Isocyanide dichloride, reaction

The isocyanide dichlorides are particularly attractive 1,1-bielectrophiles, and the N-sulfonyl derivative (138) underwent reaction with the iV-hydroxythioamide (137) to give the 1,3,5-oxathiazole derivative (139) (71AP763). Yields varied from 62% for R = Me and were slightly less for R = Ph (57%) and R = p-MeOC6H4 (50%). 

Dichlorocarbene reacts exothermically under soliddiquid two-phase conditions with azides to produce, initially, isocyanide dichlorides, RN=CC12, which can react further to give A-alkyltetrachloroaziridines [50], The aziridines are the major products (60-70%) with simple alkyl azides, but the reaction tends to stop at the isocyanide step (50-60%), when the alkyl group is highly fluorinated. 

To some extent this reaction is followed by one yielding an isocyanide dichloride ... 

Ph, R = NHj, with phosgene gives a novel bicyclic heterocyclic system which can be represented as a bicyclic meso-ionic l,3,4-thiadiazol-2-one (493) (Section VII,H,1). A similar reaction using A -benzoyl isocyanide dichloride (PhCO.N=(i Cl2) gives the novel meso-ionic 1,3,4-thiadiazol-2-imine (494) (Section VII,H,2). ... 

Reaction of isocyanide dichlorides with primary amine hydrochlorides in an inert solvent at 180°C [71]. 

Thermolysis of the formamidrazone 590, obtained from the reaction of hydrazine 488 with Vilsmeier salt 589, at 200°C or on boiling in nitrobenzene led, by intramolecular transformation, to the triazolo[4,3-c]pyrimidine 591 (90T3897). Aryl isocyanide dichlorides reacted with 488 in the presence of Et2N to give 3-anilinotriazolopyrimidines (592) (Scheme 117). 

In this lecture some new routes to phosphorus-carbon compounds with P-C multiple bonds, found in connection with our investigations on reactions of tertiary phosphanes with chlorinated carbon compounds, such as tetrachloromethane, hexachloroethane, phosgene, and isocyanide dichlorides are reported. Furthermore some stereochemical problems concerning this type of compound will be discussed. 

After the elucidation of the reaction of phenylisocyanide dichloride with phenyl(trimethylsilyl)phosphane, several other differently substituted isocyanide dichlorides react extremely slowly, so that high temperatures are necessary which prevent the... 

The story of the reaction of isocyanide dichlorides with bis(trimethylsilyl)phenylphosphane, however, does not end here. Like the reaction of t-butyl-bis(trimethylsilyl)phosphane with phosgene, the conversions with isocyanide dichlorides depend very much upon the reaction conditions. If the reaction is carried out at ambient temperature in a molar ratio of 1 1 in such a way that the isocyanide dichloride is rapidly dropped into the phos-phane solution, the hitherto unknown, 2,4-bis(phenylimino)-l,3-diphenyl-1,3-diphosphetanes are obtained besides the phosphinomethylenephosphanes. Several findings, suggest that their... 

A direct approach to 3-aryl-2-chloro-4-iminothieno[2,3-d]pyrimidines 65a from A-aryl isocyanide dichlorides and o-aminocarbonitriles 48 was devised by Shishoo and Jain (92JHC883). 3-Aryl-4-imino-2-methylthieno [2,3-rf]pyrimidines 65b were obtained by heating a mixture of 2-acetyl-aminothiophene-3-carbonitriles 64a, phosphorus pentoxide, a primary ary-lamine hydrochloride, and /V,7V-dimethylcyclohexylamine hydrochloride in a molar ratio 1 6 4 4, at 160°C (88CS195 91EUP452002). Following similar reaction conditions but adding 8 parts of water to this reaction mixture... 

The intermediate 1,3-diphosphapropenes can be synthesized in a separate reaction of bis(trimethylsilyl)phosphanes with phosgene or isocyanide dichlorides (29, 99), respectively, and can be converted to the unsymmetrically substituted pentadienes with phosphaketene [Eq. (47)]. 

The first hints of the intermediate appearance of the 1-phospha-3-azaallenes, as one may call this class of compounds, were obtained during investigations of the system bis(trimethylsilyl)phosphane/ isocyanide dichloride. Depending to the course of reaction, bis(imino)-1,3-diphosphetane or 1,3-diphosphapropene is synthesized via addition of excess silylphosphane to the primarily formed monophospha-carbodiimode or its dimerization product (31). 

Amidines with a more complicated substitution pattern have been prepared from amidines by alkylation—either at nitrogen or at nitrogen substituents. - Variations at these positions have been achieved by heteroarylation, acylation,vinylation or carboxylation with phosgene, thio-phosgene, isocyanide dichlorides or isothiocyanates. Some interesting amidines, e.g. (347)-(3S2) (Scheme 59), have been prepared in this manner. The amidine skeleton can also be varied by halogen-ation, - hydrolysis, isomerization or catalytic hydrogenation or other addition reactions if there are C=—C double bonds present as in (353 equation 173) for example. ... 

Ito and his coworkers have reported that palladium-catalyzed oxidative coupling reactions of Grignard reagents in the presence of V-substituted isocyanide dichloride afford diynes (equation 17). Isocyanide dichloride may serve as a reoxidant of the palladium catalyst in this sequence via a catalytic cycie. In addition Kiji and his coworkers have described the oxidative coupling of phenylacetylene by a Pd-Cu catalyst in the presence of 4-iodo-(3//) phenothiazin-3-one. ... 

The reaction of 3-amino-6-chloropyridazine (55) with either Y-(phenylchloromethylene)carbamic acid chloride or benzoyl isocyanide dichloride formed 2-phenylpyridazino[2,3-a][l,3,5]triazine-4-one (56) in moderate yield (Equation (9)) <72JOC2960>. Substituted aminopyridazines on reaction... 

In 1874 Sell and Zierold obtained phenylcarbonimidoyl dichloride I in the reaction of phenylisothiocyanate II with chlorine. Several years later, Nef ( 8,109 prepared carbonimidoyl dichlorides by addition of chlorine to isocyanides, such as phenyl isocyanide III. This relationship between I and isocyanides (isonitriles) led to the frequently used term isocyanide dichlorides for the compounds under discussion. 

Not only acyl chloride but also sulfonyl chloridef and isocyanide dichloride can be used in the coupling reaction (Scheme 6). 

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