Sodium carboxylic acid chloride

Nickel tetranitrophthalocyanine can be reduced to nickel tetraaminophthalocyanine with tin(II) chloride342 or sodium sulfide.319 343 To achieve better solubility, long alkanoyl side chains can be attached by the reaction of the amino groups with carboxylic acid chlorides.342 Copper(ll) tetranitrophthalocyanine 1 is reduced to the tetraamino compound 2 with sodium suinae." "... 

Curtius rearrangement of the heteroaroyl azides, obtained from the reaction of the carboxylic acid chlorides with sodium azide, provides a route to the amino-pyrroles and -indoles (e.g. B-70MI30504, B-77MI30506, 78CPB1054), which, because of the ease of synthesis of the carboxylic acids, is frequently preferable to reduction of the nitro compounds. 

Furthermore unsaturated aldehydes can be obtained by the reaction of 12 with e. g. cyclohexane carboxylic acid chloride, subsequent alkaline cleavage of the remaining silyl grouping and reduction with sodium borohydride give 3-hydroxy-3-cyclohexyl-1,1-dimethoxypropane (54) which yields 3-cyclohexyl-acrolein (JJ)51 via acid treatment under dehydratation. 

To a stirred solution of [4-(2-pyrimidinyl)piperazino]ethylamine (2.0 g, 0.01 mol) in 50 ml of methylene chloride, adamantane-l-carboxylic acid chloride (3.6 g, 0.018 mol) and triethylamine (2.9 g, 0.015 mol) were added. Stirring was continued at room temperature overnight. The methylene chloride solution was washed with water, dried over anhydrous sodium sulfate and evaporated under reduced pressure. The remaining residue was subjected to preparative HPLC. The residue was dissolved in ethyl acetate (10 ml) and subjected to flash chromatography using a 9 inch column of silica gel and ethyl acetate as the eluent. The N-[2-[4-(2-pyrimidinyl)-l-piperazinyl]ethyl]tricyclo[3.3.1.1(3,7)] decane-l-carboxamide was separated. 

To 1 gramm-equivalent (g-eq) of dimethylaminoethanethiol in 150 ml of ether, a suspension of g-eq of 50% sodium hydride in 50-ml of anhydrous ether was added. After boiling for 1 hour, the reaction mixture was cooled to 0°C, whereupon g-eq of 9,9-dimethylacridan-10-carboxylic acid chloride (prepared from 9,9-dimethylacridan and phosghene - cf. Swiss Specification No. 

A benzene solution of 2.2 parts of a-chloro-y-quinoline-carboxylic acid chloride is gradually mixed, while cooling, with 2.3 parts of unsymmetrical diethylethylenediamine. When the reaction is at an end the solution is washed with water and the new base extracted by means of hydrochloric acid. The base is precipitated by means of sodium carbonate and extracted with benzene. The solvent is distilled and the base recrystallized from petroleum ether. The a-chloro-y-quinoline-carboxylic acid diethyl-amino-ethylene amide forms colorless lamina crystals of melting point 74°C. With acids the base forms neutral salts soluble in water. 

The mixture was refluxed for 45 minutes, cooled under nitrogen, and 19.8 g (0.10 mol) of 1-amino-l-cyclohexane-carboxylic acid chloride HCI was added portionwise at -10°C over 20 minutes. The mixture was stirred for an additional hour while the temperature rose to 20°C. The reaction mixture was poured into 200 ml of cold water with stirring and the two-phase mixture clarified by filtration. Dilute sodium hydroxide solution was added to the filtrate at 5° to 10°C to pH 5.4. 

Aluminum chloride Thiophene-2-carboxylic acid chloride Sodium hydroxide... 

With very few exceptions ketenes cannot be isolated pure at room temperature (cf. Section 15.4). Consequently, they are prepared in situ and in the presence of the heteroatom nucleophile. The Wolff rearrangement of a-diazoketones is often used for this purpose (Section 14.3.2). a-Diazoketones can be obtained, for example, by the reaction between a carboxylic acid chloride and diazomethane (Figure 8.13 see also Figure 14.27) or hy treating the sodium enolate of a-formylketones with tosyl azide (Figure 14.29). 

A promising method for the synthesis of unsymmctrical diorgano tellurium compounds uses carboxylic acid derivatives and diaryl ditellurium as starting materials. The carboxylic acid chloride, prepared in quantitative yield from the acid and oxalyl chloride is added slowly to a mixture of a diary] ditellurium and the sodium salt of 2-mercaptopyridine N-oxide in toluene at 35°. Under normal laboratory light the aryl tellurium radicals... 

A large number of stable /e-organo tellurocarboxylates were prepared from tellurolates and aliphatic1,2 or aromatic2 carboxylic acid chlorides or aliphatic carboxylic acid anhydrides . The tellurolates were obtained by reduction of diorgano ditelluriums with sodium borohydride. 

Sodium tellurono(tellurolo)carboxylates were obtained as dark-red oils in almost quantitative yields from equimolar amounts of carboxylic acid chlorides and disodium telluride1. 

The second method is the reaction of a uracildiamine with a carboxylic acid chloride to give the amide, which is then cyclized with aqueous sodium hydroxide, e.g. formation of 11. ... 

Sodium 1-methylethanetellurolate and hexadecanetellurolate were obtained from sodium hydrogen telluride and the appropriate alkyl halide in THF or THF/ethanol. The sodium hydrogen telluride was prepared from tellurium and sodium borohydride in water. Equimolar amounts of disodium telluride combined with aliphatic carboxylic acid chlorides in tetrahydrofuran at — 30" and with aromatic carboxylic acid chlorides in tetrahydrofuran at 0° to give sodium tellurolates that have an acyl group bonded to the tellurium atom. These tellurolates, the sodium salts of tellurolocarboxylic acids, are dark-red substances that were obtained in almost quantitative yields. 

Te-Esters of tellurocarboxylic acids were prepared from tellurolates and carboxylic acid chlorides or anhydrides, and from sodium telluride and aroyl chlorides". The following types of 7e-organo tellurocarboxylates have thus far been synthesized ... 

The reaction of oxovinylidenetriphenylphosphorane or its dimer with aromatic carboxylic acid chlorides leads not to cyclobutanedione derivatives but to pyrone compounds, which can be converted to open chained bisphosphoranes with sodium methoxide (equation 104). If the acid chlorides carry an... 

Method A Disproportionation of the dithiocarbazates. B Dithiocarbazate and carboxylic acid chlorides. C Dithiocarbazate and ethyl formamidate. D Dithiocarbazate and sodium dithioformate. 

Sodium fluoride [1, 1073-1074, before reference]. Sodium fluoride suspended in nonaqueous tetramethylene sulfone, acetonitrile, or DMF has been found to exchange halogen readily with carboxylic acid chlorides, a-chloro ethers, trichloro-methanesulfenyl chloride, POCl3, etc.2 ZG. W. Tullock and D. D. Coffman, J. Org.. 25, 2016 (1960)... 

Carboxylic acid chlorides from carboxylic acids and 2,2,2-trichloro-l,3,2-benzodioxa-phosph(v)ole 1127 A mixture of the acid (0.02 mole) and the trichloride (0.02 mole) is heated and the acid chloride is then separated by distillation. Yields are acetyl chloride 67% (after 30 min at 100° b.p. 50-51°) benzoyl chloride 81 % (after 60 min at 100° b.p. 82-85°/ll mm) chloroacetyl chloride 77% (after 30 min at 150° b.p. 105-108°). In other cases the reaction mixture can be diluted with ether, poured on ice, and well shaken therewith the aqueous phase should be extracted again with ether, the organic phases then being washed with sodium hydrogen carbonate solution and with water and dried over Na2S04, the ether removed, and the residue distilled. 

The zwitterionic perhydropyrrolo[l,2-c]imidazole (122) has been obtained by reaction of 2-aminomethylpyrrolidine-5-carboxylic acid chloride with sodium hydroxide and cyanogen bromide (Scheme 23) <84MI 802-02>. 

Similarly, reaction of carboxylic acid halides with sodium azide led to the formation of the respective acyl azides, which are stable. " By contrast, reaction of carboxylic acid chlorides with sodium azide in toluene at 70-100 °C transpires via a Curtins rearrangement to generate isocyanates. The details of these transformations are outlined in eqs 41-43. 

The amide can be easily prepared in high yield and high purity by the reaction of 2,3-dichloro-4-hydroxy-aniline and 1-methylcyclohexane-carboxylic acid chloride, e.g., in toluene with sodium hydroxide as a base (Scheme 17.24). The starting aniline can be made by a Bamberger rearrangement of the intermediate hydroxyl-amine obtained by partial reduction of the corresponding nitro aromatic [109]. 

Another useful chain reaction involves the PTOC (pyridine-2-thione-N-oxycarbonyl) esters developed by Barton. Reaction of a carboxylic acid chloride (RCOCl) with the sodium salt on N-hydroxypyridine-2-thione produces an ester designated as R-PTOC. Addition of radical Y" (formed by an earUer initiation step) to the R-PTOC leads to the carboxy radical RCOj. The carboxy radical then decarboxylates to produce the radical R, which can continue the chain reaction or can undergo other reactions. 

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