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.     

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 characterization of trialkyltin esters of pyridinecarboxylic acids and crystal structure of [nBu3SnO2CC5H4N‐2]∞

Reactions of trialkyltin oxides with 2‐, 3‐, and 4‐pyridinecarboxylic acids in 1:1 stoichiometry yield 10 corressponding trialkyltin esters R₃SnO₂CC₅H₄N. All compounds are characterized by elemental analysis, IR, ¹H, ¹¹³C, and ¹¹⁹Sn NMR. The crystal structure of tributyltin ester of 2‐pyridinecarboxylic acid is determined by single crystal X‐ray diffraction. In this compound, the tin atom is rendered five‐coordinate in a trigonal bipyramidal structure by coordinating with 2‐pyridinecarboxylate group. The resulting structure is a linear polymer containing Sn O bonds (0.2278(5) and 0.2308(6) nm). © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:524–529, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20057     

Alkylated styrene ionomers with variable length spacers. I. Synthesis

Two analogous series of ionomer precursors based on 4-substituted styrene copolymers were prepared with substituents R = -(CH_2)nCO₂Me (n = 1, 5, 10), or R = -O(CH₂)_nCO₂Me (n = 1, 4, 10), and degrees of substitution from 10 to 15 mol%. The synthesis of the alkyl series compounds involved either chloromethylation of polystyrene or bromoalkylation via lithiation of a styrene-4-bromostyrene copolymer, followed by conversion to the nitriles. Methyl esters were then produced by reaction of the nitriles with methanol/HCl gas. The ether series compounds were obtained directly by reacting a styrene-4-hydroxystyrene copolymer with the methyl esters of the corresponding ω-bromoaliphatic carboxylic acids in a Williamson ether-type synthesis.     

Synthesis and oxidation of 1,4-dihydroisonicotinic acid derivatives

Dimorpholinoacetic acid morpholide was used as an aldehyde in the Hantzsch synthesis, and the morpholides of the corresponding 1,4-dihydroisonicotinic acid derivatives were obtained. The direct esterification of the morpholides of the 1,4-dihydroisonicotinic acid derivatives gave their methyl, ethyl, and isopropyl esters. The oxidation of 2,6-dimethyl-3,5-dicarbethoxy-l, 4-dihydroisonicotinic acid and its morpholide with sodium nitrite occurs with cleavage, while the oxidation of the methyl esters takes place with retention of the substituent. The morpholide of 10,12-dioxo-5,10,11,12-tetrahydrodiindeno[1,2-b;2',1'-e]pyridinecarboxylic acid is oxidized with retention of the substituent.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 354–356, March, 1972.     

Synthesis and Reactions of Derivatives of 2-Deoxyoct-3-Ulosonic Acids

Abstract

Decarboalkoxylations of branched chain 2-deoxyoct-3-ulosonic acid derivatives furnished the unbranched 2-deoxyoct-3-ulosonic acid esters and nitriles, respectively. The O-methylation and halogenalion of 2-deoxyoct-3-ulosonates are described.     

Alkyl Esters of 2-[5-Chloro(bromo)-6-methoxy-4-methylpyrimidinyl-2-oxy]alkanoic Acids

The reaction of a mixture of formaldehyde and sodium cyanide or of lactic acid nitrile with trimethyl(6-methoxy-4-methylpyrimidinyl-2)ammonium chloride give the 2-(6-methoxy-4-methylpyrimidinyl-2-oxy)alkanoic acid nitriles. They were subsequently converted to the corresponding alkyl esters by a Pinner reaction and then to their 2-(5-halo-6-methoxy-4-methylpyrimidinyl-2-oxy) derivatives using N-halosuccinimides.     

Synthesis and properties of azoles and their derivatives. 32. Synthesis and some transformations of hydrochlorides of imido esters of indolecarboxylic acids

The Pinner reaction with the nitriles of indole-3-carboxylic and 3-indolylacetic acids was studied. The hydrochlorides of the imido esters of these acids, which were converted to the free bases, amides, and esters, were synthesized. Imid-azolines, benzimidazoles, and benzoxazoles that contain indole substituents were obtained by condensation of the hydrochlorides of the imido esters of the indolecarboxylic acids with ethylenediamine, o-phenylenediamine, and o-aminophenol.See [1] for communication 31.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 645–650, May, 1980.     

Polyampholytes from chloromethylated diphenyl oxide-formaldehyde oligomer,polyamines, and pyridinecarboxylic acids and their nitriles

Conclusions The optimum conditions were found for the synthesis of some new polyampholytes from a chloromethylated diphenyl oxide-formaldehyde oligomer, polyamines, and either pyridinecarboxylic acids or their nitriles, and their properties were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1652–1654, July, 1978.     

Synthesis of some 4-substituted-2-(o-halogenophenyl)-1,2,3-triazoles

Mesoaldehyde 1,3-dioxime was treated with either 2,4,6-trichlorophenyl- (a), o-fluorophenyl- (b), or o-bromophenyl- (c) hydrazine to give the corresponding mesoaldehyde 1,3-dioxime-2-halogenophenylhydrazones (1a,b,c). The latter were O-acetylated with acetic anhydride, and cyclized to triazole 4-oximes (3b, c) or triazole 4-O-acetyloximes ( 6a,b,c ) with cesium carbonate, then converted to nitriles ( 7a,b,c ) by refluxing with acetic anhydride followed by pyrolysis, or to aldehydes ( 4a,b,c ) by hydrolysis. The nitriles ( 7a,b,c ) were also converted to acids ( 9a,b,c ), esters ( 10a,b,c ), amides ( 8a,c ), an alcohol (11a), and an amine ( 12a ). In addition, tetrazoles of two types were prepared. The first ( 13d,e ) were obtained from the acid chlorides by the action of 5-aminotetrazole, whereas the second ( 14f ) was produced from the respective nitrile by the action of ammonium azide.     

Synthesis of Branched Chain 2-Deoxyoct-3-Ulosonic Acid Derivatives as Precursors for C-Nucleoside Analogues

Abstract

Reaction of 2,3,4,5,6-penta-O-acetyl-D-galactonic 1 and D-gluconic acid chloride 2, respectively, with derivatives of malonic acid furnished substituted 2-deoxyoct-3-ulosonic acid esters, amides, and nitriles. Further modification was carried out by O-acylation and halogenation.     

Esterification of pyridinecarboxylic acids in the presence of cation-exchange resins

Pyridinecarboxylic acids undergo esterification on refluxing with alcohols in the presence of cation-exchange resins. In the case of pyridine-2,6-dicarboxylic acid, in which the basicity of the nitrogen atom is reduced, esterification products are obtained in high yields. In the case of pyridinecarboxylic acids, in which the pyridine nitrogen atom displays considerable basicity, the cations of the acids are tied up by the cation-exchange resin, and the yields of preparatively isolable esters do not exceed 60%.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 233–237, February, 1976.     

S(N)1-like reactions of bicyclic alpha-amino ethers with sulfur,nitrogen, and carbon nucleophiles. Synthesis of 1-azabicyclo[3.2.2]nonanes functionalized at carbon C2 and C6 with complete stereocontrol

[reaction: see text] In the presence of nucleophiles, Lewis acid mediated cleavage of alpha-amino ethers derived from quincorine and quincoridine affords a variety of C2-substituted and C6-vinylated 1-azabicyclo[3.2.2]nonanes. These are enantiopure and are formed in S(N)1-like reactions with complete stereocontrol. There is no leakage into 2-Nu en route to product 1-Nu or vice versa. Me(3)SiCN provides new Strecker-type alpha-amino nitriles. In the presence of TTMPP-BF(3).OEt(2), the ketene acetal Me(2)C=C(OMe)OSiMe(3) delivers enantiopure bicyclic beta-amino acid esters.     

Heterocyclization of functionalized heterocumulenes with C,N- and C,O-binucleophiles: IV. Reactions of 1-chloroalkylheterocumulenes and <Emphasis Type="Italic">N</Emphasis>-(1-chloroalkylidene)carbamates with 2-benzimidazolylacetonitriles and methyl 2-benzimidazolylacetates

1-Chloroalkyl isocyanates and 1-chloroalkylcarbodiimides undergo regioselective cyclization with nitriles and esters of 2-benzimidazolylacetic acid to give derivatives of 1-oxo and 1-arylimino-1,2,3,5-tetrahydrobenzo[4,5]imidazo[1,2-c]pyrimidine respectively. The cyclocondensation of 1,1-dichloroalkyl isocyanates or N-(1-chloroalkylidene)carbamates with nitriles and esters of 2-benzimidazolylacetic acid afforded 1,5-dihydrobenzo[4,5]imidazo[1,2-c]pyrimidin-1-one derivatives.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11, 2004, pp. 1715–1724.Original Russian Text Copyright © 2004 by Vovk, Lebed, Pirozhenko, Tsymbal.For communication III see [1].     

Ferrocene compounds XXIII. Synthesis and reactions of the new type of methyl ferrocyloxyalkanoates

The new types of ferrocenyloxaaliphatic acid ester, FcCHROCHR′COOMe (R = H, Me, Ph; R′ = H, Me) (7) have been prepared by the action of alkoxides derived from methyl glycolate or methyl lactate on the corresponding ferrocenylcarbinyl acetates (2) or N,N,N-trimethylferrocylammonium iodides (4). The esters obtained were accompanied by a small quantity of oligomeric esters, FcCHR(OCHR′CO)_n OMe (9), and with more or less ferrocyl methyl ethers (8). As opposed to the alkaline hydrolysis of the analogous methyl benzoxyacetate (6) into benzoxyacetic acid (5) the acidification of sodium alkanoates 10 obtained by saponification of esters 7 gave unexpectedly the corresponding ferrocenylcarbinols 1. In a similar way the esters 7 were converted into mixtures of the mentioned carbinols and diferrocyl ethers 11 under action of aqueous hydrochloric acid. The mechanisms of the reactions 10 → 1 and 7 → 1, 11 are discussed.     

Hetaryl‐1,5 Benzodiazepines—Part I: Synthesis of 3‐pyrimidinyl‐ and Imidazolyl‐1,5‐benzodiazepines

Nucleophilic substitution of 3‐bromo‐4‐phenyl‐1H‐[1,5]benzodiazepin‐2‐one ( 1 ) with thiourea or guanidine in presence of potassium carbonate afforded 1,5‐benzodiazepin‐3‐ylimidothiocarbamate 2 or 1,5‐benzodiazepin‐3‐ylguanidine 3 , respectively. Pyrimidylthiobenzodiazepines 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 were obtained via the reaction of compound 2 with malononitrile dimer, diethyl malonate, methylenemalononitriles, or a mixture of an aldehyde and β‐keto esters or acetylacetone, catalyzed using ceric ammonium nitrate. Reaction of compound 2 or 3 with α‐halo esters, nitriles, and/or ketones afforded imidazoles 14 , 15 , 16 , 17 , 18 , 19 , 20 , respectively.     

Preparation of polyfunctional aryl azides from aryl triazenes. A new synthesis of ellipticine, 9-methoxyellipticine, isoellipticine, and 7-carbethoxyisoellipticine

The preparation of polyfunctional aryl azides by the reaction of aryl triazenes with NaN3 in the presence of KHSO4 or BF3.OEt2/TFA (trifluoroacetic acid) has been described. A variety of functional groups (halides, esters, ketones, nitriles, aldehydes, and boronic esters) are tolerated under the Lewis acidic conditions. By using this methodology, the potent antitumor agents, ellipticine and 9-methoxyellipticine, have been synthesized. In addition, isoellipticine and a related derivative, 7-carbethoxyisoellipticine, were also prepared.     

Synthesis of 2-amino-5-(2-aryl-2-oxoethylidene)-4-oxo-1<Emphasis Type="Italic">H</Emphasis>-4,5-dihydrofuran-3-carboxylic acids derivatives by recyclization of 5-arylfuran-2,3-diones under the action of cyanoacetic acid derivatives

Recyclization of 5-arylfuran-2,3-diones under the action of ethyl cyanoacetate or of malonic acid dinitrile resulting in the corresponding esters or nitriles of 2-amino-5-(2-aryl-2-oxoethylidene)-4-oxo-1Н-4,5-dihydrofuran-3-carboxylic acids was investigated.     

Synthesis and spectroscopic properties of some dideuterated cyanopyridines

4‐Cyanopyridine‐2,6‐d₂ ( 5a‐2,6‐d₂ ), 3‐cyanopyridine‐2,6‐d₂ ( 5b‐2,6‐d₂ ), and 2‐cyanopyridine‐4,6‐d₂ ( 5c‐4,6‐d₂ ) were synthesized from the corresponding 2‐, 3‐ or 4‐pyridinecarboxylic acid N‐oxides. These dideuterated products were characterized by their mass and NMR spectra.     

Synthesis of γ-N-acylamino-β-keto esters and ethyl 5-oxazoleacetates via Ritter reaction and hydration of γ-hydroxy-α,β-alkynoic esters

The classical Ritter reaction on γ-hydroxy-α,β-alkynoic esters produced γ-N-acylamino-β-keto esters or ethyl 5-oxazoleacetates using alkyl or aryl nitriles, respectively. The γ-N-acylamino-β-keto esters resulting from alkyl nitriles are useful intermediates in the synthesis of a variety of building blocks. We also show that these can be converted into ethyl 5-oxazoleacetates using an additional step involving POCl₃.