Amorphous RuCoP Ultrafine Nanoparticles Supported on Carbon as Efficient Catalysts for Hydrogenation of Adipic Acid to 1,6-Hexanediol

As an important raw material for organic synthesis, the 1,6-hexanediol (HDOL) is synthesized by the complicated two-step process traditionally. The hydrogenation of adipic acid (AA) is a potential way to prepare 1,6-hexanediol. At present, amorphous RuMP (M: Co, Ni, Fe, etc.)-based alloys with low Ru content were developed by co-precipitation as the efficient catalysts for converting AA to HDOL via hydrogenation. Among these RuMP catalysts, RuCoP alloys exhibited the highest selectivity and yield to HDOL owing to the electronic effect. The selectivity and yield of HDOL for the optimized RuCoP/C sample was achieved to 80% and 64%, respectively, at 65 bar and 220 °C. A series of RuCoP alloys with different degrees of crystallinity and particle sizes were prepared to investigate the effect of morphology and structure on its catalytic performance. The results indicated that the high catalytic activity of RuCoP/C resulted from its rich active sites due to its amorphous phase and small particle size.     

Studies of peptide antibiotics. XLVI. Syntheses of gramicidin S analogs containing D-α, β-diaminopropionic acid or α,β-dehydroalanine*

A gramicidin S (GS) analog ([d -Dpr^4,4] GS) containing d -α,β-diaminopropionic acid (D-Dpr) in place of D-Phe at 4,4′ positions was derived from [l -Orn(δ-formyl)^2,2, d -Dpr(β-Z)^4,4′]GS, which was synthesized by conventional method in solution. An analog [ΔAla^4,4′]GS was synthesized from [l -Orn(δ-Boc)^2,2′, d -Dpr^4,4′]GS through Hofmann degradation of the d -Dpr residues. Antimicrobial activities of these analogs were tested; [d -Dpr(β-Z)^4,4′]GS and [ΔAla^4,4′]GS showed high antimicrobial activities against Gram-positive bacteria. [d -Dpr^4,4′]-GS showed an appreciable activity against Gram-negative bacteria such as Escherichia coli. Four semigramicidin S (semiGS) analogs such as [ΔAla⁴]semiGS were synthesized; these had no antimicrobial activity. Analogs containing ΔAla residues were hydrogenated, and the formation of l -Ala or d -Ala residues was determined. The ΔAla residues in [ΔAla^4,4′] GS were reduced to dl -Ala, and ΔAla in [ΔAla⁴]semiGS mostly to l -Ala. The relationships of the antimicrobial activity, CD curves and asymmetric hydrogenation to the structure were discussed.     

丁醛加氢制丁醇反应器的数学模拟

在对混合丁醛加氢制丁醇的反应体系进行热力学与动力学分析的基础上。采用一维拟均相数学模型对丁醛加氢制丁醇管壳式固定床反应器进行数学模拟设计。预测了反应温度、冷却介质温度、反应压力和反应空速对加氢反应结果的影响。结果表明：丁醛加氢制丁醇的数学模拟结果与生产数据吻合良好。     

蒽醌加氢催化剂Pd/Al_2O_3的制备

对浸渍法制备Pd/Al_2O_3的一些影响因素进行了考察。发现经1173K焙烧的氧化铝作为载体最好,其表面积为109m~2/g,孔径分布以2～10nm的孔为主,其晶型为θ型与δ型的混合物。载体载钯为0.3(wt)%时,催化剂的活性较好。用H_2-O_2滴定法测得0.3(wt)%Pd/Al_2O_3的金属分散度为22.0%。研究了Pd/Al_2O_3上氢的热脱附,并对脱附峰进行了分析,区分了氢的脱附与吸附水的脱附峰。     

煤和煤焦在压力下加氢气化的动力学研究——Ⅰ.温度的影响

在固定床加压反应器和加压热天平上,对五种中国气化用煤及其煤焦进行了加氢气化的动力学研究。发现在升温过程中各类产品气体的生成速率都随温度而变化,甲烷和乙烷的生成速率在600℃左右可达到最大值。沈北、蔚县煤焦在850～1000℃,2.1 MPa下加氢反应的表观活化能分别为108和95kJ/mol。随着煤焦制备温度的提高,煤焦加氢反应的平均比气化速率和最终转化率都下降。     

硫酸沙丁胺醇的合成研究Ⅰ

以水杨醛与叔丁胺为起始原料，经缩合、酯化、Ｆｒｉｅｓ重排三步一锅反应制成２－氯－１－｛［（１，１－二甲基乙基）亚胺基甲基］－４－羟基苯基｝－乙基酮（４）．再经缩合、水解、成盐三步一锅反应转化成５－｛［（１，１－二甲基乙基）胺基］乙酰基｝－２－羟基苯甲醛盐酸盐（５），再经甲醇钠中和、催化转移氢化还原、成盐即得硫酸沙丁胺醇（１），总收率约５０％。     

新型手性配体的合成及其在沙美特罗关键中间体合成中的应用

目的合成沙美特罗的关键手性中间体。方法设计合成新型手性配体单磺酰化1，2-双-（3，5-二甲基苯基）乙二胺，通过与金属铑配合生成手性催化剂，利用该催化剂催化沙美特罗的关键手性中间体的不对称氢转移反应。结果与结论新型手性配体具有良好的催化活性和对映体选择性，催化合成得到的沙美特罗中间体的对映体选择性的ee％值为91％。     

10,11-二氢-5H-二苯并[b,f]氮杂的合成

以邻硝基甲苯为起始原料 ,经缩合、加氢还原、磷酸成盐得 2 ,2′-二氨基联苄二磷酸盐 ,再经环合制得 10 ,11-二氢 - 5 H -二苯并 [b,f]氮杂。总收率 6 3.5 %。     

2-巯基-5-甲氧基苯并咪唑合成工艺的研究

目的改进2-巯基-5-甲氧基苯并咪唑的合成工艺。方法以对氨基苯甲醚为起始原料,采用醋酸硝酰作硝化剂进行硝化;采用雷尼镍催化加氢法进行还原。结果制得了奥美拉唑中间体2-巯基-5-甲氧基苯并咪唑,总收率78.5%。结论值得推广到工业化生产。     

萘呋胺酯的新法合成

以糠醛和丙二酸二乙酯为原料，经Ｋｎｏｅｖｅｎａｇｅｌ缩合ＲａｎｅｙＮｉ催化加氢，酯交换，烷基化和水解脱羧合成了萘呋胺酯。