公开(公告)号：US06486353B2

公开(公告)日：2002-11-26

申请号：US10098358

申请日：2002-03-18

申请人： Shinya Yamada ,  Yoshiki Okeda ,  Yoji Hori ,  Toshimitsu Hagiwara

发明人： Shinya Yamada ,  Yoshiki Okeda ,  Yoji Hori ,  Toshimitsu Hagiwara

IPC分类号： C07C20960

CPC分类号： C07C209/68 ,  C07B2200/07 ,  C07C29/141 ,  C07C33/025 ,  C07C45/42 ,  C07C47/21 ,  C07C211/21

摘要： Cis-3,7-dimethyl-2,7-octadienylamine containing from 2 to 10% by weight cis-3,7-dimethyl-2,7-octadienylamine is prepared by subjecting a mixture of an alkylamine and isoprene in a molar ratio of 1:4 to 1:4.5 to telomerization at 80 to 100° C. for from 2.5 to 3.5 hours in the presence of an alkyllithium catalyst and/or phenyllithium catalyst.

摘要翻译： 含有2〜10重量％顺式-3,7-二甲基-2,7-辛二烯基的顺式-3,7-二甲基-2,7-辛二烯胺是通过使烷基胺和异戊二烯的混合物以 1：4至1：4.5以在烷基锂催化剂和/或苯基锂催化剂存在下在80至100℃下调聚2.5至3.5小时。

公开(公告)号：US06489522B2

公开(公告)日：2002-12-03

申请号：US09827334

申请日：2001-04-06

申请人： Shinya Yamada ,  Yoshiki Okeda ,  Yoji Hori ,  Toshimitsu Hagiwara

发明人： Shinya Yamada ,  Yoshiki Okeda ,  Yoji Hori ,  Toshimitsu Hagiwara

IPC分类号： C07C3500

CPC分类号： C07C209/68 ,  C07B2200/07 ,  C07C29/141 ,  C07C33/025 ,  C07C45/42 ,  C07C47/21 ,  C07C211/21

摘要： Provided is citronellol, which has an elegant rosy fragrance and is extremely useful for fragrance impartation to aromatic articles. A mixture of an alkylamine and isoprene in a molar ratio of from 1:4 to 1:4.5 is subjected to telomerization at 80 to 100° C. for 2.5 to 3.5 hours in the presence of an alkyllithium catalyst and/or phenyllithium catalyst to obtain a nerylamine compound containing 2 to 10 wt % &agr;-nerylamine compound represented by general formula (4). From this nerylamine compound, citronellol containing 2 to 10 wt % optically active 3,7-dimethyl-7-octenol is produced through the reaction steps of asymmetric isomerization, hydrolysis, and hydrogenation.

摘要翻译： 提供香茅醇，其具有优雅的玫瑰香，并且对芳香物品的芳香赋予非常有用。 摩尔比为1:4〜1:4.5的烷基胺和异戊二烯的混合物在烷基锂催化剂和/或苯基锂催化剂存在下，在80〜100℃下进行2.5〜3.5小时的调聚，得到 含有通式（4）表示的2-10重量％α-椰子胺化合物的橙花胺化合物。由该橙花胺化合物，通过反应步骤产生含有2至10重量％光学活性的3,7-二甲基-7-辛烯醇的香茅醇 的不对称异构化，水解和氢化。

公开(公告)号：US5981771A

公开(公告)日：1999-11-09

申请号：US100755

申请日：1998-06-22

申请人： Yoshiki Okeda ,  Yoji Hori ,  Toshimitsu Hagiwara

发明人： Yoshiki Okeda ,  Yoji Hori ,  Toshimitsu Hagiwara

IPC分类号： C07D305/12 ,  B01J31/24 ,  C07B53/00 ,  C07B61/00 ,  C07D315/00 ,  C07F15/00

CPC分类号： B01J31/2452 ,  C07D315/00 ,  C07F15/0053 ,  B01J2231/645 ,  B01J2531/0266 ,  B01J2531/821 ,  B01J31/2208 ,  B01J31/2295 ,  C07B2200/07

摘要： The present invention provides a catalyst which exhibits a high catalytic activity and allows asymmetric reaction in a high asymmetric yield to obtain a reaction product having a high optical purity. The present invention also provides a process for the preparation of an optically active 4-methyl-2-oxetanone having a high optical purity useful as starting material of polymer in a high yield in a short period in the presence of the foregoing catalyst. A novel ruthenium-iodo-optically active phosphine complex is provided, represented by the following general formula (1):Ru--I.sub.2 -(R.sup.1 -BINAP) (1)wherein R.sup.1 -BINAP represents an optically active tertiary phosphine represented by the following general formula (2): ##STR1## wherein R.sup.1 represents an aryl group which may have a substituent selected from the group consisting of a C.sub.1-4 lower alkyl group, a C.sub.1-4 lower alkoxy group, a C.sub.1-4 lower alkylamino group, and a halogen atom or a C.sub.3-8 cycloalkyl group.

摘要翻译： 本发明提供一种催化活性高的催化剂，能够以不对称产率进行不对称反应，得到光学纯度高的反应产物。 本发明还提供了在上述催化剂存在下，在短时间内以高收率制备具有高光学纯度的光学纯度高的光学活性4-甲基-2-氧杂环丁酮的方法。 提供了由以下通式（1）表示的新型钌 - 碘 - 光学活性膦配合物：Ru-I2-（R1-BINAP）（1）其中R1-BINAP表示由以下通式表示的光学活性叔膦 式（2）：其中R1表示可以具有选自C 1-4低级烷基，C 1-4低级烷氧基，C 1-4低级烷基氨基和卤素原子的取代基的芳基 或C 3-8环烷基。

公开(公告)号：US6043380A

公开(公告)日：2000-03-28

申请号：US307750

申请日：1999-05-10

申请人： Yoshiki Okeda ,  Tsutomu Hashimoto ,  Yoji Hori ,  Toshimitsu Hagiwara

发明人： Yoshiki Okeda ,  Tsutomu Hashimoto ,  Yoji Hori ,  Toshimitsu Hagiwara

IPC分类号： B01J31/24 ,  C07D315/00 ,  C07F15/00 ,  C07F9/02 ,  C07D305/00

CPC分类号： B01J31/2409 ,  B01J31/2452 ,  B01J31/2457 ,  C07D315/00 ,  C07F15/0053 ,  B01J2231/645 ,  B01J2531/0266 ,  B01J2531/821

摘要： This invention is concerned with a ruthenium-iodo-optically active bidentate phosphine complex of the formula (I):[Ru--(I).sub.q --(T.sup.1).sub.n (SOL).sub.r (L)].sub.m (T.sup.2).sub.p (I).sub.s (I)wherein T.sup.1 represents a carboxylic acid anion, SOL represents a polar solvent, L represents an optically active bidentate phosphine ligand, T.sup.2 represents an anion different from halogen atom anions and carboxylic acid anions, n denotes 0 or 1, r denotes 0, 3 or 4, m denotes 1 or 2, q denotes 0 or 1, or where m is 2, q may represent 1 or 1.5, p denotes 0 or 1, and s denotes 0, 1 or 2 is prepared. Said phosphine complex is usefull as an efficient catalyst for asymmetrically hydrogenating 4-methylene-2-oxetanone into optically active 4-methyl-2-oxetanone.

摘要翻译： 本发明涉及式（I）的钌 - 碘 - 光学活性二齿膦络合物：[Ru-（I）q-（T1）n（SOL）r（L）] m（T2）p（I） s（I）其中T1表示羧酸阴离子，SOL表示极性溶剂，L表示光学活性二齿膦配体，T2表示不同于卤素阴离子和羧酸阴离子的阴离子，n表示0或1，r表示0 3或4，m表示1或2，q表示0或1，或其中m为2，q可以表示1或1.5，p表示0或1，s表示0,1或2。 所述膦配合物可用作用于将4-亚甲基-2-氧杂环丁酮不对称氢化成光学活性的4-甲基-2-氧杂环丁酮的有效催化剂。

公开(公告)号：US5981782A

公开(公告)日：1999-11-09

申请号：US963619

申请日：1997-11-04

申请人： Yoshiki Okeda ,  Yoji Hori ,  Toshimitsu Hagiwara

发明人： Yoshiki Okeda ,  Yoji Hori ,  Toshimitsu Hagiwara

IPC分类号： C07D305/12 ,  B01J31/24 ,  C07B53/00 ,  C07B61/00 ,  C07D315/00 ,  C07F15/00

CPC分类号： B01J31/2452 ,  C07D315/00 ,  C07F15/0053 ,  B01J2231/645 ,  B01J2531/0266 ,  B01J2531/821 ,  B01J31/2208 ,  B01J31/2295 ,  C07B2200/07

摘要： The present invention provides a catalyst which exhibits a high catalytic activity and allows asymmetric reaction in a high asymmetric yield to obtain a reaction product having a high optical purity. The present invention also provides a process for the preparation of an optically active 4-methyl-2-oxetanone having a high optical purity useful as starting material of polymer in a high yield in a short period in the presence of the foregoing catalyst. A novel ruthenium-iodo-optically active phosphine complex is provided, represented by the following general formula (1):Ru--I.sub.2 --(R.sup.1 -BINAP) (1)wherein R.sup.1 -BINAP represents an optically active tertiary phosphine represented by the following general formula (2): ##STR1## wherein R.sup.1 represents an aryl group which may have a substituent selected from the group consisting of a C.sub.1-4 lower alkyl group, a C.sub.1-4 lower alkoxy group, a C.sub.1-4 lower alkylamino group, and a halogen atom or a C.sub.3-8 cycloalkyl group.

摘要翻译： 本发明提供一种催化活性高的催化剂，能够以不对称产率进行不对称反应，得到光学纯度高的反应产物。 本发明还提供了在上述催化剂存在下，在短时间内以高收率制备具有高光学纯度的光学纯度高的光学活性4-甲基-2-氧杂环丁酮的方法。 提供了由以下通式（1）表示的新型钌 - 碘 - 光学活性膦配合物：Ru-I2-（R1-BINAP）（1）其中R1-BINAP表示由以下通式表示的光学活性叔膦 式（2）：其中R1表示可以具有选自C 1-4低级烷基，C 1-4低级烷氧基，C 1-4低级烷基氨基和卤素原子的取代基的芳基 或C 3-8环烷基。

公开(公告)号：US06570035B2

公开(公告)日：2003-05-27

申请号：US09759134

申请日：2001-01-16

申请人： Shinya Yamada ,  Yoshiki Okeda ,  Toshimitsu Hagiwara ,  Akio Tachikawa ,  Kouji Ishiguro ,  Shunichi Harada

发明人： Shinya Yamada ,  Yoshiki Okeda ,  Toshimitsu Hagiwara ,  Akio Tachikawa ,  Kouji Ishiguro ,  Shunichi Harada

IPC分类号： C07C6966

CPC分类号： C07C67/343 ,  C07C69/716

摘要： A process for producing a pivaloylacetic acid ester comprises reacting pivaloyl chloride with an acetoacetic acid ester of an alkyl group having 1 to 4 carbon atoms in the presence of at least one nitrogen-containing basic compound (a) selected from among pyridine compounds, N,N-dialkylanilines and imidazole compounds and from 0.01 to 0.5 mole equivalent, based on the pivaloyl chloride, of a magnesium compound (b) to thereby prepare a pivaloylacetoacetic acid ester and then alcholyzing or alkali-hydrolyzing the pivaloylacetoacetic acid ester to thereby give a pivaloylacetic acid ester having a high purity at a low cost.

摘要翻译： 一种生产新戊酰乙酸酯的方法，包括在至少一种选自吡啶化合物，N，N-二甲基甲酰胺的含氮碱性化合物（a）的存在下，使新戊酰氯与具有1至4个碳原子的烷基的乙酰乙酸酯反应， N-二烷基苯胺和咪唑化合物，和基于新戊酰氯的0.01至0.5摩尔当量的镁化合物（b），从而制备新戊酰乙酰乙酸酯，然后将新戊酰乙酰乙酸酯进行共沸或碱解水解，从而得到新戊酰乙酸 酸酯以低成本具有高纯度。

公开(公告)号：US06365776B1

公开(公告)日：2002-04-02

申请号：US09946468

申请日：2001-09-06

申请人： Mitsuhiko Fujiwara ,  Ken Suzuki ,  Tohru Kobayashi ,  Yoji Hori ,  Toshimitsu Hagiwara

发明人： Mitsuhiko Fujiwara ,  Ken Suzuki ,  Tohru Kobayashi ,  Yoji Hori ,  Toshimitsu Hagiwara

IPC分类号： C07C21100

CPC分类号： C07C209/10 ,  C07C211/54

摘要： The present invention provides an activator in arylamination using a palladium compound as a catalyst, which is superior to conventional phosphines in stability and performance. With the phosphine sulfide as an activator, an arylamination reaction achieves improved selectivity to produce a desired aromatic amine in an obviously increased yield as compared with a reaction using the corresponding phosphine compound. Moreover, the phosphine sulfide of the invention is impervious to oxidation and exists stably in air and therefore sufficiently withstands use on an industrial scale.

摘要翻译： 本发明提供使用钯化合物作为催化剂的芳基化活化剂，其在稳定性和性能方面优于常规膦。 与使用相应的膦化合物的反应相比，以硫化氢作为活化剂，芳基化反应实现了以明显增加的产率产生所需芳族胺的选择性。 此外，本发明的硫化膦不能氧化，在空气中稳定地存在，因此能够充分地耐受工业规模的使用。

公开(公告)号：US6075154A

公开(公告)日：2000-06-13

申请号：US124791

申请日：1998-07-30

申请人： Yoshiharu Gonda ,  Yoji Hori ,  Akio Yamaguchi ,  Toshimitsu Hagiwara

发明人： Yoshiharu Gonda ,  Yoji Hori ,  Akio Yamaguchi ,  Toshimitsu Hagiwara

IPC分类号： C07F9/48 ,  C07C67/31 ,  C07F9/50 ,  C07F9/52 ,  C07F15/00 ,  C07F15/04 ,  C07D305/12 ,  C07C69/66 ,  C07C69/76

CPC分类号： C07F15/045 ,  C07C67/31 ,  C07F15/004 ,  C07F15/0053 ,  C07F15/0066 ,  C07F15/008 ,  C07F9/5027

摘要： A novel phosphine compound usable as a catalyst in various asymmetric synthetic reactions is disclosed. The compound is a 2,2'-bis(diarylphosphino)-6,6'-bis(trifluoromethyl)-1,1'-biphenyl of (1): ##STR1## where R is a phenyl group or a phenyl group substituted by lower alkyl group, lower alkoxy group, halogen atom, or lower haloalkyl group.

摘要翻译： 公开了一种在各种不对称合成反应中可用作催化剂的新型膦化合物。 化合物是（1）的2,2'-双（二芳基膦基）-6,6'-双（三氟甲基）-1,1'-联苯：其中R是苯基或被低级烷基取代的苯基 ，低级烷氧基，卤素原子或低级卤代烷基。

公开(公告)号：US06545112B2

公开(公告)日：2003-04-08

申请号：US09233204

申请日：1999-01-19

申请人： Yoji Hori ,  Yoshiharu Gonda ,  Toshimitsu Hagiwara

发明人： Yoji Hori ,  Yoshiharu Gonda ,  Toshimitsu Hagiwara

IPC分类号： C08F12400

CPC分类号： C08G63/823 ,  C08G61/08 ,  C08G63/08

摘要： The object of the invention is to provides a process in which a high-molecular-weight &bgr;-butyrolactone homopolymer or copolymer being biodegradable, absorbable into the living body, useful as a functional polymeric material and superior in physical characteristics is produced with high yield and good productivity. This object is solved by a process for producing the homopolymer or copolymer of the invention, which comprises ring-opening polymerization of sole &bgr;-butyrolactone subjected previously to acid removal and dehydration treatment, or of said &bgr;-butyrolactone with other lactones, in the presence of a tin compound represented by the following formula (1) and/or formula (2): wherein R1 and R2 and R4 to R7 independently represent an alkyl group containing 1 to 12 carbon atoms which may have a branched chain, or a cycloalkyl group containing 5 to 7 carbon atoms, or a phenyl or naphthyl group which may have a substituent group, R3 represents an alkylene group containing 2 to 12 carbon atoms which may have a substituent group, a cyclopentane-1,2-ylene group or a cyclohexane-1,2-ylene group, and n is an integer of 1 to 10.

摘要翻译： 本发明的目的是提供一种方法，其中生产可降解的可分解生物降解的高分子量β-丁内酯均聚物或共聚物可用作生物体，用作功能性聚合物材料并且具有优异的物理特性，其产率高， 良好的生产力。 该目的通过本发明的均聚物或共聚物的制备方法来解决，该方法包括先前进行酸去除和脱水处理的底部β-丁内酯或所述β-丁内酯与其它内酯的开环聚合， 的由下式（1）和/或式（2）表示的锡化合物：其中R 1和R 2和R 4至R 7独立地表示可以具有支链的含有1至12个碳原子的烷基或环烷基 或者可以具有取代基的苯基或萘基，R3表示可以具有取代基的含有2〜12个碳原子的亚烷基，环戊烷-1,2-亚基或环己烷 -1,2-亚基，n为1〜10的整数。

公开(公告)号：US06455720B1

公开(公告)日：2002-09-24

申请号：US09891304

申请日：2001-06-27

申请人： Ken Suzuki ,  Tohru Kobayashi ,  Takenobu Nishikawa ,  Yoji Hori ,  Toshimitsu Hagiwara

发明人： Ken Suzuki ,  Tohru Kobayashi ,  Takenobu Nishikawa ,  Yoji Hori ,  Toshimitsu Hagiwara

IPC分类号： C07F950

CPC分类号： C07F15/006 ,  C07B37/04 ,  C07C1/321 ,  C07C2531/24 ,  C07F9/5013 ,  C07F15/0066

摘要： A novel 2,2-(diaryl)vinylphosphine compound represented by the following general formula (1): (wherein R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, etc.; R2, R3, R4, R5, R6, and R7 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, etc., provided that R4 and R5 taken together and/or R6 and R7 taken together may represent a fused benzene ring, a substituted fused benzene ring, a trimethylene group, etc.; and p, q, r, and s each is 0 to 5, provided that p+q and r+s each is in the range of from 0 to 5); a palladium-phosphine catalyst obtained by causing a palladium compound to act on the novel 2,2-(diaryl)vinylphosphine compound; and a process for obtaining an arylamine, a diaryl and an arylalkyne in the presence of the palladium-phosphine catalyst.

摘要翻译： 由以下通式（1）表示的新型2,2-（二芳基）乙烯基膦化合物：其中，R 1为氢原子，碳原子数1〜6的烷基，碳原子数5〜7的脂环族基等 R 2，R 3，R 4，R 5，R 6和R 7可以相同或不同，各自为碳原子数为1〜6的烷基，碳原子数5〜7的脂环族基等。 R 5和R 6一起代表稠合苯环，取代稠合苯环，三亚甲基等; p，q，r和s各自为0至5，条件是p + q和r + s各自在0至5的范围内）; 通过使钯化合物作用于新的2,2-（二芳基）乙烯基膦化合物而获得的钯 - 膦催化剂; 以及在钯 - 膦催化剂存在下获得芳基胺，二芳基和芳基炔的方法。