The transmission of polar effects. Part X. The esterification with diazodiphenyl-methane and the ionization of 9-substituted 10-anthroic and 8-substituted 1-naphthoic acids

Bowden, Keith; Parkin, D. C.

doi:10.1139/v69-025

Cited by 19 publications

(4 citation statements)

References 17 publications

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“…14 Estimates of the true pK a T values of the (phenylimino)methylcarboxylic acids in 30% aqueous DMSO can be made from the values of 2-substituted benzoic acids in the same medium 15 and of 8-substituted 1naphthoic acids and 4-phenanthroic acid in aqueous alcohols. 16 The para-σ value of the CH᎐ ᎐ NPh group is 0.42. 17 Thus, the estimated pK a T values of 2-[(phenylimino)methyl]benzoic, 8-[(phenylimino)methyl]-1-naphthoic and 5-[(phenylimino)methyl]-4-phenanthroic acids in 30% aqueous DMSO at 30 ЊC are 3.4 (±0.1), 3.5 (±0.1) and 3.3 (±0.2), respectively.…”

Section: Pk a Valuesmentioning

confidence: 97%

Ring–chain tautomerism. Part 9.1 2-Acylbenzamides, 8-acyl-1-naphthamides and 5-acyl-4-phenanthramides

Bowden¹,

Hiscocks²,

Perjéssy³

1998

J. Chem. Soc., Perkin Trans. 2

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Ring-chain tautomerism inN-methyl-and N-(substituted phenyl)-2-formylbenzamides, 2-benzoylbenzamides, 8-formyl-1-naphthamides, 8-benzoyl-1-naphthamides and 5-formyl-4phenanthramides has been investigated by IR and 1 H NMR spectroscopy and the measurement of their pK a values in 30% (v/v) dimethyl sulfoxide-water. The tautomeric pair synthesised, i.e. hydroxylactamacylamide or aminolactone-iminocarboxylic acid, appears to be a function of the method of preparation and/or the basicity of amine used. The cyclic tautomer, i.e. hydroxylactam or aminolactone, is predominant in all cases studied. However, equilibrium constants have been estimated from the pK a values for aminolactone-iminocarboxylic acid tautomerisation in which the effect of the links follow similar trends as found for the corresponding hydroxylactone-acylcarboxylic acid tautomeric systems.

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Section: Pk a Valuesmentioning

confidence: 97%

Ring–chain tautomerism. Part 9.1 2-Acylbenzamides, 8-acyl-1-naphthamides and 5-acyl-4-phenanthramides

Bowden¹,

Hiscocks²,

Perjéssy³

1998

J. Chem. Soc., Perkin Trans. 2

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“…Acids with Diazodiphenylmethane The rate coefficients for the esterification of the arylaliphatic carboxylic acids with diazodiphenylmethane in ethanol at 30" are shown in Table I (acids [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17].…”

Section: Esterijication Of the Arylaliphatic Carboxylicmentioning

confidence: 99%

Transmission of polar effects. Part XI. Polar and steric effects in the reactions of arylaliphatic carboxylic acids

Bowden¹,

Young²

1969

Can. J. Chem.

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The rate coefficients for the reaction with diazodiphenylmethane in ethanol at 30" and the acidcatalyzed esterification with methanol at 60' of a number of arylaliphatic carboxylic acids and their pK, values in 80% Zmethoxyethanol-water have been measured. Rate coefficients havealso been measured for the alkaline hydrolysis in 70% dioxan-water of their 2-diethylaminoethyl esters at 45". The pK, values and diazodiphenylmethane esterification rate coefficients were also measured for a series of 2-substituted fluorene-9-carboxylic acids. The latter results have been correlated by Hammett equations and the transmission of polar effects in fluorene is discussed. Polar and steric substituent constants are evaluated for the arylaliphatic systems. These values are used to successfully correlate the hydrolysis and ionization reactions using the Taft-Ingold equation.

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“…However the preparation of a mixture of acid 4 and its 5-isomer was described by Whitmore and Fox 4. Although acid 1 has been the subject of several physical organic studies, either no reference is given to the method of synthesis, or reference was given to the Whitmore-Rule procedure 6–9. Shechter’s group modified the classical Whitmore procedure and employed it for the preparation of 8-bromo acid ( 5 ) and extended it to the preparation of 8-iodo-1-naphthoic acid ( 6 ) 10.…”

mentioning

confidence: 99%

8-Chloro- and 5,8-Dichloro-1-naphthoic Acids

Chen¹,

Smith²,

Huffman³

2010

Organic Preparations and Procedures International

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In connection with our program directed toward the development of structure-activity relationships of cannabimimetic 1-alkyl-3-(1-naphthoyl)indoles 1,2 we needed synthetically useful quantities of 8-chloro-1-naphthoic acid (1). The synthesis of acid 1 from 1,8-naphthalic anhydride (2) via anhydro-8-hydroxymercuri-1-naphthoic acid (3) and 8-chloromercuri-1-naphthoic acid (4) by treatment with the elemental halogen was described originally by Whitmore during the course of his studies on the mercuration of aromatic compounds is shown in Scheme 1. 3,4 A modification of the Whitmore procedure was employed by Rule and Barnett to obtain modest yields of acid 1 and 8-bromo-1-naphthoic acid (5). 5 Although Rule and Barnett mention that 8-chloromercuri-1-naphthoic acid was prepared as described by Leuck et al. 3 there is no mention of chloromercuri acid 4 in the paper which was cited. However the preparation of a mixture of acid 4 and its 5-isomer was described by Whitmore and Fox. 4 Although acid 1 has been the subject of several physical organic studies, either no reference is given to the method of synthesis, or reference was given to the Whitmore-Rule procedure. 6-9 Shechter's group modified the classical Whitmore procedure and employed it for the preparation of 8-bromo acid (5) and extended it to the preparation of 8-iodo-1-naphthoic acid (6). 10 These workers employed anhydro-8-hydroxymercuri-1-naphthoic acid (3) as an intermediate, however treatment of 3 with chlorine gave 5,8-dichloro-1-naphthoic acid (7) as the only isolable product.We were able to repeat the preparation of anhydro acid 3 and its reaction with bromine and iodine to provide bromo and iodo acids 5 and 6 in unoptimized yields of 84% and 52% respectively. 11 Initially, in order to avoid the use of elemental chlorine and hopefully to suppress the formation of 5,8-dichloro-1-naphthoic acid, numerous attempts were made under a variety of conditions to prepare acid 1 by reaction of anhydro acid 3 with Nchlorosuccinimide or 1,3-dichloro-5,5-dimethylhydantoin as a chlorine source. In one experiment a 36% yield of crude acid 1 was obtained; however, this compound could not be obtained even under apparently identical conditions. In another run, the crude reaction products were converted to mixtures of methyl esters, which were analyzed by GC/MS. The principal constituents of this mixture were methyl 8-chloro-1-naphthoate (41%) and a dichloro ester, presumably methyl 5,8-dichloro-1-naphthoate (53%). A methyl trichloro-1-naphthoate (7%) was found in low yield but was not otherwise characterized.

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The transmission of polar effects. Part X. The esterification with diazodiphenyl-methane and the ionization of 9-substituted 10-anthroic and 8-substituted 1-naphthoic acids

Cited by 19 publications

References 17 publications

Ring–chain tautomerism. Part 9.1 2-Acylbenzamides, 8-acyl-1-naphthamides and 5-acyl-4-phenanthramides

Ring–chain tautomerism. Part 9.1 2-Acylbenzamides, 8-acyl-1-naphthamides and 5-acyl-4-phenanthramides

Transmission of polar effects. Part XI. Polar and steric effects in the reactions of arylaliphatic carboxylic acids

8-Chloro- and 5,8-Dichloro-1-naphthoic Acids

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