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.     

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 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

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.     

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.     

3-Phenoxy-1,2,3,4-tetrahydrobenzo[h]-quinoline

Thionyl chloride chlorinates 3-phenoxy-1,2,3,4-tetrahydrobenzo[h]quinolines in the 6 position at room temperature, but at 75–80°C it also partially chlorinates these compounds in the 4 position, which is accompanied by aromatization of the tetrahydropyridine ring. In the case of 3-(2,4,6-tribromophenoxy)-1,2,3,4-tetrahydrobenzo[h]quinoline, a tribromophenol residue is partially split out to give 4,6-dichlorobenzo[h]quinoline.     

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.     

Condensed pyridine bases. Reactions of 1-oxo-3,3,6-trimethyl-1,2,3,4-tetrahydrobenzo[b]furo-, benzo[b]thieno-, and indolo[2,3-c]quinolines with electrophilic reagents

A study has been made of thenitrationand bromination of 1-oxo-3,3,6-trimethyl-1,2,3,4-tetrahydrobenzo[bjfuro-, benzo[b]thieno-, and indolo[2,3-c]quinolines. It has been shown that the nitration is directed to the benzene ring (position 10). Bromination by molecular bromine takes place at the 6-CH₃ group of the pyridine fragment and yields a mixture of the corresponding nwnobromomethyl and dibromomethyl derivatives, whereas a dimethylacetamide-bromine complex bronzinates the methylene group in position 2, forming the -bromoketone. The Schmidt reaction of 1-oxo-3,3,6-trimetliyl-1,2,3,4-tetrahydrobenzo[b]furo-, benzol[b]thieno-, and indolo[2,3-c]quinolines have been investigated, as well as conversions of their oximes under conditions of the Beckmann rearrangement.L. M. Litvinenko Institute of Physical Organic Chemistry and Coal Tar Chemistry, National Academy of Sciences of the Ukraine, Donetsk 340114. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1124–1130, August, 1995. Original article submitted December 30, 1994; revision submitted May 28, 1995.     

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.     

Aroxydihydropyrans

The reaction of vinyl ethers and vinyl Sulfides of the quinoline series with unsaturated aldehydes gives 3,4-dihydro-2-pyranyloxy(mercapto)quinolines, in the hydrogenation of which, depending on the conditions, the multiple bonds in the pyran or pyridine ring are reduced. The ionization constants of the adducts were established by potentiometry. The vinyl ethers of 6-hydroxyquinoline, 8-hydroxy-1,2,3,4-tetrahydroquinoline, and 8-(S-vinyl)mercaptoquinoline were obtained for the first time.See [1] for communication X.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 375–378, March, 1976.     

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.     

Enamines of the 1,2,3,4-tetrahydroiso-quinoline series in the Chichibabin synthesis of pyrrolo[2,1-a]isoquinolines and in reaction with oxalyl chloride

It has been shown that the Chichibabin reaction of enamines of the 1,2,3,4-tetrahydroisoquinoline series and 1,2,3,4-tetrahydrobenzo[f]isoquinoline series with p-bromophenacyl bromide leads to pyrrolo[2,1-a]isoquinoline derivatives. The same heterocyclic system is obtained on interaction of 1-alkyl-3,4-dihydroisoquinolines or their benzo[f]-analogs with oxalyl chloride. The obtained dioxopyrrolines form derivatives of benzo[g]quinoxalino[2,3-b]indolizine on condensation with o-phenylenediamine. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1068–1074, July, 2007.     

Synthesis of 6-phenylthiobenzo[b]thiophenes

A method of synthesizing 2-acetylamino-7-hydroxy-6-phenylthio-3-carbethoxybenzo[b]thiophenes from 6-phenylthio-7-oxo-4,5,6,7-tetrahydrobenzo[b]thiophenes has been developed. A method is also proposed for synthesis of 7-phenylthiobenzothieno[2,3-d]pyrimidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 534–536, April, 1991.     

Autoxidative transformations of 2-substituted 3-alkyl-4-hydroxy-1-oxo-1, 2-dihydroisoquinolines

A method for the preparation of 2-substituted 3-alkyl-4-hydroxy-1-oxo-1, 2-dihydroisoquinolines is described. It is shown that 2, 3-dialkyl-substituted derivatives readily undergo autoxidation and dealkylation to give N-methylphthalonimide and 3-hydroperoxy and 3-hydroxy-2, 3-dialkyl-1, 4-dioxo-1,2,3,4-tetrahydroisoquinolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 789–792, June, 1978.     

Synthesis of dihydro-1,3-thiazine derivatives. II

1-Oxo-3-thioxo-5-hydroxy-2-acyl-2,3-dihydro-1H-1,3-thiazino[6,5-c]quinolines were obtained for the first time by condensation of 2-hydroxy-3-mercaptoquinoline-4-carboxylic acid with acyl isothiocyanates. Alkyl and acyl isothiocyanates react with 1-methyl-2-oxo-3-mercapto-1, 2-dihydroquinoline-4-carboxylic acid to give 1,5-dioxo-3-thioxo-2-alkyl (acyl)6-methyl-2, 3,5,6-tetrahydro-1H-1,3-thiazino [6,5-c] quinolines.See [1] for communication I.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 641–643, May, 1973.     

Condensed pyridine bases synthesis of some benzo[b]furo[2,3-c]-, benzo[b]- thieno[2,3-c]-, and benzo[b]selenopheno[2,3-c]-quinolines

Summary Condensation of benzo[b]furan-3(2H-one, benzo[b]thiophen-3(2H)-one and benzo[b]selenophen-3(2H)-one with dimedone gives 2-(3-heteryl)dimedones. Acylation of the latter leads to the corresponding tetracyclic pyrylium salts, from which condensed quinolines are obtained. Some condensed quinoline derivatives are obtained by reaction of 1-oxo-1,2,3,4-tetrahydroheterene[2,3-c]quinolines with sodium borohydride, hydrazine, and hydroxylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 321–326, March, 1994.     

Researches on 2, 1, 3-thia- and selenadiazole

4-Hydroxy-, 4-hydroxy-5-methyl-, 4-hydroxy-7-methylbenzo-2,1,3-thiadiazoles are polymorphous.4-Hydroxybenzo-2,1,3-thiadiazole (I), 4-hydroxy-5-methyl- and 4-hydroxy-7-methylbenzo-2, 1, 3-thiadiazoles (II and III) melt at 114–115°, 110–112°, 100–102° C, respectively, after recrystallization from water [2–4], but after recrystallization from petrol ether [5] they melt at 128–129°, 124–125°, and 119–120° C [5]. In this connection we recrystallized these phenols repeatedly from petrol ether after recrystallizing them from water, and their melting points rose as expected [5]. On the other hand, the compounds with melting points 128–129°, 124–125°, 119–120° C (ex petrol ether), after repeated crystallization from water melted at 114–115°, 110–112°, 100–102° C, respectively.For Part XXXVIII see [1].     

Pyrroles from ketoximes and acetylene. 30. The synthesis of 3-alkyl-2-arylpyrroles

Conditions were found for the synthesis of 3-alkyl-2-arylpyrroles using the Trofimov reaction at 50–70 °C both at elevated and atmospheric pressure. O-Vinyloximes and 3H-5-hydroxy-4,5-dihydropyrroles were isolated as intermediates.Communication 29, see ref. [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1501–1505, November, 1985.     

Investigation of naphthyridines. VII. Synthesis of 10-alkylamino-1,2,3,4-tetrahydrobenzo[b]-1,6-naphthyridines

10-Alkylamino-2-methy1-1,2,3,4-tetrahydrobenzo[b]-1,6-naphthyridines were obtained by cyclization of alkylamides of N-(1-methyl-4-piperidylidene)anthranilic acids and also by reaction of 10-chloro-2-methyl-1,2,3,4-tetrahydrobenzo-[b]-1,6-naphthyridines with amine hydrochlorides.See [1] for communication VI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 263–265, February, 1976.     

Reaction of arylenedioxytrihalophosphoranes with acetylenes 12. Alkylacetylenes in the reaction with 2,2,2-trihalobenzo-1,3,2-dioxaphospholes

A reaction of 2,2,2-trihalobenzo-1,3,2-dioxaphospholes with terminal alkylacetylenes proceeds under mild conditions (～20 °C) and leads to the formation of 4-alkylbenzo[e]-1,2-oxaphosphinine 2-oxide derivatives. The presence of aliphatic substituents in acetylene decreases (as compared to their aromatic counterparts described earlier) regioselectivity of halogenation of benzo fragment in 4-alkylbenzo[e]-1,2-oxaphosphinines: besides predominant 4-alkyl-2,6-dihalobenzo[e]-1,2-oxaphosphinines, minor 2,7- and 2,8-dihalo-substituted 4-alkylbenzo[e]-1,2-oxaphosphinines are formed. An unusual thermal isomerization of 4-alkyl-2-fluorobenzo[e]-1,2-oxaphosphinines to 4-alkylidene-2-fluoro-3,4-dihydrobenzo[e]-1,2-oxaphosphinines was discovered. Molecular and supramolecular structures of some 4-alkylbenzo[e]-1,2-oxaphosphinines were studied by X-ray diffraction analysis.