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：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：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：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：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：US06313365B1

公开(公告)日：2001-11-06

申请号：US09666049

申请日：2000-09-20

申请人： Yoji Hori ,  Yukiharu Iwaya ,  Tsutomu Hashimoto ,  Toshimitsu Hagiwara

发明人： Yoji Hori ,  Yukiharu Iwaya ,  Tsutomu Hashimoto ,  Toshimitsu Hagiwara

IPC分类号： C07C604

CPC分类号： C07C6/04 ,  B01J31/0231 ,  B01J31/2286 ,  B01J31/2295 ,  B01J31/24 ,  B01J31/2404 ,  B01J31/30 ,  B01J2231/14 ,  B01J2231/543 ,  B01J2531/821 ,  C07C2531/24

摘要： The invention has an object of safely and simply preparing a large amount of a ruthenium metathesis catalyst, which is used as a catalyst for a carbon-carbon bond formation using, particularly, a metathesis reaction. The metathesis catalyst has the following complex composition (A) or (B). The composition (A) includes RuX12(arene)(PR1R2R3) and R4CHX22, R5C ≡CH or R4CHX2 and a reducing agent, wherein X1 and X2 respectively are a halogen atom; arene is a hydrocarbon having a benzene ring; R1, R2 and R3, which may be the same or different, respectively are an alkyl group having 1-8 carbon atoms, a cycloalkyl group having 3-8 carbon atoms or an optionally substituted aryl group, wherein the substituent group is an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, an alkylamino group having 1-8 carbon atoms or a halogen atom; R4 is an alkyl group which has 1-8 carbon atoms and may have an ether bond or an ester bond, an optionally subsituted aryl group, wherein the substituent group is a halogen atom or a hydroxyl group; or cycloalkyl group having 3-8 carbon atoms; and R5 is an optionally substituted alkyl group which has 1-8 carbon atoms and may have an ether bond or an ester bond, wherein the substituent group is a halogen atom or a hydroxyl group, an aryl group or a cycloalkyl group having 3-8 carbon atoms. The composition B includes [RuX12(arene)]2, PR1R2R3, R5C≡CH or R4CHX2 and a reducing agent, wherein X1, arene, R1, R2, R3, R4 and R5 are the same as defined above.

摘要翻译： 本发明的目的是安全简单地制备大量的钌复分解催化剂，其用作碳 - 碳键形成催化剂，特别是用于复分解反应。 复分解催化剂具有以下复合组成（A）或（B）。 组合物（A）包括RuX12（芳烃）（PR1R2R3）和R4CHX22，R5C = CH或R4CHX2和还原剂，其中X1和X2分别是卤素原子; 芳烃是具有苯环的烃; R 1，R 2和R 3可以相同或不同，分别为具有1-8个碳原子的烷基，具有3-8个碳原子的环烷基或任选取代的芳基，其中取代基是烷基 具有1-8个碳原子，具有1-8个碳原子的烷氧基，具有1-8个碳原子的烷基氨基或卤素原子; R4是具有1-8个碳原子并且可以具有醚键或酯键的烷基，任选取代的芳基，其中取代基是卤素原子或羟基; 或具有3-8个碳原子的环烷基; R5是具有1-8个碳原子并且可以具有醚键或酯键的任意取代的烷基，其中取代基是卤素原子或羟基，芳基或具有3-8个碳原子的环烷基 碳原子。 组合物B包括[RuX 12（芳烃）] 2，PR 1 R 2 R 3，R 5 C = CH或R 4 CHX 2和还原剂，其中X 1，R 6，R 1，R 2，R 3，R 4和R 5与上述定义相同。

公开(公告)号：US06175047B1

公开(公告)日：2001-01-16

申请号：US09219351

申请日：1998-12-23

申请人： Yoji Hori ,  Yukiharu Iwaya ,  Tsutomu Hashimoto ,  Toshimitsu Hagiwara

发明人： Yoji Hori ,  Yukiharu Iwaya ,  Tsutomu Hashimoto ,  Toshimitsu Hagiwara

IPC分类号： C07C604

CPC分类号： C07C6/04 ,  B01J31/0231 ,  B01J31/2286 ,  B01J31/2295 ,  B01J31/24 ,  B01J31/2404 ,  B01J31/30 ,  B01J2231/14 ,  B01J2231/543 ,  B01J2531/821 ,  C07C2531/24

摘要： The invention has an object of safely and simply preparing a large amount of a ruthenium metathesis catalyst, which is used as a catalyst for a carbon-carbon bond formation using, particularly, a metathesis reaction. The metathesis catalyst has the following complex composition (A) or (B). The composition (A) includes RuX12(arene)(PR1R2R3) and R4CHX22, R5C≡CH or R4CHX2 and a reducing agent, wherein X1 and X2 respectively are a halogen atom; arene is a hydrocarbon having a benzene ring; R1, R2 and R3, which may be the same or different, respectively are an alkyl group having 1-8 carbon atoms, a cycloalkyl group having 3-8 carbon atoms or an optionally substituted aryl group, wherein the substituent group is an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, an alkylamino group having 1-8 carbon atoms or a halogen atom; R4 is an alkyl group which has 1-8 carbon atoms and may have an ether bond or an ester bond, an optionally subsituted aryl group, wherein the substituent group is a halogen atom or a hydroxyl group; or cycloalkyl group having 3-8 carbon atoms; and R5 is an optionally substituted alkyl group which has 1-8 carbon atoms and may have an ether bond or an ester bond, wherein the substituent group is a halogen atom or a hydroxyl group, an aryl group or a cycloalkyl group having 3-8 carbon atoms. The composition B includes [RuX12(arene)]2, PR1R2R3, R5C≡CH or R4CHX2 and a reducing agent, wherein X1, arene, R1, R2, R3, R4 and R5 are the same as defined above.

摘要翻译： 本发明的目的是安全简单地制备大量的钌复分解催化剂，其用作碳 - 碳键形成催化剂，特别是用于复分解反应。 复分解催化剂具有以下复合组成（A）或（B）。 组合物（A）包括RuX12（芳烃）（PR1R2R3）和R4CHX22，R5C = CH或R4CHX2和还原剂，其中X1和X2分别是卤素原子; 芳烃是具有苯环的烃; R 1，R 2和R 3可以相同或不同，分别为具有1-8个碳原子的烷基，具有3-8个碳原子的环烷基或任选取代的芳基，其中取代基是烷基 具有1-8个碳原子，具有1-8个碳原子的烷氧基，具有1-8个碳原子的烷基氨基或卤素原子; R4是具有1-8个碳原子并且可以具有醚键或酯键的烷基，任选取代的芳基，其中取代基是卤素原子或羟基; 或具有3-8个碳原子的环烷基; R5是具有1-8个碳原子并且可以具有醚键或酯键的任意取代的烷基，其中取代基是卤素原子或羟基，芳基或具有3-8个碳原子的环烷基 碳原子。 组合物B包括[RuX 12（芳烃）] 2，PR 1 R 2 R 3，R 5 C = CH或R 4 CHX 2和还原剂，其中X 1，R 6，R 1，R 2，R 3，R 4和R 5与上述定义相同。

公开(公告)号：US06774269B2

公开(公告)日：2004-08-10

申请号：US10045157

申请日：2002-01-15

申请人： Takeshi Iwata ,  Yoshiki Okeda ,  Yoji Hori

发明人： Takeshi Iwata ,  Yoshiki Okeda ,  Yoji Hori

IPC分类号： C07C3508

CPC分类号： C07C29/56 ,  C07C2601/14 ,  C07C35/17

摘要： A process for producing l-isopulegol by simple operations with safety in high yield. A process for producing isopulegol, which comprises selectively cyclizing citronellal in the presence of a tris(2,6-diarylphenoxy)aluminum catalyst represented by the following general formula (3): wherein Al represents an aluminum atom, Ar1 and Ar2 each represent a substituted or unsubstituted aryl group or a heteroaryl group; and R1, R2 and R3 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atom(s), an alkoxy group having 1 to 8 carbon atom(s), a substituted or unsubstituted aryl group, a dialkylamino group having 1 to 4 carbon atom(s), or a nitro group.

摘要翻译： 通过简单的操作以高产率安全地生产l-异头孢烯的方法。 一种生产异胡醇的方法，其包括在由以下通式（3）表示的三（2,6-二芳基苯氧基）铝催化剂存在下选择性环化香茅醛：其中Al表示铝原子，Ar 1和Ar 2， 2>各自表示取代或未取代的芳基或杂芳基; R 1，R 2和R 3各自表示氢原子，卤素原子，碳原子数为1〜8的烷基，碳原子数1〜8的烷氧基， 取代或未取代的芳基，碳原子数为1〜4的二烷基氨基或硝基。

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。