氨基呋咱氧化为氨基硝基呋咱的合成研究

研究开发了将氨基呋咱转化为氨基硝基呋咱新的高收率氧化方法. 采用甲烷磺酸为介质, 以过氧化氢、碱或碱土金属和胺为基的氧化物(如钨酸钠或过硫酸铵)混合物的新氧化体系[H2O2/CH3SO3H/Na2WO4或(NH4)2S2O8]代替以硫酸为介质的过氧化氢和过硫酸铵混合物氧化体系, 分别对3,4-二氨基呋咱(DAF)、3,3’-二氨基-4,4’-氧化偶氮呋咱(DAAF)和3,3’-二氨基-4,4’-偶氮呋咱(DAAzF)进行氧化, 以高于65%的产率获得了3-氨基-4-硝基呋咱(ANF)和3-氨基-3’-硝 基-4,4’-氧化偶氮呋咱(ANAF), 并以15%的收率合成得到新化合物3-氨基-3’-硝基-4,4’-偶氮呋咱(ANAzF). 研究表明甲烷磺酸/过氧化氢/碱或碱土金属和胺为基的氧化物混合物是制备同时含有氨基和硝基基团的系列呋咱化合物非常有效的氧化体系.     

Preparation and synthetic utility of fluorinated phosphonium salts,bisphosphonium salts and phosphoranium salts

The synthesis and mechanism of formation of phosphonium salts of the type [R₃$\text{P}\text{+}$CFXY]Z^? (where X = F, Cl, Br; Y = Br, Cl; Z = Br, Cl), $\text{bis}$-phosphonium salts of the type [R₃$\text{P}\text{+}$CF₂$\text{P}\text{+}$R₃]2Br^?, and phosphoranium salts of the type [R₃$\text{P}\text{+}$$\text{C}\text{?}$F$\text{P}\text{+}$R₃]X^? (X = Br, Cl) will be presented. The applicability of these substrates in the generation of useful nucleophilic or electrophilic synthetic intermediates will be discussed.     

Aziridiniminium salts

Stable aziridiniminium salts have been obtained from the reaction of 2-amino-1-azirines with trityl tetrafluoroborate or trimethylsilyl triflate. These new derivatives of α-lactams react with carbanions to give 2-amino-1-aziridines.     

Thienopyrylium salts

The catalytic acylation and subsequent heterocyclization of- and-acetonyl derivatives of thiophene were studied. Mechanisms for the synthesis of thienopyrylium salts, the reaction of which with ammonia leads to the difficult-to-obtain thienopyridines, are proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 320–325, March, 1971.     

Pyranyltriphenylphosphonium salts

The reaction of pyrylium salts having a free or position with triphenylphosphine has given pyranylphosphonium salts. 2,4,6-Trisubstituted pyrylium salts do not react with triphenylphosphine. The properties and IR spectra of the compounds synthesized are discussed.     

Pentafluorosulfanylnitramide salts

The synthesis and properties of a new class of inorganic salts, named pentafluorosulfanylnitramide salts (or pentafluorosulfanylnitraminic acid salts) [Z+SF5NNO2-], are described. A number of SF5-nitramide salts (Z+SF5NNO2-) were successfully prepared via nucleophilic displacements from carbamates and/or ion exchange techniques, but some salts [M(SF5NNO2)x; M = Li, Mg, Al] decomposed during isolation procedures and appear to be unstable in the solid state. Single-crystal X-ray diffraction was used to fully characterize the Z+SF5NNO2-, and their properties/structures are compared with those of the corresponding dinitramide salts (or dinitraminic acid salts), Z+N(NO2)2-. X-ray crystallography revealed major structural differences between N(NO2)2- and SF5N(NO2)- salts concerning the N-N distances and the angles subtended at the central nitrogen atom. In the N(NO2)2- salts, there are two nonequivalent N-N (average lengths 1.372(2) and 1.354(2) A) distances and an average N-N-N angle of 115.8(3) degrees (falls between sp3 and sp2 hybridization). In the SFsNNO2- salts, the average N-N distance is much shorter, 1.308(9) A, and the average N-N-S angle is 120.0(5) degrees (closely fits sp2 hybridization). The SF5NNO2- salts show a remarkable metrical similarity for the SF5 moiety in all structures, indicating a lack of sensitivity to its steric and electronic environment. This is in marked contrast to N(NO2)2-, where there is a wide variation in conformations adopted by these anions which can be related to their environment.     

Dialkyldialkoxyphosphonium salts

Conclusions Dialkyldialkoxyphosphonium halides are stable only in the case of branched alkoxy groups. The stability is explained by the difficulty of attack of the isoalkoxy group by halide anions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 415–417, February, 1971.     

Alkylselenophosphonium salts

Conclusions Methylselenophosphonium salts have been obtained for the first time by the reaction of full amides of phosphoroselenoic and alkylphosphonoselenoic acids with methyl iodide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, p. 169, January, 1969.     

Pyridinium salts

New 4- (benzazol-2-yl)pyridinium salts have been synthesized. Their reduction in a neutral medium with sodium tetrahydroborate has given 2-(1,2,5,6-tetrahydropyridin-4-yl)benzazoles. The catalytic hydrogenation of the latter leads to piperidine derivatives which have also been synthesized by an independent route.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 104–107, January, 1974.     

Dioxolanium salts

A new method was developed for the synthesis of dioxolanium salts by the condensation of 1,2-glycols of the pinacol series with aliphatic acid anhydrides in the presence of perchloric acid. The dioxolanium ring is opened to form monoacylates of the starting pinacols under the influence of water, alcohol, and ammonia. A method was developed for the acetylation of aromatic compounds by dioxolanium salts.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1023–1026, August, 1971.     

Synthesis of mono-amino-functionalised ferrocene, ferrocene salts and ferrocenium salts

A number of mono-amino-functionalised ferrocenes, ferrocene salts and a mono-amino-functionalised ferrocenium salt have been synthesised and characterised. This represents a novel method of accessing these important classes of molecules. In the cases of some of the ferrocene salts, there are some interesting structural features in the solid state. These include N-H...O and N-H...F hydrogen bonds.     

An efficient synthesis of imidazolinium salts using vinyl sulfonium salts

The synthesis of imidazolinium salts from the reaction of formamidines and (2-bromoethyl)diphenylsulfonium triflate is described. A variety of symmetrical and unsymmetrical imidazolinium triflate salts were synthesized in high yield in short reaction times under mild conditions. Aromatic and aliphatic N-substituents work well. The reaction is proposed to proceed via generation of a vinyl sulfonium salt intermediate from the bromoethylsulfonium triflate.     

2-Benzopyrylium salts

The condensation of 1-alkyl-3-carbalkoxy-2-benzopyrylium salts with diamines leads to the synthesis of piperazino[3,4-b]- and quinoxalino[3,4-b]isoquinolinium perchlorates.     

δ-Ethoxydivinylpyrylium salts

The previously unknown -ethoxydivinylpyrylium salts were obtained by reaction of -ethoxyvinylpyrylium salts with ethyl vinyl ether. Their high reactivities with respect to nucleophilic compounds are demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6. pp. 739–741, June, 1976.     

1,2-dithiolium salts

The reaction of aryl-1,2-dithiol-3-thiones with alkyl iodides and with ICH₂COOH and ICH₂COOC₂H₅ has been studied. This gives 3-alkylithio-S-carboxymethylthio-, and 3-ethoxycarbonylmethylthio-1, 2-dithiolium iodides. Compounds of the first type are formed only with lower unbranched alkyl iodides (CH₃I, C₂H₅I, and n-C₃H₇I), and salts of the last two types were previously unknown.     

α-Ferrocenylcarbonium salts

Conclusions A study was made of the effect of the dimethylamino group, found in the p-position of the benzene ring attached to the carbonium carbon, on the stability and reactivity of-ferrocenylphenylcarbonium salts.To be sure, the title of the paper is arbitrary. As is clear from the formulas given below the structure of the described salts is rather of the ammonium type.Translated from Izvestiya Akademii Nauk SSSR Seriya Khimicheskaya No. 11, pp. 2017–2019, November, 1966.