Aluminium chloride reaction with, phosgene

Unsaturated alcohols, in the presence of aluminium(III) chloride, give chlorolactones on reaction with phosgene [1579] ... 

The reaction of phosgene with dimethylaniline when carried out in the presence of aluminium trichloride or zinc chloride gives Crystal Violet,... 

When phosgene is combined with A ,iV-dimethyianiiine in the presence of aluminium(III) chloride, Michler s ketone, 4,4 -bis(dimethylamino)benzophenone, is produced (see Section 10.2.1.1), which undergoes further reaction with lV,N-dimethylaniline (also in the presence of aluminium(ni) chloride or POCij) to give the colouring material "crystal violet", used in the production of methyl violet indicator paper. When Michler s ketone is warmed with Ai-phenyl-1-naphthylamine in the presence of POCI3, Victoria blue (4.13) is formed, which is used as a dye for natural fibres [718a]. 

The reaction of phosgene with ethene has been investigated by several workers [1119-1121,1579,2103]. Pace [1579] claimed that, in the presence of an aluminium(III) chloride catalyst in toluene solution, an acid chloride ClCHjCHjCOCl was produced. However, this work could not be independently confirmed [1120,2103], and no conditions were found under which the acid chloride was formed. In toluene, only products derived from reactions with the solvent were isolated [1120,1121,2103]. CICH CHjCOCl, however, is... 

Upon protracted contact with aluminium(III) chloride at higher temperatures, and especially if the aromatic hydrocarbon is itself used as the solvent, the product of the reaction between phosgene and aromatic hydrocarbons is usually the corresponding benzophenone [2026]. Friedel and Crafts [686aa] found that COCI, reacts with benzene in the presence of a stoicheiometric amount of aluminium(III) chloride to give benzophenone ... 

Over the course of their collaboration they extended the scope of the use of catalytic aluminium chloride to a wide variety of organic reactions (1) reaction of alkyl, acyl chloride, and unsaturated compounds with aliphatic and aromatic hydrocarbons (2) reactions of acid anhydrides, oxygen, sulfur, sulfur dioxide, carbon dioxide, and phosgene with aromatic hydrocarbons (3) cracking of aliphatic and aromatic hydrocarbons, and (4) polymerization... 

Preparation by partial demethylation of 2-hydroxy-2, 4,4 -trimethoxybenzo-phenone or 2,2, 4,4 -tehamethoxybenzophenone with aluminium chloride or aluminium bromide in chlorobenzene at 90-95° (good yield). The same result is obtained using ethylene dichloride or nitrobenzene as the solvent [655], Preparation by reaction of phosgene with resorcinol dimethyl ether in the presence of aluminium chloride [215]. 

A novel method for the preparation of phosgene is based on the observation that considerable amounts of COClj are evolved when aliphatic aldehydes - CH3CHO, MejCHCHO, or (CHjO)3 - react with CCl in the presence of aluminium(III) chloride [1005,1006]. The reaction of paraformaldehyde HO(CHjO) H n = 8-100 with CCI in... 

Various chlorinating agents combine with COj, COS, or CS to form phosgene. Carbon dioxide reacts directly with Clj over heated porcelain tubes filled with charcoal to give phosgene [1379]. Also, carbon dioxide is reported to react with PbCl at 700 C, or NiClj at 550 C, to produce small yields of phosgene [168] and the reaction of CO with heated aluminium(III) chloride has been patented [2158] as a process for the production of phosgene, based on the reaction ... 

This reaction, using CO and Clj over a carbon catalyst to form the COCl in situ, was the basis of a patent for the manufacture of aluminium(III) chloride at between 500 and 800 "C [100]. The kinetics of the reaction between 7-AI2O3 and phosgene has been studied between 585 and 1085 K an apparent order of reaction of 0.75 with respect to COCl was determined, with an apparent activation energy of 128-135 kj mol [182,183]. The effect of added charcoal to the kinetics of the reaction were shown to be negligible below 650 C, but phosgene was found to be superior to a 1 1 CO Clj mixture [24]. 

Molten Na[AlCl4] catalyses the reaction at 600 C, in a three-phase system with gaseous COCl and solid y-AIjOj, to give very high purity aluminium(III) chloride [962], and this reaction (in the presence of carbon) has formed the basis of a patent for the industrial scale production of aluminium(III) chloride [909]. The chlorination of AljOj by phosgene has been studied in a LiCl-KCl eutectic melt at 470 C as a function of pO it is essentially a two-step process [1842] ... 

Phosgene can react with arenes, when in the presence of a Friedel-Crafts catalyst such as aluminium(III) chloride [1556,2026], to give predominantly benzoyl chlorides or benzophenones, depending on the reaction conditions [2196] ... 

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