STUDIES OF HETEROCYCLIC COMPOUNDS: VI1 THE MASS SPECTRA OF SOME 2-THIOPHENEMERCURIC DERIVATIVES

Abstract

The mass spectra of some 2-thiophenemercuric derivatives are determined and the fragmentation interpretations are based on mechanistic analogy and supported in some cases by metastable peaks and low energy mass spectra. They all fragment ultimately to the 2-thienyl cation formed either through a two-step process, by cleavage of Hg[sbnd]X bond to give the 2-thienylmercuric cation, followed by extrusion of mercury, or by a one-step process through cleavage of carbon-mercury bond. Their base peaks being the C₃H₃ ⁺ion (m/e 39).     

A STUDY OF THE PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES OF THE S8 MOLECULE Photochemical Reactions in the S8 + Liquid Methanol System with and without Sensitizers: Benzene,Naphthalene and Pyrene. II

Abstract

The photochemical reactions occurring in the system S₈ + CH₃OH in the liquid phase were investigated, in the presence of, and without sensitizers. The experimental conditions were identical with those employed in studying the quenching of fluorescence.¹

The decay of S₈ is more rapid in the presence of sensitizers (the quantum yield and the degree of conversion are higher). In the system studied irradiation by UV light (λ 254 nm) causes the formation of (CH₃)₂S and of trace amounts of CH₄ and C₂H₆. The process of S₈ decay is of a mixed kinetic character—a pseudo 1st order process predominating, with a contribution from a 2nd order reaction. A possible reaction scheme, associated with excitation energy transfer from sensitizers to S₈ is discussed.     

STUDIES IN CYCLODIPHOSPHAZANES. SOME REACTIONS OF HEXACHLOROCYCLO-DIPHOSPHAZANES WITH UREA AND THIOUREA DERIVATIVES

Abstract

Interaction of chlorocyclodiphosphazanes (I) with some bifunctional reagents (such as phenylurea, diphenylurea, thiourea and its phenyl derivatives) in acetonitrile furnished geminal and nongeminal aminocyclodiphosphazanes of type (II–V). The structures of the isolated products were proposed on the basis of microanalytical data, infrared, ultraviolet, ¹H n.m.r., and mass spectra. The mechanism of the nucleophilic substitution is also discussed.     

含氮杂环三烃基锡衍生物的合成及其生物活性

本文合成了14个含氮杂环三烃基锡衍生物,红外光谱,核磁共振谱和质谱的研究表明三烃基锡-1,2,4-三氮唑为以氮原子作桥联的五配位聚合结构化合物,化合物的生物活性和生物选择性主要取决于锡原子上的三烃基。     

SYNTHESIS AND REACTIONS OF SOME NEW HETEROCYCLIC COMPOUNDS CONTAINING THE THIENYLTHIENO[2,3-B]PYRIDINE MOIETY

(4-Aryl-3-cyano-6-(2-thienyl)pyridin-2-ylthio)acethydrazides (5a–c), 3-amino-4-aryl-6-(2-thienyl)thieno[2,3-b]pyridine-2-carbohydrazides (6a–c) and 3-amino-4-phenyl-6-(2-thienyl)thieno[2,3-b]pyridine-2-carboxylic acid (30) were prepared and employed as key intermediates in the synthesis of the title compounds.     

STUDIES IN THE HETEROCYCLIC SERIES. IX. SYNTHESIS OF HETEROCYCLIC THIOLS

Abstract

A survey of the chemical literature recently undertaken by us, has revealed that much greater attention is being given nowadays to organo-sulfur compounds. New products containing sulfur have emerged and many of them were isolated from coal, 3 plant, animals' and soil microbes. 6 A great majority of them are, however, man-made and are obtained by intricate but often exciting synthetic procedures which give rise to new reactions, new chemistry and a great variety of potentially useful chemical compounds. These studies led to the synthesis of derivatives of phenothiazine (1)7 the sulfur analog of phenoxazine, and to dithieno(2,3-b: 2′,3′-e)(l,4)thiazine (2)′, cyclopental(1,2-b: 4,3-bf)-dithiophene (3)9 and benzothienoacridine (4) derivatives which are thiophene analogs of phenothiazine, fluorene and benz(c)acridine respectively.     

MULTIPLE PATHWAYS IN THE BASE-CATALYZED REACTIONS OF S-ALLYL SULFONIUM COMPOUNDS

Abstract

Various S-allyl sulfonium salts were allowed to react with bases (EtONa/EtOH, NaH/THF). From product analyses, it was found that modes of reaction depend on both the structure of sulfonium salts and the bases employed. Among the observations, it is worthy to note the formation of cyclopropane derivatives from some allyl sulfonium salts.     

高效液相色谱分析法测定2-氯-5-三氯甲基吡啶及其类似化合物

采用高效液相色谱法对高效除草剂盖草能的中间体2-氯-5-三氯甲基吡啶(TCMP)及相关化合物的分析条件进行了探讨和优化。使用Zorbax eclipse XDB-C18色谱柱,以乙腈-水(30+70,体积比)为流动相,控制流速1 mL.min-1,采用紫外可变波长检测器,检测波长为240 nm,方法的线性关系良好,相关系数为0.998 4,回收率为99.05%。在实样分析中同时测定了合成TCMP过程中的两个主要副产物2-氯-5-氯甲基吡啶和2-氯-3-三氯甲基吡啶。     

SYNTHESIS,REACTIONS AND SPECTRAL PROPERTIES OF 3-CHLORO-2,6DIARYL-4H-THIOPYRAN-4-ONES. SYNTHESIS OF SOME NEW 3-CHLORO-SPIROTHIOPYRAN DERIVATIVES

3-Chloro-2-phenyl-6-p-tolyl and 3-chloro-2,6-di-p-tolyl-4H-thiopyran-4-ones have been synthesized in moderate yieldes from the reaction of 3-chloro-tetrahydrothiopyran-4-ones with phosphorus pentachloride. Their thiones, oximes, and hydrazones have been also prepared. Treatment of thiones with malononitrile gave the corresponding 3-chloro-4-thiopyrylidenemalononitriles which gave 3-chloro-spirothiopyran derivatives of pyrazole, isoxazole, 1,3-thiazines when treated with hydrazine hydrate, hydroxylamine hydrochloride, thiourea and thiosemicarbazide, respectively. While treatment of 3-chloro-thiopyrylidene-malononitriles with acetylacetone gave the corresponding 3-chloro-spirothiopyran derivatives of pyran.     

PHOSPHORUS-NITROGEN COMPOUNDS. PART 64.1 THE REACTIONS OF HEXACHLOROCYCLOTRIPHOSPHAZATRIENE WITH 2, 2-DIMETHYLPROPANE-1, 3-DIOL. NUCLEAR MAGNETIC RESONANCE STUDIES OF THE PRODUCTS

Abstract

The reactions of hexachlorocyclotriphosphazatriene, N₃ P₃ CI₆, with 2, 2-dimethylpropane-1, 3-diol yield monospiro-, N₃ P₃ Cl₄ [(OCH₂)₂ CMe₂, dispiro-, N₃ P₃ Cl₄((OCH₂)₂CMe₂|₂, and trispiroderivatives, N₃ P₃ ((OCH₂)₂, CMe₂]₃. An ansa, N₃ P₃ CI₄ [(OCH₂)₂ CMe₂]₂ and a spiro-ansa, N₃ P₃ Cl₂- ((OCH₂), CMe₂,]₂ and a doubly-bridged compound, (N₃ P₃ Cl₄,)₂[(OCH₂)]₂ were also isolated. Product types and relative yields were compared with those arising from propane-1, 3-diol. The yields of ansa products from the reactions of the dimethyl diol seem to be considerably enhanced relative to those of its unmethylated analogue. ³¹P and ¹H n.m.r. spectra are reported.     

SOME REACTIONS OF 3-AMINO-2-CARBOETHOXY-4,6-DIMETHYLTHIENO[2,3-b]-PYRIDINE. SYNTHESIS OF SOME NEW THIENOPYRIDOPYRIMIDINES

Abstract

Thienopyridine oxazinone (1) has been prepared and explored as a precursor by its reaction with some reagents namely, ammonium acetate, aliphatic amines, aromatic amines, hydrazine hydrate, thiosemicarbazide, and ethyl glycinate to give pyridothienopyrimidines (11-VII). The pyrimidinone compound (11) was converted to the 4-chloro derivative (X) by its reaction with excess POCl₃ Interaction of the 4-chlorocompound (X) with some reagents namely, hydrazine hydrate, methyl amine, aniline, sodium thiophenolate, ethyl glycinate, thiosemicarbazide and thiourea, yielded pyridothieno-pyrimidine derivatives (XI-XVII) substituted at 4-position, respectively.     

THE REACTIONS OF SOME 2-NITROPHENYL SULPHIDES IN 98% SULPHURIC ACID

Abstract

The coloured solutions of 2-nitrobenzenesulphenyl derivatives in 98% sulphuric acid have previously been suggested to contain either the conjugate acid of the sulphenyl derivative¹ or the sulphenium ion in equilibrium with the starting material. ¹⁹F n.m.r. studies on solutions of 4-trifluoromethyl-2-nitrobenzenesulphenyl derivatives show that these compounds react in sulphuric acid to give the corresponding 2-amino- and 2-nitro-benzenesulphonic acids together with other products.     

在Lewis酸催化下N-苯乙基甘氨酸衍生物的分子内环化反应研究及苯并-3-氮杂环庚酮-1衍生物的合成

本文报导了不同N-苯乙基甘氨酸衍生物在Lewis酸催化下的分子内环化反应的若干规律,以及苯并-3-氮杂环庚酮-1衍生物的合成.     

INVESTIGATION OF THE EFFECTS OF SOME HEAT SINKS IN MICROWAVE-ASSISTED SYNTHESIS OF SOME BIGINELLI COMPOUNDS

Pyrimidine derivatives 4a–ewere synthesized by Biginelli reaction under microwave irradiation. The effectiveness of different baths or containers including ceramic, silica gel, potsherd, alumina, and molecular sieve as heat sinks in mediating the microwave irradiation for the formation of 4a–ehas been investigated. All one-pot condensations of β -Ketoester 1, aryl aldehyde 2, and (thio)urea 3in heat sinks provide high yields of the desired compounds, particularly when reactions are run at low temperature. In addition, we found that potsherd and ceramic are suitable heat sinks for preparation of these cyclocondensation products under microwave irradiation.     

某些有机物在溴化银重结晶过程中的作用

卤化银晶体的习性对乳剂的照相性能起决定性作用。因此多年来人们对影响卤化银晶体物理成熟过程的各种因素进行了研究。     

过渡金属五卤苯基有机化合物研究——V.Co(Ph_2PR)_2(C_6Cl_5)_2的ESR谱

测量了室温下粉末状Co(Ph_2PR)_2(C_6Cl_6)_2(R=n—Pr,n—Bu)配合物的ESR,求出各配合物的波谱参数和键参数,对其结构进行了讨论。钴(Ⅱ)—有机磷化合物在羰基合成反应中具有一定活性,我们用ESR方法对其结构进行研究。     

SYNTHESIS AND APPLICATION OF SOME NEW 5-SULPHONYL-N-HETEROCYCLO-8-HYDROXYQUINOLINE DERIVATIVES AS POTENTIAL DRUGS

Abstract

Some new sulphonyl-N-heterocyclo-8-hydroxy quinolines have been synthesised by the reaction of 8-hydroxyquinoline-5-sulphonyl hydrazide with different active methylene compounds. The pyrazole, pyrazoline, pyrazolidine and pyridazine derivatives were reacted with some metal cations to give the corresponding chelates. All synthesized compounds have been screened in vitro for their biological activities.     

1—羟基—2（1H）—吡啶硫酮及其甲基衍生物与Cr（Ⅲ）配合物的合成和性质

Edrissi认为Cr(Ⅲ)与1-羟基-2(1H)-吡啶硫酮(HPT)的甲基衍生物不能给出任何反应,并且将与HPT的配合物注明为绿色溶液。本文在过去工作的基础上合成了S-(1-氧化-2-吡啶基)硫代苯甲酸酯(PTB)和3-CH_3-PTB;并合成了3个铬配合物。通过元素分析,紫外-可见,红外光谱,摩尔电导和TG-DTA-DTG作了表征。探讨了形成机理并研究了抑菌活性。