公开(公告)号：US07893294B2

公开(公告)日：2011-02-22

申请号：US12375684

申请日：2007-08-13

申请人： Makoto Itagaki ,  Ryo Minamida ,  Kouji Yoshikawa

发明人： Makoto Itagaki ,  Ryo Minamida ,  Kouji Yoshikawa

IPC分类号： C07C69/74

CPC分类号： C07C67/30 ,  C07C67/313 ,  C07C67/347 ,  C07C67/60 ,  C07C2601/02 ,  C07C69/757

摘要： A process for production of a trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester comprising: (A) a step of obtaining a mixture containing a trans-2,2-dimethyl-3-(hydroxymethyl)cyclopropanecarboxylic acid ester, (B) a step of conducting an oxidation treatment of the mixture obtained in the step (A) to obtain a mixture containing a crude trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester, (C) a step of contacting the mixture obtained in the step (B) with an aqueous alkali metal hydrogen sulfite solution to obtain an alkali metal salt of a trans-2,2-dimethyl-3-[(hydroxy)(sulfo)methyl]cyclopropanecarboxylic acid ester, and (D) a step of contacting the alkali metal salt obtained in the above-mentioned step (C) with a base or the like to obtain a trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester.

摘要翻译： 一种制备反式-2,2-二甲基-3-甲酰基环丙烷羧酸酯的方法，包括：（A）获得含有反式-2,2-二甲基-3-（羟甲基）环丙烷羧酸酯的混合物的步骤，（ B）对步骤（A）中获得的混合物进行氧化处理以获得含有粗反式-2,2-二甲基-3-甲酰基环丙烷羧酸酯的混合物的步骤，（C）使获得的混合物 在步骤（B）中用碱金属亚硫酸氢盐水溶液洗涤，得到反式-2,2-二甲基-3 - [（羟基）（磺基）甲基]环丙烷羧酸酯的碱金属盐，（D） 使上述工序（C）中得到的碱金属盐与碱等接触的工序，得到反式-2,2-二甲基-3-甲酰基环丙烷羧酸酯。

公开(公告)号：US07709651B2

公开(公告)日：2010-05-04

申请号：US10572391

申请日：2004-09-17

申请人： Makoto Itagaki ,  Katsuhisa Masumoto ,  Ryo Minamida

发明人： Makoto Itagaki ,  Katsuhisa Masumoto ,  Ryo Minamida

IPC分类号： C07F1/08 ,  C07C69/74

CPC分类号： C07C67/347 ,  C07B2200/07 ,  C07C68/06 ,  C07F1/005 ,  C07C69/757 ,  C07C69/96

摘要： A process for producing an optically active cyclopropane compound represented by the formula (4): wherein R3, R4, R5 and R6 are the same or different, and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, and so on; and R7 represents a C1-6 alkyl group; and * represents an asymmetric carbon atom, which comprises reacting a prochiral olefin represented by the formula (2): wherein R3, R4, R5, and R6 are as described above, with a diazoacetic acid ester represented by the formula (3): N2CHCO2R7  (3) wherein R7 is as defined above, in the presence of an asymmetric copper complex prepared from an optically active cycloalkylidenebisoxazoline compound represented by the formula (1): wherein R1 represents a hydrogen atom, a C1-6 alkyl group, and so on; R2 represents a C1-6 alkyl group and so on; and n represents an integer of 0 to 3; provided that, two R1s may be bonded each other together with the carbon atom to which they are bonded to form a ring; and * represents an asymmetric carbon atom, and a copper compound, is provided.

摘要翻译： 一种制备由式（4）表示的光学活性环丙烷化合物的方法：其中R3，R4，R5和R6相同或不同，表示氢原子，卤素原子，取代或未取代的烷基等 上; 并且R 7表示C 1-6烷基; 和*表示不对称碳原子，其包括使由式（2）表示的前手性烯烃：其中R3，R4，R5和R6如上所述与由式（3）表示的重氮乙酸酯反应：N 2 CHCO 2 R 7 在由式（1）表示的光学活性亚环烷基双恶唑啉化合物制备的不对称铜络合物存在下，其中R 7如上所定义：其中R 1表示氢原子，C 1-6烷基等 ; R2代表C1-6烷基等; n表示0〜3的整数， 条件是两个R 1可以与它们所键合的碳原子相互键合形成环; 和*表示不对称碳原子，并且提供铜化合物。

公开(公告)号：US20050288526A1

公开(公告)日：2005-12-29

申请号：US10527267

申请日：2003-09-05

申请人： Ryo Minamida ,  Makoto Itagaki

发明人： Ryo Minamida ,  Makoto Itagaki

IPC分类号： C07C51/353 ,  C07C51/367 ,  C07C67/31 ,  C07C69/74

CPC分类号： C07C51/353 ,  C07C51/367 ,  C07C67/31 ,  C07C2601/02 ,  C07C62/08 ,  C07C62/02 ,  C07C69/757

摘要： There is provided a production method of a compound of formula (2): wherein R1, R2 and R3 are as defined below, which comprises reacting a 2-(hydroxymethyl)cyclopropanecarboxylic compound of formula (1): wherein and R1 represent a hydrogen, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, R2 and R3 are the same or different and represent a hydrogen atom or a methyl group, and R4 represents C1-2 alkyl group substituted with at lest one group selected from the group consisting of a substituted aryl group and an unsubstituted aryl group, with a hydrogen-donor in the presence of a catalyst selected from the group consisting of ruthenium catalyst, cobalt catalyst, rhodium catalyst, nickel catalyst, palladium catalyst and a platinum catalyst.

摘要翻译： 提供式（2）化合物的制备方法：其中R 1，R 2和R 3如下所定义， 其包括使式（1）的2-（羟甲基）环丙烷羧酸化合物：其中和R 1表示氢，直链，支链或环状烷基，取代或未取代的芳基， SUP> 2和R 3相同或不同，表示氢原子或甲基，R 4表示被 在选自钌催化剂，钴催化剂，铑催化剂，镍催化剂，钯催化剂的催化剂存在下，使氢选自具有取代基的芳基和未取代的芳基的组中的至少一个基团 催化剂和铂催化剂。

公开(公告)号：US07705165B2

公开(公告)日：2010-04-27

申请号：US11630802

申请日：2005-06-30

申请人： Makoto Itagaki ,  Ryo Minamida

发明人： Makoto Itagaki ,  Ryo Minamida

IPC分类号： C07D307/00 ,  C07C61/04

CPC分类号： C07B53/00 ,  B01J31/1815 ,  B01J2231/325 ,  B01J2531/16 ,  C07B2200/07 ,  C07C67/347 ,  C07C2601/02 ,  C07D263/14 ,  C07C69/757

摘要： A method for producing an optically active cyclopropanecarboxylate compound represented by the formula (5): wherein R6, R7, R8 and R9 represent a C1-C6 alkyl group or the like and R10 represents a C1-C6 alkyl group, which comprises reacting an olefin represented by the formula (3): wherein R6, R7, R8 and R9 are as described above, with a diazoacetic acid ester represented by the formula (4): N2CHCO2R10  (4) wherein R10 is as described above, in the presence of an asymmetric copper complex obtained by mixing (A) at least one monovalent or divalent copper compound, (B) at least one optically active bisoxazoline compound represented by the formula (1):  wherein R1 and R2 represent a C1-C6 alkyl group or the like; R3 represents a tert-butyl group or the like; and R4 and R5 are the same and represent C1-C3 alkyl groups or the like, and (C) at least one fluorine compound represented by the formula (2): A-MF6  (2)  wherein A represents a trityl group or the like, and M represents a phosphorous atom or the like.

摘要翻译： 一种制备由式（5）表示的光学活性环丙烷羧酸酯化合物的方法：其中R 6，R 7，R 8和R 9表示C 1 -C 6烷基等，R 10表示C 1 -C 6烷基，其包括使烯烃 由式（3）表示：其中R6，R7，R8和R9如上所述与由式（4）表示的重氮乙酸酯：N2CHCO2R10（4）其中R10如上所述，在 通过混合（A）至少一种一价或二价铜化合物，（B）至少一种由式（1）表示的光学活性双恶唑啉化合物得到的不对称铜配合物：其中R1和R2表示C1-C6烷基等 ; R3表示叔丁基等; 和（C）至少一种由式（2）表示的氟化合物：A-MF6（2）其中A表示三苯甲基或类似基团 ，M表示磷原子等。

公开(公告)号：US20090314987A1

公开(公告)日：2009-12-24

申请号：US12375684

申请日：2007-08-13

申请人： Makoto Itagaki ,  Ryo Minamida ,  Kouji Yoshikawa

发明人： Makoto Itagaki ,  Ryo Minamida ,  Kouji Yoshikawa

IPC分类号： C09K3/00 ,  C07C67/333

CPC分类号： C07C67/30 ,  C07C67/313 ,  C07C67/347 ,  C07C67/60 ,  C07C2601/02 ,  C07C69/757

摘要： A process for production of a trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester comprising: (A) a step of obtaining a mixture containing a trans-2,2-dimethyl-3-(hydroxymethyl)cyclopropanecarboxylic acid ester, (B) a step of conducting an oxidation treatment of the mixture obtained in the step (A) to obtain a mixture containing a crude trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester, (C) a step of contacting the mixture obtained in the step (B) with an aqueous alkali metal hydrogen sulfite solution to obtain an alkali metal salt of a trans-2,2-dimethyl-3-[(hydroxy)(sulfo)methyl]cyclopropanecarboxylic acid ester, and (D) a step of contacting the alkali metal salt obtained in the above-mentioned step (C) with a base or the like to obtain a trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester.

摘要翻译： 一种制备反式-2,2-二甲基-3-甲酰基环丙烷羧酸酯的方法，包括：（A）获得含有反式-2,2-二甲基-3-（羟甲基）环丙烷羧酸酯的混合物的步骤，（ B）对步骤（A）中获得的混合物进行氧化处理以获得含有粗反式-2,2-二甲基-3-甲酰基环丙烷羧酸酯的混合物的步骤，（C）使获得的混合物 在步骤（B）中用碱金属亚硫酸氢盐水溶液洗涤，得到反式-2,2-二甲基-3 - [（羟基）（磺基）甲基]环丙烷羧酸酯的碱金属盐，（D） 使上述工序（C）中得到的碱金属盐与碱等接触的步骤，得到反式-2,2-二甲基-3-甲酰基环丙烷羧酸酯。

公开(公告)号：US08168816B2

公开(公告)日：2012-05-01

申请号：US12095608

申请日：2006-12-12

申请人： Kouji Yoshikawa ,  Ryo Minamida ,  Makoto Itagaki

发明人： Kouji Yoshikawa ,  Ryo Minamida ,  Makoto Itagaki

IPC分类号： C07C67/313 ,  C07C69/757 ,  C07C303/32 ,  C07C309/19

CPC分类号： C07C303/32 ,  C07C67/60 ,  C07C309/19 ,  C07C2601/02 ,  C07C69/757

摘要： A method for producing a purified formylcyclopropane compound represented by the formula (1) comprising (A) a step of reacting a crude formylcyclopropane compound represented by the formula (1): wherein R1 represents an alkyl group or the like, with an alkali metal hydrogen sulfite to obtain an alkali metal hydroxymethanesulfonate represented by the formula (2): wherein R1 represents the same meaning as defined above and M represents an alkali metal, and (B) a step of reacting an acid, a base or a water-soluble aldehyde with the alkali metal hydroxymethanesulfonate represented by the formula (2) obtained in the above-mentioned step (A) to obtain a purified formylcyclopropane compound represented by the formula (1).

摘要翻译： 一种制备由式（1）表示的精制甲酰基环丙烷化合物的方法，包括（A）使式（1）表示的粗甲酰基环丙烷化合物：其中R 1表示烷基等与碱金属氢反应的步骤 亚硫酸盐，得到由式（2）表示的碱金属羟基甲磺酸盐：其中R1表示与上述相同的含义，M表示碱金属，（B）使酸，碱或水溶性醛 与上述步骤（A）中获得的式（2）表示的碱金属羟基甲磺酸酯反应，得到由式（1）表示的精制甲酰基环丙烷化合物。

公开(公告)号：US20080027235A1

公开(公告)日：2008-01-31

申请号：US11630802

申请日：2005-06-30

申请人： Makoto Itagaki ,  Ryo Minamida

发明人： Makoto Itagaki ,  Ryo Minamida

IPC分类号： C07C61/04 ,  C07D307/79

CPC分类号： C07B53/00 ,  B01J31/1815 ,  B01J2231/325 ,  B01J2531/16 ,  C07B2200/07 ,  C07C67/347 ,  C07C2601/02 ,  C07D263/14 ,  C07C69/757

摘要： A method for producing an optically active cyclopropanecarboxylate compound represented by the formula (5): wherein R6, R7, R8 and R9 represent a C1-C6 alkyl group or the like and R10 represents a C1-C6 alkyl group, which comprises reacting an olefin represented by the formula (3): wherein R6, R7, R8 and R9 are as described above, with a diazoacetic acid ester represented by the formula (4): N2CHCO2R10  (4) wherein R10 is as described above, in the presence of an asymmetric copper complex obtained by mixing (A) at least one monovalent or divalent copper compound, (B) at least one optically active bisoxazoline compound represented by the formula (1): wherein R1 and R2 represent a C1-C6 alkyl group or the like; R3 represents a tert-butyl group or the like; and R4 and R5 are the same and represent C1-C3 alkyl groups or the like, and (C) at least one fluorine compound represented by the formula (2): A-MF6  (2) wherein A represents a trityl group or the like, and M represents a phosphorous atom or the like.

摘要翻译： 一种制备由式（5）表示的光学活性环丙烷羧酸酯化合物的方法：其中R 6，R 7，R 8和R 8， SUP> 9表示C1-C6烷基等，R10表示C1-C6烷基，其包括使由式（3）表示的烯烃：其中R R 6，R 7，R 8和R 9如上所述，用重氮乙酸酯代替 公式（4）：<？in-line-formula description =“In-line Formulas”end =“lead”？> N 2 CHCO 2 R＆ （4）<？in-line-formula description =“In-line Formulas”end =“tail”？>其中R 10如上所述，在 通过混合（A）至少一种一价或二价铜化合物，（B）至少一种由式（1）表示的光学活性双恶唑啉化合物得到的不对称铜络合物：其中R 1和R 2 > 2 表示C1-C6烷基或th e喜欢 R 3表示叔丁基等; 和R 4和R 5相同并且表示C1-C3烷基等，和（C）至少一种由式（2）表示的氟化合物， ：<？in-line-formula description =“In-line formula”end =“lead”？> A-MF （2）<？in-line-formula description =“In-line 式“end =”tail“？>其中A表示三苯甲基等，M表示磷原子等。

公开(公告)号：US20050240050A1

公开(公告)日：2005-10-27

申请号：US10521158

申请日：2003-07-04

申请人： Ryo Minamida ,  Koji Hagiya ,  Makoto Itagaki

发明人： Ryo Minamida ,  Koji Hagiya ,  Makoto Itagaki

IPC分类号： C07C67/313 ,  C07C69/74

CPC分类号： C07C67/313 ,  C07C69/757

摘要： There is provided a production method of formylcyclopropanecarboxylate compound of formula (2): wherein R1 and R2 are as defined below, which comprises reacting a cyclopropanecarboxylate compound of formula (1): wherein and R1 represent a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, R2 represents a hydrogen atom or a methyl group, with at least one oxidizer selected from the group consisting of hypohalite, N-halosuccinimide, a trichloroisocyanuric acid, and iodine, in the presence of a nitroxy radical compound.

摘要翻译： 提供式（2）的甲酰基环丙烷羧酸酯化合物的制备方法：其中R 1和R 2定义如下，其包括使式（1）的环丙烷羧酸酯化合物 ）：其中和R 1表示直链，支链或环状烷基，取代或未取代的芳基或取代或未取代的芳烷基，R 2表示氢 在硝基自由基化合物的存在下与至少一种选自次卤酸盐，N-卤代琥珀酰亚胺，三氯异氰脲酸和碘的氧化剂反应。

公开(公告)号：US20100305353A1

公开(公告)日：2010-12-02

申请号：US12095608

申请日：2006-12-12

申请人： Kouji Yoshikawa ,  Ryo Minamida ,  Makoto Itagaki

发明人： Kouji Yoshikawa ,  Ryo Minamida ,  Makoto Itagaki

IPC分类号： C07C67/48 ,  C07C309/19 ,  C07C303/32 ,  C07C67/30

CPC分类号： C07C303/32 ,  C07C67/60 ,  C07C309/19 ,  C07C2601/02 ,  C07C69/757

摘要： A method for producing a purified formylcyclopropane compound represented by the formula (1) comprising (A) a step of reacting a crude formylcyclopropane compound represented by the formula (1): wherein R1 represents an alkyl group or the like, with an alkali metal hydrogen sulfite to obtain an alkali metal hydroxymethanesulfonate represented by the formula (2): wherein R1 represents the same meaning as defined above and M represents an alkali metal, and (B) a step of reacting an acid, a base or a water-soluble aldehyde with the alkali metal hydroxymethanesulfonate represented by the formula (2) obtained in the above-mentioned step (A) to obtain a purified formylcyclopropane compound represented by the formula (1).

摘要翻译： 一种制备由式（1）表示的精制甲酰基环丙烷化合物的方法，包括（A）使式（1）表示的粗甲酰基环丙烷化合物：其中R 1表示烷基等与碱金属氢反应的步骤 亚硫酸盐，得到由式（2）表示的碱金属羟基甲磺酸盐：其中R1表示与上述相同的含义，M表示碱金属，（B）使酸，碱或水溶性醛 与上述步骤（A）中获得的式（2）表示的碱金属羟基甲磺酸酯反应，得到由式（1）表示的精制甲酰基环丙烷化合物。

公开(公告)号：US20070032659A1

公开(公告)日：2007-02-08

申请号：US10572391

申请日：2004-09-17

申请人： Makoto Itagaki ,  Katsuhisa Masumoto ,  Ryo Minamida

发明人： Makoto Itagaki ,  Katsuhisa Masumoto ,  Ryo Minamida

IPC分类号： C07F1/08 ,  C07C69/74

CPC分类号： C07C67/347 ,  C07B2200/07 ,  C07C68/06 ,  C07F1/005 ,  C07C69/757 ,  C07C69/96

摘要： A process for producing an optically active cyclopropane compound represented by the formula (4): wherein R3, R4, R5 and R6 are the same or different, and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, and so on; and R7 represents a C1-6 alkyl group; and * represents an asymmetric carbon atom, which comprises reacting a prochiral olefin represented by the formula (2): wherein R3, R4, R5, and R6 are as described above, with a diazoacetic acid ester represented by the formula (3): N2CHCO2R7  (3) wherein R7 is as defined above, in the presence of an asymmetric copper complex prepared from an optically active cycloalkylidenebisoxazoline compound represented by the formula (1): wherein R1 represents a hydrogen atom, a C1-6 alkyl group, and so on; R2 represents a C1-6 alkyl group and so on; and n represents an integer of 0 to 3; provided that, two R1s may be bonded each other together with the carbon atom to which they are bonded to form a ring; and * represents an asymmetric carbon atom, and a copper compound, is provided.

摘要翻译： 一种制备由式（4）表示的光学活性环丙烷化合物的方法：其中R 3，R 4，R 5和R 5， SUP> 6相同或不同，表示氢原子，卤素原子，取代或未取代的烷基等; R 7表示C 1-6烷基; 和*表示不对称碳原子，其包括使由式（2）表示的前手性烯烃：其中R 3，R 4，R 5， 和＆lt; 6＆gt;如上所述，用式（3）表示的重氮乙酸酯：<？in-line-formula description =“In-line Formulas”end =“lead （3）<？in-line-formula description =“In-line Formulas”end =“In-line formula”end =“In-line formula”end = 在由式（1）表示的光学活性亚环烷基双恶唑啉化合物制备的不对称铜络合物存在下，其中R 7定义如上所述：其中R 1， / SUP>表示氢原子，C 1-6烷基等; R 2表示C 1-6烷基等; n表示0〜3的整数， 条件是两个R 1可以与它们所键合的碳原子一起形成环; 和*表示不对称碳原子，并且提供铜化合物。