公开(公告)号：US08093429B2

公开(公告)日：2012-01-10

申请号：US12302362

申请日：2007-05-31

申请人： Toshio Hidaka ,  Takafumi Yoshimura ,  Shoji Hara ,  Tsuyoshi Fukuhara

发明人： Toshio Hidaka ,  Takafumi Yoshimura ,  Shoji Hara ,  Tsuyoshi Fukuhara

IPC分类号： C07C211/27

CPC分类号： C07C211/29 ,  C07C231/12 ,  Y02P20/582 ,  C07C233/65

摘要： Provided are a fluorous-tag-introduced fluoroamine of a general formula (I), its production method, a method of fluorination of a substrate having functional group containing oxygen with the fluoroamine serving as a fluorinating agent, and a method of recovering a fluorous-tag-introduced amide after the fluorination. The fluoroamine and its production method, as well as the fluorination method with the fluoroamine and the method of recovery of a fluorous-tag-introduced amide are ecological and advantageous in industrial use, as the load for separating and collecting the product after the fluorination with the fluoroamine serving as a fluorinating agent is small. (In the formula, R0 is an alkyl group or an aryl group having substituent(s) of Rf—(CH2)m—; Rf is a perfluoroalkyl group; m is from 0 to 2; R1 and R2 each are an alkyl group or an aryl group.)

摘要翻译： 提供了通式（I）的氟标记导入的氟胺，其制备方法，含氟氧基官能团的底物氟化作为氟化剂的方法，以及回收氟 - 标签引入酰胺后氟化。 氟胺及其制备方法以及氟胺的氟化方法和引入氟标签的酰胺的回收方法在工业上是生态和有利的，作为在氟化后分离和收集产物的负载 作为氟化剂的氟胺是小的。 （式中，R 0为具有Rf - （CH 2）m - 的取代基的烷基或芳基，Rf为全氟烷基，m为0〜2，R 1和R 2各自为烷基或 芳基）

公开(公告)号：US07829741B2

公开(公告)日：2010-11-09

申请号：US11718526

申请日：2005-10-20

申请人： Tsuyoshi Fukuhara ,  Shoji Hara ,  Toshio Hidaka

发明人： Tsuyoshi Fukuhara ,  Shoji Hara ,  Toshio Hidaka

IPC分类号： C07C209/68 ,  C07C209/74

CPC分类号： C07C209/74 ,  C07C213/08 ,  C07D233/02 ,  C07C211/29 ,  C07C217/58

摘要： A process for producing an α,α-difluoroamine which comprises using hydrogen fluoride and a Lewis base in specific amounts in the halogen-fluorine exchange reaction using an α,α-dihaloamine as the substrate. The process can be industrially applied, enables to obtain the object compound in a short time at a great yield and can be conducted easily with excellent productivity.

摘要翻译： 一种制备α，α-二氟胺的方法，其包括使用α，α-二卤代胺作为底物，在卤素 - 氟交换反应中使用氟化氢和路易斯碱。 该工艺可以在工业上应用，能够在短时间内以大的收率获得目标化合物，并且可以以优异的生产率容易地进行。

公开(公告)号：US20090281309A1

公开(公告)日：2009-11-12

申请号：US12065347

申请日：2006-08-30

申请人： Shoji Hara ,  Tsuyoshi Fukuhara ,  Toshio Hidaka

发明人： Shoji Hara ,  Tsuyoshi Fukuhara ,  Toshio Hidaka

IPC分类号： C07D263/12 ,  C07D265/08

CPC分类号： C07D263/12 ,  C07D263/16 ,  C07D263/56 ,  C07D265/08 ,  C07D277/10

摘要： The present invention is a method for producing a 2-oxazoline analogue or a 1,3-oxazine analogue represented by the following general formula (3) by reacting a 1,2-aminoalcohol compound or a 1,2-aminothiol compound with an α,α-dihaloamine compound.(In the formula, n represents 0 or 1, and R represents an oxygen atom or a sulfur atom. R1, R2 and R3 each represents an atom or a group shown in Group 1 to Group 3, and R0 represents an atom or a group shown in Group 2 or Group 3. Two or more of R1, R2 and R3 may be bonded to each other to form a ring.Group 1: a hydrogen atom, a halogen atom, a nitro group, a cyano group, a formyl group, a carboxyl group, a sulfonyl group, a sulfinoyl group or a sulfenyl group;Group 2: an alkyl group, which may have an arbitrary substituent, an aryl group or an aralkyl group; andGroup 3: an alkyl-substituted, aryl-substituted or aralkyl-substituted oxy group, a carbonyl group, an oxycarbonyl group, a carbonyloxy group, a thio group, a sulfonyl group, a sulfinoyl group or a sulfenyl group)

摘要翻译： 本发明是通过使1,2-氨基醇化合物或1,2-氨基硫醇化合物与α-羟基喹啉类化合物反应来制备由以下通式（3）表示的2-恶唑啉类似物或1,3-恶嗪类似物的方法， ，α-二卤代胺化合物。 （式中，n表示0或1，R表示氧原子或硫原子，R1，R2和R3各自表示1〜3族所示的原子或基团，R0表示原子或基团） 第1组：氢原子，卤素原子，硝基，氰基，甲酰基等。另外，R 1，R 2，R 3可以相互结合形成环。 ，羧基，磺酰基，亚磺酰基或亚磺酰基;第2族：可以具有任意取代基的烷基，芳基或芳烷基;第3族：烷基取代的芳基 - 取代或芳烷基取代的氧基，羰基，氧羰基，羰氧基，硫基，磺酰基，亚磺酰基或亚磺酰基）

公开(公告)号：US20090198086A1

公开(公告)日：2009-08-06

申请号：US12302362

申请日：2007-05-31

申请人： Toshio Hidaka ,  Takafumi Yoshimura ,  Shoji Hara ,  Tsuyoshi Fukuhara

发明人： Toshio Hidaka ,  Takafumi Yoshimura ,  Shoji Hara ,  Tsuyoshi Fukuhara

IPC分类号： C07C53/21 ,  C07C233/64 ,  C07C209/00 ,  C07C211/01 ,  C07C31/34

CPC分类号： C07C211/29 ,  C07C231/12 ,  Y02P20/582 ,  C07C233/65

摘要： Provided are a fluorous-tag-introduced fluoroamine of a general formula (I), its production method, a method of fluorination of a substrate having functional group containing oxygen with the fluoroamine serving as a fluorinating agent, and a method of recovering a fluorous-tag-introduced amide after the fluorination. The fluoroamine and its production method, as well as the fluorination method with the fluoroamine and the method of recovery of a fluorous-tag-introduced amide are ecological and advantageous in industrial use, as the load for separating and collecting the product after the fluorination with the fluoroamine serving as a fluorinating agent is small. (In the formula, R0 is an alkyl group or an aryl group having substituent(s) of Rf—(CH2)m—; Rf is a perfluoroalkyl group; m is from 0 to 2; R1 and R2 each are an alkyl group or an aryl group.)

摘要翻译： 提供了通式（I）的氟标记导入的氟胺，其制备方法，含氟氧基官能团的底物氟化作为氟化剂的方法，以及回收氟 - 标签引入酰胺后氟化。 氟胺及其制备方法以及氟胺的氟化方法和引入氟标签的酰胺的回收方法在工业上是生态和有利的，作为在氟化后分离和收集产物的负载 作为氟化剂的氟胺是小的。 （式中，R 0为具有Rf - （CH 2）m - 的取代基的烷基或芳基，Rf为全氟烷基，m为0〜2，R 1和R 2各自为烷基或 芳基）

公开(公告)号：US20090177012A1

公开(公告)日：2009-07-09

申请号：US11718526

申请日：2005-10-20

申请人： Tsuyoshi Fukuhara ,  Shoji Hara ,  Toshio Hidaka

发明人： Tsuyoshi Fukuhara ,  Shoji Hara ,  Toshio Hidaka

IPC分类号： C07C209/00

CPC分类号： C07C209/74 ,  C07C213/08 ,  C07D233/02 ,  C07C211/29 ,  C07C217/58

摘要： A process for producing an α,α-difluoroamine which comprises using hydrogen fluoride and a Lewis base in specific amounts in the halogen-fluorine exchange reaction using an α,α-dihaloamine as the substrate. The process can be industrially applied, enables to obtain the object compound in a short time at a great yield and can be conducted easily with excellent productivity.

摘要翻译： 一种制备α，α-二氟胺的方法，其包括使用α，α-二卤代胺作为底物，在卤素 - 氟交换反应中使用氟化氢和具有特定量的路易斯碱。 该工艺可以在工业上应用，能够在短时间内以大的收率获得目标化合物，并且可以以优异的生产率容易地进行。

公开(公告)号：US08063205B2

公开(公告)日：2011-11-22

申请号：US12065347

申请日：2006-08-30

申请人： Shoji Hara ,  Tsuyoshi Fukuhara ,  Toshio Hidaka

发明人： Shoji Hara ,  Tsuyoshi Fukuhara ,  Toshio Hidaka

IPC分类号： C07D263/12 ,  C07D263/16 ,  C07D263/56 ,  C07D265/08 ,  C07D277/10 ,  C07D279/06

CPC分类号： C07D263/12 ,  C07D263/16 ,  C07D263/56 ,  C07D265/08 ,  C07D277/10

摘要： The present invention is a method for producing a 2-oxazoline analogue or a 1,3-oxazine analogue represented by the following general formula (3) by reacting a 1,2-aminoalcohol compound or a 1,2-aminothiol compound with an α,α-dihaloamine compound.(In the formula, n represents 0 or 1, and R represents an oxygen atom or a sulfur atom. R1, R2 and R3 each represents an atom or a group shown in Group 1 to Group 3, and R0 represents an atom or a group shown in Group 2 or Group 3. Two or more of R1, R2 and R3 may be bonded to each other to form a ring.Group 1: a hydrogen atom, a halogen atom, a nitro group, a cyano group, a formyl group, a carboxyl group, a sulfonyl group, a sulfinoyl group or a sulfenyl group;Group 2: an alkyl group, which may have an arbitrary substituent, an aryl group or an aralkyl group; andGroup 3: an alkyl-substituted, aryl-substituted or aralkyl-substituted oxy group, a carbonyl group, an oxycarbonyl group, a carbonyloxy group, a thio group, a sulfonyl group, a sulfinoyl group or a sulfenyl group)

摘要翻译： 本发明是通过使1,2-氨基醇化合物或1,2-氨基硫醇化合物与α反应生成2-恶唑啉类似物或由以下通式（3）表示的1,3-恶嗪类似物的方法， ，α-二卤代胺化合物。 （式中，n表示0或1，R表示氧原子或硫原子，R1，R2和R3各自表示1〜3族所示的原子或基团，R0表示原子或基团） 第1组：氢原子，卤素原子，硝基，氰基，甲酰基等。另外，R 1，R 2，R 3可以相互结合形成环。 ，羧基，磺酰基，亚磺酰基或亚磺酰基;第2族：可以具有任意取代基的烷基，芳基或芳烷基;第3族：烷基取代的芳基 - 取代或芳烷基取代的氧基，羰基，氧羰基，羰氧基，硫基，磺酰基，亚磺酰基或亚磺酰基）

公开(公告)号：US07968751B2

公开(公告)日：2011-06-28

申请号：US12068481

申请日：2008-02-07

申请人： Shoji Hara ,  Tsuyoshi Fukuhara

发明人： Shoji Hara ,  Tsuyoshi Fukuhara

IPC分类号： C07C211/03 ,  C07C211/08

CPC分类号： C07D239/30 ,  C07B39/00 ,  C07B2200/09 ,  C07C17/093 ,  C07C17/16 ,  C07C17/18 ,  C07C29/64 ,  C07C51/60 ,  C07C67/307 ,  C07C2601/14 ,  C07C2601/16 ,  C07C2601/18 ,  C07C2601/20 ,  C07C2603/74 ,  C07H1/00 ,  C07H9/04 ,  C07H13/04 ,  C07H13/08 ,  C07H19/06 ,  C07C22/08 ,  C07C21/18 ,  C07C19/08 ,  C07C23/38 ,  C07C23/02 ,  C07C23/10 ,  C07C63/10 ,  C07C69/63 ,  C07C35/52 ,  C07C35/48

摘要： A method of fluorination comprising reacting monosaccharides, oligosaccharides, polysaccharides, composite saccharides formed by bonding of these saccharides with proteins and lipids and saccharides having polyalcohols, aldehydes, ketones and acids of the polyalcohols, and derivatives and condensates of these compounds with a fluorinating agent represented by general formula (I) thermally or under irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region. In accordance with the method, the fluorination at a selected position can be conducted safely at a temperature in the range of 150 to 200° C. where the reaction is difficult in accordance with conventional methods. The above method comprising the irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region can be applied to substrates other than saccharides. When a complex compound comprising HF and a base is reacted under irradiation with microwave, fluorination at a specific position which is difficult in accordance with conventional methods proceeds highly selectively, efficiently in a short time and safely.

公开(公告)号：US20080319228A1

公开(公告)日：2008-12-25

申请号：US12068481

申请日：2008-02-07

申请人： Shoji Hara ,  Tsuyoshi Fukuhara

发明人： Shoji Hara ,  Tsuyoshi Fukuhara

IPC分类号： C07C211/15

CPC分类号： C07D239/30 ,  C07B39/00 ,  C07B2200/09 ,  C07C17/093 ,  C07C17/16 ,  C07C17/18 ,  C07C29/64 ,  C07C51/60 ,  C07C67/307 ,  C07C2601/14 ,  C07C2601/16 ,  C07C2601/18 ,  C07C2601/20 ,  C07C2603/74 ,  C07H1/00 ,  C07H9/04 ,  C07H13/04 ,  C07H13/08 ,  C07H19/06 ,  C07C22/08 ,  C07C21/18 ,  C07C19/08 ,  C07C23/38 ,  C07C23/02 ,  C07C23/10 ,  C07C63/10 ,  C07C69/63 ,  C07C35/52 ,  C07C35/48

摘要： A method of fluorination comprising reacting monosaccharides, oligosaccharides, polysaccharides, composite saccharides formed by bonding of these saccharides with proteins and lipids and saccharides having polyalcohols, aldehydes, ketones and acids of the polyalcohols, and derivatives and condensates of these compounds with a fluorinating agent represented by general formula (I) thermally or under irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region. In accordance with the method, the fluorination at a selected position can be conducted safely at a temperature in the range of 150 to 200° C. where the reaction is difficult in accordance with conventional methods. The above method comprising the irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region can be applied to substrates other than saccharides. When a complex compound comprising HF and a base is reacted under irradiation with microwave, fluorination at a specific position which is difficult in accordance with conventional methods proceeds highly selectively, efficiently in a short time and safely.

摘要翻译： 一种氟化方法，包括使单糖，寡糖，多糖，这些糖与蛋白质和脂质结合形成的复合糖和多元醇的多元醇，醛，酮和酸的糖，以及这些化合物的衍生物和缩合物与氟化剂的代表性反应 通过通式（I）热或照射微波或具有波长在微波区域周围的波长的电磁波。 根据该方法，可以根据常规方法在150〜200℃的范围内的温度下安全地进行选择位置的氟化。 包含微波照射或微波周围波长的电磁波的上述方法可以应用于除糖以外的基材。 当包含HF和碱的络合物在微波照射下反应时，根据常规方法困难的特定位置的氟化在高速选择性地进行，在短时间内和安全地进行。

公开(公告)号：US20070191631A1

公开(公告)日：2007-08-16

申请号：US10591698

申请日：2005-03-02

申请人： Shoji Hara ,  Tsuyoshi Fukuhara

发明人： Shoji Hara ,  Tsuyoshi Fukuhara

IPC分类号： C07C69/63

CPC分类号： C07C29/124 ,  C07B39/00 ,  C07B53/00 ,  C07B2200/07 ,  C07C67/18 ,  C07D317/22 ,  C07D317/24 ,  C07C69/92 ,  C07C69/76 ,  C07C31/38

摘要： The present invention provides a process for producing an optically active fluoro compound represented by formula (3) through reaction between a specific fluoroamine and an optically active diol; and a process for producing an optically active fluoroalcohol through hydrolysis of the optically active fluoro compound. According to the process of the present invention, such optically active fluoro compounds and optically active fluoroalcohols can be produced at high optical purity and high yield in a simple manner. Such optically active fluoroalcohols are a useful source for producing drugs, pesticides, and other functional chemicals.

摘要翻译： 本发明提供一种通过特定的氟代胺和光学活性的二醇之间的反应制备由式（3）表示的光学活性的氟化合物的方法; 以及通过光学活性氟化合物的水解生产光学活性氟代醇的方法。 根据本发明的方法，可以简单的方式以高光学纯度和高产率制备这种光学活性氟化合物和光学活性氟代醇。 这种光学活性氟代醇是生产药物，杀虫剂和其它功能性化学物质的有用来源。

公开(公告)号：US20060014972A1

公开(公告)日：2006-01-19

申请号：US10537437

申请日：2003-12-01

申请人： Shoji Hara ,  Tsuyoshi Fukuhara

发明人： Shoji Hara ,  Tsuyoshi Fukuhara

IPC分类号： C07J53/00 ,  C07G17/00

CPC分类号： C07D239/30 ,  C07B39/00 ,  C07B2200/09 ,  C07C17/093 ,  C07C17/16 ,  C07C17/18 ,  C07C29/64 ,  C07C51/60 ,  C07C67/307 ,  C07C2601/14 ,  C07C2601/16 ,  C07C2601/18 ,  C07C2601/20 ,  C07C2603/74 ,  C07H1/00 ,  C07H9/04 ,  C07H13/04 ,  C07H13/08 ,  C07H19/06 ,  C07C22/08 ,  C07C21/18 ,  C07C19/08 ,  C07C23/38 ,  C07C23/02 ,  C07C23/10 ,  C07C63/10 ,  C07C69/63 ,  C07C35/52 ,  C07C35/48

摘要： A method of fluorination comprising reacting monosaccharides, oligosaccharides, polysaccharides, composite saccharides formed by bonding of these saccharides with proteins and lipids and saccharides having polyalcohols, aldehydes, ketones and acids of the polyalcohols, and derivatives and condensates of these compounds with a fluorinating agent represented by general formula (I) thermally or under irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region. In accordance with the method, the fluorination at a selected position can be conducted safely at a temperature in the range of 150 to 200° C. where the reaction is difficult in accordance with conventional methods. The above method comprising the irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region can be applied to substrates other than saccharides. When a complex compound comprising HF and a base is reacted under irradiation with microwave, fluorination at a specific position which is difficult in accordance with conventional methods proceeds highly selectively, efficiently in a short time and safely.

摘要翻译： 一种氟化方法，包括使单糖，寡糖，多糖，这些糖与蛋白质和脂质结合形成的复合糖和多元醇的多元醇，醛，酮和酸的糖，以及这些化合物的衍生物和缩合物与氟化剂的代表性反应 通过通式（I）热或照射微波或具有波长在微波区域周围的波长的电磁波。 根据该方法，可以根据常规方法在150〜200℃的范围内的温度下安全地进行选择位置的氟化。 包含微波照射或微波周围波长的电磁波的上述方法可以应用于除糖以外的基材。 当包含HF和碱的络合物在微波照射下反应时，根据常规方法困难的特定位置的氟化在高速选择性地进行，在短时间内和安全地进行。