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1. 发明授权

US5237075A Process for producing 3,4-dihydrocoumarin derivatives 失效
标题翻译： 3,4-二氢香豆素衍生物的制备方法
公开(公告)号：US5237075A
公开(公告)日：1993-08-17
申请号：US839285
申请日：1992-02-24
申请人： Tamio Shirafuji , Kiyomi Sakai , Kensen Okusako , Itaru Kawata , Yasumoto Simazu , Tetuya Suzuta
发明人： Tamio Shirafuji , Kiyomi Sakai , Kensen Okusako , Itaru Kawata , Yasumoto Simazu , Tetuya Suzuta
IPC分类号： C07D311/10 , C07D311/20
CPC分类号： C07D311/10 , C07D311/20
摘要： A process for producing a 3,4-dihydrocoumarin compound represented by formula (II): ##STR1## wherein R.sub.1 to R.sub.4 are as defined in the specification, comprising the steps of:(1) heating a 3-(2-cyclohexanoyl)propionic acid ester compound represented by formula (I): ##STR2## wherein R.sub.1 R.sub.5 are as defined in the specification, in the presence of at least one solid metal catalyst, thereby to allow said compound of formula (I) to undergo ring formation and dehydrogenation to yield said 3,4-dihydrocoumarin compound of formula (II) and, as a by-product, a coumarin compound represented by formula (III): ##STR3## wherein R.sub.1 to R.sub.4 are as defined above; (2) adding a catalyst which is as defined above to said reaction mixture, or bringing said reaction mixture into contact with oxygen to activate said catalyst used in said ring formation and dehydrogenation, without separating said coumarin compound from the reaction mixture that has undergone said ring formation and dehydrogenation; and(3) partially hydrogenating said by-product coumarin compound in said reaction mixture with hydrogen so as to convert said coumarin compound to a 3,4-dihydrocoumarin compound.
摘要翻译：制备由式（II）表示的3,4-二氢香豆素化合物的方法：其中R 1至R 4如说明书中所定义，其包括以下步骤：（1）加热3-（2- 环己酰基）丙酸酯化合物：其中R1 R5如说明书中所定义，在至少一种固体金属催化剂存在下，从而使所述式（I）化合物与式进行环形成和脱氢，得到式（II）的3,4-二氢香豆素化合物，作为副产物，由式（III）表示的香豆素化合物：其中R 1至R 4为以上定义（2）向所述反应混合物中加入如上定义的催化剂，或使所述反应混合物与氧接触以活化所述环形成和脱氢中使用的所述催化剂，而不将所述香豆素化合物与已经经历所述反应混合物的反应混合物分离环形成和脱氢; 和（3）用氢将所述反应混合物中的所述副产物香豆素化合物部分氢化，以将所述香豆素化合物转化为3,4-二氢香豆素化合物。

2. 发明授权

US5231194A Process for producing coumarin derivatives 失效
标题翻译：生产香豆素衍生物的方法
公开(公告)号：US5231194A
公开(公告)日：1993-07-27
申请号：US631316
申请日：1990-12-21
申请人： Tamio Shirafuji , Kiyomi Sakai , Kensen Okusako
发明人： Tamio Shirafuji , Kiyomi Sakai , Kensen Okusako
IPC分类号： B01J23/64 , C07D311/10
CPC分类号： B01J23/64 , C07D311/10
摘要： A process for producing a coumarin derivative represented by formula (II): ##STR1## wherein R.sub.1 to R.sub.4 are as defined in the specification, comprising the step of: subjecting to a ring formation and dehydrogenation reaction a 3-(2-cyclohexanoyl)-propionic acid ester derivative represented by formula (I): ##STR2## wherein R.sub.1 to R.sub.4 are as defined in the specification, the ring formation and dehydrogenation reaction being (1) conducted by use of a catalyst comprising a carrier having supported thereon palladium and either of chromium oxide and chromium hydroxide, or (2) conducted by use of a catalyst comprising a carrier having supported thereon palladium or a catalyst comprising a carrier having supported thereon palladium and either of chromium oxide and chromium hydroxide, in the presence of a promoter which is at least one member selected from the group consisting of magnesium trisilicate, zirconia, metallic chromium, and metallic tungsten.

3. 发明授权

US5218129A Process for producing 3,4-dihydrocoumarin 失效
标题翻译：生产3,4-二氯尿嘧啶的方法
公开(公告)号：US5218129A
公开(公告)日：1993-06-08
申请号：US808499
申请日：1991-12-17
申请人： Tamio Shirafuji , Kiyomi Sakai , Kensen Okusako , Yoshitaka Nishida
发明人： Tamio Shirafuji , Kiyomi Sakai , Kensen Okusako , Yoshitaka Nishida
IPC分类号： C07D311/20
CPC分类号： C07D311/20
摘要： A process for producing 3,4-dihydrocoumarin comprising cyclization and dehydrogenation of a 3-(2-cyclohexanoyl)propionic acid ester, in which a reaction mixture obtained by the cyclization and dehydrogenation is washed with an alkali to reduce the dihydrocinnamic acid content of the reaction mixture to 1% by weight or less and/or previously distilling the reaction mixture to remove high-boiling substances, and then subjected to rectification to recover 3,4-dihydrocoumarin. The thus obtained 3,4-dihydrocoumarin has high purity and high quality sufficient for use as a perfume as it is.

4. 发明授权

US5260457A Process for producing coumarin and derivative thereof 失效
标题翻译：生产香豆素及其衍生物的方法
公开(公告)号：US5260457A
公开(公告)日：1993-11-09
申请号：US921747
申请日：1992-07-30
申请人： Yoshitaka Nishida , Tamio Shirafuji , Kiyomi Sakai , Kensen Okusako
发明人： Yoshitaka Nishida , Tamio Shirafuji , Kiyomi Sakai , Kensen Okusako
IPC分类号： C07D311/10 , C07D311/20 , C07D311/14 , C07D311/16
CPC分类号： C07D311/20 , C07D311/10
摘要： A process for producing coumarin and a derivative thereof represented by formula (2): ##STR1## wherein R.sub.1 to R.sub.4 each represents a hydrogen atom, a methyl group, or an ethyl group, provided that at least two of R.sub.1 to R.sub.4 each represents a hydrogen atom,the process comprising the step of heating a 3-(2-cyclohexanoyl)propionic acid ester represented by formula (1): ##STR2## wherein R.sub.1 to R.sub.4 are as defined above and R.sub.5 represents an alkyl group having from 1 to 4 carbon atoms,in the presence of a palladium catalyst, thereby to allow the ester of formula (1) to undergo cyclization and dehydrogenation reactions, the latter stage of the reactions, in which the conversion of the 3-(2-cyclohexanoyl) propionic acid ester used as a starting material has reached about 80% or more, being conducted at a higher temperature than that for the former stage of the reactions.

5. 发明授权

US4670612A Method for producing alicyclic alcohols 失效
标题翻译：生产脂环醇的方法
公开(公告)号：US4670612A
公开(公告)日：1987-06-02
申请号：US869612
申请日：1986-06-02
申请人： Tamio Shirafuji , Kiyomi Sakai , Itaru Kawata
发明人： Tamio Shirafuji , Kiyomi Sakai , Itaru Kawata
IPC分类号： C07C29/04 , C07C39/04
CPC分类号： C07C29/04 , C07C2101/14
摘要： A method for producing alicyclic alcohols by the hydration of olefins in the presence of an aromatic sulfonic acid, which comprises incorporating molybdic acid or its salt and/or vanadium oxide, vanadic acid or its salt in the reaction system. The alicyclic alcohols are useful as intermediates for caprolactam, adipic acid, insecticides, etc.
摘要翻译：在芳族磺酸存在下通过烯烃水合制备脂环族醇的方法，其包括在反应体系中掺入钼酸或其盐和/或氧化钒，钒酸或其盐。脂环醇可用作己内酰胺，己二酸，杀虫剂等的中间体。

6. 发明授权

US4716253A Method for producing cycloalkanols 失效
标题翻译：环烷醇的制备方法
公开(公告)号：US4716253A
公开(公告)日：1987-12-29
申请号：US929510
申请日：1986-11-12
申请人： Tamio Shirafuji , Kiyomi Sakai , Ken-ichi Hirose
发明人： Tamio Shirafuji , Kiyomi Sakai , Ken-ichi Hirose
IPC分类号： C07C29/04 , C07C35/18
CPC分类号： C07C29/04 , C07C2101/14
摘要： A method for producing a cycloalkanol important as a material for caprolactam, adipic acid and the like by the hydration of a cycloalkene with a solid acid as a catalyst, which comprises carrying out said hydration in the presence of a phenol.
摘要翻译：通过用固体酸作为催化剂水合环烯烃制备作为己内酰胺，己二酸等的材料重要的环烷醇的方法，其包括在苯酚存在下进行所述水合。

7. 发明授权

US4879422A Method for producing cycloalkanol 失效
标题翻译：环烷醇的制备方法
公开(公告)号：US4879422A
公开(公告)日：1989-11-07
申请号：US211881
申请日：1988-06-27
申请人： Tamio Shirafuji , Kiyomi Sakai
发明人： Tamio Shirafuji , Kiyomi Sakai
IPC分类号： C07C29/04
CPC分类号： C07C29/04 , C07C2101/14
摘要： A method for producing a cycloalkanol in high yield by hydrating cycloalkene with a specific catalyst is disclosed. The catalyst is obtainable by ion-exchanging all or a part of the cations of a crystalline gallium silicate with hydrogen ions. It has a specific composition defined by the general formula and is characterized by the X-ray diffraction pattern.

8. 发明授权

US5300662A Process for producing coumarin and derivatives thereof 失效
标题翻译：生产香豆素及其衍生物的方法
公开(公告)号：US5300662A
公开(公告)日：1994-04-05
申请号：US966345
申请日：1992-10-26
申请人： Yoshitaka Nishida , Kiyomi Sakai , Tamio Shirafuji
发明人： Yoshitaka Nishida , Kiyomi Sakai , Tamio Shirafuji
IPC分类号： B01J23/44 , C07B61/00 , C07D311/10 , C07D311/14 , C07D311/16 , C07D311/18
CPC分类号： C07D311/10
摘要： A process for producing coumarin or a derivative thereof, which process comprises dehydrogenation of 3,4-dihydrocoumarin or a derivative thereof in the presence of a palladium catalyst by heating under reduced pressure.
摘要翻译：一种生产香豆素或其衍生物的方法，该方法包括在钯催化剂存在下，通过在减压下加热脱氢3,4-二氢香豆素或其衍生物。

9. 发明申请

US20080279227A1 Method for Generating Terahertz Electromagnetic Waves by Using Coherent Phonons 审中-公开
标题翻译：使用相干声子产生太赫兹电磁波的方法
公开(公告)号：US20080279227A1
公开(公告)日：2008-11-13
申请号：US11885651
申请日：2006-03-03
申请人： Masaaki Nakayama , Kohji Mizoguchi , Kiyomi Sakai , Shingo Saito
发明人： Masaaki Nakayama , Kohji Mizoguchi , Kiyomi Sakai , Shingo Saito
IPC分类号： H01S3/00
CPC分类号： H01S5/30 , H01S1/02 , H01S2302/02
摘要： In a method for generating a terahertz electromagnetic wave by using coherent phonons in a quantum structure, high density of coherent phonons acting as a radiation source of the terahertz electromagnetic wave are obtained by exciting the inter-band transitions in a quantum structure under the condition that the energy difference between two inter-band transitions in the quantum structure is resonated with the energy of the coherent phonons, and the terahertz electromagnetic wave is generated by the oscillatory polarizations of the coherent phonons. High density of coherent phonons may be created through the elementary excitation generated by using instantaneous laser pulses. A quantum well structure is effective as the quantum structure, and a scattering process of coherent phonon may be suppressed by confining coherent LO phonons in a well layer. Under the condition that the difference of energies between the heavy-hole and light-hole exitons in a quantum well structure agrees with the energy of LO phonons and both the exitons are created simultaneously, high density of coherent phonons may be generated. With this method, a terahertz electromagnetic wave can be effectively and strongly emitted from the coherent phonons.
摘要翻译：在通过在量子结构中使用相干声子来产生太赫兹电磁波的方法中，通过在量子结构中激发带间跃迁来获得充当太赫兹电磁波的辐射源的高密度相干声子，量子结构中的两个带间跃迁之间的能量差异与相干声子的能量共振，并且太赫兹电磁波由相干声子的振荡极化产生。可以通过使用瞬时激光脉冲产生的基本激发来产生高密度的相干声子。量子阱结构作为量子结构是有效的，并且可以通过将相干LO声子限定在阱层中来抑制相干声子的散射过程。在量子阱结构中的重孔和光空穴之间的能量差异与LO声子的能量一致并且两者同时产生的条件下，可能产生高密度的相干声子。通过这种方法，可以从相干声子有效强地发射太赫兹电磁波。

10. 发明授权

US4568769A Method for producing a mixture containing cycloalkanones and cycloalkanols 失效
标题翻译：制备含有环烷酮和环烷醇的混合物的方法
公开(公告)号：US4568769A
公开(公告)日：1986-02-04
申请号：US622865
申请日：1984-06-20
申请人： Akira Yashima , Teruo Matsuda , Tadao Sato , Mitsuaki Takahashi , Kiyomi Sakai
发明人： Akira Yashima , Teruo Matsuda , Tadao Sato , Mitsuaki Takahashi , Kiyomi Sakai
IPC分类号： C07C29/48 , C07C45/33 , C07C45/53 , C07C409/14
CPC分类号： C07C409/14 , C07C29/48 , C07C407/00 , C07C45/33 , C07C45/53 , C07C2101/14
摘要： Disclosed in a method for producing a mixture containing cycloalkanone and/or cycloalkanol which comprises oxidizing a cycloalkane with molecular oxygen to a cycloalkyl hydroperoxide represented by the formula (1): ##STR1## (wherein m represents an integer of 4.ltoreq.m.ltoreq.11) and decomposing the cycloalkyl hydroperoxide to obtain a mixture containing cycloalkanone and/or cycloalkanol, wherein the oxidation of the cycloalkane with molecular oxygen and/or the decomposition of the cycloalkyl hydroperoxide are carried out in the presence of a catalyst composition comprising at least one metallic salt represented by the formula (2):MX.sub.n (2)(wherein M represent Co, Mn, Cr or Fe, X represents an anionic ligand and n represents 2 or 3) and at least one compound represented by the formula (3): ##STR2## (wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently represent hydrogen or a lower alkyl group) and/or a catalyst composition comprising at least one metal complex represented by the formula (4): ##STR3## (wherein M represents Co, Mn, Cr or Fe, X represents an anionic ligand, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently represent hydrogen or a lower alkyl group, p is 1 or 2 and q is 0, 1 or 2).Advantages of the method are higher conversion of cycloalkyl hydroperoxide, higher yields of cycloalkanone and cycloalkanol and higher production ratio of cycloalkanone.
摘要翻译：本发明涉及制备含有环烷酮和/或环烷醇的混合物的方法，该方法包括用分子氧将环烷烃氧化为由式（1）表示的环烷基氢过氧化物：其中m表示4的整数， = m 11）并分解环烷基氢过氧化物以获得含有环烷酮和/或环烷醇的混合物，其中环烷烃与分子氧的氧化和/或环烷基氢过氧化物的分解在催化剂存在下进行包含至少一种由式（2）表示的金属盐的组合物：MXn（2）（其中M表示Co，Mn，Cr或Fe，X表示阴离子配体，n表示2或3）和至少一种由式（3）：其中R1，R2，R3和R4独立地表示氢或低级烷基）和/或包含至少一种由式（4）表示的金属络合物的催化剂组合物：（图） 4）（其中M表示Co，Mn，Cr或Fe，X表示阴离子配体，R1，R2，R3和R4独立地表示氢或低级烷基，p为1或2，q为0,1或2）。该方法的优点是环烷基氢过氧化物的转化率较高，环烷酮和环烷醇的产率较高，环烷酮的生产率较高。

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