CN1107148A - 2-全氟代烷基-3-噁唑啉-5-酮的制备方法 - Google Patents
2-全氟代烷基-3-噁唑啉-5-酮的制备方法 Download PDFInfo
- Publication number
- CN1107148A CN1107148A CN94112990A CN94112990A CN1107148A CN 1107148 A CN1107148 A CN 1107148A CN 94112990 A CN94112990 A CN 94112990A CN 94112990 A CN94112990 A CN 94112990A CN 1107148 A CN1107148 A CN 1107148A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- acid
- halogen
- compound
- naturally
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/36—One oxygen atom
- C07D263/42—One oxygen atom attached in position 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
- C07C255/44—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms at least one of the singly-bound nitrogen atoms being acylated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Cephalosporin Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyrrole Compounds (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明提供了制备2-全氟代烷基-3-噁唑啉
-5-酮化合物的方法,包括使氨基腈与全氟代酰化剂
在溶剂的存在下反应形成全氟代烷酰基氨基腈中间
体,在酸及至少一摩尔当量的水存在下使中间体环
化。
Description
本发明涉及2-全氟代烷基-3-噁唑啉-5-酮的制备方法。
芳基吡咯腈化合物及其衍生物是很有效的杀虫、杀螨和杀软体动物剂。特别是业已发现的2-芳基-5-三氟甲基吡咯-3-腈化合物及其衍生物以极低用量施用时有广谱的活性,对抗性种类都有效,美国专利第5,030,735号揭示了在工厂制造规模上制备所述吡咯化合物的方法,它包括使适当的3-噁唑啉-5-酮与2-氯代丙烯腈进行1,3-偶极环加成反应。其中在四步合成路线中以前体的氨基腈作为起始物料。通过适当的苯基甘氨酸化合物来制得关键的中间体-3-噁唑啉-5-酮。
本发明的一个目的是提供从氨基腈前体出发二步可方便、有效地合成2-全氟代烷基-3-噁唑啉-5-酮的方法。
本发明的另一个目的是提供在制备2-全氟代烷基-3-噁唑啉-5-酮中有用的全氟代链烷酰氨基腈化合物。
本发明的再一个目的是提供在制造杀虫、杀螨和杀软体动物的芳基吡咯化合物中关键的中间产物的一个方便的来源。
本发明提供了制备下式Ⅱ2-全氟代烷基-3-噁唑啉-5-酮化合物的方法
其中n是1,2,3,4,5,6,7或8的整数;
R是
L是氢或卤素;
M和Q各自是氢,卤素,CN,NO2,C1~C4烷基,C1~C4卤代烷基,C1~C4烷氧基,C1~C4卤代烷氧基,C1~C4烷基硫代,C1~C4烷基亚磺酰基,或者当M和Q在相邻位置上时,它们可与碳原子一起连接形成环,其中MQ代表结构:-OCH2O-,-OCF2O-或-CH=CH-CH=CH-,条件是L、M和Q中的至少一个必须不是氢;R1、R2和R3各自是氢,卤素,NO2,CHO或者R2和R3与碳原子一起连接成环,其中R2R3由
R4,R5,R6和R7各自是氢,卤素,CN或NO2;W是O或S,
该方法包括使下式Ⅲ的氨基腈
其中R的定义同上,
与式Ⅳ的全氟代酰化剂
其中m是整数1或2,X是OR1,Cl或O,R1是氢或C1~C4烷基,条件是当X是O,m必须是2,当X是Cl或OR1时,m必须是1,在溶剂的存在下,也可选在碱存在下进行反应,以形成式Ⅰ的全氟代-烷酰基氨基腈中间体
在酸及至少一摩尔当量的水存在下,使式Ⅰ的中间体环化。
本发明也提供了下式Ⅰ的全氟代烷酰基氨基腈:
其中n是1,2,3,4,5,6,7或8的整数;
R是
L是氢或卤素;
M和Q各自是氢,卤素,CN,NO2,C1~C4烷基,C1~C4卤代烷基,C1~C4烷氧基,C1~C4卤代烷氧基,C1~C4烷硫基,C1~C4烷基亚磺酰基,或者当M和Q在相邻位置上时,它们可与碳原子一起连接形成环,其中MQ代表结构:-OCH2O-,-OCF2O-或-CH=CH-CH=CH-,条件是L、M和Q中的至少一个必须不是氢;R1、R2和R3各自是氢,卤素,NO2,CHO或者R2和R3与碳原子一起连接成环,其中R2R3由
R4,R5,R6和R7各自是氢,卤素,CN或NO2;W是O或S,
2-全氟代烷基-3-噁唑啉-5-酮化合物是制造杀虫、杀螨和杀软体动物吡咯化合物中关键的中间体。
芳基吡咯化合物,特别是2-芳基-5-三氟甲基吡咯-3-腈化合物是高效杀虫剂、杀螨剂及杀软体动物剂的一个新的种类。在它们制备中的一个关键中间体是式Ⅱ的2-全氟代烷基-3-噁唑啉-5-酮化合物:
其中n和R的定义同上。目前已知制备式Ⅱ的噁唑啉酮的方法是通过使氨基腈Ⅲ水解来制备合适的芳基甘氨酸化合物V。通过Streck-er合成从适当的醛前体中来得到氨基腈(W.L.Matier等,J.Med.Chem,1973 16,901)。通过使氨基腈酰化成Ⅵ,来保护Ⅲ中的氨基,然后再使氰基和保护基团酸解,由于氨基腈Ⅲ的水解条件下是不稳定的,便需要保护基团。这样所得的甘氨酸Ⅴ经三氟乙酰化后得到Ⅶ,并环化而以四步得到所需的噁唑啉酮Ⅱ。反应顺序如流程Ⅰ所示,其中R是对-氯苯基,n是1。
流程Ⅰ
现已发现直接的全氟代酰化的Stecker产物Ⅲ给出可以简便地转化所需的2-全氟代烷基-3-噁唑啉-5-酮化合物Ⅱ的全氟代烷酰基氨基腈中间产物Ⅰ。反应如流程Ⅱ所示,其中m是1或2,X是Cl、OR1或O,R1是氢或C1~C6烷基,条件是当X是O时,m必须是2。当X是Cl或OR1时,m必须是1。
流程Ⅱ
令人惊奇的是,式Ⅰ的全氟代烷酰基氨基腈的酸性水溶液条件下一步即可环化成式Ⅱ的2-全氟代烷基-3-噁唑啉-5-酮化合物,收率良好。
有利的是,所需的噁唑啉酮Ⅱ从Strecker产物氨基腈Ⅲ出发只经二步即可得到。
较好的式Ⅰ化合物是:其中n为1,2或3,最好n为1。在较好的式Ⅰ化合物中,R是任意用一至三个卤素、NO2、C1~C4卤代烷基或C1~C4卤代烷氧基所取代的苯基。
根据本发明的方法,使式Ⅲ的氨基腈与等摩尔量的式Ⅳ的全氟代酰化剂在溶剂的存在下,也可在碱的存在下,反应形成式Ⅰ的全氟代烷酰基氨基腈。式Ⅰ的化合物然后在酸性的溶液的存在下环化形成式Ⅱ化合物,即2-全氟代烷基-3-噁唑啉-5-酮。
适用于本发明的方法中的溶剂是芳烃或卤代芳烃,较好的是诸如甲苯、苯、二甲苯之类的芳烃,最好是甲苯。
适用于本发明的方法的酸包括硫酸、甲磺酸、苯磺酸、对-甲苯磺酸、萘磺酸、氟硼酸、三氟化硼配合物之类。三氟化硼配合物可以包括BF3***合物,BF3甲酸配合物,BF3乙醇配合物,BF3二水合物之类。水可以水合物的形式引入,即以对-甲苯磺酸单水合物或以如30%~60%硫酸水溶液的形式引入。
在实践中,若以全氟代酰氯,如三氟乙酰氯用作式Ⅳ的反应试剂,然后可加入等摩尔量的碱作为HCl的清除剂。在碱中,可使用的是碱金属碳酸盐或碳酸氢盐或其混合物或是叔胺类。诸如碳酸钠或碳酸钾的碱金属碳酸盐可如碳酸氢钠或钾的碳酸氢盐一样使用。
适用于本发明方法的叔胺类包括现有技术中已知的任何之取代胺,如三烷基胺、二烷基芳基胺、三芳基胺之类,较好的是三烷基胺,最好是三乙胺。
为了更清楚地理解本发明,列出下列实施例。这些实施例仅供叙述而并非用来限制本发明的范围或实施原则。
术语1H、13C和19FNMR依次是指1H、13C和19F的核磁共振谱。
实施例1
N-〔(对-氯苯基)氰甲基〕-2,2,2-三氟乙酰胺的制备
方法A:在35℃,于90分钟内用三氟乙酸酐(315克,1.5摩尔)处理搅拌着的α-氰基-对-氯苄胺(250克,1.5摩尔)在甲苯中所成的浆状物。用庚烷处理混合物,过滤所得沉淀,滤饼用甲苯/庚烷洗涤得到标题产品323.7克,得率82%,熔点127~128℃可由1H,13C和19F的核磁共振谱分析鉴定。
方法B:用三氟乙酸乙酯(85.2克,0.6摩尔)处理α-氰基-对氯苄胺(83.3克,0.5摩尔)在甲醇中的溶液,室温下搅拌约16小时,并真空浓缩得到残留物。残留物用甲苯/庚烷重结晶得到淡黄色固体状标题产物88.3克,得率67.2%,熔点127~128℃。
方法C:用三氟乙酰氯(66.2克,0.5摩尔)滴加处理α-氰基-对氯苄胺(83.3克,0.5摩尔)和三乙胺(50.6克,0.5摩尔)在甲苯中的混合物,在室温下搅拌约1小时后过滤,滤液用水洗涤一次,真空浓缩得到残留物,残留物用甲苯/己烷重结晶得到标题产品114.2克,得率87%,熔点:127~128℃。
实施例2
N-(芳基氰基甲基)-2,2,2-三氟乙酰胺的制备
用实施例1中方法A所述的基本相同的方法过程,并以取代的合适的α-氰基苄胺作为起始物质,得到下列N-(芳基氰基甲基)2,2,2-三氟乙酰胺产品,这些产品采用1H,13C和19F核磁共振谱分析鉴定。
表Ⅰ
a按Strecker合成中所用的醛计(起始物质为Strecker品)。
实施例3
N-(α-氰基噻吩基)-2,2,2-三氟乙酰胺的制备
用实施例1中方法A所述的基本相同过程,用粗制的Stecker品,α-氰基-2-硫代苯乙胺作为起始物来代替,得到标题产物,得23%,熔点73.0~74.5℃,由1H,13C和19F核磁共振谱分析鉴定。
a按Strecker合成中的起始醛计。
实施例4
N-〔(对-氯苯基)氰甲基〕2,2,3,3,4,4,4-七氟丁酰胺的制备
用实施例1中方法A所述的相同过程,用七氟丁酸酐作为全氟代酰化剂,得到白色晶体标题产品,得率95%,熔点93.0~95.0℃,用1H、13C和19F核磁共振谱分析鉴定。
实施例5
N-〔(对-氯苯基)氰甲基〕2,2,3,3,3-五氟丙酰胺的制备
基本用实施例1中方法A所述的相同过程,并以取代的五氟丙酸酐作为全氟酰化剂,得到白色晶体的标题产品,得率95%,熔点118.0~118.5℃,用1H,13C和19F核磁共振谱分析鉴定。
实施例6
4-(对-氯苯基)-2-(三氟甲基)-3-噁唑啉-5-酮的制备
方法A:在80℃,于0.75~1.0小时内,用对-甲苯磺酸单水合物(P-tsa·H2O)(0.11摩尔)分批处理N-〔(对-氯苯基)氰甲基〕-2,2,2-三氟乙酰胺(0.1摩尔)在甲苯中的溶液,在90~95℃下搅拌2~3小时,冷却并过滤。滤液用水洗涤两次,真空浓缩得到油状残留物。将油溶解在庚烷中,过滤,滤液经真空蒸馏得到油状的标题产品,得率为55.6%,沸点78℃/0.01mmHg,用1H,13C,19F核磁共振谱分析鉴定。
方法B:在80℃下用水在20分钟内处理N-〔(对-氯苯基)氰基甲基〕2,2,2-三氟乙酰胺(26.3克,0.1摩尔)在甲苯和甲磺酸中(10.7g,0.11摩尔)的溶液,在90℃下搅拌8小时,并冷却。反应混合物用水洗涤两次。真空浓缩有机层得到油状物,再经真空蒸馏得到13.7克油状标题产物,沸点80℃/0.01mmHg。
实施例7
4-(2-噻吩基-2-(三氟甲基)-3-噁唑啉-5-酮的制备
用在实施例6中方法A所述的相同过程,代以N-(α-氰基噻吩基)-2,2,2-三氟乙酰胺作为起始物质,得到淡褐色固体标题产品,得率50%,熔点62.0~65.0℃,由IR和1H、13C和19F核磁共振谱分析鉴定。
实施例8
2-全氟代烷基-3-噁唑啉-5-酮的制备
基本用实施例6中方法A所述的相同过程,以适当的全氟代烷酰基氨基腈作为起始物质,得到如表Ⅱ所示的化合物。
表Ⅱ
L M Q R mp℃ 得率%
H 4-Br H CF348.0-51.0 64
H 4-CF3H CF-3 39.0-40.5 55
3-Cl 4-Cl H CF3103°/0.1mma54
H 4-Cl H C2F539.0-42.0 72
H 4-Cl H n-C3H793.0-95.0 56
a沸点℃
Claims (10)
1、一种制备下式Ⅱ2-全氟代烷基-3-噁唑啉-5-酮化合物的方法
其中n是1,2,3,4,5,6,7或8的整数;
R是
L是氢或卤素;
M和Q各自是氢,卤素,CN,NO2,C1~C4烷基,C1~C4卤代烷基,C1~C4烷氧基,C1~C4卤代烷氧基,C1~C4烷硫基,C1~C4烷基亚磺酰基,或者当M和Q在相邻位置上时,它们可与碳原子一起连接形成环,其中MQ代表结构:-OCH2O-,-OCF2O-或-CH=CH-CH=CH-,条件是L、M和Q中的至少一个必须不是氢;
R1、R2和R3各自是氢,卤素,NO2,CHO或者R2和R3与碳原子一起连接成环,其中R2R3由
R4,R5,R6和R7各自是氢,卤素,CN或NO2;W是O或S,
该方法包括使下式Ⅲ的氨基腈
其中R的定义同上,
与式Ⅳ的全氟代酰化剂
其中m是整数1或2,X是OR1,Cl或O,R1是氢或C1~C4烷基,条件是当X是O,m必须是2,当X是Cl或OR1时,m必须是1,在溶剂的存在下,也可选碱存在下进行反应,以形成式Ⅰ的全氟代-烷酰基氨基腈中间体
在酸及至少一摩尔当量的水存在下,使式Ⅰ的中间体环化。
4、根据权利要求1所述的方法,其中的溶剂是芳烃或卤代芳烃,醇是硫酸、甲磺酸、苯甲磺酸、对-甲苯横酸、萘磺酸,氟硼酸或三氟化硼配合物。
6、根据权利要求5所述的方法。其中的酸是硫酸、甲磺酸、苯磺酸、对-甲苯磺酸,萘磺酸、氟硼酸或三氟化硼配合物。
8、根据权利要求7所述的化合物,其中n是整数1或2。
9、根据权利要求8所述的化合物,其中
且L是氢,而M和Q各自是氢、卤素或C1~C4卤代烷基。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/175,845 US5426225A (en) | 1993-12-30 | 1993-12-30 | Perfluoroalkanoyl aminonitriles |
US08/175,822 | 1993-12-30 | ||
US08/175,822 US5659046A (en) | 1993-12-30 | 1993-12-30 | Method for the preparation of 2-perfluoroalkyl-3-oxazolin-5-one |
US08/175,845 | 1993-12-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1107148A true CN1107148A (zh) | 1995-08-23 |
CN1053661C CN1053661C (zh) | 2000-06-21 |
Family
ID=26871609
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94112990A Expired - Fee Related CN1053661C (zh) | 1993-12-30 | 1994-12-06 | 2-全氟代烷基-3-噁唑啉-5-酮的制备方法 |
Country Status (20)
Country | Link |
---|---|
EP (1) | EP0662475B1 (zh) |
JP (1) | JP3848382B2 (zh) |
KR (1) | KR950017977A (zh) |
CN (1) | CN1053661C (zh) |
AT (1) | ATE165824T1 (zh) |
AU (1) | AU681727B2 (zh) |
BR (1) | BR9405302A (zh) |
CA (1) | CA2139190A1 (zh) |
CZ (1) | CZ286680B6 (zh) |
DE (1) | DE69410073T2 (zh) |
DK (1) | DK0662475T3 (zh) |
ES (1) | ES2116508T3 (zh) |
HU (1) | HU214085B (zh) |
IL (1) | IL112159A (zh) |
RU (1) | RU2134262C1 (zh) |
SG (1) | SG47670A1 (zh) |
SK (1) | SK279970B6 (zh) |
TW (1) | TW318843B (zh) |
UA (1) | UA41890C2 (zh) |
ZA (1) | ZA9410405B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5453508A (en) * | 1994-10-11 | 1995-09-26 | American Cyanamid Company | Manufacture of 4-aryl-2-perfluoroalkyl-3-oxazolin-5-one from arylglycine |
TW369525B (en) * | 1996-06-28 | 1999-09-11 | American Cyanamid Co | A process for the manufacture of 2-aryl-5-perfluoroalkylpyrrole derivatives and intermediates useful thereof |
IL140300A0 (en) | 1999-04-28 | 2002-02-10 | Ihara Chemical Ind Co | Process for the preparation of amides |
US20030187233A1 (en) | 2000-02-04 | 2003-10-02 | Masanobu Onishi | Perfluoroisopropybenzene derivative |
UA73119C2 (en) | 2000-04-19 | 2005-06-15 | American Home Products Corpoir | Derivatives of cyclic thiocarbamates, pharmaceutical composition including noted derivatives of cyclic thiocarbamates and active ingredients of medicines as modulators of progesterone receptors |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5030735A (en) * | 1990-07-31 | 1991-07-09 | American Cyanamid Company | Process for the preparation of insecticidal, acaricidal and nematicidal 2-aryl-5-(trifluoromethyl) pyrrole compounds |
DE4236400A1 (de) * | 1992-10-28 | 1994-05-05 | Bayer Ag | N-Phenylacetaminonitrile |
-
1994
- 1994-11-14 DE DE69410073T patent/DE69410073T2/de not_active Expired - Lifetime
- 1994-11-14 SG SG1996003644A patent/SG47670A1/en unknown
- 1994-11-14 ES ES94117932T patent/ES2116508T3/es not_active Expired - Lifetime
- 1994-11-14 DK DK94117932.7T patent/DK0662475T3/da active
- 1994-11-14 AT AT94117932T patent/ATE165824T1/de not_active IP Right Cessation
- 1994-11-14 EP EP94117932A patent/EP0662475B1/en not_active Expired - Lifetime
- 1994-12-06 CN CN94112990A patent/CN1053661C/zh not_active Expired - Fee Related
- 1994-12-16 CZ CZ19943188A patent/CZ286680B6/cs not_active IP Right Cessation
- 1994-12-21 SK SK1579-94A patent/SK279970B6/sk unknown
- 1994-12-27 IL IL11215994A patent/IL112159A/xx not_active IP Right Cessation
- 1994-12-27 JP JP33696694A patent/JP3848382B2/ja not_active Expired - Fee Related
- 1994-12-28 RU RU94045250A patent/RU2134262C1/ru active
- 1994-12-28 CA CA002139190A patent/CA2139190A1/en not_active Abandoned
- 1994-12-28 UA UA94129255A patent/UA41890C2/uk unknown
- 1994-12-29 ZA ZA9410405A patent/ZA9410405B/xx unknown
- 1994-12-29 AU AU81843/94A patent/AU681727B2/en not_active Ceased
- 1994-12-29 BR BR9405302A patent/BR9405302A/pt not_active Application Discontinuation
- 1994-12-29 KR KR1019940040747A patent/KR950017977A/ko not_active Application Discontinuation
- 1994-12-29 HU HU9403832A patent/HU214085B/hu not_active IP Right Cessation
-
1995
- 1995-02-13 TW TW084101245A patent/TW318843B/zh active
Also Published As
Publication number | Publication date |
---|---|
CZ318894A3 (en) | 1995-08-16 |
HU214085B (en) | 1997-12-29 |
ES2116508T3 (es) | 1998-07-16 |
RU2134262C1 (ru) | 1999-08-10 |
SK279970B6 (sk) | 1999-06-11 |
CA2139190A1 (en) | 1995-07-01 |
KR950017977A (ko) | 1995-07-22 |
SK157994A3 (en) | 1995-07-11 |
AU8184394A (en) | 1995-07-06 |
DK0662475T3 (da) | 1998-06-02 |
CZ286680B6 (en) | 2000-06-14 |
ATE165824T1 (de) | 1998-05-15 |
EP0662475A3 (en) | 1995-07-19 |
EP0662475A2 (en) | 1995-07-12 |
AU681727B2 (en) | 1997-09-04 |
UA41890C2 (uk) | 2001-10-15 |
HU9403832D0 (en) | 1995-02-28 |
RU94045250A (ru) | 1996-10-27 |
DE69410073T2 (de) | 1998-09-03 |
EP0662475B1 (en) | 1998-05-06 |
CN1053661C (zh) | 2000-06-21 |
JPH07252239A (ja) | 1995-10-03 |
ZA9410405B (en) | 1995-09-22 |
SG47670A1 (en) | 1998-04-17 |
IL112159A (en) | 1999-07-14 |
BR9405302A (pt) | 1995-10-17 |
DE69410073D1 (de) | 1998-06-10 |
IL112159A0 (en) | 1995-03-15 |
HUT72162A (en) | 1996-03-28 |
TW318843B (zh) | 1997-11-01 |
JP3848382B2 (ja) | 2006-11-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1230403C (zh) | 氟化合物的制备 | |
CN1229366C (zh) | 甲基磺酰胺基-苯并呋喃衍生物,它的制备方法与它作为合成中间体的应用 | |
CN1176080C (zh) | 茚并一,萘并一和苯并环庚二氢噻唑衍生物,它们的制备以及它们作为降低食欲药的用途 | |
CN1527814A (zh) | 氧化氮合酶抑制剂磷酸盐 | |
CN1239487C (zh) | 制备奎替阿平的中间体及所述中间体的制备方法 | |
CN1009086B (zh) | 三取代的苯甲酸中间体的制备方法 | |
CN1107148A (zh) | 2-全氟代烷基-3-噁唑啉-5-酮的制备方法 | |
CN1178942C (zh) | 结晶青霉素和它的制备方法 | |
CN101061090A (zh) | α,α-二氟胺的制备方法 | |
WO2018146285A1 (fr) | Procédé de préparation monotope de composés organo-iodés | |
CN1243725C (zh) | 制备腈类化合物的方法 | |
CN1253457C (zh) | 结晶青霉素和它的制备方法 | |
CN1230539A (zh) | 由n-全氟烷基甲基亚氨基代芳酰氯化合物制备2-芳基-5-全氟烷基吡咯化合物的方法 | |
CN1224609C (zh) | 制备具有抗肥胖和抗糖尿病性质的芳基乙醇胺衍生物的方法 | |
CN1413215A (zh) | 吡唑并哒嗪衍生物的制备方法 | |
CN100345841C (zh) | 制备1,2,4-***基甲基环氧乙烷的方法 | |
CN1093355A (zh) | 苯乙酸衍生物的制备方法 | |
CN1846696A (zh) | 对映体纯的n-甲基-n-[(1s)-1-苯基-2-((3s)-3-羟基吡咯烷-1-基)乙基]-2,2-二苯基乙酰胺的制备方法 | |
CN1803777A (zh) | 一种嘧啶硫酮的化学合成方法 | |
CN1138027A (zh) | 2-(2,6-二卤代苯氨基)苯乙酰氧乙酸衍生物的硝酸酯及其制备方法 | |
CN1198433A (zh) | 用氨基甲酸酯类制备氯酮胺类的方法 | |
CN1681768A (zh) | 高纯度烯胺类的制备方法 | |
CN1235891C (zh) | 取代的烷基胺衍生物的生产方法 | |
CN1226245C (zh) | 卤化剂和羟基的卤化方法 | |
CN1812959A (zh) | 制备二氟乙酰乙酸烷基酯的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |