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.

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.

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.

The mechanism of lead tetraacetate decarboxylation. I. Tertiary carboxylic acids

1974 ◽  
Vol 27 (8) ◽  
pp. 1673 ◽  
Author(s):  
ALJ Beckwith ◽  
RT Cross ◽  
GE Gream
Keyword(s):  
Acetic Acid ◽  
Reaction Mechanism ◽  
Carboxylic Acid ◽  
Product Distribution ◽  
Lead Tetraacetate ◽  
Copper Salts ◽  
Elimination Process ◽  
Initial Generation ◽  
Cis And Trans ◽  
Lead Species

The reactions of cis- and trans-decalin-9-carboxylic acid, 2,2,3-trimethylbutanoic acid, and adamantane-1-carboxylic acid with lead tetraacetate in benzene and, in some cases, acetic acid have been studied. In each case the nature and distribution of the products is consistent with the hypothesis that the reaction mechanism involves the initial generation of tertiary radicals which are subsequently converted into the related cations either by one-electron oxidation by lead species, or via organolead intermediates which undergo heterolysis. The change in product distribution which occurs when the reactions are conducted in the presence of copper salts indicates that tertiary radicals react rapidly with cupric species to afford organocopper intermediates from which olefins are derived by a cis-elimination process, and acetates by SNi or heterolytic mechanisms.

A useful method for preparation of carboxylic acids from terminal alkynes

1983 ◽  
Vol 61 (10) ◽  
pp. 2423-2424 ◽  
Author(s):  
Suzanne R. Abrams
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Chain Length ◽  
Good Yield ◽  
Terminal Alkynes ◽  
Terminal Acetylenes ◽  
Long Chain ◽  
Acetic Acids

Substituted acetic acids can be prepared in good yield (50–80%) from terminal acetylenes of the same chain length. The alkyne is first converted to the thiophenyl ether, which is treated without purification with mercuric sulfate in acetic acid and 2 N sulfuric acid affording the carboxylic acid. The method is particularly useful in the synthesis of long chain ω-hydroxyalkanoic acids.

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.

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.

Remarkable stereoselectivity in the hydrolysis of dioxolenium ions and orthoesters fused to anchored six-membered rings

1970 ◽  
Vol 48 (11) ◽  
pp. 1754-1769 ◽  
Author(s):  
J. F. King ◽  
A. D. Allbutt
Keyword(s):  
Acetic Acid ◽  
Good Yield ◽  
Benzoyl Chloride ◽  
Stereoselective Synthesis ◽  
Transition States ◽  
Hydroxyl Group ◽  
Potential Utility ◽  
Silver Acetate ◽  
Steric Strain ◽  
Hydrolysis Of

Hydrolysis of dioxolenium (acyloxonium) ions fused to anchored six-membered rings gives almost exclusively that hydroxyester in which the ester function is axial (and the hydroxyl group equatorial). With the exception of the orthoformate, a group of related orthoesters reacted similarly. The potential utility of these observations in stereoselective synthesis is suggested by the following examples, (a) With trans-decalin-cis-2,3-diol (21) formation of the mono-benzoate via the orthoester leads to the axial ester (23d) in good yield; this procedure is complementary to reaction with benzoyl chloride and pyridine, which gives the equatorial ester (24d) as the only isolated product, (b) The action of silver acetate and iodine in wet acetic acid (the Woodward–Prevost reaction) on trans-Δ2-octaIin gives the axial acetate–equatorial alcohol (23b) again as the only significant product. The generality of this stereoselectivity is further supported by a number of individual examples drawn from the chemistry of carbohydrates. A rationalization is offered which qualitatively accounts for the observed stereoselectivity and its absence in the hydrolysis of the orthoformate, and which is based on the differences in steric strain among the possible transition states that fulfil the stereoelectronic requirements of dialkoxycarbonium ion formation.

New Cyclodimerization Reaction of (3,5-Di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetic Acid

2001 ◽  
Vol 66 (8) ◽  
pp. 1250-1256 ◽  
Author(s):  
Peter Nesvadba ◽  
Piotr Rzadek ◽  
Günther Rist
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Methyl Ester ◽  
Structure Elucidation ◽  
Methyl Esters ◽  
Tert Butyl ◽  
Isomeric Methyl

(3,5-Di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetic acid 1a underwent on heating a new cyclodimerization reaction affording a 1 : 1 mixture of the racemic cis- and trans-isomeric lactone-acids 2. The decisive structure elucidation of 2 was carried out after its mild esterification with diazomethane and separation of the racemic isomeric methyl esters 3a and 3b. The attempted esterification of 2 with methanol and sulfuric acid gave only the methyl diarylacetate 4. In contrast to 1a, which contains the carboxylic acid functionality no cyclodimerization was observed with the corresponding methyl ester 1b or nitrile 1c.

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