Dimethylchloroformiminium chloride

Substitution of chlorine for hydroxyl at C-6 of morphine was effected098 with dimethylchloroformiminium chloride (Vilsmeier s reagent) in DMF. The resultant a-chloromorphide (90, R = H X = Cl), together with the 6a-bromo- and 6a-iodo- derivatives, was described earlier.075 199 The 6-halide configuration was determined as 6-axial by H nmr.098 The kinetics of SN2 ... 

The Vilsmeier reagent, dimethylchloroformiminium chloride, (CH3)2NCHClCr (1), has generally been prepared by the reaction of dimethylformamide with phosphoryl chloride or thionyl chloride (1, 284-285, 286-289 2, 154 3, 116 4, 186). Hepburn and Hudson now report that the crystalline reagent can be prepared in 88% yield by addition of PCI5 to an excess of DMF (exothermic reaction). 

Dimethylformamide/thionyl chloride Reactions with dimethylchloroformiminium chloride ... 

Dimethylformamide derivatives have found new applications. The complex with sulfur trioxide previously used for the formation of peptide bonds has now been used for carbon-carbon condensations as well Dimethylchloroformiminium chloride, readily available by reaction of phosgene or thionyl chloride with dimethylformamide, is a highly reactive compound and a versatile reagent... 

Two groups of investigators have found independently that acetals of dimethylformamide are excellent reagents for the preparation of esters and phenolethers under mild conditions 2,4-Disubst. s-triazines and trisubst. formamidines have been prepared with dimethylformamide diethyl acetal in particular There are other synthetically interesting derivatives of N,N-disubst. amides, e.g. their chlorides. They give a variety of valuable products, including heterocyclics, in a simple manner The most frequently used of these amide chlorides is dimethylchloroformiminium chloride, which has already been mentioned in last year s Trends... 

The formylation of 2-methylbenzothiazole by the Vilsmeier-Haack reaction using dimethylchloroformiminium chloride (82) in DMF yields the l,3-bis-dimethylamino-2-(2-benzothiazolyl)propenium salt (83), which is hydrolysed by alkali to 2-benzothiazolylmalonic dialdehyde (84). The corresponding quaternary salt (85) reacts similarly in DMF, yielding (86) as the final product. In chloroform, however, its formylation followed by hydrolysis affords the trimethine dyes (87 R = H or CHO) and (88). Their formation is ascribed to the condensation of the primary formylation products with an excess of quaternary salt. A series of reactions based on 3-methylbenzoselenazole take an entirely parallel course. ... 

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