Organic Syntheses Procedure

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Org. Synth. 1990, 69, 144

DOI: 10.15227/orgsyn.069.0144

1-CHLORO-1-(TRICHLOROETHENYL)CYCLOPROPANE

[Cyclopropane, 1-chloro-1-(trichloroethenyl)-]

Submitted by Thomas Liese, Frank Jaekel, and Armin de Meijere¹.

Checked by John R. Berry, James S. Piecara, and Bruce E. Smart.

1. Procedure

A 1-L Hastelloy C-276 shaker tube (Note 1) fitted with a temperature sensor, a rupture-disk safety device, and a gas inlet valve attached to an ethylene cylinder is charged with 120.0 g (0.675 mol) of freshly distilled tetrachlorocyclopropene (Note 2), 350 mL of dry tetrachloroethylene (Note 3), and 10 g of anhydrous sodium carbonate (Note 4). The tube is pressurized to 20 atm with ethylene and shaken for 3 hr. The ethylene cylinder is disconnected, and the pressure vessel is gradually heated to 170°C over a 30-min period and is shaken at this temperature for 19.5 hr. The vessel is allowed to cool to room temperature, and the excess ethylene is slowly released and bubbled through a wash bottle containing methylene chloride (Note 5). The light-brown liquid in the shaker tube is decanted and the remaining solid washed twice with 50 mL of methylene chloride. The organic phases are combined and the methylene chloride is removed by distillation. The residual liquid is distilled at water-aspirator vacuum through a 40-cm Vigreux column. The solvent tetrachloroethylene, bp 35°C (27 mm), is collected (Note 6), followed by 104.1–105.6 g (75–76%) of 1-chloro-1-(trichloroethenyl)cyclopropane as a colorless liquid, bp 81–83°C (27 mm) (Note 7).

2. Notes

1. The submitters used a 1-L autoclave lined with Hastelloy C-4. Hastelloy C materials are high nickel alloys. A highly resistant alloy is employed to avoid possible side reactions.

2. Tetrachlorocyclopropene was prepared from sodium trichloroacetate and trichloroethylene.²^,³ It is also available from the Aldrich Chemical Company, Inc., Eastman Organic Chemicals, and the Merck-Schuchardt Company (in Europe).

3. Tetrachloroethylene was obtained from the Aldrich Chemical Company, Inc. and distilled from phosphorus pentoxide prior to use.

4. Anhydrous sodium carbonate was obtained from the J. T. Baker Chemical Company and dried under vacuum at 130°C.

5. The wash bottle serves to trap any product carried with the ethylene vapors, to monitor and control the release of ethylene pressure and to indicate when no excess pressure remains, and to diminish the release of toxic materials.

6. The receiver was cooled in an ice bath to avoid loss of the tetrachloroethylene distillate.

7. The submitters obtained 111–116 g of product, bp 72–75°C (14–18 mm). The spectral properties of 1-chloro-1-(trichloroethenyl)cyclopropane are as follows; IR (neat) cm⁻¹: 3100 (CH), 3020 (CH), 1585 (C=C), 1415, 1170, 1040, 1015, 940, 910, 875, 800, 750, 645; ¹H NMR (CDCl₃) δ: 1.42 (m, 2 H), 1.52 (m, 2 H).

3. Discussion

Tetrachlorocyclopropene has been known for some time to be a reasonably reactive dienophile.⁴ Its thermal ring opening to perchlorovinyl carbene is in accord with the behavior of other cyclopropenes under thermolytic conditions,⁵ but the efficiency with which this vinyl carbene intermolecularly adds to a wide variety of olefins⁶^,⁷ is unprecedented. The resulting 1-chloro-1-(trichloroethenyl)cyclopropanes⁶^,⁷ can be reductively dechlorinated to vinylcyclopropanes,⁶ transformed into variously substituted cyclopropylacetylenes⁷^,⁸ or cyclopropylidenacetates.⁹ The simple cyclopropyl derivatives, accessible from the reported 1-chloro-1-(trichloroethenyl)cyclopropane, like methyl 2-chloro-2-cyclopropylidenacetate (see accompanying procedure) and 1-trimethylsilyl-1-(trimethylsilylethynyl)cyclopropane (prepared by reductive silylation with magnesium/chlorotrimethylsilane in tetrahydrofuran¹⁰), are especially useful building blocks for the construction of complex organic molecules.¹¹^,¹²^,¹³

This preparation is referenced from:

Org. Syn. Coll. Vol. 8, 373

References and Notes

Institut für Organische Chemie der Universität Hamburg, Martin-Luther-King-Platz 6, D-2000 Hamburg 13, Federal Republic of Germany. Present address: Institut für Organische Chemie der Georg-August-Universität, Tammannstrasse 2, D-3400 Göttingen, Federal Republic of Germany.
Glück, C.; Poignée, V.; Schwager, H. Synthesis 1987, 260.
Sepiol, J.; Soulen, R. L. J. Org. Chem. 1975, 40, 3791.
Law, D. C. F.; Tobey, S. W. J. Am. Chem. Soc. 1968, 90, 2376.
York, E. J.; Dittmar, W.; Stevenson, J. R.; Bergman, R. G. J. Am. Chem. Soc. 1973, 95, 5680.
Weber, W.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 138; Weber, W.; de Meijere, A. Chem. Ber. 1985, 118, 2450.
Liese, T.; Splettstösser, G.; de Meijere, A. Tetrahedron Lett. 1982, 23, 3341; Liese, T.; de Meijere, A. Chem. Ber. 1986, 119, 2995.
Liese, T.; de Meijere, A. Angew. Chem. Suppl. 1982, 34; Liese, T.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1982, 21, 65.
Liese, T.; Seyed-Mahdavi, F.; de Meijere, A. Org. Synth., Coll. Vol. VIII, 1993, 373; Liese, T.; Splettstösser, G.; de Meijere, A. Angew. Chem. Suppl. 1982, 1715; Liese, T.; Splettstösser, G.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1982, 21, 790; Liese, T.; Teichmann, S.; de Meijere, A. Synthesis 1988, 25.
de Meijere, A.; Misslitz, U. in "Methoden der Organischen Chemie" (Houben-Weyl), Regitz, M., Ed.; Thieme: Stuttgart, 1989, Vol. E, 19G/1, pp. 746f, 771ff.
Keyaniyan, S.; Apel, M.; Richmond, J. P.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1985, 24, 770; Bengtson, G.; Keyaniyan, S.; de Meijere, A. Chem. Ber. 1986, 119, 3607; Jaekel, F. Dissertation, Universität Hamburg, 1988.
Spitzner, D.; Engler, A.; Liese, T.; Splettstösser, G.; de Meijere, A. Angew. Chem. Suppl. 1982, 1722; Spitzner, D.; Engler, A.; Liese, T.; Splettstösser, G.; de Meijere, A. Angew. Chem., Int. Ed. Engl. 1982, 21, 791; Spitzner, D.; Engler, A.; Wagner, P.; de Meijere, A.; Bengston, G.; Simon, A.; Peters, K.; Peters, E.-M. Tetrahedron 1987, 43, 3213.
de Meijere, A. Chem. Ber. 1987, 23, 865; de Meijere, A.; Wessjohann, L. Synlett. 1990, 20.

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

magnesium (7439-95-4)

sodium carbonate (497-19-8)

ethylene (9002-88-4)

methylene chloride (75-09-2)

tetrachloroethylene (127-18-4)

Tetrahydrofuran (109-99-9)

trichloroethylene (79-01-6)

tetrachlorocyclopropene

sodium trichloroacetate (650-51-1)

CHLOROTRIMETHYLSILANE (75-77-4)

phosphorus pentoxide (1314-56-3)

1-CHLORO-1-(TRICHLOROETHENYL)CYCLOPROPANE,
Cyclopropane, 1-chloro-1-(trichloroethenyl)- (82979-27-9)

perchlorovinyl carbene

Methyl 2-chloro-2-cyclopropylidenacetate (82979-45-1)

1-trimethylsilyl-1-(trimethylsilylethynyl)cyclopropane

Notes

References/EndNotes

Article Compounds

Authors