1,2-丙二醇合成丙酮酸及丙酮酸甲酯

在常压下,以1,2-丙二醇为原料,采用两步法合成丙酮酸及丙酮酸甲酯.首先在固定床上以负载银的分子筛为催化剂,空气中的氧为氧化剂,气相氧化1,2-丙二醇合成丙酮醛,丙酮醛与甲醇气相预混合,以NbFeAPSO-5双功能分子筛为催化剂进行氧化酯化反应合成丙酮酸及丙酮酸甲酯.考察了反应温度、氧气与1,2-丙二醇(或丙酮醛)的物质的量比和1,2-丙二醇(或丙酮醛)液空速对反应的影响.结果表明,第一步丙二醇氧化反应制丙酮醛较优的工艺条件为320℃,氧醇物质的量比为1.2,1,2-丙二醇液空速为1.0 mL/(g·h);第二步丙酮醛的氧化酯化反应较优的工艺条件为140℃,甲醇的液空速为1.1 mL/(g·h),氧醛物质的量比为2.2.在此条件下,1,2-丙二醇的转化率可到达67.27%,丙酮醛的选择性为78.61%,丙酮酸和丙酮酸甲酯总的收率可达53.52%.     

比卡鲁胺的合成

以环氧化合物1,2-环氧-2-甲基-N-[4-氰基-3-(三氟甲基)苯基]丙酰胺为起始原料,经缩合、氧化两步反应制得非甾体类抗雄激素药物比卡鲁胺.对中间体的合成工艺进行了改进.以二甲基甲酰胺为溶剂、四丁基溴化铵为相转移催化剂、碳酸钾为缚酸剂,使反应无需控制水分,并可在温和条件下进行,反应收率由文献的67.8％提高到88.9％.     

比卡鲁胺的合成工艺改进

以甲基丙烯酰氯为原料,经N-酰化、环氧化、缩合和氧化合成了比卡鲁胺,总收率为57.6%,纯度为98.3%,并通过~1 HNMR、MS对其结构进行了确认。     

三氟丙酮酸酯的合成与应用研究

综述了分别以六氟环氧丙烷和三氟溴甲烷为原料合成三氟丙酮酸酯类化合物以及三氟丙酮酸酯化合物的应用研究进展。     

吡螨胺的合成

吡螨胺是一种新型、高效的吡唑酰胺类杀螨剂,本文以中间体1-甲基-3-乙基-4-氯-5-吡唑甲酸和4-叔丁基苄胺合成,起始原料丙酰丙酮酸乙酯和4-叔丁基苄氯,总收率为61.23%(以丙酰丙酮酸乙酯计)。     

嗪草酮中间体——三甲基丙酮酸高效液相色谱定量分析

建立一种采用高效液相色谱法定量分析除草剂嗪草酮的重要中间体三甲基丙酮酸的方法,为嗪草酮的高效合成提供有效保证。选用Agilent ZORBAX SB-Aq色谱柱、紫外检测器,以乙腈和水(0.01 mol/L KH_2PO_4)(体积比15:85)为流动相,流速1.0 mL/min,柱温为室温,波长215 nm定量分析三甲基丙酮酸。三甲基丙酮酸的色谱保留时间为4.8 min,线性相关系数为0.999 9,方法的标准偏差为0.081,变异系数为0.17%,平均回收率为99.75%。此方法分析快速、简便、分离完全、结果重现性好,所得结果可信度高,是一种实用的中间控制分析方法。     

乳酸氧气氧化法制备丙酮酸

丙酮酸是一种重要的有机合成和药物合成中间体 ,研究了以乳酸为原料 ,氧气催化氧化合成丙酮酸 ,并探讨了催化剂组成、用量、氧气用量、温度、反应时间等因素对合成反应的影响 ,确定了最佳合成条件 ,其条件为以 Pt/Pb( NO3) 2 /C为催化剂 ,其组成比为 3%∶ 5 %∶ 92 %(质量比 ) ,Pt用量为 0 .1 5 g(铂与乳酸的摩尔比为 1 .92× 1 0 -3) ,O2 加入量为 2 .33L/h(空气为 1 1 .1 L/h) ,在 45°C下反应 2 h时 ,收率为 66.0 %     

2-甲基-3-丁炔-2-胺的合成工艺研究

以甲基丁炔醇为起始原料合成3-氯-3-甲基-1-丁炔,液氨氨解得到2-甲基-3-丁炔-2-胺,并对合成条件进行了优化,探索出适合工业化生产的2-甲基-3-丁炔-2-胺的合成方法,产物用IR和GC-MS进行表征。     

3-甲基吡啶的合成

介绍了3-甲基吡啶应用及生产现状,综述了国内外以不同原料合成3—甲基吡啶的方法,包括分别以丙稀醛和氨;乙醇、甲醛和氨;乙醛、甲醛和氨;乙醛或三聚乙醛、甲醛、六次甲基四胺;丙烯醛、丙醛;三烯丙基胺;2—甲基戊二腈为原料的气固相接触催化法和以2—甲基戊二胺为原料的气液相催化法,重点介绍了以2—甲基戊二腈为原料制备3—甲基吡啶的生产工艺。     

溴代丙酮酸乙酯合成方法的改进

溴代丙酮酸乙酯是一种重要的化学试剂及中间体。用途较为广泛,可用于染料、杀菌防腐剂等的合成。溴代丙酮酸乙酯的合成方法有3种:1)三步法:以酒石酸为原料,总收率为55%;2)两步法,以乳酸乙酯为原料,总收率为51%;3)一步法,使乳酸乙酯直接与溴化剂溴代丁二酰亚胺反应制取,收率达63.5%。     

水溶性丙酮酸锌的合成工艺研究

采用丙酮酸与乙酸锌反应合成水溶性丙酮酸锌,确定了适宜的工艺条件。合成水溶性丙酮酸锌最佳的反应条件是:以乙酸乙酯和丙酸为溶剂,其体积比为1∶0.7,丙酮酸与乙酸锌摩尔配比为1∶0.55,在20~25℃温度下反应。得到的产品的结构经红外和核磁的确证,其结构式为(CH3COCOO)2Zn.1/2H2O,得到的产品在水中具有较好的溶解性。     

色氨酸酶重组基因表达及其酶法合成L-色氨酸

为实现色氨酸酶高效、低成本催化合成L-色氨酸,利用p ET30a为载体在宿主细胞E.coli BL21(DE3)中重组表达了产气肠杆菌(Enterobacter aerogenes)来源的色氨酸酶,以丙酮酸、吲哚和氨为底物,探究其酶学性质,考察了反应温度、起始p H、底物摩尔比对酶促反应的影响,并利用丙酮酸发酵液为底物酶法合成L-色氨酸。结果表明,色氨酸酶重组表达成功,色氨酸酶最佳反应条件为:温度35℃,起始p H=9.0,底物摩尔比n(吲哚)∶n(丙酮酸)=0.6∶1,底物丙酮酸浓度为0.17 mol/L。利用重组色氨酸酶全细胞催化100 m L浓度为0.57 mol/L丙酮酸发酵液,流加浓度为4.27 mol/L吲哚酒精溶液6.5 m L,反应28 h后,L-色氨酸浓度达0.25 mol/L,吲哚摩尔转化率达91.8%。     

高效液相色谱法测定发酵液中丙酮酸的含量

建立了高效液相色谱法测定发酵液中丙酮酸含量方法。采用氨基柱进行液相色谱检测,检测波长210nm,柱温30℃,流动相采用乙腈／磷酸二氢钾。对检测方法的检出限、定量限、线性、精密度、稳定性进行考察。该方法线性方程为：y=0．3246x＋0．051,在5-200μg／mL内,线性关系良好（r=0．9999）。该方法适合于发酵液中丙酮酸含量测定。     

Chemistry of Pyruvate Enolates: anti‐Selective Direct Aldol Reactions of Pyruvate Ester with Sugar Aldehydes Promoted by a Dinuclear Zinc Catalyst

A chiral dinuclear zinc complex can effectively catalyse the direct aldol reactions of pyruvic acid ester with various chiral sugar aldehydes, thus functionally mimicking the pyruvate‐dependent type II aldolases. Application of sterically hindered aryl esters allows for the elusive aldol reaction of the pyruvate donor with controlled anti‐selectivity en route to the short and efficient synthesis of 3‐deoxy‐2‐ulosonic acids. Pyruvic acid ester is here used as a chemical equivalent of phosphoenol pyruvate (PEP) in imitation of the synthetic principle used in nature. The presented biomimetic methodologies use enol formation for the highly efficient and flexible formation of various C₆–C₉ ulosonic acids. Particularly, efficient and concise syntheses of 3‐deoxy‐D ‐erythro‐hex‐2‐ulosonic acid (KDG, overall 50% yield), 3‐deoxy‐D ‐ribo‐hept‐2‐ulosonic acid (DRH, overall 53% yield) and 3‐deoxy‐D ‐glycero‐D ‐talo‐non‐2‐ulosonic acid (4‐epi‐KDN, overall 78% yield) are described. This direct efficient application of pyruvic esters does not require additional demasking steps and thus surpassess previously methodologies utilising masked pyruvic synthons such 2‐acetylthiazole and pyruvic aldehyde dimethyl acetal.

     

光滑球拟酵母发酵生产丙酮酸

丙酮酸是一种重要的有机酸 ,广泛应用于制药、日化、农用化学品和食品等工业中。相对于化工法生产的丙酮酸而言 ,发酵法生产的丙酮酸具有低成本、高质量等优势。考虑到球拟酵母属的多重维生素营养缺陷型菌株是目前发酵法生产中最常用和最具竞争力的生产菌株 ,因此重点介绍了发酵法生产丙酮酸在菌种、发酵条件优化等方面的研究进展 ,并给出了发酵法将来可能的发展方向。     

Process development and modeling of pyruvate recovery from a model solution and fermentation broth

The mono- and bi-polar electrodialysis processes for pyruvate recovery and pyruvic acid generation, respectively, were examined in order to determine their feasibility for application in the pyruvate production process. Under optimum process conditions (constant current mode i = 39.7 A m⁻², pyruvate model solution c_p = 50 g dm⁻³ in the monopolar electrodialysis experiment pyruvate flux reached 367 g m⁻² h⁻¹ and specific energy consumption was 1.4 kWh kg⁻¹. In the bi-polar electrodialysis experiment under optimum process conditions (constant current mode i = 9.6 A m⁻², pyruvate model solution c_p = 48 g dm⁻³, pyruvate flux reached 125 g m⁻² h⁻¹ and specific energy consumption was 1.5 kWh kg^-1. Generally speaking, performances of the bi-polar electrodialysis were equal to the best process conditions observed with mono-polar electrodialysis. On the other hand, current densities investigated in the bi-polar electrodialysis experiments were four-fold lower than those applied in the mono-polar electrodialysis experiments. Additionally, a mathematical model to represent the ion and water transport behavior of an electrodialysis process for concentrating pyruvic acid under the influence of different current density was developed. Estimation of both the model parameters and model validation were demonstrated in the work.     

我国丙酮酸及系列产品合成工艺10 a进展

综述了丙酮酸及系列产品近10 a来合成工艺的发展状况。介绍了目前国内生产丙酮酸的各种合成工艺方法,包括酒石酸法、乳酸氧化法、直接发酵法和酶催化法,阐述了它们的合成反应原理、工艺参数、产率等,评价了这些方法的利弊与发展前景。     

丙酮酸(酯)的合成方法评述

介绍了制备丙酮酸（酯） 的几种方法, 并对其优缺点进行了评述。     

Electrosynthesis of 2,3-dimethyltartaric acid from pyruvic acid in acid medium

This study reports the electrohydrodimerization of pyruvic acid to 2,3-dimethyltartaric acid in sulphuric acid medium (0.5 M H₂SO₄) on a lead cathode. The main products detected were lactic acid and 2,3-dimethyltartaric acid. The selectivity towards the formation of 2,3-dimethyltartaric acid was studied vs. pyruvic acid concentration in sulphuric acid solution, at −1.1 V vs. MSE. The best selectivity of 2,3-dimethyltartaric acid reached 69% for an initial concentration of 1.7 M pyruvic acid. The yield of pyruvic acid was 84%.     

Heart mitochondrial metabolism after feeding herring oil to rats and monkeys

Heart mitochondrial oxidation of palmityl CoA and pyruvic acid was studied in rats and in the monkeyMacaca fascicularis to determine the effects of feeding partially hydrogenated herring oil. Herring oil glycerides contain cetoleic acid (cis-11-docosenoic) which could have a similar effect to erucic acid (cis-13-docosenoic) in causing a rat cardiomyopathy. The initial rat heart mitochondrial response to dietary cetoleic acid (67%cis, 33%trans) was an in vitro decrease in palmityl CoA oxidation. Prolonged feeding of cetoleic acid mixture was associated with a significant metabolic adaptation, increasing pyruvate and palmityl CoA oxidation above control levels. In vitro addition of cetoleyl CoA (purecis isomer) stimulated pyruvate dehydrogenase activity, a possible response to decreased β-oxidation. There was no significant adaptive change in pyruvate or palmityl CoA use in monkeys after prolonged feeding of partially hydrogenated herring oil. Cetoleyl CoA was a good substrate for monkey heart carnitine acyl transferase even in the presence of palmityl CoA. These observations suggest that C₂₂ fatty acids may be matabolized more rapidly in monkey heart than in rat heart. Metabolic differences argue against using the rat as an experimental model for studying possible cardiotoxic effects of docosenoic acids in primates.