US 2003/0208071 A1Published application

Polyoxometalate catalysts for the preparation of sterically hindered N-substituted aryloxyamines

AssigneeCiba Specialty Chemicals Corporation

InventorsDeborah Judd, Sai P. Shum, Stephen D. Pastor

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Abstract

Sterically hindered N-substituted aryloxyamines are prepared by the Keggin polyoxometalate or the transition metal substituted polyoxometalate (TMS-POM) catalyzed decomposition of diazonium salts in the presence of a sterically hindered nitoxyl radical. These compounds are useful as thermal and light stabilizers for a variety of organic substrates.

Claims13

Dependent claims

A process for preparing a sterically hindered N-aryloxyamine of formula I, II, III, IV, V or VI

8
which process comprises
reacting a sterically hindered nitroxyl compound of formula VII, VIII, IX, X or XI
9
with a diazonium salt of an aromatic amine of formula XIII, XIII or XIV
10
in the presence of a polyoxometalate of formula (1) or (2)
11
where
M is W(VI) or Mo(VI);
or each M is independently selected from W(VI), Mo(VI), V(V), Nb(V) and Ta(V);
L is water;
X is P, Si, Sn, Ge, As, B, Al, Zn, Co or Fe;
M′ is a transition metal of Group 4, 5, 6, 7, 8, 9, 10, 11 or 12, or is a metaloid selected from Al, Si, Ga, Ge, Sn, Sb, Te and Pb;
and
Y is —CH2—, —O—, —S— or —NR8— where R8 is hydrogen or alkyl of 1 to 12 carbon atoms,
R6 and R7 are independently alkyl of 1 to 8 carbon atoms, or R6 and R7 together are tetramethylene or pentamethylene,
12
E2 is alkylene of 2 to 12 carbon atoms,
G is chloro or —N(2-ethylhexyl)2,
G1 is —CH2—, —CO— or —O—,
R is hydrogen, alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms, hydroxyl, carboxyl, amino, alkylamino of 1 to 18 carbon atoms, dialkylamino of 2 to 36 carbon atoms, oxo, alkylthio of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, aryloxy of 7 to 15 carbon atoms, benzoyloxy, alkylcarbonyloxy of 2 to 18 carbon atoms or alkylcarbonylamino of 2 to 18 carbon atoms, and
R1 to R5 are independently hydrogen, halogen, nitro, cyano, alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms, hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, aryloxy of 7 to 15 carbon atoms, alkylcarbonyloxy of 1 to 18 carbon atoms, alkylsulfonyl of 1 to 18 carbon atoms, arylsulfonyl of 6 to 15 carbon atoms, sulfo or —P(O)(OH)2 or —P(O)(OR6)2, or any two vicinal substituents connected together to form a mono or polycyclic ring, so that formula VII can represent inter alia 1-naphthylamine or 2-naphthylamine;
or any two vicinal carboxyl groups can be joined to form an imide;
or
13
where R, R6 and R7 are as defined above.

24 more elements

Dependencies are inferred from the claim text.

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Abstract

A process for preparing a sterically hindered N-aryloxyamine of formula I, II, III, IV, V or VI

8
which process comprises
reacting a sterically hindered nitroxyl compound of formula VII, VIII, IX, X or XI
9
with a diazonium salt of an aromatic amine of formula XIII, XIII or XIV
10
in the presence of a polyoxometalate of formula (1) or (2)
11
where
M is W(VI) or Mo(VI);
or each M is independently selected from W(VI), Mo(VI), V(V), Nb(V) and Ta(V);
L is water;
X is P, Si, Sn, Ge, As, B, Al, Zn, Co or Fe;
M′ is a transition metal of Group 4, 5, 6, 7, 8, 9, 10, 11 or 12, or is a metaloid selected from Al, Si, Ga, Ge, Sn, Sb, Te and Pb;
and
Y is —CH2—, —O—, —S— or —NR8— where R8 is hydrogen or alkyl of 1 to 12 carbon atoms,
R6 and R7 are independently alkyl of 1 to 8 carbon atoms, or R6 and R7 together are tetramethylene or pentamethylene,
12
E2 is alkylene of 2 to 12 carbon atoms,
G is chloro or —N(2-ethylhexyl)2,
G1 is —CH2—, —CO— or —O—,
R is hydrogen, alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms, hydroxyl, carboxyl, amino, alkylamino of 1 to 18 carbon atoms, dialkylamino of 2 to 36 carbon atoms, oxo, alkylthio of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, aryloxy of 7 to 15 carbon atoms, benzoyloxy, alkylcarbonyloxy of 2 to 18 carbon atoms or alkylcarbonylamino of 2 to 18 carbon atoms, and
R1 to R5 are independently hydrogen, halogen, nitro, cyano, alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms, hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, aryloxy of 7 to 15 carbon atoms, alkylcarbonyloxy of 1 to 18 carbon atoms, alkylsulfonyl of 1 to 18 carbon atoms, arylsulfonyl of 6 to 15 carbon atoms, sulfo or —P(O)(OH)2 or —P(O)(OR6)2, or any two vicinal substituents connected together to form a mono or polycyclic ring, so that formula VII can represent inter alia 1-naphthylamine or 2-naphthylamine;
or any two vicinal carboxyl groups can be joined to form an imide;
or
13
where R, R6 and R7 are as defined above.

24 more elements