公开(公告)号：US20080269507A1

公开(公告)日：2008-10-30

申请号：US11884203

申请日：2006-02-22

Applicant: Yasuteru Kajikawa ,  Naruhisa Hirai ,  Jun Kuwana

Inventor： Yasuteru Kajikawa ,  Naruhisa Hirai ,  Jun Kuwana

IPC: C07D493/04 ,  C07C45/33 ,  C07C35/02 ,  C07C51/21 ,  C07C35/08 ,  C07C35/06 ,  C07C51/265 ,  C07D307/89

CPC classification number: C07C51/265 ,  B01J31/0247 ,  B01J31/04 ,  B01J31/28 ,  B01J31/40 ,  B01J2231/70 ,  C07C29/50 ,  C07C35/06 ,  C07C35/08 ,  C07C45/33 ,  C07C51/00 ,  C07C51/313 ,  C07C2601/08 ,  C07C2601/14 ,  C07C2601/20 ,  Y02P20/584 ,  C07C49/403 ,  C07C49/413 ,  C07C49/395 ,  C07C63/313 ,  C07C55/14 ,  C07C35/205

Abstract: A method oxidizes an organic compound with oxygen in the presence of a catalyst, in which the catalyst contains a N-hydroxy- or N-(substituted oxy)-imide compound derivable from at least one selected from a target product, a reaction intermediate, and a reaction byproduct, and the catalyst is produced from at least one component selected from the target product, reaction intermediate, and reaction byproduct each formed as a result of the reaction and is used in the oxidation reaction so as to make up for a loss of the catalyst due to denaturation in the reaction. The method can easily and inexpensively make up for a loss of the catalyst denaturated in the course of reaction.

Abstract translation: 一种方法是在催化剂存在下用氧气氧化有机化合物，其中催化剂含有可从选自目标产物，反应中间体中的至少一种的N-羟基或N-（取代的氧）酰亚胺化合物， 和反应副产物，催化剂由选自反应产生的目标产物，反应中间体和反应副产物中的至少一种成分产生，并用于氧化反应中以弥补损失 的催化剂，由于反应变性。 该方法可以容易且廉价地补偿在反应过程中变性的催化剂的损失。

公开(公告)号：US20080171881A1

公开(公告)日：2008-07-17

申请号：US11885125

申请日：2006-03-22

Applicant: Naruhisa Hirai ,  Jun Kuwana

Inventor： Naruhisa Hirai ,  Jun Kuwana

IPC: C07D211/22 ,  C07C233/00 ,  C07D233/40 ,  C07D249/12

CPC classification number: C07D251/32 ,  Y02P20/55

Abstract: It is desirable to provide a method for easily removing catalyst-derived impurities from a product of a reaction by the catalysis of a compound having a dicarboximide skeleton and thereby efficiently yielding a target compound with high purity.Disclosed is a method for producing an organic compound through a reaction of a substrate in the presence of a catalyst, the catalyst including a compound having a dicarboximide skeleton represented by following Formula (i): wherein R represents hydrogen atom or a hydroxyl-protecting group. The method includes the step of treating a reaction product with hot water so as to decompose and remove an impurity derived from the catalyst. The temperature of the hot water is preferably 100° C. or higher.

Abstract translation: 期望提供一种通过催化具有二羧酰亚胺骨架的化合物从反应产物中容易地除去催化剂衍生的杂质的方法，从而有效地产生高纯度的目标化合物。 公开了一种在催化剂存在下通过底物的反应制备有机化合物的方法，所述催化剂包括具有由下式（i）表示的二羧酰亚胺骨架的化合物：其中R表示氢原子或羟基保护基 。 该方法包括用热水处理反应产物以分解和除去由催化剂衍生的杂质的步骤。 热水的温度优选为100℃以上。

公开(公告)号：US20060241293A1

公开(公告)日：2006-10-26

申请号：US10568597

申请日：2004-08-12

Applicant: Naruhisa Hirai

Inventor： Naruhisa Hirai

IPC: C07D251/32

CPC classification number: C07D251/34 ,  Y02P20/55

Abstract: A process produces an N,N′,N″-trisubstituted isocyanuric acid represented by following Formula (4): wherein R is a hydroxyl-protecting group, by heating an N-substituted carbamic acid derivative represented by following Formula (1): wherein R has the same meaning as defined above; and Z is a group represented by following Formula (2) or (3): wherein R′ is a hydrocarbon group or a heterocyclic group having a carbon atom at the bonding site with the adjacent oxygen atom, wherein the heating is carried out at a temperature in a range of 95° C. to 145° C. where Z is the group represented by Formula (3). This process can easily and conveniently produce the N,N′,N″-trisubstituted isocyanuric acid in a high yield.

Abstract translation: 通过加热下式（1）表示的N-取代氨基甲酸衍生物，得到下述式（4）表示的N，N'，N“ - 三取代异氰脲酸：其中，R为羟基保护基， 其中R具有与上述相同的含义; Z为由下式（2）或（3）表示的基团：其中R'为与相邻氧原子键合位置具有碳原子的烃基或杂环基，其中加热在 温度在95℃至145℃的范围内，其中Z是由式（3）表示的基团。 该方法可以容易且方便地以高收率产生N，N'，N“ - 三取代的异氰脲酸。

公开(公告)号：US06515171B1

公开(公告)日：2003-02-04

申请号：US08912229

申请日：1997-08-15

Applicant: Naruhisa Hirai

Inventor： Naruhisa Hirai

IPC: C07C2700

CPC classification number: C07C51/265 ,  C07B63/00 ,  C07C29/86 ,  C07C45/33 ,  C07C45/80 ,  C07C51/215 ,  C07C51/48 ,  C07C2603/74 ,  Y02P20/582 ,  C07C49/403 ,  C07C55/14 ,  C07C63/06 ,  C07C33/035 ,  C07C35/37 ,  C07C31/12 ,  C07C31/207

Abstract: An oxidation reaction mixture (e.g. adipic acid, benzoic acid, butenediol) and an oxidation catalyst are efficiently separated from a reaction mixture with the use of an aqueous solvent (e.g. methyl benzoate, benzonitrile) containing at least water (e.g. water) and a non-water-soluble solvent separable from the aqueous solvent, the reaction mixture being obtained by oxidizing a substrate (e.g. a hydrocarbon) in the presence of an imide compound such as N-hydroxyphthalimide shown by the following formula (1) as the oxidation catalyst, wherein R1 and R2 represents a substituent such as a hydrogen atom and a halogen atom; R1 and R2 may together form a double bond, or an aromatic or nonaromatic 5- to 12-membered ring; X stands for O or OH; and n is 1 to 3. No decomposition of the oxidation catalyst is observed in this separation process.

Abstract translation: 氧化反应混合物（例如己二酸，苯甲酸，丁烯二醇）和氧化催化剂使用至少含有水（如水）和非水溶剂的水性溶剂（例如苯甲酸甲酯，苯甲腈）与反应混合物有效分离， 可溶于水溶剂的水溶性溶剂，反应混合物通过在下述式（1）所示的酰亚胺化合物如N-羟基邻苯二甲酰亚胺的存在下氧化底物（例如烃）作为氧化催化剂而获得， 其中R1和R2表示取代基如氢原子和卤原子; R1和R2可以一起形成双键，或芳族或非芳族的5至12元环; X代表O或OH; 并且n为1至3.在该分离过程中不观察到氧化催化剂的分解。

公开(公告)号：US06235851B1

公开(公告)日：2001-05-22

申请号：US09214724

申请日：1999-01-11

Applicant: Yasutaka Ishii ,  Tatsuya Nakano ,  Naruhisa Hirai

Inventor： Yasutaka Ishii ,  Tatsuya Nakano ,  Naruhisa Hirai

IPC: C08F2000

CPC classification number: C07C67/03 ,  C07C2603/74 ,  C07C69/54

Abstract: A compound shown by the following formula: wherein each of R1a, R2a, R3a and R4a represents a substituent selected from a non-reactive atom, a non-reactive group, a hydroxyl group and an amino group, and at least two members selected from R1a, R2a, R3a and R4a are a hydroxyl group, a carboxyl group or an amino group; is subjected to an esterification reaction or an amidation reaction with a polymerizable unsaturated compound (e.g., an alcohol, a carboxylic acid, an amine) in the presence of a catalyst comprising an element selected from the Group 3 elements, such as a samarium compound, to obtain a polymerizable adamantane derivative having at least one polymerizable unsaturated group in high yield.

Abstract translation: 下式表示的化合物：其中R1a，R2a，R3a和R4a各自表示选自非反应性原子，非反应性基团，羟基和氨基的取代基，以及选自以下的至少两种： R1a，R2a，R3a和R4a是羟基，羧基或氨基; 在包含选自第3族元素的元素如钐化合物的催化剂存在下，与可聚合不饱和化合物（例如醇，羧酸，胺）进行酯化反应或酰胺化反应， 以高收率得到具有至少一个聚合性不饱和基团的聚合性金刚烷衍生物。

公开(公告)号：US20100331569A1

公开(公告)日：2010-12-30

申请号：US12919494

申请日：2009-02-27

Applicant: Minoru Takano ,  Naruhisa Hirai ,  Yasutaka Ishii

Inventor： Minoru Takano ,  Naruhisa Hirai ,  Yasutaka Ishii

IPC: C07C51/50

CPC classification number: C07C45/33 ,  B01J27/053 ,  B01J37/0201 ,  C07C29/50 ,  C07C45/36 ,  C07C51/00 ,  C07C51/265 ,  C07C2603/74 ,  Y02P20/55 ,  C07C35/37 ,  C07C47/542 ,  C07C49/417 ,  C07C63/04

Abstract: Disclosed is a process for the production of an oxygen-containing organic compound by oxidizing an organic compound with molecular oxygen in a liquid phase in the presence both of a catalytic nitrogen-containing cyclic compound and a catalyst including a solid superacid and, supported thereon, a transition metal compound, in which the nitrogen-containing cyclic compound contains, as a ring constituent, a skeleton represented by following Formula (1), wherein X represents an —OR group, and wherein R represents hydrogen atom or a hydroxyl-protecting group. The process gives the oxygen-containing organic compound in a high yield and enables easy recovery and reuse of the catalyst.

Abstract translation: 本发明公开了一种在含有催化含氮环状化合物和含有固体超强酸的催化剂存在的条件下，通过在液相中用分子氧氧化有机化合物来制备含氧有机化合物的方法， 其中含氮环状化合物含有作为环成分的由下式（1）表示的骨架的过渡金属化合物，其中X表示-OR基，其中R表示氢原子或羟基保护基 。 该方法以高产率提供含氧有机化合物，并且能够容易地回收和再利用催化剂。

公开(公告)号：US07741514B2

公开(公告)日：2010-06-22

申请号：US11504019

申请日：2006-08-15

Applicant: Yasutaka Ishii ,  Tatsuya Nakano ,  Takahiro Iwahama ,  Naruhisa Hirai

Inventor： Yasutaka Ishii ,  Tatsuya Nakano ,  Takahiro Iwahama ,  Naruhisa Hirai

IPC: C07C63/00 ,  C07C51/16 ,  C07C51/00 ,  C07D207/00

CPC classification number: C07C45/34 ,  B01J23/34 ,  B01J23/75 ,  B01J31/0247 ,  B01J31/2208 ,  B01J2231/348 ,  B01J2231/42 ,  B01J2531/72 ,  B01J2531/845 ,  C07C45/00 ,  C07C45/33 ,  C07C45/36 ,  C07C51/265 ,  C07C51/313 ,  C07D207/46 ,  C07D209/48 ,  C07D215/54 ,  Y02P20/55 ,  C07C49/403 ,  C07C49/78 ,  C07C65/32 ,  C07C63/26 ,  C07C63/04 ,  C07C55/14

Abstract: A catalyst of the invention includes an imide compound having a N-substituted cyclic imide skeleton represented by following Formula (I): wherein R is a hydroxyl-protecting group. Preferred R is a hydrolyzable protecting group. R may be a group obtained from an acid by eliminating an OH group therefrom. Such acids include, for example, carboxylic acids, sulfonic acids, carbonic acid, carbamic acid, sulfuric acid, nitric acid, phosphoric acids and boric acids. The catalyst may include the imide compound and a metallic compound in combination. In the presence of the catalyst, (A) a compound capable of forming a radical is allowed to react with (B) a radical scavenging compound and thereby yields an addition or substitution reaction product of the compound (A) and the compound (B) or a derivative thereof. This catalyst can produce an organic compound with a high selectivity in a high yield as a result of, for example, an addition or substitution reaction under mild conditions.

Abstract translation: 本发明的催化剂包括具有由下式（I）表示的N-取代的环状酰亚胺骨架的酰亚胺化合物：其中R是羟基保护基。 优选的R是可水解的保护基团。 R可以是从酸中除去OH基团而获得的基团。 这些酸包括例如羧酸，磺酸，碳酸，氨基甲酸，硫酸，硝酸，磷酸和硼酸。 催化剂可以组合包括酰亚胺化合物和金属化合物。 在催化剂存在下，使（A）能够形成自由基的化合物与（B）自由基清除化合物反应，从而得到化合物（A）和化合物（B）的加成或取代反应产物， 或其衍生物。 作为例如在温和条件下的添加或取代反应的结果，该催化剂可以以高产率生产高选择性的有机化合物。

公开(公告)号：US20070191634A1

公开(公告)日：2007-08-16

申请号：US10594212

申请日：2005-02-23

Applicant: Naruhisa Hirai ,  Masahiko Terada

Inventor： Naruhisa Hirai ,  Masahiko Terada

IPC: C07C51/16 ,  C07C51/255 ,  C07F15/00

CPC classification number: C07C51/265 ,  C07C51/00 ,  Y02P20/55 ,  C07C63/26

Abstract: A method of this invention produces an aromatic carboxylic acid, by oxidizing an aromatic compound B with oxygen in the presence of a catalytic nitrogen-containing cyclic compound A to thereby yield a corresponding aromatic carboxylic acid, the aromatic compound B having one or more hydrocarbon groups alone as substituents on its aromatic ring, and the catalytic nitrogen-containing cyclic compound A having a skeleton represented by following Formula (i): wherein X represents oxygen atom or an —OR group, and wherein R represents hydrogen atom or a hydroxyl-protecting group, as a constitutive member of its ring. The method includes the step of carrying out a reaction at a concentration of the aromatic compound B in the reaction system of 3.0 percent by weight or less, while continuously feeding the catalytic nitrogen-containing cyclic compound A, the aromatic compound B, a reaction solvent, and oxygen to a reactor and continuously extracting a reaction mixture from the reactor. This method can produce aromatic carboxylic acids with industrially good productivity without the need for special reaction facilities and without undergoing many steps.

Abstract translation: 本发明的方法通过在催化性含氮环状化合物A的存在下用氧气化芳香族化合物B，得到芳香族羧酸，得到相应的芳香族羧酸，该芳香族化合物B具有一个以上的烃基 单独作为其芳环上的取代基，和具有由下式（i）表示的骨架的催化含氮环状化合物A：其中X表示氧原子或-OR基团，其中R表示氢原子或羟基保护基 组，作为其环的组成成员。 该方法包括在反应体系中进行浓度为3.0重量％以下的芳族化合物B的浓度的反应的工序，同时连续进料含有催化剂的含氮环状化合物A，芳香族化合物B，反应溶剂 ，和氧气进入反应器并从反应器中连续提取反应混合物。 该方法可以产生工业上良好生产率的芳族羧酸，而不需要特殊的反应设备，并且不经历许多步骤。

公开(公告)号：US07994330B2

公开(公告)日：2011-08-09

申请号：US11885125

申请日：2006-03-22

Applicant: Naruhisa Hirai ,  Jun Kuwana

Inventor： Naruhisa Hirai ,  Jun Kuwana

IPC: C07D211/22 ,  C07D233/40

CPC classification number: C07D251/32 ,  Y02P20/55

Abstract: It is desirable to provide a method for easily removing catalyst-derived impurities from a product of a reaction by the catalysis of a compound having a dicarboximide skeleton and thereby efficiently yielding a target compound with high purity.Disclosed is a method for producing an organic compound through a reaction of a substrate in the presence of a catalyst, the catalyst including a compound having a dicarboximide skeleton represented by following Formula (i): wherein R represents hydrogen atom or a hydroxyl-protecting group. The method includes the step of treating a reaction product with hot water so as to decompose and remove an impurity derived from the catalyst. The temperature of the hot water is preferably 100° C. or higher.

Abstract translation: 期望提供一种通过催化具有二羧酰亚胺骨架的化合物从反应产物中容易地除去催化剂衍生的杂质的方法，从而有效地产生高纯度的目标化合物。 公开了一种在催化剂存在下通过底物的反应制备有机化合物的方法，所述催化剂包括具有由下式（i）表示的二羧酰亚胺骨架的化合物：其中R表示氢原子或羟基保护基 。 该方法包括用热水处理反应产物以分解和除去由催化剂衍生的杂质的步骤。 热水的温度优选为100℃以上。

公开(公告)号：USRE39744E1

公开(公告)日：2007-07-24

申请号：US10830494

申请日：1998-03-05

Applicant: Yasutaka Ishii ,  Tatsuya Nakano ,  Naruhisa Hirai

Inventor： Yasutaka Ishii ,  Tatsuya Nakano ,  Naruhisa Hirai

IPC: C07C35/22 ,  C07C61/12 ,  C07C211/00 ,  C07D207/40 ,  C07D207/444 ,  C07D204/24 ,  B01J31/00

CPC classification number: C07C29/50 ,  C07C35/37 ,  C07C62/06 ,  C07C62/24 ,  C07C67/05 ,  C07C67/08 ,  C07C67/29 ,  C07C67/31 ,  C07C68/02 ,  C07C69/757 ,  C07C69/96 ,  C07C205/18 ,  C07C205/41 ,  C07C205/55 ,  C07C219/24 ,  C07C233/23 ,  C07C233/32 ,  C07C233/74 ,  C07C235/40 ,  C07C265/10 ,  C07C271/34 ,  C07C2603/74 ,  C07C69/753 ,  C07C69/157

Abstract: In the presence of an imide compound (e.g., N-hydroxyphthalimide) shown by the formula (2): wherein R1 and R2 independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group; or R1 and R2 may bond together to form a double bond or an aromatic or non-aromatic ring; Y is O or OH and n=1 to 3; or the imide compound and a co-catalyst (e.g., a transition metal compound), an adamantane derivative having a functional group such as a nitro group, an amino group, a hydroxyl group, a carboxyl group, a hydroxymethyl group and an isocyanato group is oxidized with oxygen. According to the above method, an adamantane derivative having a hydroxyl group together with a functional group such as a nitro group, an amino group, a hydroxyl group, a carboxyl group, a hydroxymethyl group and an isocyanato group is efficiently obtained.

Abstract translation: 在式（2）所示的酰亚胺化合物（例如，N-羟基邻苯二甲酰亚胺）存在下，其中R 1和R 2独立地表示氢原子，卤素 原子，烷基，芳基，环烷基; 或R 1和R 2可以键合在一起形成双键或芳族或非芳族环; Y为O或OH且n = 1至3; 或酰亚胺化合物和助催化剂（例如过渡金属化合物），具有硝基，氨基，羟基，羧基，羟甲基和异氰酸基的官能团的金刚烷衍生物 被氧气氧化。 根据上述方法，有效地获得具有羟基的金刚烷衍生物与硝基，氨基，羟基，羧基，羟甲基和异氰酸基等官能团。