合成因素对V-AlPO4-5骨架钒含量和催化苯氧化性能的影响

水热法合成了V-AlPO4-5分子筛，用XRD和FT-IR对样品进行了表征．以纯V-AlPO4-5分子筛为基准，用样品单位晶胞体积的膨胀程度和红外谱图中骨架振动峰向低波数方向位移程度的大小为指标，定性地探索了钒源、加料方式、钒加入量和晶化时间等合成因素对于V-AlPO4-5分子筛中骨架钒含量的影响．结果表明以V2O5为钒源、采用(V P H2O) Al R的加料方式，V／(Al P)=1／80，200℃下水热晶化48h后得到的V-AlPO4-5分子筛中骨架钒含量最高．H2O2氧化苯制苯酚的活性实验结果表明，苯酚收率和H2O2分解率同V-AlPO4-5骨架钒含量具有明显的正相关性．溶剂效应表明反应机理是羟基自由基机理．     

麦秆水解-氧化-水解法制取草酸新工艺

研究了以麦秆为原料用水解-氧化-水解法制取草酸的工艺方法。最佳反应条件：麦秆用量50g,硫酸浓度70％,物料浸泡时间≥3h,m(硝酸)：m(麦秆)=2．1：1．0;氧化催化剂V2O5-FeCl3[n(V2O5):n(FeCl3)=1：1]用量0．1g,氧化-水解反应时间5h,反应温度65℃～70℃,草酸二水合物收率75．5％。     

Cu/V2O5-TiO2的光催化丙烯和二氧化碳合成MAA反应性能

用IR、TPD、UV-Vis和微型光反应器技术研究了CO2和C3H6在Cu／V2O5-TiO2表面上的吸附特性和光催化反应性能．实验结果表明：在Cu／V2O5-TiO2催化剂表面存在金属位Cu、Lewis酸位V^5 和Ti^4 以及Lewis碱位V-O-Ti的桥氧和V=O的端氧三类活性中心；在金属位Cu和Lewis酸位Ti^4 (或V^5 )协同作用下．CO2形成活性较高的卧式吸附态Cu-(CO)-O→Ti^4 (或V^5 )．C3H6的β-H和β-C分别吸附在Lewis碱位V=O与金属位Cu上形成Cu-C(CH2CH3)-H→O=V吸附态；Cu／V2O5-TiO2催化剂的吸光阈值红移和光吸收量的提高均有利于其光催化活性的提高；担载10％V2O5的光催化剂催化活性优于其它含量的催化剂，其光量子效率达到15．1％；C3H6转化率为5．5％，MAA选择性超过95％．根据实验结果．提出了光促表面催化合成反应的机理．     

醛氨气相合成3,5-二甲基吡啶催化剂的研究

以醛氨气相合成3,5-二甲基吡啶（DMP）为探针反应,考察了γ-Al2O3负载不同金属氧化物催化剂的催化活性。实验结果显示Cr2O3／γ-Al2O3对DMP有较好选择性和收率。较优化的反应条件为：Cr2O3／γ—Al2O3,[w（Cr2O3）=8％]1．0g,反应温度340℃-400℃,常压,V（醛）：V（氨）为1：4—1：6,V（丙醛）：V（甲醛）为1：1—1：2,GHSV 1200h～,DMP收率76．1％,丙醛转化率92．7％。     

用H2O2氧化苯乙烯合成苯甲酸

摘要：以30％H2O2做为氧化剂,钨酸钠与含O双齿有机配体(草酸)形成的络合物为催化剂,在无有机溶剂、无相转移剂的条件下,研究了苯乙烯氧化制苯甲酸的反应。研究结果表明,最佳反应条件为：苯乙烯100．0mmol,n(钨酸钠)：n(草酸)：n(苯乙烯)：n(30％H2O2)=2．0：3．2：100．0：440．0,于92℃反应24h,苯甲酸收率98．6％。用GC—MS跟踪了氧化过程中4种主要物质苯乙烯、1-苯基邻二醇、羟基苯乙酮及苯甲酸含量随反应时间的变化关系,提出了其主要氧化机理为苯乙烯经过环氧化反应、水解生成生成1-苯基邻二醇,1-苯基邻二醇再氧化为羟基苯乙酮、最后氧化为苯甲酸。     

温控相分离催化三聚丙烯氢甲酰化反应的研究

 首次将温控相分离催化概念应用于三聚丙烯氢甲酰化反应中．系统研究了各种反应条件对三聚丙烯氢甲酰化反应的影响，考察了催化剂的循环使用效果．以RhCl3·3H2O为催化剂前体，以P［p－C6H4O（CH2CH2O）nH］3为配体，在V（H2）／V（CO）＝1，p＝6MPa，θ＝130℃的反应条件下，三聚丙烯氢甲酰化反应的转化率和醛收率可分别达到76．3％和72．1％．催化剂循环使用三次，仍有较高的催化活性．     

全保护RGD三肽的合成方法研究

以两条路线、多种偶联试剂(DCC，EDCI，CDI，EEDQ)合成了全保护三肽Arg- Gly-Asp(RGD)．Boc-Arg(Tos)-OH经上述偶联剂短时活化，于合适条件下与Ts0H- G1y-OBzl缩合，均获得良好收率(43％-97％)．经Pd(OH)2／H2还原得到的Boc-Arg (Tos)-G1y-0H于22-27℃与HCl·Asp(OcHex)-OBzl偶联得到全保护三肽Boc-Arg (Tos)-Gly-Asp(OcHex)-OBzl(TM)，反应收率分别为76．4％(DCC／HOSu)，64．7％ -78．3％(DCC／HOBt)，66．7％-77．9％(EDCI／HOBt)．Boc-Gly-OH和HCl·Asp- (OcHex)-OBzl经DCC／HOBt或CDI活化，可得到碳端二肽Boc-Gly-Asp(OcHex)-OBzl (收率分别为81．2％，89．5％)，该二肽脱Boc后与Boc-Asp(Tos)-OH反应，经DCC ／HOBt，EDCI／HOBt，CDI，DCC／HOSu活化，均可生成目标分子TM，其反应收率分 别为40．4％，73．8％，67．8％，84．4％．     

正丁烷氧化制顺酐流化床催化剂的性能

 考察了前驱体制备过程中水合肼／五氧化二钒摩尔比（以下简记\r\n为n（N2H4）／n（V2O5））对催化剂性能的影响．由较高的n（N2H4）\r\n／n（V2O5）比制得的催化剂，其（VO）2P2O7相含量较多，正丁烷转化\r\n率较高．随着n（N2H4）／n（V2O5）比的减小，δ－VOPO4相的含量逐\r\n渐增多，正丁烷转化率随之升高；而顺酐选择性开始时升高，达到最大\r\n值后逐渐降低．在n（N2H4）／n（V2O5）＝0．34时制备的催化剂最佳\r\n，在丁烷浓度为4．0％、空速为500h－1及反应温度为420℃的反应条件\r\n下，顺酐收率可达49．74％．本文中细粒床催化剂有较大的操作弹性．     

N-[4-(磺酰胺)苯基](甲基)丙烯酰胺的合成

以对氨基苯磺酰胺、丙烯酰氯(或甲基丙烯酰氯)为原料合成了N-[4-(磺酰胺)苯基]丙烯酰胺(ASPAA)和N-[4-(磺酰胺)苯基]甲基丙烯酰胺(ASPMAA),其结构经^1H NMR,IR和元素分析表征。合成ASPAA的最佳条件：对氨基苯磺酰胺13．76g(80mmol),n(对氨基苯磺酰胺)：n(丙烯酰氯)=1．0：1．1,n(丙烯酰氯)：n(NaHCO3)：1．00：1．14,0℃～2℃反应3h,反应液倾入10倍体积的的甲醇-水[V(甲醇)：V(水)=1：10]中析出产物,收率在60％以上。合成ASPMAA的最佳条件：对氨基苯磺酰胺6．88g(40mmol),n(对氨基苯磺酰胺)：n(甲基丙烯酰氯)=1.00：1．05,n(三己胺)：n(甲基丙烯酰氯)：1．0：1．0,在0℃～2℃滴加甲基丙烯酰氯后先在室温下反应1h,然后在60℃反应1h,反应液倾入700mL石油醚中析出产物,收率50％～60％．     

新型高聚合度钨磷多金属氧酸盐超分子化合物的水热合成与晶体结构

首次报道了新型高聚合度钨磷多金属氧酸盐超分子化合物H16{[P4W14Na3 (H2O)7O58]2[Na4(H2O)13]2[P4W14Na2(H2O)2O56]}·24H2O的水热合成方法,用元素分析、IR和单晶X射线衍射等手段进行了表征．晶体属三斜晶系,P1空间群,a= 1．551 5(3)nm,b=1．866 4(4)an],c=2.224 9nm,α=105.10(3)°,β=96.74(3)°,γ= 95．23(3)°,V=6．127(2)nm3,Z=1,Mr=12 418.36,Dc=3．365 g·cm-3,μ=19．843 mm-1, F(000)=5 516,R=0．0 829,Rw=0．2 020．测定结果表明,标题化合物是由两个[P4W14Na3 (H2O)7O58]9-和一个[P4W14Na2(H2O)2O56]6-阴离子通过O-Na-O桥键合而成．     

Atmospheric chemistry of 3-pentanol: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX

Smog chamber/FTIR techniques were used to study the atmospheric chemistry of 3-pentanol and determine rate constants of k(Cl+3-pentanol) = (2.03 +/- 0.23) x 10 (-10) and k(OH+3-pentanol) = (1.32 +/- 0.15) x 10 (-11) cm (3) molecule (-1) s (-1) in 700 Torr of N 2/O 2 diluent at 296 +/- 2 K. The primary products of the Cl atom initiated oxidation of 3-pentanol in the absence of NO were (with molar yields) 3-pentanone (26 +/- 2%), propionaldehyde (12 +/- 2%), acetaldehyde (13 +/- 2%) and formaldehyde (2 +/- 1%). The primary products of the Cl atom initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (51 +/- 4%), propionaldehyde (39 +/- 2%), acetaldehyde (44 +/- 4%) and formaldehyde (4 +/- 1%). The primary products of the OH radical initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (58 +/- 3%), propionaldehyde (28 +/- 2%), and acetaldehyde (37 +/- 2%). In all cases the product yields were independent of oxygen concentration over the partial pressure range 10-700 Torr. The reactions of Cl atoms and OH radicals with 3-pentanol proceed 26 +/- 2 and 58 +/- 3%, respectively, via attack on the 3-position to give an alpha-hydroxyalkyl radical, which reacts with O 2 to give 3-pentanone. The results are discussed with respect to the literature data and atmospheric chemistry of 3-pentanol.     

纳米二氧化钛催化苯乙烯环氧化反应的研究(Ⅰ)

通过烯烃的环氧化反应可制得一系列活泼的有机中间体--环氧化物,再通过选择性开环或功能团转化可方便地合成多种有价值的化合物.含钛催化剂对烯烃环氧化催化效果较好,如Ti-ZSM-5、Ti-ZSM-11、α-和β-[SiW₉Ti₃O₄₀]^10-.     

2-(4′-Fluorophenyl)imidazole. Nitration studies

Reactions of 2-(4′-fluorophenyl)imidazole ( 1 ) and related compounds under various nitrating conditions are discussed. With 90% nitric acid in 20% oleum at ?10°, 1 affords 2-(4′fluorophenyl)-4(5)-nitroimidazole ( 2 ) in 80% yield. Reaction of 2 with the same reagents at 25° affords 2-(4′-fluoro-3′-nitrophenyl)-4(5)-nitroimidazole ( 4 ) in 90% yield, whereas with 90% nitric acid in acetic acid at 95°, 2 affords 4,5-dinitro-2-(4′-fluorophenyl)imidazole ( 5 ) in 80% yield. Reaction of 1 with 70% nitric acid in concentrated sulfuric acid at 25° affords 2-(4′-fluorophenyl)-5-hyroximinoimidazolin-4-one ( 6 ), which rearranges and hydrolyzes to 5-(4′-fluorophenyl)-1,2,4-oxadiazole-3-carboxylic acid. A discussion of these reactions is presented.     

Asymmetric synthesis of (1R,2S,3R)-3-methylcispentacin and (1S,2S,3R)-3-methyltranspentacin by kinetic resolution of tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate

Conjugate addition of lithium dibenzylamide to tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate occurs with high levels of stereocontrol, with preferential addition of lithium dibenzylamide to the face of the cyclic alpha,beta-unsaturated acceptor anti- to the 3-methyl substituent. High levels of enantiorecognition are observed between tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate and an excess of lithium (+/-)-N-benzyl-N-alpha-methylbenzylamide (10 eq.) (E > 140) in their mutual kinetic resolution, while the kinetic resolution of tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate with lithium (S)-N-benzyl-N-alpha-methylbenzylamide proceeds to give, at 51% conversion, tert-butyl (1R,2S,3R,alphaS)-3-methyl-2-N-benzyl-N-alpha-methylbenzylaminocyclopentane-1-carboxylate consistent with E > 130, and in 39% yield and 99 +/- 0.5% de after purification. Subsequent deprotection by hydrogenolysis and ester hydrolysis gives (1R,2S,3R)-3-methylcispentacin in > 98% de and 98 +/- 1% ee. Selective epimerisation of tert-butyl (1R,2S,3R,alphaS)-3-methyl-2-N-benzyl-N-alpha-methylbenzylaminocyclopentane-1-carboxylate by treatment with KO'Bu in 'BuOH gives tert-butyl (1S,2S,3R,alphaS)-3-methyl-2-N-benzyl-N-alpha-methylbenzylaminocyclopentane-1-carboxylate in quantitative yield and in > 98% de, with subsequent deprotection by hydrogenolysis and ester hydrolysis giving (1S,2S,3R)-3-methyltranspentacin hydrochloride in > 98% de and 97 +/- 1% ee.     

Synthesis of 2-{2-hydroxy-3-[2-(vinyloxy)ethoxy]propoxy}-benzaldehyde and Schiff bases derived therefrom

Base-catalyzed reaction of 2-hydroxybenzaldehyde with 2-{[2-(vinyloxy)ethoxy]methyl}oxirane gave 2-{2-hydroxy-3-[2-(vinyloxy)ethoxy]propoxy}benzaldehyde in 42% yield, and subsequent condensations of the product with thiosemicarbazide and primary aliphatic amines afforded the corresponding thiosemicarbazone (yield 86%) and 1-{2-[(alkylimino)methyl]phenoxy}-3-[2-(vinyloxy)ethoxy]propan-2-ols (74–81%).     

Nucleophilic substitution in the 10,11-dihydrodibenz[b,f]iodepinium cation

10,11-Dihydrodibenz[b,f]iodepinium tetrafluoroborate gave only 1-(2-azidophenyl)-2-(2-iodophenylethane with the N₃ ^– in aqueous DMSO, while with NO₂ ^– it gave 1-(2-nitrophenyl)-2-(2-iodophenyl)ethane (93%), 9,10-dihydrophenanthrene (5%), and traces of phenanthrene. Both in pure and aqueous DMSO this cation with the Br^– ion was converted into phenanthrene (80% and 68% respectively) and 1-(2-bromophenyl)-2-(2-iodophenyl)ethane (10 and 20%), while in water it gave 9,10-dihydrophenanthrene (75%) and phenanthrene (5%). A new route for the synthesis of 1-(2-aminophenyl)-2-phenylethane starting from this tetrafluoroborate has been proposed.M. V. Lomonosov Moscow State University, Moscow 119899, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, 110–115, January, 1999.     

5-(2’-羧乙基)-6-烷基-3,4-二氢吡喃酮的合成

吡喃酮是许多天然产物的结构单元,我们曾由4-异丁酰基庚二酸在过量醋酸酐及乙酰氯存在下回流得到7-氧代-8,8-二甲基-△~9-六氢香豆素.本文由二氰乙基-β-二酮进行酮解水解反应得到4-酰基庚二酸1_(a-c)。 在过量醋酸酐、乙酰氯存在下由1_a、1_c为底物进行反应没有得到双环的香豆素衍生物.其产物和单纯以乙酐为缩合剂时的产物2_a、2_c相同,产率分别为68％、63％。2_c可在硫酸铁催化     

Synthesis of carbazoles via an intramolecular cyclization of 2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines and their related molecules

Various 2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines 1a-g were treated with potassium tert-butoxide or potassium 3-ethylpentanoxide in NMP at 60 degrees C for 2 h to give the corresponding 5-substituted carbazoles 2a-g in 36-65% yields together with indoles 9a-g in 21-40% yields, respectively. Exposing the trifluoroacetamide analogues 10h-k under the same reaction conditions gave the carbazoles 2b-e in 37-57% yields and indoles 9b-e in 15-27% yields. Subsequent cyclizations of acetamide analogues 10a-g gave carbazoles 2a-g in 53-86% yields.     

Enzymatic synthesis of (-)- and (+)-acetoxyhexamides and (-)- and (+)-hydroxyhexamides.

The enantioselective hydrolysis of (+/-)-4-(1-acetoxyethyl)-N-(cyclohexylcarbamoyl)-benzenesulfona mides 3 with lipase Amano P from Pseudomonas sp. in a water-saturated solvent gave (R)-4-(1-hydroxyethyl)-N-(cyclohexylcarbamoyl)benzenesulfonamide 2 (39%, > 99% ee) and unchanged (S)-3 (50%, 62% ee). On the other hand, enantioselective esterification of (+/-)-2 with lipase Amano P in the presence of vinyl acetate provided (R)-3 (41%, > 99% ee) and unchanged (S)-2 (46%, 78% ee).     

2H-1,2,4-benzothiadiazine 1,1-dioxides 2. A condensation of 2-aminobenzenesulfonamide with chloroalkyl isothiocyanates

A reaction of 2-aminobenzenesulfonamide ( 1 ) with 2-chloroethyl or 3-chloropropyl isothiocyanate in isopropanol afforded 2-(2′-chloroethylthioureido)- and 2-(3′-chloropropylthioureido)benzenesulfonamides ( 2a,b ) in 67% and 55% yield respectively. Treatment of 2a,b with triethylamine in methanol at room temperature furnished 3-(2′-aminoethylthio)- and 3-(3′-aminopropylthio)-2H-1,2,4-benzothiadiazine 1,1-dioxides ( 9a,b ) in quantitative yield. Heating 2b to reflux in methanol under neutral conditions gave 9b but in the form of the hydrochloride 8b which could be converted into the free base 9b by treating with ammonia water. When compounds 2a,b were treated with triethylamine in methanol at elevated temperature, 3-(2′-mercaptoethylamino)- and 3-(3′-mercaptopropylamino)-2H-1,2,4-benzothiadiazine 1,1-dioxides ( 10a,b ) were obtained in good yield. Alternatively, 10a,b could also be prepared from 9a,b in 95% and 77% yield respectively.