Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings

Definitions

• the present invention relates to an improved process for the preparation of tertiary N-allyl sterically hindered amines which are suitable for stabilizing organic materials against oxidative, thermal or light-induced degradation.
• Sterically hindered amine light stabilizers which are N-allyl substituted are prepared from the corresponding sterically hindered secondary amines by alkylation with allyl halides in the presence of bases at high temperature.
• allyl halides The cost of allyl halides is increasing constantly and has a high impact on the production cost of these N-allyl stabilizers.
• a further disadvantage of using allyl halides is the fact that this synthetic route generates salts as side products which are environmentally critical and which have to be removed.
• a halide free process for the preparation of tertiary N-allyl sterically hindered amines from the corresponding sterically hindered secondary amines is therefore highly desirable.
• sterically hindered amines can be reacted with allyl alcohols in the present of a catalyst and carbon dioxide as activator to form the desired N-allyl sterically hindered amines.
• the present invention therefore relates to an improved process for the preparation of compounds of the formula I
• linking group R forms, together with the carbon atoms it is directly connected to and the nitrogen atom, a substituted 5-, 6- or 7-membered cyclic ring structure
• Ri > R 2 , R3 and R 4 independently of each other, are Ci-C 8 alkyl or d-C 5 hydroxyalkyl, or R 1 and R 2 together with the carbon atom they are attached to are C 5 -Ci 2 cycloalkyl, or R 3 and
• R 4 together with the carbon atom they are attached to are C 5 -Ci 2 cycloalkyl
• R 5 , R 6 , R 7 , Rs and R 9 are hydrogen, d-C 8 alkyl, C 2 -C 8 alkenyl, unsubstituted or with d-C 4 alkyl, d-C 4 alkoxy or halogen substituted C 5 -Ci 2 aryl; d-dhaloal- kyl, cyano, nitro, halogen or -COORi 0 ; and R 7 and R 8 together may also form a chemical bond,
• R 1 0 is d-d 2 alkyl, C 5 -Ci 2 cycloalkyl, d-C 9 phenylalkyl or phenyl,
• R, R 1 , R 2 , R 3 and R 4 are as defined above, with a compound of the formula
• R 5 , R 6 , R 7 , R 8 and R 9 are as defined above, in the presence of a catalyst.
• Alkyl having up to 12 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3- trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl or
• Hydroxyalkyl having up to 5 carbon atoms is a branched or unbranched radical which contains preferably 1 to 3, in particular 1 or 2, hydroxyl groups, such as, for example, 1- hydroxymethyl, 1-hydroxyethyl, 1-hydroxypropyl, 1-hydroxybutyl, 1-hydroxybutyl, 2- hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxybutyl, 2-hydroxypropyl or 3- hydroxybutyl.
• C 5 -Ci 2 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl.
• Alkenyl having 2 to 8 carbon atoms is a branched or unbranched radical such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2- butenyl or n-2-octenyl.
• Aryl stands for a group obeying the Debye-Hueckel rule; preferred as C 5 -Ci 2 aryl are phenyl and naphthyl.
• Halogen is for example fluoro, chloro, bromo or iodo.
• Phenylalkyl is, for example, benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl or 2-phenyl- ethyl. Preference is given to benzyl and ⁇ , ⁇ -dimethylbenzyl.
• Alkoxy having up to 4 carbon atoms is a branched or unbranched radical, for example meth- oxy, ethoxy, propoxy, isopropoxy, n-butoxy or isobutoxy.
• R 11 is nitrogen which is attached to triazine ring.
• R is R-CH
• Ri, R2, R3 and R 4 are methyl
• R 5 , R 6 , R 7 , Re and R 9 are hydrogen
• R 11 is nitrogen which is attached to triazine ring.
• the compound of the formula III is used in equimolar to 100 fold excess, for example 1 to 50 fold excess, preferably, 1 to 20 fold excess, typically 1 to 4 fold excess, with respect to each unit of secondary sterically hindered amine of the formula II.
• the catalyst is a metal catalyst.
• metal catalysts selected from the group consisting of palladium, rhodium, ruthenium, osmium, copper, nickel, manganese, iron and cobalt catalysts.
• the catalyst is used in the process for the preparation of the compounds of the formula I in an amount of from 0.01 to 30 mol%, preferably 0.01 to 20 mol%, typically 0.1 to 10 mol%, with respect to each unit of secondary sterically hindered amine of the formula II.
• phosphines are compounds of the formula IV
• Q is the same or different and is for example alkyl having 1 to 10 carbons, cycloalkyl having 4 to 10 carbons and/or aryl having 6 to 10 carbons, examples of which are methyl, butyl, cyclohexyl, phenyl, tolyl.
• at least one is aryl and most preferably, the ligand is triaryl.
• Suitable ligands having the aforementioned structure are the following: trimeth- ylphosphine, tricyclohexylphosphine, tris(m-sulfonatophenyl)phosphine (TPPTS), triphenyl- phosphine, 2,2'-bis(diphenylphosphino)-1 ,1 '-binaphthalene (BINAP).
• Preferred ligand is triphenylphosphine.
• the quantity of the ligand is from 1 to 10 moles per atom of the metal.
• An especially preferred ligand/atom metal ratio is from 2 to 6.
• the process for the preparation of compounds of the formula I may comprise additionally a solvent and/or a base.
• Useful solvents for the instant process are for example saturated and aromatic hydrocarbons, ketones, esters, water or alcohols or mixtures thereof.
• the solvent may be the compound of the formula III (allyl alcohol).
• especially preferred organic solvents are toluene, xylene, acetone, methanol or ethyl acetate.
• the bases are inorganic or organic in nature.
• Bases of special interest are for example sodium carbonate, potassium carbonate, sodium hydroxide, triethylamine or pyridine.
• the reaction temperature in the instant process for the preparation of the compounds of the formula I is for example between 10 and 18O 0 C, preferably between 20 and 14O 0 C, and pressures of 1 to 30 atmospheres absolute, preferably of 1 to 15 atmospheres absolute.
• inert gases are for example nitrogen or argon.
• mixtures of inert gases are used comprising carbon dioxide and nitrogen.
• Example 1 Preparation of compound 101 starting from compound A.
• Example 3 Preparation of compound 102 (see formula in Example 2).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Hydrogenated Pyridines (AREA)
• Plural Heterocyclic Compounds (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2007
  • 2007-11-14 EP EP07857213A patent/EP2084150B1/en not_active Not-in-force
  • 2007-11-14 JP JP2009537603A patent/JP5649822B2/ja not_active Expired - Fee Related
  • 2007-11-14 US US12/515,414 patent/US8217170B2/en not_active Expired - Fee Related
  • 2007-11-14 ES ES07857213T patent/ES2388886T3/es active Active
  • 2007-11-14 CN CN200780043150.9A patent/CN101541787B/zh not_active Expired - Fee Related
  • 2007-11-14 KR KR1020097009807A patent/KR101454703B1/ko not_active Expired - Fee Related
  • 2007-11-14 WO PCT/EP2007/062321 patent/WO2008061923A1/en not_active Ceased
  • 2007-11-21 TW TW096144063A patent/TWI408134B/zh active

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