Norquay推出新型抗紫外线稳定剂

Norquay技术公司已开始生产三种 Heliosorb系列新产品,这三种产品都是以二苯酮为原料制得的。 Heliosorb-11和Heliosorb-11DS分别以二苯酮-6和二苯酮-9为基料,都可用作防止化妆品降解的抗紫外线稳定剂。Heliosorb-20也是     

阿卡他定关键中间体的合成研究

以5H-咪唑并[2,1-b]苯并吖庚因酮和N-甲基-4-哌啶酮为起始原料,经Mc Murry偶联反应得到阿卡他定的关键中间体11-(1-甲基-4-哌啶亚基)-6,11-二氢-5H-咪唑并[2,1-b]苯并吖庚因,含量95.0%,收率80.0%,其结构经MS、1H NMR、13C NMR确认。     

1—苄基—5—乙氧基—2,4—咪唑啉二酮的合成

苄胺和氯代乙酸缩合,然后与氰酸钠或尿素反应1-苄基-2,4-咪唑啉二酮,再用溴卤化、乙醇醚化便得1-苄基-5-乙氧基-2,4-咪唑啉二酮。     

1-(2-氟苯基)-1-(4-氟苯基)环氧乙烷的合成研究

以2,4’-二氟二苯酮和锍盐(CH3)3SHSO4为原料,在碱性条件下反应生成1-(2-氟苯基)-1-(4-氟苯基)环氧乙烷。通过正交实验确定最佳工艺条件为:氢氧化钾、甲醇和2,4’-二氟二苯酮的物质的量比为6∶1.25∶1,反应温度45℃。以2,4’-二氟二苯酮计,产品收率为91.23%,含量为97.45%。     

富马酸尼唑苯酮关键中间体的合成与表征

以咪唑为原料,通过苄基取代保护﹑酰基化反应﹑硼氢还原﹑卤化反应四步反应制得富马酸尼唑苯酮重要中间体:1-苄基-2-氯甲基咪唑,并对反应路线进行优化,减少了工业设备的腐蚀,对反应中间体用核磁进行表征,最终得到白色目标产物,产率为45.32%。     

盐酸鲁拉西酮的合成工艺研究

合成了抗精神分裂药物盐酸鲁拉西酮。以苯并异噻唑-3(2H)-酮为原料,经氯代、与无水哌嗪缩合得3-(哌嗪-1-基)苯并异噻唑,其和(1R,2R)-环己-1,2-二甲醇二甲磺酸酯反应得反式-3aR,7aR-八氢异吲哚啉-2-螺-1'-[4'-(1,2-苯并异噻唑-3-基)哌嗪]甲磺酸盐,再和顺-降冰片烷-外-2,3-二甲酰亚胺反应得鲁拉西酮,最后经成盐得盐酸鲁拉西酮。目标化合物经光谱确证,三步收率为42%(以苯并异噻唑-3(2H)-酮计)。反应条件温和、操作简便,各步原料价格低廉,采用的工艺操作简便易行。     

2-芳硫基咪唑啉酮衍生物的合成

通过膦亚胺与苯异氰酸酯的ava-Wittig反应制得碳二亚胺，应用碳二亚胺与硫酚（取代硫酚）反应制得8个新的2－芳硫基咪唑啉酮衍生物，并初步探讨了反应条件。     

N-甲基-1,2-苯并异噻唑啉-3-酮的合成研究

N-甲基-1,2-苯并异噻唑啉-3-酮是一种广谱高效的杀菌剂,以邻氨基苯甲酸为原料,经重氮二硫代、酰氯化、氮酰化、Zincke二硫化物分裂以及碱性条件下环合五步反应制得目标产物,总收率为53.5%,产品含量≥99%,产品结构经红外、核磁得到确认。     

国外专利文献

新的（4-亚丙酮基-2,6,8,9-四甲基-7H-咪唑并【1,5,4-e,f】[1,5]苯并二氮杂苯）衍生物的合成 咪唑并苯并二氮杂草衍生物是通过7-氨基-2,5,6-三甲基苯并咪唑与乙酰丙酮和乙酰乙酸乙酯缩合产品的环化而得到的。     

[Bmim]Cl-AlCl_3离子液体催化1,2-苯并苊醌的合成

研究了氯代1-甲基-3-丁基咪唑-三氯化铝([Bmim]Cl-AlCl3)离子液体催化蒽与草酰氯的Friedel-Craft酰基化反应。GC/MS分析发现生成了1,2-苯并苊醌(又名1,2-蒽乙二酮),用GC法考察了不同反应条件对1,2-蒽乙二酮收率和选择性的影响。当AlCl3在[Bmim]Cl-AlCl3离子液体中的摩尔分数为0.67,m{[Bmim]Cl-AlCl3}∶m(蒽)=8∶1,n(草酰氯)∶n(蒽)=2∶1,反应温度45℃,反应时间6 h时,1,2-蒽乙二酮收率为88.2%,选择性可达100%。[Bmim]Cl-AlCl3离子液体5次循环使用后,1,2-蒽乙二酮的收率和选择性仍达88.0%和99.6%。经萃取、重结晶等方法得到了w(1,2-蒽乙二酮)=98.3%的产品,通过熔点测定、GC、GC/MS、FTIR和1HNMR对反应产物进行了定性和定量分析。     

Highly selective asymmetric synthesis of 2-hydroxy fatty acid methyl esters through chiral oxazolidinone carboximides

Highly selective asymmetric synthesis of 2-hydroxy fatty acid methyl esters has been accomplioshed through chiral imide enolates. Five chiral oleic acid imides were prepared by reaction of oleioc acid with pivaloyl chloride followed by reaction with five different lithiated chiral oxazolidinones including (R)-(+)-4-benzyl-2-, (S)-(-)-4-benzyl-2-, (4R,5S)-(+)-4-methyl-5-phenyl-2-, (4S,5R)-(-)-4-methyl-5-phenyl-2-, and (R)-(+)-4-isopropyl-2-oxazolidinones in 88–92% yileds. The chiral imides were reacted with NaN(Me₃Si)₂ at −78°C to give enolates, which subsequently reacted with 2-(phenylsulfonyl)-3-phenyloxaziridine to give hydroxylated products in 78–83% yields. Methanolysis of the hydroxylated products with magnesium methoxide gave methyl 2-hydroxyoleate. Enantiomeric excesses (ee) of the products were determined to be very high (98–99% ee) by ¹H nuclear magnetic resonance study after esterification of the hydroxy group with (S)-(+)-O-acetylmandelic acid. Enantioselective hydroxylation of other fatty acids including elaidic, petroselinic, vaccenic, and linoleic was evaluated under the similar conditions using (4R, 5S)-(+)-4-methyl-5-phenyl-2-oxazolidinone as a chiral auxiliary to give 98% ee values for all cases.     

三氮唑螺氧化吲哚衍生物的合成及表征

以1-苄基-2-氧代吲哚-3-亚氨基甲酸叔丁脂和4-取代(Z)-N-苯基苯甲酰氯为底物通过1,3-偶极环加成反应合成了9种目标产物。通过比较目标产物的产率,对反应溶剂、碱及其用量、温度等因素进行了优化,确定了最佳反应条件,即在25℃下以二氯甲烷为溶剂、三乙胺为碱,且n(Et3N)∶n(1-苄基-2-氧代吲哚-3-亚氨基甲酸叔丁脂)=2.0∶1.0时,目标化合物最高产率可达94.4%。将具有生物活性的三氮唑骨架引入到螺环氧化吲哚骨架中,为更好地发现具有生物活性的该类新化合物提供借鉴。     

8-苄基-2,8-二氮杂双环[4.3.0]壬烷的合成

采用氢化铝锂还原8-苄基-7,9-二氧代-2,8-二氮杂双环[4.3.0]壬烷（C₁₄H₁₆N₂O₂）,得目标产物8-苄基-2,8-二氮杂双环[4.3.0]壬烷（C₁₄H₂₀N₂）,确定了最佳工艺条件。结果表明,以四氢呋喃作溶剂,n(C₁₄H₁₆N₂O₂):n(LiAlH₄)=1:3.2和反应时间为16 h时,产物收率可达93.73%;产物经元素分析、红外光谱分析确认。     

Thermolysis of mono-, di- and tri-benzylamines,IV

Thermolysis of mono-, di- or tri-benzylamine for some days in the absence of promoters gave the same products: ammonia, toluene, dibenzyl, stilbene and benzaldehyde. Thermolysis of dibenzylamine in isoquinoline as a solvent gave 1-benzyl-isoquinoline together with the normal pyrolysis products. When naphthalene and 2-naphthol are used as solvents, benzylation of the solvent nuclei was observed to give 1- and 2-benzylnaphthalenes and 1-benzyl-2-naphthol respectively. In conclusion, thermolysis of tri-, di- or mono-benzylamines proceeds through a free radical mechanism with successive conversions of the tertiary, through secondary to primary alkylamines resulting in the same pyrolysis products.     

一种新型3-芳基咪唑卡宾前体的合成

以3,5-二三氟甲基苯胺、乙二醛、甲醛、氯化铵和氯化苄或1-溴癸烷为原料,经缩合、亲核取代反应得到氯化1-苄基-3-(3,5-二三氟甲基)苯基咪唑盐和溴化1-癸基-3-(3,5-二三氟甲基)苯基咪唑盐,收率分别达59.0%和76.6%;通过氯化1-苄基-3-(3,5-二三氟甲基)苯基咪唑盐和溴化1-癸基-3-(3,5-二三氟甲基)苯基咪唑盐的阴离子交换反应得到4种目标产物:1-苄基-3-(3,5-二三氟甲基)苯基咪唑四氟硼酸盐、1-癸基-3-(3,5-二三氟甲基)苯基咪唑四氟硼酸盐、1-苄基-3-(3,5-二三氟甲基)苯基咪唑六氟磷酸盐和1-癸基-3-(3,5-二三氟甲基)苯基咪唑六氟磷酸盐,产物结构通过1HNMR、13CNMR得以确认。考察了溶剂对亲核取代反应的影响,得出最佳反应溶剂为甲苯。     

Synthesis of 3-alkylated triacetonamine derivatives

Reaction of a lithiated imine derivative of 2,2,6,6-tetramethyl-4-piperidone (triacetonamine, 1 ) with activated or less reactive alkyl halides or styrene oxide and subsequent hydrolysis afforded 3-alkylated triacetonamine derivatives. Thus, 3-benzyl-2,2,6,6-tetramethyl-4-piperidone ( 3 ), 3-(n-butyl)-2,2,6,6-tetramethyl-4-piperidone ( 4 ), 3-(3-chloropropyl)-2,2,6,6-tetramethyl-4-piperidone ( 5 ), 2,2,3,6,6-pentamethyl-4-piperidone ( 6 ) and two diastereomers of 3-(2-hydroxy-2-phenylethyl)-2,2,6,6-tetramethyl-4-piperidone ( 7 ) were prepared in 26–53% yield. Reaction of the imine anion derived from 1 with benzyl bromide to give 3 has to be performed at low temperatures in order to avoid a competing proton transfer. No reaction at the unprotected piperidine nitrogen was observed.     

（R，R）-2，8-二氮杂双环[4．3．0]壬烷的合成

（R,R）-2,8-二氮杂双环[4．3．0]壬烷是莫西沙星合成过程中的一个副产物,对莫西沙星成品质量有较大影响。本文以8-苄基-2,8-二氮杂双环[4．3．0]壬烷为起始原料,经L-（＋）-酒石酸拆分,Pd／C催化加氢脱苄基,纯化制得含量〉99．5％的（R,R）-2,8-二氮杂双环[4．3．0]壬烷,总收率66．5％,并优化了合成工艺。     

Studies on 4-thiazolidinones. VIII. The role of substituents at position-3 on the mode of cleavage of 5-Arylmethylene-2,4-dioxothiazolidines

Hydrazine hydrate, morpholine and benzylamine react with 3-aryl-5-arylmethylene-2,4-dioxothiazolidines 1a – d to give mixtures of thiolopropenamides 2 , ethylideneamino-biuret 3 and/or 4-arylaminocarboxamides 4 in varying proportions. However, 3-benzyl-5-arylmethylene 2,4-dioxothiazolidines 1e – f afford mixtures of pyrazolinones 5 and 4-benzyl-hydrazinocarboxamide 6 upon treatment with hydrazine hydrate. The formation of these products is rationalized and discussed on the basis of the role of the substituent at the 3-position. Structures 2 – 6 have been established.     

2-R-9-苄基-9H-嘌呤的合成

采用 (Ph3 P) 2 PdCl2 为催化剂 ,DMF为溶剂 ,对 2 碘 9 苄基 9H 嘌呤与有机锡试剂RSnBu3 (R =乙烯基、2 噻吩基、2 呋喃基、苯乙炔基和苯基等 )之间的Stille偶合反应进行了研究 ,合成出 5种 2位取代的嘌呤衍生物。在反应温度为 6 0℃ ,n(2 碘 9 苄基 9H 嘌呤 )∶n(RSnBu3 )∶n〔(Ph3 P) 2 PdCl2 〕 =1 0∶1 2∶0 0 5的较佳工艺条件下 ,产品收率 43%～ 92 %。用1H NMR、13 C NMR和MS对产物进行了表征。     

The polymerization behaviour of 1-benzyl-2,2-dimethylaziridine

Summary The polymerization of 1-benzyl-2,2-dimethylaziridine (BDMA) with triethyioxonium tetrafluoroborate (TEFB) under different reaction conditions was found to be impossible, although the initiation reaction (formation of 1-benzyl-1-ethyl-2,2-dimethylaziridinium tetrafluoroborate) was fast and quantitative. BDMA does copolymerize with 1-benzylaziridine (BA) but the amount of BDMA in the copolymer is always inferior to 50%. The reactivity parameters of the copolymerization (in dichloromethane at 20°C) are r_BA = 3.1 and r_BDMA = 0.0. These results demonstrate the importance of the presence of substituents on the polymerization behaviour of N-alkylaziridines.