SYNTHESIS OF 1,1-DI-( p-CARBOXYPHENYL)ETHANE AND ITS ESTERS

1956 ◽  
Vol 34 (3) ◽  
pp. 383-386
Author(s):  
Henry Bader ◽  
W. A. Edmiston
Keyword(s):  
Hydrogen Fluoride ◽  
Alkaline Hydrolysis ◽  
Diacid Chloride ◽  
Cuprous Cyanide ◽  
High Yields ◽  
Hydrolysis Of

The condensation of chlorobenzene with ethylidene diacetate in presence of fluosulphonic acid – hydrogen fluoride catalyst has been improved to give high yields of 1,1-di-(p-chlorophenyl)ethane, which was converted into the corresponding dinitrile by a modification of the cuprous cyanide method. Alkaline hydrolysis of the dinitrile gave 1,1-di-( p-carboxyphenyl)ethane. Its methyl and 2-ethylhexyl esters were prepared directly from the diacid or via the diacid chloride.

Synthesis of Pentacoordinated Spiro[4,4]phosphoranes by Reaction of Cyclic Phosphazenyl Anions with Epoxides. Study of their P-Remote Functionalization and Hydrolysis

Synthesis ◽  
2021 ◽  
Author(s):  
Pablo Manuel Sansores Peraza ◽  
Jesús García López ◽  
Yolanda Navarro ◽  
María José Iglesias ◽  
Fernando López Ortiz
Keyword(s):  
Benzoic Acid ◽  
Alkaline Hydrolysis ◽  
Phosphorus Atom ◽  
Bidentate Ligand ◽  
New Family ◽  
Acid Catalyzed ◽  
High Yields ◽  
Hydrolysis Of ◽  
Carbon Based

The synthesis of a new family of pentacoordinated spiro[4,4]phosphoranes stabilized by the ortho-benzamide bidentate ligand (oBA,-C6H4-2-C(O)NH-) through reaction of Cα -Cortho-dilithiated phosphazenes with oxiranes is reported. Mixtures of epimers that differ in configuration at the phosphorus atom were obtained with moderate to high yields and diastereoselectivities. C3-disubstituted derivatives could be separated, which provided access to enantiopure products arising from the reaction with (R)-2-phenyloxirane. Stereomutation was observed by heating the spirophosphoranes at 100 ºC. Directed ortho lithiation of spirophoshoranes followed by electrophilic quench reactions including carbon-based and heteroatom-based electrophiles afforded derivatives functionalized in remote position with respect to the phosphorus atom. Benzoic acid catalyzed hydrolysis of spirophosphoranes furnished ortho-(hydroxyalkylphosphoryl)benzamides by cleavage of the P‒O and P‒N bonds with retention of the phosphorus configuration. In contrast, alkaline hydrolysis led to the formation of γ-hydroxyphosphinic acids and benzamide.

Transformations of 3-(methylene)dihydro-2(3H)-furanone derivatives

1984 ◽  
Vol 49 (11) ◽  
pp. 2509-2519 ◽  
Author(s):  
Ctibor Mazal ◽  
Zdeněk Jurka ◽  
Jaroslav Jonas
Keyword(s):  
Vinyl Ether ◽  
Sodium Salt ◽  
Alkaline Hydrolysis ◽  
Sodium Azide ◽  
Potassium Cyanide ◽  
Aqueous Acetone ◽  
H Nmr ◽  
Nmr Spectrometry ◽  
High Yields ◽  
Hydrolysis Of

(E) and (Z)-3-(4-toluenesulfonyloxymethylene)dihydro-2(3H)-furanones ((E)-I) and ((Z-I) react with piperidine, pyrrolidine, morpholine, butanethiol, 4-toluenethiol, and 2-naphthalenethiol to give (E)-isomers of the corresponding enamines II-IV and thiomethylene derivatives V-VII in high yields. As has been shown, the reactions proceed with retention of configuration; the initially formed (Z)-II, (Z)-III, (Z)-IV, and (Z)-V isomerize rapidly to the thermodynamicaly more stable (E)-isomers. Ether IX was obtained by reaction of (E)-I with the (E)-isomer of sodium salt of 3-(hydroxymethylene)dihydro-2(3H)-furanone ((E)-VIII) and a mixture of ethers IX and X resulted from reaction of (Z)-I with sodium salt of (E)-VIII. Compounds (E)-I and (Z)-I afforded the corresponding azides(E)-XI and (Z)-XI upon treatment with sodium azide, and hydroxybutanoic acids (E)-XII and (Z)-XII with sodium hydroxide in aqueous acetone. Chloride (E)-XIII, prepared by reacting (E)-I with methanolic hydrogen chloride, furnished with piperdine, pyrrolidine, morpholine, or 2-naphthalenethiol the corresponding (E)-II, (E)-III, (E)-IV, and (E)-VII. Potassium cyanide reacted with (E)-I in dimethylsulfoxide to yield nitrile (E)-XIV. Cycloaddition of the azide (E)-XI to isobutyl vinyl ether or cyclohexyl vinyl ether proceeds quantitatively to give the respective triazolines (E)-XV and (E)-XVI. Alkaline hydrolysis of IX afforded the acid XVII. reduction of (E)-I, (Z)-I, and (E)-VII with chloralane gave the respective butanediols (E)-XVIII, (Z)-XVIII, and (E)-XIX, respectively. Configurations of these substances were elucidated by 1H NMR spectrometry.

Influence of medium on alkaline hydrolysis of succinic acid monomethyl and monopropyl esters

1980 ◽  
Vol 45 (11) ◽  
pp. 2873-2882
Author(s):  
Vladislav Holba ◽  
Ján Benko
Keyword(s):  
Succinic Acid ◽  
Kinetic Parameters ◽  
Alkaline Hydrolysis ◽  
Specific Interactions ◽  
Nonaqueous Media ◽  
The Media ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of alkaline hydrolysis of succinic acid monomethyl and monopropyl esters were studied in mixed aqueous-nonaqueous media at various temperatures and ionic strengths. The results of measurements are discussed in terms of electrostatic and specific interactions between the reactants and other components of the reaction mixture. The kinetic parameters in the media under study are related to the influence of the cosolvent on the solvation sphere of the reactants.

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).

Kinetic study of hydrolysis of benzoates. part xxvii. ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous Bu4NBr

2009 ◽  
Vol 74 (1) ◽  
pp. 29-42 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Signe Vahur ◽  
Oksana Travnikova ◽  
Ilmar A. Koppel
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Pure Water ◽  
Substituent Effects ◽  
Benzoic Acids ◽  
Resonance Effects ◽  
The Media ◽  
Substituted Benzoic Acids ◽  
Hydrolysis Of ◽  
Ortho Substituent

The second-order rate constants k (in dm3 mol–1 s–1) for alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2C6H5, have been measured spectrophotometrically in aqueous 0.5 and 2.25 M Bu4NBr at 25 °C. The substituent effects for para and meta derivatives were described using the Hammett relationship. For the ortho derivatives the Charton equation was used. For ortho-substituted esters two steric scales were involved: the EsB and the Charton steric (υ) constants. When going from pure water to aqueous 0.5 and 2.25 M Bu4NBr, the meta and para polar effects, the ortho inductive and resonance effects in alkaline hydrolysis of phenyl esters of substituted benzoic acids, became stronger nearly to the same extent as found for alkaline hydrolysis of C6H5CO2C6H4-X. The steric term of ortho-substituted esters was almost independent of the media considered. The rate constants of alkaline hydrolysis of ortho-, meta- and para-substituted phenyl benzoates (X-C6H4CO2C6H5, C6H5CO2C6H4-X) and alkyl benzoates, C6H5CO2R, in water, 0.5 and 2.25 M Bu4NBr were correlated with the corresponding IR stretching frequencies of carbonyl group, (ΔνCO)X.

Kinetic Study of Hydrolysis of Benzoates. Part XXVI. Variation of the Substituent Effect with Solvent in Alkaline Hydrolysis of Substituted Alkyl Benzoates

2006 ◽  
Vol 71 (11-12) ◽  
pp. 1557-1570 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Ilmar A. Koppel
Keyword(s):  
Kinetic Study ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Substituent Effect ◽  
Substituent Effects ◽  
Alkyl Substituent ◽  
Solvent Parameters ◽  
Substituent Constants ◽  
Hydrolysis Of ◽  
Main Factor

The second-order rate constants k2 (dm3 mol-1 s-1) for the alkaline hydrolysis of substituted alkyl benzoates C6H5CO2R have been measured spectrophotometrically in aqueous 0.5 M Bu4NBr at 50 and 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH, CH2C6H5, CH2CH2Cl, CH2CH2OCH3, CH2CH3) and in aqueous 5.3 M NaClO4 at 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH). The dependence of the alkyl substituent effects on different solvent parameters was studied using the following equations:      ∆ log k = c0 + c1σI + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆EσI + c7∆YσI + c8∆PσI     ∆ log k = c0 + c1σ* + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆Eσ* + c7∆Yσ* + c8∆Pσ* .  ∆ log k = log kR - log kCH3. σI and σ* are the Taft inductive and polar substituent constants. E, Y and P are the solvent electrophilicity, polarity and polarizability parameters, respectively. In the data treatment ∆E = ES - EH2O , ∆Y = YS - YH2O , ∆P = PS - PH2O were used. The solvent electrophilicity, E, was found to be the main factor responsible for changes in alkyl substituent effects with medium. When σI constants were used, variation of the polar term of alkyl substituents with the solvent electrophilicity E was found to be similar to that observed earlier for meta and para substituents, but twice less when σ* constants were used. The steric term for alkyl substituents was approximately independent of the solvent parameters.

scholarly journals MW irradiation and ionic liquids as green tools in hydrolyses and alcoholyses

2020 ◽  
Vol 10 (1) ◽  
pp. 001-010 ◽  
Author(s):  
Nikoletta Harsági ◽  
Betti Szőllősi ◽  
Nóra Zsuzsa Kiss ◽  
György Keglevich
Keyword(s):  
Ionic Liquids ◽  
Alkaline Hydrolysis ◽  
Alkyl Group ◽  
Phosphinic Acid ◽  
Reaction Times ◽  
Alternative Possibility ◽  
First Order ◽  
Pseudo First Order ◽  
Mw Irradiation ◽  
Hydrolysis Of

Abstract The optimized HCl-catalyzed hydrolysis of alkyl diphenylphosphinates is described. The reaction times and pseudo-first-order rate constants suggested the iPr > Me > Et ∼ Pr ∼ Bu order of reactivity in respect of the alkyl group of the phosphinates. The MW-assisted p-toluenesulfonic acid (PTSA)-catalyzed variation means a better alternative possibility due to the shorter reaction times, and the alkaline hydrolysis is another option. The transesterification of alkyl diphenylphosphinates took place only in the presence of suitable ionic liquids, such as butyl-methylimidazolium hexafluorophosphorate ([bmim][PF6]) and butyl-methylimidazolium tetrafluoroborate ([bmim][BF4]). The application of ethyl-methylimidazolium hydrosulfate ([emim][HSO4]) and butyl-methylimidazolium chloride ([bmim][Cl]) was not too efficient, as the formation of the ester was accompanied by the fission of the O–C bond resulting in the formation of Ph2P(O)OH. This surprising transformation may be utilized in the phosphinate → phosphinic acid conversion.

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