Zur Synthese von N-(Chlormethyl)carbimidoylchloriden / Synthesis of N-(Chloromethyl)carboximidoyl Chlorides

Abstract

<jats:title>Abstract</jats:title><jats:p> From N-(hydroxymethyl)- and N-(chloromethyl)carboxylic acid amides (3) and (4) respectively by treatment with 2 or 1 mol phosphorus pentachloride respectively N- (chloromethyl)carboximidoyl chlorides (10) are formed. As side products in addition to acyl chloride (6) and carbonitrile (14) can be isolated tris(chloromethyl)amine (7), N- (chloromethyl)carboximidic acid chloromethylester (15), N-bis(chloromethyl)phosphoramidic dichloride (11) and l,3-bis(chloromethyl)-2,2,2,4,4,4-hexachloro-2,2,4,4-tetrahydro- l,3,2,4-diazadiphosphetidin (12)</jats:p>

Efficient Microwave Access to Polysubstituted Amidines from Imidoylbenzotriazoles

“…These results illustrate the general applicability of this method for the preparation of amidines under mild conditions (80−120 °C) and short reaction times (10 min). Imidoylbenzotriazoles are stable crystalline solids that can be purified and stored at room temperature; their use also avoids side reactions, toxic reagents, and special handling procedures involved with imidoyl chlorides, iminium triflates, and imidate fluoroborates 3a4 Preparation of Amidines 7 A − Aa from Imidoylbenzotriazoles 6 a − w entryR 1 R 2 R 3 R 4 product a (yield %)mp (°C)lit.…”

“…Imidoyl chlorides ( 1 ) are generally prepared in situ by treatment of the corresponding amides with phosgene, thiophosgene, oxalyl chloride, phosphorus penta - and trihalides, thionyl chloride, sulfuryl chloride, and halogens 3a. Chlorides 1 are labile toward hydrolysis, and with amines at elevated temperatures, side reactions have been reported if α-CH groups are present in the imidoyl chlorides 3b. Many amidines can be obtained in one step by heating the monosubstituted amide with amine and phosphorus pentachloride; in some cases, the imidoyl chloride has to be isolated 2g.…”

Preparation of Heterocycle-Masked β-Enamino Acids

“…They also can be prepared from isocyanides, nitriles, isocyanates, imines, and amines . Although the preparation of imidoyl chlorides normally provides good yields, side-reactions such as self-condensation have been reported at elevated temperatures if α-CH groups are present in the imidoyl chloride . A major disadvantage in the use of imidoyl chlorides is their extreme lability toward hydrolysis.…”