β-氨基环己醇的合成

考察并优化了以1,2-环氧环己烷为起始原料,通过分子内Ritter反应并经唑啉环中间体制备β-氨基环己醇的各种反应条件.同时尝试了以1,2-环己二醇为起始物,进行分子内Ritter反应合成β-氨基环己醇的反应.由于1,2-环己二醇的反应活性相对较差,质子酸不能有效地催化该反应,使得后者制备β-氨基环己醇的产率较低.以环氧环己烷为起始物制备β-氨基环己醇的方法,具有操作简便、原料廉价等优点,其产品(2-氨基环己醇的盐酸盐)总收率达到了50%~60%.     

一种制备(1R,3S)-3-氨基-1-环己烷羧酸的新方法

介绍了一种简单的制备(1R,3S)-3-氨基1环己烷羧酸的方法。以环己烷-1,3-二羧酸的顺反混合物为原料。经过关环得顺式的酸酐,然后酯化,在脂肪酶AY-30的作用下进行去对称性水解。得光学活性的环己烷-1,3-二羧酸的单乙酯产物,经过改进的Curtis重排反应后,羧酸基团转变为氨基。然后经过酯水解、去保护基团,得到光学纯的(1R,3S)-3-氨基-1-环己烷羧酸。     

反-4-乙基环己烷甲酸的制备

通过顺-4-乙基环己烷甲酸的异构化反应制备了反-4-乙基环己烷甲酸。优化反应条件为:4-乙基环己烷甲酸634 mmol,无机碱与4-乙基环己烷甲酸的摩尔比为1.3∶1.0,氮气压力5.0 MPa,温度210℃,反应时间8h,反-4-乙基环己烷甲酸与顺-4-乙基环己烷甲酸的质量比可达98∶2。     

4-(4'-丙基环己基)环己醇的合成

钌/碳催化剂应用于4-(4'-丙基环己基)苯酚(3PCO)的加氢反应,合成了4-(4'-丙基环己基)环己醇.以环己烷为溶剂,在98℃/2MPa,3PCO的转化率为100.0%,催化剂可以重复使用两次.     

5,5-二甲基-2-氧代-2-(N,N＇-对苯二胺基-二苄基)- 二-1,3,2-氧磷杂环己烷的合成及表征

以新戊二醇、三氯化磷和乙醇为原料制得中间体5,5-二甲基-1,3,2-二氧磷杂环己烷-2-氧(DPDO),用DPDO)与由芳醛和对苯二胺缩合制得的席夫碱SBⅠ～SBⅢ加成,合成了膨胀型阻燃剂5,5-二甲基-2-氧代-2-(N,N′-对苯二胺基-二苄基)-二-1,3,2-氧磷杂环己烷(DPPO Ⅰ～DPPOⅢ),通过元素分析,IR,NMR和MS对其结构进行表征,并对其在醇酸清漆中的应用进行了讨论.     

低压加氢法制备1,4-环己烷二甲醇的研究

1,4-环己烷二甲醇是生产改性聚酯的中间单体。采用铜系催化剂，以1,4-环己烷二甲酸二甲酯为原料，低压加氢生成1,4-环己烷二甲醇。考察了反应温度、反应压力等对反应活性的影响，进行了200 h的催化剂寿命评价，并对催化剂进行了表征。结果表明，在反应温度200 ℃，反应压力3.0 MPa的条件下，1,4-环己烷二甲酸二甲酯的转化率大于95%，1,4-环己烷二甲醇的选择性大于98%，XRD谱图说明金属铜是该催化剂的主要活性中心。     

4-（4′-丙基环己基）环己醇的合成

钌／碳催化剂应用于4-(4′-丙基环己基)苯酚(3PCO)的加氢反应，合成了4-(4′-丙基环己基)环己醇。以环己烷为溶剂，在98℃／2MPa，3PCO的转化率为100．0％，催化剂可以重复使用两次。     

8-羟基喹啉对V2O5催化氧化环己烯的调变作用

研究了8-羟基喹啉对丙酮中V2O5催化氧化环己烯合成环己烯酮的调变作用,考察了8-羟基喹啉的用量、反应温度、反应时间、溶剂和催化剂用量对环己烯氧化反应的影响,发现在该催化体系中生成的环己烯醇和环氧环己烷可转化成环己烯酮,在适当的反应条件下可抑制环己烯醇和环氧环己烷的生成.结果表明,当五氧化二钒的用量为1%,五氧化二钒与8-羟基喹啉之比为1∶2,在20℃以下反应时,过氧化氢几乎定向地将环己烯氧化成环己烯酮.认为是8-羟基喹啉与钒的配位作用促进了环己烯酮的生成.     

液晶材料4-[2-(反-4-丙基环已基)]乙基氟苯的全合在研究

主要对向列型液晶材料-4-[2-(反-4-丙基环己基)]乙基氟苯的全合成进行研究,设计和改进了合成反应的反应条件,提高了收率.最后一步酮基的还原成次甲基采用与乙二硫醇缩合后用Raney镍在无水乙醇条件下进行氢化还原和Wolff-Kishner-黄鸣龙还原反应两种方法,都获得了高纯度的目标化合物.同时,通过使用DFT量子化学从头计算和实验的验证,解释了Wolff-Kishner-黄鸣龙还原反应在合成化合物1过程中产生副产物10(1-三缩乙二醇取代-4-反式-4'-丙基取代环己烷乙基苯)的原因.通过改进反应条件,将文献报道的一锅一步反应改成一锅两步反应,成功地合成了目标化合物,降低了生产的成本,产品气相色谱纯度达到98%以上,质量完全符合实际的使用要求.     

5,5-二甲基-2-氧代-2-(N,N-对苯二胺基-二苄基)-二-1,3,2-氧磷杂环己烷的合成及表征

以新戊二醇、三氯化磷和乙醇为原料制得中间体 5 ,5 -二甲基 -1 ,3,2 -二氧磷杂环己烷 -2 -氧 ( DPDO) ,用DPDO与由芳醛和对苯二胺缩合制得的席夫碱 SB ～ SB 加成 ,合成了膨胀型阻燃剂 5 ,5 -二甲基 -2 -氧代 -2 -( N,N -对苯二胺基 -二苄基 ) -二 -1 ,3,2 -氧磷杂环己烷 ( DPPO ～ DPPO ) ,通过元素分析 ,IR,NMR和 MS对其结构进行表征 ,并对其在醇酸清漆中的应用进行了讨论     

福司氟康唑杂质——2-(2,4-二氟苯基)-1-(1H-1,2,4-三氮唑-1-基)-3-(4H-1,2,4-三氮唑-4-基)-2-丙基磷酸二氢酯的合成

以1,3-二氟苯为起始原料,依次经傅－克酰基化,1H-三氮唑取代,环氧化,胺解,4H-三氮唑环化,磷酸酯化和钯碳加氢反应等7步反应合成了福司氟康唑的主要杂质--2-(2,4-二氟苯基-1-(1H-1,2,4-三氮唑-1-基)-3-(4H-1,2,4-三氮唑-4-基)-2-丙基磷酸二氢酯,纯度98%,总收率7.8%,其结构经¹H NMR确证。     

一种新型噁唑烷酮类抗生素的合成

以2,4-二溴吡啶为原料,经Weinreb酰胺酰化、Noyori不对称氢转移反应、脱Boc保护基、环化、Suzuki偶联、磷酸单酯化及成盐共七步反应制得一种新型噁唑烷酮类抗生素【【(3R,3aS)-7-{6-［(S)3-甲基-2-噁唑烷酮-5-基］吡啶-3-基}-1-氧-1,3,3a,4-四氢苯并［b］噁唑［3,4-d］［1,4］噁嗪-3-基】甲基】磷酸单酯二钠盐,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI）确征,总收率7%,纯度99.7%。     

Peculiarities in the hydrogenation of alkenylfurans with a double bond situated in the 2, 3 position to the ring

Up to the present there has been no doubt about the possibility of selective hydrogenation of the side chain double bond in alkenylfurans [1]. In particular, catalysts consisting of palladium on carriers (SrCO₃ [2], BaSO₄ [3, 4]) have been used. They have been used to hydrogenate compounds with the double bond at various positions in the side chain [2–4], but not alkenylfurans with the double bond at the 2, 3 position. Having synthesized compounds of this latter type [5], the present authors attempted to hydrogenate selectively 2-(3-methylbuten-2-yl) furan and 2-(2,3-dimethylbuten-2-yl) furan, but it was unexpectedly found that with Pd/BaSO₄ and at atmospheric pressure hydrogenation was non-selective, and gave the corresponding alkyltetrahydrofurans. Hydrogen uptake rate fell uniformly, and slowed down greatly when hydrogenation was complete.     

Asymmetric synthesis of N-3 substituted phenoxypropyl piperidine benzimidazol-2-one derivatives, potent and selective NOP agonists

The asymmetric synthesis of the potent selective NOP agonist 2-(3-{1-[3-(5-methoxy-2-methyl-phenoxy)-4-methyl-pentyl]-piperidin-4-yl}-2-oxo-2,3-dihydro-benzimidazol-1-yl)-N-methyl-acetamide and analogues was developed. The key step, chiral reduction of methyl isobutyryl acetate, was achieved using a mild Noyori-type asymmetric hydrogenation.     

Synthesis of novel chiral tetraaza ligands and their application in enantioselective transfer hydrogenation of ketones

Novel chiral tetraaza ligands(R)-N,N′-bis[2-(piperidin-1-yl)benzylidene]propane-l,2-diamine 6 and(S)-N-[2-(piperidin-l- yl)benzylidene]-3-{[2-(piperidin-1-yl)benzylidene]amino}-alanine sodium salt 7 have been synthesized and fully characterized by NMR,IR,MS and CD spectra.The catalytic property of the ligands was investigated in Ir-catalyzed enantioselective transfer hydrogenation of ketones.The corresponding optical active alcohols were obtained with high yields and moderate ees under mild reaction conditions.     

常山酮中间体的合成工艺改进

以2-乙酰呋喃为起始原料,经扩环、甲基化、去质子化、亲核加成、缩酮化、Rh/C催化氢化及水解等反应合成了常山酮中间体--1-(3-甲氧基哌啶-2-基)丙酮,总收率40.2%,其结构经¹H NMR和ESI-MS确证。     

New synthetic route to the important (S)-5-(1-(tert-butoxycarbonyl)pyrrolidin-2-yl)-2-methylthiophene-3-carboxylic acid intermediate for the synthesis of a novel glucokinase activator

To obtain an efficient and practical route to a novel glucokinase activator, we investigated a novel synthetic method for the preparation of its key intermediate (S)-5-(1-(tert-butoxycarbonyl)pyrrolidin-2-yl)-2-methylthiophene-3-carboxylic acid through the asymmetric transfer hydrogenation of a pyrroline derivative. The hydrogenation of this pyrroline derivative using the iridium (III)-prolinamide complex Cp*IrCl[(R)-PA] at atmospheric pressure provided an initial intermediate in approximately 50% ee. Further purification via recrystallization provided the desired key intermediate in an excellent enantiopurity, which was applicable to practical use.     

Room-temperature Ru(II)-catalyzed transfer hydrogenation of ketones and aldehydes in air

Transfer hydrogenation (TH) of ketones and aldehydes was efficiently carried out in 2-propanol at room temperature by means of a ruthenium(II) complex catalyst bearing a 2-(benzoimidazol-2-yl)-6-(pyrazol-1-yl)pyridine ligand. TH of the ketone substrates proceeded in air, reaching final TOFs of up to 59,400 h⁻¹, and the reduction of aldehydes proceeded under a nitrogen atmosphere to achieve final TOFs of up to 5940 h⁻¹.     

Transfer hydrogenation via generation of hydride intermediate and base-free alcohol oxidation activity studies on designed ruthenium complexes derived from NNN pincer type ligands

Ruthenium complexes( 1 – 3 ) have been synthesized using pincer-type ligands L¹ = (E)-2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)pyridine, L² = (E)-2-(1-phenyl-2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)pyridine, L³ = (E)-2-(phenyl(2-phenyl-2-(pyridin-2-yl)hydrazono) methyl)pyridine. The molecular structures of all the complexes 1 , 2 and 3 were determined by using single crystal X-ray diffraction. These complexes showed excellent catalytic activities such as transfer hydrogenation and alcohol oxidation. Theoretical calculations have been performed to understand the electronic properties of all the complexes using B3LYP as a function and LANL2DZ as a basis set.     

Synthesis of antidepressant duloxetine via asymmetric transfer hydrogenation

Antidepressant duloxetine （1） was prepared via asymmetric transfer hydrogenation of 3-（dimethylamino）-1-（thiophen-2- yl）propan-1-one （3）. The Ru（Ⅱ）, Rh（Ⅲ） and Ir（Ⅲ） complexes of several chiral ligands were examined as the catalyst and （S,S）-N-tosyl-1,2-diphenyl ethylenediamine （TsDPEN）-Ru（Ⅱ） complex was found to provide good yield and excellent enantioselectivity. 2007 Ming Yan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.