Propane-1,3-dinitrile

Davis and co-workers have carried out the first examples of the Knoevenagel condensation and Robinson annulation reactions [61] in the ionic liquid [HMIM][PFg] (HMIM = l-hexyl-3-methylimidazolium) (Scheme 5.1-33). The Knoevenagel condensation involved the treatment of propane-1,3-dinitrile with a base (glycine) to generate an anion. This anion added to benzaldehyde and, after loss of a water molecule, gave l,l-dicyano-2-phenylethene. The product was separated from the ionic liquid by extraction with toluene. 

Problem 18.47 What is the product of catalytic hydrogenation of (a) acetone oxime, b) propane-1,3-dinitrile, (c) propanal and methylamine M... 

Q The nitroso group exhibits similar behaviour to a carbonyl group. Predict the products from the reaction of nitrosobenzene with (a) malononitrile (propane-1,3-dinitrile), (b) hydroxylamine and (c) aniline. Suggest a mechanism for the last reaction. 

The Knoevenagel reaction (Scheme 6.20) involves the reaction of aromatic aldehydes with a variety of molecules CH2XY. The groups X and Y may be the same or different, but are invariably electron withdrawing, so creating an activated methylene group from which the carbanion CHXY is produced. The reaction is usually carried out in pyridine solution, with piperidine as the basic catalyst. The reactions of benzaldehyde with propane-1,3-dinitrile [malononitrile, CH2(CN)2] and diethyl propane-1,3-dioate [diethyl malonate, CH.,(CO,Et)2] are illustrative. In both cases, manipulation of the CH=CX2 group in the product allows the synthesis of other compounds. 

This chapter reports about an investigation on the catalytic gas-phase armnoxidation of u-hexane aimed at the production of 1,6-Ce dinitriles, precursors for the synthesis of hexamethylenediamine. Catalysts tested were those also active and selective in the ammoxidation of propane to aciylonitrile mtile-type V/Sb and SnA /Nb/Sb mixed oxides. Several A-containing compounds formed however, the selectivity to cyano-containing aliphatic linear Ce compounds was low, due to the relevant contribution of side reactions such as combustion, cracking and formation of heavy compounds. 

Indol 3-(2-Dimethylamino-ethyl)-5-hydroxy- IV/lb, 803 Malonsaure (3-Oxo-3,4,4-trimethyl-cyclohexyl)- -dinitril E5, 1518 I(NC)2CH2 + 3-Oxo—1-en] Propan 2,2-Dimethyl-l-(2-methyl-phenyl)-l-nitrosimino- E14b, 746 (N-Nitrosier.)... 

SYNS CYANOACETONITRILE DICYANOMETH-ANE DWUMETYLOSULFOTLENKU (POLISH) MALONIC DINITRILE METHYLENE CYANIDE NITRIL KYSELINY MALONOVE (CZECH) PROPANE-... 

The submitter states that a number of aromatic mono-and dinitriles have been prepared by this procedure vvith slight or no modification in the temperature. The reaction mixtures were usually worked up by the acetone-ammonia method described in Note 6. Among the compounds prepared by this method are o-nitrobenzonitrile, o-bromobenzonitrile, w-methoxy-benzonitrile, 4,4 -dicyanodiphenylsulfone, 4,4 -dicyanostilbene, a,7-di-(4-cyanophenoxy)propane. With the last, a temperature of 185 190° for 20 minutes gave the best results. The yields before purification ranged between 75% and 95% and after purification between 63% and 79%. Aliphatic acids give low yields of the corresponding nitriles and, in some cases, chlorinated by-products. 

CggHgtNgO .. y-Triphenyl-/J-[at-o y-bens yl]-propan-gt.y-dioaibonsSure-dinitril 10, 635. 

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