THE ACTION OF SULPHURIC ACID ON CERTAIN DERIVATIVES OF CYCLOPROPANE

1933 ◽  
Vol 9 (2) ◽  
pp. 159-168 ◽  
Author(s):  
Charles F. H. Allen ◽  
Raymond Boyer
Keyword(s):  
Acetic Acid ◽  
Sulphuric Acid ◽  
Hydrogen Bromide ◽  
Cyclopropane Ring ◽  
Secondary Reaction ◽  
Derivatives Of ◽  
Cyclopropane Derivatives

A considerable variety of ketocyclopropanes has been submitted to the action of sulphuric acid, alone or in acetic acid. In general, the mode of reaction was similar to, though less drastic than, that of hydrogen bromide; this indicated a similar mechanism. When the cyclopropane ring was attacked, the product isolated was apparently formed by the addition of a molecule of water or acetic acid, or was the result of a secondary reaction dependent on a primary product so formed. The nitriles were hydrolyzed to amides without opening of the ring. A mechanism is suggested to account for the ring scission of cyclopropyl alcohols, which takes place in a different manner from most cyclopropane derivatives.

scholarly journals XX. On some compounds and derivatives of acid

1863 ◽  
Vol 153 ◽  
pp. 437-452
Keyword(s):  
Inorganic Chemistry ◽  
Acetic Acid ◽  
Oxalic Acid ◽  
Sulphuric Acid ◽  
Glycolic Acid ◽  
Glyoxylic Acid ◽  
Careful Study ◽  
Organic Substances ◽  
Derivatives Of

Organic substances of simple composition, like marsh-gas, ethylene, alcohol, and acetic acid, are deserving of most careful study, not merely on account of their being repre­sentative members of numerous and important classes of bodies, but also because they form connecting links between the compounds of inorganic chemistry and the more complicated forms of organic nature. Glyoxylic acid belongs to this class of bodies, because it bears the same relation to oxalic acid that sulphurous acid does to sulphuric acid, and because it stands to glycolic acid as common aldehyde, C 2 H 4 O, does to alcohol, C 2 H 6 O. These relations suggested the experiments which will be described in the following pages.

ON THE OXIDATION OF 1, 1, 1-TRICHLORO-2,2-BIS- (p-TOLYL) -ETHANE

1953 ◽  
Vol 31 (1) ◽  
pp. 4-8 ◽  
Author(s):  
Yvon Perron
Keyword(s):  
Acetic Acid ◽  
Sulphuric Acid ◽  
Glacial Acetic Acid ◽  
Chloral Hydrate ◽  
Chromium Trioxide ◽  
Condensation Product ◽  
Potassium Dichromate ◽  
Oxidative Degradation ◽  
Amide Derivatives ◽  
Derivatives Of

The condensation of benzene with chloral hydrate in the presence of concentrated sulphuric acid gave rise to 1,1,1-trichloro-2,2-bis-(p-tolyl)-ethane. The oxidation of this condensation product with potassium dichromate in dilute sulphuric acid at the boiling temperature yielded 1,1-dichloro-2,2-bis-(p-carboxyphenyl)-ethylene, the structure of which was shown by its oxidative degradation to 4,4′-dicarboxybenzophenone. When the oxidation of the same condensation product was carried out in the cold, with the aid of chromium trioxide in glacial acetic acid and acetic anhydride, 1,1,1-trichloro-2,2-bis-(p-carboxyphenyl)-ethane was obtained in a good yield. This last compound was converted to the dichloroethylenic-dicarboxylic acid upon refluxing with a methanolic solution of sodium hydroxide. The corresponding amide derivatives of both the dichloro and trichlorodicarboxylic acids were also prepared.

Fluorinated tricyclic neuroleptics with prolonged action: 8-Methoxy, 8-ethoxy, 8-ethylthio and 8-hydroxy derivatives of 3-fluoro-10-(4-methylpiperazino)-10,11-dihydrodibenzo[b,f]thiepin

1982 ◽  
Vol 47 (5) ◽  
pp. 1382-1391 ◽  
Author(s):  
Jiří Jílek ◽  
Josef Pomykáček ◽  
Jiřina Metyšová ◽  
Miroslav Protiva
Keyword(s):  
Acetic Acid ◽  
Polyphosphoric Acid ◽  
Prolonged Action ◽  
Substitution Reactions ◽  
Methoxy Derivative ◽  
Chloro Derivatives ◽  
Boron Tribromide ◽  
Derivatives Of ◽  
Central Depressant ◽  
Boiling Toluene

Acids IIa-c were prepared by reactions of (4-fluoro-2-iodophenyl)acetic acid with 4-methoxythiophenol, 4-ethoxythiophenol and 4-(ethylthio)thiophenol and cyclized with polyphosphoric acid in boiling toluene to dibenzo[b,f]thiepin-10(11H)-ones IIIa-c. Reduction with sodium borohydride afforded the alcohols IVa-c which were treated with hydrogen chloride and gave the chloro derivatives Va-c. Substitution reactions with 1-methylpiperazine resulted in the title compounds Ia-c out of which the methoxy derivative Ia was transformed by demethylation with boron tribromide to the phenol Id. Compounds Ia-d are very potent neuroleptics exhibiting a clear prolongation of the central depressant and some prolongation of the cataleptic activity.

ChemInform Abstract: DIHALO DERIVATIVES OF NAPHTHOSTYRIL-N-ACETIC ACID

1978 ◽  
Vol 9 (34) ◽  
Author(s):  
A. P. KARISHIN ◽  
A. A. PECHKA ◽  
N. F. GRINEVA
Keyword(s):  
Acetic Acid ◽  
Derivatives Of

ChemInform Abstract: Anionic Derivatives of Pentafluoro-λ6-sulfanyl (Fluorosulfonyl) Acetic Acid Esters.

ChemInform ◽  
2010 ◽  
Vol 25 (7) ◽  
pp. no-no
Author(s):  
R. WINTER ◽  
G. L. GARD ◽  
R. MEWS ◽  
M. NOLTEMEYER
Keyword(s):  
Acetic Acid ◽  
Derivatives Of ◽  
Acetic Acid Esters ◽  
Acid Esters

The synthesis of norbornanes with functionalized carbon substituents at a bridgehead. 1-(3-Oxonorborn-1-yl)ethanone and 1-(3-oxonorborn-1-yl)-2-propanone

1992 ◽  
Vol 70 (5) ◽  
pp. 1492-1505 ◽  
Author(s):  
Peter Yates ◽  
Magdy Kaldas
Keyword(s):  
Acetic Acid ◽  
Carboxylic Acid ◽  
Hydrogen Bromide ◽  
Tertiary Alcohol ◽  
Ethyl Bromoacetate ◽  
Second Molar ◽  
Molar Equivalent ◽  
Acid Lactone ◽  
Basic Hydrolysis ◽  
Hydrolysis Of

Treatment of 2-norobornene-1-carboxylic acid (7) with one equivalent of methyllithium in ether followed by a second molar equivalent after dilution with tetrahydrofuran gave 1-(norborn-2-en-lyl)ethanone (10) and only a trace of the tertiary alcohol 11. Reaction of 7 with formic acid followed by hydrolysis gave a 4:3 mixture of exo-3- and exo-2-hydroxynorbornane-1-carboxylic acid (16 and 17), whereas oxymercuration–demercuration gave only the exo-3-hydroxy isomer 16. Oxidation of 16 and 17 gave 3- and 2-oxonorbornane-1-carboxylic acid (27 and 29), respectively. Oxymercuration–demercuration of 10 gave exclusively 1-(exo-3-hydroxynorborn-1-yl)ethanone (30), which was also prepared by treatment of 16 with methyllithium in analogous fashion to that used for the conversion of 7 to 10. Oxidation of 30 gave 1-(3-oxonorborn-1-yl)ethanone (1). Dehydrobromination of exo-2-bromonorbornane-1-acetic acid and dehydration of 2-hydroxy-norbornane-2-acetic acid derivatives gave 1-(norborn-2-ylidene) acetic acid derivatives to the exclusion of norborn-2-ene-1 -acetic acid derivatives. Treatment of exo-5-acetyloxy-2-norobornanone (52) with ethyl bromoacetate and zinc gave ethyl exo-5-acetyloxy-2-hydroxynorbornane-(exo- and endo-2-acetate (53 and 54). Reaction of 53 with hydrogen bromide gave initially ethyl endo-3-acetyloxy-exo-6-bromonorbornane-1-acetate (59), which was subsequently converted to a mixture of 59 and its exo-3-acetyloxy epimer 61. Catalytic hydrogenation of this mixture gave a mixture of ethyl endo- and exo-3-acetyloxynorbornane-1 -acetate (62 and 63). Basic hydrolysis of this gave a mixture of the corresponding hydroxy acids, 70 and 71; the former was slowly converted to the latter at pH 5. Oxidation of the mixture of 70 and 71 gave 3-oxonorbornane-1-acetic acid (72). Treatment of the mixture with methyllithium as for 16 gave a mixture of 1-(endo- and exo-3-hydroxynorborn-1-yl)-2-propanone (73 and 74), which was oxidized to 1-(3-oxo-norborn-1-yl)-2-propanone (2). Reaction of exo-2-hydroxynorbornane-1-acetic acid lactone (75) with methyllithium in ether gave (1-(exo-2-hydroxynorborn-1-yl)-2-propanone (76), which on oxidation gave the 2-oxo isomer 78 of 2.

Sign in / Sign up

Export Citation Format

Share Document