Method of making aromatic hydrazines

Abstract: A method for preparing a 2,3,5,6-tetrahalo- or 2,3,4,5,6-pentahalophenylhydrazine which comprises reacting the corresponding 1-nitro compound with hydrazine hydrate in a polar solvent, provides the desired compounds in a single step process and in good yields.

Description: The invention relates to a method of making aromatic hydrazines and, in particular, polyhalophenylhydrazines. A number of methods are known for making polyhalophenylhydrazines. In a paper by H. Suschitzky et al, J. Chem. Soc, c, (1), 67-74, 1971 there is described a process in which (1) pentachloronitrobenzene is reduced with iron filings in hydrochloric acid, (2) the so-formed amine is diazotised and (3) the diazo salt is reduced with stannous chloride. This is a multistep method and when employed for large scale preparation problems are encountered. For example, large volumes of solvent are needed to carry out the reduction with stannous chloride without which the reaction mixture is difficult to stir. The inventor has now found a single step method which is easy to perform to provide the desired compounds in good yields. According to the present invention there is provided a method for preparing a 2,3,5,6-tetrahalo-or 2,3,4,5,6-pentahalophenylhydrazine which comprises reacting the corresponding 1-nitro compound with hydrazine hydrate in a polar solvent. The hydrazine compounds which may be prepared by the present method have the formula: wherein each X is independently a halogen, e.g. Br, Cl or F and Y is a halogen or hydrogen. The polar solvent may be dimethylformamide or, preferably, dimethylsulphoxide. The reaction may take place at ambient temperatures, e.g. between 15°C and 22°C. Preferably each halogen, X, is chlorine. Other compounds which can be prepared include the following: The following examples are included for a better understanding of the invention. EXAMPLE 1 Preparation of pentachlorophenylhydrazine Pentachloronitrobenzene containing 5-10% Hexachlorobenzene, (3.0g, 10.1 mmole) was dissolved in dimethylsulphoxide (35ml) and hydrazine hydrate (1.25g, 25 mmole) added dropwise with stirring at 25°C. A slight 4-5°C increase in temperature was recorded and the solution became red-brown. After approximately 20 mins a white solid began to be precipitated. Stirring was continued for a further 1 hr after which time TLC (1:1 ethyl acetate : 60-80°C petrol) indicated that the reaction was complete. The mixture was poured into stirred water (200ml) and the solid filtered off and dried at 50°C overnight. The TLC and IR was identical to an authentic sample of pentachlorophenyl-hydrazine. Yield = 2.27g, 80%. EXAMPLE 2 Preparation of 2,3,5,6-tetrachlorophenylhydrazine The method of Example 1 was repeated using 2,3,5,6-tetrachloronitrobenzene to provide the product in 81% yield.

Claims: A method for preparing a 2,3,5,6-tetrahalo- or 2,3,4,5,6-pentahalophenylhydrazine which comprises reacting the corresponding 1-nitro compound with hydrazine hydrate in a polar solvent. A method as claimed in Claim 1 in which the polar solvent is dimethylformamide or dimethylsulphoxide. A method as claimed in claim 1 or 2 in which the hydrazine prepared has the formula: wherein each X is independently a halogen, e.g. Br, Cl or F and Y is a halogen or hydrogen. A method as claimed in any of claims 1 - 3 in which the hydrazine prepared has one of the formulae: Method as claimed in any of claims 1 - 4 in which the reaction takes place at a temperature of 15 to 22 °C.

Inventors: CRAWLEY MICHAEL W, CRAWLEY, MICHAEL W.
Applicants: EASTMAN KODAK CO, KODAK LTD, EASTMAN KODAK COMPANY, KODAK LIMITED
Application year: 1989
Main classification: C07C243
IPC codes: C07C241, C07C67, C07C243