The hydrolysis of (π-C6H6)Cr(π-C6F5CO2C2H5): an unexpected decarboxylation

1986 ◽  
Vol 64 (6) ◽  
pp. 1170-1172 ◽  
Author(s):  
Michael J. McGlinchey ◽  
Hao Nguyen
Keyword(s):  
Carboxylic Acid ◽  
Good Yield ◽  
Compound C ◽  
Sandwich Compound ◽  
Basic Hydrolysis ◽  
Hydrolysis Of

The attempted basic hydrolysis of the ester sandwich compound (C6H6)Cr(C6F5CO2Et) did not yield the expected carboxylic acid but instead produced (C6H6)Cr(C6F5H) in good yield together with traces of (C6H6)Cr(C6HF4OMe). Attempts to trap a benzyne intermediate were unsuccessful and the mechanism of decarboxylation is discussed in terms of internal chelation at the chromium centre.

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.

1,4-Cycloheptadienes: preparation and comparison of their proton magnetic resonance spectra with those of the corresponding cycloheptatrienes

1977 ◽  
Vol 55 (2) ◽  
pp. 251-258 ◽  
Author(s):  
Ivan Pikulik ◽  
Ronald F. Childs
Keyword(s):  
Magnetic Resonance ◽  
Good Yield ◽  
Proton Magnetic Resonance ◽  
Copper Complexes ◽  
Ring Current ◽  
Catalytic Reduction ◽  
Azo Compounds ◽  
Pmr Spectra ◽  
Basic Hydrolysis ◽  
Hydrolysis Of

A general route to 3-substituted cyclohepta-1,4-dienes is described in this paper. 7-Substituted cycloheptatrienes were used as starting materials and these were reacted with 4-phenyl-1,2,4-triazoline-3,5-dione to give 4 + 2 cycloaddition products of the norcaradiene form of the cycloheptatrienes. Catalytic reduction of these adducts gave 9-substituted 4-phenyl-2,4,6-triazatetracyclo[5.3.2.02,6.08,10]dodeca-3,5-diones in good yield. Basic hydrolysis of the hetero-cyclic ring of these products followed by Cu2+ oxidation of the resulting hydrazo compounds gave the copper complexes of substituted 6,7-diazatricyclo[3.2.2.02,4]non-6-enes. The azo compounds, formed on decomplexation of the copper complexes, readily lost nitrogen to give 3-substituted cyclohepta-l,4-dienes. Care had to be taken during these last steps as the cyclo-heptadienes with carboxylate substituents very readily isomerized to the conjugated isomers. The pmr spectra of the cyclohepta-l,4-dienes and related cycloheptatrienes are compared and discussed in terms of the presence of an induced diamagnetic ring current in the latter systems.

THE STRUCTURE OF RYANODINE. I

1951 ◽  
Vol 29 (11) ◽  
pp. 905-910 ◽  
Author(s):  
R. B. Kelly ◽  
D. J. Whittingham ◽  
K. Wiesner
Keyword(s):  
Carboxylic Acid ◽  
Alkaline Hydrolysis ◽  
Periodic Acid ◽  
Crystalline Substance ◽  
Alkaline Fusion ◽  
Compound C ◽  
Hydrolysis Of

Ryanodine consumes one mole of periodic acid and gives oxoryanodine C25H33O9N. Splitting off water from ryanodine gives anhydroryanodine C25H33O8N. The analyses of these two derivatives are therefore in agreement with the formula for ryanodine C25H35O9N. Alkaline hydrolysis of ryanodine gives pyrrole-α-carboxylic acid and an alcohol C20H32O8. This alcohol splits off water to give a compound C20H30O7. Alkaline hydrolysis of oxoryanodine consumes three moles of alkali and gives a mixture of low molecular acidic products. Alkaline fusion of oxoryanodine gives a neutral aromatic nitrogen-free crystalline substance.

A FACILE SYNTHESIS AND REACTIONS OF AMINO SELENOLO[2,3-b]PYRIDINE CARBOXYLATE

2015 ◽  
Vol 12 (1) ◽  
pp. 3910-3918 ◽  
Author(s):  
Dr Remon M Zaki ◽  
Prof Adel M. Kamal El-Dean ◽  
Dr Nermin A Marzouk ◽  
Prof Jehan A Micky ◽  
Mrs Rasha H Ahmed
Keyword(s):  
Biological Activity ◽  
Carbonyl Compounds ◽  
Mass Spectra ◽  
The Other ◽  
Pyridine Derivatives ◽  
Facile Synthesis ◽  
High Biological Activity ◽  
Basic Hydrolysis ◽  
Pyridine Carboxylate ◽  
Hydrolysis Of

 Incorporating selenium metal bonded to the pyridine nucleus was achieved by the reaction of selenium metal with 2-chloropyridine carbonitrile 1 in the presence of sodium borohydride as reducing agent. The resulting non isolated selanyl sodium salt was subjected to react with various α-halogenated carbonyl compounds to afford the selenyl pyridine derivatives 3a-f  which compounds 3a-d underwent Thorpe-Ziegler cyclization to give 1-amino-2-substitutedselenolo[2,3-b]pyridine compounds 4a-d, while the other compounds 3e,f failed to be cyclized. Basic hydrolysis of amino selenolo[2,3-b]pyridine carboxylate 4a followed by decarboxylation furnished the corresponding amino selenolopyridine compound 6 which was used as a versatile precursor for synthesis of other heterocyclic compound 7-16. All the newly synthesized compounds were established by elemental and spectral analysis (IR, 1H NMR) in addition to mass spectra for some of them hoping these compounds afforded high biological activity.

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

The inner salt 4-carboxy-2-(pyridinium-4-yl)-1H-imidazole-5-carboxylate monohydrate

2006 ◽  
Vol 62 (7) ◽  
pp. o2751-o2752 ◽  
Author(s):  
Ting Sun ◽  
Jian-Ping Ma ◽  
Ru-Qi Huang ◽  
Yu-Bin Dong
Keyword(s):  
Carboxylic Acid ◽  
Dihedral Angle ◽  
Title Compound ◽  
Acid Group ◽  
Planar Structure ◽  
Carboxyl Group ◽  
Carboxylic Acid Group ◽  
Pyridyl Group ◽  
Compound C

In the title compound, C10H7N3O4·H2O, one carboxyl group is deprotonated and the pyridyl group is protonated. The inner salt molecule has a planar structure, apart from the carboxylic acid group, which is tilted from the imidazole plane by a small dihedral angle of 7.3 (3)°.

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