Adamantylation of nitro-substituted aromatic amines in protic acids

Adamantylation of mono-and dinitro-substituted aromatic amines in sulfuric and phosphoric acids and in a mixture of phosphoric and acetic acids gives mainly the corresponding N-adamantyl derivatives. The results of kinetic measurements showed reversible character of the process.     

A study of the reaction products from epichlorohydrin and aromatic amines

A method of preparing N-phenyl-3-hydroxy-1, 2, 3, 4-tetrahydroquinoline is developed, and some of its conversion products are obtained. The structures of N-phenyl-3-chloro-1, 2, 3, 4-tetrahydroquinoline and N-phenyl-1, 2, 3, 4-tetrahydroqunoline. are proved, the latter being formed by heating N-phenyl-3-hydroxy-1, 2, 3, 4-tetrahydroquinoline with concentrated hydrochloric acid.     

Oxidation of aromatic amines with chromyl chloride-II : Studies on the intermediate solid adducts

Oxidation of aromatic primary amines with chromyl chloride results in the formation of intermediate solid Etard adducts (C. Nallaiah and J.A. Strickson, Tetrahedron 42,4083 ( 1986)). Elemental analysis of the adducts indicates that the anilines, which give 1,4-benzoquinone anils in good yields, form adducts close to a 1:1 stoichiometry with the oxidant while those forming 1,4-benzoquinones in substantial yields form 1:2 adducts. Magnetic measurements on the adducts reveal that chromium atoms are mainly present m the oxidation state chromium(IV). IR studies indicate that the adducts comprise of 1,4-benzoquinone imines and di-imines as ligands and that giant molecules are formed by chloro and hydroxy bridges.     

Investigation of the products of reaction of epichlorohydrin with aromatic amines

It is shown that the reaction of thionyl chloride with 1, 2, 3, 4-tetrahydro-3-hydroxy-6-methyl[h]benzoquinoline leads not only to aromatization of the tetrahydroquinoline ring, but also to chlorination of the methyl group.For Part II see [3].     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

4-Hydroxy- and 4-oxo-1,2,3,4-tetrahydrobenzo[h]quinolines were synthesized. Benzo[h]-quinoline, 1,2,3,4-tetrahydrobenzo[h]quinoline, and a dimeric compound are formed when the 4-hydroxy derivative is heated with hydrochloric acid or without it. The reaction of 4-hydroxy-1,2,3,4-tetrahydrobenzoth]quinoline with thionyl chloride was carried out.See [1] for communication X.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 548–551, April, 1972.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

The synthesis of 2-(hydroxymethyl)benz [g]indoline derivatives by heating N-acyl derivatives of 2-(chloromethyl)benz[g]indoline in dimethyl sulfoxide is described. 3,6-Dichloro-1,2,3,4-tetrahydrobenzo[h]quinoline, 5-chloroazirido[1,2-a]benz[g]indoline, and derivatives of 2-substituted 5-chlorobenz [g]indoline were synthesized.See [1] for communication XITranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1111–1116, August, 1972.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

N-(-Chloro--hydroxy)propyl derivatives of 5-chloro-1-naphthylamine, 8-chloro-1-naphthylamine, and 5-cyano-1-naphthylamine were obtained. They were cyclized to 1,2,3,4-tetrahydro-3-hydroxy-7-chlorobenzo[f]quinoline (II), 1,2,3,4-tetrahydro-3-hydroxy-10-chlorobenzo-[fJquinoline (VII), and 1,2,3,4-tetrahydro-3-hydroxy-7-cyanobenzo[f]quinoline (X). Chlorination at the 6 position to form 1,2,3,4-tetrahydro-3-hydroxy-6,7-dichlorobenzo[f]quinoline occurs under the action of thionyl chloride on II at room temperature. The action of thionyl chloride on II, VII, and X at elevated temperatures leads not only to chlorination at the 6 position but also to aromatization of the tetrahydropyridine ring to form, respectively, 6,7-dichlorobenzo[f]quinoline (V), 6,10-dichlorobenzo[f]quinoline (VIII), and 6-chloro-7-cyanobenzo[f]quinoline (XIII).See [5] for Communication V.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1522–1525, November, 1970.     

Investigations of the products of the reaction of epichlorohydrin with aromatic amines

Heating 3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline with phosphorus oxychloride gave a mixture of isomeric 3-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline and 2-(chloromethyl)-benz[g]indoline, which are converted to a mixture of 3-benzoyloxy-1,2,3,4-tetrahydrobenzo-[h]quinoline and 2-(benzoyloxymethyl)benz[g]indoline on reaction with potassium benzoate. Saponification of 2-(benzoyloxymethyl)benz[g]indoline gave 2-(hydroxymethyl)benz[g]indoline. The reaction of the isomeric chloro derivatives with potassium cyanide gave 2-(benz[g]-indolinyl)acetonitrile.See [1] for communication IX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 362–366, March, 1972.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

The ethyl group of 3-hydroxy-6-ethyl-1,2,3,4-tetrahydrobenzo[h]quinoline is chlorinated and the tetrahydropyridine ring is aromatized under the influence of thionyl chloride. The corresponding 6-alkylbenzo[h]quinolines and 6-alkyl-1,2,3,4-tetrahydrobenzo[h]quinolines are formed when 3-hydroxy-6-alkyl-1,2,3,4-tetrahydrobenzo[h]quinolines are heated with polyphosphoric acid at 200–205°C, but only 6-alkylbenzo[h]quinolines are formed at up to 270°.See [1] for communication VIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1403–1406, October, 1971.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

The action of hydrogen halides on 7a,8-dihydro-7H-azirino[1,2-]benz[g]indole gives 2-halomethyl-2,3-dihydro-1H-benz[g]indoles and 3-halo-1,2,3,4-tetrahydrobenzo[h]quinolines, which were converted to the corresponding N-nitroso derivatives and then to the isonitroso derivatives. 2-(Benzoxymethyl)-2,3-dihydro-1H-benz[g]indole hydrohalides were obtained by heating 1-benzoyl-2-halomethyl-2,3-dihydro-1H-benz[g]indoles. The reaction of 3-halo-1,2,3,4-tetrahydrobenzo[h]quinolines with thionyl chloride at room temperature gives 3-halo-6-chloro-1,2,3,4-tetrahydrobenzo[h]quinolines, while refluxing with thionyl chloride gives 6-chlorobenzo[h]quinoline.See [1] for communication XVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 342–346, March, 1973.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

A relatively simple method is proposed for the preparation of 4-hydroxyquinoline derivatives from the corresponding 4-oxo-1,2,3,4-tetrahydroquinoline derivatives. 4-Hydroxy-6-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline is readily converted to a mixture of 6-chlorobenzo[h]-quinoline and 6-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline.See [1] for communication XIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1224–1227, September, 1972.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

5,6-Dichlorobenzo[f]quinoline is formed by the action of thionyl chloride on 3-hydroxy-5-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline hydrochloride. 7-Chlorobenzo[f]quinoline and 7-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline are obtained in good yields by heating 3-hydroxy-7-chloro-1,2,3,4-tetrahydrobenzo[f]quinoline with orthophosphoric acid, while benzo[f]quinoline is also obtained by heating it with polyphosphoric acid.See [1] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 108–111, January, 1971.     

Regioselective copper-catalyzed amination of bromobenzoic acids using aliphatic and aromatic amines

A chemo- and regioselective copper-catalyzed cross-coupling procedure for amination of 2-bromobenzoic acids is described. The method eliminates the need for acid protection and produces N-aryl and N-alkyl anthranilic acid derivatives in up to 99% yield. N-(1-Pyrene)anthranilic acid has been employed in metal ion-selective fluorosensing. Titration experiments showed that this pyrene-derived amino acid forms an equimolar complex with Hg(II) in water resulting in selective fluorescence quenching even in the presence of other metal ions such as Zn(II) and Cd(II).     

Structure and reactivity of the condensation products of aromatic amines with aliphatic aldehydes

A number of previously undescribed propylidenearylamine dimers have been synthesized by the interaction of propionaldehyde with a series of para-substituted anilines(R=H, CH₃, OCH₃, F, Cl, Br, I) and with-naphthylamine. The structure of the bis-propylidenearylamines has been established by a study of their IR and UV spectra. It has been shown that all the bis-propylidenearylamines, except for bis(propylidene-p-fluoroaniline), have the structure of 2-ethyl-3-methyl-4-arylamino-1, 2, 3, 4-tetrahydroquinolines. The dipole moments of the bis(propylidene-p-R-anilines) have been determined. Comparison of the values obtained with the calculated values indicates that the most favorable molecular conformation of the bispropylidenearylamines is a tetrahydroquinoline half-chain with quasi-equatorial positions for the 4-NHAr and NH groups and an equatorial 3-CH₃ group. In contrast to the bis-ethylideneanilines, we did not succeed in finding other stable conformers for the bis-propylidene derivatives. It has been established that bis (propylidene-p-fluoroaniline) has the 1, 3-bis (p-fluorophenylamino)-2-ethyl-1-hexene structure.For communication VI, see [1].     

A study of the products of the reaction of epichlorohydrin with aromatic amines

The halogenation of 1,2,3,4-tetrahydrobenzo[h]quinoline and of 3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline and its O-benzoyl and N,O-dibenzoyl derivatives has been studied. The action of thionyl chloride or bromide on 1,2,3,4-tetrahydrobenzo[h]quinoline at room temperature gives 6-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline and 6-bromo-1,2,3,4-tetrahydrobenzo[h]quinoline. When 6-chloro-3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline is heated with thionyl chloride, aromatization of the tetrahydropyridine ring takes place, and when 6-bromo-3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline is heated with thionyl chloride, in addition to the aromatization of the tetrahydropyridine ring the bromine atom is replaced by a chlorine atom with the formation of 6-chlorobenzo[h]quinoline. 6-Bromobenzo[h]quinolme has been obtained by heating 3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline with thionyl bromide.For Communication IV, see [6].Translated from Khimiya Geterotsiklicheskikh Soedinenii.Vol. 6,No.7, pp. 969–973, July, 1970.     

Determination of aromatic amines formed from azo colorants in toy products

A study for the determination of the aromatic amines formed after reduction of the azo colorants mostly used in toys was conducted. Sodium dithionite was used in the reductive cleavage of the azo group for the dyes, and the released amines were subsequently analysed by high-performance liquid chromatography with UV detection. The influence of different variables related to the reduction process was investigated by the use of a full-level factorial design, where most significant parameters as well as order interactions were studied. Reduction profiles for each colorant were obtained by studying the changes in the amount of amine obtained with different dithionite/colorant ratios. The expected aromatic amines forming azo colorants were detected, and in the presence of a nitro group a further reduction was observed. The yield of the total reduction process was determined by using standard addition of different quantities of amines to the colorants.