Acetylenic acids. III. The synthesis of pyridylpropiolic acids and esters and their reaction with thionyl chloride

1978 ◽  
Vol 31 (3) ◽  
pp. 617 ◽  
Author(s):  
WN Lok ◽  
AD Ward
Keyword(s):  
Thionyl Chloride ◽  
Convenient Route ◽  
Synthetic Routes ◽  
Hydrolysis Of ◽  
Acetylenic Acids

A variety of synthetic routes to pyridinylpropiolic acids and esters have been investigated. The most convenient route to the esters involves the formation of the corresponding ethyl 3-oxo-3-pyridinyl-2-triphenylphosphoranediylpropanoates and their subsequent pyrolysis. The acids can be obtained by careful hydrolysis of the esters. The reaction of thionyl chloride with these compounds has been examined; in one case a low yield of a thieno[2,3-b]pyridine was obtained.

Synthesis of des-A-B-secocholestanes

1984 ◽  
Vol 62 (6) ◽  
pp. 1081-1084 ◽  
Author(s):  
Wojciech J. Szczepek ◽  
Jacek W. Morzycki ◽  
Zbigniew Bończa-Tomaszewski ◽  
Michał Chodyński ◽  
Władysław J. Rodewald
Keyword(s):  
Hydroxyl Group ◽  
Dioic Acid ◽  
Ruthenium Tetroxide ◽  
Enol Acetate ◽  
Synthetic Routes ◽  
Hydrolysis Of

Two independent synthetic routes to 10-oxo-5, 10-seco-des-A-cholestan-5-oic acid (5) are described. The route including the Baeyer–Villiger rearrangement of (10R)-des-A-cholestan-5-one (2a), followed by hydrolysis of the lactone 3a obtained and oxidation of the C-10 hydroxyl group, seems to be superior to ozonolysis of the 5(10)-enol acetate 6 of des-A-ketone which resulted in the formation of 5,10-seco-des-A-19-norcholestan-5,10-dioic acid (7), in addition to the compound 5. Product 7 and its 6-nor analog 12 have also been obtained by ruthenium tetroxide oxidation of the respective A-ring phenols 8, 9, and 11.

Enamines of 2,2-bis(ethylthio)ethanal: a convenient route to γ-keto crotonate derivatives

1983 ◽  
Vol 61 (11) ◽  
pp. 2466-2475 ◽  
Author(s):  
Gordon S. Bates ◽  
S. Ramaswamy
Keyword(s):  
Potassium Salt ◽  
Alkylating Agents ◽  
High Yield ◽  
Convenient Route ◽  
High Yields ◽  
Hydrolysis Of ◽  
Potential Precursor ◽  
Chiral Potential

A new α-oxoaldehyde reagent, 2,2-bis(ethylthio)ethanal 1, has been prepared in high yield from ethanedial. Alkylation of the potassium salt of the enamines of 1 with various alkylating agents followed by insitu hydrolysis of the intermediate imine afforded high yields of the alkylation products of 1. This new reagent was used in the synthesis of a chiral potential precursor of the macrocyclic fragment of cytochalasins A, B, and F, as well as in the syntheses of the physiologically active diolides pyrenophorin and norpyrenophorin.

Organophosphorus compounds. P-Arylated perhydro-1,2-azaphosphorines

1977 ◽  
Vol 30 (3) ◽  
pp. 579 ◽  
Author(s):  
DG Hewitt ◽  
GL Newland
Keyword(s):  
Thionyl Chloride ◽  
Good Yield ◽  
Aqueous Ammonia ◽  
Organophosphorus Compounds ◽  
Phosphinic Acid ◽  
Sodium Hydride ◽  
Hydrolysis Of ◽  
Phenylmagnesium Bromide

Treatment of ethyl 4-bromobutylphosphonochloridate with phenylmagnesium bromide, followed by acid-catalysed hydrolysis of the product, gave 4- bromobutyl(phenyl)phosphinic acid. This was converted into the corresponding phosphinamide by treatment with thionyl chloride and then with aqueous ammonia. Cyclodehydrobromination with sodium hydride in warm xylene then gave a good yield of 2-phenylperhydro-1,2- azaphosphorine 2-oxide. Some other routes to this compound were investigated.

Synthesis of 5-Phenylcytosine Nucleoside Derivatives

1996 ◽  
Vol 61 (4) ◽  
pp. 645-655 ◽  
Author(s):  
Marcela Krečmerová ◽  
Hubert Hřebabecký ◽  
Antonín Holý
Keyword(s):  
Acetic Anhydride ◽  
Thionyl Chloride ◽  
Alkaline Hydrolysis ◽  
Hydrogen Bromide ◽  
Analogous Reaction ◽  
Final Reaction Product ◽  
Cyclic Sulfite ◽  
Higher Temperature ◽  
Hydrolysis Of ◽  
Tin Tetrachloride

Reaction of silylated 5-phenylcytosine with 1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribose, catalyzed with tin tetrachloride, and subsequent methanolysis afforded 5-phenylcytidine (2). This compound reacted with thionyl chloride in acetonitrile to give cyclic sulfite 3 which on heating in dimethylformamide was converted into 2,2'-anhydro-1-(β-D-arabinofuranosyl)-5-phenylcytosine (4). Analogous reaction of compound 2 with thionyl chloride at reflux gave 5'-chloro-5'-deoxy-2',3'-cyclic sulfite 5. Its heating in dimethylformamide afforded 5'-chloro-2,2'-anhydro derivative 6, mild alkaline hydrolysis led to 5'-chloro-5'-deoxy-5-phenylcytidine (7). Alkaline hydrolysis of 5-phenyl-2,2'-anhydrocytidine (4) gave 5-phenylcytosine arabinoside 8, whereas the 2,2'-anhydro derivative 6 afforded 1-(5-chloro-5-deoxy-β-D-arabinofuranosyl)-5-phenylcytosine (11). At higher temperature, the final reaction product was 2,5'-anhydro-5-phenylcytidine (12). 5'-Chloro-5'-deoxynucleosides 7 and 11 reacted with tri-n-butyl- stannane to give 5'-deoxyribofuranosyl and 5'-deoxyarabinofuranosyl derivatives 15 and 16. 5-Phenylcytidine (2) was converted into the N4-acetate 17 with acetic anhydride. Further reaction with acetic anhydride and hydrogen bromide in acetic acid afforded a mixture of peracetylated 2'-bromo and 3'-bromo derivatives 18 and 19. Reaction with Zn/Cu couple gave 5'-O-acetyl-5-phenyl-2',3'-didehydro derivative 20 and 2',3',5'-tri-O-acetyl-5-phenylcytidine (21). Compound 20 was deblocked to 1-(2,3-dideoxy-β-D-glycero-pent-2-enofuranosyl)-5-phenylcytosine (22). Catalytic hydrogenation of compound 20 over palladium and subsequent deblocking of the protected 2',3'-dideoxy derivative 23 gave 1-(2,3-dideoxy-β-D-glycero-pentofuranosyl)-5-phenylcytosine (24).

Intermediate stages of the sulfohaloform reaction. Preparation of α-halosulfoxides and sulfinyl chlorides. Oxygen-transfer reactions

1977 ◽  
Vol 55 (3) ◽  
pp. 421-426 ◽  
Author(s):  
J. Stuart Grossert ◽  
William R. Hardstaff ◽  
Richard F. Langler
Keyword(s):  
Acetic Acid ◽  
Thionyl Chloride ◽  
Oxygen Transfer ◽  
Redox Reactions ◽  
Methylene Chloride ◽  
Transfer Reactions ◽  
Sulfur Species ◽  
Synthetic Routes ◽  
Dialkyl Sulfides

Details are provided of synthetic routes from dialkyl sulfides to both α-halosulfoxides and sulfinyl chlorides. In the case of the former, oxidation of α-halosulfides to the sulfoxide stage is achieved by chlorine in acetic acid containing controlled amounts of water. Sulfinyl chlorides are prepared by chlorination of α-polyhalosulfoxides in methylene chloride. During investigations into the details of the sulfohaloform reaction, a number of novel redox reactions involving oxygen transfer between sulfur species have been observed and these are presented. They include a reduction of a sulfoxide with thionyl chloride.

Preparation of antidotes for anticholinesterase poisoning. IV. Synthesis and protective effectiveness of 2′-(cis- and trans-2″-hydroxycyclohexyl)aminoethyl 1-phenylcyclopentanecarboxylate hydrochlorides

1970 ◽  
Vol 48 (9) ◽  
pp. 1377-1382 ◽  
Author(s):  
R. A. B. Bannard ◽  
J. H. Parkkari
Keyword(s):  
Thionyl Chloride ◽  
Similar Reaction ◽  
Cis And Trans ◽  
Hydrolysis Of ◽  
Protective Effectiveness

The syntheses of cis- and trans-2-aminocyclohexanols and of cis- and trans-2-ethylaminocyclohexanols are described. The cis isomers were prepared by treatment of the corresponding trans-2-acetamidocyclohexanols with thionyl chloride followed by hydrolysis of the resulting intermediate oxazolines. The 2-aminocyclohexanols were converted to 2′-(cis- and trans-2″-hydroxycyclohexyl)aminoethyl 1-phenyl-cyclopentanecarboxylate hydrochlorides (1 and 2, R = H) by treatment with 2′-bromoethyl 1-phenyl-cyclopentanecarboxylate, but attempts to convert the 2-ethylaminocyclohexanols to 1 and 2 (R = C2H5) by a similar reaction were unsuccessful. The anticholinesterase activities of several of the compounds are discussed, as are the potencies of 1 and 2 (R = H) in protecting mice and rats from sarin poisoning.

Preparation of 1,3-thiazines: Sulphur analogues of nucleic acid pyrimidine bases

1970 ◽  
Vol 23 (1) ◽  
pp. 51 ◽  
Author(s):  
EN Cain ◽  
RN Warrener
Keyword(s):  
Acid Hydrolysis ◽  
Intramolecular Cyclization ◽  
Ring Closure ◽  
Synthetic Methods ◽  
Cyclization Reactions ◽  
Dithiocarbamic Acid ◽  
Pyrimidine Bases ◽  
Propiolic Acid ◽  
Hydrolysis Of ◽  
Acetylenic Acids

Sulphur analogues of uracil and thymine have been prepased, in which the N1 atom of the pyrimidine base has been replaced by a sulphur atom. A number of general synthetic methods are described for the synthesis of these 1,3-thiazines. The uracil analogues were prepared from the related 2-thio-1,3-thiazines, by acid hydrolysis of the 2-alkylthio derivative. 3,4-Dihydro-4-oxo-2-thio-2H-1,3-thiazine, its N-methyl and N-ethyl derivatives were obtained by cyclization of the addition compound resulting from the reaction of propiolic acid and the appropriate dithiocarbamic acid. The generality of this reaction, when propiolic acid is replaced with other acetylenic acids or their related esters, is discussed. The crystalline addition compounds obtained from dithiocarbamic acid and either propiolic acid or methyl propiolate were all shown by p.m.r, spectroscopy to have cis stereo-chemistry. The thymine analogues were prepared by an alternative route, which utilized the intramolecular cyclization of S-ethyl-N-(β-methoxymethacryloyl)dithiocarbamate to form 2-ethylthio-6-methyl-4-oxo-4H-1,3-thiazine, followed by acid hydrolysis of the 2-ethylthio group. Related intramolecular cyclization reactions of N-acyl-dithiocarbamates formed the 5-acetyl-, the 5-cyano-6-methyl-, the 5-cyano-6-ethyl-, and the 6-methyl-2-ethylthio-1,3-thiazine derivatives. A third approach involved the successful acid catalysed ring-opening-ring- closure of a. 4-oxo-2-thio-1,3-oxazine to the isomeric 2,4-dioxo-1,3-thiazine.

1-(3-Dimethylamino-1-phenylpropyl)piperazines and related compounds: Synthesis and pharmacological screening

1981 ◽  
Vol 46 (11) ◽  
pp. 2729-2733 ◽  
Author(s):  
Jiří Jílek ◽  
Josef Pomykáček ◽  
Jiří Němec ◽  
Miroslav Protiva
Keyword(s):  
Short Duration ◽  
Secondary Amine ◽  
Thionyl Chloride ◽  
Local Anaesthetic ◽  
Antiarrhythmic Action ◽  
Substitution Reactions ◽  
Pharmacological Screening ◽  
Hydrolysis Of ◽  
Related Compounds ◽  
Antiarrhythmic Effects

Substitution reactions of N,N-dimethyl-3-chloro-3-phenylpropylamine with 1-methylpiperazine and a series of analogues afforded 1-(3-dimethylamino-1-phenylpropyl)piperazines I-V. A similar substitution with piperidine resulted in the diamine VIII. Hydrolysis of the carbamate V gave the secondary amine VI which was transformed by alkylation with cyclopropylmethyl bromide to compound VII. 3-Dimethylamino-3-phenylpropanol was treated with thionyl chloride to give N,N-dimethyl-3-chloro-3-phenylpropylamine (IX) which reacted with 1-methylpiperazine and afforded the triamine X. The maleates of the amines prepared exhibited hypotensive effects of short duration (III, IV, VI, VII, X) and moderate antiarrhythmic effects (V-VIII). The phenylpiperazine derivative III showed a significant antiarrhythmic action and a high local anaesthetic activity.

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