拉诺康唑的合成工艺研究

以1-咪唑基乙腈碳和氢氧化钾反应得到二钾盐,再与2-（1,2-二氯乙基）氯苯环合反应得到目标化合物拉诺康唑,总收率为34．0％。关键中间体2-（1,2-二氯乙基）氯苯以邻氯苯乙烯为原料,经氯气加成得到。并研究了拉诺康唑异构体的转化。     

3-(2-氯苯基)-5-甲基-4-异唑甲酸的合成研究

以邻氯苯甲醛、羟胺和乙酰乙酸乙酯为主要原料，经过肟化、氯代、环合和水解反应，合成了氯唑青霉素中间体———３－（２－氯苯基）－５－甲基－４－甲基异唑甲酸。总收率达５０％以上。     

相转移催化合成环丙基－4－氯苯酮肟－O－（3－苯氧基苄基）醚

本文采用季铵盐相转移催化剂，在碱性条件下，使环丙基－４－氯苯酮肟与３－苯氧基千氯反应，合成环丙基－４－氯苯酮肟－ｏ－（３－苯氧基苄基）醚。该化合物是肟醚菊酯中生物活性较高的一种。产物经元素分析、ＩＲ和’ＨＮＭＲ鉴定。     

创制杀菌剂烯肟菌酯异构体的鉴定及杀菌活性

[目的]对烯肟菌酯异构体进行分离以及4个异构体的杀菌活性进行研究。[方法]柱层析法分离异构体,质谱和核磁进行结构鉴定。[结果]确定了烯肟菌酯4个异构体的空间构型,对黄瓜霜霉病、小麦白粉病的杀菌活性进行测定。[结论]烯肟菌酯的(E,E)和(E,Z)构型的2个异构体表现出很好的杀菌活性。     

相转移催化合成环丙基—4—氯苯酮肟—O—（3—苯氧基苄基）醚

本文采用季铵盐相转移催化剂，在碱性条件下，使环丙基－４－氯苯酮肟与３－苯氧基苄氯反应，合成环丙基－４－氯苯酮肟－Ｏ－（３－苯氯基苄基）醚。该化合物是肟醚菊酯中生物活性较高的一种。产物经元素分析，ＩＲ和＾１ＨＮＭＲ鉴定。     

3—（2—氯苯基）—5—甲基—4—异恶唑甲酸的合成研究

以邻氯苯甲醛，羟胺和乙酰乙酸乙酯为主要原料，经过肟化，氯代，环合和水解反应，合成了氯唑青霉素中间体－３－（２－氯苯基）－５－甲基－４－甲基异恶唑甲酸。总收率达５０％以上。     

气相色谱法分析六六六无效体催化脱氯加氢反应产物

目前六六六仍是我国重要的农药品种之一,它的有效体(即γ异构体)含量只有12％～14％,经甲醇提纯后可达95％以上。但是分离出来的大量无效体(α、β等异构体)却毫无用途,又污染环境。为了变害为利消除对环境的污染,大搞综合利用。我们对无效体在氯化亚铜催化剂存在下,进行了脱氯加氢的研究。获得有用的化工原料——苯、氯苯、二氯苯、三氯苯的混合物。本文主要讨论反应产物的色谱快速分析方法。根据文献资料报道,我国氯苯生产厂分析氯苯及其杂质(主要是二氯苯)的含量,     

1-(2-溴乙氧基)-4-硝基苯异构体的气相色谱分离分析

采用气相色谱法对1-(2-溴乙氧基)-4-硝基苯异构体混合物进行分离和测定,比较了4种不同固定液毛细管柱的分离效果,发现该类异构体在非极性色谱柱上分离度较好,达到基线分离;采用峰面积归一化法定量,相对标准偏差在0．46％-1．13％。     

氯氰菊酯立体异构体的毛细管气相色谱分离与测定

采用30m×0.25mmi.d.OV-1石英毛细管柱,FID氢火焰离子化检测器,在柱温220℃,对氯氰菊酯四个立体异构体进行了完全分离。该法快速、简便、重现性好,可同时完成混合物中顺反立体异构体的含量及总量的定量分析。回收率97.3％～98.6％。     

邻、间、对氯苯甲酰氯异构体的气相色谱检测

建立了直接进样法和衍生化法对于邻、间、对氯苯甲酰氯中微量位置异构体杂质分离分析的气相色谱法。在200℃的气化温度下,采用OV-17的固定液分离,将间/对/邻氯苯甲酰氯直接注入色谱仪,面积归一法测定各组分含量;同时也可将间/对/邻氯苯甲酰氯进行甲酯化衍生成稳定的酯,采用OV-200或者Bentent固定液分离,面积归一化法测定各酯的含量。实验表明上述两种方法异构体间分离度好、分析快速、精密度高,能满足化工企业质量检测要求。     

Field evidence of synergism and inhibition in the sesiidae sex pheromone system

The E,Z, Z,Z, and Z,E geometric isomers of 3,13 octadecadien-1-ol acetate were used singly and in binary combinations to trap sesiids in Wisconsin cherry orchards. The Z,E isomer alone did not capture any sesiids. A synergistic effect, however, of Z,E onSynanthedon pictipes response to its pheromone E,Z was demonstrated for the first time. Strong inhibitory effects of the Z,Z isomer onS. pictipes response to E,Z, and of the E,Z isomer onS. scitula response to Z,Z, were found. As little as 0.5% of Z,Z in E,Z completely inhibited theS. pictipes response. This species' response was also reduced by 85% when Z,Z was evaporated at 4 points, each ca. 6 m from the pheromone trap. Consistencies and discrepancies of the data with relevant experimental results from other geographical areas are briefly discussed.Lepidoptera: Sesiidae (=Aegeriidae), the clearwing moths.Research supported by the College of Agriculture and Life Sciences, University of Wisconsin, Madison, and by the Wisconsin Red Tart Cherry Ind. Market. Order.     

吉法酯中几何异构体的研究

胃粘膜保护剂吉法酯为Z/E两种几何构型的混合物。利用硝酸银处理的硅胶色谱方法分离了市售吉法酯片中的两个几何异构体,并用1HNMR、红外、质谱、元素分析进行了结构鉴定。最后分别根据气相色谱数据和1HNMR数据明确了吉法酯药品中4Z和4E两种构型的比例关系,为化学药的仿制研究及药品的质量控制提供方法依据和参考。     

Rubber substrates and their influence on isomerization of conjugated dienes in pheromone dispensers

Release rate and degree of isomerization of pheromones with conjugated double bonds were studied in dispensers prepared from several rubber substrates. The substrates compared were made of rubber, cured with elemental sulfur or accelerators based on organic sulfur compounds or organic peroxides. Isomerization of the double bonds occurs immediately after impregnation of the substrate, and the degree of isomerization increases during field use and/or storage. The propensity of the isomers to isomerize corresponds to their proportion in the equilibrium mixture. AnE,Z isomer is isomerized faster than theE,E isomer, and finally a near-equilibrium mixture of the four isomers is present. Minimal isomerization was found in non-sulfur-cured substrates which are the material of choice.     

Solid-State Photolysis of Azobis-3-Phenyl-3-Pentane. Crystal-Lattice Control of the Stereochemistry of Radical Disproportionation

The 3-phenyl-3-pentyl radicals from photolysis of azobis-3-phenyl-3-pentane (APP) in solution give 3,4-diethyl-3,4-diphenylhexane and a photolabile product assumed to arise by para coupling. Photolysis of APP as a crystalline solid at ?78° gives the disproportionation products 3-phenylpentane (PPH) and 3-phenyl-2-pentene (PP) as a 3:1 mixture of the E and Z isomers. This stereoisomeric ratio is surprising in terms of the solid-state molecular conformations, for which a topochemical scheme predicts predominance of the Z isomer. Isotopic distributions in PPH, Z-PP and E-PP from photolysis of solid APP which was 82% deuterated in its methylene groups shows: (1) that Z-PP is formed under strong lattice control; (2) that E-PP is formed in a process with greater, but not complete, molecular freedom; and (3) that there is often a dynamic competition for hydrogen-atom donation between the two radicals involved in disproportionation.     

Gaschromatographische Untersuchung stereoisomerer Cyclotrideca-1,5,9-triene

Gas Chromatographic Investigation of Stereoisomeric Cyclotrideca-1,5,9-trienes Using achiral phases of different polarity in capillary gas chromatography on the one hand and a chiral cyclodextrine phase on the other hand it is demonstrated, that a ring-enlargement sequence starting from (E, E, Z)-cyclododeca-1,5,9-triene yields five of the six theoretically possible isomeric cyclotrideca-1,5,9-trienes and (E, Z)-trans-bicyclo[10.1.0]trideca- 4,8-diene. With all achiral phases only three of the isomeric trienes and the bicyclic isomer were separated from each other; (E, Z, E)- and (Z, E, Z)-cyclotrideca-1,5,9-triene are eluated in only one (the fifth) peak, these isomers were separated on the cyclodextrine phase. Moreover, this chiral phase separates the enantiomers of the bicyclic isomer.     

(Z,E)-3,5-Tetradecadien-1-ol acetate sex attractant for the carpenterworm moth,prionoxystus robiniae (peck) (Lepidoptera: Cossidae)

Electroantennogram analyses of female gland extract and of male antennal responses to synthetic standards suggested that (Z,E)-3,5-tetradecadien-1-ol acetate is a pheromone component for the carpenterworm moth,Prionoxystus robiniae (Peck). The four 3,5-geometrical isomers were synthesized and bioassayed in the laboratory and the field in 1972, 1973, and 1974. TheZ,E isomer was found to be active in the laboratory and a good attractant in the field. The synthesis of theZ,E isomer also produced considerable quantities of theE,E isomer, which is difficult to remove completely. TheE,E isomer does not inhibit the response of males to theZ,E isomer when it is present in amounts up to 20% of theZ,E isomer. The addition of a keeper, a volatility modifier, or an antioxidant prolonged the activity of the attractant for as much as 43 days. (Z,E)-3,5-Tetradecadien-1-ol acetate may be a natural pheromone, but it has not been chemically defined from female extract. There is EAG evidence that a second pheromonal component may be present. The attractant nevertheless provides a tool for population survey, behavioral studies, evaluation of economic impact, and possibly control.     

苯氧菌酯的合成研究

以苯酞和邻甲酚为起始原料 ,生成物经酰氯化、酰氰化、水解反应得苯基草酸甲酯衍生物 ,再与甲氧基氨盐酸反应得Z/E构型混合物。该混合物经转位反应得苯氧菌酯。反应总收率为 5 7 2 % (以苯酞计 ) ,产品纯度为 95 %。该工艺流程简单 ,易于工业化生产     

C18-saturated cyclic acids from linseed oil: A structural study

The preparation of C₁₈-saturated cyclic acids from linseed oil by heat treatment in the presence of alkali, followed by hydrogenation and subsequent isolation of the cyclic fraction, gives rise to a series of at least 11 isomers as evidenced by GLC. Eight of these isomers have now been shown to be geometric pairs of positional isomers with the following general formula: {fx244-1} An unequivocal synthesis of isomers (x=0,1,2 and 3) indicates that the principal positional isomer (ca. 55%) of HCal is 9-(2′-n-propylcyclohexyl)-nonanoic acid. This isomer undoubtedly results from the cyclization of 10,12,14-octadecatrienoic acid present in the isomerized mixture. The predominance of this isomer is further substantiated by mass spectral analysis. The four positional isomers prepared constitute about 80% of the mixture as determined by gas-liquid chromatography. The four synthetic aromatic positional isomers show single peaks whereas their hydrogenated counterparts show two peaks. Thus each of the positional isomers of saturated cyclic acids is composed of two geometric isomers.     

Sex pheromone of Egyptian cotton leafworm (Spodoptera littoralis)

Samples of pheromone carriers, after use for 4–5 weeks in traps in the field, were analyzed. Partial isomerization of prodlure, (Z,E)-9,11-tetradecadienyl acetate (TDDA), the main component of the sex pheromone of femaleSpodoptera littoralis, took place. All three other possible isomers were formed to yield a mixture of 50% (Z,E)-9,11 -TDDA, 30% (E,E)-9,11-, 13% (E,Z)-9,11-, and 7% (Z,Z)-9,11 isomer. The process was found to be photochemically induced; none of these isomers was found under heating alone. Most of the pheromone, however, decomposed under field conditions.     

Sex pheromone candidates with a conjugated triene system: Synthesis and chemical characterization

Sex pheromone candidates with a conjugated triene system, 8,10,12-, 9,11,13- and 11,13,15-hexadecatrienyl acetates (double bond positional isomers of theGlyphodes pyloalis pheromone, 10,12,14-triene) were synthesized by introducing anE configuration stereospecifically to two of three double bonds and rather nonspecifically to another double bond, so as to obtain two geometrical isomers;E,E,E andE,E,Z orE,Z,E isomers. The two geometrical isomers of each triene acetate were separated on a reverse-phase HPLC column and characterized by¹H NMR analysis. The¹³C NMR signals in the olefinic region of each isomer were assigned by two-dimensional NMR techniques and also by an empirical rule based on the changes of the chemical shifts by converting the configuration. Based on the assignments, substituent parameters for calculating the chemical shifts of 1,6-dialkyl conjugated trienes were generated. Electron impact mass spectrometry showed characteristic fragment ions that enabled the double bond positional isomers to be distinguished from each other.