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  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
  • C07D295/24—Oxygen atoms
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  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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  • C07D211/94—Oxygen atom, e.g. piperidine N-oxide
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  • C07D303/02—Compounds containing oxirane rings
  • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
  • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
  • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
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  • 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
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  • C07—ORGANIC CHEMISTRY
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  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/10—Spiro-condensed systems
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  • C08F4/00—Polymerisation catalysts
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
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  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
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  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member

Definitions

• the instant invention pertains to a process for preparing amine ethers, e.g. N-hydro- carbyloxy substituted hindered amine compounds, by the reaction of the corresponding N- oxyl intermediate with a hydrocarbon in presence of an organic hydroperoxide and an iodide catalyst.
• amine ethers e.g. N-hydro- carbyloxy substituted hindered amine compounds
• Unites States Patent No 5,374,729 describes a process for the preparation of N- methoxy derivatives of hindered amines from the reaction of the corresponding N-oxyl compound with methyl radicals produced from dimethyl sulfoxide by decomposing aqueous hydrogen peroxide in presence of a metal salt or by thermal decomposition of di-tert.butyl peroxide.
• the aliphatic hydrocarbon compound may be any compound selected from alkane, alkene, alkyne, or cyclic or polycyclic analogues thereof, and optionally may be substituted, e.g. by aryl, halogen, alkoxy etc., provided that an aliphatic CH (or CH 2 , CH 3 ) moiety is contained.
• E' is C1-C36 alkyl; C3-C1 Q alkenyl; C2-C18 alkinyl; C5-C18 cycloalkyl; C5-C18 cycloalkenyl; a radical of a saturated or unsaturated aliphatic bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms; C2-C7alkyl or C ⁇ -Cyalkenyl substituted by halogen, CrC 8 alkoxy or phenoxy; C 4 -C 12 heterocycloalkyl; C -C 12 heterocycloalkenyl; C7-C15 aralkyl or-C 4 -C 12 heteroaralkyl, each of which is unsubstituted or substituted by C1-C4 alkyl or phenyl; or E' is a radical of formula (VII) or (VIII)
• T' is tertiary C 4 -C ⁇ 8 alkyl or phenyl, each of which are unsubstituted or substituted by halogen,
• R 2 5 s OH, C C ⁇ 8 alkoxy, benzyloxy, N(R 18 ) 2 ; which process comprises reacting a N-oxyl hindered amine of formula III or Ilia
• cycloalkyl examples include cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, dimethylcyclopentyl and methylcyclohexyl.
• Gi and G 2 and/or G 3 and G forming, together with the linking carbon atom, a C 3 - C 12 cycloalkyl radical, preferably form a C 5 -C 12 cycloalkyl radical, especially cyclopentylene, cyclohexylene or cycloheptylene.
• Z is O or NR 8 ;
• Rg, R ⁇ o > R11, i2 > R 1 3 and R 14 are independently hydrogen, phenyl, or C ⁇ -C ⁇ 8 alkyl;
• the sterically hindered aminoxides also referred to as N-oxyl educts for the instant process which include compounds of formulae B, III or Ilia, are largely known in thaart; they may be prepared by oxidation of the corresponding N-H hindered amine with a suitable oxygen donor, e.g. by the reaction of the corresponding N-H hindered amine with hydrogen peroxide and sodium tungstate as described by E. G. Rozantsev et al., in Synthesis, 1971 , 192; or with tert-butyl hydroperoxide and molybdenum (VI) as taught in United States Patent No. 4,691 ,015, or obtained in analogous manner.
• a suitable oxygen donor e.g. by the reaction of the corresponding N-H hindered amine with hydrogen peroxide and sodium tungstate as described by E. G. Rozantsev et al., in Synthesis, 1971 , 192; or with tert-butyl
• the preferred amount of hydrocarbon for the instant process depends to some extent on the relative number of reactive hydrogens on the hydrocarbon reactant and the hindered amine nitroxyl compound.
• the reaction is typically carried out with a ratio of 1 to 100 moles of hydrocarbon per mole of nitroxyl moiety with the preferred ratio being 1 to 50 moles per mole of nitroxyl moiety, and the most preferred ratio being 1 to 30 moles of hydrocarbon per mole of nitroxyl moiety.
• the organic hydroperoxide used in the process of present invention can be of the formula R-OOH, wherein R usually is a hydrocarbon containing 1-18 carbon atoms.
• the organic hydroperoxide preferably is a peroxoalcohol containing 3-18 carbon atoms.
• R is often aliphatic, preferably C C ⁇ 2 alkyl.
• Most preferred organic hydroperoxide is tert.butyl hydroperoxide.
• the reaction is preferably run at 0° to 100°C; more preferably at 20° to 100°C, especially in the range 20-80°C.
• Ar is C 6 -C 0 aryl or C 5 -C 9 heteroaryl
• G 55 is H, CH 3 or phenyl
• G 6 6 is -CN or a group of the formula -COOR 4 or -CH 2 -O-G 4 ;
• L is a carbon centered radical formed from propane, butane, pentane, 2,2-dimethyl-propane, xylene.
• a solvent may be used, especially if the hydrocarbon, such as the compound of of formula IV or V, is a solid at the temperature of the reaction or if the catalyst is not very soluble in the hydrocarbon.
• Inert solvents should have less active carbon-hydrogen bonds; typical inert solvents are acetonitrile, aromatic hydrocarbons like benzene, chlorobenzene, CCI 4 , alcohols (e.g. methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether), or, especially for reactions with activated hydrocarbons like alkylated aromats or alkenes, also alkanes like hexane, decane etc., or mixtures thereof.
• Inorganic solvents such as water are possible as well.
• the reaction can be carried out in one liquid phase or in separate phases.
• the iodide catalyst may be selected from any iodide compound, including organic and inorganic iodide compounds. Examples are alkaline or alkaline earth metal iodides, or onium iodides such as ammonium or phosphonium or sulfonium iodides. Suitable metal iodides are, inter alia, those of lithium, sodium, potassium, magnesium or calcium.
• onium iodides which are soluble in organic solvents.
• Suitable onium iodides embrace quaternary ammonium , phosphonium or sulfonium iodides.
• the structure of the onium cation is less important provided the solubility in organic solvents is high enough; the latter can be increased by increasing the hydrophobicity of the hydrocarbon residues attached to the onium cation.
• Some readily available materials are tetra-CrC 12 alkylated ammonium iodides and/or the following compounds:
• the onium iodides can be bound to an organic or inorganic polymer backbone, rendering a homogeneous or heterogenous catalytic system.
• the instant process can be run in air or in an inert atmosphere such a nitrogen or argon.
• the instant process can be run under atmospheric pressure as well as under reduced or elevated pressure. Elevated pressure can especially be useful in reactions with a hydrocarbon, which is gaseous under atmospheric pressure and the reaction temperature; in this case, pressure/temperature conditions are advantageous where the hydrocarbon forms a liquid phase or is at least partially dissolved in a suitable solvent.
• a second variation of the instant process is to simultaneously add separate solutions of the hydroperoxide and the nitroxyl compound to a mixture of the hydrocarbon, cosolvent (if used) and catalyst.
• the nitroxyl compound may be dissolved in water or the alcohol solvent used in the reaction. Some of the nitroxyl compound may be introduced into the reaction mixture prior to starting the peroxide addition, and all of the nitroxyl compound should be added prior to completing the peroxide addition.
• R 2 is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms; n is 1 to 4;
• R 3 is alkyl of 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms;
• p 1 to 3
• R is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms
• R 5 is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, an acyl radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R 4 and R 5 together are -(CH 2 )5CO-, phthaloyl or a divalent acyl radical of maleic acid;
• R 6 is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -NHalkyl of 1 to 18 carbon atoms or -N(alkyl) 2 of 2 to 36 carbon atoms,
• R 6 is a tetravalent alkoxy radical of a saturated or unsaturated aliphatic tetraol containing 4 to 18 carbon atoms
• R 9 is oxygen, or R g is nitrogen substituted by either hydrogen, alkyl of 1 to 12 carbon atoms or Ti
• R 10 is hydrogen or methyl
• Rn and R 12 are independently hydrogen or the group T 2
• R 3 is hydrogen, phenyl, straight or branched alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, straight or branched alkyl of 1 to 4 carbon atoms substituted by phenyl, cycloalkyl of 5 to 8 carbon atoms, cycloalkenyl of 5 to 8 carbon atoms, alkenyl of 2 to 12 carbon atoms, glycidyl, allyloxy, straight or branched hydroxyalkyl of 1 to 4 carbon atoms, or silyl or silyloxy substituted three times independently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms;
• R ⁇ is hydrogen or silyl substituted three times independently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms;
• h 0 to 4.
• k 0 to 5;
• x is 3 to 6;
• y is 1 to 10;
• z is an integer such that the compound has a molecular weight of 1000 to 4000 amu, e.g. z may be from the range 3-10;
• R 15 is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, -N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, or -N(alkyl) 2 of 2 to 16 carbon atoms,
• R 16 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorine and once by R 15 , or s-triazinyl substituted twice by R 15 with the condition that the two R 15 substituents may be different;
• R 17 is chlorine, amino substituted by alkyl of 1 to 8 carbon atoms or by T ⁇ -N(alkyl)T- ⁇ with alkyl of 1 to 8 carbon atoms, -N(alkyl) 2 of 2 to 16 carbon atoms, or the group T 3
• R s is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by -N(alkyl) 2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by -N(alkyl)T ⁇ with alkyl of 1 to 8 carbon atoms;
• R14, d,h, k, m, q, and Ti have the same meanings as in formulas (1) to (15);
• R 19 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms;
• R 20 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;
• R 2 3 is hydrogen, alkyl of 1 to 4 carbon atoms or acyl of 2 to 6 carbon atoms;
• R 24 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;
• R 2 5 is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -NHalkyl of 1 to 18 carbon atoms or -N(alkyl) 2 of 2 to 36 carbon atoms,
• R 26 is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18 carbon atoms, -NH-alkylene-NH- of 2 to 18 carbon atoms or -N(alkyI)-alkylene-N(alkyl)- of 3 to 18 carbon atoms.
• E is a carbon centered radical formed preferably from a C -Cnphenylalkane, especially toluene, ethylbenzene, isopropylbenzene; or C 5 -C ⁇ 2 cycloalkane, especially cyclohexene; or C 5 -C 12 cycloalkene, especially cyclohexene; or C 3 -C 8 alkene, especially propene; or a benzene which is substituted by C ⁇ -C alkyl and a further substituent selected from CrC alkoxy, glycidyl or glycidyloxy.
• Products of the present process can be employed with advantage for stabilizing organic material against the damaging effect of light, oxygen and/or heat, especially for stabilizing synthetic organic polymers or compositions containing them. They are notable for high thermal stability, substrate compatibility and good persistence in the substrate.
• thermoplastic polymers of most importance in present compositions are polyolefines and their copolymers, thermoplastic polyolefin (TPO), thermoplastic polyurethan (TPU), thermoplastic rubber (TPR), polycarbonate, such as in item 19 above, and blends, such as in item 28 above.
• TPO thermoplastic polyolefin
• TPU thermoplastic polyurethan
• TPR thermoplastic rubber
• polycarbonate such as in item 19 above
• blends such as in item 28 above.
• PE polyethylene
• PP polypropylene
• PC polycarbonate
• the regulator/initiator compound is present in an amount of from 0.01 mol-% to 30 mol-% , more preferably in an amount of from 0.1 mol-% to 20 mol-% and most preferred in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture.
• the reaction mixture is cooled down to 25°C and stirred with 61 g of an aqueous solution of Na 2 SO 3 (10%) until the disappearance of excess t-butylhydroperoxide.
• the aqueous phase is then separated and washed with ethylbenzene.
• the combined organic phases are washed with brine, dried over MgSO 4 , filtered, and the solvent is distilled off on a rotary-evaporator.
• the crude product is purified by flash-chromatography (silica gel, hexane : ethylacetate 9 : 1), yielding 5 g (60 % of theory) of a yellow oil.
• Example 2 Example 1 is repeated except that 32 mmol of 2,2,6,6-Tetramethylpiperidine-N- oxide are replaced by the equivalent amount of 2,2,6,6-Tetramethylpiperidine-4-one-N-oxide,
• a stirred mixture of 0.5g (3.2 mmol) TEMPO, 1.14 g (6.4 mmol) of 2-(4-ethyl-phenoxymethyl)- oxirane, 0.0118 g (0.032 mmol) of tetrabutylammoniumiodide and 0.62 g (4.8 mmol) of t- butylhydroperoxid (70% aqueous solution) is brought to 60°C. The temperature is maintained at 60°C for 4 hours until all of the TEMPO has reacted. The reaction mixture is cooled down to 25°C and stirred with 20g of a 10% aqueous Na 2 SO 3 solution until the disappearance of excess t-butylhydroperoxide.
• aqueous phase is then separated and washed with ethylbenzene.
• the combined organic phases are passed through a plug of silica gel, washed with brine, dried over MgSO 4 , filtered and the solvent distilled off on a rotary-evaporator, yielding 0.9 g of a colorless oil.
• Quantitative HPLC-analysis reveals a product-concentration of 65% w/w, corresponding to an overall yield of 54.8%.
• Example 5 A mixture of 4 mmol) of the product of Example 5 and 0.2 g Pd on charcoal (10%) in 10 ml of methanol is hydrogenated at 25°C and 4 bar of hydrogen. Filtration and evaporation of the solvent yields the title product as a slightly orange oil.
• the temperature is maintained at 60°C for another 24 hours, cooled down to 25°C and stirred with 120 g of a 10% aqueous Na 2 SO 3 solution until the disappearance of excess t-butylhydroperoxide.
• the aqueous phase is then separated and washed with ethylbenzene.
• the combined organic phases are washed with brine, dried over MgSO 4 , filtered and the solvent distilled off on a rotary-evaporator.
• the crude product is purified by flash-chromatography (silica gel, hexane : Ethylacetate 9 : 1), yielding the title product as a yellow oil.
• the reaction mixture is cooled down to 25°C and stirred with 47g of an aqueous 10% Na 2 SO 3 solution until the disappearance of excess t-butylhydroperoxide.
• the aqueous phase is then separated and washed with cyclohexane.
• the combined organic phases are washed with brine, dried over MgSO 4 , filtered and the solvent distilled off on a rotary-evaporator, yielding 12.2 g of a brownish oil partially crystallizing at low temperature.
• the title product is obtained as an off-white solid, mp 106°C - 110°C.
• reaction mixture is cooled down to 25°C and stirred with 18.9 g of an aqueous 10% Na 2 SO 3 solution until the disappearance of excess t-butylhydroperoxide.
• the aqueous phase is then separated and washed with cyclohexane.
• the combined organic phases are washed with brine, dried over MgSO 4 , filtered and the solvent distilled off on a rotary-evaporator, yielding 1.1 g g of a reddish solid.
• Purification by flash-chromatography (silica gel, hexane : ethylacetate 9 : 1) yields the title product as a white solid, mp 86°C - 90°C.
• reaction mixture is cooled down to 25°C and stirred with 132 g of an aqueous 10% Na 2 SO 3 solution until the disappearance of excess t-butylhydroperoxide.
• the aqueous phase is then separated and washed with cyclohexane.
• the combined organic phases are washed with brine, dried over MgSO 4 , filtered and the solvent distilled off on a rotary-evaporator, yielding 10 g of a reddish oil.
• Purification by flash-chromatography (silica gel, hexane : ethylacetate 9 : 1 ) yields the title product as a yellowish oil.
• Example 14 Preparation of the compound of Example 1 with the catalyst Bu 4 NI generated in situ from Bu 4 NCI / Nal; yield determination by HPLC
• Example 15 Preparation of the compound of Example 12 using immobilized onium iodide. This allows the catalyst be filtered off after the reaction.
• the reaction mixture is cooled down to 25°C and the catalyst filtered off.
• the filtrate is stirred with 57 g of an aqueous 10% Na 2 SO 3 solution until the disappearance of excess t- butylhydroperoxide.
• the aqueous phase is then separated and washed with cyclohexane.
• the combined organic phases are washed with brine, dried over MgSO 4 , filtered and the solvent distilled off on a rotary-evaporator, yielding 10.7 g (94% of theory) of the title product as a slightly orange oil.

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