Cyclization of Phenacyl 2-{[2,2-Di(ethoxycarbonyl)vinyl]amino}benzoate

1998 ◽  
Vol 63 (4) ◽  
pp. 520-524 ◽  
Author(s):  
Pavel Hradil ◽  
Lubomír Kvapil ◽  
Jan Hlaváč ◽  
Karel Lemr ◽  
Juraj Ševčík
Keyword(s):  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Ethyl Ester ◽  
Polyphosphoric Acid ◽  
Diphenyl Ether ◽  
Thermal Cyclization ◽  
Prolonged Heating ◽  
Independent Synthesis ◽  
Hydrolysis Of

Reaction of phenacyl anthranilate (1) with diethyl (ethoxymethylidene)malonate afforded phenacyl 2-{[2,2-di(ethoxycarbonyl)vinyl]amino}benzoate (2) which on heating in polyphosphoric acid underwent degradation. Thermal cyclization of 2 in diphenyl ether gave phenacyl 3-(ethoxycarbonyl)-4-oxo-1,4-dihydroquinoline-8-carboxylate (4). The phenacyl group did not cyclize even on prolonged heating at 250 °C. Heating in sulfuric acid resulted in hydrolysis of the ethyl ester under formation of 4-oxo-8-[(phenacyloxy)carbonyl]-1,4-dihydroquinoline-3-carboxylic acid (6). The structure of 4 was confirmed by an independent synthesis.

Improved synthesis of anti-sesquinorbornene

1984 ◽  
Vol 62 (9) ◽  
pp. 1840-1844 ◽  
Author(s):  
Karl R. Kopecky ◽  
Alan J. Miller
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Lead Tetraacetate ◽  
Carboxyl Group ◽  
Silver Acetate ◽  
Benzenesulfonyl Chloride ◽  
Methoxide Ion ◽  
Hydrolysis Of ◽  
Monomethyl Ester

Treatment of methyl hydrogen decahydro-1,4:5,8-exo,endo-dimethanonaphthalene-4a,8a-dicarboxylate with lead tetraacetate in benzene – acetic acid replaces the carboxyl group by an acetoxy group. Hydrolysis of this product with 25% sulfuric acid at 130 °C forms 8a-hydroxydecahydro-1,4:5,8-exo,endo-dimethanonaphthalene-4a-carboxylic acid 10. The reaction between 10 and benzenesulfonyl chloride in pyridine containing triethylamine at 95 °C produces anti-sesquinorbornene 1 in 34% yield. In the absence of triethylamine 1 is converted to the hydrochloride. The iodohydroperoxide of 1 is converted by silver acetate at 0 °C to the diketone in a luminescent reaction. The 1,2-dioxetane could not be isolated. Decahydro-1,4:5,8-exo,exo-dimethanonaphthalene-4a,8a-dicarboxylic anhydride is converted slowly by methoxide ion in methanol at 150 °C to the monomethyl ester which then undergoes demethylation. The isomeric exo,endo anhydride undergoes reaction readily with methoxide ion at 80 °C.

Isocarbostyrils. II. The Conversion of 2-Methyl-4-acyl-5-nitroisocarbostyrils to 2-Substituted Indole-4-carboxylic Acids

1971 ◽  
Vol 49 (17) ◽  
pp. 2797-2802 ◽  
Author(s):  
D. E. Horning ◽  
G. Lacasse ◽  
J. M. Muchowski
Keyword(s):  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Alkaline Hydrolysis ◽  
Mannich Reaction ◽  
Reductive Cyclization ◽  
Acid Catalyzed ◽  
Acid Anhydrides ◽  
Hydrolysis Of ◽  
Derivatives Of

The sulfuric acid catalyzed acylation of 2-methyl-5-nitroisocarbostyril with carboxylic acid anhydrides gave the corresponding 4-acylated derivatives 3, which underwent reductive cyclization to 2-substituted derivatives of 4-methyl-1,3,4,5-tetrahydropyrrolo[4.3.2.de]isoquinolin-5-one (4). Alkaline hydrolysis of the six-membered lactam in 4 was accompanied by a retro-Mannich reaction to produce 2-substituted indole-4-carboxylic acids in about 40 % overall yield from 3.

Thiohydantoins. X. Kinetic Studies of the Acid Hydrolysis of 1-Acyl-2-thiohydantoins

1972 ◽  
Vol 50 (23) ◽  
pp. 3767-3779 ◽  
Author(s):  
Wayne Irvine Congdon ◽  
John Thomas Edward
Keyword(s):  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Acid Hydrolysis ◽  
Kinetic Studies ◽  
Steric Effects ◽  
Aqueous Sulfuric Acid ◽  
Hydrolysis Of

The rates of hydrolysis of 22 1-acyl-2-thiohydantoins in aqueous sulfuric acid to give 2-thiohydantoin and a carboxylic acid have been determined. In 0–90% sulfuric acid, hydrolysis takes place by an A-2 mechanism, and the rate reaches a maximum in about 70% acid. In acid more concentrated than about 90%, hydrolysis takes place by an A-1 mechanism, and the rate increases monotonically. Evidence for the two mechanisms comes from Yates r and Bunnett-Olsen [Formula: see text] parameters; from entropies of activation; from pσ and pσ+ relations; and from steric effects.

The Chemistry of Ethyl 2-Ethoxycarbonyl-5,5-Diphenylpenta-2,3,4-Trienoate, a Potential Precursor of Ph2c=C=C=C=C=O

1987 ◽  
Vol 40 (10) ◽  
pp. 1675 ◽  
Author(s):  
NR Browne ◽  
RFC Brown ◽  
FW Eastwood ◽  
GD Fallon
Keyword(s):  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Wittig Reaction ◽  
Cyclization Reactions ◽  
X Ray ◽  
X Ray Crystallography ◽  
Concentrated Sulfuric Acid ◽  
Triphenylphosphonium Bromide ◽  
Hydrolysis Of ◽  
Potential Precursor

The title diester , Ph2C=C=C=C( COOEt )2 (2), has been prepared by a Wittig reaction between (2-bromo-3,3-diphenylprop-2-en-1-yl) triphenylphosphonium bromide and diethyl 2-oxopropane-1,3-dioate ( mesoxalic ester). The diester (2) undergoes cyclization reactions in concentrated sulfuric acid to give diethyl 2-(3'-phenyl-1H-inden-1'-y1idene)propane-l,3-dioate (4) and triethyl 3-oxo-3',9-diphenyl-2,3-dihydrospiro[lH-fluorene-1,l'-[1H]indene]-2,2,4-tricarboxylate (6), the structure of which was determined by X-ray crystallography. The title diester (2)adds cyclopentadiene across the 2,3-C=C bond to give diethyl 3-(2',2'-diphenylethenylidene)bicyclo[2.2.l]hept-5-ene-2,2-dicarboxylate (10). Alkaline hydrolysis of diester (10) gives an unstable colourless acid and a stable yellow crypto acid shown by X-ray crystallography to be 3-(2',2'-diphenylethenyl)bicyclo[2.2.l]hepta-2,5-diene-2-carboxylic acid (12). Attempts to convert diesters (2) and acid (12) into derivatives suitable for pyrolytic generation of Ph2C=C=C=C=C=O failed; The mono-acid chloride (14) yielded a small phenylazulene fraction on pyrolysis at 780-800°/0.02 mm.

Silica sulfuric acid-catalyzed expeditious environment-friendly hydrolysis of carboxylic acid esters under microwave irradiation

2008 ◽  
Vol 62 (6) ◽  
Author(s):  
Zheng Li ◽  
Jing Liu ◽  
Xue Gong ◽  
Xuerong Mao ◽  
Xiunan Sun ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Microwave Irradiation ◽  
High Yield ◽  
Silica Sulfuric Acid ◽  
Environment Friendly ◽  
Acid Catalyzed ◽  
Work Up ◽  
Hydrolysis Of ◽  
Acid Esters

AbstractSilica sulfuric acid was found to be an efficient, recoverable, reusable and environment-friendly catalyst for the fast hydrolysis of various carboxylic acid esters in high conversions and selectivities under microwave irradiation conditions. This protocol has the advantages of no corrosion, no environmental pollution, high reaction rate, high yield, and simple work-up procedure.

Synthesis of Normuramic Acid Carba Analog and Its Glycopeptide Derivative Resistant to β-Elimination Splitting of the Side Chain

2000 ◽  
Vol 65 (11) ◽  
pp. 1726-1736 ◽  
Author(s):  
Miroslav Ledvina ◽  
Radka Pavelová ◽  
Anna Rohlenová ◽  
Jan Ježek ◽  
David Šaman
Keyword(s):  
Ethyl Ester ◽  
Alkaline Hydrolysis ◽  
Benzyl Ester ◽  
Side Chain ◽  
Propanoic Acid ◽  
Hydrolysis Of

Carba analogs of normuramic acid, i.e., 3-(benzyl 2-acetamido-2,3-dideoxy-4,6-O-isopropylidene-α-D-glucopyranosid-3-yl)propanoic acid derivatives (nitrile or esters) 3a-3c were prepared by addition of radicals generated from benzyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-3-O-[(methylsulfanyl)thiocarbonyl]- (2a) or -3-O-(phenoxythiocarbonyl)-α-D-glucopyranoside (2b) with Bu3SnH to acrylonitrile or acryl esters. Alkaline hydrolysis of ethyl ester 3c afforded 3-(benzyl 2-acetamido-2,3-dideoxy-4,6-O-isopropylidene-α-D-glucopyranosid-3-yl)propanoic acid (5). Coupling of acid 5 with L-2-aminobutanoyl-D-isoglutamine benzyl ester trifluoroacetate and subsequent deprotection of the intermediate 6 furnished N-[3-(2-acetamido-2,3-dideoxy-α-D-glucopyranosid-3-yl)propanoyl]-L-2-aminobutanoyl-D-isoglutamine (7).

Carboxylic acid-catalysed hydrolysis of rhamnogalacturonan in subcritical water media

2021 ◽  
pp. 105268
Author(s):  
Carla S. Valdivieso Ramirez ◽  
Feral Temelli ◽  
Marleny D.A. Saldaña
Keyword(s):  
Carboxylic Acid ◽  
Subcritical Water ◽  
Water Media ◽  
Hydrolysis Of

Carboxylic acid-catalysed hydrolysis of polygalacturonic acid in subcritical water media

2020 ◽  
pp. 105103
Author(s):  
Carla S. Valdivieso Ramirez ◽  
Jose E. Sanchez Gallego ◽  
Michael Gänzle ◽  
Feral Temelli ◽  
Marleny D.A. Saldaña
Keyword(s):  
Carboxylic Acid ◽  
Subcritical Water ◽  
Polygalacturonic Acid ◽  
Water Media ◽  
Hydrolysis Of
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