To provide a solid catalyst containing a cyclic imide skeleton which is easily available and easily separable from reaction products and which is easily recovered and regenerated, and free from reaction inhibitory factors; and a process for oxidation of organic compounds with the solid catalyst.

An immobilized cyclic imide catalyst having a structure represented by following Formula (1), wherein X is oxygen or an -OR group (wherein R is hydrogen atom or a hydroxyl-protecting group); n is 0 or 1; Z¹ is a five- or six-membered cyclic imide skeleton to which an aromatic or nonaromatic ring Z² may be adjacent; elliptically shaped moiety S is an inorganic support; A¹ is a group linking silicon atom with the cyclic imide skeleton Z¹ or with the ring Z² and is either a divalent hydrocarbon group or a group composed of a divalent hydrocarbon group and an amide bond (-NHCO-); and the cyclic imide skeleton Z¹ and the ring Z² may each be substituted.

Gegenstand der Erfindung ist ein Verfahren zur Ozonolyse ungesättigter Einsatzstoffe, welches sich dadurch auszeichnet, dass man die Reaktion in einem strukturierten Reaktor durchführt.

In the presence of an imide compound (e.g., N-hydroxyphthalimide) shown by the following formula (1):    wherein R¹ and R² represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group and a cycloalkyl group, and R¹ and R² may bond together to form a double bond, or an aromatic or non-aromatic ring, and Y is an O or OH, and n denotes 1 to 3;

a substrate is allowed to contact with at least one reactant selected from (i) a nitrogen oxide and (ii) a mixture of carbon monoxide and oxygen to be introduced with at least one functional group selected from a nitro group and a carboxyl group. The nitrogen oxide includes, for example, a compound represented by the formula N_xO_y (e.g., N₂O₃, NO₂). The substrate includes, for example, a compound having a methine carbon atom (e.g., adamantane), a compound having a methyl group or a methylene group at an adjacent moiety of an aromatic ring. According to such reaction, the substrate can be efficiently nitrated or carboxylated even in a mild or moderate condition.

Process for the preparation of a heterocyclic o-dicarboxylic acid containing at least one N atom, in which a corresponding benzo-fused heterocyclic compound containing at least one N atom is oxidised in the presence of hydrogen peroxide, a Brönsted acid and an iron compound.

Preferably Fe(NO₃)₃ is used as the iron compound and HNO₃ as the Brönsted acid. The amount of iron compound to be used preferably lies between 0.1 and 2 mol.%, relative to the amount of employed benzo-fused heterocyclic compound containing at least one N atom. Even higher yields can be obtained if a copper compound or an organic electron-transferring compound is also used, in addition to the iron compound.

In particular, the process according to the invention can be used to prepare 2,3-pyridine dicarboxylic acids from corresponding quinoline compounds.

Herstellung von aromatischen Carbonsäuren der Formel I







        Ar(COOH)_n   I







(Ar = iso- oder heteroaromatischer Rest, n = 1 bis 4), durch Oxidation einer Verbindung II







        Ar(CH₃)_n   II







mit einer oxidierenden Stickstoff/Sauerstoff-Verbindung (III) in Gegenwart von Schwefelsäure und einer Vanadium-Verbindung (IV) bei 120 bis 180°C in flüssiger Phase, indem im Reaktionsgemisch pro Mol II 20 bis 100 Mol-% der Vanadium-Verbindung (IV) für die Oxidation zur Verfügung stehen.

A preparative method for carboxylic acids is disclosed in the present invention. The method is characterized in that: compounds (II) are reacted in the presence of hydrogen peroxide and base to produce target products (I), as represented by the following reaction scheme: wherein R¹ is aryl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl, thiadiazolyl, C_1-6 alkyl, C_3-6 cycloalkyl, C_2-6 alkenyl, C_2-6 alkynyl and hydrogen; R² is alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyl, alkylthiolcarbonyl, cyano, sulfonyl, sulfinyl, carbonyl, aldehyde, carboxyl, nitro, alkyl and hydrogen; R³ is alkoxycarbonyl, alkyl amido carbonyl, aminocarbonyl, cyano, sulfonyl, sulfinyl, carbonyl, carboxyl and nitro. The present invention has the following main benefits: cheap and readily available starting materials, safe processes, high yield, good quality, which facilitates industrial production.

The present invention discloses a method for the preparation of carboxylic acid comprising contacting β-ketosulfone of Formula (I) with nitrous acid.

The present invention suggests 2-oxo-1,3-dioxolane-4-acyl halides of formula (I), wherein X is selected from F, Cl, Br, I and mixtures thereof, preferably Cl, processes for the preparation of said 2-oxo-1,3-dioxolane-4-acyl halides, the use of said 2-oxo-1,3-dioxolane-4-acyl halides for the preparation of 2-oxo-1,3-dioxolane-4-carboxylic esters of formula (II), the use of said 2-oxo-1,3-dioxolane-4-acyl halides for the preparation of 2-oxo-1,3-diox-olane-4-carboxamides of formula (III), and also the use of said 2-oxo-1,3-dioxolane-4-acyl halides as agents for the blocking of amines.