Action Of Thionyl Chloride Research Articles

Reaction of Bacterial Poly-3-Hydroxybutyrate with Thionyl Chloride in the Presence of Zinc Chloride, and the Preparation of Chlorine-Containing Oligomers

The degradation patterns of bacterial poly-3-hydroxybutyrate (PHB) in chloroform solution under the action of thionyl chloride in the presence of zinc chloride were studied. When 2.5.mol of zinc chloride and 100 mmol of thionyl chloride were introduced into the solution of 25 mmol PHB, a decrease in the molecular weight of the polymer was observed. During the reaction, a relatively rapid decrease in the molecular weight of the polymer was noted in the first hour of the experiment; thus, the values of the weight-average molecular weight decreased from 840 kDa to 483, 167, 58.6, and 16.7 kDa after 1, 5, 24, and 96 h of the experiment, respectively. The polydispersity also gradually decreased from 2.69 at the beginning to 1.92 at the end of the experiment. Oligomers of PHB containing 3-chlorobutyric acid and 3-hydroxybutyryl chloride residues at the O and C ends of the polymer chain, respectively, were obtained. The results confirm the ability of thionyl chloride to interact with aliphatic esters in the presence of zinc compounds, and demonstrate the possibility of using this reaction to produce oligomeric derivatives of polyesters bearing chloralkyl and acid chloride functional groups.

Synthesis of 2- and 3-acetylfuran carbethoxyhydrazones and investigation of their reaction with thionyl chloride

By the reaction of 2- and 3-acetylfurans with ethoxycarbonyl hydrazine in presence of acetic acid a series of carboethoxyhydrazones was synthesized. On the basis of the 1H NMR spectra it was shown that in the compounds obtained furyl substituent and ethoxycarbonyl group might be located both in Z- and in E-position with respect to the C=N bond. The isomer ratio for various types of substitution in the furan ring was established. It was shown that the introduction of two methyl groups in the positions adjacent to the hydrazone group leads to thermal lability of the corresponding hydrazone. 2-Acetyl-, 5-methyl-2-acetyl-, and 3-acetylfuran carbethoxyhydrazones under the action of thionyl chloride undergo cyclization to 4-furyl-1,2,3-thiadiazoles. In the case of 3-methyl-5-acetyl- and 2-methyl-3-acetylfuran a mixture of corresponding thiadiazoles and the products of chlorination of carbethoxyhyrazone fragment was formed. It was shown that the introduction of methyl group in the furan ring leads to thermal lability of furylthiadiazoles.

Intramolecular cyclization of dialkyl[2-(5-chloro-2-hydroxyphenyl)-2-phenylethenyl]phosphine oxides by the action of thionyl chloride

An efficient procedure has been proposed for the synthesis of quasiphosphonium salts, 2,2-dialkyl-6-chloro-4-phenyl-2H-1,2-benzoxaphosphinin-2-onium chlorides, via cyclization of dialkyl[2-(5-chloro-2-hydroxyphenyl)-2-phenylethenyl]phosphine oxides under the action of thionyl chloride.

Formation pathway of bis-(1,3,5-trimethylpyrazol-4-yl)methane at chlorination of 4-hydroxymethyl-1,3,5-trimethylpyrazole

Synthesis of 4-chloromethylpyrazoles by 4-hydroxymethylpyrazoles chlorination was reported earlier [1]. Gandberg et al. failed to obtain 4-chloromethyl derivatives at the action of thionyl chloride on hydroxymethyl derivatives of 1-alkylpyrazoles. Compound II was found to be the reaction product. They believed that in 1-alkylpyrazoles series hydroxymethyl moiety in the position 4 is extremely labile and behaves as 1-oxymethyl group, which readily departed at the action of acidic agents [2]. Due to this compound I transforms smoothly into bis(1,3,5trimethylpyrazol-4-yl)methane II. DOI: 10.1134/S1070363210060289

Synthesis of methylidene phthalide, its polymerization, and properties of poly(methylidene phthalide)

Different approaches to the synthesis of methylidene phthalide, which shows promise as a monomer for the obtainment of polymerization heat-resistant (co)polymers, are considered. Regularities are established for the best variant of methylidene phthalide synthesis through the action of thionyl chloride on o-acetylbenzoic acid in DMF. Optimum conditions are found for the synthesis of methylidene phthalide with a high yield and purity. Polymerization of high-purity methylidene phthalide yields (co)polymers in the form of absolutely colorless optically transparent heat-resistant glasses. Methylidene phthalide copolymers with styrene, methyl methacrylate, acrylonitrile, and methyl acrylate containing ≥40 mol % methylidene phthalide units have glass-transition temperatures as high as 220–260°C. In addition, methylidene phthalide (co)polymers are promising as smart polymers.

Synthesis of substituted 1,3,4-oxadiazole derivatives

Monosubstituted oxadiazoles were synthesized by the reaction of hydrazides with triethyl orthoformate. Their reactions with benzoyl chloride gave benzoylcarbohydrazides, which under the action of thionyl chloride were cyclized to the respective 2,5-disubstituted oxadiazoles. 1-Aryl-4-(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)-pyrrolidin-2-ones were synthesized from acid hydrazides using carbon disulfide under basic conditions.

Reactions of Furoxandicarbaldehyde Dioxime with Dehydrating Agents

Dehydration of furoxan-3,4-dicarbaldehyde dioxime by the action of thionyl chloride or trifluoroacetic anhydride in the presence of a base under certain conditions can be stopped at the stage of formation of 4(3)-hydroxyiminomethylfuroxan-3(4)-carbonitrile.

Synthesis and Estrogenic Activity Screening of Some 6,9-Disubstituted Estradiol Derivatives

Oxidation of estradiol dipropionate (1) with chromium(VI) oxide-3,5-dimethylpyrazole complex yielded 9α-hydroxy-6-oxoestra-1,3,5(10)-triene-3,17β-diyl dipropionate (2) and 6-oxoestra-1,3,5(10)-triene-3,17β-diyl dipropionate (3). Dehydration of compound 2 with phosphorus(V) oxide or acetic anhydride gave 6-oxoestra-1,3,5(10),9(11)-tetraene-3,17β-diyl dipropionate (5). Reduction of compounds 2 and 5 with sodium borohydride afforded 3,6β,9α-trihydroxyestra-1,3,5(10)-triene-17β-yl propionate (4) and 3,6β-dihydroxyestra-1,3,5(10),9(11)-tetraene-17β-yl propionate (6), respectively. The action of thionyl chloride on compound 2 yielded 6-hydroxyestra-1,3,5(10),6,8-pentaene-3,17β-diyl dipropionate (7). Biological tests in vivo of these compounds showed a moderate antiestrogenic activity of compound 4.

One Step Synthesis of γ-Chlorobutyrolactones via Thionyl Chloride Re-Investigated Action on γ-Ketoacids

The action of thionyl chloride on γ -ketoacids was revisited. The reaction does not yield the corresponding γ-ketoacyl chlorides as reported earlier, but instead efficiently produces γ -chlorobutyrolactones. The chemical properties of this function are summarily explored, along with some characteristic spectroscopic data.

Stereospecific substitution of a hydroxy group by a chlorine atom in isomeric 2,3-disubstituted 3-hydroxytetrahydrothiophenes

The stereospecific synthesis of the three possible isomers of 4-amino-3-chloro-2-(4-methoxycarbonylbutyl)tetrahydrothiophene hydrohalides from the corresponding isomers of 4-amino-3-hydroxytetrahydrothiophene by the action of thionyl chloride was realized. Three isomers of 4-ureido-3-chloro-2-(4-methoxycarbonylbutyl)tetrahydrothiophene were obtained from the 3-chlorotetrahydrothiophene derivatives. The configurations of the isomeric compounds obtained were proved by 1H and 13C NMR spectroscopy.

Synthesis of monodispers macromolecular diisocyanate

The synthesis of a monodisperse macromolecular ( $$\overline {Mn} $$ =850) diisocyanate was done in three steps with an averall yield of 80%. The first one consist of the addition of the dithiol HS-(CH2)2O(CH2)2SH to undecylenic acid, the diacid obtained[(HO-CO-(CH2)10-S-(CH2)2]-O is then transformed to the acid dichloride by the action of thionyl chloride (SOCl2), finally the acid dichloride is transformed to diisocyanate[OCN-(CH2)12-S-(CH2)2]2-O by CURTIUS reaction. We not that the product is cristalline and its purity and that of the intermediates were determined by 1H NMR.

Polymers containing metal chelate units III. Binuclear copper(II) complex with salicyloylacrylamide immobilised on polytetrafluoroethylene and its use as a polymeric antifriction coating

A method of functionalization of a polytetrafluoroethylene (PTFE) surface by the gas phase graft (-g-) polymerization of acrylic acid (AA) with PTFE has been developed. A new macromolecular ligand PTFE-g-poly(salicyloylacrylamide) has been synthesized by the interaction of salicylamide with PTFE-g-PAA under the action of thionyl chloride. The macromolecular metal complex has been prepared by mixing a suspension of polymeric ligand with copper(II) acetate in alcohol. Its composition, IR spectrum and magnetic properties in the temperature range 80–300 K have been investigated. The immobilised binuclear complex was used in the production of antifriction self-lubricated coatings.

Condensed imidazo-1,2,4-azines. 14. Synthesis and reactivity of 3-chlorine-substituted imidazo[1,2-b]-1,2,4-triazines

When boiled with phosphorus pentachloride in phosphorus oxychloride, 2-methyl-6-phenyl-imidazo[1,2-b]1,2,4-triazin-4H-3-one gives a mixture of mono- and dichloro derivatives, whereas the action of thionyl chloride in chloroform with a catalytic amount of DMFA gives only the monosubstituted product 2-methyl-3-chloro-6-phenylimidazo[1,2-b]-1,2,4-triazine. The reactivity of the 3-chloro derivatives of imidazo[1,2-b]-1,2,4-triazine in reactions with diethylamine, piperidine, morpholine, aniline, hydrazine hydrate and thiourea was investigated.

Photoinduced rearrangement of hydroxymethylisoxazolines, a route to enaminoaldehydes

3-Aryl-4-R-carbamoyl-5-hydroxymethylisoxazolines (IV) were synthesized by allowing R-NH2 amines with R = H, CH3, C3H7, C6H5C2H5, and NH2 to act on 3-(X-phenyl)-4-oxo-3a,4,6,6a-tetrahydrofuro[3,4-d]isoxazoles (III) with X = H, 4-CH3, 4-OCH3, 2-OCH3, 4-Cl, 2-Cl, 4-F, 2-F, 4-Br, 4-NO2, and 3-NO2. Exposed to radiation, the substances IV give Z-2-hydroxymethylamino-2-aryl-1-formylacrylamides (V) in good yields. The 4-Cl and 4-F substituted Z-derivatives V isomerize irreversibly to the E-derivatives VI if allowed to stand in solvent; the remaining derivatives V are stable. The quantum yields of the photoreaction are from 0.012 to 0.106 in dependence on the substituent X. In all cases where the compounds IV were used for the preparation of condensed heterocycles in conditions of acid-catalyzed reactions, lactones III were preferentially formed; the action of thionyl chloride on IV results in the formation of chloromethyl derivatives VIII, which do not undergo further cyclization.

Reaction of 2-thiobenzazoles with thionyl chloride

A new reaction in the benzimidazole series, viz., replacement of the mercapto group by chlorine by the action of thionyl chloride on 2-thiobenzimidazoles, was discovered. Benzoxazolone is formed by treatment of 2-thiobenzoxazole with thionyl chloride, and 2,2′-dithiobis(2-benzothiazole) is formed from 2-thiobenzothiazole.

ChemInform Abstract: SYNTHESIS OF SOME TRIAZOLE, TETRAZOLE, AND TETRAZINE DERIVATIVES FROM N‐β‐NAPHTHALENESULFONYLBENZOHYDRAZIDOYL CHLORIDES

AbstractDie Benzoylhydrazide (I) kondensieren mit 2Naphthylsulfonsäurechlorid (II) z′u den Sulfonylhydraziden (III), aus denen mit Thionylchlorid die lmidoylhydrazide (IV) erhalten werden.

Synthesis of some triazole, tetrazole, and tetrazine derivatives from N‐β‐naphthalenesulfonylbenzohydrazidoyl chlorides

AbstractA series of N‐β‐naphthalenesulfonylbenzohydrazidoyl chlorides 8a‐d has been prepared by the action of thionyl chloride on the corresponding hydrazides 7a‐d. Treatment of 8 with triethylamine and morpholine afforded the tetrazines 10 and the amidrazones 11 respectively. Acid hydrolysis of 11 yielded the hydrazides 7. Reaction of 8 with phenylhydrazine gave 3,5‐diaryltetrazoles 14. However, reaction of 8 with aroylhyrazines yielded 3,5‐diaryl‐4‐β‐naphthalenesulfonylamino‐4H‐1,2,4‐triazoles 15. The structures of the products were assigned upon the basis of their spectra, elemental analyses and alternate synthesis whereever possible.

1H- and 2H-indazoles by thermal and photolytic decomposition of o-azidobenzoic acid and o-azidobenzaldehyde derivatives

Ethyl o-azidobenzimidate (6) and o-azidobenzamidine (7) on thermolysis yield 3-ethoxy-(9; X = OEt) and 3-amino-1H-indazole (9; X = NH2), respectively. The former product is also obtained on irradiation of the imidate in methanol–tetrahydrofuran solution.2-Aryl- and 2-heteroaryl-3-chloro-2H-indazoles have been prepared by the action of hot thionyl chloride on o-azidoanilides. The trichloro-2H-indazoles obtained by the action of phosphorus pentachloride on o-azidobenzanilide (12) and by the action of thionyl chloride on N-(o-azidobenzoyl)-2-aminopyridine have been identified as the 3,5,7-trichloro derivatives. The reductive dehalogenation, nitration, and reactivity of the halogen towards nucleophiles, of 3-chloro-2-phenyl-2H-indazole (19) are reported.A new practicable synthesis of o-azidobenzaldehyde (31; X = O) is described. Thermolysis of its phenylhydrazone and semicarbazone derivatives yields 2H-indazoles.

Synthesis of pyrano[3,4‐c]pyrazole and pyrazolo[3,4‐d][1,2]diazepine derivatives

AbstractBy the action of thionyl chloride on 3(5)‐R‐4‐phenacylpyrazole‐5(3)‐carboxylic acid (3c,d), 3‐R‐5‐phenylpyrano[3,4‐c]pyrazole‐7‐(1H)ones (4c,d) were obtained. When 4c,d were treated with hydrazine hydrate followed by refluxing in ethanol containing acetic acid, 4,7‐dihydro‐3‐R‐5‐phenylpyrazolo[3,4‐d][1,2]‐diazepin‐8‐(1H)ones (6c,d) were formed. Compounds 6c,d, in turn, were refluxed in ethanol saturated with hydrochloric acid to yield 6‐amino‐1,6‐dihydro‐3‐R‐5‐phenyl‐7H‐pyrazolo[3,4‐c]pyridin‐7‐ones (7c,d). Compounds 7c,d could be obtained directly from 5c,d. The starting materials 3c,d were prepared by hydrolysis of the oxime of 3(5)‐R‐4‐phenacyl‐5(3)carboalcoxypyrazoles (1a,b). Structural assignments rested on correct elemental analysis, molecular weights determined by mass spectrometry, and spectroscopic evidence.

Functional derivatives of thiophene

We have found that 4-oxothieno[2,3-d]oxazines (lla-h) can be obtained by the action of thionyl chloride on 2-aroylaminothiophene-3-carboxylic acids (la-h) in the presence of dimethylformamide (DMF), i.e., under the conditions of the synthesis of arenecarboxylic acid chlorides. The reaction evidently proceeds through a step involving the formation of thiophenecarboxylic acid chlorides. We obtained thiophenecarboxylic acids la, c, h for the first time by the method described in [2].