2-取代的6-溴甲基-4(3H)-喹唑啉酮的合成

2-取代的6-溴甲基-4(3H)-喹唑啉酮的合成;4(3H)-喹唑啉酮;苯并噁嗪酮;N-溴代琥珀酰亚胺; 合成     

Synthesis and Reactivity of Carbohydroximoyl Azides: I. Aliphatic and Aromatic Carbohydroximoyl Azides and 5-Substituted 1-Hydroxytetrazoles Based Thereon

Chlorination of 1-hydroxyiminopentane gave 1-chloro-1-nitrosopentane which reacted with sodium azide in DMF to form pentanohydroximoyl azide. The azidation of benzohydroximoyl chlorides was always accompanied by decomposition to benzonitriles. Treatment of carbohydroximoyl azides in ether with gaseous hydrogen chloride afforded 5-butyl- and 5-aryl-1-hydroxytetrazoles which reacted with acetic anhydride to form the corresponding acetates.     

1,1-Diethynylsilacycloalkanes and Propellanes Based Thereon

Previously unknown 1,1-diethylnylsilacycloalkanes (CH₂)4nSi(C& = CH)₂ (n = 3, 4) were prepared by the reaction of HC& = CMgBr with 1,1-dichlorosilacycloalkanes (CH₂)4nSiCl₂ (n = 3, 4). The reaction of (CH₂)₄Si(C& = CMgBr)₂ with (CH2)4SiCl2 in THF under conditions of high dilution gives cyclo(tetramethylene)- silethynes [(CH2)4SiC& = C]4 with an admixture of cyclodi(tetramethylene)silethyne [(CH2)4SiC& = C]2. The re- action of Me2Si(C& = CSiMe2C& = CMgBr)2 with (CH2)4SiCl2 was used to prepare 1,1,4,4,7,7-hexamethyl-10,10- tetramethylene-1,4,4,10-tetrasilacyclododeca-2,5,8,11-tetrayne.     

Alkylidynephosphines - Syntheses and Reactivity

Abstract

In the past, different methods have been utilized for the preparation of alkylidynephosphines. Whereas, however, small amounts of thermally instable derivatives might be obtained from reactions in the gas phase, the synthesis of phosphines which are stable under an inert atmosphere, as for instance those with a tert-butyl or a 1-adamantyl substituent at the carbon atom of the PEC group, is best started with tris (trimethylsilyl) phosphine itself or with the more reactive lithium bis (trimethylsilyl) phosphide.2 tetrahydrofuran complex. Treatment of either compound with acyl halides results in the formation of acylbis (trimethylsilyl) phosphines which, at room temperature, rearrange to the corresponding trimethylsilyl [1-(trimethylsiloxy) alkylidene] isomers. As traces of hydrogen halide accelerate the conversion of tris (trimethylsilyl) phosphine to the triacyl derivatives, the use of the lithium phosphide is strongly recommended in all cases where impure acyl halides are used. In the presence of small amounts of solid sodium hydroxide suspended in an etherial solvent, the thus prepared trimethyl[1-(trimethylsiloxy)-alkylidene]phosphines eliminate hexamethyldisiloxane to yield the required alkylidyne compounds. Running the decomposition without a solvent at a higher temperature, Regitz and coworkers were able to improve this method further.     

Products of Reaction of Tricyclo[4.1.0.02,7]heptane and 1-Bromotricyclo[4.1.0.02,7]heptane with Hydrogen Sulfide,and Syntheses Based Thereon

By reactions of 1-R-tricyclo[4.1.0.02,7]heptanes (R = H, Br) with hydrogen sulfide initiated by UV irradiation endo-6-bicyclo[3.1.1]heptanethiols and bis(endo-6-bicyclo[3.1.1]heptyl) sulfides were synthesized. The sulfides were oxidized to the corresponding sulfoxides and sulfones. The results of HBr elimination from the bromine-substituted sulfoxides and sulfones effected by potassium tert-butylate are discussed. The latter reaction results in the recovery of the system of 1-substituted tricyclo[4.1.0.02,7]heptane.     

5-Bromotrimellitic Acid and Metal Phthalocyanines Based Thereon

5-Bromotrimellitic acid, its amide, and corresponding metal phthalocyanines on their basis were synthesized. The electronic absorption spectra of the latter are much affected by the nature of the complexing metal and the solvent.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 1026–1030.Original Russian Text Copyright © 2005 by Kulinich, Shaposhnikov, Gorelov, Doronina.     

5-Acylamino-4-phenoxyphthalodinitriles and Metal Phthalocyanines Based Thereon

Tetra(5-acetylamino-4-phenoxy)-, tetra(5-benzoylamino-4-phenoxy)-, and tetra(5-octanoylamino-4-phenoxy)phthalocyanines are synthesized, and their electronic absorption spectra are studied.     

Reactions of Diethyl [(3-Bromomethyl-2-Thienyl)-Methylene]Propanedioate with Hydrazines: Syntheses of Dihydropyridazines,Pyridazines and O-Dimethylaminomethylarenecarbonitriles

Facile syntheses of dihydropyridazines, pyridazines, and o-dimethylaminomethylarenecarbonitriles have been achieved by the retro-malonate addition reaction. Bromoalkylidenemalonates 1,7, and 10 were treated with hydrazine to give dihydropyridazines 4, 8, and 11 in quantitative yields. DDQ or air oxidation of 4, 8, and 11 gave pyridazines 5, 9, and 12, Alternatively, treatment of 1, 7, and 10 with 1,1-dimethylhydrazine afforded o-dimethylaminomethylarenecarbonitriles 6,13, and 14 in good yields.     

Synthesis and Dehydrobromination of 3-Bromomethyl- and 3-Bromo-3-methoxymethylcyclobutane-1-carbonitriles and Methyl 3-Bromomethyl- and 3-Bromo-3-methoxymethylcyclobutane-1-carboxylates

The anti-Markownikoff products of bromination and bromomethoxylation of 3-methylenecyclobutane-1-carbonitrile and methyl 3-methylenecyclobutane-1-carboxylate were subjected to dehydrobromination by the action of potassium tert-butoxide in THF. The reaction takes two elimination pathways: 1,3-dehydrobromination to give bicyclobutane derivatives and 1,2-dehydrobromination leading to substituted methylenecyclobutane. Structural factors in the substrate were revealed, which are responsible for the ratio of the two concurrent elimination processes.     

E-苯甲酰二茂铁亚胺的合成、晶体结构和反应性

由苯甲酰二茂铁和一系列伯胺出发,用4A分子筛作为催化剂合成了6种相应的E-构型亚胺化合物,产率为50%～85%.该方法具有很好的通用性,同时适用于芳胺和脂肪胺,并且对杂原子具有耐受性.与文献中使用Al2O3作为催化剂的方法相比,该方法可使反应时间和催化剂的活化时间均大大缩短.所合成的席夫碱用于探索生物碱(一)-Sparteine促进的对映选择性地合成平面手性二茂铁中的反应性.根据所测定的化合物3d晶体结构数据,分析了这类化合物反应活性低的原因是空间位阻所致.而空间位阻较小的二茂铁醛亚胺用于该反应能够顺利进行.     

Syntheses of some 2-hydroxypyrazine 1-oxides

A series of 2-hydroxypyrazine 1-oxides were prepared from the corresponding chloropyrazines by two methods, including oxidation processes in satisfactory yields. The treatment of 2,3-diphenylpyrazine 1,4-dioxide ( 6 ) led to 2,3-dichloro-5,6-diphenylpyrazine ( 7 ) and 2-chloro-5,6-diphenylpyrazine 1-oxide ( 8 ), and the latter was converted to 5,6-diphenyl-2-hydroxypyrazine 1-oxide ( 9 ) by an alkaline hydrolysis.     

A Simple and Novel Ipso-Bromination of 1-Bromomethyl-4-t-butyl-2,6-dimethylbenzene

IPSoeleCtroPhlicsubstitutionbasattraCtedcontinuousintereStfOrInanyear."'Herein,we~anew~ndonoflboethy~wt-2,6dimethylbenzene1tytreatInentwhhnitriceddinaicohol,chchyteldslds~-2,edInethpenzene2(Schemel).,ThisreaCtionseernstobeverysmpletympce.Hme,thereactionmecbosmunderhengtheprocessviachchtheips-natedPrododfOnnsisCOInPletelyOuOfourknOwiedg.InordertoinveStigatreaction1indendl,wefirstdesgnedboOtherreactionsllandIII(Scheme2).Towhomco~ndenceshouldbeaddrssedInreactionIIandIII.wefoundthat.…     

3-Bromo-5-sulfobenzene-1,2,4-tricarboxylic Acid and Cobalt Phthalocyanine Based Thereon

3-Bromo-5-sulfobenzene-1,2,4-tricarboxylic acid and cobalt(II) phthalocyanine based thereon were synthesized.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 1022–1025.Original Russian Text Copyright © 2005 by Lutsenko, Kulinich, Shaposhnikov.     

过渡金属重卡拜的合成、结构与反应性

过渡金属硅卡拜、锗卡拜、锡卡拜和铅卡拜是过渡金属分别与硅、锗、锡和铅之间形成三键的化合物。自从1996年首次发现钼锗卡拜以来,相继得到了一系列过渡金属锗卡拜、锡卡拜和铅卡拜化合物,而首例过渡金属硅卡拜则于2010年得以成功制备,标志着过渡金属与第14族元素之间形成三键的空白被全部填满。这些化合物的出现大大丰富和完善了过渡金属主族元素化学在成键、结构和反应方面的内容,引起化学界的重视。本文结合这方面最新的实验研究进展,系统全面总结了这些化合物的合成、结构和反应性,并对该领域的发展前景作了讨论。     

基于1-(2-吡啶甲基)-1,2,4-三唑的金属有机化合物的合成及反应研究(英文)

合成了1-(2-吡啶甲基)-1,2,4-三唑(L)并研究了其与有机锡和羰基钼(钨)的配位反应,合成了通过三唑4位氮原子以单齿形式配位的有机锡衍生物L2SnR2Cl2(R=Me,n-Bu或Ph)和羰基金属配合物LM(CO)5(M=Mo或W),以及N,N螯合双齿配位的四羰基金属配合物LM(CO)4。当用氯化苄处理L时,制得了相应的三唑盐,该盐用氧化银处理后与M(CO)5THF或M(CO)4(NHC5H10)2(NHC5H10为哌啶)反应,得到了基于三唑的氮杂环卡宾衍生物L′M(CO)5和L′M(CO)4(L′=1-(2-吡啶甲基)-4-苄基-1,2,4-三唑-5-碳烯)。X-射线单晶衍射分析表明,在L′M(CO)5中氮杂环卡宾配体L′表现为通过卡宾碳配位的单齿配体;而在L′M(CO)4中,L′表现为通过卡宾碳和吡啶氮原子配位的螯合[C,N]双齿配体。     

Reactivity of an o-indoloquinone to 1- and 2-azadienes

The cycloaddition reactions of o-indoloquinone 4 to azadienes are described. With 1-azadiene 2, quinone 4 works as a dienophile to give the directly aromatized cycloadduct 6. In contrast, when 2-azadiene 3 is used, the cycloaddition occurs with CO-4, indicating that this system functions as a heterodienophile.     

Syntheses and Crystal Structures of Two 1D Chain Coordination Polymers Based on 2-Benzoylbenzoic Acid

Two new coordination polymers,[Co(BYBA)2(4,4'-bpy)(H2O)2]·H2O (1) and [Zn(BYBA)2(4,4'-bpy)] (2) (4,4'-bpy=4,4'-bipyridine,BYBAH= 2-benzoylbenzoic acid),have been synthesized by hydrothermal conditions and characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra and fluorescence spectrum.Crystal data for 1:C38H32CoN2O9,Mr= 719.59,monoclinic,space group P2/c,a=22.981(2),b=11.4438(11),c=12.9327(12),β=94.642(1)°,V=3390.0(5)3,Z=4,Dc=1.410 g/cm3,F(000)=1492,R=0.0488 and wR=0.1201;and those for 2:C38H26ZnN2O6,Mr=672.00,triclinic,space group P1,a=8.7032(10),b=11.4882(13),c=16.872(2),α=107.146(1),β=99.055(1),γ=90.851(2)°,V=1588.5(3)3,Z= 2,Dc=1.405 g/cm3,F(000)=692,R=0.0409 and wR=0.0894.Complex 1 exhibits 1D polymeric chains which are linked into a 2D sheet by π···π interactions.Complex 2 is composed by 1D zigzag chains connected through C-H···π stacking interactions to generate a 2D layer.     

Synthesis and Study of Carboxysulfo Derivatives of Phthalic Acid and Octasubstituted Metal Phthalocyanines Based Thereon

Carboxysulfo derivatives of phthalic acid and phthalimide, as well as octasubstituted metal phthalocyanines based thereon were synthesized and spectrally characterized.     

Syntheses of 2-(2-arylethyl)-1-methylimidazoles

2-(2-Arylethyl)-1-memylimidazoles 3 could be prepared by different methods. The best method was the Wittig reaction of aryltriphenylphosphonium chloride 8 with 2-formyl-1-methylimidazole to give compound 6 . Reduction of compound 6 with Raney nickel gave compound 3 .