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ORGANIC REACTIONS

bath at 180-200. A complete list of the ketenes prepared and the conditions employed (if reported) is given in Table IV. TABLE IV
PREPARATION'OP KETENES BY PYROLYSIS OP KETENE DIMERS

Conditions of Depolymerization of the Dimer CH2=C=O CH 3 CH=C=O (CH 3 ) 2 C=C=O CH3C(CO2CH3)==C=O C 2 H 6 C(CO2C 2 H 6 )=C=O (C 2 H 6 O 2 C) 2 C=C=O C6H6C (CO 2 CH 3 )=C=O C 6 H 6 C(CH 3 )=C=O (C6H 6 ) 2 C=C=O

Yield

Reference

Hot platinum filament Quant. 117 Hot tube (550-600) Quant. 117 Hot Nichrome wire 115 Hot Nichrome wire 86% 116 Hot platinum spiral 118 Treatment with NaOCHrCH3OH * 119 Heat at 200/15 mm. 80-90% 120 Distillation at 15 mm. 30% 36 Treatment with CeHgMgBr 36 -t Heat at 150 121 Distillation in "abs." vacuum 122 70% Heat at 150 121 Distillation 121, 123 Pyrolysis 121, 124

* The product isolated was CHsCH(CO2CH3)2, evidently formed from the ketene. t The product isolated was ethyl a-benzoylbutyrate.

Dehalogenation of a-Haloacyl Halides The oldest procedure for the synthesis of ketenes is the dehalogenation of a-haloacyl halides by treatment with zinc.125 There have been no
R' 0 Zn

R' C=C=O + ZnX2 R

RCC
X
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Staudinger and Klever, Ber., 44, 2215 (1911). Schroeter, Ber., 49, 2697 (1916). Staudinger and St. Bereza, Ber., 42, 4908 (1909). m Staudinger and Hirzel, Ber., 50, 1024 (1917). m Staudinger and Hirzel, Ber., 49, 2522 (1916). 123 Staudinger and Ruzicka, Ann., 380, 278 (1911). m Staudinger, Ber., 44, 521 (1911). 126 Staudinger, Ber., 38, 1735 (1905).
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