Imidoyl cyanide

In the reaction of dimethylfoimamide chloride with the imidoyl cyanide (299 equation 160) the amidine (300) is formed. Isoxazolines, prepared from amide chlorides and hydroxylamine, rearrange on heating or irradiation to give 2-aminoazirine (301 Scheme 46). Azirines (302) can also be prepared by treating chloroenamines with base and sodium azide. ... 

The combination of diethylaluminum chloride with trimethylsilyl cyanide has been successfully utilized for the general synthesis of imidoyl cyanides from various oxime sulfonates (equation 19). ... 

Imidoyl isocyanides PhN=C(R)NC, formed by the action of silver cyanide on imidoyl bromides in chloroform, differ from the structurally related and better known iV-acyl isocyanides in that, on heating, they undergo isomerization to the thermodynamically more stable isomeric imidoyl cyanides ArN=C(Ph)CN rather than trimerization/ Also formed, in minor amount (10—30%), is 2,2 -diphenyl-4,4 -bisquinazoline (220), probably via head-to-tail dimerization of the isocyanide followed by a double electrocyclic ring-closure of the extended TT-system (219). Attempts to transform /3-styryl isocyanides into 2,2 -... 

The solid-phase synthesis of the 2(lff)-pyrazinone scaffold is based on a Strecker reaction of commercially available Wang amide linker with appropriate aldehyde and tetramethylsilyl (TMS) cyanide, followed by cyclization of a-aminonitrile with oxalyl chloride resulting in the resin linked pyrazinones. This approach allows a wide diversity at the C-6-position of pyrazinone scaffold (Scheme 35, Table 1). As it has been shown for the solution phase, the sensitive imidoyl chloride moiety can easily undergo an addition/elimination reaction with in situ-generated sodium methoxide affording the resin-linked... 

Cyanoboration (4, 445-447 5, 446-447) ketone synthesis. Symmetrical ketones can be prepared in high yield by conversion of trialkylboranes into sodium trialkylcyanoborates (1) by reaction with sodium cyanide. Reaction of (1) with an electrophile (an imidoyl chloride, benzoyl chloride, or especially,... 

Organogold carbene compounds [Au(carbene)(CN) j iR ] can be obtained from com-plexed cyanides [Au(CN)m(C6F5) ] (n = 1 or 3, m = 1 and n = m = 2) by sequential alkylation (to form isocyanide complexes) and nucleophilic attack of amine" . Gold(III) diisocyanides [Au(CNR)2(CgF5)2]+ (R = Ph or p-tolyl), which can also be obtained by isocyanide substitution of ether in [Au(C6F5)2(OEt2)2] > react with hydrazobenzene NH(Ph)NHPh and hydrazine or phenyUiydrazine according to the reactions in Scheme 32 to furnish cyclic bis(carbene) and cyclic carbene-imidoyl compounds . ... 

Iminium halides are intermediates in the hydrolysis of nitriles and in a variety of chemical reactions. For example, in the Ritter reaction addition of a nitrile or hydrogen cyanide to a carbonium ion occurs, leading to the intermediate formation of a nitrilium salt. Nitrilium salt intermediates have also been postulated in the Schmidt reaction and in the Beckmann rearrangement, provided the latter was performed in concentrated sulfuric acid. However, since we are predominantly concerned with imidoyl halides, these reactions are not discussed in this monograph. 

The reaction of imidoyl chlorides with potassium cyanide, to yield the corresponding nitrile (CLXIX has been reported by Mumm... 

A common synthetic approach to GABOB uses epichlorohydrin (6.29) as a starting material. In a simple example, 6.29 was treated with potassium phthalimide and sodium cyanide to give GABOB (6.27), after hydrolysis and removal of the phthalimidoyl group.3 In one variation of this reaction, the intermediate phthal-imidoyl product was isolated prior to ti atment with cyanide. 2 The reaction can be... 

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