Chloroacetyl chloride, reaction with

When an amino group is in a peri position with respect to the heteroatom [as in (54 after reduction)], an imidazole ring may be built to join the two by reaction with a carboxylic acid and PPE [2SI3]. Replacing the carboxylic acid by urea in the cyclization of (54.5) leads to the formation of a doubly fused imidazol-2-one ring [2513]. An imidazol-4-one may be constructed by the reaction of cither phenylglyoxal [3039, 3188] or the phenylazo derivative of chloroacetyl chloride [2366] with a 2-aminoazine. 

Alachlor and its related compounds are prepared from azomethines substituted at the phenyl group with alkyl groups by reaction first with chloroacetyl chloride, then with the respective alcohol (Olin, 1965). Intermediate azomethine is prepared from alkylaniline with formaldehyde. 

The antimony pentachloride-benzyltriethyl ammonium chloride complex (SbCls-TEBA, Figure 3.1), shows quite interesting catalytic efficiency in the acylation of activated aromatic compounds (i.e., toluene, xylenes, aryl ethers) with aromatic and chloroacetyl chlorides. Reactions are carried out with SbCls-TEBA (5% mol) in boiling nitromethane, giving ketones in 73%-96% yield. The catalyst has many advantages, such as ready access, minimal toxicity, reusability, insensitivity to atmosphere and moisture. 

The l,4-selenazin-3-one 168 was prepared as an analog of the cardiotonic drug bemoradan (where Se = 0) <1992JME172>. This ring system can be prepared in a series of reactions by the treatment of the amine 165 with bromine-potassium selenocyanate, followed by sodium sulfide (Scheme 46). The resulting aminoselenol 166 can be cyclized to the selenazinone 167 by treatment with chloroacetyl chloride. Treatment with hydrazine completes the synthesis of 168. 

In early 1983, the Korean company Shin Poong pursued a low-cost strategy to produce PZQ-(76) in bulk and to circumvent extensive patent protection, and thus became by 1993 the largest global producer of PZQ-(76). Their strategy involves treatment of chloroacetyl chloride (74) with phenylethylamine (77) to give (78), which then undergoes an amino alkylation reaction with amino acetaldehyde... 

Manufacture. Most chloroacetic acid is produced by the chlorination of acetic acid using a suitable catalyst such as acetic anhydride (9—12). The remainder is produced by the hydrolysis of trichloroethylene with sulfuric acid (13,14) or by reaction of chloroacetyl chloride with water. 

Chloroacetyl chloride [79-04-9] (CICH2COCI) is the corresponding acid chloride of chloroacetic acid (see Acetyl chloride). Physical properties include mol wt 112.94, C2H2CI2O, mp —21.8 C, bp 106°C, vapor pressure 3.3 kPa (25 mm Hg) at 25°C, 12 kPa (90 mm Hg) at 50°C, and density 1.4202 g/mL and refractive index 1.4530, both at 20°C. Chloroacetyl chloride has a sharp, pungent, irritating odor. It is miscible with acetone and bensene and is initially insoluble in water. A slow reaction at the water—chloroactyl chloride interface, however, produces chloroacetic acid. When sufficient acid is formed to solubilize the two phases, a violent reaction forming chloroacetic acid and HCl occurs. 

Chloroacetyl chloride is manufactured by reaction of chloroacetic acid with chlorinating agents such as phosphoms oxychloride, phosphoms trichloride, sulfuryl chloride, or phosgene (42—44). Various catalysts have been used to promote the reaction. Chloroacetyl chloride is also produced by chlorination of acetyl chloride (45—47), the oxidation of 1,1-dichloroethene (48,49), and the addition of chlorine to ketene (50,51). Dichloroacetyl and trichloroacetyl chloride are produced by oxidation of trichloroethylene or tetrachloroethylene, respectively. 

Chloroacetate esters are usually made by removing water from a mixture of chloroacetic acid and the corresponding alcohol. Reaction of alcohol with chloroacetyl chloride is an anhydrous process which Hberates HCl. Chloroacetic acid will react with olefins in the presence of a catalyst to yield chloroacetate esters. Dichloroacetic and trichloroacetic acid esters are also known. These esters are usehil in synthesis. They are more reactive than the parent acids. Ethyl chloroacetate can be converted to sodium fluoroacetate by reaction with potassium fluoride (see Fluorine compounds, organic). Both methyl and ethyl chloroacetate are used as agricultural and pharmaceutical intermediates, specialty solvents, flavors, and fragrances. Methyl chloroacetate and P ionone undergo a Dar2ens reaction to form an intermediate in the synthesis of Vitamin A. Reaction of methyl chloroacetate with ammonia produces chloroacetamide [79-07-2] C2H ClNO (53). 

The structure of ( )-169 is determined to have a ( )-3a,3a -bispyrrolo[2,3-(j] indole skeleton by carrying out X-ray single crystallographic analysis of its derivative 252 (99H1237). Compound 252 is obtained from ( )-169 by the following sequence of reactions (1) alkaline hydrolysis of ( )-169 to 249 (88%), (2) conversion of 249 to 251 (71%) by treatment with NaH and chloroacetyl chloride, (3) substitution of chlorine on the chloroacetyl group for acetate 252 (93%) by the reaction with NaOAc. 

In a similar vein, acylation of ami noketone 67 with chloroacetyl chloride affords the corresponding chloroamide 68. Reaction of that intermediate with ammonia serves to form the diazepine ring, possibly via the glycinamide. The product bentazepam (69) is described as a tranquilizer. ... 

Alkylation of piperazine with the amide formed by reaction of chloroacetyl chloride with pyrrolidine gives amide 133. Acylation with 3,4,5-trimethoxy-... 

Commercial phenacyl chloride may be used if unavailable the chloride may be prepared in 85-88% yield by a Friedel-Crafts reaction, using 234 g. (265 ml., 3 moles) of dry benzene and 79.5 g. (53 ml., 0.70 mole) of chloroacetyl chloride, in the presence of 103 g. (0.77 mole) of powdered anhydrous aluminum chloride the product distils at 120-125°/4 mm. and melts at 56-57°. Phenacyl chloride is a strong lachrymator and vesicant it should he handled with care. 

In an analogous reaction, 1,2-diaminopyridines 133 were transformed to 2,3,6-trioxopyridotriazines 134 by treatment with oxalyl chloride in the presence of triethylamine. 2,6-Dioxo analogs of 134 were also prepared by the reaction of 133 with chloroacetyl chloride (Equation 17) <1998SC3331>. 

Another methodology for the construction of the terminal ring is given in Scheme 13. Thus, the reaction of 115 with chloroacetyl chloride in boiling toluene under basic conditions provided the diketone 116, the subsequent cyclocondensation of 116 with benzylamine furnished the cyclic trione 117 <1996JHC1737>. 

A useful and simple preparation of the thiazolo[3,2-tf]benzoimidazol-3(2//)-one 391 is the reaction of 2-mercapto-benzimidazole 390 with chloroacetyl chloride (Equation 177) <1996MI442>. 

Chlorine, positive , iodometric determination of, 48, 5 reaction with 2-butyne, 46, 34 a-Chloroacetamide, reaction with oxalyl chloride to give a-chloroacetyl isocyanate, 46, 16... 

Chemical/Physical. Anticipated products from the reaction of 1,2-dichloroethane with ozone or OH radicals in the atmosphere are chloroacetaldehyde, chloroacetyl chloride, formaldehyde, and CIHCHO (Cupitt, 1980). 

Alkylation of pyrrolo-benzodiazepine dione 244 with methyl iodide occurs on both positions N9 and ClOa, while reaction with 2-bromo diethylaminoethane leads to the low yield of the 4-substituted 248. Acylations with benzoyl and 2-chloroacetyl chlorides are directed exclusively to position 4 to afford 247 (Scheme 52, Section 3.1.1.4 (1992CE649, 2005H2451)). Alkylation of 5H-benzo[/]-pyrrolo[l,2-d][l,4]diazepin-6(7H)-one with a substituted phenethyl bromide has been reported (Scheme 36, Section 3.1.1.1 (1992BMCL1639)). 

As outhned in Scheme 12.2, the process route to fluvastatin (1) commenced with Friedel-Crafts acylation of fluorobenzene (20) with chloroacetyl chloride (21) in the presence of AICI3 to prepare a-chloroketone 22 (Repic et al., 2001). Reaction of 22 with N-i-Pr aniline at elevated temperature generated tertiary amine 23, which was engaged... 

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