| 摘要 |
<p>1,226,446. Process for the production of octahydro - 1,2,4 - methenopentalenyl - 5 - exo - isocyanate. J. R. GEIGY A.G. 19 June, 1969 [20 June, 1968], No. 31157/69. Heading C2C. [Also in Division A5] The invention relates to a process for the production of octahydro-1,2,4-methenopentalenyl-5-exo-isocyanate by reacting an exo-endo isomer mixture of octahydro-1,2,4-methenopentalene - 5 - carboxylic acid - lower alkoxy alkyl ester, having from 1 to 4 C atoms in the alkoxy alkyl moiety, e.g. the beta-ethoxy ethyl ester consisting essentially of exo-isomer with hydrazine to obtain the corresponding carboxylic acid-hydrazide, freeing this from endo isomer by recrystallization from lower halo-alkanes, having from 1 to 4 C atoms, e.g. 1,2-dichloroethane, converting the acid hydrazide thus purified with nitrous acid in the acid azide and decomposing this with heat. In an example hydrazine hydrate is reacted with octahydro-1,2,4-methenopentalene - 5 - carboxylic acid - beta - ethoxyethyl ester to produce the crude hydrazide which is purified and reacted with sodium nitride in hydrochloric acid to produce the azide which is subsequently heated to produce the required isocyanate. The starting material octahydro - 1,2,4 - methenopentalene - 5 - carboxylic acid-beta-ethoxyethyl ester may be produced by reacting acrylic acid-beta-ethoxyethyl ester with 2,5-norbornadiene. 1-(p-Tolylsulphonyl) - 3 - [octahydro - 1,2,4 - methenopentantalenyl-(5)] urea may be obtained by reacting compounds of the invention with arylsulphonamides. The corresponding carbamic acid esters and acetyl amines can be hydrolysed to octahydro - 1,2,4 - methenpentalenyl - (5)- exo-amine.</p> |
