Molecular and crystal structure of 1-amino-3,5-diphenyl-2,4,4,6,6-Pentacyano-cyclohex-1-ene and 1-amino-3,5-diphenyl-2,4,4,6-tetracyanocyclohex-1-ene

Molecular and crystal structures of 1-amino-3,5-diphenyl-2,4,4,6,6-pentacyano-cyclohex-1-ene (I) and 1-amino-3,5-diphenyl-2,4,4,6-tetracyanocyclohex-1-ene (II) are studied to examine intermolecular interactions. Crystal data for (I): space group P2₁, a=11.172(3), b=6.561(2), c=16.390(4) Å, β=100.25(2)⁰, V=1182.1 ų, Z=2, R=0.046; for (II): space group P1, a=10.756(3), b=10.890(3), c=12.999(3) Å, α=62.20(2), β=70.73(2), γ=65.42(2)⁰, V=1207.2 ų, Z=2, R=0.074. Intermolecular bonds via the aminonitrile fragment in (I) lead to formation of chains along they axis: N1…N6′ (1?x, ?1/2+y, 1?z) of 3.465(8) Å, N6…N1″ (1?x, 1/2+y, 1?z), and the contact with the solvent (acetone) O1…N1 of 2.984(7) Å. In compound (II), the intermolecular contacts N1…N5′ (?x+1, ?y, ?z+1) of 3.064(7) Å link the molecules into dimeric associates.     

Cyclization reactions of nitriles. 26. Synthesis,structure, and properties of 2-amino-4-methylthio-5-cyano-6(1H)-pyrimidinethione

2-Amino-4-methylthio-5-cyano-6(1H)-pyrimidinethione has been prepared via treatment of N-cyanodimethyldithioimidate or 1,1-di(methylthio)-2-thiocar-bamoyl-2-cyanoethylene with cyanothioacetamide or cyanamide. The structure of the complex formed between 2-amino-4-methylthio-5-cyano-6(1H)-pyrimidinethione and urea has been studied by x-ray structural analysis. Thieno[2,3-d]pyrimidines and thiazolo[3,2-c]pyrimidinium salts have been synthesized based on the 6(1H)-pyrimidinethione.For Communication 25, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1377–1384, October, 1987.     

Reaction of 4-diethylaminosalicylaldehyde with malononitrile

The composition of the products from the reaction of 4-diethylaminosalicylaldehyde with malononitrile depends on the reaction conditions. A suitable method for the preparation of 2-dicyanomethylene-2H-1-benzopyrans is proposed. The dissociative ionization under electron impact of coumarin analogs has been studied. The relation between the polarity of the exocyclic double bond at C₂ of coumarin, the position of the ¹H NMR signal, and the position of the long-wavelength absorption band in the electronic spectrum is established.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1043–1052, August, 1992.     

Reaction of N-alkoxycarbonylaziridines with nitriles

The acid catalysed reaction of acetonitrile or benzonitrile with N-alkoxycarbonylaziridines, 1a and 1b yields the corresponding 1-alkoxycarbonyl-2-imidazolines, 2ax, 2ay, and 2bx. The imidazolines obtained by the reaction of N-ethoxycarbonyl-2,3-tetramethyleneaziridine (1c) with acetonitrileor benzonitrile are labile and are readily hydrolysed to trans-cyclohexane-1,2-diamine derivatives (3cx or 3cy). The nitrile-addition supposedly proceeds S_N2 type CN bond cleavage and CN bond formation.     

Syntheses with nitriles. 62. 3,5-Dicyanopyridine derivatives by vilsmeier formylation of malononitrile and tetracyanopropenides

Reaction of malononitrile with dimethylformamide and phosphorus oxychloride gave (dimethylamino-methylene)malononitrile ( 1 ), 4-chloro-7-methyl-5,7-diaza-1,3,5-octatriene-1,1,3-tricarbonitrile ( 3a ) and the pyridine 2 . Compounds 3a and 3b as well as the triaza-derivative 3c may also be obtained by treatment of tetracyanopropenides 4a-c with dimethylformamide and phosphorus oxychloride. Ring closures were achieved by heating 3 under alkaline or acidic conditions. Substitution of chlorine in 3a with aromatic amines provided 1-aryl-1,2-dihydro-2-imino-3,5-pyridinedicarbonitriles 7 . Hydrolysis of 7 gave the 2-oxo-derivatives 8 .     

Reaction of metalated nitriles with enones

[reaction: see text] There have been a number of reports of the kinetic conjugate (1,4) addition of metalated arylacetonitriles to enones. Several proposals have been made to explain this behavior based on nucleophile structure or aggregation state or on the HSAB properties of the reactants. A reexamination of these studies showed that in each case the 1,4 adducts resulted from equilibration of the kinetically formed 1,2 adducts to the more stable 1,4 adducts. Thus, no conclusions about the origins of 1,4 selectivity can be drawn from these experiments. The 1,2 addition, retro-1,2 addition, 1,4 addition, and retro-1,4 addition of lithiophenylacetonitrile to benzylideneacetone were examined, and a free energy level diagram was constructed for the reaction.     

Reaction of the nitrile of 3,3-diphenyl-2-propenic acid with the carbanions of some α-branched nitriles Short communication

Reaction of the nitrile of 3,3-diphenyl-2-propenic acid with -branched nitriles in the presence of lithium amide in liquid ammonia does not give the correspondingMichael adducts but the ,-unsaturated nitriles6. Conc. sulfuric acid transforms these nitriles into the -lactones7.

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Reaktion von 3,3-Diphenyl-2-propensäurenitril mit den Carbanionen einiger -verzweigter Nitrile (Kurze Mitteilung)

Zusammenfassung Die Reaktion von 3,3-Diphenyl-2-propensäurenitril mit -verzweigten Nitrilen in Gegenwart von Lithiumamid in flüssigem Ammoniak führt nicht zu den entsprechendenMichael-Addukten, sondern zu den ,-ungesättigten Nitrilen6. Durch Einwirkung von konz. Schwefelsäure entstehen aus diesen Nitrilen die -Lactone7.

     

The Free-Radical Cyclization Reaction of 1, 6-Dienes with Selenosulfonate

A sulfonyl radical induced addition-cyclization reaction of 1, 6-dienes with p-tolyl benzeneselenosulfonate giving functionalized cyclopentane system is described.     

Reaction of 1-amino-, 2-amino-, and 1,2-diaminoimidazoles with β-diketones

1,2-Diamino-4-phenylimidazolium perchlorate condenses with 2 mole of β-diketones to give pyrimido[2′,1′:2,3]imidazo[1,5-b]pyridazinium derivatives, while, like 1-amino-2-mercapto-4-phenylimidazole, to give imidazo[1,5-b]pyridazine derivatives. Salts of 1-benzylideneamino- and 1-(2-thiazolyl)-2-aminoimidazoles react with β-diketones to give substituted imidazo[1,2-a]pyrimidinium derivatives.     

Reaction of chlorine fluosulfate with perfluorocarboxylic acid nitriles

Conclusions The reaction of chlorine fluosulfate with perfluorocarboxylic acid nitriles, using an equimolar ratio of the reactants and the corresponding order of mixing them, gives N-chloroiminoperfluoroacyl fluosulfates in high yield, while the use of excess chlorine fluosulfate gives perfluoroacyl fluosulfates and pyrosulfuryl difluoride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2370–2373, October, 1981.     

2-氨基-3-羟基环戊烯-1-腈衍生物的合成和晶体结构

用低价钛试剂(TiCl~4-Zn)与α,α-(4-氯苯基)(二氰甲基)甲基苯基酮反应合成了非对映消旋体(3R,5S;3S,5R)和(3R,5R;3S,5S)2-氨基-3-羟基-3-苯基-5-对氯苯基环戊烯-1-腈。并用X射线衍射分析确定了这两个非对映异构体的构型。     

Syntheses with nitriles. 60. Preparation of 4-amino-5-cyano-6-phenylpyrimidines from 2-amino-1,1-dicyano-2-phenylethene

The reaction of 2-amino-1,1-dicyanobut-1-ene and 2-amino-1,1-dicyano-2-phenylethene, respectively, with N,N-dimethylformamide dimethylacetal provided the corresponding (N,N-dimethylaminomethylene)amino derivatives. 2-[(N,N-Dimethylaminomethylene)amino]-1,1-dicyano-2-phenylethene was converted into 4-amino-5-cyano-6-phenylpyrimidines by treatment with primary aliphatic and aromatic amines. The structure of the reaction products was confirmed by ¹³C nmr spectroscopy.