Oxalyl chloride reaction

Oxalyl chloride, reaction with a chloro-acetamide, 46,16... 

Alkyl oxalyl chlorides, reactions, 228 Aryl nickel halides, formation, 227 3-Arylpropanenitriles, preparation, 229... 

In his synthesis of the [4.4.4] propellane 19, Paquette made the diester 16 easily but wanted the mono methyl ketone 18. Rather than add MeLi directly, he first hydrolysed one ester to the free acid 17 and then made the acid chloride with oxalyl chloride. Reaction with Me2CuLi gave the ketone in excellent yield.5... 

Oxalyl chloride (reaction c) is more reactive than phthaloyl chloride and its use enables the chlorides to be obtained from sensitive carboxylic acids1116 or their Na salts in benzene1117 at ambient temperature or below. Some of the nitro derivatives of benzoic acid afford only the mixed anhydrides when 2 moles of the acid are heated with 1 mole of oxalyl chloride.1118 To obtain the free acid chloride, and not its hydrochloride, from basic carboxylic acids an alkali salt of this acid may be treated with oxalyl chloride. 

Mancuso, A. J. Swern, D. Activated Dimethyl Sulfoxide Useful Reagents for Synthesis Synthesis 1981,165-185. Mancuso, A. J. Brownfain, D. S. Swern, D. Structure of the Dimethyl Sulfoxide-Oxalyl Chloride Reaction Product. Oxidation of Heteroaromatic and Diverse Alcohols to Carbonyl Compounds /. Org. Chem. 1979, 44, 4148-4150. Mancuso, A. J. Huang, S-L. Swern, E. Oxidation of Long-Chain and Related Alcohols to Carbonyls by Dimethyl Sulfoxide Activated by Oxalyl Chloride J. Org. Chem. 1978, 45, 2480-2482. Omura, K. Swern, D. Oxidation of Alcohols by Activated Dimethyl Sulfoxide. A Preparative Steric and Mechanistic Study Tetrahedron 1978, 54, 1651-1660. 

Oxalic ester synthesis 16, 812 Oxalyl chloride, reaction with amines 16, 502 Oxamic acid derivatives... 

The reaction giving A is chloromethylation, a reliable metliod of adding a CH2OH equivalent to an aromatic ring. You may have been surprised at the use of reagent B to make an acid chloride. B is oxalyl chloride and is often used when pure acid chlorides are wanted - the other products are gases (which ). 

Specialty Isocyanates. Acyl isocyanates, extensively used in synthetic appHcations, caimot be direcdy synthesized from amides and phosgene. Reactions of acid haUdes with cyanates have been suggested. However, the dominant commercial process utilizes the reaction of carboxamides with oxalyl chloride [79-37-8]. CycHc intermediates have been observed in these reactions which generally give a high yield of the desired products (86). 

Commercially important arenesulfonyl isocyanates are not directly accessible from the corresponding sulfonamides via phosgenation due to lack of reactivity or by-product formation at elevated temperatures. A convenient method for their preparation consists of the reaction of alkyl isocyanates with sulfonamides to produce mixed ureas which, upon phosgenation, yield a mixture of alkyl and arenesulfonyl isocyanates. The desired product can be obtained by simple distillation (16). Optionally, the oxalyl chloride route has been employed for the synthesis of arenesulfonyl isocyanate (87). 

Oxahc acid reacts with various metals to form metal salts, which are quite important as the derivatives of oxahc acid. It also reacts easily with alcohols to give esters. Crystalline dimethyl oxalate is, for example, produced by the reaction of oxahc acid dihydrate and methanol under reflux for a few hours. When oxahc acid is treated with phosphoms pentachloride, oxalyl chloride, ClCOCOCl, is formed (6). 

Oxalyl Chloride. This diacid chloride [79-37-8], ClCOCOCl, mol wt 126.9, is produced by the reaction of anhydrous oxaUc acid and phosphoms pentachloride. The compound vigorously reacts with water, alcohols, and amines, and is employed for the synthesis of agrochemicals, pharmaceuticals, and fine chemicals. 

Sorbic acid anhydride [13390-06-2] can be prepared by heating the polyester of 3-hydroxy-4-hexenoic acid with sorboyl chloride [2614-88-2] or by reaction of sorbic acid with oxalyl chloride (15,16). Preparation of the esters of sorbic acid must be controlled to prevent oxidation and polymerization. The lower sorbic acid esters have a pleasant odor. 

Because of the structural requirements of the bielectrophile, fully aromatized heterocycles are usually not readily available by this procedure. The dithiocarbamate (159) reacted with oxalyl chloride to give the substituted thiazolidine-4,5-dione (160) (see Chapter 4.19), and the same reagent reacted with iV-alkylbenzamidine (161) at 100-140 °C to give the 1 -alkyl-2-phenylimidazole-4,5-dione (162) (see Chapter 4.08). Iminochlorides of oxalic acid also react with iV,iV-disubstituted thioureas in this case the 2-dialkylaminothiazolidine-2,4-dione bis-imides are obtained. Thiobenzamide generally forms linear adducts, but 2-thiazolines will form under suitable conditions (70TL3781). Phenyliminooxalic acid dichloride, prepared from oxalic acid, phosphorus pentachloride and aniline in benzene, likewise yielded thiazolidine derivatives on reaction with thioureas (71KGS471). 

Of particular interest is the reaction of 5,5-disubstituted sulfur diimides (188) with oxalyl chloride in dilute solution in the presence of triethylamine. The l,2,5-thiadiazole-3,5-dione (189) was formed in almost quantitative yield (72LA(759)107). 

A more practical solution to this problem was reported by Larson, in which the amide substrate 20 was treated with oxalyl chloride to afford a 2-chlorooxazolidine-4,5-dione 23. Reaction of this substrate with FeCL affords a reactive A-acyl iminium ion intermediate 24, which undergoes an intramolecular electrophilic aromatic substitution reaction to provide 25. Deprotection of 25 with acidic methanol affords the desired dihydroisoquinoline products 22. This strategy avoids the problematic nitrilium ion intermediate, and provides generally good yields of 3-aryl dihydroisoquinolines. 

The early literature on the reactions of the indole Grignard reagents with the simple diacid chlorides, in particular with carbonyl chloride and oxalyl chloride (see Section III,C,4,b), is both conflicting and confusing and much of the work reported warrants repetition since the evidence presented in support of many of the structural assignments made is not entirel3 convincing. 

The ready access to compound 204 also provided efficient routes to additional monosubstituted indolo[3,2-()]carba2oles, as reaction with ethyl oxalyl chloride... 

Reaction of 4-hydroxyquinoline-2-one 598 with oxalyl chloride gave oxazoloquinoline 599 (970PP211). The oxazoloquinoline 600 was obtained as a byproduct during the synthesis of pyranoquinoline alkaloids 601 by reaction of 598 with 2-methyl-2-chlorobutyne under phase transfer catalysis (87JHC869) (Scheme 101). 

The ionic species 5, as well as 6, represent the so-called activated dimethyl sulfoxide. Variants using reagents other than oxalyl chloride for the activation of DMSO are known. In the reaction with an alcohol 1, species 5, as well as 6, leads to the formation of a sulfonium salt 7 ... 

To a stirred suspension of p-(p-methoxvbenzyloxy)-phenylmalonic acid (125 mg) in methylene chloride (3 ml) are added triethylamine (55 All) and oxalyl chloride (26 AH) at -15°C, and the suspension is stirred for 40 minutes at 0°C. The mixture Is added to a solution of diphenylmethyl 7 -amino-7a-methoxy-3-(1 -methyltetrazol-5-yl)thiomethyl-1 -oxadethia-3-cephem-4methylene chloride (3 ml) and pyridine (63 AH), and the mixture is stirred for 30 minutes at 0°C. The reaction mixture is diluted with ethyl acetate, washed with aqueous 2 N-hydrochloric acid and water, dried over sodium sulfate, and concentrated to give crude product (212 mg), which Is chromatographed on silica gel (20 g) and... 

The present method is that described by Rinderknecht and Ma.3 4 It is equally applicable to a variety of other heterocyclic, aromatic, and aliphatic anhydrides.4,6 Nicotinic anhydride was first prepared by reaction of nicotinoyl chloride with sodium nicotinate,6,7 and more recently by reaction of potassium nico-tinate with oxalyl chloride in anhydrous benzene.2... 

Reaction of the biphenyl-2,2 -diamine 1 with oxalyl chloride leads to the dibenzo[< ,g][l,4]di-azocine system 2.19... 

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