The sixth meeting of CCQM, April 2000

A report is given of the sixth meeting of the Consultative Committee on Amount of Substance (CCQM). The CCQM has been active since 1993. It is the committee, established by the Comite International des Poids et Mesures, which is responsible for issues regarding metrology in chemistry. It has four established working groups in the fields of organic analysis, inorganic analysis, gas analysis and electrochemical analysis. A further twoad hoc working groups in the fields of surface analysis and metrology in biotechnology were established during the meeting. The working groups are involved in the identification, development and execution of a series of key comparisons, which will establish the technical basis for the mutual recognition of measurement capabilities among the National Measurement Institutes. 17 key comparisons are currently planned for the period 1999–2002, with 29 other international comparisons planned for the same period.     

Steroids and sex hormones. Synthesis of 5- and 5- -17-oxo-19-hydroxy-3-aza-3, 19-cyclo-A-homo-androstane

The synthesis of the novel title compounds ( 2 and 3 ) is described. These two isomers differ from structure 1 , ascribed to the salamander alkaloid cycloneosamandione, with respect to ring A/B fusion and to the ketone position.     

Steroidal heterocycles. 15. 4,4-Dialkyl-delta 5-3-oxosteroids, 1,4'-spiro [cycloalkyl-delta 5-3-oxo-steroids] and derivatives

Homologs of 17-hydroxy-4,4-17α-trimethyl-3-oxo-androst-5-ene-2α-carbonitrile ( 6d ), such as the 4,4-diethyl-( 6a ), 4,4-cyclopentyl-( 6c ) and 4,4-cyclohexyl-( 6b ) analogs were synthesized.     

5-[5-(3-吡啶)-2H-四唑亚甲基]-2-芳酰氨基-1,3,4-噻二唑的合成

正如前文报道,l,3,4—噻二唑类杂环之所以有除草,植物生长调节,驱虫以及消炎等多种生物活性,无疑起因于噻唑母核。尽管母核上取代基不起主导作用,但它作为辅助基,在改善分子溶解性以及药效方面所产生的影响是不能忽略的。因而深入研究各种生物活性基团导入噻二唑环母核以制得多结构单元聚集于同一分子中的噻二唑新衍生物,对于开发多功能新药具有一定的理论意义和实际价值。     

Indole derivatives. 136. 4-, 5-, 6-, and 7-Nitro-3-indolesulfonic chlorides and sulfonamides

The reaction of nitroindoles with chlorosulfonic acid in the presence of sodium sulfate was used to synthesize 4-, 5-, 6-, and 7-nitroindole-3-sulfonyl chlorides. Under the influence of ammonia and several amines these compounds were convened to nitroindole-3-sulfonamides which were reduced with hydrazine hydrate in the presence of Raney nickel to the corresponding amines.See [1] for Communication 135.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1341–1345, October, 1990.     

Syntheses of 3-, 4-, and 5-O-feruloylquinic acids

The efficient synthesis of 3-, 4-, and 5-O-feruloylquinic acids starting from d-(?)-quinic acid is described. Esterification of suitably protected quinic acid derivatives with 3-(4-acetoxy-3-methoxyphenyl)-acryloyl chloride and subsequent hydrolysis of all the protecting groups afforded the title products in overall yields of 33%, 15%, and 45%, respectively, (from quinic acid).     

1, 2λ5-azaphosphinines and a new 1λ5, 3λ5-. Diphosphinine

The 1,2-azaphosphinine, 9 , and the 1,3-diphosphinine, 10 , can be isolated from a mixture resulting from the reaction of 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , and ethyl isothiocyanate. The reaction of 1 with phenyl isothiocyanate yields the 1,2-azaphosphinine, 16 . Mechanisms for the formation of the compounds 9 , 10 , and 16 are suggested. The properties, the NMR, mass, and IR spectra, and the molecular and crystal structures of 9 and 10 are described and discussed.     

2-芳氧基-5-苯基-1,3,4-噁二唑类化合物的合成

本文通过芳氧基负离子在2—甲磺酰基—苯基—1,3,4—噁二唑环2—位上的亲核取代反应制得9个新的2—芳氧基—5—苯基—l,3,4—噁二唑衍生物。所有化合物的结构经元素分析,IR,~1H NMR和MS确认。初步抗菌实验表明这些化合物具有一定的抑制枯草芽孢杆菌繁殖的活性。 2,5—二取代l,3,4—噁二唑衍生物具有广泛的生物活性,如抗菌,抗黄球菌,除草杀棉花牙虫等。Madhavan等曾通过芳胺在2— 甲磺酰基—5—芳基1,3,4—噁二唑环上的亲核取代反应,制得了2—芳氨基—5—芳基—l,3,4—噁二唑衍生物,我们也曾通过酰肼等亲核试剂在2—甲磺酰基—5—(3,4,5—三甲氧基苯基)—1,3,4—噁二唑环上的亲核取代反应,得到了2—取代酰肼基—5—(3,4,5—三甲氧基苯基)—l,3,4—噁二唑衍生物。在此基础上,我们拟通过Aro在2—甲磺酰基     

Steroids and sex hormones. 241. The partial synthesis of 3-methoxy--3-, 9- -oxido-7- hydroxy-11- -acetoxy-5- steroids

The preparation of the title compounds 11 , 37 , and 39 is described. 37 will serve as starting material for a partial synthesis of the steroidal alkaloid batrachotoxinin A ( 1 ).