对氯苯基丙酮的合成

研究了以对氯氯苄为主要原料 ,合成药物中间体对氯苯基丙酮的新工艺。该工艺由对氯苄基氯化锌和苯基丙酮的两步合成反应组成。优化的工艺条件为n(对氯苄基氯 )∶n(Zn)∶n(乙酐 ) =1∶1.2∶2 .5 ;对氯苄基氯化锌的合成温度 60～ 65℃ ,反应时间3h ;对氯苯基丙酮合成温度 3 0～ 3 5℃ ,反应时间 5h。总收率 78%。     

2-甲氧基-4-丙烯基苯基苄基醚的相转移催化合成研究

在相转移催化剂存在下,以2-甲氧基-4-丙烯基苯酚、氯化苄为原料合成2-甲氧基-4-丙烯基苯基苄基醚,分别研究了反应温度、反应时间、原料配比、催化剂用量等条件对合成反应的影响．确定了最佳工艺条件。该方法合成2-甲氧基-4-丙烯基苯基苄基醚的最佳工艺条件是：反应温度95℃;反应时间2h;n(2-甲氧基-4-丙烯基苯酚)：n(氯化苄)=1：1,05;n(2-甲氧基-4-丙烯基苯酚)：n(氢氧化钾)=1：1．10;催化剂=5．89％(相对于2-甲氧基-4-丙烯基苯酚质量分数),2-甲氧基-4-丙烯基苯基苄基醚的收率可达到92．52％以上,产品纯度98．5％。     

2-氨基-6-硝基苯并噻唑的合成研究

研究了以对硝基苯胺为原料，在催化剂的作用下，合成2－氨基－6－硝基苯并噻唑。其适宜的工艺条件为：n（对硝基苯胺）：n（硫氰酸胺）：n(苯）＝1：1．15：6．5，反应温度为80－85℃，反应时间为10h；n(对硝基苯基硫脲）：n(催化剂）＝1：0．093，室温反应，反应时间为2h。产品收率为64．5％，纯度≥99％。     

活性炭负载浓硫酸催化间二甲苯与氯化苄的烷基化反应

以活性炭负载浓硫酸作为固体催化剂,以间二甲苯与氯化苄为原料进行合成反应,研究了反应温度、反应时间、原料配比和催化剂用量对反应的影响,确定了最佳工艺条件:即n(间二甲苯)∶n(氯化苄)=3∶1,反应温度100℃,反应时间9h,催化剂用量13.2%(相对于氯化苄),2-苄基-1,5-二甲苯产率为59.3%;n(间二甲苯)∶n(氯化苄)=3∶1,反应温度100℃,反应时间8h,催化剂用量18.5%(相对于氯化苄),3-苄基-1,5-二甲苯产率为18.0%。     

浓H_2SO_4改性活性炭催化乙苯与氯化苄的苄基化反应

以活性炭负载浓硫酸作为固体催化剂,以乙苯与氯化苄为原料进行合成反应,研究了反应温度、反应时间、原料配比和催化剂用量对反应的影响,确定了最佳反应条件:即n(乙苯)∶n(氯化苄)=3∶1,反应温度90℃,反应时间8h,催化剂用量为13.2%(相对于氯化苄),邻苄基乙苯产率29.9%;n(乙苯)∶n(氯化苄)=3∶1,反应温度90℃,反应时间9h,催化剂用量18.4%(相对于氯化苄),对苄基乙苯产率40.1%;n(乙苯)∶n(氯化苄)=3∶1,反应温度90℃,反应时间7h,催化剂用量18.4%(相对于氯化苄),间苄基乙苯产率8.1%。     

香料乙酸苄酯的合成

实验以氯化苄、醋酸钠为原料，研究了在相转移催化剂的存在下，一步反应制得乙酸苄酯的合成工艺。结果表明，最佳反应条件为：催化剂用量为n（氯化苄）：n（四丁基溴化铵）=1：1．6×10^-2，反应物为n（氯化苄）：n（乙酸钠）：1：1．05，反应时间是4．5h，反应温度为110℃，收率为92％，产品纯度可达99％。[编者按]     

正癸基缩水甘油醚的合成与工艺优化

研究了相转移催化剂存在下，癸醇与环氧氯丙烷为原料合成癸基缩水甘油醚的工艺条件下，考察了n(癸醇）：n(环氧氯丙烷）、反应温度和反应时间等因素对反应影响，通过正交实验优化了合成工艺条件。实验表明：苄基三乙基氯化铵为相转移催化剂；n(癸醇）：n(环氧氯丙烷）为1：1．15，反应温度为70℃，反应时间为3．5h，癸基缩水甘油醚收率90％以上。     

苯基丁基醚的相转移催化合成研究

在相转移催化剂存在下，以苯酚、溴丁烷为原料合成苯基丁基醚。分别研究了反应温度、反应时间、原料配比、催化剂用量等条件对合成反应的影响，确定了最佳工艺条件，该方法合成苯基丁基醚的最佳工艺条件是：反应温度85℃、反应时间4h、n（苯酚）：n（溴丁烷）=1：1．10；n（苯酚）：n（氢氧化钾）=1：1．15；相转移催化剂用量为0．5g（基于0．1mol苯酚），苯基丁基醚的收率可达到95.20％以上，产品纯度w（苯基丁基醚）为98．5％。     

相转移催化合成对甲苯苄醚

在相转移催化剂存在下，以对甲苯酚、氯化苄为原料合成对甲苯苄醚，研究了反应温度、反应时间、原料配比和催化剂用量等条件对合成反应的影响，确定了较佳工艺条件。该方法合成对甲苯苄醚的较佳工艺条件是：110℃、反应3h、n(对甲苯酚)：n(氯化苄)为1：1．2、n(对甲苯酚)：n(氢氧化钠)为1：1．1；催化剂用量为9．26％(相对于对甲苯酚)，对甲苯苄醚的收率可达到93．43％以上，产品纯度为98．5％(质量分数)。     

2,4-二氟苯腈的合成

以2，4－二氯苯腈和活性氟化钾为原料，用环丁砜作溶剂合成2，4－二氟苯腈。最佳工艺条件：n(2,4-二氯苯腈）：n（氟化钾）＝1：2．5；环丁砜回流温度255－265℃；反应时间：5．5h。产品产率87％，纯度≥98％。     

苯基丙酮新合成方法的研究

通过苯并咪唑盐与Grignard试剂的加成-水解反应合成了苯基丙酮,并对反应机理进行了探讨。     

Study on ketalization reaction of poly(vinyl alcohol) by ketones. VII. Reaction between poly(vinyl alcohol) and aromatic ketones and behavior of poly(vinyl ketal) in water

The ketalization reaction of poly(vinyl alcohol) (PVA) by aromatic ketones, with dimeth-ylsufoxide (DMSO) as solvent, under the presence of an acidic catalyst in homogeneous system, was carried out. The synthesis of poly(vinyl ketal) (PVKL) for the case of phenylacetone and benzylacetone was thus successfully performed, but for the case of acetophenone was performed only with a ketalization degree of a few molecular percent, and for the case of benzophenone it could not be performed at all. It seems that these different behaviors in synthesis are due to steric hindrance of the bulky side chain of ketones. The equilibrium constant at 40°C was ca. 0.12. in the case of phenylacetone and benzylacetone, and the value is somewhat higher compared with that of aliphatic ketones, but somewhat lower compared with the case of cyclic ketones. Because the heat of reaction is 7.5 kcal/mol in these two aromatic ketones, all ketalization reactions are considered to proceed by the same reaction mechanism. The rate of hydrolysis, contact angle, surface free energy, moisture regain, and water vapor permeability of PVKL films were measured. All results show the PVKL obtained from phenylacetone is nearly equal to PVKL obtained from methyl n-butyl ketone. However PVKL obtained from benzylacetone shows different behavior compared with other ketones, because the side chain of benzylacetone is flexible and bulky. The hydrophobicity of PVKL seems to depend upon the kind of the original ketones and the flexibility of the side chain. © 1995 John Wiley & Sons, Inc.     

微波促进合成β-苯胺基苯丙酮

采用微波辐射技术,以盐酸作为催化剂,三聚甲醛、苯乙酮、苯胺为原料一步反应合成了β苯胺基苯丙酮。研究了盐酸的用量、微波功率和时间对合成反应的影响。通过熔点测定、红外光谱和1HNMR谱图等对所得产物进行了表征。所得化合物结构与用常规合成方法所得产物一致。     

微波促进合成β-苯胺基苯丙酮

采用微波辐射技术，以盐酸作为催化剂三聚甲醛、苯乙酮、苯胺为原料一步反应合成β-苯胺基苯丙酮。研究了盐酸的用量、微波功率和时间对合成反应的影响。通过熔点测定、红外光谱和^1HNMR谱图等对所得产物进行了表征。所得化合物结构与用常规合成方法所得产物一致。     

重组大肠杆菌全细胞用于苯乙酮酸的绿色生物合成

苯乙酮酸是化学合成中重要的合成砌块,可用于合成多种药物中间体,探索苯乙酮酸的绿色合成工艺具有重要的意义。以包含D-扁桃酸脱氢酶LhDMDH编码基因的重组大肠杆菌全细胞为催化剂,考察了它在无辅酶和辅底物添加的条件下对D-扁桃酸生物转化的效果,并对催化产物进行了纯化和鉴定。结果表明,本研究成功实现了在无辅酶和辅底物添加条件下苯乙酮酸的生物合成,产物的得率和纯度分别为45%和99%左右。成果也为外消旋扁桃酸的手性拆分及苯乙酮酸的生物合成奠定了基础。     

Highly regioselective,base-catalyzed,biginelli-type reaction of aldehyde,phenylacetone and urea/thiourea kinetic vs. thermodynamic control

An efficient one-pot regioselective synthesis of various novel 3,4-dihydropyrimidin-2(1H)-one (DHPMs) via a three-component Biginelli-type condensation of aldehyde, phenylacetone and urea/thiourea under two different based-catalyzed conditions is described. In kinetic control path, lithium N, N-diisopropylamide (LDA-20 mol % generated in situ from n-BuLi and diisopropylamine) was used as the base, in tetrahydroforane (THF) as the solvent at 0°C. Thermodynamic control path was run with NaH as the base, in EtOH as the solvent under reflux status. The simple procedure, mild base-catalytic reaction conditions, no column chromatography and good to high yields are important features of this protocol.     

Pyryliumverbindungen. XXIX [1] Substituierte Benzophenone aus 2,4,6-Triaryl-pyryliumsalzen und Methyl(en)ketonen

Pyrylium Compounds. XXIX. Substituted Benzophenones from 2,4,6-Triarylpyrylium Salts and Methyl(ene) Ketones In the presence of piperidine acetate (or similar salts of certain dialkylamines), 2,4,6-triarylpyrylium perchlorates 5 react with methyl(ene) ketones 6 to give benzophenones 7 , the structure of which was proved by spectroscopic methods as well as by independent synthesis. Besides acetone and other acyclic ketones (e. g. alkyl methyl ketones, phenylacetone, desoxybenzoin, dibenzyl ketone) cyclic ketones (e. g. cyclopentanone, cyclohexanone, cycloheptanone, acenaphthenone) can also be used as ketone component 6 ; acetophenones react differently leading to hydrocarbons of the 1,3,5-triarylbenzene type 15 . The varying efficiency of the diverse amine salts and the mode of incorporation of the unsymmetrically substituted ketones suggest the intermediate formation of enamines 10 as crucial step of the ring transformations observed. This assumption is supported by isolation of the iminium salt 18 on reacting 3,5-dimethyl-2,4,6-triphenylpyrylium perchlorate ( 16 ) with acetone/piperidine acetate.     

Beta–type zeolites as selective and regenerable catalysts in the Meerwein–Ponndorf–Verley reduction of carbonyl compounds

Zeolite Beta, in the Al–form as well as in the Al–free, Ti–containing form, appears to be a selective and regenerable catalyst in the Meerwein–Ponndorf–Verley and Oppenauer (MPVO) reactions. In the liquid–phase MPV reduction of 4–tert–butylcyclohexanone with secondary alcohols, both catalysts display a high stereoselectivity to cis–4–tert–butylcyclohexanol, the isomer of industrial relevance. This stereoselectivity can be explained by considering the two transition states inside the pores of zeolite Beta. By using (S)–2–butanol as the reductant enantioselective reduction of phenylacetone was observed. 4–methylcyclohexanone was studied as the substrate in the gas–phase MPV reduction. Catalyst deactivation is much more pronounced with the acidic Al–Beta catalyst than with the non–acidic Ti–Beta. This revised version was published online in June 2006 with corrections to the Cover Date.     

A Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase mutant derivative highly active and stereoselective on phenylacetone and benzylacetone

The secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus 39E (TeSADH) is highly thermostable and solvent-stable, and it is active on a broad range of substrates. These properties make TeSADH an excellent template to engineer an industrial catalyst for chiral chemical synthesis. (S)-1-Phenyl-2-propanol was our target product because it is a precursor to major pharmaceuticals containing secondary alcohol groups. TeSADH has no detectable activity on this alcohol, but it is highly active on 2-butanol. The structural model we used to plan our mutagenesis strategy was based on the substrate's orientation in a horse liver alcohol dehydrogenase*p-bromobenzyl alcohol*NAD(+) ternary complex (PDB entry 1HLD). The W110A TeSADH mutant now uses (S)-1-phenyl-2-propanol, (S)-4-phenyl-2-butanol and the corresponding ketones as substrates. W110A TeSADH's kinetic parameters on these substrates are in the same range as those of TeSADH on 2-butanol, making W110A TeSADH an excellent catalyst. In particular, W110A TeSADH is twice as efficient on benzylacetone as TeSADH is on 2-butanol, and it produces (S)-4-phenyl-2-butanol from benzylacetone with an enantiomeric excess above 99%. W110A TeSADH is optimally active at 87.5 degrees C and remains highly thermostable. W110A TeSADH is active on aryl derivatives of phenylacetone and benzylacetone, making this enzyme a potentially useful catalyst for the chiral synthesis of aryl derivatives of alcohols. As a control in our engineering approach, we used the TbSADH*(S)-2-butanol binary complex (PDB entry 1BXZ) as the template to model a mutation that would make TeSADH active on (S)-1-phenyl-2-propanol. Mutant Y267G TeSADH did not have the substrate specificity predicted in this modeling study. Our results suggest that (S)-2-butanol's orientation in the TbSADH*(S)-2-butanol binary complex does not reflect its orientation in the ternary enzyme-substrate-cofactor complex.     

茴脑氧化合成茴香醛工艺进展

详细介绍了以天然产物茴脑为原料合成茴香醛的工艺发展过程,综述了茴脑传统氧化法、电化学氧化法和臭氧化法氧化制取茴香醛的工艺发展过程及最新的研究进展,并对各种方法的优点及缺陷做出了评述。