Thionyl chloride, reaction with

The dichlorides of aliphatic glycols are obtained by reaction with thionyl chloride in the presence of a small quantity of pyridine, for example ... 

Acyl chlorides are readily available They are prepared from carboxylic acids by reaction with thionyl chloride... 

Reaction with thionyl chloride (Sec tion 4 13) Thionyl chloride converts alcohols to alkyl chlorides... 

Sahcyhc acid can be converted to sahcyloyl chloride [1441 -87-8] hy reaction with thionyl chloride in boiling ben2ene. The formation of acyl haUde may also extend to reaction with the phenoHc hydroxyl. The reaction with phosphoms tri- and pentachlorides is not restricted to the formation of the acid chloride. Further interaction of the phosphoms haUde and the phenoHc hydroxyl results in the formation of the phosphoric or phosphorous esters. 

Sulfamoyl chloride [7778 2-9] forms from reaction with thionyl chloride (15,16) ... 

Acid Chloride Formation. Neopentanoic acid can be converted to neopentanoyl chloride [3282-30-2] by reaction with thionyl chloride (2), phosgene (3), phosphoms pentachloride, phosphoms trichloride, or by the reaction with henzotrichloride ia the presence of Eriedel-Crafts catalysts (4). A laboratory procedure usiag tetramethyl-a-halogenoenamines at room temperature has also been reported (5). 

Because tertiary alcohols are so readily converted to chlorides with hydrogen chloride, thionyl chloride is used mainly to prepare primary and secondary alkyl chlorides. Reactions with thionyl chloride are nonrrally carried out in the presence of potassium carbonate or the weak organic base pyridine. 

Isomeric 4,5-dihydro[4,5-/]derivative 76 has been prepared from 7,8-dihydro-5(6//)-quinolinone via a semicarbazone and its subsequent reaction with thionyl chloride (95JHC177). 

The a -halosulfone, required for the Ramberg-Backlund reaction, can for example be prepared from a sulfide by reaction with thionyl chloride (or with N-chlorosuccinimide) to give an a-chlorosulfide, followed by oxidation to the sulfone—e.g. using m-chloroperbenzoic acid. As base for the Ramberg-Backlund reaction have been used alkoxides—e.g. potassium t-butoxide in an etheral solvent, as well as aqueous alkali hydroxide. In the latter case the use of a phase-transfer catalyst may be of advantage. ... 

Reaction of dibenzylamine with ethylene oxide affords the amino alcohol, 82. Treatment of that product with thionyl chloride gives the a-sympathetic blocking agent, dibenamine (83). (Condensation of phenol with propylene chlorohydrin (84) gives the alcohol, 85. Reaction with thionyl chloride affords the chloride (86). Use of the halide to alkylate ethanolamine affords the secondary amine (87). Alkylation of this last with benzyl chloride... 

The 3-o-ch orophenvl-5-methvlisoxa2ole4-carboxylic acid, from which the acid chloride was prepared, was obtained by hydrolysis of the ester product of the reaction between o-chloro-benzohydroxamic chlorideand ethyl acetoacetate in methanolic sodium methoxide. Reaction with thionyl chloride gave the starting material. 

Acid chlorides are prepared from carboxylic acids by reaction with thionyl chloride (SOCl2), as we saw in the previous section. Similar reaction of a carboxylic acid with phosphorus tribromide (PB ) yields the acid bromide. 

Direct bromination of phenoxazine (103 X = O) gave rise to a mixture of 3-bromo- and 3,7-dibromo-phenoxazine. Reaction with thionyl chloride gave the 1,3,7,9-tetrachloro derivative (60JGU1872). 

Most substitutions have lower atom economies than this and produce more hazardous and a greater variety of by-products. Hexanol is much less reactive than 2-methylpropan-2-ol in substitution reactions one way of converting this to the chloride involves reaction with thionyl chloride (Scheme 1.11) here the unwanted by-products are HCl and SO2 reducing the overall atom economy to 55%. This readily illustrates how, even in... 

PLLA-fr-PCL) multiblock copolymers were prepared from the coupling reaction between the bischloroformates of carboxylated PLLA with diol-terminated PCL in the presence of pyridine [140]. LLA was polymerized with SnOCt2 and 1,6-hexanediol followed by the reaction with succinic anhydride to provide the dicarboxylated PLLA. The carboxyl end groups were subsequently transformed to acid chloride groups by the reaction with thionyl chloride (Scheme 65). As expected, the molecular weight distributions were broad for all samples (1.84 < Mw/Mn < 3.17). 

Ester 324 is hydrolyzed to acid 325 by refluxing in 10% NaOH. In a reaction with thionyl chloride, acid 325 is converted to acid chloride 326, which is isolated as a solid in 96% yield and consecutively converted into amide 327 in 85% yield. Treatment of amide 327 with LDA extracts a proton from the methyl group. The generated anion is trapped by added benzonitrile. Subsequent cyclocondensation of the obtained imine anion with the amide group provides derivative 328 in 62% isolated yield (Scheme 50) <2003EJM983>. 

Chloromethyl-l,2,4-triazoles can be valuable intermediates in the synthesis of more complex compounds containing a 1,2,4-triazole moiety, and they can be accessed using a number of established methods for the synthesis of the triazole ring system. However, these processes often give variable yields and require much work to construct the starting material. A more convenient procedure has been developed, by which a hydroxymethyl-1,2,4-triazole is converted to the chloromethyl derivative by reaction with thionyl chloride (Equation 20 and Table 6) <2006S156>. 

Bakulev et al. reported the synthesis of 5//-[l,2,3]triazolo[5,l-i>] [l,3,4]thiadiazines starting from 5-N-nitrosylamino-l,2,3-thiadiazole 68. Reduction of 68 with SnCh and 1A/HC1 and then subsequent reaction with a ketone gave the imine 69. Treatment of 69 with thionyl chloride at -80 °C led to the formation of the isolable triazolothiazine 70 which on further reaction with thionyl chloride at room temperature gave the corresponding chloro derivative 71 <00MC19>. 

The synthesis of the corresponding naphthyridone scaffold was carried out according to the methods reported by Chu et al. [12] and Sanchez et al. [13]. Namely, the hydrolysis of ethyl 2,6-dichloro-5-fluoronicotinate (3) [14] followed by reaction with thionyl chloride results in the formation of 2,6-dichloro-5-fluoronicotinyl chloride (4). Treatment of this compound with monoethyl malonate in THF under n-butyllithium followed by acidification and decarboxylation gives rise to ethyl 2,6-dichloro-5-fluoronicotinylacetate (5). Reaction of compound 5 with ethyl orthoformate in acetic acid followed by cyclopropylamine results in the formation of 3-cyclopropylamino-2-(2,6-dichloro-5-fluoronicotinyl)acrylate (6), the cyclization reaction of which under NaH/THF gives rise to the required ethyl l-cyclopropyl-6-fluoro-7-chloro-l,4-dihydro-4-oxo-l,8-naphthyridine-3-carboxylate (7), as shown in Scheme 3. 

The natural antipode of corynantheine (35, 155, 20/ ) has elegantly been prepared by Autrey and Scullard (168), starting from yohimbone (305), synthesized and resolved previously by Swan (169). Yohimbone (305) was converted to 18-formylyohimbone (306) and then through 307 to oxime 308. On reaction with thionyl chloride, 308 underwent a Beckmann fragmentation to the trans-substituted indolo[2,3-a]quinolizine 310, which after desulfurization and esterification resulted in the levorotatory methyl corynantheate (304). This product... 

Acyl chlorides of the stronger acidic groups are formed by the reaction with thionyl chloride 35, 45). The amount of easily hydrolyzed chloride was equivalent to the NaHCOj neutralization or to the difference between NajCOj and NaHCOa neutralization. Both values were equal in most examples. About twice this amount of chlorine was bound at the same time in a form that was resistant to hydrolysis. The nature of the chlorine bonding is not yet known there was no sulfur in the samples. 

Information concerning the position of the carboxyl groups relative to each other was obtained from the neutralization behavior after reaction with thionyl chloride 35, 47). More base ought to be consumed by such products because additional alkali is used for the neutralization of the hydrochloric acid liberated on hydrolysis. As is shown in Table VII, the additional alkali consumption was equivalent to the quantity of chloride ions found in the solution. However with all the samples which had been activated with carbon dioxide, less sodium ethoxide was consumed than had been expected. The deficit was equivalent to half the NaHCOj neutralization value. This strange behavior can be explained only by... 

Analysis of the reaction products showed that the boron content was nearly equimolar to the chloride content after reaction with thionyl chloride. About twice this amount of aluminum was retained by the samples, however. Since the presence of unchanged aluminum chloride could not entirely be ruled out, the balance of aluminum versus chloride was established. From the chloride deficit was substracted the number of silanol groups as determined by the thionyl chloride reaction. This difference was ascribed to molecular water. About one molecule of free water was found for each two silanol groups in the temperature range of 100 to 350°. The sample treated with BCI3 contained considerably less... 

Fig. 3. Content of ailanol groups in Aerosil as determined by reaction with thionyl chloride [after Gdk9ek (231)1.

Esterification of Aerosil with Methanol Vapor at ca. 0.1 mm Hg and Subsequent Reaction with Thionyl Chloride [after Qokfek (231)]... 

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