WO2000014076A1 - Procede de fabrication de composes de triazine 2,4-dihydroxyphenyle et 2-hydroxy-4-alcoxyphenyle substituee - Google Patents

Procede de fabrication de composes de triazine 2,4-dihydroxyphenyle et 2-hydroxy-4-alcoxyphenyle substituee Download PDF

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Publication number
WO2000014076A1
WO2000014076A1 PCT/US1999/020170 US9920170W WO0014076A1 WO 2000014076 A1 WO2000014076 A1 WO 2000014076A1 US 9920170 W US9920170 W US 9920170W WO 0014076 A1 WO0014076 A1 WO 0014076A1
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Prior art keywords
formula
compound
reaction
reaction mixture
amount
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PCT/US1999/020170
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English (en)
Inventor
Ram B. Gupta
Dennis J. Jakiela
Sampath Venimadhavan
Russell C. Cappadona
Venkatrao K. Pai
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Ciba Specialty Chemicals Holding Inc.
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Priority to AU59073/99A priority Critical patent/AU5907399A/en
Publication of WO2000014076A1 publication Critical patent/WO2000014076A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/20—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with no nitrogen atoms directly attached to a ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms

Definitions

  • the invention relates to a process of making substituted triazine compounds and mixtures of substituted triazine compounds.
  • the invention particularly relates to a process of making mono- and bis-(2-hydroxy-4-alkoxyphenyl) substituted triazines, mono- and bis- (2,4-bishydroxyphenyl) substituted triazines, and mixtures thereof.
  • the invention further relates to triazine compounds and mixtures of triazine compounds formed by the process.
  • UV radiation Although exposure to sunlight and other sources of ultraviolet (UV) radiation can cause the embrittlement and yellowing of some polymers, this polymer degradation may be inhibited by mixing or coating susceptible polymers with compounds known as UV stabilizers.
  • Trisaryltriazine compounds are particularly effective UV stabilizers, especially those of Formula I:
  • Ar, and Ar 2 are aryl or substituted aryl, and R indicates any type of substitution about the 2-hydroxyphenyl ring.
  • 2-(2-hydroxyl-4-alkoxyphenyl)-4,6-bisaryl- 1,3,5- triazine compounds exhibit high inherent light stability and permanence.
  • UV stabilizers such as benzotriazoles and benzophenones
  • 2-(2-hydroxyl-4-alkoxyphenyl)-4,6-bisaryl- 1,3,5- triazine compounds exhibit high inherent light stability and permanence.
  • Ar, and Ar 2 are aryl or substituted aryl, and R is alkyl or substituted alkyl.
  • R is alkyl or substituted alkyl.
  • 2-(2 -hydroxyl-4-alkoxyphenyl)-4,6-bisaryl- 1,3,5- j Q triazine compounds include Tinuvin® 1577, Cyasorb® UV-1164, Cyasorb® UV-1164L, and Tinuvin® 400.
  • U.S. Patent No. 5,726,310 instead discloses a one pot method of making 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-triazine in which cyanuric chloride is reacted with m-xylene in the presence of a Lewis acid to produce the intermediate 2-chloro-
  • U.S. Patent No. 3,244,708 discloses a method of producing ether substituted aryl triazines from resorcinol substituted triazines wherein a base is used to deprotonate the phenolic proton prior to addition of an alklylhalide.
  • U.S. Patent Nos. 5,084,570 and 5,106,972 disclose a process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-diaryl-triazines from an intermediate 2-methylthio-4,6-diaryl- r triazine.
  • this reaction can provide sufficient amounts of certain 2-chloro-4,6-aryl-l,3,5-triazine compounds.
  • These 30 may then be reacted with resorcinol in another reaction catalyzed by aluminum chloride to form the corresponding 2-chloro-4,6-bis(2,4-dihydroxyphenyl)-l,3,5-triazine compounds, as shown in Scheme II:
  • R Alkyl group
  • 35 aryl groups typically forms a mixture of products that are difficult to separate.
  • Another disadvantage of this process is that the type of aryl group initially reacted with cyanuric chloride can have a dramatic effect on the resulting product mixture. Consequently, variation of the aryl group can lead to unanticipated extraction, separation and purification problems. These problems render the formation of mixed aryl triazine compounds especially difficult.
  • the present invention addresses these problems and provides a more economical, efficient, and straight-forward means of making mixed aryl triazine compounds.
  • the present invention avoids the problems described above in part by employing the catalyzed reaction of aryl ethers and halogenated triazine compounds. Many of these reactions are heretofor uncharacterized. For example, the present inventors could not find in the literature a description of the reaction of 3-alkoxyphenol and a 2,4-bischloro-6-aryl- 1 ,3,5-triazine. It was consequently unclear what such a reaction would yield, as shown in Scheme V:
  • the present invention encompasses a process for preparing compositions comprising j 0 triazine compounds.
  • the invention further encompasses specific triazine compounds especially useful as UV inhibitors.
  • Formula B 30 and Ar is a radical of a compound of Formula C:
  • R,, R 2 , R 3 , R 4 , R 5 , Rg, R 7 , R 8 , R , and R, 0 are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 10 24 carbon atoms, alkoxy, amine, or thiol, and R t and R 7 taken together, R 7 and R 8 taken together, R 8 and R, taken together, or R > and R, 0 taken together may be part of a fused carbocyclic ring optionally containing O, N or S atoms.
  • This process has two steps. In step one, a suitable amount of a compound of Formula D:
  • This reaction is conducted at a suitable temperature and pressure and for a time sufficient to produce a first reaction mixture.
  • step two of this embodiment the first reaction mixture is reacted with a suitable 25 amount of a compound of Formula C in the presence of a second catalyst.
  • This reaction is conducted at a suitable temperature and pressure and for a time sufficient to produce a second reaction mixture comprising the composition.
  • a second embodiment of the present invention also encompasses a process for making compositions comprising compounds of Formula A.
  • a 3 compound of Formula F is also encompasses a process for making compositions comprising compounds of Formula A.
  • R,, R 2 , R 3 , R 4 , R 5 , R ⁇ , R', and R" are the same or different and are each hydrogen, cycloalkyl, aralkyl or aryl, X is CH 2 , O, NRs or S, Y is halogen, and n is 0, 1 or 2. These compounds are particularly effective UV stabilizers.
  • This invention relates to a new process of making substituted triazine compounds wherein a di-halogenated triazine compound is reacted with one or more aromatic compounds.
  • This process solves a variety of the synthetic difficulties characteristic of prior art processes.
  • the present invention encompasses a process of making a composition comprising at least one triazine compound of Formula A:
  • R,, R 2 , R 3 , R 4 , R 5 , Rg, R 7 , R g , R,, and R, 0 are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, alkoxy, amine, or thiol, and Rg and R 7 taken together, R 7 and R 8 taken together, R 8 and , taken together, or R, and R, 0 taken together may be part of a fused carbocyclic ring optionally containing O, N or S atoms.
  • Formula B in the present disclosure is understood to include substituted phenol wherein the substitution group may be in any position on the ring.
  • the alkoxy group includes but is not limited to an ether of formula -OR, wherein the R group comprises an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, septyl, octyl, nonyl, decyl, saturated or unsaturated, in straight chain, branched, or cyclic form.
  • the R group may be substituted with at least one additional group, such group including hydroxy, alkyl saturated or unsaturated, in straight chain, branched, or cyclic form, alkoxy (e.g.
  • aryl groups indicated by Ar may be substituted or unsubstituted aryl groups, including but not limited to phenyl, alkylphenyl, alkoxyphenyl, halophenyl, alkoxyhalophenyl, aminophenyl, biphenyl, substituted biphenyl, naphthalene, teralin, substituted naphthalenes and tetralins, or any oxy, alkoxy, nitro, amide, amine. thiol, alkylthiol, or halogen derivatives thereof.
  • the process of the present invention is based in part upon the inventors' unexpected discovery that under certain conditions, specific reactions such as the catalyzed reaction of monoaryl-bishalogenated triazines and 3-alkoxyphenol, yield mono- and bis(2-hydroxy-4- alkoxy)-l,3,5-triazine compounds with good selectivity.
  • This reaction may be a single-pot reaction.
  • the reaction of monoaryl-bishalogenated triazines and trialkoxyphenyl or dialkoxyphenyl compounds, such as 1,3-dialkoxyphenyl causes the selective dealkylation of the alkoxypheny compounds.
  • the compound of Formula B preferably is in sufficient amount to react with the dihalogenated triazine compound of Formula D to produce a compound of Formula F in as high a yield as possible.
  • the amount should be between about 0.8 to 2 mol equivalents based on the amount of halogens present in the triazine compound of Formula D.
  • a catalyst and more preferably by a Lewis acid catalyst.
  • the catalyst should be present in a sufficient amount to react with the number of halogens being substituted.
  • Suitable Lewis acid catalysts may be, for example. A1C1 3 , AlBr 3 , or any other Lewis acid suitable for a Friedels-Craft reaction.
  • the preferred Lewis acid is aluminum chloride. Based on the amount of 2,4-chloro-6-bisaryl-l,3,5-triazine, the preferred amount of Lewis acid is between about 0.25 to 7.0 mol equivalents to each chloride present in the precursor chlorotriazine compound.
  • the reaction shown in Scheme VIII is conducted in a solvent, which may be any of those known by those skilled in the art to be suitable for Friedels-Craft reactions. It is preferred, however, that the solvent be a halogenated benzene such as chlorobenzene, dichlorobenzene, trichlorobenzene, 1,1,2,2-tetrachloroethane, bromobenzene, dibromobenzene, tribromobenzene, etc., toluene, dimethylbenzene, trimethylbenzene, in any substitution pattern, nitrobenzene, anisole, or mixtures of these with one another.
  • a solvent which may be any of those known by those skilled in the art to be suitable for Friedels-Craft reactions. It is preferred, however, that the solvent be a halogenated benzene such as chlorobenzene, dichlorobenzene, trichlorobenzene, 1,1,2,2-tetrachloroethane, bromobenzen
  • the temperature range for the reaction shown in Scheme VIII is between 0°C to about 120°C, more preferably between about 10°C to 80°C. Precise temperatures are varied, however, depending upon the type of catalyst used, the pressure under which the reaction occurs, and the exact identities of the compounds of Formulas B and D. Similarly, the time required for the reaction to go to completion will vary with catalyst and reactants, as well as with temperature and pressure. The present processes are preferably performed at about atmospheric pressure, however, and so the preferred reaction time is between about 0.5 hours and about 40 hours, more preferably between about 2.5 hours and about 20 hours.
  • Reaction completion may be determined by conventional means known to those of skill in the art, including, for example, 'H NMR, visible, UV and IR optical spectroscopy, and chromatography.
  • Step two of the process of this invention may commence immediately following the completion of step one. If step one does not entail the isolation of a compound of Formula F from the first reaction mixture, then step two may also commence after the reaction mixture has cooled down. It has been found that the duration of cooling depends upon several factors, such as the temperature at which the reaction of step two is to be conducted, and the stability of reaction intermediates. It is preferred, however, that if cooling is allowed, that it be done for a period of time of between about 0.25 hours and about 5 hours.
  • Step two involves the reaction of the product or product mixture of step one with a compound of Formula C:
  • R, R 2 , R 3 , R 4 , R 5 , R ⁇ , R 7 , R 8 , R ⁇ > , and R, 0 are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, , alkoxy, amine, or thiol, and R ⁇ and R 7 taken together, R 7 and R 8 taken together, R 8 and R, taken together, or R, and R, 0 taken together may be part of a fused carbocyclic ring optionally containing O, N or S atoms.
  • the compound of Formula C may be substituted or unsubstituted aryl groups, including but not limited to phenyl, alkylphenyl, alkoxyphenyl, halophenyl, alkoxy halophenyl, aminophenyl, biphenyl, substituted biphenyl, naphthalene, teralin, substituted naphthalenes and tetralins, or any oxy, alkoxy, nitro, amide, amine, thiol, alkylthiol, or halogen derivatives thereof.
  • aryl groups including but not limited to phenyl, alkylphenyl, alkoxyphenyl, halophenyl, alkoxy halophenyl, aminophenyl, biphenyl, substituted biphenyl, naphthalene, teralin, substituted naphthalenes and tetralins, or any oxy, alkoxy, nitro, amide,
  • step two of the process utilizes the crude reaction mixture formed in step one or the isolated compound of Formula F
  • the fundamental reaction of step two is shown in Scheme IX:
  • the compound of Formula C should be in sufficient amount to react with the halogenated triazine compound of Formula F to produce the desired final composition. Preferably the amount should be between about 0.8 to 2 mol equivalents of the triazine compound of Formula F.
  • This reaction like the first, is facilitated by a catalyst, and more preferably a Lewis acid catalyst.
  • the catalyst should be present in a sufficient amount to react with the number of halogens being substituted.
  • Suitable Lewis acid catalysts may be, for example, A1C1 3 , AlBr 3 , or any other Lewis acid suitable for a Friedels-Craft reaction. The list is not intended to be all encompassing, simply demonstrative.
  • the preferred Lewis acid is aluminum chloride. Based on the amount of 2,4-chloro-6-bisaryl-l,3,5-triazine, the preferred amount of Lewis acid is between about 0.25 to 7.0 mol equivalents to each chloride present in the precursor chlorotriazine compound.
  • the reaction shown in Scheme IX is also conducted in a solvent, which may be any of those known to those skilled in the art to be suitable for Friedels-Craft reactions. It is preferred, however, that the solvent be a halogenated benzene such as chlorobenzene, dichlorobenzene, trichlorobenzene, 1,1,2,2-tetrachloroethane, bromobenzene, dibromobenzene, tribromobenzene, etc., toluene, dimethylbenzene, trimethylbenzene. in any substitution pattern, nitrobenzene, anisole, or mixtures of these with one another.
  • a solvent which may be any of those known to those skilled in the art to be suitable for Friedels-Craft reactions. It is preferred, however, that the solvent be a halogenated benzene such as chlorobenzene, dichlorobenzene, trichlorobenzene, 1,1,2,2-tetrachloroethane, bromo
  • the compound of Formula C may also be the solvent.
  • the usefulness of this approach clearly depends upon the melting point of the compound of Formula C. as those of skill in the art will recognize. In this case, the exact molar ratio of the reactants is of little concern.
  • Another, more significant advantage of this approach is that the solvent in which the first reaction (Scheme VIII) is conducted can be the reactant of Formula C in the second reaction. This allows the efficient, economical two step process described above to be treated as a single step process.
  • a further advantage of using the compound of Formula C as both a solvent and a reactant is that it avoids the need to use halogenated solvents, and so avoids the environmental and health concerns associated with halogenated solvents.
  • the temperature range for the reaction shown in Scheme IX is between 0°C to about 120°C, more preferably between about 10°C to 80°C. Precise temperatures are varied, however, depending upon the type of catalyst used, the pressure under which the reaction occurs, and the exact identities of the compounds of Formulas F and C. Similarly, the time required for the reaction to go to completion will vary with catalyst and reactants, as well as with temperature and pressure. The present processes are preferably performed at about atmospheric pressure, however, and so the preferred reaction time is between about 0.5 hours and about 40 hours, more preferably between about 2.5 hours and about 20 hours. Reaction completion may be determined by conventional means known to those of skill in the art, including, for example, 'H NMR, visible, UV and IR optical spectroscopy, and chromatography.
  • compositions formed during step two of the reaction of the present invention are particularly useful as UV stabilizers. Furthermore, it has been found that the individual compounds isolated from the product compositions are themselves efficient and stable UV absorbers.
  • hydroxyl groups of compounds 3 and 4 can be alkylated by one of ordinary skill in the art using well known procedures.
  • hydroxyl groups of compounds 7 and 8 can be alkylated by one of ordinary skill in the art using well known procedures.

Abstract

L'invention concerne un procédé de fabrication de composés de triazine substituée et de mélanges de composés de triazine substituée. L'invention concerne notamment un procédé de fabrication de triazines mono- et bis-(2-hydroxy-4-alcoxyphényle) substituées, de triazines mono- et bis-(2,4-bishydroxyphényle) substituées, et de mélanges de celles-ci. L'invention concerne de plus des composés de triazine et des mélanges de composés de triazine élaborés selon le procédé.
PCT/US1999/020170 1998-09-04 1999-09-02 Procede de fabrication de composes de triazine 2,4-dihydroxyphenyle et 2-hydroxy-4-alcoxyphenyle substituee WO2000014076A1 (fr)

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AU59073/99A AU5907399A (en) 1998-09-04 1999-09-02 Process for making 2,4-dihydroxyphenyl and 2-hydroxy-4-alkoxyphenyl substituted triazine compounds

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US9931298P 1998-09-04 1998-09-04
US60/099,312 1998-09-04

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005506384A (ja) * 2001-10-18 2005-03-03 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 有機材料の安定剤としてのナフチルトリアジン
WO2010081625A2 (fr) 2009-01-19 2010-07-22 Basf Se Pigments noirs organiques et leur préparation
US8741901B2 (en) 2004-07-15 2014-06-03 Albany Molecular Research, Inc. Aryl- and heteroaryl-substituted tetrahydroisoquinolines and use thereof to block reuptake of norepinephrine, dopamine, and serotonin
US8802696B2 (en) 2009-05-12 2014-08-12 Albany Molecular Research, Inc. 7-([1,2,4]triazolo[1,5-a]pyridin-6-yl)-4-(3,4-dichlorophenyl)-1,2,3,4-tetrahydroisoqu inoli and use thereof
US8815894B2 (en) 2009-05-12 2014-08-26 Bristol-Myers Squibb Company Crystalline forms of (S)-7-([1,2,4]triazolo[1,5-a]pyridin-6-yl)-4-(3,4-dichlorophenyl)-1,2,3,4-tetrahydroisoquinoline and use thereof
US9034899B2 (en) 2009-05-12 2015-05-19 Albany Molecular Research, Inc. Aryl, heteroaryl, and heterocycle substituted tetrahydroisoquinolines and use thereof
US9498476B2 (en) 2008-06-04 2016-11-22 Albany Molecular Research, Inc. Crystalline form of 6-[(4S)-2-methyl-4-(2-naphthyl)-1,2,3,4-tetrahydroisoquinolin-7-yl]pyridazin-3-amine

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005506384A (ja) * 2001-10-18 2005-03-03 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 有機材料の安定剤としてのナフチルトリアジン
US7087753B2 (en) 2001-10-18 2006-08-08 Ciba Specialty Chemicals Corp. Naphthyltriazines as stabilizers for organic material
US8741901B2 (en) 2004-07-15 2014-06-03 Albany Molecular Research, Inc. Aryl- and heteroaryl-substituted tetrahydroisoquinolines and use thereof to block reuptake of norepinephrine, dopamine, and serotonin
US9085531B2 (en) 2004-07-15 2015-07-21 Albany Molecular Research, Inc. Aryl- and heteroaryl-substituted tetrahydroisoquinolines and use thereof to block reuptake of norepinephrine, dopamine, and serotonin
US9499531B2 (en) 2004-07-15 2016-11-22 Albany Molecular Research, Inc. Aryl- and heteroaryl-substituted tetrahydroisoquinolines and use thereof to block reuptake of norepinephrine, dopamine, and serotonin
US9498476B2 (en) 2008-06-04 2016-11-22 Albany Molecular Research, Inc. Crystalline form of 6-[(4S)-2-methyl-4-(2-naphthyl)-1,2,3,4-tetrahydroisoquinolin-7-yl]pyridazin-3-amine
WO2010081625A2 (fr) 2009-01-19 2010-07-22 Basf Se Pigments noirs organiques et leur préparation
US8802696B2 (en) 2009-05-12 2014-08-12 Albany Molecular Research, Inc. 7-([1,2,4]triazolo[1,5-a]pyridin-6-yl)-4-(3,4-dichlorophenyl)-1,2,3,4-tetrahydroisoqu inoli and use thereof
US8815894B2 (en) 2009-05-12 2014-08-26 Bristol-Myers Squibb Company Crystalline forms of (S)-7-([1,2,4]triazolo[1,5-a]pyridin-6-yl)-4-(3,4-dichlorophenyl)-1,2,3,4-tetrahydroisoquinoline and use thereof
US9034899B2 (en) 2009-05-12 2015-05-19 Albany Molecular Research, Inc. Aryl, heteroaryl, and heterocycle substituted tetrahydroisoquinolines and use thereof
US9173879B2 (en) 2009-05-12 2015-11-03 Bristol-Myers Squibb Company Crystalline forms of (S)-7-([1,2,4]triazolo[1,5-a ]pyridin-6-yl)-4-(3,4-dichlorophenyl)-1,2,3,4-tetrahydroisoquinoline and use thereof
US9604960B2 (en) 2009-05-12 2017-03-28 Albany Molecular Research, Inc. Aryl, heteroaryl, and heterocycle substituted tetrahydroisoquinolines and use thereof

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