Reaction of 1-(2,3-O-isopropylidene-β-D-ribofuranosyl) uracil with excess thionyl chloride: Formation of bis[1-(2,3-O-isopropylidene-β-D-ribofuranosyl) uracil] 5′-sulfite

1973 ◽  
Vol 27 (2) ◽  
pp. 455-459 ◽  
Author(s):  
Prem C. Srivastava ◽  
Robert J. Rousseau
Keyword(s):  
Thionyl Chloride ◽  
Excess Thionyl Chloride

REARRANGEMENT STUDIES WITH 14C: XIX. THE REACTION OF 2-PHENYL-1-14C-ETHANOL WITH THIONYL CHLORIDE

1964 ◽  
Vol 42 (5) ◽  
pp. 1130-1136 ◽  
Author(s):  
C. C. Lee ◽  
D. J. Kroeger ◽  
D. P. Thornhill
Keyword(s):  
Thionyl Chloride ◽  
Ion Pairs ◽  
Aqueous Sodium Hydroxide ◽  
Covalent Bonding ◽  
Ion Pair ◽  
Aqueous Sodium ◽  
Carbonium Ion ◽  
Partial Completion ◽  
The Stability ◽  
Excess Thionyl Chloride

The reaction of 2-phenyl-1-14C-ethanol with thionyl chloride in pyridine, dioxane, toluene, or excess thionyl chloride as solvent gave 2-phenylethyl chloride showing, respectively, about 0, 15, 44, and 48% rearrangement of the 14C-label from the C-1 to the C-2 positions. When reactions of 2-phenyl-1-14C-ethauol or 2-p-anisyl-1-14C-ethanol with thionyl chloride in dioxane or excess thionyl chloride were carried only to partial completion and the undecomposed chlorosulphites hydrolyzed by aqueous sodium hydroxide, the recovered alcohols showed only 0.1 to 0.5% isotope position rearrangement. This indicated a lack of return from ion-pairs to isotopically rearranged 2-arylethylchlorosulphite and suggested that the first stage of ionization may involve ion-pairs with structures that will not result in rearrangement on return to covalent bonding, or that the first ion-pair may decompose faster than it can return to reactant. The possibility that rearrangements via rigidly oriented ion-pairs and via the concerted SNi′ mechanism may represent the two extremes of a graded series is discussed. It is suggested that the relative contributions from the ion-pair and from the SNi′ mechanisms will depend on the stability of the carbonium ion as well as on the nature of the reaction solvent.

REARRANGEMENT STUDIES WITH C14: XIV. THE REACTION OF 2-p-ANISYLETHANOL-1-C14 WITH THIONYL CHLORIDE

1963 ◽  
Vol 41 (3) ◽  
pp. 620-624 ◽  
Author(s):  
C. C. Lee ◽  
Donna Newman ◽  
D. P. Thornhill
Keyword(s):  
Thermal Decomposition ◽  
Thionyl Chloride ◽  
Ion Pair ◽  
Excess Thionyl Chloride

Reaction between 2-p-anisylethanol-1-C14 and thionyl chloride was carried out with pyridine, n-hexane, toluene, dioxane, or excess thionyl chloride as solvent. The 2-p-anisylethyl chloride obtained showed rearrangement of the C14 label from the C-1 to C-2 positions ranging from about 0.5% for the reaction in pyridine to about 46% for the reaction in excess thionyl chloride. The results can be explained on the basis of varying degrees of involvement of the ethylene-p-methoxyphenonium chlorosulphite ion pair, thus supporting the suggestion that thermal decomposition of alkyl chlorosulphites to give chlorides may be considerably ionic in character.

On the Reaction of Deacetylvindoline with Thionyl Chloride

2000 ◽  
Vol 65 (5) ◽  
pp. 789-796 ◽  
Author(s):  
Josef Hájíček ◽  
Vladimír Hanuš
Keyword(s):  
Thionyl Chloride ◽  
Mass Spectra ◽  
2D Nmr ◽  
Single Product ◽  
Complex Transformation ◽  
Excess Thionyl Chloride

Reaction of deacetylvindoline (2) with excess thionyl chloride gave rise to hexacyclic 6,10-dichloro-6,17-epithio-11-methoxy-1-methyltabersonine (4) as a single product in 43.5% yield. The structure was deduced from 1H and 13C 1D and 2D NMR experiments as well as from mass spectra. A tentative mechanism of this complex transformation was also proposed.

Some 1-substitution derivatives of 4-aryl-2,3-dihalogeno-1-naphthols

1984 ◽  
Vol 49 (1) ◽  
pp. 110-121 ◽  
Author(s):  
Jiří Křepelka ◽  
Drahuše Vlčková ◽  
Milan Mělka
Keyword(s):  
Thionyl Chloride ◽  
Oxirane Ring ◽  
Secondary Amines ◽  
Two Phase ◽  
Lytic Effect ◽  
Primary And Secondary Amines ◽  
Phase Medium ◽  
Chloro Derivatives ◽  
Derivatives Of

Alkylation of derivatives of 4-aryl-1-naphthols (I-V) by 2,3-epoxypropyl chloride in methanolic sodium hydroxide gave epoxy derivatives VI, VIII, IX, XI and XII, apart from products of cleavage of the oxirane ring, VII and X. Analogous alkylation of compounds I, IV and V by 2-(N,N-diethylamino)ethyl chloride hydrochloride in a two-phase medium afforded basic ethers XIII to XV. The cleavage of the oxirane ring in compound VI by the action of primary and secondary amines, piperidine and substituted piperazines led to compounds XVI-XXIV. Reaction of thionyl chloride with compounds XXI, XXII and XXIV gave chloro derivatives XXV-XXVII.Exposure of compound XXII to 4-methylbenzenesulfonyl chloride produced compound XXVIII, retaining the secondary alcoholic group. In an antineoplastic screening in vivo none of the compounds prepared had an appreciable activity. Compound XVII, being an analogue of propranolol, was used in the test of isoproterenolic tachycardia, and showed a beta-lytic effect comparable with that of propranol.

Photoinduced rearrangement of hydroxymethylisoxazolines, a route to enaminoaldehydes

1986 ◽  
Vol 51 (10) ◽  
pp. 2167-2180 ◽  
Author(s):  
Lubor Fišera ◽  
Nadezhda D. Kozhina ◽  
Peter Oravec ◽  
Hans-Joachim Timpe ◽  
Ladislav Štibrányi ◽  
...  
Keyword(s):  
Thionyl Chloride ◽  
Quantum Yields ◽  
Acid Catalyzed ◽  
Catalyzed Reactions ◽  
Photoinduced Rearrangement ◽  
Condensed Heterocycles

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.

Preparation of Chloro and Sulfanyl Derivatives of 1-(2-Deoxy-4-C-hydroxymethyl-α-L-threo-Pentofuranosyl)uracil

1997 ◽  
Vol 62 (7) ◽  
pp. 1114-1127 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Jan Balzarini ◽  
Antonín Holý
Keyword(s):  
Nucleophilic Substitution ◽  
Hydrogen Chloride ◽  
Thionyl Chloride ◽  
Sodium Methoxide ◽  
Thioacetic Acid ◽  
Uracil Derivatives ◽  
Derivatives Of ◽  
Hiv 1

3'-Chloro and 3'-acetylsulfanyl derivatives of 1-(2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil were prepared by reaction of 2,3'-anhydro-1-{5'-O-benzoyl-4'-C-[(benzoyloxy)methyl]-2'-deoxy-α-L-erythro-pentofuranosyl}uracil (3) with hydrogen chloride and thioacetic acid, respectively. The reaction with hydrogen chloride gave a mixture of N-1 and N-3 substituted uracil derivatives 12 and 14. Reaction of 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-α-L-threo-pentofuranosyl}uracil (7) with thionyl chloride and subsequent debenzoylation afforded 1-(4-C-chloromethyl-2-deoxy-β-D-erythro-pentofuranosyl)uracil (19). Nucleophilic substitution with lithium thioacetate, followed by deacylation, converted 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (9) into 1-(2-deoxy-4-C-sulfanylmethyl-β-D-erythro-pentofuranosyl)uracil (21). The obtained thiols were oxidized with iodine or air to give 1,1'-[disulfandiylbis(2,3-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-3,1-diyl]di(pyrimidine-2,4-(1H,3H)-dione) (17) and 1,1'-[disulfandiylbis(2,5-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-5,1-diyl]di(pyrimidine-2,4(1H,3H)-dione) (22). Reaction of 1-{3-acetylsulfanyl-5-O-methanesulfonyl-4-C-[(benzoyloxy)methyl]-2,3-dideoxy-α-L-threo-pentofuranosyl)}uracil (24) with methanolic sodium methoxide afforded 1-(3,5-anhydro-2,3-dideoxy-4-C-hydroxymethyl-3-sulfanyl-α-L-threo-pentofuranosyl)uracil (25). The same reagent was used in the preparation of 1-(3,5-anhydro-2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil (26) from 1-{4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (8). From the series of 4'-substituted 2'-deoxyuridine derivatives, synthesized in this study, solely the 4'-chloromethyl derivative 19 and the oxetane derivative 26 exhibited an appreciable activity against HIV-1 and HIV-2.

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