Process for the synthesis of amine ethers from secondary amino oxides

Process for the preparation of an amine ether of the formula A

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• wherein
• a is 1 or 2;
• when a is 1, E′ is E
• when a is 2, E′ is L;
• E is C1-C36 alkyl;
• C3-C18 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 C3-C7alkenyl substituted by halogen, C1-C8alkoxy or phenoxy;
• C4-C12heterocycloalkyl;
• C4-C12heterocycloalkenyl;
• C7-C15 aralkyl or C4-C12heteroaralkyl, each of which is unsubstituted or substituted by C1-C4 alkyl or phenyl;
• or E is a radical of formula (VII) or (VIII)
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• Ar is C6-C10aryl or C5-C9heteroaryl;
• X is phenyl, naphthyl or biphenyl, which is substituted by 1, 2, 3 or 4 D and optionally further substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino;
• D is a group
• 50
• a group C(O)—G13 or a group C(O)—G9—C(O)—G13;
• G1 and G2, independently of each other, are hydrogen, halogen, NO2, cyano, —CONR5R6, —(R9)COOR4, —C(O)—R7, —OR8, —SR8, —NHR8, —N(R18)2, carbamoyl, di(C1-C18alkyl)carbamoyl, —C(═NR5)(NHR6), C1-C18alkyl;
• C3-C18alkenyl;
• C3-C18alkinyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C2-C12heterocycloalkyl;
• C1-C18alkyl or C3-C18alkenyl or C3-C18alkinyl or C7-C9phenylalkyl, C3-C12cycloalkyl or C2-C12heterocycloalkyl substituted by OH, halogen, NO2, amino, cyano, carboxy, COOR21, C(O)—R22, —C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino or a group —O—C(O)—R7;
• C2-C18alkyl which is interrupted by at least one O atom and/or NR5 group;
• or are C6-C10aryl;
• or phenyl or naphthyl which are substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, COOR21, C(O)—R22, C1-C4alkylamino or di(C1-C4alkyl)amino;
• or G1 and G2 together with the linking carbon atom form a C3-C12cycloalkyl radical;
• G5 and G6 are independently of each other H or CH3;
• G9 is C1-C12alkylene or a direct bond;
• G13 is C1-C18alkyl;
• G14 is C1-C18alkyl, C5-C12cycloalkyl, 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;
• G55 is H, CH3 or phenyl;
• G66 is —CN or a group of the formula —COOR4 or —CONR5R6 or —CH2—O—G14;
• L is alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18 carbon atoms, alkylene of 1 to 12 carbon atoms substituted by phenyl or by phenyl substituted by alkyl of 1 to 4 carbon atoms;
• or is alkylene of 4 to 18 carbon atoms interrupted by COO and/or phenylene;
• T′ is tertiary C4-C18alkyl or phenyl, each of which are unsubstituted or substituted by halogen, OH, COOR21 or C(O)—R22;
• or T′ is C5-C12cycloalkyl;
• C5-C12cycloalkyl which is interrupted by at least one O or —NR18—;
• a polycyclic alkyl radical having 7-18 carbon atoms, or the same radical which is interrupted by at least one O or —NR18—;
• or T′ is —C(G1)(G2)—T″;
• or C1-C18alkyl or C5-C12cycloalkyl substituted by
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• T″ is hydrogen, halogen, NO2, cyano, or is a monovalent organic radical comprising 1-50 carbon atoms;
• or T″ and T′ together form a divalent organic linking group completing, together with the hindered amine nitrogen atom and the quaternary carbon atom substituted by G1 and G2, an optionally substituted five- or six-membered ring structure;
• and
• R4 is hydrogen, C1-C18alkyl, phenyl, an alkali metal cation or a tetraalkylammonium cation;
• R5 and R6 are hydrogen, C1-C18alkyl, C2-C18alkyl which is substituted by hydroxy or, taken together, form a C2-C12alkylene bridge or a C2-C12-alkylene bridge interrupted by O or/and NR18;
• R7 is hydrogen, C1-C18alkyl or C6-C10aryl;
• R8 is hydrogen, C1-C18alkyl or C2-C18hydroxyalkyl;
• R9 is C1-C12alkylene or a direct bond;
• R18 is C1-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR21 or C(O)—R22;
• R21 is hydrogen, a alkali metal atom or C1-C18alkyl;
• and
• R22 is C1-C18alkyl;
• which process comprises
• reacting a N-oxyl amine of formula B
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• with a compound of formula IV or V
• E—H (IV)H—L—H (V)
• in the presence of an organic hydroperoxide and a catalytic amount of copper or a copper compound.