Dimethylcarbamyl Chloride

An interesting formation of a tetrahydro-l,3-oxazine derivative (5) occurs on reacting the vinyl ether of 3-aminopropan-l-ol with A jA-dimethylcarbamyl chloride/... 

Figure 14.6 Resonance stabilization of reactive intermediates from (i) bis(chloromethyl) ether, (ii) aliphatic nitrogen mustard, (iii) allyl chloride, (iv) benzyl chloride, (v) bis(morpholino)methane, (vi) benzoyl chloride, and (vii) dimethylcarbamyl chloride.

In contrast to this demonstration of bimolecularity, Hall and Lueck82 showed the possibility of acylium ion formation from benzoyl chloride by its reaction with mercuric perchlorate. In common with dimethylcarbamyl chloride, dimethylsulphamyl and tetramethyldiamidophosphochloridate, benzoyl chloride reacted readily to form the corresponding acylium ion /i-butyl chloroformate however was inert. Kivinen138 studied the effect of mercuric chloride on the ethanolysis of 4-methoxybenzoyl chloride, benzoyl chloride and 4-nitrobenzoyl chloride and obtained the following approximate relative rates for the effect of mercuric chloride (0.30 M) in ethanol, 4-MeO, 2.91 4-H, 1.00 4-NOz, 1.03, confirming the SN2 character of the 4-nitro-... 

Rate parameters for the hydrolyses of some alkyl and acyl chlorides are compared in Table 20. The value of AS for dimethylcarbamyl chloride is close to that observed for the hydrolysis of /-butyl chloride in 90% water/10% dioxan566 (+ 8 eu). 

Several less widely used methods for preparing benzo[6]thienyl ketones will now be mentioned. A low yield of di(2-benzo[6]thienyl) ketone is obtained by treating 2-benzo[6]thienyllithium with N,N dimethylcarbamyl chloride.667 The ketone (284) is prepared by... 

Diethylnitrosamine Benzyl chloride N-Nitrosppyrrolidine Dimethylnitrosamine Dimethylcarbamyl chloride N-Mitroecmorpholine Di-n-propylnitrosamine... 

A mixture of the Step 1 product (1.00 mmol) and dimethylcarbamyl chloride (1.1 mmol) dissolved in 2 ml apiece THF and pyridine was treated with triethy-lamine (2 mmol) then stirred 24 hours. The mixture was diluted with 20 ml water then extracted three times with 20 ml CH2C12, washed with 30 ml brine, dried with Na2S04, and concentrated. The residue was purified by chromatography using methyl alcohol/CH2Cl2/0.880 ammonia with a gradient of 10 989 1 to 30 967 3 and the product isolated in 91% yield as a yellow oil. 

L acetone, dimethylcarbamyl chloride (2.83 mol), TEA (2.83 mol), N,N-dimethylaminopyridine (0.156 mol) added, and the mixture stirred 2 hours. Thereafter, an additional 265 ml dimethylcarbamyl chloride and 25 g of N,N-dimethylaminopyridine were added, the mixture refluxed 16 hours, then poured into an ice brine solution. The mixture rested 40 hours and the product isolated by filtration. H-NMR, MS, and HPLC data supplied. 

Allerhand and Gutowsky (1964) also report Ea = 14-0 + 0-9 kcal mole-1 and log A = 10-9 + 0-6 for the barrier in AA-dimethylcarbamyl chloride from spin-echo measurements. 

DIMETHYLCARBAMYL CHLORIDE (79-44-7) or N,Al-DIMETHYLCARBAMYL CHLORIDE (79-44-7) Combustible liquid (flash point 155°F/68°C). Rapidly hydrolyzed in water to dimethylamine, carbon dioxide, and hydrogen chloride. Violent reaction with... 

If the reaction is carried out as a single-stage reaction starting from chlorobenzene, without isolation of the intermediate chlorobenzenesulfonyl chloride, care must be taken to ensure that sulfonic acid, thionyl chloride and sulfur chlorides, as impurities in the thionyl chloride, are no longer present in the reaction mixture, since the free sulfonic acid causes deactivation of the catalyst, and thionyl chloride and sulfur chlorides Ukewise lead to undesirable byproducts. A further difficulty is that iVA -dimethyl-formamide is required for complete conversion of chlorobenzenesulfonic acid with thionyl chloride into the corresponding sulfonyl chloride, carcinogenic A,A-dimethylcarbamyl chloride being formed as a byproduct. 

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