SYNTHESIS OF DIACIDS, DIALDEHYDES, OR DIAMINES FROM THF-DIOLS

    公开(公告)号:WO2015057365A3

    公开(公告)日:2015-04-23

    申请号:PCT/US2014/057399

    申请日:2014-09-25

    发明人: STENSRUD, Kenneth

    摘要: A simple and elegant chemical process for the synthesis of oxygenated products, such as acids and aldehydes, or other derivative products, such as amines and nitriles, of cyclic bifunctional molecules made from renewable, bio-based sources such as HMF and/or its reduction product, 2,5-bis(hydroxymethyl)-tetrahydrofuran (bHMTHF) is described. In general, the process involves: a) generating a tetrahydrofuran-2,5-diyl-bis(methylene)-bis(sulfonate) from bHMTHFs using a sulfonate; b) displacing nucleophilically at least a sulfonate leaving group from the tetrahydrofuran-2,5-diyl-bis(methylene)-bis(sulfonate) to form a THF-dinitrile; and either c) oxidizing the THF-dinitrile with an acid having a pKa of ≤ 0 to generate a di-acid, or d) reducing partially the THF-dinitrile to generate a di-aldehyde, or e) reducing fully the THF-dinitrile to generate a di-amine.

    PROCESS FOR PREPARING 2-AMINO-5-CYANOBENZOIC ACID DERIVATIVES
    4.
    发明申请
    PROCESS FOR PREPARING 2-AMINO-5-CYANOBENZOIC ACID DERIVATIVES 审中-公开
    制备2-氨基-5-氰基苯甲酸衍生物的方法

    公开(公告)号:WO2009085816A1

    公开(公告)日:2009-07-09

    申请号:PCT/US2008/087151

    申请日:2008-12-17

    摘要: Disclosed is a method for preparing a compound of Formula 1 comprising contacting a compound of Formula 2 with a metal cyanide reagent, a copper(I) salt reagent, an iodide salt reagent and at least one compound of Formula 3 wherein R 1 is (NHR 3 or OR 4 ; R 2 is CH 3 or Cl; R 3 is H, C 1 -C 4 alkyl, cyclopropyl, cyclopropylcyclopropyl, cyclopropylmethyl or methylcyclopropyl; R 4 is H or C 1 -C 4 alkyl; X is Br or Cl; and R 5 , R 6 , R 7 , R 8 and R 9 are as defined in the disclosure. Also disclosed is a method for preparing a compound of Formula 4 wherein R 12 , R 13 , R 14 and Z are as defined in the disclosure, using a compound of Formula 1 characterized by preparing the compound of Formula 1 by the method disclosed above or using a compound of Formula 1 prepared by the method disclosed above.

    摘要翻译: 公开了一种制备式1化合物的方法,包括使式2的化合物与金属氰化物试剂,铜(I)盐试剂,碘化物盐试剂和至少一种式3化合物(其中R 1是(NHR 3或OR 4) ; R 2为CH 3或Cl; R 3为H,C 1 -C 4烷基,环丙基,环丙基环丙基,环丙基甲基或甲基环丙基; R 4为H或C 1 -C 4烷基; X为Br或Cl;且R 5,R 6,R 7,R 8和R 9为 还公开了制备式4化合物的方法,其中R 12,R 13,R 14和Z如本公开所定义,使用式1的化合物,其特征在于通过方法制备式1的化合物 或使用通过上述方法制备的式1的化合物。

    PROCESS FOR PREPARING 2-AMINO-5-CYANOBENZOIC ACID DERIVATIVES
    5.
    发明申请
    PROCESS FOR PREPARING 2-AMINO-5-CYANOBENZOIC ACID DERIVATIVES 审中-公开
    制备2-氨基-5-氰基苯甲酸衍生物的方法

    公开(公告)号:WO2009061991A1

    公开(公告)日:2009-05-14

    申请号:PCT/US2008/082739

    申请日:2008-11-07

    摘要: Disclosed is a method for preparing a compound of Formula 1 comprising contacting a compound of Formula 2 with at least one alkali metal cyanide of Formula 3 and a compound of Formula 4 wherein R 1 is NHR 3 or OR 4 ; R 2 is CH 3 or Cl; R 3 is H, C 1 -C 4 alkyl, cyclopropyl, cyclopropylcyclopropyl, cyclopropylmethyl or methylcyclopropyl; R 4 is H or C 1 -C 4 alkyl; X is Br, Cl or I; and R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are as defined in the disclosure. Also disclosed is a method for preparing a compound of Formula 4 wherein R 9 and R 10 together are a cycloalkadiene bidentate ligand, comprising contacting a compound of Formula 5 wherein Y is Cl, Br or I, with a cycloalkadiene bidentate ligand, at least one metal reducing agent and a nitrile solvent. Also disclosed is a method for preparing a compound of Formula 1 comprising preparing a compound of Formula 4 by contacting a compound of Formula 5 with a cycloalkadiene bidentate ligand and at least one metal reducing agent, and then contacting the reaction mixture comprising the compound of Formula 4 with a compound of Formula 2 and at least one alkali metal cyanide of Formula 3; and further disclosed is a method for preparing a compound of Formula 6 wherein R 15 , R 16 , R 17 and Z are as defined in the disclosure using a compound of Formula 1, characterized by preparing the compound of Formula 1 by a method disclosed above.

    摘要翻译: 公开了制备式1化合物的方法,包括使式2的化合物与式3的至少一种碱金属氰化物和式4化合物(其中R 1是NHR 3或OR 4)接触; R2是CH3或Cl; R3是H,C1-C4烷基,环丙基,环丙基环丙基,环丙基甲基或甲基环丙基; R4是H或C1-C4烷基; X是Br,Cl或I; 并且R5,R6,R7,R8,R9和R10如本公开所定义。 还公开了制备式4化合物的方法,其中R 9和R 10一起是环二烯二齿配体,包括使式5的化合物(其中Y为Cl,Br或I)与环二烯二齿配体,至少一种金属还原 助剂和腈溶剂。 还公开了制备式1化合物的方法,包括通过使式5的化合物与环二烯二齿配体和至少一种金属还原剂接触来制备式4的化合物,然后使包含式 4与式2的化合物和至少一种式3的碱金属氰化物反应; 并且进一步公开了制备式6化合物的方法,其中R 15,R 16,R 17和Z如本公开中所定义,使用式1的化合物,其特征在于通过上述方法制备式1的化合物。

    PROCESS FOR PREPARING 2-AMINO-5-CYANOBENZOIC ACID DERIVATIVES
    6.
    发明申请
    PROCESS FOR PREPARING 2-AMINO-5-CYANOBENZOIC ACID DERIVATIVES 审中-公开
    制备2-氨基-5-氰基苯甲酸衍生物的方法

    公开(公告)号:WO2008070158A1

    公开(公告)日:2008-06-12

    申请号:PCT/US2007/025005

    申请日:2007-12-05

    IPC分类号: C07C253/14

    摘要: Disclosed is a method for preparing a compound of Formula (1) comprising contacting a compound of Formula (2) with at least one compound of Formula 3 in the presence of a solvent comprising one or more organic solvents selected from ethers and nitriles and a catalytically effective amount of a palladium complex comprising at least one tertiary phosphine ligand of Formula (4) wherein R 1 is NHR 3 or OR 4 ; R 2 is CH 3 or Cl; R 3 is H, C 1 - C 4 alkyl, cyclopropyl, cyclopropylmethyl or methylcyclopropyl; R 4 is H or C 1 -C 4 alkyl; M 1 is an alkali metal; and R 5 , R 6 and R 7 are defined in the disclosure; provided that when R 2 is Cl, then X is Br. Also disclosed is a method for preparing a compound of Formula 5 wherein R 14 , R 15 , R 16 and Z are as defined in the disclosure using a compound of Formula 1 characterized by preparing the compound of Formula (1) by the aforedescribed method.

    摘要翻译: 公开了一种制备式(1)化合物的方法,包括使式(2)化合物与至少一种式3的化合物在包含一种或多种选自醚和腈的有机溶剂和催化剂的溶剂的存在下接触 有效量的包含至少一种式(4)的叔膦配体的钯络合物,其中R 1是NHR 3或OR 4; R 2是CH 3或Cl; R 3是H,C 1 -C 4烷基,环丙基,环丙基甲基或甲基环丙基; R 4是H或C 1 -C 4烷基; M 1是碱金属; 和R 5,R 6和R 7定义在本公开内容中; 条件是当R 2为Cl时,则X为Br。 还公开了制备式5化合物的方法,其中R 14,R 15,R 16和Z如本公开所定义 使用通过上述方法制备式(1)化合物的式1化合物。

    3−ホルミル−5−トリフルオロメチルベンゾニトリル誘導体とその製造方法
    7.
    发明申请
    3−ホルミル−5−トリフルオロメチルベンゾニトリル誘導体とその製造方法 审中-公开
    3-甲基-5-三氟甲基苯并噻吩衍生物及其制备方法

    公开(公告)号:WO2005090289A1

    公开(公告)日:2005-09-29

    申请号:PCT/JP2005/002399

    申请日:2005-02-17

    发明人: 三枝 浩 成塚 智

    IPC分类号: C07C253/14

    摘要: A process for producing 3-formyl-5-trifluoromethylbenzonitrile which comprises a first step in which a 3-dihalogenomethylbenzotrifluoride represented by the general formula [1]: [Chemical formula 12] [1] [wherein X and Y represent the same or different halogeno (fluorine, chlorine, bromine, or iodine)] is brominated to obtain a 1-bromo-3-dihalogenomethyl-5-trifluoromethylbenzene represented by the general formula [2]: [Chemical formula 13] [2] [wherein X and Y represent the same or different halogeno (fluorine, chlorine, bromine, or iodine)], a second step in which the 1-bromo-3-dihalogenomethyl-5-trifluoromethylbenzene is hydrolyzed to obtain 1-bromo-3-formyl-5-trifluoromethylbenzene, and a third step in which the 1-bromo-3-formyl-5-trifluoromethylbenzene is cyanated with a cyano compound to obtain 3-formyl-5-trifluoromethylbenzonitrile.

    摘要翻译: 制备3-甲酰基-5-三氟甲基苄腈的方法,其包括第一步,其中由通式[1]表示的3-二卤甲基三氟甲苯:[化学式12] [1] [其中X和Y表示相同或不同的卤代 (氟,氯,溴或碘)]溴化,得到由通式[2]表示的1-溴-3-二卤代甲基-5-三氟甲基苯:[化学式13] [2] [其中X和Y表示 相同或不同的卤代(氟,氯,溴或碘)],其中1-溴-3-二卤代甲基-5-三氟甲基苯水解得到1-溴-3-甲酰基-5-三氟甲基苯的第二步, 和第三步,其中1-溴-3-甲酰基-5-三氟甲基苯用氰基化合物氰化,得到3-甲酰基-5-三氟甲基苄腈。

    CONTINUOUS PROCESS FOR THE CYANATION OF HYDROGENATED BETA-KETOESTERS
    8.
    发明申请
    CONTINUOUS PROCESS FOR THE CYANATION OF HYDROGENATED BETA-KETOESTERS 审中-公开
    氢化β-酮醇酯的连续反应过程

    公开(公告)号:WO2003097581A1

    公开(公告)日:2003-11-27

    申请号:PCT/GB2003/002173

    申请日:2003-05-21

    IPC分类号: C07C253/14

    摘要: The present invention relates to a continuous process for the cyanation of hydrogenated β-ketoesters in a cyanation zone maintained under conditions of temperature and pressure effective for cyanation of a hydrogenated R-ketoester. A substrate comprising a hydrogenated β-ketoester is continuously supplyed to the cyanation zone together with a cyanide. The substrate is contacted with the cyanide in the cyanation zone for a period effective for at least partial cyanation of the hydrogenated β-ketoester and a product stream is continuously extracted from the cyanation zone.

    摘要翻译: 本发明涉及在温度和压力条件下保持氰化氢化的R-酮酯氰化氢化β-酮酯的连续方法。 包含氢化β-酮酯的底物与氰化物一起连续供应到氰化区。 基底与氰化区中的氰化物接触一段有效期至少部分氰化氢化β-酮酯的时间,产物流从氰化区连续提取。

    CHEMICAL PROCESSES
    9.
    发明申请
    CHEMICAL PROCESSES 审中-公开
    化学工艺

    公开(公告)号:WO0021922A3

    公开(公告)日:2000-11-09

    申请号:PCT/EP9908135

    申请日:1999-10-11

    摘要: (57) Abstract The invention relates to a process for the preparation of a compound of formula (I): wherein, R represents C1-4 alkoxy; fluorine, chlorine or bromine; and R represents hydrogen or C1-4 alkoxy; which process comprises the reaction of the corresponding orthonitrohalobenzene of formula (II): wherein R and R are as hereinbefore defined and X represents a fluorine, chlorine or bromine atom, with, when X represents a fluorine atom: a) an alkali metal cyanide, in a non aqueous solvent optionally in the presence of a catalyst; or when X represents a chlorine atom: b) cuprous cyanide and a source of bromide selected from hydrogen bromide, bromine and a tetraalkylammonium bromide; optionally in the presence of an alkali metal bromide or an alkaline earth metal bromide; or c) an alkali metal cyanide or a tetraalkylammonium cyanide, in the presence of an alkali metal bromide or an alkaline earth metal bromide; or c) an alkali metal cyanide or a tetraalkylammonium cyanide, in the presence of cuprous bromide and a phase transfer catalyst; or d) cuprous cyanide and lithium iodide; or when X represents a bromine atom: e) cuprous cyanide optionally in the presence of a catalyst selected from an alkali metal bromide or an alkaline earth metal bromide; or f) an alkalie metal cyanide in the presence of a catalytic amount of cuprous cyanide and a phase transfer catalyst.

    摘要翻译: (57)摘要本发明涉及制备式(I)化合物的方法:其中R 1表示C 1-4烷氧基; 氟,氯或溴; 并且R 2表示氢或C 1-4烷氧基; 该方法包括相应的式(II)的邻硝基苯:其中R 1和R 2如上所定义,X代表氟,氯或溴原子,当X表示氟原子时:a )碱金属氰化物,在非水溶剂中,任选地在催化剂存在下; 或当X表示氯原子时:b)氰化亚铜和选自溴化氢,溴和四烷基溴化铵的溴化物源; 任选地在碱金属溴化物或碱土金属溴化物的存在下; 或c)碱金属氰化物或四烷基氰化铵在碱金属溴化物或碱土金属溴化物的存在下反应; 或c)在溴化亚铜和相转移催化剂存在下的碱金属氰化物或四烷基氰化铵; 或d)氰化亚铜和碘化锂; 或当X表示溴原子时:e)氰化亚铜,任选地在选自碱金属溴化物或碱土金属溴化物的催化剂存在下; 或f)在催化量的氰化亚铜和相转移催化剂存在下的碱金属氰化物。

    PROCESS FOR THE PREPARATION OF CYCLOPROPYLACETONITRILE
    10.
    发明申请
    PROCESS FOR THE PREPARATION OF CYCLOPROPYLACETONITRILE 审中-公开
    制备环丙基胆碱酯的方法

    公开(公告)号:WO00063163A1

    公开(公告)日:2000-10-26

    申请号:PCT/US2000/007878

    申请日:2000-03-24

    摘要: Disclosed is a process for the preparation and recovery of cyclopropylacetonitrile by a novel combination of process steps beginning with a mixture of cyclopropylmethyl halide, a cyclobutyl halide and a 4-halo-1-butene. The process permits the recovery of substantially pure cyclopropylacetonitrile and cyclobutyl halide, e.g., cyclopropylacetonitrile and cyclobutyl halide each having a purity greater than 95 %.

    摘要翻译: 公开了一种通过以环丙基甲基卤化物,环丁基卤化物和4-卤代-1-丁烯的混合物开始的方法步骤的新组合制备和回收环丙基乙腈的方法。 该方法允许回收基本上纯的环丙基乙腈和环丁基卤化物,例如各自具有大于95%纯度的环丙基乙腈和环丁基卤。