4-羟基-5(4′-氯苯基)双环[4,4,0]-1-氮杂癸烷的合成

以 4′ 氯哌醋甲酯为原料,研究了作为潜在的治疗可卡因滥用症的药物———4 羟基- 5- (4′- 氯苯基 )双环 [4,4, 0]- 1 氮杂癸烷的合成。4′- 氯哌醋甲酯首先用乙酸酐在室温下进行乙酰基化,然后在 -70℃下经二异丙基胺锂(LDA)作用关环得中间产物(±)- threo -2, 4 -二氧代- 5- (4′- 氯苯基)双环[4, 4, 0] -1 氮杂癸烷,产率 60%。中间体先用硼氢化钠在甲醇中室温下选择性地将酮羰基还原,粗产物经V(石油醚)∶V(乙酸乙酯) =1∶1重结晶后,在四氢呋喃中于回流温度下用乙硼烷 四氢呋喃络合物进一步还原酰胺基,得到(±) threo 4α 羟基- 5 -(4′- 氯苯基 )双环[4, 4, 0]- 1 氮杂癸烷,两步产率为 67%。所得α位羟基产物经过Swern氧化,然后在四氢呋喃中在 -78℃下用三(仲丁基)硼氢化钾选择性还原,立体专一性地得到 (±) threo- 4β 羟基- 5 (4′- 氯苯基 )双环 [4, 4, 0]- 1 氮杂癸烷,氧化 还原反应总产率为 70%。     

Reaction of ethyl N-(6-ethoxycarbonyl-2-methylthiothieno[2,3-d]-pyrimidin-5-yl) formimidate with alkyl- and arylhydrazines: Formation of modified thieno[2,3-d]pyrimidines and thieno[2,3-d:4,5-d]dipyrimidin-4-ones

The reaction of ethyl N-(6-ethoxycarbonyl-2-methyl-thiothieno[2,3-d]pyrimidin-5-yl)formimidate ( 1 ) with methyl-hydrazine, N,N′-dimethyl- and N,N′-diphenylhydrazines separately in refluxing ethanol resulted in hydrolysis of formimidate group to give ethyl 5-amino-2-methylthiothieno[2,3-d] pyrimidine-6-carboxylate ( 2 ). The reaction on 1 with methyl-hydrazine without solvent afforded ethyl 5-amino-2-(1-methyl-hydrazino)thieno[2,3-d]pyrimidine-6-carboxylate ( 3 ), which underwent hydrazone formation with p-nitrobenzaldehyde to give 4 . Treatment of 1 with N,N-dimethylhydrazine afforded a mixture of 3-dimethylamino-7-methylthiothieno[2,3-d:4,5-d']dipyrimidin-4(3H)-one ( 5 ) and 2 . Displacement of methylthio group in 5 with morpholine, piperidine and 4-methylpiperazine gave the corresponding 7-substituted derivatives 6a-c . The reaction of 1 with para-substituted phenylhydrazines resulted in the formation of 3-(p-substituted phenylamino)7-methylthiothieno[2,3-d:4,5-d']dipyrimidin-4 (3H)ones ( 7a-c ).     

Synthesis of polyazaheterocycles by Michael addition of CH acids to α,β-unsaturated nitriles. Synthesis of pyrido[1,2-a]benzimidazole and pyrimido[5′,4′: 5,6]pyrido[1,2-a]benzimidazole derivatives

Addition of 1H-benzimidazole-2-carbonitrile ( 1 ) to arylidenemalononitrile ( 2 ) gave 1-amino-3-aryl pyrido[1,2-a]benzimidazole-2,4-dicarbonitrile ( 3 ), 2-aryl-benzimidazole ( 4 ) and 1H-benzimidazole-2-acetonitrile,α-(arylmethylene) ( 5 ). Compounds ( 3 ) reacted with formamide yielding 4-amino-5-aryl pyrimido[5′,4′: 5,6]pyrido[1,2-a]benzimidazole ( 6 ).     

Synthesis of pyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles and pyrazolo[4′,3′:5,6]pyrazino[2,3-d]pyrimidines and their application to polyester fibres

4-Nitroso-1-phenyl-3-methyl-5-aminopyrazole ( 1 ) was condensed with ethylcyanoacetate ( 2 ), malononitrile ( 4a ) and 2-cyanomethylbenzimidazole ( 4b ) to yield 6-hydroxy-5-cyano, 6-amino-5-cyano and 6-amino-5-(benzimidazol-2-yl)-3-methylpyrazolo [3,4-b]pyrazines 3, 5a and 5b , respectively. 5-Cyano-6-chloro derivative 6 obtained from 3 was converted to 3-aminopyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles 8a and 8b by the treatment with hydrazin hydrate ( 7a ) and phenylhydrazine ( 7b ), respectively. Compound 5a was treated with formamide ( 9a ), urea ( 9b ) and thiourea ( 9c ) to give 4-aminopyrazolo[4′,3′:5,6]pyrazino[2′3′-d]pyrimidines 10a–10c. With refluxing acetic anhydride compounds 8a, 8b and 10a gave corresponding acetamido derivatives 8c, 8d and 10d. Compound 5a was treated with ethylorthoformate ( 11 ), acetic anhydride ( 12 ) or benzoylchloride ( 13 ) to give fused benzimidazopyrazolo[4′,3′:5,6]pyrazino[2′,3′-d]pyrimidines, viz., benzimidazol[1,2-c]pyrazolo[4,3-g]pteridines ( 14a–14c ). Some of the compounds 8, 10 and 14 were applied to polyester as disperse dyes and their fastness properties were studied.     

Z-2′-[1-(1,2,4-三唑)基]-O-(α-甲基对卤苄基)-2,4-二氯苯乙酮肟硝酸盐的合成

以 2 ,4 二氯氯代苯乙酮、1,2 ,4 三唑和羟胺为原料 ,合成了Z 2′ [1 (1,2 ,4 三唑 )基 ] 2 ,4 二氯苯乙酮肟 (Ⅰ ) ,以对氯 (对溴 )苯乙酮合成对氯 (对溴 ) α 氯乙苯 (ⅡA 和ⅡB) ,Ⅰ分别与ⅡA和ⅡB 反应生成Z 2′ [1 (1,2 ,4 三唑 )基 ] O (α 甲基对卤苄基 ) 2 ,4 二氯苯乙酮肟硝酸盐两个化合物 ,产率为 6 2 .5 %和 5 8.8% ,化合物结构经元素分析、IR和1HNMR确定。     

Untersuchungen zum anodischen Verhalten von Carbazolen und Indolo[3,2-b]carbazolen in Acetonitril

Investigations on the Anodic Behaviour of Carbazoles and Indolo[3,2-b]carbazoles The anodic oxidation of some substituted or condensed carbazole derivatives 1 – 6 has been investigated in acetonitrile using platinum electrodes. Substitution of the carbazoles in the 3-, 6-, and 9-positions prevents the anodic dimerization occurring otherwise in these positions. In these cases the electrochemical formation of stable cation radicals is possible. A stabilization of these anodie primary products and a decrease of the half-wave potentials is also effected by enlarging the π-electron system as in N-p-anisyl-dibenzo[e,g]carbazole 2 , in the indolo[3,2-b]-carbazoles 3 and in 9,9′-diphenyl-3,3′-dicarbazyl 4 . Due to the distortion of the C N-bonds neither a change of half-wave potentials nor a stabilization of the cation radicals by donor substitution or mesomeric effects has been observed in the case of N-p-anisylcarbazole 1 h , 1,4-bis-(9-carbazyl)-benzene 5 and 4,4′-bis-(9-carbazyl)-biphenyl 6 in comparison with N-phenyl-carbazole 1 e . The electrochemical preparation of 4 and the spectroscopical investigation of the cation radicals of some of the compounds are described.     

3-[N-(3-烷氧基-2-羟基丙基)-N,N-二甲基铵]-2-羟基丙基酸性磷酸酯甜菜碱的合成

以高级脂肪醇、环氧氯丙烷、二甲胺和磷酸二氢钠为原料,合成了一类新型的磷酸酯甜菜碱两性表面活性剂3-[N-(3-烷氧基-2-羟基丙基)-N,N-二甲基铵]-2-羟基丙基酸性磷酸酯甜菜碱(简称AHDHPB),并通过红外光谱对其结构进行了分析,测定了表面活性。研究了AHDHPB．12和阴离子表面活性剂(As)复配体系的降低表面张力能力、降低表面张力效率的增效作用。结果表明,合成的两性表面活性剂AHDHPB结构独特,具有较高活性和复配性能。     

Synthesis and Characterisation of Polyamides and Polyimides from Amino/Methylene bis[Benzenamine] Styryl Pyridines

Polyamides and polyimides containing diamines, with potential non-linear optical characteristics, were prepared using (E)-4,4′-[[[2-(4-pyridinyl)ethenyl]phenyl]amino]bis[benzenamine] and (E)-4-4′-[[[2-(4-pyridinyl)ethenyl]2-methyl phenyl]amino]bis[benzenamine] condensed with pyromellitic dianhydride to obtain poly(amic acid)s. The poly(amic acid)s were soluble in polar aprotic solvents, such as dimethylformamide, dimethylsulphoxide and dimethylacetamide, and could be cast into transparent, tough, flexible films. Amorphous thermally stable polyimides were formed by cyclodehydration. Similarly, (E)-4,4′-[[[2-(4-pyridinyl)ethenyl]phenyl]methylene]bis[benzenamine] and (E)-4,4′-[[[2-(4-pyridinyl)ethenyl]phenyl]methylene]bis[N-ethylbenzenamine] were condensed with 3-methyladipoyl chloride to obtain other new polyamides. Characterisation using infra-red and nuclear magnetic resonance spectroscopy, X-ray diffraction and thermogravimetric analysis are reported. © 1997 SCI.     

Ring closure reaction of 5-hydroxy-pyrido[2,3-d]pyrimidine-2,4,7-triones to benzo[b]pyrimido[4,5-h]1,6-naphthyridine-1,3,6-triones

N-Substituted aminouracils ( 1 ) react with malonates by cyclocondensation to 5-hydroxy-pyrido[2,3-d]pyrimidine-2,4,7-triones ( 2 ), which give with triethylorthoformate and aniline 6-(phenylaminomethylene)-pyrido[2,3-d]pyrimidine-tetraone ( 3 ). Halogenation of 2a - d (with R² = Me) with phosphorylchloride leads to 5,7-dichloro-pyrido[2,3-d]pyrimidine-2,4-diones ( 4 ) by cleavage of the methyl group at N-8, whereas Vilsmeier reaction of 2 affords 5-chloro-6-formyl derivatives ( 6 ), which cyclize with arylamines to give benzo[b]pyrimido[4,5-h] 1,6-naphthyridines ( 9 ). Compounds 9 were obtained independently by amination of the tosylates 5 to the 5-arylamino compounds 8 , and Vilsmeier formylation to yield 9 .     

N,N-二甲基色胺衍生物合成研究

以四氢呋喃和对氰甲基盐酸苯肼 (Ⅹ )为主要原料合成了色胺衍生物N ,N 二甲基 2 { 5 [(3 氨基 1,2 ,4 口恶二唑 5 基 )甲基 ] 1 氢 吲哚 3 基 }乙胺 (Ⅶ )。四氢呋喃和氯化氢反应 ,得到4 氯丁醇 ( ) ,产率为 6 2 % ;用氯铬酸吡啶盐氧化得 4 氯丁醛 ( ) ,产率为 6 1% ;经缩醛化得 4 氯丁醛缩甲醇 ( ) ,产率为 5 6 % ;用二甲胺取代得 4 (N ,N 二甲胺基 )丁醛缩甲醇(Ⅸ ) ,产率为 86 % ;Ⅸ与Ⅹ经环化得N ,N 二甲基 2 [5 (氰甲基 ) 1氢 吲哚 3 基 ]乙胺 (Ⅺ ) ,产率为 76 % ;Ⅺ经酯化得N ,N 二甲基 2 [5 (乙酯甲基 ) 1氢 吲哚 3 基 ]乙胺 (Ⅻ ) ,产率为 82 % ;Ⅻ与羟基硫酸胍缩合得产物 (Ⅶ ) ,产率为 6 6 %。     

Blue organic light-emitting diodes using novel spiro[fluorene-benzofluorene]-type host materials

Deep blue colored, fluorescent, spiro-type host materials, 5-[4-(1-naphthyl)phenyl]-spiro[fluorene-7,9′-benzofluorene] and 5,9-bis[4-(1-naphthyl)phenyl]-spiro[fluorene-7,9′-benzofluorene] were designed and successfully prepared by the Suzuki reaction. The electroluminescence characteristics of the two compounds as blue host materials doped with blue dopant materials, diphenyl[4-(2-[1,1;4,1]terphenyl-4-yl-vinyl)phenyl]amine and 1,6-bis[(p-trimethylsilylphenyl)amino]pyrene (SPP) were evaluated. The device used comprised ITO/N,N′-bis-[4-(di-m-tolylamino)phenyl]-N,N′-diphenylbiphenyl-4,4′-diamine)/bis[N-(1-naphthyl)-N-phenyl]benzidine/Host:5% dopant/tris(8-hydroxyquinolinato)aluminium/Al–LiF. The device obtained from 5-[4-(1-naphthyl)phenyl]-spiro[fluorene-7,9′-benzofluorene] doped with 1,6-bis[(p-trimethylsilylphenyl)amino]pyrene displayed high color purity (0.138, 0.138) and high efficiency (3.70 cd/A at 7 V).     

Blue light-emitting diodes from 2-(10-naphthylanthracene)-spiro[fluorene-7,9′-benzofluorene] host material

A novel, spiro-type host material 2-(10-naphthylanthracene)-spiro[fluorene-7,9′-benzofluorene] was prepared by reacting 2-bromo-spiro[fluorene-7,9′-benzofluorene] with 9-(2-naphthylanthracene)-10-boronic acid via the Suzuki reaction. 2-4′-(Phenyl-4-vinylbenzeneamine)phenyl-spiro[fluorene-7,9′-benzofluorene], 4-[2-naphthyl-4′(phenyl-4-vinylbenzeneamine)]phenyl and diphenyl-[4-(2-[1,1;4,1]terphenyl-4-yl-vinyl)-phenyl]-amine were used as dopant materials. Devices with the configuration of ITO/N,N′-bis[4-(di-m-tolylamino)phenyl]-N,N′-diphenylbiphenyl-4,4′-diamine)/bis[N-(1-naphthyl)-N-phenyl]benzidine/2-(10-naphthylanthracene)-spiro[fluorene-7,9-benzofluorene]:5% dopant/aluminum tris(8-hydroxyquinoline)/Al-LiF showed a maximum power efficiency of 3.7 cd/A at 17.93 mA/cm² and a maximum luminance of 5018 cd/m² at 10 V with a turn-on voltage of 4.5 V.     

Regioselective synthesis of new 5-methyl-5H-pyrimido[4′,5′:4,5][1,3]thiazino [3,2-a]perimidines

A convenient and efficient regioselective synthesis of new pyrimido[4′,5′:4,5] [1,3]thiazino[3,2-a]perimidines is described through intermolecular heterocyclization of 2,4-dichloro-5-(chloromethyl)-6-methylpyrimidine and 1H-perimidine-2(3H)-thione in short reaction times under mild conditions.     

In situ FTIR spectroelectrochemistry of poly[2-(3-thienyl)ethyl acetate] and its hydrolyzed derivatives

Poly[2-(3-thienyl)ethyl acetate] (PTEtAc) was chemically synthesized and transformed to partially hydrolyzed PTEtAc (PTEtAcOH) and poly[2-(3-thienyl)ethanol] (PTEtOH). The influence of the acetoxy and hydroxyl terminal functionalities in the side groups on the electrochemical properties of these polyalkylthiophenes was studied by cyclic voltammetry and in situ FTIR spectroelectrochemistry. The cyclic voltammograms point to a chemically reversible behaviour of the p-doping process for PTEtAc and PTEtAcOH, while for PTEtOH the redox activity of the polymer film is lost during consecutive potential scans.The attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) was used to investigate the p-doping of the three different type of thiophene polymer films. In situ FTIR spectra taken at different electrode potentials in a cyclovoltammetric scan display the doping induced changes of the polymer pattern. Important differences in the behaviour of the polymers were observed and interpreted in terms of different film structures.     

N-[4-(4-溴丁氧基)-2-硝基苯基]乙酰胺的合成

以对乙酰氨基苯酚为原料,经烷基化、硝化合成N [4 (4 溴丁氧基) 2 硝基苯基]乙酰胺。用正交实验确定了烷基化反应的适宜条件为n(KOH)∶n(1,4 二溴丁烷)∶n(对乙酰氨基苯酚)=1 2∶2 8∶1,68～70℃反应80min,重结晶后收率为77 42%。硝化反应的适宜原料配比为n(HNO3)∶n(乙酸酐)∶n〔N [4 (4 溴丁氧基)苯基]乙酰胺〕=1 9∶9 6∶1,温度低于10℃反应收率可达92 2%。用薄层色谱、IR、1HNMR对产物进行了结构鉴定。分析目标产物及相关化合物的1HNMR谱,结果表明,在邻硝基乙酰苯胺及其衍生物中芳环上乙酰氨基邻位质子化学位移比按经验公式计算的预测值大0 6～1 3,这一特征是硝基和乙酰氨基相互作用的结果。     

A short-cut to 2,7-dihydrothiopyrano[2,3-b]pyrrole

A simple original approach to earlier unknown parent 2,7-dihydrothiopyrano[2,3-b]pyrrole (5) from allyl isothiocyanate and propargyl bromide via one-pot synthesis and thermal rearrangement of 2-(prop-2-ynylsulfanyl)-1H-pyrrole (4) has been developed. The compound 5 in the present study was successfully examined as 2,7-dihydrothiopyrano[2,3-b]pyrrole scaffold in the synthesis of corresponding N- and C-pyrrolecarbodithioates.     

Synthese neuer Thieno [2′,3′; 4,5]imidazo[1,2-a]pyridiniumsalze

Syntheses of New Salts of Thieno[2′,3′;4,5]imidazo[1,2-a]pyridines Mesomeric 1-[2-amino-1-cyano-2-thio-]ethene-pyridinium ylides 1 are cyclizized to imidazo[1,2-a]pyridinium ylides 2 in the presence of HgO. S-alkylation of 2 leads to derivatives of 1-R¹-2-thio-3-cyano-imidazo[1,2-a]pyridinium halides 3 or 4 . Alkylation products from 2 with α-haloketones are cyclizized to thieno[2′,3′ 4,5]imidazo[1,2-a]pyridinium salts 5 .     

1H-NMR-spektroskopische Analyse von 2-Dimethylamino-[1,3,2]dioxarsolan und -dithiarsolan

¹H-n.m.r. Spectroscopic Analysis of 2-Dimethylamino-[1,3,2] dioxarsolane and Dithiarsolane The ¹H-n.m.r. spectra of (CH₂)₂X₂As N(CH₃)₂ (X = O, S) show an AA′BB′ spin system for the protons of the methylene group which is reduced to an A₄ system by addition of HN(CH₃)₂. This reduction proves a rapid exchange of the N(CH₃)₂ group. This assumption is proved by isotope marking with ¹⁵N-marked dimethylamine.     

Synthesis of pyrazolo[4′,3′:5,6]pyrido[1,2-a]benzimidazole derivatives and study of their fluorescence properties

Synthesis of pyrazolo[4′,3′ :-5,6′pyrido]1,2-a benzimidazoles was achieved by the condensation of 1-chloro-2-formyl-3-methyl pyrido[1,2-a]benzimidazole-4-carbonitrile and 1-chloro-3-methyl pyrido[1,2-a]benzimidazole-2,4-dicarbonitrile with hydrazine hydrate and phenyl hydrazine. The fluorescence properties of the resulting compounds were studied. Some of the compounds when applied on polyester fibres as fluorescent brighteners gave excellent results.     

Two-component,one-pot synthesis of pyrimido[1,2-b] [1,2,4,5]tetrazines

Derivatives containing the cyclohepta4′,5′thieno[2′,3′:4,5]pyrimido[1,2-b][1,2,4,5]-tetrazin-6-one system were prepared from the reaction of 3-amino-2-thioxo-1,2,3,5,6,7,8,9-octahydro-4H-cyclohepta[4,5]thieno[2,3-d]pyrimidin-4-one (5) or its 2-methylthio derivative 6 with hydrazonoyl chlorides 9. The mechanism of the studied reactions has been discussed and the biological activity of the isolated products has been evaluated.