hz), 164.82 and
164.83 (=CCl and C=O). Found, %: C 30.46; H
3.14; Cl 45.93. [M]+ 232 (for 35Cl). C6H7Cl3O3.
Calculated, %: C 30.87; H 3.02; Cl 45.55. M 233.48.
Dehydrochlorination of 3,3,4,4,4-pentachloro-
butanoic acid. A mixture of 5 g (19.2 mmol) of
3,3,4,4,4-pentachlorobutanoic
acid,
4.56
g
Hydrolysis of methyl 3,4,4,4-tetrachloro-2-
butenoate (VII). A mixture of 3.05 g (12.8 mmol)
of ester VII and 30 ml of 20% aqueous HCl was
stirred at 100 C for 10 h. On cooling the mixture to
25 C the reaction product was extracted with di-
chloromethane, extract was dried on CaCl2, the
solvent was removed, and by vacuum distillation was
isolated 1.15 g (40%) of 2,3,4,4-tetrachloro-3-
butenoic acid (IX), mp 80 81 C [11]. 13C NMR
spectrum, , ppm: 57.88 (CHCl, JC H 150.5 Hz),
125.72 and 127.02 (CCl2=CCl ), 170.02 (C=O).
Found, %: C 21.72; H 1.21; Cl 63.44. Meq 220.
C4H2Cl4O2. Calculated, %: C 21.46; H 0.90; Cl
63.35. M 223.87.
(57.6 mmol) of pyridine, and 15 ml of methanol was
stirred for 8 h at 60 C (GLC monitoring), then the
mixture was cooled and poured into cold water,
acidified with HCl to pH 3, and the reaction product
was extracted with dichloromethane. The extract was
dried with CaCl2, the solvent was removed, and the
solid residue was recrystallized from hexane. We
obtained 2.37 g (55%) of Z-3,4,4,4-tetrachloro-2-
butenoic acid (VI), mp 83 85 C in agreement with
1
the published data [6]. IR spectrum, cm : 781, 817
(C Cl), 1620 (C=C), 1699 (C=O), 3083 (C H).
1H NMR spectrum, , ppm: 7.13 s (1H, =CH),
10.78 br.s (1H, COOH). 13C NMR spectrum,
,
ppm: 95.29 (CCl3), 119.15 (=CH, JC H 168.1 Hz),
147.36 (=CCl), 168.27 (C=O). Found, %: C 21.59;
H 1.09; Cl 63.01. Meq 222. C4H2Cl4O2. Calculated,
%: C 21.46; H 0.90; Cl 63.35. M 223.87.
Hydrolysis of methyl 3-methoxy4,4,4-tetra-
chloro-2-butenoate (VIII) was carried out similarly,
but the reaction took 3 h.
Dehydrochlorination of methyl 3,3,4,4,4-penta-
chlorobutanoate (V) was carried out in a similar
way, but the product was purified by vacuum distil-
lation. Yield of methyl 3,4,4,4-tetrachloro-2-buteno-
ate (VII) 38%, bp 50 52 C ( 1 mm Hg). d240 1.523.
3,4,4-Trichloro-3-butenoyl chloride (X). To a
solution of 2.86 g (15.1 mmol of 3,4,4-trichloro-3-
butenoic acid (I) in 10 ml of CCl4 was added drop-
wise 3.3 ml (45.4 mmol) of thionyl chloride, the
reaction mixture was stirred for 30 min and boiled to
the end of HCl liberation (monitoring with litmus
paper and GLC). Then the solvent and excess thionyl
chloride were distilled off, and the residue was
distilled in a vacuum. We obtained 2.99g (95%) of
acyl chloride X, bp 38 39 C (1 mm Hg). d420
nD20 1.5120. IR spectrum, cm : 781), 821 (C Cl),
1
1
1634 (C=C), 1741 (C=O), 3084 (C H). H NMR
spectrum, , ppm: 3.83 s (3H, OCH3), 7.06 s (1H,
=CH). 13C NMR spectrum, , ppm: 52.87 (OCH3,
JC H 147.7 Hz), 95.28 (CCl3), 119.67 (=CH, JC H
167.4 Hz), 144.82 (=CCl), 163.12 (C=O). Found,
%: C 24.89; H 1.39; Cl 60.01. [M]+ 236 (for 35Cl).
C5H4Cl4O2. Calculated, %: C 25.24; H 1.69; Cl
59.61. M 237.90.
1.558. nD20 1.5135. IR spectrum, cm : 761, 792
1
1
(C Cl), 1607 (C=C), 1800 (C=O). H NMR spec-
trum, , ppm: 4.12 s (2H, CH2). Found, %: C 23.02;
H 1.37; Cl 68.55. [M]+ 206 (for 35Cl). C4H2Cl4O.
Calculated, %: C 23.11; H 0.97; Cl 68.22. M207.87.
Methyl 3-methoxy-4,4,4-trichloro-2-butenoate
(VIII). To a solution of 2 g (8.4 mmol) of methyl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

1104
POTKIN et al.
3,3,4,4,4-Pentachlorobutanoyl chloride (XI) was
product obtained was recrystallized from hexane. We
obtained 0.35 g (46%) of 3,3,3-trichloro-1-propynyl
phenyl ketone (XVIII), mp 84 86 C. Found, %: C
48.68; H 1.87; Cl 42.58. [M]+ 246 (for 35Cl).
C10H5Cl3O. Calculated, %: C 48.53; H 2.04; Cl
42.97. M 247.51.
obtained in a similar way from acid VI and thionyl
chloride. Yield 74%, bp 67 68 C (2 mm Hg). d420
1.673. n2D0 1.5308. IR spectrum, cm : 740, 788, 823
1
1
(C Cl), 1827 (C=O). H NMR spectrum, , ppm:
4.16 s (2H, CH2). Found, %: C 17.01; H 0.59; Cl
76.28. [M]+ 276 (for 35Cl). C4H2Cl6O. Calculated,
%: C 17.23; H 0.72; Cl 76.30. M 278.78.
REFERENCES
2,3,3-Trichloroallyl phenyl ketone (XII). To
2.26 g (10.88 mmol) of 3,4,4-trichloro-3-butenoyl
1. Shcheglov, Yu.V., Nikishin, G.I., Dyusenov, M.I.,
Musikaev, D.A., Yakovets, V.I., and Yakovets, V.P.,
USSR Inventor,s Certificate, 218563, 1967; SSSR
Byull. Izobr., 1968, no. 17; US Patent 3803189,
1974; Ref. Zh. Khim., 50363P, 1975; US Patent
2921220, 1980, 1981, vol. 94, no. 11, 83622u;
German Patent 2925012, 1980. Chem. Abstr., 1981,
vol. 94, no. 11, 156335q; German Patent 1534599,
1968. Chem. Abstr., 1969, vol. 71, no. 4, 13992r.
2. Ol,dekop, Yu.A., Kaberdin, R.V., and Zhid-
kov, Yu.N., Zh. Org. Khim., 1978, vol. 14, no. 3,
pp. 484 487.
chloride (X) at 10 12 C was added 1.46
g
(10.94 mmol) of anhydrous AlCl3, and the reaction
mixture was stirred for 20 min. Then to the mixture
was added 1.02 g (13.06 mmol) of benzene, and the
stirring was continued for 3 h at room temperature
and then for 2 h at 60 C. After completion of the
reaction (GLC monitoring) the reaction mixture was
diluted with carbon tetrachloride (1: 1) and poured on
ice. The organic layer was separated, washed with
water, with diluted solution of potassium carbonate,
again with water, and dried with magnesium sulfate.
The solvent was distilled off in a vacuum, and the
solid residue was recrystallized from ethanol. We
obtained 1.90 g (70%) of trichloroallyl phenyl ketone
(XII), mp 45 46 C.
3. German Patent 961406; Chem. Abstr., 1960, vol. 54,
3843; German Patent 1024952, 1960; Chem. Abstr.,
1960, vol. 54, 7562.
4. Takhistov, V.V., Prakticheskaya mass-spektro-
metriya organicheskikh soedinenii (Practical Mass
Spectrometry of Organic Compounds), Leningrad:
Leningrad. Gos. Univ., 1977, pp. 264 266.
5. Takhistov, V.V., Rodin, A.A., and Maksimova, B.N.,
Usp. Khim., 1991, vol. 60, no. 10, pp. 2143 2167.
6. Kaberdin, R.V., Nikolaeva, E.E., Potkin, V.I., and
Ol,dekop, Yu.A., Zh. Org. Khim., 1985, vol. 21,
no. 3, pp. 494 498.
Ketones XIII XVI were obtained by a similar
procedure from acyl chloride X and an appropriate
substituted benzene. The synthesis of 2,2,3,3,3-
pentachloropropyl phenyl ketone XVII was carried
out likewise from pentachlorobutanoyl chloride XI
and benzene. The yields and physical characteristics
of compounds obtained are presented in the table.
7. Kimpenhaus, W., Auf der Heyde W., Lieb. Ann.,
1983, no. 3, pp. 378 392.
Chlorination of 2,3,3-trichloroallyl phenyl
ketone (XII). Through a solution of 1.77 g
(7.1 mmol) of 2,3,3-trichloroallyl phenyl ketone
(XII) in 10 ml of was passed a stream of chlorine for
4 h (GLC monitoring). Then the solvent was removed,
and the residue was recrystallized from ethanol. We
obtained 2.09 g (02%) of ketone XVII. Dehydro-
chlorination of 2,2,3,3,3-pentachloropropyl phenyl
ketone (XVII). To 0.16 g (0.7 mmol) of triethyl-
benzylammonium chloride in 30 ml of 20% water
solution of KOH at vigorous stirring was added a
solution of 1 g (3.12 mmol) of 2,2,3,3,3-pentachloro-
propyl phenyl ketone XVII in 5 ml of ethyl ether.
The stirring continued for 3 h. Then the organic layer
was separated, the solvent was removed, and the
8. Brown, D.W., Floyd, A.J.,
and
Sainsbury, M.,
Organic Spectroscopy, New York: J. Wiley 1988.
9. Pilgram, K. and Hass, K., J. Med. Chem., 1975,
vol. 18, no. 12, pp. 1204 1211.
10. Freidlina, R.Kh., Velichko, F.K., Chukov-
skaya, E.Ts., Khorlina, M.Ya., Krentsel,, B.A., Il,-
ina, D.E., Kruglova, N.E., Mayants, L.S., and
Gasanov, R.G., Metody elementoorganicheskoi khi-
mii. Khlor. Alifaticheskie soedineniya (Methods of
Organoelemental Chemistry, Chlorine, Alifatic Com-
pounds), Nesmeyanov, A.N. and Kocheshkov, K.A.,
Eds., Moscow, 1973, pp. 117 125.
11. Roedig, A. and Ritschel, W., Lieb. Ann., 1983,
no. 9, pp. 1496 1503.
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