Synthesis and Novel Rearrangement of 1,1,1-Trichloro-2-alken-4-ones

1971 ◽  
Vol 49 (18) ◽  
pp. 2964-2976 ◽  
Author(s):  
Eberhard Kiehlmann ◽  
Pui-Wah Loo ◽  
B. C. Menon ◽  
Nora McGillivray
Keyword(s):  
Acetic Acid ◽  
Nucleophilic Substitution ◽  
Thionyl Chloride ◽  
Strong Acid ◽  
Mineral Acids

Strong mineral acids convert 1,1,1-trichloro-2-hydroxy-4-alkanones to 1,1,1-trichloro-2-aIken-4-ones and 1,1,5-trichloro-1-alken-4-ones via an intramolecular chlorine shift from C-1 to −5 of an enol allylic system. Alternatively, 1,1,1-trichloro-2-alken-4-ones may be synthesized from 1,1,1-trichloro-2-hydroxy-4-alkanones by acetylation and elimination of acetic acid or by nucleophilic substitution with thionyl chloride followed by dehydrohalogenation. The two diastereomeric 1,1,1-trichloro-2-hydroxy-3-methyl-4-hexanones do not epimerize during acetylation, and the erythro-acetate resists elimination of acetic acid. Pyrolysis of 2-(1-hydroxy-2,2,2-trichloroethyl-)cyclohexanone yields 2-(2,2-dichlorovinyl)-2-cyclohexenone while treatment of 1,1,1,7,7,7-hexachloro-2,6-dihydroxy-4-heptanone with strong acid leads to the formation of 1,1,1,7,7,7-hexachloro-2,5-heptadien-4-one.

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.

Confirmatory Tests for Aflatoxin B1

1964 ◽  
Vol 47 (5) ◽  
pp. 801-803 ◽  
Author(s):  
Peter John Andrellos ◽  
George R Reid
Keyword(s):  
Acetic Acid ◽  
Thin Layer ◽  
Formic Acid ◽  
Thionyl Chloride ◽  
Aflatoxin B1 ◽  
Trifluoroacetic Acid ◽  
Reaction Products ◽  
Confirmatory Tests ◽  
Aflatoxin B ◽  
Layer Chromatography

Abstract Three confirmatory tests have been devised to identify aflatoxin B±. Portions of the isolated toxin are treated with formic acid-thionyl chloride, acetic acid-thionyl chloride, and trifluoroacetic acid, respectively, and aliquots of the three fluorescent reaction products are spotted on thin-layer chromatography plates. Standards treated with each of the three reagents, plus an untreated standard, are spotted on the same plate, and after development the spots are compared under ultraviolet light.

Reaction of Aflatoxin B1 with Acetic Acid-Thionyl Chloride

1969 ◽  
Vol 52 (1) ◽  
pp. 75-76
Author(s):  
Mabry Wiley ◽  
Anthony C Waiss ◽  
Nancy Bennett
Keyword(s):  
Acetic Acid ◽  
Thionyl Chloride ◽  
Aflatoxin B1 ◽  
Confirmatory Test

Abstract The two main products of the reaction of acetic aeid-thionyl chloride with aflatoxin B1, used as a confirmatory test for aflatoxin B1, were identified as the α- and β-isomers of l-acetyl-2-hydro-6-methoxydifurocoumarone

scholarly journals Studies and Synthesis of Substituted 4-Biphenyl Acetamide Derivatives

2019 ◽  
Vol 31 (3) ◽  
pp. 510-514
Author(s):  
Anju Khullar
Keyword(s):  
Acetic Acid ◽  
Thionyl Chloride ◽  
Spectral Methods ◽  
Aromatic Amines ◽  
Acetyl Chloride ◽  
Acid Amide ◽  
Primary Amines ◽  
Curvularia Lunata ◽  
Fusarium Udum ◽  
Amide Derivatives

A new series of substituted 4-biphenylamides have been synthesized by condensation of 4-biphenyl acetic acid with different primary amines (aromatic and aliphatic). 4-Biphenyl acetic acid was first treated with thionyl chloride in dry benzene to prepare substituted 4-biphenyl acetyl chloride, which is then treated with different aliphatic or aromatic amines to synthesize various substituted 4-biphenyl acid-amide derivatives. The structure of newly synthesized compounds has been established by analytical and spectral methods. These synthesized compounds have shown antifungal properties against Fusarium udum and Curvularia lunata.

Experiment illustrating the Modern Theory of Salt-Solution

1897 ◽  
Vol 21 ◽  
pp. 57-58
Author(s):  
Crum Brown
Keyword(s):  
Acetic Acid ◽  
Hydrochloric Acid ◽  
Sodium Acetate ◽  
Strong Acid ◽  
Zinc Sulphide ◽  
Zinc Salt ◽  
Modern Theory ◽  
Hydrogen Ions ◽  
Limiting Value ◽  
Sulphuretted Hydrogen

It is well known to all chemists that sulphuretted hydrogen does not give a precipitate of zinc sulphide in a solution of zinc chloride or zinc sulphate if a sufficient (quite small) quantity of a strong acid, such as hydrochloric or sulphuric acid, has been added to the solution. It is also quite well known that if we add a sufficient quantity of a solution of sodium acetate to the clear solution containing the zinc salt sulphuretted hydrogen and strong acid, we throw down the whole of the zinc as sulphide. This used to be explained as follows:—Hydrochloric acid acts on zinc sulphide thus, ZnS + 2HCl = H2S + ZnCl2, and therefore the opposite action ZnCl2 + H2S = ZnS + 2HCl cannot take place in the presence of hydrochloric acid. But as acetic acid is too weak an acid to act on zinc sulphide, the presence of acetic acid does not prevent the precipitation of zinc sulphide, and the hydrochloric acid originally there, as well as that produced by the reaction, acts on the sodium acetate to form sodium chloride and acetic acid. On the modern theory the explanation is this:—The zinc sulphide is attacked not by the hydrochloric acid, but by the hydrogen ions; these are present in the solution of hydrochloric acid; and that acid being to a great extent “ionised,” we have a great concentration of hydrogen ions. There is a limiting value for the concentration of hydrogen ions, above which the action ZnS + 2H. = Zn.. + H2S takes place, so that zinc sulphide cannot be formed by the action of sulphuretted hydrogen on a zinc salt in a solution containing hydrogen ions with a concentration above this limiting value.

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