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WO2001055063A1 - Nouveaux composes a base de bisadamantane, procedes de production et nouveaux derives de bisadamantane - Google Patents

Nouveaux composes a base de bisadamantane, procedes de production et nouveaux derives de bisadamantane Download PDF

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Publication number
WO2001055063A1
WO2001055063A1 PCT/JP2001/000355 JP0100355W WO0155063A1 WO 2001055063 A1 WO2001055063 A1 WO 2001055063A1 JP 0100355 W JP0100355 W JP 0100355W WO 0155063 A1 WO0155063 A1 WO 0155063A1
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Prior art keywords
group
methyladamantyl
adamantyl
general formula
biadamantane
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Ceased
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PCT/JP2001/000355
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English (en)
Japanese (ja)
Inventor
Shunji Katai
Shintaro Suzuki
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Idemitsu Petrochemical Co Ltd
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Idemitsu Petrochemical Co Ltd
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Filing date
Publication date
Priority claimed from JP2000015341A external-priority patent/JP2001206859A/ja
Priority claimed from JP2000065930A external-priority patent/JP2001253853A/ja
Application filed by Idemitsu Petrochemical Co Ltd filed Critical Idemitsu Petrochemical Co Ltd
Publication of WO2001055063A1 publication Critical patent/WO2001055063A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/605—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system
    • C07C13/615—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system with an adamantane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the present invention relates to a novel (bis) adamantane-based compound which is a novel 2- (2-methyladamantyl) -12'-adamantylmethane-based compound, a method for producing the same, and a method for producing 3,3, dialkoxycarbone.
  • ' Relates to a new biadamantane derivative that is biadamantane. More specifically, a 2- (2-methyladamantyl) -12'-adamantyl methane compound, which has excellent heat resistance, water resistance and optical properties, and is useful as a component in coating materials and optical materials, etc.
  • the present invention relates to a novel biadamantane derivative which is well-produced, and which has excellent solubility in various solvents while maintaining the properties of biadamantans.
  • adamantanes have a very stable carbon skeleton and exhibit a unique function, so that they can be used for various applications.
  • optical disk substrates, optical fibers, It is used for lenses and the like Japanese Unexamined Patent Publication No. Hei 9-310207, Japanese Unexamined Patent Publication No. Hei 6-304504.
  • adamantane is mainly composed of a polymer having a monoadamantane compound as a monomer, and a substance having two or more adamantane skeletons and a derivative thereof are known, but the adamantane skeleton has a methylene group.
  • adamantane skeleton has a methylene group.
  • biadamantanes having two or more adamantane skeletons are more expensive. Heat resistance and unique functions are expected.
  • the present invention provides a novel asymmetric bisadamanone-based compound having an adamantane skeleton bonded via a methylene group, which is excellent in heat resistance, water resistance, optical properties, and the like;
  • An object of the present invention is to provide a novel biadamantane which is excellent in water resistance and optical properties and is excellent in solubility in various solvents.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, a 2- (2-methyladamantyl) -12′-adamantylmethane compound having a specific structure has not been published in the literature. It is a novel compound that has excellent heat resistance, water resistance, optical properties, etc., and that it can be efficiently produced by a specific process. Also, an alkoxycarbonyl group having 3 or more carbon atoms (carbon number Biadamantane having a specific structure having two or more alkoxy groups) is a novel compound that has not been published in the literature and has excellent heat resistance, water resistance, optical properties, etc., and excellent solubility in various solvents. Was found. The present invention has been completed based on such findings.
  • ⁇ 2 are each a hydrogen atom, a halogen atom, a hydrocarbyl group A hydroxyl group, a hydrocarbyloxy group, a carboxyl group or a hydrocarboxycarbonyl group, which may be the same or different.
  • R represents an alkyl group having 2 to 8 carbon atoms.
  • FIG. 1 is a ' ⁇ -NMR spectrum chart of the compound obtained in Example 1
  • FIG. 2 is a' 3 C-NMR spectrum chart of the compound obtained in Example 1)
  • FIG. 3 is an infrared analysis chart of the compound obtained in Example 1.
  • Figure 4 ' is t Figure 5 is .eta.
  • NMR spectrum chart of the compound obtained in Example 2' of the compound obtained in Example 2 is 3 C-NMR spectrum chart ( FIG. 6 is an infrared analysis chart of the compound obtained in Example 1.
  • the 2- (2-methyladamantyl) -1 2'-adamantyl methane compound of the present invention has the following general formula (I)
  • Y 1 and Y 2 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a hydroxyl group, a hydrocarbyloxy group, a carboxy group or a hydrocarbylcarbonyl group.
  • preferred examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the hydrocarbyl group include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an aralkyl group having 7 to 15 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various benzyl groups, various hexyl groups, various octyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups, etc.
  • the aryl group having 6 to 15 carbon atoms and the aralkyl group having 7 to 15 carbon atoms may have a substituent such as a lower alkyl group on the ring, and examples thereof include a phenyl group, a tolyl group, Xylyl, naphthyl, methylnaphthyl, benzyl, methylbenzyl, phenethyl, naphthylmethyl and the like.
  • hydrocarbyl group constituting the hydrocarbyloxy group and the hydrocarbyloxycarbonyl group examples include the same as those described above for the hydrocarbyl group.
  • Y 1 and Y 2 may be the same or different from each other.
  • 2- (2-methyladamantyl) -1′-adamantylmethane in which Y 1 and Y 2 are both hydrogen atoms and the general formula (I) In which at least one of Y 1 and Y 2 is a hydroxyl group and the remainder is a hydrogen atom (that is, both are hydroxyl groups, or one is a hydroxyl group and the remainder is a hydrogen atom).
  • Damantyl) — 1 ' a Damantimyl hydroxide is preferred.
  • the method for producing the 2- (2-methyladamantyl) -12'-adamantyl methane compound represented by the general formula (I) of the present invention is not particularly limited, but the method of the present invention shown below is provided. If it follows, it can manufacture efficiently.
  • 2-methyl-2-adamantanol (111) is dehydrated and dimerized in the presence of an acid catalyst to obtain a compound (IV), and then hydrogenated to give 2- (2-methyladamantyl)
  • 2- (2-methyladamantyl) One 2'-adamantylmethane (V) is obtained.
  • a solvent in the dehydration-dimerization reaction, the presence of a solvent is not essential, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction and is capable of dissolving the raw materials and products, and examples thereof include aliphatic hydrocarbon compounds such as hexane, heptane, and octane. Aromatic hydrocarbon compounds such as benzene, toluene and xylene are preferably used.
  • the acid catalyst examples include mineral acids such as sulfuric acid and hydrochloric acid, as well as heteropoly acids, zeolites, and ion exchange resins. These acid catalysts are based on 2-methyl-_ 2 Adaman evening Nord raw materials usually used in the proportion of ⁇ 1 0 weight 0/0.
  • the raw material concentration in the reaction system is not particularly limited, but the catalyst concentration is preferably about 0.1 to 5% by weight.
  • the temperature in the dehydration-dimerization reaction is selected in the range of usually room temperature to 150 ° C, preferably 50 to 10 ° C.
  • the reaction time depends on the reaction temperature, type and amount of catalyst, etc. The time is usually 1 to 24 hours, preferably about 1 to 3 hours.
  • the compound (IV) thus dehydrated and dimerized is isolated according to a conventional method, and is subjected to the next hydrogenation reaction.
  • a solvent in this hydrogenation reaction, the presence of a solvent is not essential, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction and is capable of dissolving the raw material and the product. Examples thereof include aliphatic hydrocarbon compounds such as hexane, heptane, and octane; Aromatic hydrocarbon compounds such as benzene, toluene and xylene are preferably used.
  • a known hydrogenation catalyst represented by, for example, a Pt catalyst, Pd / C, Ru / C, Raney Ni or the like is used as a catalyst. These hydrogenation catalysts are usually used in an amount of about 1 to 10% by weight based on the raw materials.
  • the raw material concentration in the reaction system is not particularly limited, but the hydrogenation catalyst concentration is preferably about 0.1 to 5% by weight.
  • the temperature in the hydrogenation reaction is selected in the range of usually room temperature to 250 ° C, preferably 100 to 200 ° C.
  • the hydrogen pressure is usually selected in the range of 0.5 to 5 MPa, preferably in the range of 2 to 3 MPa.
  • the reaction time depends on the reaction temperature, the hydrogen pressure, the type of the catalyst, and the like, and cannot be unconditionally determined, but is usually 1 to 1 hour, preferably about 1 to 6 hours.
  • X 1 and X 2 are halogen atom and the remainder is a hydrogen atom).
  • halogenation method various methods can be used depending on the type of halogen.
  • the case where the halogen is bromine will be described.
  • a solvent is not essential, but a solvent can be used if necessary.
  • a solvent for example, a polar solvent such as methylene chloride or carbon tetrachloride is preferably used.
  • a Lewis acid such as aluminum trihalide or boron tribromide can be used as a catalyst.
  • the temperature of the bromination reaction is usually from room temperature to about 60 ° C. A reaction time of about 1 to 10 hours is sufficient.
  • the product brominated in this manner is isolated according to a conventional method. When this product is used as a raw material and a bromine atom in a molecule is converted to another group, it can be used as a crude product without purification. Purified according to the method.
  • the desired 2- (2-methyladamantyl) -2′-adamantyl methane bromide [in the general formula (10, at least one of X ′ and X 2 is a bromine atom and the remaining Are hydrogen atoms, that is, both are bromine atoms, or one is a bromine atom and the other is a hydrogen atom).
  • 2_ (2-meth) represented by the general formula ( ⁇ ) Ladamantyl) Starting from 1'2'-adamantyl methane halide, converting at least one halogen atom into a hydrocarbyl, hydroxyl, hydrocarbyloxy, carboxyl or hydrocarbyloxycarbonyl group,
  • the 2- (2-methyladamantyl) -12'-adamantylmethane derivative of the present invention having the above-mentioned various groups in the molecule can be produced.
  • the bromide obtained as described above is preferable from the viewpoint of reactivity.
  • R, MgX, R'Li or R 'RLi R' is a hydrocarbyl group and X is a halogen atom
  • R' is a hydrocarbyl group and X is a halogen atom
  • a polar solvent such as tetrahydrofuran, 2- ( 2-methyl-adamantyl) 1 2'-adamantyl
  • 2- ( 2-methyl-adamantyl) 1 2'-adamantyl can introduce a hydrocarbyl group or hydrocarbyloxy group into methane
  • a hydrogen halide scavenger such as an organic base such as pyridine, triethylamine or dimethylformamide at a temperature of about 100 to 200 ° C for about 1 to 24 hours
  • a hydroxyl group can be introduced into 2— (2-methyladamantyl) -1 2′-adamantylmethane.
  • the hydroxyl obtained in the above (2) is used.
  • a compound having a carboxylic group is reacted with a carboxylating agent such as carbon monoxide and formic acid to carbonylate the hydroxyl group at the hydroxyl group to give 2- (2-methyladamantyl) -1 2'-adamantyl.
  • Carboxyl groups can be introduced into methane.
  • a solvent is not essential, but if necessary, a hydrocarbon solvent such as hexane can be used.
  • an R'OH R '
  • the esterification of the carboxyl group can introduce a hydrocarbyloxycarbonyl group into 2- (2-methyladamantyl) -1′-adamantylmethane.
  • a solvent is not essential, but an appropriate solvent can be used if necessary.
  • the compound of the above (3) may be treated with thionyl chloride, phosphorus pentachloride or the like to synthesize acid chloride, and then reacted with R'OLi.
  • the biadamantane derivative of the present invention has the following general formula (VI)
  • R represents an alkyl group having 2 to 8 carbon atoms (linear or branched alkyl group), specifically, an ethyl group, an ⁇ -propyl group, an isopropyl group, an ⁇ -butyl group, an isobutyl group , Sec-butyl, tert-butyl, n-amyl, isoamyl, n-hexyl, n-heptyl, n-octyl or isooctyl.
  • the two Rs in the general formula (VI) are usually the same, but may be different depending on the case.
  • the biadamantane derivative of the present invention is 3,3′-dialkoxycarbone-l-biadamantane represented by the general formula (VI), and specifically, 3,3′-diethoxycarbonyl_1, One viadamantane, 3, 3 'di ⁇ -propoxycarbone 1, one viadamantane, 3, 3' diisopropoxycarbone 2, 1, one viadamantane, 3, 3 '— di ⁇ -butoxycarbo Two-way 1 'one-viadamantane, 3, 3'-diisobutoxycarbone 1, 1, 1' one-viadamantane, 3, 3 'di-t-butoxycarbone two-one, one-viadamantane, 3, 3'- Diamiloxycarbone and one viadamantane.
  • VI 3,3′-dialkoxycarbone-l-biadamantane represented by the general formula (VI), and specifically, 3,3′-diethoxycarbonyl_1, One viadamantane, 3, 3 'di ⁇ -
  • the method for producing the biadamantane derivative of the present invention is not particularly limited.
  • Examples of the acid catalyst include mineral acids such as sulfuric acid and hydrochloric acid; organic acids such as p-toluenesulfonic acid; and Lewis acids such as boron fluoride ether.
  • Examples of reagents for converting (COOH) to acid halide (COX) include phosphoryl chloride, thionyl chloride, phosphorus pentachloride, and phosphorus trichloride.
  • the 3,3′-dicarboxy-1,1,1′-biadamantane represented by the formula (VII) used as a raw material here is biadamantane, 3,1,3′-biadamantane or 3,3′-dihydroxy It is synthesized by using 1,1'-biadamantane as a starting material and reacting it with formic acid in the presence of a strong acid such as fuming sulfuric acid, concentrated sulfuric acid or concentrated nitric acid, or in a carbon monoxide atmosphere.
  • a strong acid such as fuming sulfuric acid, concentrated sulfuric acid or concentrated nitric acid, or in a carbon monoxide atmosphere.
  • reaction solution was poured into 100 g of water, neutralized with an aqueous solution of sodium carbonate, and the product was extracted with n-heptane. The oil layer was washed with water. Thereafter, n-heptane was distilled off with a dry evaporator to obtain 29.9 g of a crude product. Next, the crude product was passed through a silica gel column, recrystallized, and dried. 6.2 g of solid A1 were obtained.
  • a 300 milliliter autoclave was charged with 15.0 g of the solid A obtained in (1) above, 3.0 g of 5% by weight Pd / C, and 150 milliliter of ⁇ -octane, and charged with 150 ml of hydrogen. It was pressurized to MPa and reacted at 20 ° C. for 5 hours.
  • Example 2 In a 100 milliliter four-necked flask equipped with a cooling tube and a dropping funnel, 6.0 g (20 millimoles) of the solid B obtained in Example 1 was charged, and the mixture was added dropwise while stirring the inside with a stirrer. 25 g of bromine was slowly dropped from the funnel. After completion of the dropwise addition, the mixture was heated to 60 ° C. in an oil bath and reacted for 4 hours.
  • the reaction solution was cooled, poured into a flask containing 100 g of ice and 50 milliliter of carbon tetrachloride, and excess bromine was treated with sodium hydrogen sulfite. After that, extraction with carbon tetrachloride, washing with water and evaporation of the solvent were performed to obtain 12.2 g of a crude bromide. Next, the crude bromide, 50 ml of pyridine and 18 ml of water were charged into a 100 ml autoclave and reacted at 150 ° C. for 6 hours. After completion of the reaction, sodium carbonate was added to the reaction solution to decompose pyridine monohydrobromide generated in the reaction.
  • Example 3 (1) Synthesis of 3,3, dimethoxycarbone 1'-biadamantane In Example 3, methanol was used in place of n-propanol, methanol was added to the reaction solution, and the filtrate was filtered. Except for concentrating and recrystallizing with methanol, the same procedure as in Example 3 was carried out to obtain 0.35 g, 98.5% purity of 3,3'-dimethoxycarbone and 1'-biadamantane. I got
  • the 2- (2-methyladamantyl) -adamantyl methane compound of the present invention is a novel asymmetric bisadamantane compound having an adamantane skeleton bonded through a methylene group, and has heat resistance and water resistance. It has excellent properties and optical properties, and is useful as a component of coating materials and optical materials. This can be efficiently produced by the method of the present invention.
  • 3,3′-dialkoxy force 1′-biadamantane a novel biadamantane derivative of the present invention, is excellent in heat resistance, water resistance, optical properties, etc., and is excellent in solubility in various solvents. It is something. Therefore, it can be used in a variety of applications, and can be widely used as optical materials such as optical disc substrates, optical fibers, lenses, and intermediates of organic chemicals.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention a trait à des composés à base de 2-(2-méthyladamantyl)-2'-adamantylméthane correspondant à la formule générale (I). Dans cette formule, Y1 et Y2 peuvent être identiques ou différents et représenter, chacun, un hydrogène, un halogéno, un hydrocarbyle, un hydroxy, un hydrocarbyloxy, un carboxyle ou un hydrocarbyloxycarbonyle. L'invention concerne également des dérivés de 3,3'-dialcoxycarbonyl-1,1'-bisadamantane correspondant à la formule générale (VI). Dans cette formule, R représente un alkyle porteur de 2 à 8 atomes de carbone. Ces nouveaux composés à base de bisadamantane et leurs dérivés font preuve de remarquables propriétés de résistance à la chaleur, à l'eau et font montre d'excellentes qualités optiques.
PCT/JP2001/000355 2000-01-25 2001-01-19 Nouveaux composes a base de bisadamantane, procedes de production et nouveaux derives de bisadamantane Ceased WO2001055063A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2000-15341 2000-01-25
JP2000015341A JP2001206859A (ja) 2000-01-25 2000-01-25 新規（ビス）アダマンタン系化合物及びその製造方法
JP2000065930A JP2001253853A (ja) 2000-03-10 2000-03-10 新規なビアダマンタン誘導体
JP2000-65930 2000-03-10

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Cited By (21)

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WO2010010174A1 (fr) 2008-07-25 2010-01-28 Boehringer Ingelheim International Gmbh Acides 1,1’-diadamantyl carboxyliques, médicaments contenant de tels composés et application associée
EP2117009A4 (fr) * 2007-02-28 2012-04-04 Sumitomo Bakelite Co Matériau isolant organique, vernis pour film isolant organique utilisant celui-ci, film isolant organique et dispositif à semi-conducteur
US8497281B2 (en) 2009-11-06 2013-07-30 Vitae Pharmaceuticals, Inc. Aryl- and heteroarylcarbonyl derivatives of hexahydroindenopyridine and octahydrobenzoquinoline
US8637505B2 (en) 2009-02-04 2014-01-28 Boehringer Ingelheim International Gmbh Cyclic inhibitors of 11beta-hydroxysteroid dehydrogenase 1
US8680093B2 (en) 2009-04-30 2014-03-25 Vitae Pharmaceuticals, Inc. Cyclic inhibitors of 11beta-hydroxysteroid dehydrogenase 1
US8686149B2 (en) 2010-11-05 2014-04-01 Boehringer-Ingelheim International Gmbh Aryl- and heteroarylcarbonyl derivatives of hexahydroindenopyridine and octahydrobenzoquinoline
US8703765B2 (en) 2009-06-02 2014-04-22 Boehringer Ingelheim International Gmbh Cyclic inhibitors of 11β-hydroxysteroid dehydrogenase 1
US8735585B2 (en) 2011-08-17 2014-05-27 Boehringer Ingelheim International Gmbh Indenopyridine derivatives
US8748444B2 (en) 2007-12-11 2014-06-10 Vitae Pharmaceuticals, Inc. Cyclic urea inhibitors of 11β-hydroxysteroid dehydrogenase 1
US8754076B2 (en) 2008-07-25 2014-06-17 Vitae Pharmaceuticals, Inc./Boehringer-Ingelheim Cyclic inhibitors of 11beta-hydroxysteroid dehydrogenase 1
US8765780B2 (en) 2008-05-13 2014-07-01 Boehringer Ingelheim International Gmbh Alicyclic carboxylic acid derivatives of benzomorphans and related scaffolds, medicaments containing such compounds and their use
US8765744B2 (en) 2010-06-25 2014-07-01 Boehringer Ingelheim International Gmbh Azaspirohexanones
US8829027B2 (en) 2008-10-23 2014-09-09 Boehringer Ingelheim International Gmbh Urea derivatives of substituted nortropanes, medicaments containing such compounds and their use
US8835426B2 (en) 2007-02-26 2014-09-16 Vitae Pharmaceuticals, Inc. Cyclic urea and carbamate inhibitors of 11β-hydroxysteroid dehydrogenase 1
US8846668B2 (en) 2008-07-25 2014-09-30 Vitae Pharmaceuticals, Inc. Inhibitors of 11beta-hydroxysteroid dehydrogenase 1
US8846613B2 (en) 2010-11-02 2014-09-30 Boehringer Ingelheim International Gmbh Pharmaceutical combinations for the treatment of metabolic disorders
US8859580B2 (en) 2007-11-16 2014-10-14 Boehringer Ingelheim International Gmbh Aryl- and heteroarylcarbonyl derivatives of benzomorphanes and related scaffolds, medicaments containing such compounds and their use
US8883778B2 (en) 2009-07-01 2014-11-11 Vitae Pharmaceuticals, Inc. Cyclic inhibitors of 11 beta-hydroxysteroid dehydrogenase 1
US8927539B2 (en) 2009-06-11 2015-01-06 Vitae Pharmaceuticals, Inc. Cyclic inhibitors of 11β-hydroxysteroid dehydrogenase 1 based on the 1,3-oxazinan-2-one structure
US8933072B2 (en) 2010-06-16 2015-01-13 Vitae Pharmaceuticals, Inc. Substituted 5-,6- and 7-membered heterocycles, medicaments containing such compounds, and their use
US9079861B2 (en) 2007-11-07 2015-07-14 Vitae Pharmaceuticals, Inc. Cyclic urea inhibitors of 11β-hydroxysteroid dehydrogenase 1

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US8835426B2 (en) 2007-02-26 2014-09-16 Vitae Pharmaceuticals, Inc. Cyclic urea and carbamate inhibitors of 11β-hydroxysteroid dehydrogenase 1
EP2117009A4 (fr) * 2007-02-28 2012-04-04 Sumitomo Bakelite Co Matériau isolant organique, vernis pour film isolant organique utilisant celui-ci, film isolant organique et dispositif à semi-conducteur
US9079861B2 (en) 2007-11-07 2015-07-14 Vitae Pharmaceuticals, Inc. Cyclic urea inhibitors of 11β-hydroxysteroid dehydrogenase 1
US8859580B2 (en) 2007-11-16 2014-10-14 Boehringer Ingelheim International Gmbh Aryl- and heteroarylcarbonyl derivatives of benzomorphanes and related scaffolds, medicaments containing such compounds and their use
US8748444B2 (en) 2007-12-11 2014-06-10 Vitae Pharmaceuticals, Inc. Cyclic urea inhibitors of 11β-hydroxysteroid dehydrogenase 1
US8765780B2 (en) 2008-05-13 2014-07-01 Boehringer Ingelheim International Gmbh Alicyclic carboxylic acid derivatives of benzomorphans and related scaffolds, medicaments containing such compounds and their use
US9073870B2 (en) 2008-05-13 2015-07-07 Boehringer Ingelheim International Gmbh Alicyclic carboxylic acid derivatives of benzomorphans and related scaffolds, medicaments containing such compounds and their use
US8846668B2 (en) 2008-07-25 2014-09-30 Vitae Pharmaceuticals, Inc. Inhibitors of 11beta-hydroxysteroid dehydrogenase 1
US8309597B2 (en) 2008-07-25 2012-11-13 Boehringer Ingelheim International Gmbh 1,1′-diadamantyl carboxylic acids, medicaments containing such compounds and their use
JP2011529031A (ja) * 2008-07-25 2011-12-01 ベーリンガー インゲルハイム インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツング １，１’−ジアダマンチルカルボン酸、このような化合物を含有する医薬及びその使用
WO2010010174A1 (fr) 2008-07-25 2010-01-28 Boehringer Ingelheim International Gmbh Acides 1,1’-diadamantyl carboxyliques, médicaments contenant de tels composés et application associée
US8754076B2 (en) 2008-07-25 2014-06-17 Vitae Pharmaceuticals, Inc./Boehringer-Ingelheim Cyclic inhibitors of 11beta-hydroxysteroid dehydrogenase 1
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