Acetylene接触加水反応に伴う副反応(I)

Abstract

Supplementary observations on the chemistry of Mercarbide, Mercuroform and their related substances. A) Mercuroform (M. F.) and Mercarbide (M.) 1) A certain kind of trimercuri-acetaldehyde (Trim. Acet. Ald.) such as Hofmann's nitrate and chlorate gives M. F-base and alkaliformate by the action of alkali, (M. F-decomposition.) Another group of Trim. Acet. Ald. such as Deniges' sulfate and OHC-C ?? yields M-base. [via the hypothetical substance, hydroxymercuroform. CH≡(HgOH)3] (M-decomposition) The only exceptional case is the reaction of OHC-C (HgCl)3 with Alkali by which Alkaliformate and M. F-dichloride, CH ?? are formed. 2) Trim. Acetone-(or Trim. Acetophenone-) nitrate gives acetyl-(or benzoyl-) -M. F. by the reaction with alkali without liberation of acetic (or benzoic-) acid and formation of M-Structure. 3) M. and M. F. are changed to their respective sulfates by the action of dil H2SO4 from which M is obtained by saponification. Thus, M. F. is able to be indirectly transfered to M. 4) When M is immers ed in aqueous solution of alkalihalide, it is perfectly changed to its halide (-Hg- ?? )n, however, the yield of M. F-halide ?? is always less than 50 % even by the immersion of long time. 5) M. reacts with conc. or dil. HX-acid to yield the substances CH≡(HgX)3 or CH ?? and these products are identical with those prepared from F. M. [X=Cl, Br] CH≡(HgI)3 and CH ?? are not obtainable by the action of HI, on either of M. or M. F, however, CH≡(HgI)3 can be easily prepared from M. by the action of (KI+I2)-reagent. The actio ns of dil HI solution on M. and M. F. are quite unique, i. e. M is easily transfered to its normal iodide -Hg- ?? )n, on the contrary, the yield of M. F-iodide ?? is always limited less than 30 % of theoretical value, even by the treating of long time with the renewed solution. Of the halogen derivatives of hydroxymercuroform, CH ?? is the only substance whith could not be obtained from either of M. or M. F. 6) Space formula of Mercarbide molecule was examined by Prof. UHARA and KATO basing on the following Physical data. Covalent radius; C, 0.77, 0, 0.66. Hg, 1.29 A, Valence angle; C, 109°28′. O, 105°. Hg, 180°. It was concluded that the heteroring of M-molecule is twelve-membered irregular and non-coplanar hexagon composed of six atoms of Hg and each three atoms of C and O, and two radicals (-H, -HgOH) are combined with each C atom. B) a-Str. C=Hg and a′-Str. ( ?? -Hg-)n By the examination of behaviors of OHC-C ?? (Hofmann's formula.) its structure is assigned to gem-Dimercuripolymer type. ( ?? )n. (Matterson's expression). Heteroring of such substance is considered to be regular and coplanar pentagon composed of each five atoms of C and Hg. C) The latent polymeric structure of organo mercury compounds. Taking the cas e of OHC-C (HgCl)3 as an example, the present authors have presumed the polymeric structure of the products obtained by the reaction of Hg-salt solution with acetylene or acetaldehyde.