h-线敏感光致产碱剂PNCDP的合成与表征

设计并合成了一种对高压汞灯发射光谱中的h-线(405 nm)敏感的新型光致产碱剂(PBG)——N-{[(5-哌啶-2-硝基苄基)氧]-羰基}-2,6-二甲基哌啶(PNCDP).通过红外(IR)、核磁(NMR)以及元素分析对PNCDP的结构进行了表征.紫外-可见光谱(UV-Vis)测试结果表明,与传统的i-线(365 nm)敏感PBG——N-{[(4,5-二甲氧基-2-硝基苄基)氧]-羰基}-2,6-二甲基哌啶(DNCDP)相比,PNCDP的最大紫外吸收波长为395.5 nm,较DNCDP红移了52.5 nm.初步光刻实验表明,PNCDP对h-线具有较好的敏感度.     

Synthese eines Pentapeptidderivates der Insulinsequenz A17-A21

Synthesis of a Pentapeptide Derivative of the Insulin Sequence A₁₇–A₂₁ The synthesis of the protected pentapeptide derivative N-2-(p-biphenylyl) isopropyloxycarbonyl-γ-t-butyl-L -glutamyl-L -asparaginyl-O-t-butyl-L-tyrosyl-S-diphenylmethyl-L -cysteinyl-L-asparagine t-butyl ester is described. Its amino acid sequence corresponds to the sequence 17–21 of the insulin A-chain.     

Darstellung und Reaktionen von 2-Arylazo-2-nitro-keten-aminalen

Synthesis and Reactions of 2-Arylazo-2-nitro-keten Aminals N,N′-Disubstituted 1-nitro-2,2-diamino ethylenes 1 undergo azo-coupling to form the title compounds 2 . Their treatment with oxalyl chloride yields the imidazolidin-4,5-dione-derivatives 4. 2 react with phosgene and thiophosgene to form 6-nitro-2,4-diaryl-5-arylimino−2,3,4,5-tetrahydro-1,2,4-triazin-3-ones 5 and -thiones 6 respectively. From 2 and N-(dichloromethylene)-arylsulfoamides the 6-nitro-2,4-diaryl-5-arylimino-3-aryl-sulfonylimino-2,3,4,5-tetrahydro-1,2,4-triazines 7 arise. The reduction of 2 yields the substituted oxalic amidines 9     

N-(2-氟-4-氯-5-环戊氧基苯基)氨基甲酸乙酯的合成

环戊口恶草酮是一种新型口恶唑啉二酮类除草剂,N-(2-氟-4-氯-5-环戊氧基苯基)氨基甲酸乙酯是合成该除草剂的重要中间体之一.本文以5-硝基-2-氯-4-氟苯酚为原料,经催化加氢还原、烷基化反应等合成了N-(2-氟-4-氯-5-环戊氧基苯基)氨基甲酸乙酯.该方法操作简便,四步总收率达56.7%.     

New Intermediates and Dyes for Synthetic-polymer Fibres Derivatives of 2-Chloro-4-nitro-4‘-(N-β-hydroxyethyl-N- β-cyanoethylamino)azobenzene

Condensation of 2-chloro-4-nitro-4^t-(N-(β-hydroxyethyl-N-β-cy anoethylamino)azobenzene with various acid chlorides, chloroformates, isocyanates, isothiocyanates and reactive halogeno compounds gives dyes of excellent fastness to light and sublimation on polyester fibres.     

烯啶虫胺合成方法的研究

介绍了一种合成杀虫剂烯啶虫胺的方法。以2-氯-5-氯甲基吡啶和偏二氯乙烯为起始原料,先制成中间体N-(6-氯-3-吡啶基甲基)-N-乙胺和1,1-二氯-2-硝基乙烯,再通过二者的缩合反应制成产品烯啶虫胺。反应总收率可达72%(以2-氯-5-氯甲基吡啶计),纯度为97%。     

催化加氢法绿色合成N-(3-氨基-4-甲氧基苯基)乙酰胺

N-(3-氨基-4-甲氧基苯基)乙酰胺是生产偶氮型分散染料的一类重要中间体。现有的工业生产方法仍全部采用铁粉还原。笔者开发了一种高效的Pd/C催化剂,分别选用甲醇和水作为反应溶剂,实现了高活性、高选择性和高稳定性地催化加氢制备N-(3-氨基-4-甲氧基苯基)乙酰胺。为了抑制原料和产物在水溶液中的副反应,添加少量碱性助剂可以提高目标产物的选择性,最高达到99.3%。     

5-硝基苯并三唑-1-乙酸镝与1,10-邻菲啰啉配合物的合成和性质研究

采用溶液合成法,合成了标题化合物,通过元素分析、摩尔电导率、紫外光谱、红外光谱和热分析法确定配合物的组成为Dy(L)3phen.1.5H2O(HL=5-硝基苯并三唑-1-乙酸;phen=1,10-邻菲啰啉)。荧光光谱表明:镝配合物的荧光强度较强,说明配体5-硝基苯并三唑-1-乙酸和1,10-邻菲啰啉是很好的敏化剂。     

Synthesis of poly(ethyl vinyl ethers) containing two dipolar electronic systems and their properties

Summary 5-Nitro-2-(2′-vinyloxyethoxy)benzylidenemalononitrile (2a), methyl 5-nitro-2-(2′-vinyloxyethoxy)benzylidenecyanoacetate (2b), 3-nitro-4-(2′-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl 3-nitro-4-(2′-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of 5-nitro-2-(2′-vinyloxyethoxy)benzaldehyde (1) and 3-nitro-4-(2′-vinyloxyethoxy)benzaldehyde (3) with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2a-b and 4a-b were polymerized with boron trifluoride etherate as a cationic initiator to yield poly(vinyl ethers) 5-6 having nitrooxybenzylidenemalononitrile and nitrooxycyanocinnamate, which is effective chromophore for second-order nonlinear optical applications. Polymers 5-6 were soluble in common organic solvents such as acetone and DMSO. T _g values of the resulting polymer were in the range of 70–81°C. Electrooptic coefficient (r₃₃) of the poled polymer films were in the range of 19–27 pm/V, which was improved by introducing of nitro group. Polymers 5–6 showed a thermal stability up to 300°C in TGA thermograms, which is acceptable for NLO device applications. Received: 24 November 1998/Revised version: 19 January 1999/Accepted: 29 January 1999     

抗高血压药缬沙坦的新合成方法

以2N-三苯甲基-5-(4'-溴甲基联每2-基)四氮唑为原料,与L-缬氨酸甲酯盐酸盐反应制得N-[[2'-(2N-三苯甲基-四氮唑-5-基)-(1,1'-二苯基)-4-基]-甲基]-L-缬氨酸甲酯,然后经过脱三苯甲基保护、酰化、水解得到标题化合物,总收率49.8%.     

Darstellung und Reaktionen von 2-Arylamino-3-nitrochinolinen

Synthesis and Reactions of 2-Arylamino-3-nitroquinolines Condensation of 1-nitro-2,2-bis(methylthio)ethylene with esters of anthranilic acid yields 2-arylamino-3-nitro-4-quinolones. 2 . Analogously, from 1-nitro-2-anilino-2-methylthioethylene and o-aminoketones, 2-anilino-3-nitroquinolines 4 are obtained which can be reduced to 2-anilino-3-amino-quinolines 7 . The latter undergo cyclizations by usual methods to yield substituted triazolo-, imidazolo-, diazepino- and pyrazino-quinolines 9–12 . Reaction of ethyl-2-aminothiophene-3-carboxylates with 1-nitro-2-anilino-2-methylthio-ethylene affords 2-anilino-3-nitrothieno[2,3-b]-4-pyridones 5 .     

Voltammetric oxidation of Hantzsch 1,4-dihydropyridines in protic media: substituent effect on positions 3,4,5 of the heterocyclic ring

A detailed study was done of the electrochemical oxidation of some 1,4-dihydropyridine (1,4-DHP) derivatives in order to determine the influence of the substituents in the heterocyclic ring. Two types of derivatives were synthesized, namely, 3,5-(substituted)-4-(5′-nitro-2′-furyl)-1,4-DHP for series A, and 3,5-dicarboethoxy-4-(substituted or non-substituted)-1,4-DHP for series B. Voltammetry, coulometry, controlled potential electrolysis, UV-vis spectroscopy and GC-MS techniques were employed to collect data that permitted to postulate oxidation mechanisms in a protic medium. In acid media, at pH < 4, all derivatives follow oxidation mechanisms obeying the ECE sequence. However, at pH > 4, series A derivatives follow an ECEC sequence, while series B derivatives obey a DISP1 mechanism. In both cases, the uptake of proton at N-1 by the OH⁻ ion of the media was the rate-determining step.     

Cyclisierungen mit 1-Nitro-2-anilino-äthylenen

Cyclizations with 1-nitro-2-anilino-ethylenes The reaction of 1-nitro-2-anilino-2-methylthio-ethylenes 1 with oxalyl chloride yields the substituted 4-nitropyrrol-2,3-diones 4 , and with chlorocarbonyl-sulfenylchloride the 5-nitro-thiazolones 6 . The methylthio group from 6 can be exchanged by amines. From 1-nitro-2,2-bis(anilino)ethylenes 2 – available from 1-nitro-2,2-bis(methylthio)-ethylene and anilines – and the same reagents, the substituted 2-nitromethylene-imidazolidine-4,5-diones 5 and the thiazolo[4,5-d]thiazoledione 9 result. The condensation of 1-nitro-2-anilino-2-hydrazino-ethylene 3 with derivatives of carboxylic acids yields 2-nitromethyl-s-triazole 12 , with diacetyl the substituted 3-nitromethylene-as-triazine 13 .     

氟噻草胺的合成

改进了除草剂氟噻草胺的合成方法。以肼基二硫代甲酸甲酯、三氟乙酸为原料合成2-甲砜基-5-三氟甲基-1,3,4-噻二唑(4),反应收率81.5%;以对氟硝基苯、丙酮经过催化加氢、酰化、醇解合成N-(4-氟苯基)-N-异丙基-2-羟甲基乙酰胺(8)。化合物(4)与(8)反应合成氟噻草胺,得率94.2%。改进后的工艺反应条件温和,三废少,产品纯度和收率高。     

单氨基改性PBO的AB型新单体的合成

研究了以4-(甲氧羰基)-2-硝基苯甲酸(β-MNT)与4-氨基-6-硝基间苯二酚盐酸盐(ANR·HCl)为原料经酰氯化、N-酰化、环合、水解和催化加氢还原等一系列反应合成得到中间体4-((2,4-二羟基-5-硝基)氨甲酰基)-3-硝基苯甲酸甲酯(3-NMNC)、4-(5-硝基-6-羟基-2-苯并 唑基)-3-硝基苯甲酸甲酯(3-NMNB)、4-(5-硝基-6-羟基-2-苯并 唑基)-3-硝基苯甲酸(3-NNBA)及单氨基改性PBO的AB型新单体4-(5-氨基-6-羟基-2-苯并 唑基)-3-氨基苯甲酸(3-AABA),并对环合、水解和催化还原加氢的反应条件进行了优化.结果表明:对于环合反应,以二乙二醇二甲醚为溶剂,PPA为环合脱水剂其中P₂O₅含量84%,w(PPA):w(3-NMNC)=9.5:1,反应温度140℃,反应时间8h,3-NMNB收率73.16%,HPLC纯度99.10%;水解反应,以乙醇与水为溶剂,n(K₂CO₃):n(3-NMNB)= 1.8:1,加热水解2h,3-NNBA收率74.19%,HPLC纯度为98.59%;催化加氢还原反应,甲醇为溶剂,w(10%Pd/C):w(3-NNBA)=1:20,1 MPa氢压,80℃反应5h得3-AABA,HPLC纯度99.43%,收率65.08%.中间体和产物结构经FT-IR、¹³C-NMR和ESI-MS表征确认.     

Structure and Tautomerism of ANTA (aminonitrotriazole)

Energy and dipole moment calculations show 3-nitro-5- amino-1,2,4-triazole is the most stable tautomer of ANTA either in the gas phase and polar solvents, in agreement with X-ray findings. Our calculations predict that the 5-nitro-3-amino-1,2,4-triazole tautomer is more sensitive to shock or impact. Some discrepancies between semiempirical (AMI and PM3) calculations and ab initio (up to 6-31G*//6-31G) are studied.     

Isomerization of 4-Bromo-2-methyl-5-nitro-1-phenacylimidazoles into 5-Bromo-2-methyl-4-nitro-1-phenacylimidazoles

4-Bromo-2-methyl-5-nitro-1-phenacylimidazoles ( 1a-e ) dissolved in EtOH in presence of sodium bicarbonate (or without it) heated under reflux were isomerized into 5-bromo-2-methyl-4-nitro-1-phenacylimidazoles ( 5a-e ). The structures of 5a-e were assigned using SFORD (Single Frequency Off Resonance Decoupling) and COLOC (Correlation Spectroscopy for Long Range Coupling) NMR techniques. A conceivable mechanism of isomerization is discussed.     

2（3—（5—硝基并异噻唑）偶氮）—6—异丙基苯酚的合成及其性质研究

以２－氰基－４－硝基苯为原料合成了３－氨基－５－硝基－２，１－苯并异噻唑，并使之与邻异丙基苯酚偶联，得到２－（３－５－硝基苯并异噻唑）偶氮）－６－异丙基苯酚，它有可能成为一个敏锐的酸碱指示剂和Ｃｕ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋等离子的显色剂。     

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 %。     

内和外N-烷基酰亚胺的杀虫增效活性研究

利用硅胶柱层析方法 ,提纯增效剂 A1得到内 ( endo) N- ( 2 -乙基 )己基 - 1 -异丙基 - 4-甲基二环 [2 ,2 ,2 ]- 5-辛烯 - 2 ,3-二甲酰亚胺 ( 1 )。由 α-松油烯合成外 ( exo) α-松油烯 -马来酸酐加成物 ,再与 2 -乙基己胺反应合成外 ( exo) N- ( 2 -乙基 )己基 - 1 -异丙基 -4-甲基二环 [2 ,2 ,2 ]- 5-辛烯 - 2 ,3-二甲酰亚胺 ( 2 )。利用元素分析、IR和 1H NMR对 1和 2的结构进行鉴定。杀虫增效活性试验证明 :内型结构 ( endo) 1的增效活性强于外型结构 ( exo) 2。