SYNTHESIS AND REACTIONS OF HALO DERIVATIVES OF 4-ISOPROPYL-2H-1,4-THIAZIN-3-ONE

Abstract

Reaction of 4-isopropyl-2H-1,4-thiazin-3-one 1 (R [dbnd] i-Pr) with N-chloro- and N-bromosuccinimide occurred exclusively at the 6-position to give 6-chloro and 6-bromo derivatives of 1 (R [dbnd] i-Pr), respectively, in high yield, in sharp contrast to the 2-aroyloxylation by benzoyl peroxide or m-chloroperbenzoic acid reported earlier.² Reaction of 1 (R [dbnd] i-Pr) with methanesulfonyl chloride in the presence of aluminum chloride afforded an addition compound, 4-isopropyl-5,6-dichloro-1,4-tetrahydrothiazin-3-one. The 2-chloro derivative 6 of 1 (R [dbnd] i-Pr) was successfully prepared by hydrolysis of the 2-m-chloroben-zoyloxy derivative of 1 (R [dbnd] i-Pr) followed by treatment with thionyl chloride. Derivative 6 reacted readily under mild conditions with water, alcohols, thiols, ammonia and amines to give various 2-substituted compounds of 1 (R [dbnd] i-Pr). With phenol as a nucleophile, 1 (R [dbnd] i-Pr) reacted exclusively at the para position. Reaction at carbon atoms also occurred with N,N-dimethylaniline and 2,6-xylidine.     

SYNTHESIS OF 3-(2-MERCAPTO-4-THIAZOLYL)-2H-1-BENZOPYRAN-2-ONE AND ITS DERIVATIVES

Abstract

Treatment of 3-(2-bromoacetyl)coumarins with ammonium dithiocarbamate provides 3-2-mercapto-4-thiazolyl)-2H-1-benzopyran-2-one (11) but not 4-hydroxy-4-(3-coumaririnyl) thiazolidine-2-thione (I). II undergoes smooth condensation with alkyl, aralkyl, phenacyl and acid halides to give corresponding thioethers and thioesters (III) respectively. The structures of the newly synthesized compounds were established on the basis of spectral data (IR, PMR and MS).     

SYNTHESIS OF SULFONES OF 4H-1,4-BENZOTHIAZINES AND PHENOTHIAZINES

Conversion of 5/7-chloro-4H-1,4-benzothiazines and 1/3-chlorophenothiazines into sulfones is reported. The 5/7-chloro-4H-1,4-benzothiazines were synthesized by the condensation and oxidative cyclization of 2-amino 3/5-chlorobenzenethiol with β diketones in DMSO. The phenothiazines have been synthesized via Smiles rearrangement by the reaction of 2-amino-3/5-chlorobenzenethiol with halonitrobenzenes. 4H-1,4-Benzothiazine and phenothiazine sulfones have been prepared by the oxidation of benzothiazines and phenothiazines with 30% hydrogen peroxide in glacial acetic acid. The structure of all the synthesized compounds has been confirmed by IR and NMR spectral studies.     

SYNTHESIS AND REACTIONS OF 2H-1,3-THIAZETES

Abstract

2H-1,3-Thiazetes have been supposed to be the intermediates of the photoaddition of thiocarbonyl compounds to nitriles, yielding N-(alkylidene)thiocarboxamides¹é. Using the stabilizing effect of trifluoromethyl groups on small ring systems² we succeeded in synthesizing 2H-1,3-thiazetes as stable compounds³. At elevated temperatures a thermal mobile valence tautomeric equilibrium with N-(perfluoroisopropylidene)thiocarboxamides was observed, which competes with a [2+2] cycloreversion process.     

SYNTHESIS AND STRUCTURE OF ADDUCT OF 1, 9-DIHYDRO-8,9-DIPHENYL-1, 2, 4-TRIAZOLO [4, 3-d] 1, 2, 4-TRIAZINE-3, 5-DITHIONE WITH TRIETHYLAMINE

<正> C16H13N5S2· (C2H5)3N: Mr = 440. 64, monoclinic, space group C2/c with a = 18.956(7)(?), b = 12. 866(7)(?), c = 20. 830(9)(?) , β=115. 63(3)°; Z=8; V = 4580(7)(?)3; Dc = 1. 278gcm-3; F (000) = 1872, μ= 2. 423cm-1 (MoKa). Final R is 0. 069. C16H13N5S2is non-planar with two rings, a five-member and a six-member with conformations of envelope and twist boat forms respectively, and the two substituted phenyl groups are in equatorial and axial positions.     

2-BENZAZEPINES III1, 2 IMPROVED SYNTHESIS OF 2, 3, 4, 5-TETRAHYDRO-2-BENZAZEPIN-1-ONE

3-Methylfuran is an important building block of terpenoid compounds¹⁾ and some of these compounds are biologically active, for example as a defence substance of animal.²⁾ Though many methods have been developed for the syntheses of 3-substituted furan derivatives,³⁾ most of them lack the generality as a synthetic method of (3-furanyl) methyl derivative. Tannis has recently reported the construction of 3-substituted furan derivative by using 3-(lithiomethyl) furan or 3-(chloromagnesium methyl) furan, and demonstrated the generality of his method.⁴⁾     

2,5-取代-1,3,4-噁二唑化合物库的固相合成

本文使用组合化学方法以聚苯乙烯亚磺酸钠树脂（1）为载体合成了2，5-取代-1，3，4-二唑化合物库。树脂1首先与溴代乙酸乙酯反应生成聚合物支载的乙酸酯（2）。肼解后所得的肼树脂进一步与取代的苄氯反应得双欧讲树脂（4）。树脂4与三氯氧磷回流得聚合物支载的2，5-取代-1，3，4-二唑（5）。用W-溴代乙酰苯酮烷基化后聚合物支载的产物用三乙胺解脱得2-芳基-5-芳甲酰亚乙烯基-1，3，4-二唑化合物库，产率15％-36％。     

SYNTHESIS AND FUNGICIDAL ACTIVITIES OF DERIVATIVES OF 2-ALKYLTHIO-3-AMINO-4H-IMIDAZOL-4-ONE

2-Alkylthio-3-phenylamino-5-arylmethylene-4H-imidazol-4-ones 5 were synthesized by S-alkylation of 3-phenylamino-2-thioxo-4-imidazolidinones 4, which were obtained via cyclization of isothiocyanates 2 with phenylhydrazine in presence of solid potassium carbonate. Compound 5 exhibited fungicidal activity.     

SYNTHESIS, STRUCTURE AND SOME PHYSICAL PROPERTIES OF 2-METHYL-4-NITROPYRIDINE-1-OXIDE

<正> INTRODUCTION. Some relationship have been discovered among frequency doubling effect, moleculer electronic structure, and molecular orientation in some organic crystals by Li Songxian et al. This paper reports synthesis, structure, molecular dipole moment and frequency doubling effect of the title compound.     

SYNTHESIS OF 4,6-DISUBSTITUTED 5-THIOXO-1,2,4-TRIAZIN-3-ONE FROM BENZOTHIOFORMANILIDE

A method of synthesis of 4,6-disubstituted 5-thioxo-1,2,4-triazin-3-ones from benzothioformanilides and semicarbazide is described.And six newcompounds were synthesized by this method.     

A CONVENIENT SYNTHESIS OF NEW PYRIDOTHIENOPYRIMIDIN-4 (3H) ONES AND PYRIDOTHIENOPYRIMIDIN-2, 4(1H, 3H) DIONES

New derivatives of 2-substituted pyrido[3′,2′:4,5]thieno[3,2-d]pyri-midin-4(3H) ones and 3-substituted pyrido[3′,2′:4,5]thieno[3,2-d]pyri-midin-2,4(1H,3H) diones have been prepared by base catalyzed cyclocondensation of ethyl-3-aminothieno[3,2-b]pyridine-2-carboxylate with aryl nitriles and aryl- or alkyl isocyanates respectively.     

La2NiO4复合氧化物的合成及性能研究

采用Ｐｅｃｈｉｎｉ方法合成了Ｌａ２ＮｉＯ４＋δ粉体，通过ＸＲＤ，Ｏ２－ＴＰＤ，ＴＧ和ＸＰＳ等对其物相、氧非计量以及表面状态进行了表征；制备了Ｌａ２ＮｉＯ４＋δ致密透氧膜并考察了其透氧性能。发现其非计量氧的脱出、补充有可逆性；表面吸附氧可转化成Ｏ＾δ－物种，在膜操作状态下，通过体相填隙氧浓差扩散到低氧压侧，以Ｏ２形式脱出，实现连续透氧。     

Synthesis of chalcogeno lactones. II. 3, 4-dihydro-1 H-2-benzothiin-3-one, 3,4-dihydro-1H-2-benzoselenin-3-one and 3,4-dihydro-1H-2-benzotellurin-3-one

The synthesis of 3, 4-dihydro-1H-benzothiin-3-one and its selenium and tellurium analogs is reported from o-bromomethylphenylacetyl chloride and sodium hydrogen chalcogenates, via phase-transfer catalysis.     

SYNTHESIS AND FUNGICIDAL ACTIVITIES OF 2-BENZOTHIAZOLYLTHIO-SUBSTITUTED 4H-IMIDAZOL-4-ONES AND 4(3H)-QUINAZOLINONES

4H-Imidazol-4-ones 4 or 4(3H)-quinazolinones 8 were synthesized by base catalytic reactions of 2-mercaptobenzothiazole with carbodiimides 2 or 6, respectively, which were obtained via aza-Wittig reaction of iminophosphorane 1 or 5 with aromatic isocyanates. 4 and 8 exhibited fungicidal activity.     

三(1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5)二水合镱(Ⅲ)的晶体结构

本文合成了Yb(PMBP)₃(H₂O)₂,并用X-射线单晶衍射法测定了晶体和分子的结构.配合物的晶体为单斜晶系,空间群为P2₁/n,a=24.498(3)Å,b=14.735(3)Å,c=14.888(5)Å,β=101.14(2)Å,V=5285.1ų;Z=4.三个PMBP及两个水分子提供八个氧与镱配位形成四方反棱柱配位多面体.     

三(1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5)二水合镱(Ⅲ)的晶体结构

本文合成了Yb(PMBP)_3(H_2O)_2,并用X-射线单晶衍射法测定了晶体和分子的结构.配合物的晶体为单斜晶系,空间群为P2_1/n,a=24.498(3)(?),b=14(?)35(3)(?),c=14.888(5)(?),β=101.14(2)(?),V=5285.1(?)~3;Z=4.三个PMBP及两个水分子提供八个氧与镱配位形成四方反棱柱配位多面体.     

THE FIRST SYNTHESIS OF A 2H-1,4-BENZOTHIAZINE-BASED PHOSPHINE OXIDE AND SULFIDE

Abstract

The synthesis of a cyclic α-amino phosphine oxide and sulfide with an incorporated benzo-thiazine moiety is described. The products can be regarded as analogues of the biologically active thiazolidinylphosphonates, in which several characteristic functional groups have been modified.