Phosgene method

Benzotriazepinones 5 are also produced in the reaction of hydrazones of 2-aminoaryl ketones with phosgene (Method B).352... 

Two methods which are used for preparation are (i) directphosgenation (ii) ester interchange. In direct phosgenation method phosgene is passed into a solution of Bisphenol A in chloroform and pyridine at... 

Formaldehyde and Phosgene Methods.—Two other processes for the commercial preparation of fuchsin are the formaldehyde and the phosgene, COCI2, processes. For details in regard to them special books on dyes should be consulted, e.g. Cain Thorpe. 

Although other (non-phosgene) methods [676] can be employed to prepare carbonates, these will not be described here. 

The isocyanides can be prepared by the phosgene method of Ugi and co-wotkers, except for CNMe and CNBu , and the dinitrogen ffmy-fM(N2)2(dppe)2] (M = Mo or W) complexes can also be prepared by published methods. 

NCA s of trans-3-ethylproline were prepared using the phosgene method,... 

The reaction of diphosgene with aniline [161] was carried out under conditions similar to those employed in the phosgene method. 

Other acetyl chloride preparations include the reaction of acetic acid and chlorinated ethylenes in the presence of ferric chloride [7705-08-0] (29) a combination of ben2yl chloride [100-44-7] and acetic acid at 85% yield (30) conversion of ethyUdene dichloride, in 91% yield (31) and decomposition of ethyl acetate [141-78-6] by the action of phosgene [75-44-5] producing also ethyl chloride [75-00-3] (32). The expense of raw material and capital cost of plant probably make this last route prohibitive. Chlorination of acetic acid to monochloroacetic acid [79-11-8] also generates acetyl chloride as a by-product (33). Because acetyl chloride is cosdy to recover, it is usually recycled to be converted into monochloroacetic acid. A salvage method in which the mixture of HCl and acetyl chloride is scmbbed with H2SO4 to form acetyl sulfate has been patented (33). 

Preparation from Amines. The most common method of preparing isocyanates, even on a commercial scale, involves the reaction of phosgene [75-44-5] and aromatic or aUphatic amine precursors. The initial reaction step, the formation of N-substituted carbamoyl chloride (1), is highly exothermic and is succeeded by hydrogen chloride elimination which takes place at elevated temperatures. 

A variation of this method involves the conversion of the amine into the amine hydrochloride prior to treatment with phosgene. This method has the advantage of producing generally cleaner products by retarding the secondary reaction of the free amine with carbamoyl chloride. 

Oligomers of phosgene, such as diphosgene [503-38-8] (COCl2)2, have found use in the laboratory preparation of isocyanates. Carbamoyl chlorides, A[,A/-disubstituted ureas, dimethyl- and diphenylcarbonates, and arylsulfonyl isocyanates have also been used to convert amines into urea intermediates, which are subsequendy pyroly2ed to yield isocyanates. These methods have found appHcations for preparation of low boiling point aUphatic isocyanates (2,9,17). 

More convenient is the use of aryl a2ides which are readily converted into isocyanates upon heating in nonreactive solvents via the loss of nitrogen. The latter method is useful for the synthesis of isocyanates with additional substituents which could not be prepared with phosgene (20). 

Reportedly, simple alkyl isocyanates do not dimerize upon standing. They trimerize to isocyanurates under comparable reaction conditions (57). Aliphatic isocyanate dimers can, however, be synthesized via the phosgenation of A[,A[-disubstituted ureas to yield /V-(ch1orocarhony1)ch1oroformamidine iatermediates which are subsequendy converted by partial hydrolysis and base catalyzed cycUzation. This is also the method of choice for the synthesis of l-alkyl-3-aryl-l,3-diazetidiones (mixed dimers of aromatic and aUphatic isocyanates) (58). 

Aromatic Isocyanates. A variety of methods are described in the Hterature for the synthesis of aromatic isocyanates. Only the phosgenation of amines or amine salts is used on a commercial scale (5). Much process refinement has occurred to minimise the formation of disubstituted ureas arising by the reaction of the generated isocyanate with the amine starting material. A listing of the key commercially available isocyanates is presented in Table 1. 

Attempts have been made to develop methods for the production of aromatic isocyanates without the use of phosgene. None of these processes is currently in commercial use. Processes based on the reaction of carbon monoxide with aromatic nitro compounds have been examined extensively (23,27,76). The reductive carbonylation of 2,4-dinitrotoluene [121 -14-2] to toluene 2,4-diaLkylcarbamates is reported to occur in high yield at reaction temperatures of 140—180°C under 6900 kPa (1000 psi) of carbon monoxide. The resultant carbamate product distribution is noted to be a strong function of the alcohol used. Mitsui-Toatsu and Arco have disclosed a two-step reductive carbonylation process based on a cost effective selenium catalyst (22,23). 

Commercially important arenesulfonyl isocyanates are not directly accessible from the corresponding sulfonamides via phosgenation due to lack of reactivity or by-product formation at elevated temperatures. A convenient method for their preparation consists of the reaction of alkyl isocyanates with sulfonamides to produce mixed ureas which, upon phosgenation, yield a mixture of alkyl and arenesulfonyl isocyanates. The desired product can be obtained by simple distillation (16). Optionally, the oxalyl chloride route has been employed for the synthesis of arenesulfonyl isocyanate (87). 

Phosphates and siUcates of metals often react with phosgene at elevated temperatures and yield the metal chloride and phosphoms oxychloride or sihcon dioxide. The reaction with ferric phosphate at 300—350°C has been proposed as a synthetic method for phosphoms oxychloride, POCl. ... 

Waste Gas Streams. Several methods of decomposing phosgene in waste gas streams are used. The outlet gas from the phosgene decomposition equipment is continuously monitored for residual phosgene content to ensure complete decomposition. 

Combustion. The waste gas stream is burnt to convert phosgene to carbon dioxide and HCl. An advantage of this method is that all components of the waste gas, such as CO and solvent, are burnt (34). 

Phosgene in air and in mixture with other gases can be detected by a variety of methods (35). Trace quantities to a lower limit of 0.05 f-lg/L air can be detected by uv spectroscopy (36). Both in and gas chromatography have been used extensively to measure phosgene in air at 1 ppb—1 ppm (7,37,38). Special... 

Methods and iastmments that are used to monitor phosgene content ia air are well developed and have been reviewed (46—48). One detection iastmment is a porous tape that measures the concentration of phosgene ia air ia quantities as small as 6 ppb (49). Fourier transform ir spectrometry techniques have been developed to permit line and area monitoring ia the area around phosgene plants (50). 

Liquid phosgene is assayed by an iodometric method which iavolves the foUowiag reaction (52). The released iodine is titrated with sodium thiosulfate. 

Waste Disposal. Because of its low Boiling poiat and high, toxicity, measures must be taken to prevent the entrance of phosgene iato drains or sewers. If recycle of phosgene is not feasible, phosgene waste can be handled by one of the decomposition methods mentioned above, ie, caustic scmbbiag, moist activated carbon towers, or combustion. 

Phosgene addition is continued until all the phenoHc groups are converted to carbonate functionahties. Some hydrolysis of phosgene to sodium carbonate occurs incidentally. When the reaction is complete, the methylene chloride solution of polymer is washed first with acid to remove residual base and amine, then with water. To complete the process, the aqueous sodium chloride stream can be reclaimed in a chlor-alkah plant, ultimately regenerating phosgene. Many variations of this polycarbonate process have been patented, including use of many different types of catalysts, continuous or semicontinuous processes, methods which rely on formation of bischloroformate oligomers followed by polycondensation, etc. 

In another method, phosgene is gradually passed into 1,2-propylene glycol (9). The chloroformate is washed, dried, and distilled at 266 Pa (2 mm Hg) and added slowly to a mixture of aHyl alcohol and pyridine below 15°C. The purified monomer 1,2-propylene glycol bis(aHyl carbonate) (C H O ) heated with lauroyl peroxide at 70°C gives a hard clear, polymer. 

In the ketone method, the central carbon atom is derived from phosgene (qv). A diarylketone is prepared from phosgene and a tertiary arylamine and then condenses with another mole of a tertiary arylamine (same or different) in the presence of phosphoms oxychloride or zinc chloride. The dye is produced directly without an oxidation step. Thus, ethyl violet [2390-59-2] Cl Basic Violet 4 (15), is prepared from 4,4 -bis(diethylamino)benzophenone with diethylaruline in the presence of phosphoms oxychloride. This reaction is very useful for the preparation of unsymmetrical dyes. Condensation of 4,4 -bis(dimethylamino)benzophenone [90-94-8] (Michler s ketone) with AJ-phenjl-l-naphthylamine gives the Victoria Blue B [2580-56-5] Cl Basic Blue 26, which is used for coloring paper and producing ballpoint pen pastes and inks. 

More recendy, preparation of carbonic esters by nonphosgene routes, such as the reactions of CO or CO2 with appropriate substances in the presence of catalysts, has been preferred. These methods are more economic in many cases and naturally less ha2ardous than phosgene routes. 

Carbonates ate manufactured by essentially the same method as chloroformates except that more alcohol is required in addition to longer reaction times and higher temperatures. The products are neutralized, washed, and distilled. Corrosion-resistant equipment similar to that described for the manufacture of chloroformates is requited. Diaryl carbonates are prepared from phosgene and two equivalents of the sodium phenolates or with phenols and various... 

Fatty acid chlorides are very reactive and can be used instead of conventional methods to faciUtate production of amides and esters. lmida2oles are effective recyclable catalysts for the reaction with phosgene (qv) (24). 

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