Imidoyl halide

Spanedda, V.M., Ourevitch, M., Crousse, B., Begue, J.-P., and Bonnet-Delpon, D. (2004) Tetrahedron Lett., 45, 5023-5025. 

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In fluorinated isocyanide dihalides and imidoyl halides the halogens are replaeed by alkoxyls [19 20, 21] (equation 18)... 

Further evidenee for the intermediacy of the imidoyl halide 24 can be taken from the formation of the aminodicyanostyrene 22, formed as a minor product in the amination of 20 (Scheme 11.19) (73RTC471). As already mentioned, 22 eontains the same content as the starting material, and based on this experimental result its formation from the imidoyl halide seems now straightforward. In this strong basic solution the tautomeric con-... 

Since the electrophilic character of carbonyl groups in acid halides is more pronounced than in carboxylic anhydrides, the former are better suited for aza-Wittig reactions. Zbiral et al. studied the reaction of imino-phosphoranes with acid halides and obtained imidoyl halides (69LA29 72PS35). A -alkyl and A -aryl iminophosphoranes can be set to use in this reaction (72PS35). 

Grignard reagents and other carbon nucleophiles can react with imidoyl halides 438 to produce imines 439 (equation 186). Other nucleophiles may be used to displace successfully the halide. 

Intramolecular azomethine ylide cycloaddition to the C—O double bond of an aldehyde was reported in 197369 and cycloaddition to the C—C double bond was first reported in 1975.70 Competition between 1,1- and 1,3-cycloaddition is observed in intramolecular reactions, although intermolecular reactions give only 1,3-cycloaddition. Photolysis of 2//-azirines is one generation method of nitrile ylides applicable to intramolecular cycloaddition.70 Another method involves the base-catalyzed 1,3-elimination of hydrogen halide from alkenyl imidoyl halides. Still other procedures involve thermolytic and photolytic cycloreversions of oxazolinones and dihydrooxazaphospholes. 

H. Ulrich, The Chemistry of Imidoyl Halides, Chapter 7, p. 173. Plenum, New York, 1968. 

The activation of cyclopropylamides through the corresponding imidoyl halides prepared in situ in the presence of PPI13 and CX4 gave ring-expanded IV-substituted pyrrolidin-2-ones (Scheme 40).66... 

The reaction of compound 90 with imidoyl halides without added base gives the hydrochloride salts of 1,2,4-thiadiazol-5-imines 95. The corresponding free bases can be liberated from the salts 95 with weak bases such as bicarbonate, but these imines are labile and decompose readily to form the W-cyanamide 96 and sulfur. The free base can be treated in situ with a second electrophile, such as an acid chloride, imidoyl chloride, or aryldiazonium salt, affording pentalene derivatives 97-99. It should be noted that the compound 98 cannot be prepared in a one-pot procedure from compound 90 and 2 equiv of imidoyl chloride in the presence of base, in contrast to the corresponding dioxa compound 91 (Scheme 22) <1981BSB89, 1992JHC1317>. 

Dipolar cycloadditions.1 On treatment with DBU, imidoyl halides 1, prepared by reaction of acid chlorides with isocyanides, undergo 1,3-dehydrochlorina-... 

M. F. Lappert, and A. J. Oliver, A Three-Fragment Oxidative Addition Reaction as a Route to Transition Metal Carbene Complexes Imidoyl Halides and Rhodium(I) Compounds as Precursors for Rhodium(III) Carbenes, J. Chem Soc., Chem. Comm. 1972, 274-275. 

The yields are lower because of competing hydrolysis during the aqueous work-up. Lithioynamines 44 must be used with unreactive halides such as carbamoyl chlorides and imidoyl halides (93) The scope of this reaction seems to be limited only by the availability of the requisite acyl chlorides. It is less surprising, therefore, that a single paper reports the preparation of about sixty push-pull acetylenes In contrast, silylated ynamines, react only with very strong acylation agents, e.g. trichloroacetyl and nitrobenzoyl chloride as well as with phosgeniminium chloride. 

Phosphorylation of the imidoyl halide (233) by reaction with dialkyl fluorophosphite results in the formation of the rearrangement product (234 X = F) which, at a higher temperature, rearranges prototropically and irreversibly to the phosphonate (235 ... 

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