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    • 4. 发明申请
    • Method for Producing Substituted Diamantanes
    • 生成取代的金刚烷的方法
    • US20100036153A1
    • 2010-02-11
    • US12086058
    • 2006-12-04
    • Peter R. SchreinerAndrey A. Fokin
    • Peter R. SchreinerAndrey A. Fokin
    • C07C35/44C07C239/08C07C233/08C07C61/125C07C69/753
    • C07C203/08C07C29/12C07C51/353C07C67/11C07C2603/90C07C35/44C07C61/135C07C69/013C07C69/14
    • The invention at hand provides at least dinitroxylated diamantanes. In addition, it provides methods for producing substituted diamantanes with high yields and selectivity.According to the invention, dinitroxylated diamantanes are suitable for being reacted with nucleophiles to form the corresponding disubstituted diamantanes. Surprisingly, it was discovered that at least dinitroxylated or hydroxylated diamantanes are rearranged in the presence of a strong acid, creating at least 4,9-nitroxylated or hydroxylated diamantanes. On the basis of this, 4,9-substituted diamantanes are able to be produced in a targeted manner by reaction with further nucleophiles.Thus, the invention at hand provides the following methods according to the present invention for producing at least disubstituted diamantanes: a) at least dinitroxylation, followed by the substitution of all nitroxy groups by a nucleophile or b) at least dinitroxylation, subsequent rearrangement in the presence of a strong acid, after realised rearrangement all nitroxy groups are replaced by a nucleophile or c) at least dinitroxylation, subsequent reaction with water (as nucleophile), rearrangement of the at least dihydroxylated compound in the presence of a strong acid, after realised rearrangement all hydroxy groups are replaced by another nucleophile.
    • 本发明至少提供二硝基甲酰化的二金刚烷。 此外,它提供了以高产率和选择性生产取代的二金刚烷的方法。 根据本发明,二硝基氧化的二金刚烷适于与亲核试剂反应以形成相应的二取代的二金刚烷。 令人惊奇的是,发现在强酸存在下重新排列了二硝基氧化或羟基化的二金刚烷,产生了至少4,9-氨基氧化或羟基化的金刚烷。 基于此,4,9-取代的二金刚烷可以通过与另外的亲核试剂反应而以目标方式制备。 因此,本发明提供了根据本发明的用于生产至少二取代的二金刚烷的以下方法:a)至少二硝基甲酰化,然后用亲核试剂取代所有硝基,或b)至少二硝基甲酰化,随后在 强酸的存在,在实现重排之后,所有的硝基都被亲核试剂取代,或c)至少二硝基甲酰化,随后与水(作为亲核试剂)反应,在强酸存在下重排至少二羟基化的化合物, 重排所有羟基被另一个亲核试剂取代。
    • 5. 发明授权
    • Method for producing substituted diamantanes
    • 取代的二金刚烷的制备方法
    • US08716539B2
    • 2014-05-06
    • US12086058
    • 2006-12-04
    • Peter R. SchreinerAndrey A. Fokin
    • Peter R. SchreinerAndrey A. Fokin
    • C07C13/28
    • C07C203/08C07C29/12C07C51/353C07C67/11C07C2603/90C07C35/44C07C61/135C07C69/013C07C69/14
    • Dinitroxylated diamantanes are suitable for being reacted with nucleophiles to form the corresponding disubstituted diamantanes. Surprisingly, at least dinitroxylated or hydroxylated diamantanes are rearranged in the presence of a strong acid and at least 4,9-nitroxylated or hydroxylated diamantanes are created. On this basis, 4,9-substituted diamantanes are able to be produced in a targeted manner by reaction with further nucleophiles. Methods for producing at least disubstituted diamantanes include: (a) at least dinitroxylation, followed by the substitution of all nitroxy groups by a nucleophile; or (b) at least dinitroxylation, the subsequent rearrangement in the presence of a strong acid, after realized rearrangement all nitroxy groups are replaced by a nucleophile; or (c) at least dinitroxylation, then subsequent reaction with water (as nucleophile), and rearrangement of the at least dihydroxylated compound in the presence of a strong acid, all hydroxy groups being replaced by another nucleophile in the event of a successful rearrangement.
    • 二硝基甲酰基二金刚烷适于与亲核试剂反应形成相应的二取代二金刚烷。 令人惊讶的是,至少在强酸存在下重新排列二硝基甲氧基化或羟基化的金刚烷,并产生至少4,9-硝酰化或羟基化的二金刚烷。 在此基础上,能够通过与另外的亲核试剂反应,以目标方式制备4,9-取代的二金刚烷。 生产至少二取代的二金刚烷的方法包括:(a)至少二硝基甲酰化,然后用亲核试剂代替全部硝基; 或(b)至少二硝基甲酰化,随后在强酸存在下的重排,在实现重排之后,所有的硝酰基被亲核试剂替代; 或(c)至少二硝基甲酰化,然后随后与水(作为亲核试剂)反应,并且在强酸存在下重排至少二羟基化的化合物,在成功重排的情况下,所有羟基都被另一个亲核试剂取代。
    • 7. 发明申请
    • Amidoadamantanes and Method for Producing the Same
    • 酰胺金刚烷及其制备方法
    • US20090299096A1
    • 2009-12-03
    • US12224545
    • 2007-02-20
    • Peter R. SchreinerAndrey A. FokinLukas WankaDerek M. Wolfe
    • Peter R. SchreinerAndrey A. FokinLukas WankaDerek M. Wolfe
    • C07C233/03C07C231/08
    • C07C233/03C07C231/08C07C2603/74
    • The invention relates to 1-formamido-adamantane derivatives of formula (I), which carry the substituents R1, R2 or R3 in 3, 5 and/or 7 position, the substituents being defined as follows: hydrogen, a linear or branched alkyl, alkenyl or alkinyl group with up to 6 C atoms, an aliphatic or aromatic, cyclic or heterocyclic hydrocarbon group with up to 10 carbon atoms, and formamides of hydrocarbons from the group of diamondoids, for example diamantane, triamantane, tetramantane and pentamantane, however, with the exception of 1-formamido-3,5-dimethyladamantane. The invention also relates to a method for the direct formation of formamide or acetamide of adamantane, adamantane derivatives with the aforementioned definition of substituents or of a hydrocarbon from the group of diamondoids, characterized by reacting the adamantane, the adamantane derivative or the diamondoid with formamide, acetamide or acetonitrile in concentrated acids, while avoiding SO3 containing sulfuric acid or 100% azotic acid.
    • 本发明涉及式(I)的1-甲酰氨基 - 金刚烷衍生物,其在3,5和/或7位上具有取代基R 1,R 2或R 3,取代基定义如下:氢,直链或支链烷基, 具有至多6个C原子的链烯基或炔基,具有至多10个碳原子的脂族或芳族,环状或杂环烃基,以及来自金刚石类的例如金刚烷,三金刚烷,四聚烷和五金刚烷烃的甲酰胺, 除了1-甲酰氨基-3,5-二甲基金刚烷外。 本发明还涉及直接形成甲酰胺或乙酰胺的金刚烷,金刚烷衍生物,具有上述定义的取代基或来自金刚石类的烃,其特征在于使金刚烷,金刚烷衍生物或金刚石与甲酰胺反应 ,乙酰胺或乙腈在浓缩酸中,同时避免SO 3含硫酸或100%偶氮酸。
    • 9. 发明申请
    • MONOETHERIFIED DIOLS OF DIAMONDOIDS
    • 单一的DIAMONDOID DIOLS
    • US20110124912A1
    • 2011-05-26
    • US12996399
    • 2009-06-02
    • Peter R. SchreinerHartmut Schwertfeger
    • Peter R. SchreinerHartmut Schwertfeger
    • C07C227/02C07C43/196C07C41/09C07C231/06C07C213/02
    • C07C41/09C07C43/196C07C215/44C07C217/52C07C229/50C07C233/23C07C2603/90Y02P20/55
    • The invention at hand describes functionalized diols of diamondoids, in which one of the two hydroxy groups is masked by a protective group, as well as methods for producing these functionalized diols. The protective group is a group —CHR1R2, wherein R1 and R2 stand for alkyl groups and the protective group comprises at least one halogen atom. The monoethers of the diamondoid diols according to the present invention are produced by reacting the diamondoid diol with a halogenated alcohol CHOHR1R2 in the presence of a catalyst acid.The monoetherified diols allow for the targeted production of derivatives of diamondoids, for example, of the corresponding aminoalcohols and aminocarboxylic acids. For that purpose, the diamondoid monoether is reacted in a first step with a halogen nitrile in a Ritter reaction to the corresponding monoether amide. From this monoether amide, the corresponding aminoalcohol can be produced by reacting the protective group —CHR1R2 first with trifluoroacetic acid to the alkanoyloxy group and by subsequently obtaining the aminoalcohol by reaction with thiourea, ethanol and glacial acetic acid.The aminoalcohol can be reacted with a sulfuric acid/formic acid or oleum/formic acid to the corresponding aminocarboxylic acid.The amino, hydroxy and carboxylic groups of the diamondoids can be converted into many other functional groups.
    • 本发明描述了金刚石的官能化二醇,其中两个羟基中的一个被保护基掩蔽,以及制备这些官能化二醇的方法。 保护基是基团-CHR1R2,其中R1和R2代表烷基,保护基包括至少一个卤素原子。 根据本发明的金刚石二醇的单醚通过在催化剂酸的存在下使类金刚石二醇与卤代醇CHOHR1R2反应来制备。 单醚化的二醇允许目标生成类金刚石衍生物,例如相应的氨基醇和氨基羧酸。 为此,金刚石单醚在第一步中与Ritter反应中的卤素腈与相应的单醚酰胺反应。 从该单醚酰胺可以通过使保护基-CHR1R2与三氟乙酸首先与烷酰氧基反应,随后通过与硫脲,乙醇和冰醋酸反应得到氨基醇来制备相应的氨基醇。 氨基醇可以与硫酸/甲酸或发烟硫酸/甲酸反应至相应的氨基羧酸。 金刚石的氨基,羟基和羧基可以转化为许多其他官能团。