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    • 1. 发明授权
    • Production of nabumetone or precursors thereof
    • 萘丁酮或其前体的生产
    • US5907069A
    • 1999-05-25
    • US9510
    • 1998-01-20
    • Brian F. BecnelMahmood SabahiKevin J. Theriot
    • Brian F. BecnelMahmood SabahiKevin J. Theriot
    • B01J31/24B01J31/34C07B61/00C07C37/00C07C39/38C07C41/16C07C41/42C07C43/225C07C45/00C07C45/51C07C45/62C07C45/68C07C45/69C07C45/74C07C47/575C07C49/255C07C39/14C07C41/00C07C47/52
    • C07C49/255C07C37/00C07C41/16C07C41/34C07C41/40C07C41/42C07C45/004C07C45/512C07C45/62C07C45/68C07C45/74C07C47/575
    • In producing nabumetone or precursor thereof, use is made of 2-bromo-6-methoxynaphthalene formed by (a) methylating 6-bromo-2-naphthol with methyl bromide or methyl chloride, in a halogen-free liquid solvent comprising at least about 40% by weight of one or more compounds of the formula RZ where R is a hydrogen atom or an alkyl group, and Z is a hydroxyl group or a cyanide group with the proviso that if Z is a cyanide group, R is an alkyl group, and in the presence of at least one strong base; and (b) recovering and purifying 2-bromo-6-methoxynaphthalene so formed. The 6-bromo-2-naphthol in turn is preferably formed by reacting 1,6-dibromo-2-naphthol with hydrogen in a halogen-containing liquid solvent comprising at least about 50% by weight of (A) at least one liquid organic halide solvent in which the halogen content has an atomic number of 35 or less or (B) a mixture of water and at least one such liquid organic halide solvent, and in the presence of catalytic amounts of (i) a tungsten carbide-based catalyst, and (ii) at least one phase transfer catalyst, most preferably while purging HBr from the reaction mixture as it is formed. In this way, the quantities of by-products formed in the overall operation are reduced, the need for use of excess iron and/or dimethyl sulfate as reaction components is avoided, and the overall efficiency of plant operation is improved especially when conducted on a large scale.
    • 在制备萘布酮或其前体时,使用通过(a)在含卤素的液体溶剂中将6-溴-2-萘酚与甲基溴或甲基氯甲基化形成的2-溴-6-甲氧基萘,所述无卤液体溶剂包含至少约40 重量%的一种或多种式RZ化合物,其中R是氢原子或烷基,Z是羟基或氰基,条件是如果Z是氰基,则R是烷基, 并且在至少一个强碱的存在下; 和(b)回收和纯化如此形成的2-溴-6-甲氧基萘。 优选6-溴-2-萘酚通过在含卤素的液体溶剂中使1,6-二溴-2-萘酚与氢反应形成,该溶剂包含至少约50重量%的(A)至少一种液体有机物 卤素溶剂,其中卤素含量为35或更小的原子序数或(B)水和至少一种这样的液体有机卤化物溶剂的混合物,并且在催化量(i)碳化钨基催化剂 ,和(ii)至少一种相转移催化剂,最优选当其形成时从反应混合物中吹扫HBr。 以这种方式,减少了在整个操作中形成的副产物的数量,避免了使用过量的铁和/或硫酸二甲酯作为反应组分的需要,并且特别是当在 大规模
    • 2. 发明授权
    • Production of racemic 2-(6-methoxy-2-naphthyl) propionic acid of
precursors thereof
    • 外消旋的2-(6-甲氧基-2-萘基)丙酸的前体的制备
    • US5792886A
    • 1998-08-11
    • US780309
    • 1997-01-08
    • Mahmood SabahiKevin J. TheriotBrian F. Becnel
    • Mahmood SabahiKevin J. TheriotBrian F. Becnel
    • B01J31/34C07B61/00C07C29/58C07C37/00C07C39/38C07C41/09C07C41/16C07C41/30C07C41/40C07C41/42C07C43/215C07C43/225C07C51/09C07C51/14C07C59/64C07C59/72C07C67/343C07C69/734C07F3/02C07F3/06C07C62/06
    • C07C41/16C07C29/58C07C59/64
    • In producing (.+-.)-2-(6-methoxy-2-naphthyl)propionic acid or precursor thereof from 2-bromo-6-methoxynaphthalene, use is made of 2-bromo-6-methoxynaphthalene formed by (a) methylating 6-bromo-2-naphthol with methyl chloride in a solvent comprising one or more compounds, RZ, where R is a hydrogen atom or an alkyl group, and Z is --OH or --CN provided that if Z is --CN, R is alkyl, and in the presence of a strong base; and (b) recovering and purifying 2-bromo-6-methoxynaphthalene so formed. Preferably, the 6-bromo-2-naphthol is formed by (1) reacting 1,6-dibromo-2-naphthol with hydrogen, in a solvent comprising (a) organic halide in which the halogen has an atomic number of 35 or less or (b) a mixture of water and such organic halide, and in the presence of catalytically effective amounts of (i) a tungsten carbide-based catalyst, and (ii) phase transfer catalyst; and (2) separating 6-bromo-2-naphthol from the organic halide solvent so that the 6-bromo-2-naphthol is substantially free of halogen-containing impurities before use in the above methylation reaction. This technology makes possible reductions in quantities of co-products formed, eliminates need for use of excess iron and/or dimethyl sulfate as reaction components, and makes possible improvements in plant operating efficiency. Precursors of (.+-.)-2-(6-methoxy-2-naphthyl)propionic acid formed from such 2-bromo-6-methoxynaphthalene are Grignard reagent of 2-bromo-6-methoxynaphthalene, bis(6-methoxy-2-naphthyl)zinc, 6-methoxy-2-naphthylzinc halide, 6-methoxy-2-naphthyllithium, 6-methoxy-2-naphthylcopper(I), bis(6-methoxy-2-naphthyl)cadmium, 6-methoxy-2-naphthylcadmium halide, and 6-methoxy-2-vinylnaphthalene.
    • 在2-溴-6-甲氧基萘中制备(+/-) - (6-甲氧基-2-萘基)丙酸或其前体时,使用通过(a)甲基化形成的2-溴-6-甲氧基萘 6-溴-2-萘酚与甲基氯在溶剂中的一种或多种化合物RZ,其中R是氢原子或烷基,Z是-OH或-CN,条件是如果Z是-CN,则R是 烷基,并在强碱存在下进行。 和(b)回收和纯化如此形成的2-溴-6-甲氧基萘。 优选地,6-溴-2-萘酚通过以下步骤形成:(1)使1,6-二溴-2-萘酚与氢反应,在包含(a)卤素原子数为35以下的有机卤化物的溶剂中 和(b)水和这种有机卤化物的混合物,并且在催化有效量的存在下,(i)碳化钨基催化剂和(ii)相转移催化剂; 和(2)从有机卤化物溶剂中分离出6-溴-2-萘酚,使得6-溴-2-萘酚在上述甲基化反应中使用前基本上不含含卤杂质。 该技术可以减少形成的共同产品的数量,消除了使用过量的铁和/或硫酸二甲酯作为反应组分的需要,并且可以提高设备运行效率。 由这种2-溴-6-甲氧基萘形成的(+/-) - (6-甲氧基-2-萘基)丙酸的前体是2-溴-6-甲氧基萘的格利雅试剂,双(6-甲氧基-2 - 萘基)锌,6-甲氧基-2-萘基锌卤化物,6-甲氧基-2-萘基锂,6-甲氧基-2-萘基铜(I),双(6-甲氧基-2-萘基)镉,6-甲氧基-2 - 萘基镉卤化物和6-甲氧基-2-乙烯基萘。
    • 3. 发明授权
    • Production of nabumetone or precursors thereof
    • 萘丁酮或其前体的生产
    • US5756851A
    • 1998-05-26
    • US731806
    • 1996-10-21
    • Brian F. BecnelMahmood SabahiKevin J. Theriot
    • Brian F. BecnelMahmood SabahiKevin J. Theriot
    • B01J31/24B01J31/34C07B61/00C07C37/00C07C39/38C07C41/16C07C41/42C07C43/225C07C45/00C07C45/51C07C45/62C07C45/68C07C45/69C07C45/74C07C47/575C07C49/255C07C49/115C07C41/00
    • C07C49/255C07C37/00C07C41/16C07C41/34C07C41/40C07C41/42C07C45/004C07C45/512C07C45/62C07C45/68C07C45/74C07C47/575
    • In producing nabumetone or precursor thereof, use is made of 2-bromo-6-methoxynaphthalene formed by (a) methylating 6-bromo-2-naphthol with methyl bromide or methyl chloride, in a halogen-free liquid solvent comprising at least about 40% by weight of one or more compounds of the formula RZ where R is a hydrogen atom or an alkyl group, and Z is a hydroxyl group or a cyanide group with the proviso that if Z is a cyanide group, R is an alkyl group, and in the presence of at least one strong base; and (b) recovering and purifying 2-bromo-6-methoxynaphthalene so formed. The 6-bromo-2-naphthol in turn is preferably formed by reacting 1,6-dibromo-2-naphthol with hydrogen in a halogen-containing liquid solvent comprising at least about 50% by weight of (A) at least one liquid organic halide solvent in which the halogen content has an atomic number of 35 or less or (B) a mixture of water and at least one such liquid organic halide solvent, and in the presence of catalytic amounts of (i) a tungsten carbide-based catalyst, and (ii) at least one phase transfer catalyst, most preferably while purging HBr from the reaction mixture as it is formed. In this way, the quantities of by-products formed in the overall operation are reduced, the need for use of excess iron and/or dimethyl sulfate as reaction components is avoided, and the overall efficiency of plant operation is improved especially when conducted on a large scale.
    • 在制备萘布酮或其前体时,使用通过(a)在含卤素的液体溶剂中将6-溴-2-萘酚与甲基溴或甲基氯甲基化形成的2-溴-6-甲氧基萘,所述无卤液体溶剂包含至少约40 重量%的一种或多种式RZ化合物,其中R是氢原子或烷基,Z是羟基或氰基,条件是如果Z是氰基,则R是烷基, 并且在至少一个强碱的存在下; 和(b)回收和纯化如此形成的2-溴-6-甲氧基萘。 优选6-溴-2-萘酚通过在含卤素的液体溶剂中使1,6-二溴-2-萘酚与氢反应形成,该溶剂包含至少约50重量%的(A)至少一种液体有机物 卤素溶剂,其中卤素含量为35或更小的原子序数或(B)水和至少一种这样的液体有机卤化物溶剂的混合物,并且在催化量(i)碳化钨基催化剂 ,和(ii)至少一种相转移催化剂,最优选当其形成时从反应混合物中吹扫HBr。 以这种方式,减少了在整个操作中形成的副产物的数量,避免了使用过量的铁和/或硫酸二甲酯作为反应组分的需要,并且特别是当在 大规模。
    • 8. 发明授权
    • Process for preparing Michael addition products
    • 迈克尔加成产物的制备方法
    • US5347043A
    • 1994-09-13
    • US169261
    • 1993-12-20
    • Mahmood SabahiRobert G. Irwin
    • Mahmood SabahiRobert G. Irwin
    • C07C67/343C07C69/34C07C67/00C07C67/465C07C69/38
    • C07C67/343
    • Dialkyl malonate/alkyl acrylate Michael addition product mixtures having at least three acceptor moieties in a substantial number of the molecules can be consistently prepared without the need for long reaction times or the use of a large excess of the acceptor when the reaction is effected by gradually adding one molar proportion of a dialkyl malonate to at least three molar proportions of an alkyl acrylate which has been preheated to 60.degree.-80.degree. C. in admixture with an initiator and a phase transfer catalyst. In a preferred embodiment, the preheated mixture is maintained at 60.degree.-80.degree. C. for at least one hour before the dialkyl malonate is added in order to increase the percentage of product composed of the heavier components.
    • 丙二酸二烷基酯/丙烯酸烷基酯在相当数量的分子中具有至少三个受体部分的迈克尔加成产物混合物可以一致地制备,而不需要长的反应时间或当反应通过逐渐地进行反应时使用大量过量的受体 将1摩尔比例的丙二酸二烷基酯加入到至少三摩尔比例的丙烯酸烷基酯中,该丙烯酸烷基酯与引发剂和相转移催化剂混合预热至60-80℃。 在优选的实施方案中,将预热的混合物在加入丙二酸二烷基酯之前保持在60-80℃至少1小时以增加由较重组分组成的产物的百分比。
    • 10. 发明授权
    • Diimines and secondary diamines
    • 二亚胺和仲胺
    • US08212078B2
    • 2012-07-03
    • US11909824
    • 2005-12-30
    • John Y. LeePaul L. WigginsJudit OrgadMahmood SabahiVernon O. BrandtDavid W. Owens
    • John Y. LeePaul L. WigginsJudit OrgadMahmood SabahiVernon O. BrandtDavid W. Owens
    • C07C211/00
    • C07C211/12C07C211/51C08G18/10C08G18/3234C08G18/324C08G18/325C08G18/5024C08G18/6685C08G18/7671Y02P20/582
    • This invention provides aromatic diimines where the diimines have imino groups with at least two carbon atoms, and either are in the form of one benzene ring having two imino groups on the ring, which imino groups are meta or para relative to each other, and in which each position ortho to an imino group bears a hydrocarbyl group, or are in the form of two benzene rings connected by an alkylene bridge and having one imino group on each ring, and in which each position ortho to an imino group bears a hydrocarbyl group. This invention also provides aromatic secondary diamines where the diamines have amino hydrocarbyl groups with at least two carbon atoms, and either are in the form of one benzene ring having two amino groups on the ring, which amino groups are meta or para relative to each other, and in which each position ortho to an amino group bears a hydrocarbyl group, or are in the form of two benzene rings connected by an alkylene bridge and having one amino group on each ring, and in which each position ortho to an amino group bears a hydrocarbyl group. Also provided are processes for forming diimines and secondary diamines from primary diamines, including the aromatic diimines and aromatic secondary diamines of the invention.
    • 本发明提供芳族二亚胺,其中二亚胺具有至少两个碳原子的亚氨基,并且是环上具有两个亚氨基的一个苯环的形式,该亚氨基相对于彼此是间位或对位的,并且在 其中每个位于亚氨基的邻位具有烃基,或者是由亚烷基桥连接并在每个环上具有一个亚氨基的两个苯环的形式,并且其中亚氨基的邻位各有一个烃基 。 本发明还提供芳族仲二胺,其中二胺具有至少两个碳原子的氨基烃基,并且是环上具有两个氨基的一个苯环的形式,该氨基相对于彼此是间位或对位的 并且其中氨基的每个位置具有烃基,或者为两个苯环的形式,其通过亚烷基桥连接并且在每个环上具有一个氨基,并且其中氨基的邻位各自承载 烃基。 还提供了由伯二胺形成二亚胺和仲二胺的方法,包括本发明的芳族二亚胺和芳族仲二胺。