Hot-Tube Reactions of Dehydroabietic Acid with Ketene-Producing Reagents. Pyrolysis of the Acid Chloride and Symmetrical and Mixed Anhydride Derivatives of Dehydroabietic Acid

1973 ◽  
Vol 51 (19) ◽  
pp. 3236-3241 ◽  
Author(s):  
Ray F. Severson ◽  
Walter H. Schuller
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Acid Chloride ◽  
Acetyl Chloride ◽  
Dehydroabietic Acid ◽  
Mixed Anhydride ◽  
Temperature Range ◽  
Acid Isomerization ◽  
Derivatives Of ◽  
Isopropenyl Acetate

Dehydroabietic acid (1a) was reacted with diketene, acetic acid, acetic anhydride, isopropenyl acetate, acetyl chloride, and acetone on Vycor rod at 450 °C in a hot tube. Dehydroabietic anhydride (1b) and acetyl dehydroabietate (1c) were pyrolyzed at 450 °C and dehydroabietyl chloride (1d) was pyrolyzed over a temperature range of 290–500 °C. The major olefin products resulting from decarboxylation of the various derivatives were 19-norabieta-4,8,11,13-tetraene (2), 19-norabieta-4(18),8,11,13-tetraene (3), 19-norabieta-3,8,11,13-tetraene (4), and cis-1,10a-dimethyl-7-isopropyl-1,2,3,9,10,10a-hexahydrophenanthrene (5). High conversions to these compounds were obtained. In the presence of the ketene-producing reagents the olefins were oxidized to yield substantial amounts of retene (6), compounds 2 and 5 being the most readily dehydrogenated. The acid isomerization of 2, 3, 4, and 5 was studied using p-toluenesulfonic acid in toluene at 110 °C.

Acetylation and Formylation of 3-Ferrocenylpyrroles

1999 ◽  
Vol 64 (1) ◽  
pp. 99-106
Author(s):  
Battsengel Gotov ◽  
Štefan Toma ◽  
Eva Solčániová
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Aluminum Chloride ◽  
Acetyl Chloride ◽  
Trifluoroacetic Anhydride ◽  
Acid Mixture ◽  
Chloride Method

Acetylations of 3-ferrocenyl-1-methylpyrrole as well as 3-cyano-4-ferrocenylpyrrole and 3-cyano-4-ferrocenyl-1-methylpyrrole were performed. The course of the acylation is highly dependent on the acylation agent, that is acetyl chloride/aluminum chloride (method A), trifluoroacetic anhydride-acetic acid mixture (method B) or acetic anhydride/Sc(OTf)3 (method C). Method A gives the acetylation on ferrocene moiety, method B affords the trifluoroacetylation on pyrrole moiety and method C affords pyrrole moiety acetylation. Vielsmeier-Haack formylation gives the products of substitution on pyrrole moiety.

Steroid and bile acids amide conjugates with D-glucosamine

2011 ◽  
Vol 76 (1) ◽  
pp. 65-74
Author(s):  
Zdena Nováková ◽  
Jana Tomanová ◽  
Lucie Štěrbová ◽  
Pavel Drašar
Keyword(s):  
Acetic Acid ◽  
Bile Acids ◽  
Acid Chloride ◽  
Acetyl Chloride ◽  
Glucosamine Hydrochloride ◽  
Negative Results ◽  
Step Procedure ◽  
One Step ◽  
New Type

New type of amide conjugates of steroid and bile acids with D-glucosamine 1 and 2 were prepared. Title compounds are prepared via acid chloride or using N-[({[(1E)-1-cyano-2-ethoxy-2-oxoethylidene]amino}oxy)(dimethylamino)methylidene]-N-methylmethanaminium tetrafluoroborate as condensation agent. They were examined for gelation properties with negative results. Per-O-acetylated D-glucosamine hydrochloride was prepared in one step procedure from D-glucosamine hydrochloride by acetylation in a mixture of acetyl chloride and acetic acid.

Thiohydantoins. III. Anhydride Intermediates in the Formation of 1-Acyl-2-thiohydantoins from Acylamino Acids

1952 ◽  
Vol 5 (4) ◽  
pp. 728
Author(s):  
JM Swan
Keyword(s):  
Carbon Dioxide ◽  
Acetic Acid ◽  
Acetic Anhydride ◽  
Hippuric Acid ◽  
Ammonium Thiocyanate ◽  
High Yield ◽  
Mixed Anhydride

Linear anhydrides are formed by the action of acetic anhydride on p-toluene-sulphonylglycine and carbobenzyloxy-glycine, -phenylalanine, and -β-alanine. The anhydrides from the first two acids yield the corresponding 2-thiohydantoin with ammonium thiocyanate in acetic acid. Other methods for the preparation of l-p-toluenesulphonylglycine anhydride, and its 2-thiohydantoin, are also given. Hippuric acid, with ethyl chlorocarbonate and triethylamine yields ethyl hippurate, probably via the mixed anhydride and 2-phenyloxazol-5-one. The inclusion of ammonium thiocyanate gives 1-benzoyl-2-thiohydantoin in high yield. The N-carboxy anhydride of phenylalanine (4-benzyloxazolid-2,5-dione) also reacts with ammonium thiocyanate to give carbon dioxide and 5-benzyl-2-thiohydantoin.

Studies in Thiohydantoin Chemistry. I. Some Aspects of the Schlack-Kumpf Reaction

1996 ◽  
Vol 49 (5) ◽  
pp. 541 ◽  
Author(s):  
BM Duggan ◽  
RL Laslett ◽  
JFK Wilshire
Keyword(s):  
Amino Acids ◽  
Acetic Acid ◽  
Acetic Anhydride ◽  
Ammonium Thiocyanate ◽  
Sodium Thiocyanate ◽  
Side Chains ◽  
Derivatives Of

An investigation has been carried out into the Schlack-Kumpf reaction, i.e., the reaction of amino acids with a mixture of acetic anhydride, acetic acid and sodium thiocyanate (occasionally ammonium thiocyanate was used). Particular emphasis was placed on the reactions with amino acids containing sensitive or functional side chains, i.e., serine, threonine , arginine , proline , lysine, histidine , cysteine , and aspartic and glutamic acids. The reaction of serine, and of certain of its O- and N-substituted derivatives, takes an unusual course to give an acetylated thiohydantoin derivative of cysteine. Correspondingly, threonine gives an acetylated thiohydantoin derivative of β- methylcysteine. Similar reactions occurred with the 3-phenylthiohydantoin derivatives of serine and of threonine to give acetylated thiohydantoin derivatives of cysteine and of β-methylcysteine respectively.

scholarly journals An Unusual Course of a Nitro Sugar Acetylation: Formation of a Crystalline Nitronic Acid – Acetic Acid Mixed Anhydride

1971 ◽  
Vol 49 (19) ◽  
pp. 3236-3238 ◽  
Author(s):  
Werner Rank ◽  
Hans H. Baer
Keyword(s):  
Acetic Acid ◽  
Acetyl Chloride ◽  
Acetyl Derivative ◽  
Acid Anhydride ◽  
Mixed Anhydride ◽  
Nitronic Acid

Whereas acetylation of methyl 4,6-O-benzylidene-3-deoxy-3-nitro-β-D-mannopyranoside (1) and its β-D-galacto isomer 2 with acetyl chloride and triethylamine in ether furnished the expected 2-O-acetylated nitro glycosides, 1a and 2a, the same method applied to the α-D-talo isomer 3 gave the 2-O-acetyl derivative of the corresponding nitronic acid – acetic acid anhydride, 4.

Nitration of 3,4-Dimethylacetophenone and 3,4-Dimethylbenzophenone. Formation and Rearomatization of Adducts

1975 ◽  
Vol 53 (11) ◽  
pp. 1570-1578 ◽  
Author(s):  
Alfred Fischer ◽  
Colin Campbell Greig ◽  
Rolf Röderer
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Nitro Group ◽  
Nitrous Acid ◽  
Main Product ◽  
Intermediate Formation ◽  
Nitro Derivatives ◽  
Acidic Conditions ◽  
Cis And Trans ◽  
Derivatives Of

Nitration of 3,4-dimethylacetophenone in acetic anhydride gives a mixture of cis-and trans-2-acetyl-4,5-dimethyl-4-nitro-1,4-dihydrophenyl acetate as the main product, together with 3,4-dimethyl-2-, 3,4-dimethyl-5-, and 3,4-dimethyl-6-nitroacetophenone. Analogous products are obtained from 3,4-dimethylbenzophenone. Rearomatization of the adducts under mildly acidic conditions occurs via 1,4-elimination of nitrous acid to form 2-acetyl- and 2-benzoyl-4,5-dimethylphenyl acetate, respectively. In strongly acidic conditions elimination of acetic acid accompanied by 1,2- and 1,3-shifts of the nitro group occurs to form the 2- and 5-nitro derivatives of the parent ketones. The rearomatization to the nitro derivatives involves the intermediate formation of an ipso-cyclohexadienyl cation which may be trapped by anisole or mesitylene to form biphenyl derivatives.

Potential nootropic agents: Synthesis of some (2-oxo-1-pyrrolidinyl)acetamides and some related compounds

1990 ◽  
Vol 55 (11) ◽  
pp. 2756-2764 ◽  
Author(s):  
Vladimír Valenta ◽  
Jiří Holubek ◽  
Emil Svátek ◽  
Martin Valchář ◽  
Ivan Krejčí ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Survival Time ◽  
Acetyl Chloride ◽  
The Other ◽  
Anticonvulsant Effect ◽  
Mixed Anhydride ◽  
Ester Exchange ◽  
Nootropic Agents ◽  
The One ◽  
Related Compounds

Ethyl (2-oxo-1-pyrrolidinyl)acetate was transformed by ester exchange to the 2-dimethylaminoethyl ester VI which was converted to the choline iodide ester VII. The mixed anhydride of (2-oxo-1-pyrrolidinyl)acetic acid and monoethyl carbonate was reacted with ethyl aminoacetate to give the ester VIII which was transformed on the one hand to the amide IX, and to the 2-dimethylaminoethyl ester X on the other. Reaction of the latter with methyl iodide afforded a further choline iodide ester XI. Reactions of (2-oxo-1-pyrrolidinyl)acetyl chloride with 4-chloroaniline and 3-aminopyridine gave the amides XII and XIV. The anilide XIII was obtained from 2-(2-oxo-1-pyrrolidinyl)butyric acid and 4-chloroaniline by means of dicyclohexylcarbodiimide. The benzo analogue (XV) of piracetam (I) was synthesized from oxindole via the ester XVI. The anilide XII (V⁄FB-16 536) was found to potentiate significantly the anticonvulsant effect of diazepam in mice, to prolong the survival time of mice under conditions of nitrogen anoxia, and to prolong significantly the duration of the "gasping reflex" in mice.

Color Reactions of Rubber and Gutta-Percha

1929 ◽  
Vol 2 (2) ◽  
pp. 193-196
Author(s):  
F. Kirchhof
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Zinc Chloride ◽  
Trichloroacetic Acid ◽  
Acetyl Chloride ◽  
Oxidation Products ◽  
Arsenic Trichloride ◽  
Gutta Percha ◽  
Long Time ◽  
Color Reactions

Abstract THE present paper was suggested by a recent publication of Pauly on the same subject, who applied the well known sterol reactions of Hesse, Liebermann, Tschugajeff, etc., to the hydrocarbons of rubber and gutta-percha. These reactions depend either upon the action of concentrated H2SO4 on chloroform solutions of the substances in the presence or absence of acetic anhydride (Liebermann, Burchard and Hesse reactions) or other solvents, or condensation reagents are used, such as acetyl chloride and zinc chloride by Tschugajeff, and acetic acid with arsenic trichloride by Kahlenberg, and trichloroacetic acid with a trace of formaldehyde by Godoletz. All the known sterol reactions take place also with rubber or gutta-percha, with the appearance of intense red or violet colorations of varying stability, the color depending in part upon the quality and in part upon the purity of the samples. The Burchard reaction in particular is very sensitive in these respects. Thus with rubber purified with alkali by the Pummerer method, the color is a Bordeaux red which does not change for a long time, whereas solutions of unpurified rubber change rapidly, a change which is rightly ascribed by Pauly to relatively rapid oxidation in the presence of oxidation products in the case of the unpurified rubber.

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