Phthaloyl chloride, hydrolysis

A hydrolysis of seven tons of phthaloyl chloride that was carried out in a herbicide synthesis workshop went out of control and detonated, causing the workshop to be destroyed. 

More commonly, but incorrectly, named thiophthalic anhydride and sometimes referred to as phthaloyl monosulfide or o-phthalyl sulfide, this compound (104) may be prepared by heating phthalic anhydride with sodium sulfide125 or by heating phthaloyl chloride with potassium hydrogen sulfide,126 hydrogen sulfide,127 or ethanolic sodium disulfide.128 The reaction between phthaloyl chloride and hydrogen sulfide also gives phthalic anhydride and di-o-phthaloyl disulfide.127 Early attempts to prepare 104 have been described by Chakravarti.126 4-Nitrophthalic thioanhydride may be prepared by hydrolysis of 8 (R = N02 X = C1) (Section III, A).22... 

Melphalan and the racemic analog have been prepared by two general routes (Scheme I). In Approach (A) the amino acid function is protected, and the nitrogen mustard moiety is prepared by conventional methods from aromatic nitro-derivatives. Thus, the ethyl ester of N-phthaloyl-phenylalanine was nitrated and reduced catalytically to amine I. Compound I was reacted with ethylene oxide to form the corresponding bis(2-hydroxyethyl)amino derivative II, which was then treated with phosphorus oxychloride or thionyl chloride. The blocking groups were removed by acidic hydrolysis. Melphalan was precipitated by addition of sodium acetate and was recrystallized from methanol. No racemization was detected [10,28—30]. The hydrochloride was obtained in pure form from the final hydrolysis mixture by partial neutralization to pH 0.5 [31]. Variants of this approach, used for the preparation of the racemic compound, followed the same route via the a-acylamino-a-p-aminobenzyl malonic ester III [10,28—30,32,33] or the hydantoin IV [12]. 

Treatment of 11 with excess aroyl chloride ArCOCl followed by hydrolysis gives a mixture of ArCONH2 and (ArCO)2NH, while the reaction of 12 with phthaloyl dichloride or phthalic anhydride results in the formation of phthalim-ide. Aroylpalladium complexes, prepared from ArX (X=Br, I) and [Pd(PPh3)4] under CO, also react with 12 to yield the aroylimides and/or aroylamides aifter... 

Kinetic studies of the solvolysis of cinnamoyl chloride in aqueous MeCN and acetone pointed to an 5 2 mechanism in the presence of HgCl2, there was an increase in the rate of solvolysis, but it was concluded there was no change in the mechanism. Studies of the hydrolysis of phthaloyl and terephthaloyl chloride suggested the intermediate... 

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