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WO2003006420A1 - Procede catalytique pour transformer des composes aryle en arylamines - Google Patents

Procede catalytique pour transformer des composes aryle en arylamines Download PDF

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Publication number
WO2003006420A1
WO2003006420A1 PCT/US2002/021919 US0221919W WO03006420A1 WO 2003006420 A1 WO2003006420 A1 WO 2003006420A1 US 0221919 W US0221919 W US 0221919W WO 03006420 A1 WO03006420 A1 WO 03006420A1
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WIPO (PCT)
Prior art keywords
substituted
aryl
unsubstituted
group
compound
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PCT/US2002/021919
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English (en)
Inventor
John F. Hartwig
Morten Jorgensen
Sunwoo Lee
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Yale University
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Publication of WO2003006420A1 publication Critical patent/WO2003006420A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/66—Preparation of compounds containing amino groups bound to a carbon skeleton from or via metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/28—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/66—Nitrogen atoms not forming part of a nitro radical

Definitions

  • the present invention relates to generation of aniline compounds from aryl compounds, and more particularly to generation of aniline compounds from aryl halide compounds using an alkali metal bis(trimethylsilyl) amide as a reactant and a transition metal catalyst.
  • Present processes that form arylamines from aryl halides suffer several disadvantages. Some of the substrates require metal-catalyzed cleavage of the protective group, and others are relatively expensive. What is needed in the art are inexpensive and readily available substrates that are effective as ammonia equivalents, and that provide for facile conversion of substituted aryl halides to aryl amines. The present invention is believed to be an answer to that need.
  • the present invention is directed to a method of converting an aryl compound to an aniline compound, comprising the steps of: (1) providing an aryl compound containing a halide group or a sulfur-containing group; (2) reacting the aryl compound with an a reactant having the structure
  • Ri, R 2 , and R 3 are each independently selected from the group consisting substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted heteroarylalkyl, and combinations thereof;
  • R is selected from the group consisting hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted arylalkyl, substituted or unsubstitute
  • the present invention is directed to a method of converting an aryl compound to an aniline compound, comprising the steps of: (1) providing an aryl compound containing a halide group or a sulfur-containing group; (2) reacting said aryl compound with an a reactant having the structure
  • Me 3 Sr SiMe 3 in the presence of Pd(dba) 2 and P(t-Bu) 3 for from 30 minutes to 24 hours and from about 20°C to about 100°C at atmospheric pressure, to form an aryl silylamine intermediate; and (3) converting said aryl silylamine intermediate to said aniline compound.
  • a substituted or unsubstituted aryl compound containing a leaving group (X) is reacted with a silyl amide reactant, such as an alkali metal bis(trimethylsilyl) amide reactant (or silylamine and base), in the presence of a Group 8 transition metal catalyst to form the corresponding substituted or unsubstituted aryl amine (aniline).
  • a silyl amide reactant such as an alkali metal bis(trimethylsilyl) amide reactant (or silylamine and base
  • the leaving group X may be a halogen group, such as chloride, bromide, fluoride, iodide, and the like, or a sulfur- containing leaving group (e.g., triflate, sulfonate, tosylate, and the like).
  • suitable aryl compounds include substituted or unsubstituted aryl bromides, substituted or unsubstituted aryl chlorides, substituted or unsubstituted aryl fluorides, and substituted or unsubstituted aryl iodides.
  • aryl halides such as aryl bromides and aryl chlorides, are preferred.
  • R may be a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or other substituted or unsubstituted group as described in more detail below. Additionally, R may be in any position on the aryl ring, however the para and meta positions are preferred.
  • aryl halide compounds include substituted or unsubstituted aryl bromides and substituted or unsubstituted aryl chlorides such as the following compounds:
  • Ri, R 2 , and R are each independently selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted heteroarylalkyl, and combinations thereof.
  • Particularly useful groups are short chain alkyl groups and aryl groups, such as methyl, ethyl, propyl, n-butyl, t-butyl, isopropyl, phenyl, and the like.
  • the P group in the above reactant is selected from the group consisting hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted heteroarylalkyl, and SiR ⁇ R 2 R , wherein Ri, R 2 , and R 3 are defined above.
  • the A component of the above reactant may be H or an alkali metal such as lithium, sodium, potassium, and the like. Lithium is a preferred alkali metal for use in the present invention.
  • a preferred reactant is lithium bis(trimethylsilyl) amide, having the structure
  • the reaction preferably takes place in the presence of a Group 8 transition metal catalyst.
  • Any Group 8 transition metal may be used, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • the Group 8 metal is palladium, platinum, or nickel, and most preferably, palladium.
  • the Group 8 metal may exist in any oxidation state ranging from the zero-valent state to any higher variance available to the metal.
  • the Group 8 transition metal atom is preferably complexed with a monovalent anionic ligand, including for example a halide, such as chloride or bromide; a carboxylate, such as acetate; or an alkyl sulfonate, such as triflate.
  • the Group 8 transition metal may also be complexed with a divalent anionic ligand, such as sulfonate or carbonate.
  • the Group 8 transition metal can be complexed by a neutral dative ligand such as dibenzylidene acetone, cyclooctadiene, ethylene, triphenylphosphine, or other neutral ligand.
  • the Group 8 transition metal is complexed with dibenzylidene acetone.
  • the Group 8 transition metal complex is further complexed with an additional ligand to form the Group 8 transition metal catalyst.
  • additional ligand examples include
  • tributyl phosphine P(t-Bu) 3
  • PCy P(o-Tol) 3
  • PPh 3 PPh 3
  • l,l'-bis(diphenylphosphino)ferrocene DPPF
  • BINAP l,l'-bis(diphenylphosphino)-2,2'-binaphthyl
  • Tol-BINAP l,l'-bis(di-p- tolylphosphino)-2,2'-binaphthyl
  • a particularly preferred ligand is P(t-Bu) 3 .
  • the transition metal catalyst may be synthesized first and thereafter employed in the reaction process.
  • the catalyst can be prepared in situ in the reaction mixture. If the latter mixture is employed, then a Group 8 catalyst precursor compound and the desired ligand are independently added to the reaction mixture wherein formation of the transition metal catalyst occurs in situ.
  • Suitable precursor compounds include alkene and diene complexes of the Group 8 metals, preferably, di(benzylidene)acetone
  • (dba) complexes of the Group 8 metals as well as, monodentate phosphine complexes of the Group 8 metals, and Group 8 carboxylates.
  • suitable precursor compounds include [bis-di(benzylidene)acetone]palladium (0), tetrakis-
  • Any of the aforementioned catalyst precursors may include a solvent of crystallization.
  • Group 8 metals supported on carbon preferably, palladium on carbon
  • the catalyst precursor compound is bis-
  • the Group 8 transition metal catalyst may be anchored or supported on a catalyst support, including a refractory oxide, such as silica, alumina, titania, or magnesia; or an aluminosilicate clay, or molecular sieve or zeolite; or an organic polymeric resin.
  • a refractory oxide such as silica, alumina, titania, or magnesia
  • an aluminosilicate clay such as molecular sieve or zeolite
  • organic polymeric resin such as silica, alumina, titania, or magnesia
  • the quantity of catalyst used in the reaction is a catalytic amount, which means that the catalyst is used in an amount which is less than stoichiometric relative to the reactants.
  • the amount of transition metal catalyst useful in the reaction preferably ranges from about 0.1 mol% to about 10 mol%, based on the total moles of the aryl compound, and more preferably from about 0.2 mol% to about 5 mol%, based on the total moles of the aryl compound.
  • a proviso with respect to the method of the present invention is that when A is hydrogen in the reactant, a base is added to the reaction mixture.
  • suitable bases include alkali metal hydroxides, such as lithium, sodium and potassium hydroxides; alkali metal alkoxides, such as sodium t-butoxide; metal carbonates, such as potassium carbonate, cesium carbonate, and magnesium carbonate; phosphates; alkali metal aryl oxides, such as potassium phenoxide; alkali metal amides, such as lithium amide, lithium diisopropyl amide, or lithium hexamethyldisilazide; tertiary amines, such as triethylamine and tributylamine; (hydrocarbyl)ammonium hydroxides, such as benzyltrimethylammonium hydroxide and tetraethylammonium hydroxide; and diaza organic bases, such as l,8-diazabicyclo[5.4.0]-
  • the quantity of base which is used can be any quantity which allows for the formation of the aniline product.
  • the molar ratio of base to arylating compound ranges from about 1 : 1 to about 3:1, and more preferably between about 1 : 1 and 2:1.
  • the above reaction produces an aryl silylamine intermediate, which is subsequently converted to the corresponding aniline by aqueous workup with acid, or by addition of fluoride. Any acid may be used, however, HC1 is preferred.
  • the process described herein may be conducted in any conventional reactor designed for catalytic processes. Continuous, semi-continuous, and batch reactors can be employed. If the catalyst is substantially dissolved in the reaction mixture as in homogeneous processes, then batch reactors, including stirred tank and pressurized autoclaves, can be employed. If the catalyst is anchored to a support and is substantially in a heterogeneous phase, then fixed-bed and fluidized bed reactors can be used. In the typical practice of this invention the reactants and catalyst are mixed in batch, optionally with a solvent, and the resulting mixture is maintained at a temperature and pressure effective to prepare the product.
  • Suitable aprotic solvents include, but are not limited to, aromatic hydrocarbons, such as toluene and xylene, chlorinated aromatic hydrocarbons, such as dichlorobenzene, and ethers, such as tetrahydrofuran.
  • Suitable protic solvents include, but are not limited to, water and aliphatic alcohols, such as ethanol, isopropanol, and cyclohexonol, as well as glycols and other polyols.
  • the amount of solvent which is employed may be any amount, preferably an amount sufficient to solubilize, at least in part, the reactants.
  • a suitable quantity of solvent typically ranges from about 1 to about 100 grams solvent per gram reactants. Other quantities of solvent may also be suitable, as determined by the specific process conditions and by the skilled artisan.
  • the process of the invention may also be conducted without any solvent. Generally, the reactants may be mixed together or added to a solvent in any order.
  • Air is preferably removed from the reaction vessel during the course of the reaction, however this step is not always necessary. If it is desirable or necessary to remove air, the solvent and reaction mixture can be sparged with a non-reactive gas, such as nitrogen, helium, or argon, or the reaction may be conducted under anaerobic conditions.
  • the process conditions can be any operable conditions which yield the desired product. Beneficially, the reaction conditions for this process are mild. For example, a preferred temperature for the process of the present invention ranges from about ambient, taken as about 20°C, to about 150°C, and preferably, from about 20°C to about 100°C.
  • the process may be run above or below atmospheric pressures if necessary, but typically proceeds sufficiently well at about atmospheric pressure.
  • the process is generally run for a time sufficient to convert as much of the starting materials to product as possible.
  • the reaction time is less than 40 hours (typically between about 30 minutes and 24 hours).
  • the product can be recovered by conventional methods known to those skilled in the art, including, for example, distillation, crystallization, sublimation, and gel chromatography.
  • the yield of product will vary depending upon the specific catalyst, reagents, and process conditions used.
  • yield is defined as the mole percentage of product recovered. Typically, the yield of product is greater than about 30 mole percent. Preferably, the yield of product is greater than about 60 mole percent, and more preferably, greater than about 80 mole percent.
  • Table 1 summarizes reactions of lithium bis-trimethylsilamide with 4-t-butyl bromobenzene catalyzed by palladium complexes of several ligands.
  • Aryl chlorides are generally less reactive than bromides and often require higher temperatures for reaction. If this were the case for reactions of the silylamide reagent, then benzyne and possibly radical intermediates would be generated. However, the high activity of the catalyst derived from Pd(dba) 2 and P(t-Bu) 3 allowed for reaction of the aryl chlorides under relatively mild conditions. The results in Table 2 show that many aryl chlorides underwent regiospecific reaction with bis(trimethylsilyl)amide to form the parent aniline in high yield. In general, the substrate scope for reactions of aryl chlorides was similar to that for reactions of aryl bromides, but reactions required 50°C with 5 mol% catalyst to occur at reasonable rates.
  • the ligand and silylamide reagent used in this reactions are air sensitive, convenient procedures can be followed without a drybox. Both the silylamide and ligand are commercially available as a solution in hydrocarbon solvents and can, therefore, be delivered to the reaction solution by syringe.
  • the preformed Pd(0) catalyst Pd[P(t-Bu) ] 2 is commercially available and is air stable. Combining this air-stable species with the air-stable and commercially available Pd(dba) or Pd 2 (dba) 3 in a 1 : 1 molar ratio to metal, as done previously by Fu (Littke, A.; Dai, C; Fu, G. J. Am. Chem. Soc.
  • P NMR spectra obtained on reactions of aryl chlorides using a 1 : 1 ratio of Pd(dba) and P(t-Bu) 3 show that the Pd(0) complex Pd[P(t-Bu) ] 2 is the major palladium-phosphine complex in solution. Roughly 20 h after consumption of the aryl chloride 40% cyclometallated complex is formed. In contrast, little Pd[P(t-Bu) 3 ] 2 is observed during the reaction of aryl bromides. Two identified complexes with chemical shifts 10-20 ppm upfield of free ligand were observed by 31 P NMR spectro etry. These are not formed by reaction of aryl halide or by reaction of the silylamide with Pd[P(t-Bu) 3 ] . Further studies will be needed to determine the structures of these species.
  • Example 16 3-(Trifluoromethyl)aniline (Tables 2 and 3, entry 15).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de transformation d'un composé aryle en un composé aniline, qui consiste à : (1) fournir un composé aryle contenant un groupe halure ou un groupe soufré; (2) faire réagir le composé aryle avec un réactif représenté par la structure (I), dans laquelle R1, R2, et R3 sont individuellement sélectionnés dans le groupe constitué par alkyle substitué ou non, alcényle substitué ou non, alcynyle substitué ou non, hétéroalkyle substitué ou non, aryle substitué ou non, hétéroaryle substitué ou non, arylalkyle substitué ou non, hétéroarylalkyle substitué ou non, ainsi que des combinaisons de ceux-ci; R4 est sélectionné dans le groupe constitué par hydrogène, alkyle substitué ou non, alcényle substitué ou non, alcynyle substitué ou non, hétéroalkyle substitué ou non, aryle substitué ou non, hétéroaryle substitué ou non, arylalkyle substitué ou non, hétéroarylalkyle substitué ou non, et SiR1R2R3; et A représente H ou un métal alcalin; l'opération de réaction est exécuté en présence d'un catalyseur de métal de transition du groupe 8 dans des conditions de réaction qui permettent d'obtenir un intermédiaire d'arylsilylamine, à condition que lorsque A représente H dans le réactif, l'opération de réaction comprend une base ; et enfin, (3) transformer l'intermédiaire d'arylsilylamine en composé aniline.
PCT/US2002/021919 2001-07-12 2002-07-11 Procede catalytique pour transformer des composes aryle en arylamines WO2003006420A1 (fr)

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US60/304,859 2001-07-12

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006124283A1 (fr) * 2005-05-12 2006-11-23 Boehringer Ingelheim International, Gmbh Bis-amination d'halogenures d'aryle
EP1581467A4 (fr) * 2002-12-09 2008-08-13 Massachusetts Inst Technology Ligands pour métaux et processus a catalyse par métaux améliorés basés sur ces ligands
WO2009050366A2 (fr) 2007-09-28 2009-04-23 Centre National De La Recherche Scientifique (C.N.R.S.) Procede de synthese d'arylamines
US7560582B2 (en) 1998-07-10 2009-07-14 Massachusetts Institute Of Technology Ligands for metals and improved metal-catalyzed processes based thereon
US7560596B2 (en) 2005-01-10 2009-07-14 Massachusetts Institute Of Technology Transition-metal-catalyzed carbon-nitrogen and carbon-carbon bond-forming reactions
US7586007B2 (en) 2007-04-03 2009-09-08 Exxonmobil Research And Engineering Company Lubricating compositions containing ashless catalytic antioxidant additives
US7759295B2 (en) 2007-04-03 2010-07-20 Exxonmobil Research And Engineering Company Lubricating compositions containing ashless catalytic antioxidant additives
US7858784B2 (en) 2007-12-12 2010-12-28 Massachusetts Institute Of Technology Ligands for transition-metal-catalyzed cross-couplings, and methods of use thereof
US7977286B2 (en) 2006-05-09 2011-07-12 Exxonmobil Research And Engineering Company Lubricating compositions containing ashless catalytic antioxidant additives
US8048833B2 (en) 2007-08-17 2011-11-01 Exxonmobil Research And Engineering Company Catalytic antioxidants
US8080601B2 (en) 2007-04-03 2011-12-20 Exxommobil Research And Engineering Company Lubricating compositions containing ashless catalytic antioxidant additives
CN102993090A (zh) * 2012-10-11 2013-03-27 南通市华峰化工有限责任公司 一种2,6-二氨基吡啶的合成方法
JP2020091192A (ja) * 2018-12-05 2020-06-11 学校法人北里研究所 化合物及びその使用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUANG ET AL.: "New ammonia equivalents for the Pd-catalyzed amination of aryl halides", ORG. LETT., vol. 3, no. 21, September 2001 (2001-09-01), pages 3417 - 3419, XP002958148 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7560582B2 (en) 1998-07-10 2009-07-14 Massachusetts Institute Of Technology Ligands for metals and improved metal-catalyzed processes based thereon
EP1581467A4 (fr) * 2002-12-09 2008-08-13 Massachusetts Inst Technology Ligands pour métaux et processus a catalyse par métaux améliorés basés sur ces ligands
US8378145B2 (en) 2005-01-10 2013-02-19 Massachusetts Institute Of Technology Transition-metal-catalyzed carbon-nitrogen and carbon-carbon bond-forming reactions
US7560596B2 (en) 2005-01-10 2009-07-14 Massachusetts Institute Of Technology Transition-metal-catalyzed carbon-nitrogen and carbon-carbon bond-forming reactions
US8735630B2 (en) 2005-01-10 2014-05-27 Massachusetts Institute Of Technology Transition-metal-catalyzed carbon-nitrogen and carbon-carbon bond-forming reactions
WO2006124283A1 (fr) * 2005-05-12 2006-11-23 Boehringer Ingelheim International, Gmbh Bis-amination d'halogenures d'aryle
JP2008540526A (ja) * 2005-05-12 2008-11-20 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 ハロゲン化アリールのビスアミノ化
US7977286B2 (en) 2006-05-09 2011-07-12 Exxonmobil Research And Engineering Company Lubricating compositions containing ashless catalytic antioxidant additives
US8080601B2 (en) 2007-04-03 2011-12-20 Exxommobil Research And Engineering Company Lubricating compositions containing ashless catalytic antioxidant additives
US7759295B2 (en) 2007-04-03 2010-07-20 Exxonmobil Research And Engineering Company Lubricating compositions containing ashless catalytic antioxidant additives
US7586007B2 (en) 2007-04-03 2009-09-08 Exxonmobil Research And Engineering Company Lubricating compositions containing ashless catalytic antioxidant additives
US8048833B2 (en) 2007-08-17 2011-11-01 Exxonmobil Research And Engineering Company Catalytic antioxidants
WO2009050366A2 (fr) 2007-09-28 2009-04-23 Centre National De La Recherche Scientifique (C.N.R.S.) Procede de synthese d'arylamines
US8399680B2 (en) 2007-09-28 2013-03-19 Centre National De La Recherche Scientifique (C.N.R.S.) Arylamine synthesis method
US7858784B2 (en) 2007-12-12 2010-12-28 Massachusetts Institute Of Technology Ligands for transition-metal-catalyzed cross-couplings, and methods of use thereof
CN102993090A (zh) * 2012-10-11 2013-03-27 南通市华峰化工有限责任公司 一种2,6-二氨基吡啶的合成方法
JP2020091192A (ja) * 2018-12-05 2020-06-11 学校法人北里研究所 化合物及びその使用
JP7193842B2 (ja) 2018-12-05 2022-12-21 学校法人北里研究所 化合物及びその使用

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