Fast and Efficient Nitration of Salicylic Acid and Some Other Aromatic Compounds over H3PO4/TiO2-ZrO2Using Nitric Acid

Salicylic acid and p-nitrophenol are almost quantitatively diiodinated when treated in alcoholic solution with iodine, hydrogen peroxide, and sulphuric, nitric, hydrochloric, or phosphoric acid. In glacial acetic acid solution salicylic acid gives good yields of the diiodo compound only in the presence of hydrochloric acid. No appreciable iodination occurs in the presence of sulphuric or nitric acid whilst 3,5-dibromosalicylic acid is formed with hydrobromic acid. Cinnamic acid reacts slowly with iodine, hydrogen peroxide, and sulphuric acid in methanol and ethanol solutions to give the corresponding α-iodo-β-alkoxy-β-phenylpropionic acids. Benzene homologues are readily iodinated in alcoholic solution in the presence of sulphuric or nitric acid although benzene does not react appreciably under similar conditions.

Download Full-text

Infrared spectra of aqueous sodium benzoates and salicylates in the carboxyl-stretching region: chelation in aqueous sodium salicylates

Canadian Journal of Chemistry ◽

10.1139/v69-758 ◽

1969 ◽

Vol 47 (24) ◽

pp. 4577-4588 ◽

Cited By ~ 34

Author(s):

G. E. Dunn ◽

R. S. McDonald

Keyword(s):

Salicylic Acid ◽

Carbon Tetrachloride ◽

Infrared Spectra ◽

Aromatic Compounds ◽

Deuterium Oxide ◽

Substituent Effects ◽

Good Evidence ◽

Frequency Region ◽

Aqueous Sodium ◽

Substituent Constants

Infrared spectra in the frequency region 1300–1760 cm−1 are reported for 41 substituted sodium benzoates and 10 substituted sodium salicylates in deuterium oxide solution, and for 9 substituted salicylic acids in chloroform and carbon tetrachloride solutions. Carboxylate stretching frequencies of benzoates and salicylates correlate poorly with substituent constants, but the asymmetric frequencies of benzoates and salicylates correlate well with each other, and the asymmetric frequencies of benzoates correlate well with the asymmetric frequencies of the corresponding nitrobenzenes. It is suggested that, among substituted aromatic compounds, group vibrations which couple with the ring vibrations may correlate well with similar vibrations of other groups, but not with coupled vibrations of different symmetry, uncoupled vibrations, or substituent constants. Chelation in chloroform solutions of salicylic acid dimers can be detected by its influence on substituent effects, but infrared spectra provide no good evidence for chelation in aqueous sodium salicylates.

Download Full-text

Addition Reactions in the Nitration of Some Polycyclic Aromatic Compounds

Canadian Journal of Chemistry ◽

10.1139/v72-538 ◽

1972 ◽

Vol 50 (20) ◽

pp. 3367-3372 ◽

Cited By ~ 6

Author(s):

A. Fischer ◽

D. R. A. Leonard

Keyword(s):

Nitric Acid ◽

Acetic Anhydride ◽

Nitro Group ◽

Aromatic Compounds ◽

Addition Reaction ◽

Polycyclic Aromatic Compounds ◽

Addition Reactions ◽

Polycyclic Aromatic ◽

Acetyl Nitrate

Reaction of 3-oxo-1,2,3,7,8,9,10,10a-octahydrocyclohepta[de]naphthalene with nitric acid in acetic anhydride gives two stereoisomeric 4-acetoxy-6a-nitro-3-oxo-1,2,3,4,6a,7,8,9,10,10a-decahydrocyclohepta[de]-naphthalenes as well as the expected nitro substitution products. Formation of these adducts from a substrate containing a meta-directing deactivating substituent shows that the 1,4-addition reaction of acetyl nitrate is more general than previously suspected. 1,4-Acetyl nitrate adducts are also formed from tetralin, benzsuberane, 5,6,7,8-tetrahydrocyclohepta[fg]acenaphthene, and 1,2,3,4,7,8,9,10-octahydrodicyclohepta[de,ij]naphthalene. Decomposition of the last two adducts gives in each case a product with the nitro group substituted into the alicyclic ring.

Download Full-text