Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
1999-11-24
2002-03-12
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S325000, C540S484000, C502S167000, C502S152000
Reexamination Certificate
active
06355842
ABSTRACT:
The oxidation reaction is one of the most fundamental reactions in organic chemistry and the literature therefore describes many variants. Recently, N-hydroxyphthalimide (NHPI) was disclosed as a suitable catalyst for oxidation reactions under mild conditions. According to EP-A1-0 824 962, NHPI or other imide compounds is or are combined with a metal cocatalyst and used for the oxidation of a multiplicity of organic substances. The oxidation of isoprenoids which have an allylic group to give hydroperoxides, which are then converted into the corresponding alcohols, aldehydes or ketone, is described in EP 0 198 351. N-hydroxydicarboximides are used as a catalyst. As a variant, Einhorn in Chem. Commun. 1997, pages 447-448, describes the use of NHPI in combination with acetaldehyde as catalysts for the oxidation of organic substrates, in particular of hydrocarbons.
There is nevertheless a lack of oxidation systems with oxygen as oxidizing agent which guarantee selective oxidation under conditions which are as mild as possible, since the variants known to date have a low selectivity and low reaction rate as disadvantages in the case of many compounds.
Unexpectedly, it has now been found that the use of a combination consisting of imide compound and metal cocatalyst in the presence of an aldehyde as cosubstrate permits the oxidation of a multiplicity of organic substrates under extremely mild conditions with high selectivity and high reaction rate.
The present invention accordingly relates to a process for the oxidation of substrates containing methyl (CH
3
), methylene (CH
2
) or methine (CH) groups by means of oxygen oxidation with the use of a catalyst system comprising an imide compound and a metal cocatalyst, wherein the substrates are oxidized together with an aromatic or aliphatic aldehyde having 2-20C. atoms in the presence of a catalyst system consisting of
a) an imide compound of the formula
in which R
1
and R
2
may denote H, OH, halogen, a C
1
-C
20
-alkyl, alkenyl or alkoxy group, an aryl group, a C
1
-C
6
-acyl group, a carboxyl or a C
1
-C
10
-alkoxycarbonyl group, or R
1
and R
2
together form a double bond in the formula I or form an aromatic or nonaromatic ring system in the formula I or II, X may denote O or OH and n may be an integer from 1 to 3, and
b) a cocatalyst containing one or more elements from the group consisting of the transition metals and of the 2A and 3A elements of the Periodic Table,
in an organic solvent to give the corresponding oxo compounds.
Substrates containing methyl, methylene or methine groups serve as a starting compound for the process according to the invention. Suitable substrates are described, for example, in EP-A1-0 824 962 and include aliphatic, alicyclic or aromatic hydrocarbons which may be saturated or mono- or polyunsaturated, heterocycles, alcohols, esters, aldehydes, ketones and amines. The substrates may have one or more substituents, such as, for example, halogens (F, Cl, Br, I), C
1
-C
6
-alkyl groups, oxo groups, hydroxyl groups, C
1
-C
6
-alkoxy groups, hydroxy-C
1
-C
4
-alkyl groups, carboxyl groups, C
1
-C
6
-alkoxycarbonyl groups, C
1
-C
6
-acyl groups, amino groups, substituted amino groups, cyano groups, nitro groups and the like.
Compounds which contain an aryl-CH
2
group, such as, for example, indanes, 1,2-diphenylethane and dibenz[b,f]azepines, e.g. 10,11-dihydro-5H-dibenz[b,f]-azepinecarboxamide, or compounds which contain methylene groups activated by carboxyl or carbonyl groups are preferably oxidized using the process according to the invention.
The process according to the invention uses a catalyst system consisting of 2 components, in combination with an aldehyde as cosubstrate. A suitable catalyst system is described, for example, in EP 0 824 962. Suitable imide compounds of the formula I for component a) are accordingly compounds of the formula I in which R
1
and R
2
may thus be identical or different and denote hydrogen, hydroxyl, halogen, such as I, Cl, F or Br, C
1
-C
10
-alkyl or alkoxy.
C
1
-C
20
-Alkyl are to be understood as meaning straight-chain, branched or cyclic alkyl radicals, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, decyl, dodecyl, etc. C
1
-C
15
-Alkyl groups are preferred, particularly preferably C
1
- to C
12
-alkyl groups. C
1
-C
20
-Alkenyl are to be understood as meaning straight-chain or branched alkenyl radicals. Examples of these are propenyl, hexenyl, octenyl, decenyl, dodecenyl, etc. C
4
- to C
18
-Alkenyl groups are preferred, particularly preferably C
6
- to C
12
-alkenyl groups. C
1
-C
20
-Alkoxy groups are to be understood as meaning, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy and hexyloxy groups, etc. C
1
-C
6
-Alkoxy groups are once again preferred, particularly preferably C
1
-C
4
-alkoxy groups. R
1
and R
2
may furthermore denote an aryl group, such as, for example, a phenyl group or a naphthyl group, a C
1
-C
6
-acyl group, such as, for example, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, etc. R
1
and R
2
may also be a carboxyl group or an alkoxycarbonyl group. Suitable alkoxycarbonyl groups are those which contain 1-10 C atoms in the alkoxy moiety. Examples of these are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, etc. Preferred groups are those which contain 1-6 C atoms, particularly preferably 1-4 C atoms, in the alkoxy moiety.
However, R
1
and R
2
may also together form a double bond in the formula I or an aromatic or nonaromatic ring system in the formula I or II, which ring system consists of one or more fused rings. Aromatic or nonaromatic ring systems having 5-12 C atoms, preferably having 6-10 C atoms, are preferred. The rings may also be heterocycles. Examples of these are cyclohexane or other cycloalkane rings which may optionally be substituted, and cyclohexene or other cycloalkene rings which once again may optionally be substituted, nonaromatic, bridged rings, a benzene ring, a naphthalene ring and other optionally substituted aromatic rings. Compounds of the formula I may have either a saturated or an unsaturated N-containing 6-membered ring. X in the formula I or formula II denotes O or OH. Depending on the meaning of X, the bond between N and X denotes either a double bond or a single bond. n denotes an integer from 1 to 3, preferably 1 or 2.
Preferred imide compounds are N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N,N′-dihydrocyclohexanetetracarboximide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytrimellitimide, N,N′-dihydroxynaphthalenetetracarboximide, N-hydroxy(dodecenyl)succinimide, N-hydroxy(octenyl)-succinimide, N-hydroxynaphthalimide, etc.
A cocatalyst is used as component b). The cocatalysts described in EP 0 824 962 are suitable for the catalyst system according to the invention. The cocatalyst accordingly contains one or more elements from the group consisting of 2A elements of the Periodic Table, such as Mg, Ca, Sr, Ba, or of the 3A elements, such as B or Al, or of the transition elements. Suitable transition elements are, for example, elements of the Periodic Table from group 3B, such as Sc, Y, La, Ce, Sm or lanthanoids, Ac or other actinoids, from group 4B (Ti, Zr, Hf), group SB (V, Nb, Ta), group 6B (Cr, Mo, W), group 7B (Mn, Tc, Re), group 8 (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), group 1B (Cu, Ag, Au) and from group 2B (e.g. Zn, Cd).
Preferably used cocatalysts are those which contain Ti, Zr or other group 4B elements, V or other 5B elements, Cr, Mo, W or other group 6B elements, Mn, Tc, Re or other group 7B elements, Fe, Ru, Co, Rh, Ni or other group 8 elements or Cu or other group 1B elements.
Combinations of elements of group 6B and/or 8 or 1B are particularly preferred. The cocatalysts
Alsters Paul
Bouttemy Sabine
DSM Fine Chemicals Austria Nfg GmbH & CoKG
Patel Sudhaker B.
Raymond Richard L.
Wenderoth Lind & Ponack LLP
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