SYNTHESIS
Short Papers
964
ethylene or dichloroacetylene.10,16 Ethynyl derivative 3
probably results from a halogenophilic reaction of any an-
ion present in the system with 4.16
and concentrated in vacuo. The residue was purified by column chro-
matography (Merck silica gel 60, eluent: hexane) to give the ketone 5
(0.95 g, 80%); (Lit.23 bp 160–161°C/38 Torr).
1H NMR: δ = 6.39 (s, 1 H, =CH), 7.26–7.44 (m, 3 H, ArH), 7.75–7.82
(m, 2 H, ArH).
In summary, we have presented an attractive method for
the preparation of dichlorovinyl-substituted nitriles 2.
Furthermore, a simple cleavage of α-heteroatom-substi-
tuted nitriles 2 opens up a convenient route for the synthe-
sis of aryl dichlorovinyl ketones.
Anal. C9H6Cl2O (201.1): calcd C, 53.75; H, 3.00; Cl, 35.26; found C,
53.60; H, 3.06; Cl, 34.96.
Support of this work by the State Committee for Scientific Research
(Grant No. 3 T09A 155 09) is gratefully acknowledged.
Melting points (capillary tube) and boiling points are uncorrected. 1H
NMR spectra were recorded on a Varian Gemini 200 spectrometer in
CDCl . GC/MS were recorded on a Hewlett–Packard 5972A-MSD
3
(1) Hopf, H.; Witulski, B. In Modern Acetylene Chemistry; Stang,
P. J.; Diederich, F., Eds.; VCH: Weinheim, 1995; p 48.
(2) Pielichowski, J.; Popielarz, R. Synthesis 1984, 433.
(3) Pielichowski, J.; BogdaΩ, D. J. Prakt. Chem. 1989, 331, 145.
(4) Dehmlow, E.V.; Dehmlow, S.S. Phase Transfer Catalysis, 3rd
ed.; Verlag Chemie: Weinheim, 1993.
apparatus. GC analyses were carried out on a Hewlett–Packard 5890
apparatus equipped with a glass capillary column (30 m) and FID.
The following nitriles were prepared according to literature proce-
dures: 1a,b,17 1c–e,18 1f,19 1g,20 1h–j,21 1k22 and 3.13 Other reagents
and all solvents are commercially available.
Starks, C. M.; Liotta, C. L.; Halpern, M. Phase-transfer Cataly-
sis; Chapman & Hall: New York, London, 1994.
M˛akosza, M.; Fedorynski, M. Polish J. Chem. 1996, 70, 1093.
M˛akosza, M.; Fedorynski, M. In Handbook of Phase Transfer-
Catalysis; Sasson, Y.; Neumann, R., Eds.; Blackie Academic &
Professional: London, 1997; p 135.
Caution: Fumes of dichloroacetylene may explode on contact with
air.
Dichlorovinyl-Substituted Nitriles 2; General Procedure:
A stirred mixture of nitrile 1 (20 mmol), 50% aq NaOH (6.0 g,
4.0 mL, 75 mmol) and TBAHS (1.0 g, 3.0 mmol) was cooled to
5–10°C. Then, a solution of trichloroethylene (3.15 g, 2.2 mL,
24 mmol) in Et2O (1.9 g, 2.7 mL, 26 mmol) was added at 5–10°C
over 30 min. The mixture was stirred at 5–10°C for the time indicated
in Table 1, diluted with H2O (20 mL), and the phases were separated.
The H2O phase was extracted with benzene (2 × 10 mL). The combined
organic phases were washed with H2O (2 × 10 mL), dried (MgSO4),
and the solvent was evaporated on a rotary evaporator. The residue was
distilled in vacuo (2a–c,h–k) and additionally purified by column chro-
matography (2a,c) or crystallized (2d–g) (Tables 1 and 2).
(5) Trichlorovinyl anion generated from trichloroethylene under
PTCconditionswastrappedwithCCl4togivetetrachloroethylene:
Jonczyk, A.; Kwast, A.; M˛akosza, M. J. Org. Chem. 1979, 44,
1192.
(6) Pielichowski, J.; Popielarz, R. Tetrahedron 1984, 40, 2671.
(7) BogdaΩ, D.; Pielichowski, J. Polish J. Chem. 1994, 68, 2439,
and references cited therein.
(8) Pielichowski, J.; BogdaΩ, D. Polish J. Chem. 1988, 62, 483.
(9) Martynov, A. V.; Mirskova, A. N.; Kalikhman, U. D.; Voron-
kov, M. G. Zh. Org. Khim. 1988, 24, 509; Chem. Abstr. 1989,
110, 153 824.
(10) Kende, A. S.; Fludzinski, P.; Hill, J. H.; Swenson, W.; Clardy,
J. J. Am. Chem. Soc. 1984, 106, 3551, and references cited
therein.
(11) Donetti, A.; Boniardi, O; Ezhaya, A. Synthesis 1980, 1009.
(12) Yuste, F.; Origel, A. E.; Breña, L. J. Synthesis 1983, 109.
(13) Jonczyk, A.; Kulinski, T.; Czupryniak, M.; Balcerzak, P. Synlett
1991, 639.
(14) Deslongchamps, P. Stereoelectronic Effects in Organic Chemis-
try. Organic Chemistry Series, Vol. 1; Baldwin, J. E., Ed.; Per-
gamon Press: Oxford, 1983; p 291.
(15) Jonczyk, A.; Pakulski, Z. Tetrahedron Lett. 1996, 37, 8909, and
references cited therein.
(16) Miller, S. I.; Dickstein, J. I. Acc. Chem. Res. 1976, 9, 358.
(17) Jonczyk, A.; Ludwikow, M.; M˛akosza, M. Org. Prep. Proced.
Int. 1979, 11, 275.
Reaction of Nitrile 1c with Trichloroethylene in DMSO:
A mixture of nitrile 1c (1.0 g, 6 mmol), 50% aq NaOH (3.0 g, 2.0 mL,
38 mmol) and DMSO (0.05 g, 0.06 mmol) was stirred and heated to
ca. 55°C. To this mixture was added dropwise a solution of trichlo-
roethylene (1.0 g, 0.7 mL, 8 mmol) in dipropyl ether (0.9 g, 1.2 mL,
9 mmol) at 50–55°C over 20 min. The mixture was stirred at
50–55°C for 4 h, cooled, diluted with H2O (15 mL), and the phases
were separated. The H2O phase was extracted with CH2Cl2 (2 ×
5 mL), and the combined organic phases were washed with H2O
(2 × 7 mL) and dried (MgSO4). The solvent was evaporated and the
residue was distilled (bp 90–110°C/0.2 Torr, 1.3 g). GC analysis
showed the presence of 2c (46%), 3 (3%) and 4 (36%).The distillate
was also analysed by GC/MS.
GC/MS (EI): m/z (relative intensity,%) = 2c, 253 (M+, 11); 3, 183
(M+, 1); 4, 217 (M+, 1).
The above obtained mixture (0.10 g) and Cu powder (0.05 g, 0.83
mmol) were suspended in THF (10 mL). Then AcOH (1 mL) was
added, the mixture heated for 2 h at 70°C, cooled, diluted with H2O
and extracted with CH2Cl2 (3 × 5 mL). The organic extracts were
dried (MgSO4) and the solvent was evaporated. The residue (0.095 g)
was analysed by GC to show 2c (62%), 3 (30%) and 4 (0.5%).
(18) M˛akosza, M.; Serafinowa, B. Roczniki Chem. 1965, 39, 1401;
Chem. Abstr. 1966, 64, 17474.
(19) Hauser, C. R.; Taylor, H. M.; Ledford, T. G. J. Am. Chem. Soc.
1960, 82, 1786.
(20) Bennett, D. J.; Kirby, G. W.; Moss, V. A. J. Chem. Soc. (C)
1970, 2049.
1,2-Dichlorovinyl Phenyl Ketone (5):
(21) M˛akosza, M.; Goetzen, T. Roczniki Chem. 1972, 46, 1059;
Chem. Abstr. 1972, 77, 164582.
(22) Ejmocki, Z.; Eckstein, Z. Roczniki Chem. 1971, 45, 345; Chem.
Abstr. 1971, 75, 63348.
(23) U. S. Patent 2 415 796, 1942 (Wingfoot Corp.); Chem. Abstr.
1947, 41, P3127.
A mixture of the amino nitrile 2f (1.50 g, 5.9 mmol), CuSO4•5H2O
(1.50 g, 5.9 mmol) and EtOH (5 mL) was refluxed for 15 min and
cooled. To this mixture was added benzene (5 mL) and the phases
were separated. The H2O phase was extracted with benzene
(2 × 5 mL), and the combined organic phases were dried (MgSO4)