Reaction Of Chloroacetyl Chloride Research Articles

Grafting studies onto cellulose by atom‐transfer radical polymerization

AbstractStyrene (Sty), methyl methacrylate (MMA), methacrylamide (MAm) and acrylomorpholine (AcM) were grafted onto powder cellulose by atom‐transfer radical polymerization. Cellulose chloroacetate (Cell‐ClAc), as a macro‐initiator, was first prepared by the reaction of chloroacetyl chloride with primary alcoholic OH groups on powder cellulose. CuBr and 1,2‐dipiperidinoethane were used as a transition‐metal compound and as a ligand, respectively. These reactions were monitored by FT‐IR and weight increase in Cell‐ClAc. In case of styrene, although some weight increase occurred, no evidence of grafting could be observed in the FT‐IR spectrum, while there were strong evidence of grafting with MMA, MAm and AcM. Cell‐graft‐MAm, Cell‐graft‐AcM and Cell‐graft‐MMA showed new carbonyl bands at 1665, 1640 and 1735 cm−1, respectively. Dye‐uptake and dye‐absorption properties of cellulose, for alizarin yellow (basic dye) and bromocresol green (acidic dye), and its moisture‐ and water‐uptake capacities improved with the grafting, but some decrease was observed in thermal stability. Copyright © 2004 Society of Chemical Industry

Thiylation of Functionalized Electrophiles with Sulfur in Basic Reductive Systems

Functionalized electrophiles, specifically acetyl chloride, benzoyl chloride, chloroacetylchloride, benzenesulfonyl chloride, and N,N,4-trichlorobenzenesulfonamide, were brought into reaction with sulfur in the systems hydrazine hydrate-NaOH and sodium sulfide-water-ethanol. The efficiencies of these systems were compared. The reaction of chloroacetyl chloride with sulfur in the system hydrazine hydrate-base afforded new types of polymeric compounds, poly[(diacylhydrazine)polysulfides]. The reaction mechanisms were discussed.

Thermal degradation behaviour of two methacrylate polymers with side chain amide groups

2-Oxo-2-phenylamino)ethylene methacrylate (PAMA) and (2-oxo-2-benzylamino)ethylene methacrylate (BAMA) were prepared by reaction of sodium methacrylate with N-phenyl chloroacetamide and N-benzyl chloroacetamide, respectively, which were obtained from reaction of chloroacetyl chloride with aniline or benzylamine. The thermal degradations of poly(PAMA) and poly(BAMA) prepared by a free-radical procedure were investigated by thermogravimetric analysis (TG) and by programmed heating of the polymer from ambient temperature to 500 °C under vacuum, followed by product collection, and using IR spectra of partially degraded polymer. The products volatile at degradation temperature but not at ambient temperature were collected on the cooled upper part of the degradation tube [cold ring fraction, CRF P for poly(PAMA), CRF B for poly(BAMA)]. Product analysis studies showed that only N-benzyl hydroxyacetamide formed as major product in thermal degradation of poly(BAMA) and the monomer did not, whereas in the case of poly(PAMA) N-phenyl hydroxyacetamide and the monomer both formed as major products. For poly(BAMA), the activation energy of cyclization is calculated as 47.4 kJ mol −1; for poly(PAMA) the activation energy of the depolymerization is calculated as 58 kJ mol −1. The mechanism of thermal degradation including formation of the major products is discussed.

Stereoselective Cycloaddition of Monosubstituted Ketene to a Methyl Glyoxylate- and Threonine-Derived Imine: Synthesis of Optically Pure β-Lactamic α-Amino Ester with High Functionality

The reaction of chloroacetyl chloride and triethylamine with a chiral imine derived from the combination of methyl glyoxylate and protected L-threonine gave two optically active α-amino acid derivatives with a cis-substituted β-lactam skeleton in a 72:28 ratio. The major product is obtained in 59% yield by simple crystallisation.

Researches on pyridodiazepines. Behavior of 7,8,9,10‐tetrahydro‐5‐methylcyclopenta[e]pyrido[3,2‐b][1,4]‐diazepin‐6(5H)‐one with chloroacetyl chloride

AbstractFollowing a previous experiment, an original heteropolycyclic structure 4 was obtained by a reaction of chloroacetyl chloride with compound 3 bearing a conjugated double bond system. The condensation develops with an initial NH‐chloroacetylation and ring closure by quaternarization of the pyridine nitrogen. This is achieved through an 1,4‐cycloaddition of chloroketene to make a pyranone ring.

The synthesis of [U‐14C phenyl] LS 840606, an agricultural fungicide

Abstract2,2′4′‐Trichloro‐[ring U‐14C]acetophenone 3 was the key intermediate of this synthesis patterned after the industrial route. An unexpected poor yield was observed during the preparation of 3 by the Friedel‐Crafts reaction of chloroacetyl chloride with 1,3‐dichloro‐[U‐14C]benzene 10, possibly the result of an isotope effect although this poor yield might be explained by other factors.Two routes were checked for the preparation of 1,3‐dichloro‐[U‐14C]benzene 10. The action of CCL4 with 1,3‐dinitro‐[U‐14C]benzene at 280°C was entailed with explosions. A safer route started from [U‐14C]aniline via 2,4‐dichloro‐[ring U‐14C]acetanilide.Friedel‐Crafts reaction of 10 with acetyl chloride gave rise in 52% yield to 2′,4′‐dichloro‐[ring U‐14C]acetophenone 16 which was brominated to 2‐bromo‐2′,4′‐dichloro‐[ring U‐14C]acetophenone 17;17 was condensed with 2,2‐(ethylenedioxy)ethylmagnesium bromide to compound 18; 18 was condensed with 1,2,4‐triazole to 5 then successively treated with HCl:water:dioxane and 2,2,2‐trifluoroethanol/HCl. Separation of the two diastereomers by medium pressure liquid chromatography. 7% overall radioactive yield from [U‐14C]aniline. Radiochemical purity 99%.

A facile synthesis of 2-methyl-[3,4-di- o-acetyl-6- o-(chloroacetyl)-1,2-dideoxy-α- d-glucopyrano]-[2′,1′:4,5]-2-oxazoline

The use of the chloroacetyl group as a protecting group has been studied for a 2-methylglyco-[2′,1′:4,5]-2-oxazoline. The reaction of chloroacetyl chloride or chloroacetic anhydride with 2-acetamido-1,3,4-tri- O-acetyl-2-deoxy-β- d-glucopyra-nose provided 2-acetamido-1,3,4-tri- O-acetyl-6- O-(chloroacetyl)-2-deoxy-β- d-glucopyranose which, on treatment with anhydrous ferric chloride in dichloromethane, produced the desired oxazoline. The glycosylating capability of the oxazoline has been investigated with aglycon hydroxides, to give the corresponding 2-acetamido-2-deoxy-β- d-glucopyranosides. The chloroacetyl group can be selectively removed by treatment with thiourea, and migration of O-acetyl groups was not observed under these conditions.