Process for the preparation of cyclic N-hydroxydicarboximides

Details Process for the preparation of cyclic N-hydroxydicarboximides Process for the preparation of cyclic N-hydroxydicarboximides

2000-09-07

2001-11-13

Owens, Amelia (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06316639

ABSTRACT:

BACKGROUND OF THE INVENTION
1) Field of the Invention
The invention relates to a process for the preparation of cyclic N-hydroxydicarboximides.
2) Background Art
N-Hydroxydicarboximides are used widely in industry. For example, they are used in the synthesis of organic compounds. EP-A 664479 and JP-A 06301168 disclose the use of N-hydroxyphthalimide as oxidizing agents in photographic developers. U.S. Pat. No. 5,332,637 describes the use of N-hydroxyphthalimide in toners.
N-Hydroxyphthalimide is also used widely for the synthesis of O-substituted hydroxylamines, which are frequently used for the formation of the oxime in pharmacologically effective compounds and compounds effective as pesticides.
EP-A 25199, EP-A 810318 and U.S. Pat. No. 4,709,025 disclose processes for the preparation of highly antibacterially effective O-substituted aminoxy or iminoxy compounds, in particular, from the group of betalactams, using N-hydroxyphthalimide.
WO 95/25090 describes the use of N-hydroxydi-carboximides as initiators in polymerization reactions. DE-A 19723961 and DE-A 19723890 disclose that N-hydroxyphthalimide and derivatives thereof can also be used for selective oxidation reactions.
For the synthesis of cyclic N-hydroxydicarboximides, the corresponding dicarboxylic anhydride and a hydroxylammonium salt, for example, hydroxylammonium chloride or hydroxylammonium sulfate, have hitherto always been used with the addition of a base.
L. F. Fieser and M. Fieser, “Reagents for Organic Synthesis”, Wiley N.Y., 1967, pp. 485-486 and K. Kurita, H. Imajo and Y. Iwakura, J. Polym. Science A-1 1979, 17, 1619-1629 propose, for example, the synthesis of N-hydroxyphthalimide using pyridine as the base.
DE-A 130680, H. Gross and I. Keitel, J. Prakt. Chem. 1969, 311, 692-693 and CN-A 1051170 disclose the syntheses of cyclic N-hydroxydicarboximides using hydroxylamine hydrochloride in aqueous solution, with sodium carbonate serving as the base.
A. Rougny and M. Daudon, Bull. Soc. Chim. Fr. 1976, 833-838 describe a synthesis route of N-hydroxy-phthalimide in which sodium acetate is used as the base.
WO 95/25090 discloses a process for the preparation of cyclic N-hydroxyimides using sodium hydroxide as the base.
It is a considerable disadvantage that in the case of all of the processes described, salts are formed during the synthesis which have to be subsequently disposed of as waste products. Moreover, free hydroxylamine is difficult to handle and for this reason is not used. An additional disadvantage of the processes described is that only the dicarboxylic anhydrides, and not the free dicarboxylic acids, can be used since the latter are rapidly deactivated via the acid/base reaction.
The object was therefore to find a process for the preparation of cyclic N-hydroxydicarboximides which does not require the addition of a base and therefore does not have the disadvantages of the prior art.
SUMMARY OF THE INVENTION
The invention provides a process for the preparation of cyclic N-hydroxydicarboximides, which comprises reacting dicarboxylic acids or anhydrides thereof with a salt of hydroxylamine in solution without the further addition of a base. In the process according to the invention, the corresponding dicarboxylic acids or anhydrides thereof are reacted with a salt of hydroxylamine.
The salts of hydroxylamine are compounds of the general composition
(H
3
NOH)
+
m
.H
+
n
.X
(m+n)−
where m is 1, 2 or 3, n is 0, 1 or 2, with the proviso that m+n=1, 2 or 3, and X is a phosphate, sulfate, nitrate, halide, acetate, trifluoroacetate, trichloroacetate, tetrafluoroborate or sulfonate R
Y
SO
3
−
.
The radical R
Y
is a C
1
-C
3
-alkyl, phenyl or 4-methylphenyl group. The salts of hydroxylamine can also be used in the form of their hydrates.
In the process according to the invention, preference is given to using salts of hydroxylamine from the group consisting of hydroxylammonium phosphate, hydroxylammonium sulfate, hydroxylammonium chloride and hydroxylammonium trifluoroacetate.
The reaction of the dicarboxylic acids or the dicarboxylic anhydrides is carried out with 1 to 5 equivalents, preferably with 1 to 2 equivalents, of the hydroxylammonium salt at temperatures between 60° C. and 180° C., preferably 80° C. to 150° C., and particularly preferably, 100° C. to 140° C.
Solvents which may optionally be added are water or inert solvents, for example aliphatic or aromatic hydrocarbons, alcohols, chlorinated hydrocarbons or ethers or else mixtures thereof. The amount of solvent here is between 10% and 5000%, based on the hydroxylammonium salt used.
Preferred solvents are water, methanol, ethanol, ligroin, benzene, toluene, nitrobenzene, xylene or methyl tert-butyl ether.
The reaction times are 10 min to 10 hours, preferably 1 hour to 6 hours.
The dicarboxylic anhydrides used, or the dicarboxylic acids obtainable therefrom by the addition of water, are preferably compounds which contain at least one five- or six-membered ring. The ring can be substituted or unsubstituted.
Particularly preferred dicarboxylic anhydrides are compounds having the general formulae Ia, Ib, Ic and Id.
Particularly preferred free dicarboxylic acids are compounds having the general formulae IIa, IIb, IIc and IId.
The radicals R
1
to R
16
can be identical or different and can be a halogen radical, carboxyl radical, salt or ester of a carboxyl radical, hydrogen, hydroxyl, formyl, carbamoyl, sulfono radical, ester or salt of the sulfono radical, sulfamoyl, nitro, amino, phenyl, aryl-C
1
-C
5
-alkyl, C
1
-C
12
-alkyl, C
1
-C
5
-alkoxy, C
1
-C
10
-carbonyl, carbonyl-C
1
-C
6
-alkyl, phospho, phosphono, phosphonooxy radical, ester or salt of the phosphonooxy radical.
The carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or mono- or polysubstituted by a further radical R
17
.
The aryl-C
1
-C
5
-alkyl, C
1
-C
12
-alkyl, C
1
-C
5
-alkoxy, C
1
-C
10
-carbonyl, carbonyl-C
1
-C
6
-alkyl radicals can be saturated or unsaturated, branched or unbranched and can be mono- or polysubstituted by a further radical R
17
.
This radical R
17
can be identical or different and can be a hydroxyl, formyl, carboxyl radical, ester or salt of the carboxyl radical, carbamoyl, sulfono radical or salt of the sulfono radical, sulfamoyl, nitro, amino, phenyl, C
1
-C
5
-alkyl, C
1
-C
5
-alkoxy radical.
The radicals R
7
and R
8
or R
9
and R
10
must not be a hydroxyl or amino radical at the same time.
In each case, two of the substituents R
1
to R
4
, R
5
to R
6
, R
7
to R
10
and/or R
11
to R
16
, can each be linked to a radical —E—, where —E— has one of the four following meanings:
—(—CH═CH)—
n
where n=1 to 3 or —CH═CH—CH═N—
The radicals R
7
to R
10
can also be connected to one another by one or two bridging elements —F—, where —F— is identical or different and is —O—, —S—, —CH
2
— or —CR
18
═CR
19
—. The radicals R
18
and R
19
can be identical or different and have the meaning of R
1
.
The cyclic N-hydroxydicarboximides obtained by the process of the invention are preferably compounds of the general structure which contain at least one five- or six-membered ring. The ring can be substituted or unsubstituted.
Particularly preferred N-hydroxydicarboximides are compounds having the general formulae IIIa, IIIb, IIIc and IIId.
Examples of compounds of the formula IIIa are N-hydroxyphthalimide and substituted N-hydroxyphthalimide derivatives, such as 3-amino-N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 4-methyl-N-hydroxyphthalimide, N-hydroxybenzene-1,2,4-tricarboxylic acid imide, N,N′-dihydroxybenzophenone-3,3′,4,4′-tetracarboxylic acid diimide or N,N′-dihydroxypyromellitic acid bisimide.
Examples of compounds of the formula IIIb are N-hydroxymaleimide and substituted N-hydroxymaleimide derivatives, such as pyridine-2,3-dicarboxylic acid N-hydroxyimide, N-hydroxynaphthalic acid imide and optionally, substituted N-hydroxynaphthalic acid imide derivatives.
Examples of compounds of the formula IIIc are N-hydroxysuccinimi

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