3,3-二甲基-4-戊烯酸甲酯合成方法的改进及表征

采用相模法以原乙酸三甲酯与3-甲基-2-丁烯醇为原料,经过重排反应和酯交换反应,合成了除虫菊酯类杀虫剂的重要中间体3,3-二甲基-4-戊烯酸甲酯。改进相模的工艺更适应工业生产,收率达到85.6%,产品纯度达到99.2%。     

3,3-二甲基-4-戊烯酸-3''''-甲基-2''''-丁烯酯的回收与利用

针对目前工业上回收3,3-二甲基-4-戊烯酸-3'-甲基-2'-丁烯酯(MBDP)工艺复杂、异戊烯大量分解问题,研究了MBDP直接返回循环使用工艺,MBDP与甲醇、原乙酸三甲酯或与甲醇原乙酸三甲酯混合溶液进行酯交换反应的回收新工艺,比较了四异丙基钛酸酯、甲醇钠、氢氧化钾用作酯交换催化剂的效果,筛选出回收MBDP“一锅煮”最佳工艺:按照n(MBDP)∶n(原乙酸三甲酯)∶n(甲醇)∶n(甲醇钠)=1.0∶9.8∶9.2∶0.05物质的量比投料,74℃～78℃反应21h,MBDP转化为贲亭酸甲酯和异戊烯醇,单程转化率87.7%,用85%的磷酸中和甲醇钠,蒸出甲醇,直接用于合成贲亭酸甲酯。     

2-(2-苄氧羰基氨基噻唑-4-基)-5-(3-甲基-2-丁烯氧羰基)-2-戊烯酸合成

对头孢布烯的关键中间体2-(2-苄氧羰基氨基噻唑-4-基)-5-(3-甲基-2-丁烯氧羰基)-2-戊烯酸(1)的制备工艺进行了研究。选用2-(2-苄氧羰基氨基噻唑-4-基)-2-戊烯二酸(2)与1-溴-3-甲基-2-丁烯进行选择酯化反应制得目标化合物1,反应总收率82.5%,该工艺操作简单,生产成本较低。     

顺/反-异戊烯基-3-甲基丁二烯醚的合成研究

以异戊烯醛和异戊烯醇为原料,经异戊烯酸催化缩醛化反应得到3-甲基-2-丁烯醛二异戊烯基缩醛,再经磷酸催化消除反应得到顺/反-异戊烯基-3-甲基丁二烯醚.对缩醛化反应条件和消除反应条件等工艺条件进行了详细研究.结果表明,以0.3%异戊烯酸为酸性催化剂,70～75℃共沸脱水反应8 h,异戊烯醛的单程转化率达到63%～64%...     

大孔磺酸树脂催化FCC汽油烷基化脱硫降烯烃性能的研究

针对大孔磺酸树脂催化FCC汽油组分烷基化脱硫和降烯烃的问题,研究了FCC汽油内部关键组分之间的反应规律。结果表明,NKC-9、D005-Ⅱ、Amberlyst 35和Amberlyst 36 4种大孔磺酸树脂中Amberlyst 36的催化效果最好,最佳反应温度是90℃。在Amberlyst 36催化下,与含硫化合物反应时,烯烃的活性顺序是:异戊烯2,3-二甲基-2-丁烯2,3-二甲基-1-丁烯2-戊烯1-戊烯1-己烯。含硫化合物中硫醇反应活性最高,3-甲基噻吩反应活性大于噻吩。Amberlyst 36催化下,异戊烯、2,3-二甲基-2-丁烯和2-戊烯可以与异戊烷发生烷基化反应,降烯烃效果明显。而1-戊烯、2,3-二甲基-1-丁烯和1-己烯主要是发生自身异构化反应。     

3，3-二甲基-4-戊烯酸-3′-甲基-2′-丁烯酯的回收与利用

针对目前工业上回收3，3-二甲基-4-戊烯酸-3′-甲基-2′-丁烯酯（MBDP）工艺复杂、异戊烯大量分解问题，研究了MBDP直接返回循环使用工艺，MBDP与甲醇、原乙酸三甲酯或与甲醇原乙酸三甲酯混合溶液进行酯交换反应的回收新工艺，比较了四异丙基钛酸酯、甲醇钠、氢氧化钾用作酯交换催化剂的效果，筛选出回收MBDP“一锅煮”最佳工艺：按照n（MBDP）：n（原乙酸三甲酯）：n（甲醇）：n（甲醇钠）=1．0：9．8：9．2：0．05物质的量比投料，74℃-78℃反应2lh，MBDP转化为贲亭酸甲酯和异戊烯醇，单程转化率87．7％，用85％的磷酸中和甲醇钠，蒸出甲醇，直接用于合成贲亭酸甲酯。     

2-甲基戊-4-烯-2-胺盐酸盐的合成

以2,2-二甲基-4-戊烯酸为原料,在叠氮磷酸二苯酯和三乙胺作用下,经过Curtis重排反应合成得到目标化合物2-甲基戊-4-烯-2-胺盐酸盐,产物结构经1H NMR及ESI-MS确证,同时考察了影响反应的因素,优化反应条件:物料比n(DPPA):n(2,2-二甲基-4-戊烯酸)=1.1:1;反应温度80℃;反应时间3 h。在优化条件下,反应收率为83.2%。     

2-对甲苯磺酰氧基丁烯-[2]二酸二甲酯及2-甲基磺酰氧基丁烯-[2]二酸二甲酯的合成

用对甲苯磺酰氯和甲基磺酰氯分别在室温下与酒石酸二甲酯反应,以83%和96%的产率得2-对甲苯磺酰氧基丁烯-[2]二酸二甲酯及2-甲基磺酰氧基丁烯-[2]二酸二甲酯。     

异戊烯异构化工艺的改进

对异戊烯装置的异构化工序进行了改造,采用添加叔戊醇的异构化工艺,可以降低产物中重组分的含量。改造后异构化工艺运行结果表明:2-甲基-1-丁烯的转化率由60.2%增加到68.6%,二聚物含量由2.36%降低到0.35%,产物中2-甲基-2-丁烯与2-甲基-1-丁烯质量比由8.87增加到11.24,催化剂寿命达到了4年。     

催化裂化汽油戊烯的分离及利用

本文介绍了催化裂化汽油戊烯的分离方法——硫酸萃取吸收法、醚化分离法和烷基酚烷基化法;同时,介绍了其利用途径,其中包括1-戊烯、2-戊烯、2-甲基-1-丁烯和2-甲基-2-丁烯的利用,并指出了其分离利用的经济意义。     

Chemical modification of poly(epichlorohydrin) with unsaturated potassium carboxylates

Poly(epichlorohydrin) was modified by nucleophilic substitution with some aliphatic potassium carboxylates containing terminal double bonds (10-undecenoate, 4-pentenoate and 3-butenoate). In order to monitor the degree of substitution achieved, different reaction conditions were tested. The polyethers obtained were characterized by spectroscopic techniques, elemental analysis, thermal methods, viscosity determinations and osmometric measurements. A slight crosslinking and the reported main chain cleavage were both detected. Finally, it must be pointed out that, during the substitution reaction with the vinylacetate, isomerization to crotonic ester took place.     

Identification and Synthesis of a Male-Produced Pheromone for the Neotropical Root Weevil <Emphasis Type="Italic">Diaprepes abbreviatus</Emphasis>

An unsaturated hydroxy-ester pheromone was isolated from the headspace and feces of male Diaprepes abbreviatus, identified, and synthesized. The pheromone, methyl (E)-3-(2-hydroxyethyl)-4-methyl-2-pentenoate, was discovered by gas chromatography-coupled electroantennogram detection (GC-EAD), and identified by gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (NMR). The synthesis yielded an 86:14 mixture of methyl (E)-3-(2-hydroxyethyl)-4-methyl-2-pentenoate (active) and methyl (Z)-3-(2-hydroxyethyl)-4-methyl-2-pentenoate (inactive), along with a lactone breakdown product. The activity of the synthetic E-isomer was confirmed by GC-EAD, GC-MS, NMR, and bioassays. No antennal response was observed to the Z-isomer or the lactone. In a two-choice olfactometer bioassay, female D. abbreviatus moved upwind towards the synthetic pheromone or natural pheromone more often compared with clean air. Males showed no clear preference for the synthetic pheromone. This pheromone, alone or in combination with plant volatiles, may play a role in the location of males by female D. abbreviatus.     

6-硝基-4-二甲氨基甲基-5-羟基-1-甲基-2-苯硫甲基-1H-吲哚-3-羧酸乙酯的合成

以对苯醌和3-(甲基氨基)-2-丁烯酸乙酯为起始原料,经Nenitzescu反应、乙酰化、硝化、溴代、缩合、Mannich反应得到一个新化合物6-硝基-4-二甲氨基甲基-5-羟基-1-甲基-2-苯硫甲基-1H-吲哚-3-羧酸乙酯,总产率19.3％.反应中间产物和目标产物结构采用1 HNMR和质谱确认.     

3-甲基-2-[5-(2-氯-4-三氟甲基苯氧基)-2-硝基苯甲酸基]-3-丁烯酸乙酯的合成及其除草活性

标题化合物(SYP-249)是沈阳化工研究院正在进行前期开发的除草剂,由5-(2-氯-4-三氟甲基苯氧基)-2-硝基苯甲酸经两步反应制得,提纯后总收率50%。其结构经红外、核磁共振谱和元素分析确证。标题化合物在温室条件下150 g a.i./hm2可防除多种杂草,在600 g a.i./hm2对大豆安全。     

6-硝基-4-二甲氨基甲基-5-羟基-1-甲基-2-苯硫甲基一1H-吲哚-3-羧酸乙酯的合成

以对苯醌和3-（甲基氨基）-2-丁烯酸乙酯为起始原料,经Nenitzescu反应、乙酰化、硝化、溴代、缩合、Man—nich反应得到一个新化舍物6-硝基-4-二甲氨基甲基-5-羟基-1-甲基-2-苯硫甲基-1H-吲哚-3-羧酸乙酯,总产率19．3％。反应中间产物和目标产物结构采用。HNMR和质谱确认。     

采用锌铜齐-二碘甲烷试剂合成2,2-二甲基环丙烷甲酸甲酯

2,2二甲基环丙烷甲酸甲酯是重要的医药中间体。以异戊烯酸为原料,经酯化、烯键的环丙烷化两步反应得到2,2-二甲基环丙烷甲酯。采用锌铜齐-二碘甲烷作环丙烷化试剂,通过单因素选优法得到最佳反应条件为：n（异戊烯酸甲酯）∶n（二碘甲烷）∶n（锌铜齐Ⅲ）=1∶3.0∶3.0;混合溶剂为V（二氯甲烷）∶V（无水乙醚）=6∶1;回流温度下反应9h。在此条件下,2,2-二甲基环丙烷甲酯的收率达到84.6%。此路线步骤简单、成本较低、收率较高。     

Enantiomeric synthesis of dominicalure,aggregation pheromone of lesser grain borer,Rhyzopertha dominica (F.)

(S)-(+)-1-Methylbutyl (E)-2-methyl-2-pentenoate,1, and (S)-(+)-1-methylbutyl (E)-2,4-dimethyl-2-pentenoate2, the aggregation pheromone for lesser grain borerRhyzopertha dominica (F). were synthesized from crotylaldehyde in an overall yield of 30%. The chiral intermediate6 was prepared in 90% enantiomer excess, employing the Sharpless asymmetric epoxidation.     

Dominicalure 1 and 2: Components of aggregation pheromone from male lesser grain borerRhyzopertha dominica (F.) (Coleoptera: Bostrichidae)

Volatiles from lesser grain borers,Rhyzopertha dominica (F.) (Coleoptera: Bostrichidae), were collected on Porapak Q, and those from the male beetles were shown to contain two compounds, that were attractive individually and in combination to both sexes. These compounds were identified as (S)-(+)-1-methylbutyl (E)-2-methyl-2-pentenoate and (S)-(+)-1-methylbutyl (E)-2,4-dimethyl-2-pentenoate by spectrometry and comparison with synthesized compounds. The two compounds have been assigned the trivial names dominicalure 1 and dominicalure 2, respectively. Synthesized samples of these compounds, individually and in combination, were effective in trapping both sexes in field studies.Presented in part at the Northeastern Regional Meeting of the American Chemical Society, June 25–28, 1978, Boston.Approved as TA-14927 by the director of the Texas Agricultural Experiment Station in cooperation with the USDA-FR-SEA.     

Specificity of Response to Sex Pheromones Among Sweetpotato Weevils, Cylas puncticollis and C. brunneus

Trapping experiments were carried out in Uganda and Indonesia with decyl (E)-2-butenoate and dodecyl (E)-2-butenoate, previously identified as components of the female sex pheromones of the African species of sweetpotato weevil, Cylas puncticollis and C. brunneus, respectively. In Uganda, decyl (E)-2-butenoate attracted only C. puncticollis males, but dodecyl (E)-2-butenoate attracted males of both C. brunneus and C. puncticollis. Catches of C. puncticollis with both compounds were higher when they were dispensed from polyethylene vials rather than rubber septa, while dodecyl (E)-2-butenoate dispensed from rubber septa gave higher catches of C. brunneus and was more selective for this species. Release rates of the two compounds from the two types of dispenser were measured in the laboratory and possible explanations for differences in dispenser performance considered. Lures containing decyl (E)-2-butenoate were as attactive to male C. puncticollis as 10 live virgin female C. puncticollis weevils, but lures containing dodecyl (E)-2-butenoate were not always as attractive to male C. brunneus as the conspecific virgin female weevils. Dose–response relationships with the synthetic pheromones varied between repeat experiments and with the type of dispenser. Addition of dodecyl (E)-2-butenoate to decyl (E)-2-butenoate either did not affect or increased catches of C. puncticollis males, but adding 1% or more of decyl (E)-2-butenoate to dodecyl (E)-2-butenoate significantly reduced attractiveness to C. brunneus. Traps baited with synthetic lures captured male C. brunneus weevils mostly early in the evening while the majority of male C. puncticollis were trapped between 01:00 hr and 03:00 hr. This clear temporal separation of activity of males of the two species helps to ensure species specificity of mating in these sympatric species. In Indonesia, dodecyl (E)-2-butenoate but not decyl (E)-2-butenoate attracted C. formicarius males, but this attractiveness was less than 0.4% that of the pheromone of C. formicarius, (Z)-3-dodecenyl (E)-2-butenoate.     

氨基甲酸酯基丙烯酸酯的合成及其光固化性能

利用碳酸亚乙酯与1,6-己二胺、异佛尔酮二胺反应，制备出两种含氨基甲酸酯基的二元醇，基于氨基甲酸酯二元醇与1,6-己二醇二丙烯酸酯（HDDA）、新戊二醇二丙烯酸酯（NPGDA）及三羟甲基丙烷三丙烯酸酯（TMPTA）本体条件下的Oxa-Michael加成反应及酯交换反应，合成出6种含氨基甲酸酯基的丙烯酸酯混合物。利用FTIR及高分辨质谱分析了产物结构，用FTIR考察了所合成氨基甲酸酯基丙烯酸酯光固化过程的动力学,测定了光固化膜的性能。结果表明，在含占总质量分数3% 的2-羟基-2-甲基-1-苯基-1-丙酮（1173）光引发剂的引发下，氨基甲酸酯基丙烯酸酯能在30s内固化形成表面平整、柔韧性（0.5~2.5mm）良好、透明或半透明的膜；固化膜的凝胶率及铅笔硬度分别为92%~96%、4~5H，对玻璃的附着力为0~1级。