3,5-Dijodthyronin

Ohne Zusammenfassung     

Mercury complexes with 1,2,6,7-tetracyano-3,5-dihydro-3,5-diimino-pyrrolizinide

The anion 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (L′, C₁₁H₂N₇⁻), after isomerization to 1,2,6,7-tetracyano-3,5-dihydro-3,5-diimino-pyrrolizinide (L), forms different metal-complexes with mercury depending on the experimental conditions. Pure compounds were isolated from the reactions HL+CH₃HgAc in CH₃CN and NaL′+HgAc₂ in AcH/H₂O. They are CH₃HgL and HgL₂. From their optical spectra, compared to those of phthalocyaninato- or other well-known pyrrolizinato-complexes, the coordination geometry of Hg(II) in these species is supposed to be trigonal planar and trigonal monopyramidal, respectively. CH₃HgL was characterized also by ¹H NMR: (CD₃CN, δ, ppm) 0.886 (CH₃), 8.733 (NH). From the reactions in water between NaL′ and HgCl₂ or HgClO₄ complex mixtures of polynuclear complexes were isolated of composition: 0.826 [Hg₂ClL₂(OH)]·0.174 [Hg₄L₃(OH)₅]·2.06 H₂O (A) or 0.588 [Hg₂L₂]·0.412 [Hg₂L(OH)₃]·3.53 H₂O (B), respectively. The formulae A and B were based on thermogravimetric and elemental analysis data. Indirect evidences, based on XPS data, for the existence of the pyrrolizinato–Hg(I) complex are also given.     

一种合成3,5-二氨基吡啶及3,5-二甲氧羰基氨基吡啶的新路线

以3,5-二甲基吡啶为起始原料,经氧化、酰胺化,酰胺在不同的霍夫曼降解条件下合成3,5-二氨基吡啶及3,5-二甲氧羰基氨基吡啶,总收率分别为64%和68%。利用1H NMR、MS/MS、IR等方法对各化合物的结构进行了表征。讨论了氧化反应及霍夫曼降解反应的主要影响因素。反应均在常压下进行,反应条件温和,后处理简单,效率高。     

Synthesis of 3,5-Diaryl and 3,5-Dialkyl-1,2-dithiolylium-4-olates

Abstract

Sulfurization of 2-acetoxy or 2-benzoyloxy-1,3-propanediones gives the corresponding 1,2-dithiolylium salts which are used as starting materials for preparation of 1,2-dithiolylium-4-olates.

The reaction was studied under different conditions in order to obtain the best sulfurization yields.

A new 3-p-dimethylaminophenyl-5-phenyl-1,2-dithiolylium-4-olate is also described. It is formed by nucleophilic attack on a 3-alkylthio substituted or a 5 unsubstituted position of a 1,2-dithiolylium ion by N, N-dimethylaniline.     

Synthesis of 3,5-dicya nopyridine by oxidative ammonolysis of 3,5-lutidine

Pyridine-3,5-dicarboxylic acid was synthesized by oxidative ammonolysis of 3,5-lutidine and hydrolysis of the resulting 3,5-dicyanopyridine.Communication XCIV from the series Oxidation of Organic Compounds; see [1] for communication XCIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 819–820, June, 1973.     

3,5-Disubstituted-1,2,4-oxadiazoles and 4,5-dihydro-3,5-disubstituted-1,2,4-oxadiazoles

A series of 3,5-disubstituted-1,2,4-oxadiazoles ( 2 ) were prepared from a mono- or dichlorophenyl-substituted amidoxime and (i) an acid chloride, (ii) an isatoic anhydride, or (iii) a β-keto ester. Although cyclizations of the same amidoximes with acetaldehyde gave 4,5-dihydro-5-methyl-substituted derivatives ( 5 ), that annulation procedure either failed or gave low yields with other aldehydes. A novel alternative method, the diborane reduction of 2 , has been found to be a generally applicable procedure for preparing 5 . The reduction is regioselective, i.e., only the 4,5-(C=N) linkage is reduced even when a large excess of diborane is present.     

Alkylation of pyridine-3,5-dicarboxamide and pyridine-3,5-dicarbonitriles by radical substitution

Structural modification of NAD(P) model compounds, N,N,N',N'-tetramethylpyridine-3,5-dicarboxamide ( 1 ), pyridine-3,5-dicarbonitrile ( 2 ), and 4-methylpyridine-3,5-dicarbonitrile ( 3 ), have been explored by the reaction with alkyl radicals such as the 1-adamantyl, tert-butyl, and isopropyl radicals. The alkyl substitutions of compounds 1 , 2 , and 3 with the 1-adamantyl and the tert-butyl radical gave both 2-mono and 2,6-disubstitution products, whereas the reaction of compound 2 with the isopropyl radical gave 2-mono 6c , 2,4-di 7c, 2,6-di 8c , and 2,4,6-trisubstitution 9c products.     

Vibrational frequencies and structural determinations of 3,5-dibromo-1,2,4-trithia-3,5-diborolane

The vibrational frequencies and corresponding normal mode assignments of 3,5-dibromo-1,2,4-trithia-3,5-diborolane (B2S3Br2) are examined theoretically using the Gaussian98 set of quantum chemistry codes. All normal modes were successfully assigned to one of six types of motion predicted by a group theoretical analysis (B-S stretch, B-Br stretch, S-S stretch, S-B-S bend, B-Br wag, B(SSBr) umbrella motion) utilizing the C2v symmetry of the molecule. The vibrational modes of the naturally isotopically substituted (1-10B and 2-10B) forms of B2S3Br2 were also calculated and compared against experimental data. The molecular orbitals of B2S3Br2 are examined. The calculations suggest that a considerable amount of pi bonding occurs in B2S2Br2.     

Syntheses and Crystal Structures of 3,5-Diiodo-salicylalidehyde and 3,5-Diiodo-salicylalidene-4-nitroaniline

The title compounds, C7H4I2O2 1 and C13H7I2N2O3 2, have been synthesized and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a = 9.802（2）, b = 13.867（3）, c = 7.364（2） A, β = 109.74（3）°, V= 942.1（3） A^3, Dc= 2.636 g/cm^3, C7H4I2O2, Mr= 373.90, F（000） = 672, μ = 6.627 mm^-1, Z = 4, R = 0.0459 and wR = 0.1018 for 1805 observed reflections （I 〉 2 σ（I））. Compound 2 belongs to the monoclinic system, space group P21/n with a = 9.015（2）, b = 12.024（2）, c = 14.072（3） A, β = 103.91（3）°, V = 1480.6（5） A^3, Dc= 2.216 g/cm^3, C13H7I2N2O3, Mr= 494.01, F（000） = 920, p = 4.255 mm^-1, Z = 4, R = 0.0777 and wR = 0.1757 for 2896 observed reflections （I 〉 2σ（I））. Compounds 1 and 2 were assayed for antibacterial activities against three Gram positive bacterial strains （B. subtilis, S. aureus and S. faecalis） and three Gram negative bacterial strains （E. coli, P. aeruginosa and E. cloacae） by MTr method. Fortunately, compound 2 is found to show potent antibacterial activity against these six bacterial strains.     

Synthesis of 3,5-diaroylpyridines

Previously unknown 3,5-diaroylpyridines have been synthesized by the condensation of 1,3-diketones according to the Hantzsch reaction.