Substituent Effects of Phosphorus and Arsenic Containing Groups in Aromatic Substitution. IV. Nitration of Aromatic Phosphine Oxides

The nitration of some tertiary phosphine oxides ArP(O)R2 in aqueous sulfuric acid has been investigated. All compounds studied react as conjugate acids. When the phosphinyl group is bonded directly to the benzene ring, high deactivation and meta-orientation is found, accompanied in most cases by some substitution at the ortho position. The substituent effects of the "quasiphosphonium" group P(OH)R2+are compared with those of structurally related systems and are discussed in terms of pπ–dπ, interactions of the oxygen and the phosphorus atom.

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ChemInform Abstract: SUBSTITUENT EFFECTS OF PHOSPHORUS AND ARSENIC CONTAINING GROUPS IN AROMATIC SUBSTITUTION PART 4, NITRATION OF AROMATIC PHOSPHINE OXIDES

Chemischer Informationsdienst ◽

10.1002/chin.197539265 ◽

1975 ◽

Vol 6 (39) ◽

pp. no-no

Author(s):

EDMUND MALINSKI ◽

ANTONINA PIEKOS ◽

TOMASZ A. MODRO

Keyword(s):

Substituent Effects ◽

Phosphine Oxides ◽

Aromatic Substitution

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ChemInform Abstract: SUBSTITUENT EFFECTS ON IRON DIIMINE COMPLEXES. I. CORRELATIONS WITH THERMODYNAMIC AND SPECTRAL PROPERTIES IN AQUEOUS SULFURIC ACID

Chemischer Informationsdienst ◽

10.1002/chin.197640073 ◽

1976 ◽

Vol 7 (40) ◽

pp. no-no

Author(s):

H. LI CHUM ◽

T. RABOCKAI

Keyword(s):

Sulfuric Acid ◽

Spectral Properties ◽

Substituent Effects ◽

Aqueous Sulfuric Acid ◽

Diimine Complexes

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ChemInform Abstract: ELECTROPHILIC AROMATIC SUBSTITUTION. PART 23. THE NITRATION OF PHENOL AND THE E CRESOLS IN AQUEOUS SULFURIC ACID

Chemischer Informationsdienst ◽

10.1002/chin.198003191 ◽

1980 ◽

Vol 11 (3) ◽

Author(s):

R. G. COOMBES ◽

J. G. GOLDING ◽

P. HADJIGEORGIOU

Keyword(s):

Sulfuric Acid ◽

Electrophilic Aromatic Substitution ◽

Aromatic Substitution ◽

Aqueous Sulfuric Acid

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The Meyer Reaction of Phenylnitromethane in Acid. I. The Reactions of Phenyl-aci-nitromethane in Acid

Canadian Journal of Chemistry ◽

10.1139/v71-582 ◽

1971 ◽

Vol 49 (21) ◽

pp. 3483-3488 ◽

Cited By ~ 20

Author(s):

J. T. Edward ◽

P. H. Tremaine

Keyword(s):

Sulfuric Acid ◽

Room Temperature ◽

Isotope Effects ◽

Substituent Effects ◽

Benzohydroxamic Acid ◽

Aqueous Sulfuric Acid

Phenyl-aci-nitromethane reacts in aqueous sulfuric acid at room temperature to form phenylnitromethane and benzohydroxamic acid. The relative amounts of these two products depend on the concentration of the acid. Benzohydroxamic acid is formed by reaction of the intermediate, benzonitrile oxide, with water.Solvent effects, substituent effects, and isotope effects have been studied to determine mechanisms for these reactions of phenyl-aci-nitromethane.

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ChemInform Abstract: ELECTROPHILIC AROMATIC SUBSTITUTION. PART 16. THE NITRATION OF ANISOLE, O-METHYLANISOLE, AND P-METHYLANISOLE IN AQUEOUS SULFURIC ACID

Chemischer Informationsdienst ◽

10.1002/chin.197715141 ◽

1977 ◽

Vol 8 (15) ◽

pp. no-no

Author(s):

J. W. BARNETT ◽

R. B. MOODIE ◽

K. SCHOFIELD ◽

J. B. WESTON ◽

R. G. COOMBES ◽

...

Keyword(s):

Sulfuric Acid ◽

Electrophilic Aromatic Substitution ◽

Aromatic Substitution ◽

Aqueous Sulfuric Acid

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THE APPLICATION OF THE HAMMETT EQUATION TO ORTHO-SUBSTITUTED BENZENE REACTION SERIES

Canadian Journal of Chemistry ◽

10.1139/v60-338 ◽

1960 ◽

Vol 38 (12) ◽

pp. 2493-2499 ◽

Cited By ~ 35

Author(s):

Marvin Charton

Keyword(s):

Benzene Ring ◽

Substituent Effects ◽

Para Position ◽

Steric Effects ◽

Side Chain ◽

Ortho Position ◽

Reaction Site ◽

Hammett Equation ◽

Reaction Series ◽

Electrical Effect

The Hammett equation is directly applicable to ortho-substituted benzene reaction series in which reaction site and benzene ring are separated by some group Z, apparently due to the absence of steric effects in these series. The σp values are used in the correlations. Fourteen ortho-substituted benzene reaction series have been correlated. The electrical effect of a substituent in the ortho position is found to be about 0.75 times its effect in the para position. The effect of the side-chain Z in the transmission of substituent effects is OCH2 > SCH2 > CH = CH > SeCH2 > CH2CH2.

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