Synthesis and properties of sym-triazine derivatives. 3. alkoxylation of 2-alkyl-4,6-bis(trichloromethyl)-sym-triazines containing higher alkyl radicals

Nucleophilic substitution reactions of trichloromethyl groups in 2-alkyl-4,6-bis-(trichloromethyl)-sym-triazines by alkoxy radicals were studied. It was shown that in the presence of sodium alcoholates, two CCl₃ groups are replaced, and the corresponding 2,4-dialkoxy-6-alkyl-sym-triazines are formed. The products of partial replacement, 2-alkoxy-4-trichloromethyl-6-alkyl-sym-triazines, were synthesized by heating the initial sym-triazines with alcohols in the presence of tertiary amines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1674–1677, December, 1984.     

Synthesis and properties of sym-triazine derivatives

N-Substituted 2,4-diamino-6-furyl-sym-triazines were synthesized by cyclocondensation of furancarboxylic acid esters with biguanides. 2-Amino-4,6-disubstituted sym-triazines containing furyl residues were obtained by reacting furancarboxylic acid nitriles with guanidine or furancarboxylic acid esters with N-imidoylguanidines. Aminotriazines of this type are also formed in condensation of N-acylguanidines with nitriles or imino esters.See [1] for 8.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1250–1256, September, 1992.     

sym-triazine derivatives. 9. Reaction of sym-triazines containing trichloromethyl and ethoxycarbonyl groups with phenylhydrazine

Using the example of the reaction of 1,3,5-triazines simultaneously containing trichloromethyl and ethoxycarbonyl substituents with phenylhydrazine, it was shown that the presence of even one ester group leads to ring transformation. Depending on the number of the ester groups in the initial 1,3,5-triazine, the reaction products are either 1,2,4-triazole or 1,2,4-triazine derivatives.For Communication 8, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1655–1664, December, 1990.     

Synthesis and properties of derivatives of sym-triazines. 11. Synthesis of 2-amino-sym-triazines containing alkyl radicals

2-Amino-4,6-dialkyl-sym-triazenes were synthesized by the condensation of aliphatic nitriles with guanidine. 2-Amino-4-alkyl-6-substituted sym-triazines were prepared by the reaction of N-acylguanidines with nitriles or imino esters. Aminotriazines of this type are also formed in the condensation of N-imidoylguanidines with esters.For Communication 10, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1271–1276, September, 1993.     

Synthesis and properties of derivatives of sym-triazine. 5. Synthesis and mass spectrometric study of carbamide derivatives of sym-triazine

The reaction of 2-amino- and 2,4-diamino-sym-triazines with nitrourea and phenyl isocyanate was studied; it gives N-mono- and N,N-disubstituted ureas that contain sym-triazine segments. General features were established for the decomposition of carbamide derivatives of sym-triazine under electron impact.For communication 4, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 356–362, March, 1987.     

Synthesis and properties of derivatives ofsym-triazine. 15. Synthesis of amine derivatives ofsym-triazine that contain indole groups

By the cyclocondensation of imino esters of acids of the indole series with N-acylguanidines, 2-amino-4,6-disubstituted sym-triazine are obtained that contain indole groups. The reaction of N-(indolyl-3-imidolyl)-guanidine with esters of carboxylic acids leads to 2-amino-4-(3-indolyl)-6-substituted sym-triazines. Indolyl-containing N-subsitituted 2,4-diamino-sym-trizines are synthesized by the reaction of imino esters of indole acids with biguanides. Similar products are also formed when 2-amino-4-trichloromethyl-sym-triazines that contain indole substituents react with dimethylamine, morpholine, or furfurylamine.I. M. Gubkin State Petroleum and Gas Academy, Moscow, 117917. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 214–223, February, 1995. Original article submitted December 21, 1994.     

Synthesis and properties of derivatives of symtriazine. 17. Synthesis of 2-methyl-4,6-disubstituted and 2,4-dimethyl-6-substituted sym-triazines by reduction of the corresponding trichloromethyl derivatives

The reduction of trichloromethyl groups in sym-triazine derivatives to methyl groups is studied. It is shown that 2-R-4, 6-bis (trichloromethyl)-sym-triazines can be reduced to 2-R-4, 6-dirnethyl-sym-triazines with zinc dust in ethanol or with lithium aluminum hydride in THF. 2-Amino, N-substituted 2-amino-, and 2-alkoxy-4-trichloromethyl-6-R-sym-triazines are reduced to the corresponding methyl derivatives by boiling with lithium aluminum hydride in dibutyl ether.I. M. Gubkin State Petroleum and Gas Academy, Moscow 117917. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 667–673, May, 1995. Original article submitted March 23, 1995.     

Synthesis and properties of derivatives ofsym-triazine. 16. Synthesis of amine and diamine derivatives ofsym-triazine containing sterically hindered phenol groups from 6-alkyl(aryl)thio-2,4-bis(trichloromethyl)-sym-triazine

The reaction of 6-alkyl(aryl)thio-2,4-bis(trichloromethyl)-sym-triazines with ammonia and primary and secondary amines is studies. It is shown that, depending on the reaction conditions, the replacement of either one or both of the trichloromethyl groups takes place. 6-alkyl(aryl)thio-2,4-diamono-sym-triazines containing sterically hindered phenol groups are synthesized.I. M. Gubkin State Petroleum and Gas Academy, Moscow, 117917. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 224–231., Ferbruary, 1995. Original article submitted December 21, 1994.     

Synthesis and properties of sym-triazene derivatives 12. Synthesis of 2,4-bis(trichloromethyl)-6-substituted sym-triazenes containing a sterically hindered phenol group

6-Substituted 2,4-bis(trichloromethyl)-sym-triazet:es containing the 2,6-di-tert-butylphenol group are synthesized by simultaneous cyclotrimerization of trichloroacetonitrile with the nitrile or thiocyanate derivative of the sterically hindered phenol in the presence of gaseous HCl. Significant amounts of 2,4,6-tris(trichloromethyl)-sym-triazene are formed as a byproduct.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 240–243, February, 1994. Original article submitted January 19, 1994.     

Nuclear Quadrupole Resonance and Stereochemistry III. Trichloromethyl derivatives

³⁵Cl nuclear quadrupole resonance frequencies are reported of the chlorine atoms in the trichloromethyl group of benzotrichlorides and trichloromethyl derivatives of heterocyclic molecules. They are compared with previously reported results for the same group attached to other planar conjugated radicals. In such compounds the three chlorine atoms cannot be equivalent and all the results are discussed from the point of view of possible orientation-dependant hyperconjugation between the C? Cl bonds and the conjugated moiety, particularly with reference to the marked effects observed in trichloromethyl ethers reported in part I of this series. In the benzo-trichloride and indeed most of the compounds discussed such effects are small.     

Synthesis and properties of sym-triazine derivatives. 7. Synthesis of pyridyl-substituted 2-amino- and 2,4-diamino-sym-triazines

N-Substituted 2,4-diamino-6-pyridyl-sym-triazines were synthesized by cyclocondensation of pyridinecarboxylic acid esters with biguanides. 4,6-Disubstituted 2-amino-sym-triazines containing pyridyl residues were obtained by the reaction of pyridinecarboxylic acid nitriles with guanidine or of pyridinecarboxylic acid esters with N-imidoylguanidines. Aminotriazines of this type are also formed in the condensation of N-acylguanidines with nitriles or imino esters. The general principles of the fragmentation of 2-amino-4-dialkylamino-6-pyridyl-sym-triazines under the influence of electron impact were established.See [1] for Communication 6.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 674–680, May, 1988.     

Synthesis and properties of sym-triazines. 10 Synthesis of 2,4-diamino-sym-triazines containing a sterically hindered phenol substituent

Condensation of N-(4-hydroxy-3,5-di-tert-butylphenyl)biguanide with esters in the presence of catalytic amounts of sodium ethylate gives 2-amino-4-(4-hydroxy-3,5-di-tert-butylanilino)-6-substituted sym-triazines. When the trichloroacetate ester is used the main product is 2-amino-4-(4-hydroxy-3,5-di-tert-butylanilino)-6-oxo-1(5)H-sym-triazine.For communication 9 see [1]Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1395–1399, October, 1992.     

Herbicidal hydroxylamine derivatives

The energies of intermolecular hydrogen bonding for eight amino derivatives of sym-triazines were obtained from the temperature dependence of the equilibrium constants, which were determined by ebullioscopic and cryoscopic methods. It is shown that the investigated compounds form cyclic, centrosymmetrical dimers under the influence of hydrogen bonds. The nitrogen in the 1 or 5 position of the ring is a proton acceptor.See [1] for communication XXXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 124–128, January, 1972.     

Synthesis and properties of sym-triazine derivatives. 2. Synthesis of amino-sym-triazines containing fragments of sterically hindered phenol

The reaction of mono- and dichloro-sym-triazines with 4-hydroxy-3,5-di-tert-butyl-aniline was studied. N-substituted derivatives of 2,4,6-triamino-sym-triazine were synthesized, containing fragments of sterically hindered phenol.For article 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No.12, pp. 1678–1682, December, 1984.     

Synthesis and properties of derivatives ofsym-triazines 14. Cyanoethylation of 4,6-disubstituted 2-amino-sym-triazines

The cyanoethylation of 4,6-disubstituted 2-amino-sym-triazines containing alkyl trichloromethyl, and pyridyl groups was studied, and the corresponding dicyanoethyl derivatives were synthesized. It was shown that the yield of the latter and the duration of the reaction depend on the nature of the substituents in the ring of the initial amino-sym-triazines. A method of obtaining 2-(2-cyanoethyl)amino-sym-triazines is proposed based on the decyanoethylation and disproportionation of the dicyanoethyl derivatives as well as the trans-cyanoethylation.I. M. Gubkin State Petroleum and Gas Academy, Moscow 117917. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 111–129, January, 1995. Original article submitted November 2, 1994.     

Synthesis and properties of sym-triazine derivatives. 6. Synthesis of 2-amino- and 2,4-diamino-sym-triazines containing sterically hindered phenol segments

2-Amino-4,6-disubstituted-sym-triazines containing sterically hindered phenol segments were synthesized by cyclocondensation of N-acrylguanidines with nitriles or thiocyanates. The same compounds can be obtained by condensation of N-acylguanidine with iminoester hydrochlorides. The reaction of methyl -(4-hydroxy-3,5-di-tert-butylphenyl)propionate with biguanides gives N-substituted 2,4-diamino-6-R-sym-triazines that contain a shielded phenol residue.For Communication 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1392–1397, October, 1987.     

Synthesis and physiochemical property evaluation of carbamate derivatives of scutellarin methyl ester

A series of carbamate prodrugs of scutellarin methyl ester (4a-4e) were prepared in the presence of bis(trichloromethyl) carbonate (BTC) with scutellarin methyl esters and L-amino acid tert-butyl ester hydrochloride as starting materials. In vitro stability and aqueous solubility of target compounds were evaluated. The results indicated that compounds 4d and 4e have higher solubility and in vitro stability than scutellarin respectively.     

Synthesis of methylpyridine derivatives—XXXIIIChem. Pharm. Bull.25, 203 (1977).: Phosphonylation and chlorination of methylpyridine and 3-nitro-methylpyridine derivatives

Novel phosphonylation of the active Me group of pyridine derivatives is described.Reaction of 2 (and 4) -methylpyridine (3 and 5) with PCl₅ in POCl₃ gave 2 (and 4) -trichloromethylpyridine (4 and 6). Similarly, reaction of 4 (and 6) methyl-3-nitropyridine (7 and 9) afforded the corresponding trichloromethyl derivative (8 and 10). However, the similar reaction of 2-methyl-3-nitropyridine (11) gave dichloro-(3-nitro-2-pyridyl)-methylphosphonic dichloride (12).Mechanisms of the formation of these products are discussed.     

Diaza crown ethers based on sym-triazine derivatives

The reaction of 2-dialkylamino-4,6-dichloro-1,3,5-triazines with the disodium derivatives of di- and triethyleneglycols, has given four new diaza crown ethers. The structures of the compounds synthesized have been established by IR and PMR spectroscopy and elementary analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1277–1279, September, 1984.     

Synthesis of 5-azaadenine derivatives from N-(1,2,4-triazol-5-yl)amidines

A method is proposed for the synthesis of N-substituted 5-azaadenines. The condensation of N-(1,2,4-triazol-5-yl)amidines with trichloroacetonitrile gives trichloromethyl derivatives of 1,2,4-triazolo[1,5-a]-1,3,5-triazines, which are converted by the action of primary or secondary amines into N-alkylamino- or N,N-dialkylamino-1,2,4-triazolo-[1,5-a]-1,3,5-triazines (5-azaadenines).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 241–243, January, 1991.