Catalytic alkane oxidation process

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to catalytic oxidation of saturated hydrocarbons with oxygen-containing gas. Process according to invention comprises contacting alkane with oxygen source in presence of catalyst including compound of general formula: , where R1 and R2 independently represent hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxy, alkoxy, carboxyl, alkoxycarbonyl, or acyl, or R1 and R2 can together form double bond or aromatic or non-aromatic ring; Y represents oxygen atom; X oxygen atom to hydroxyl group; m is integer 1 or 2; and n = 1. Process is conducted at 20 to 100°C. Advantageously, catalyst includes cocatalyst.

EFFECT: increased efficiency of catalytic system.

14 cl, 5 tbl, 6 ex

 

The scope of the invention

The present invention relates to a method of catalytic oxidation of alkanes.

Prior inventions

Oxidation of saturated hydrocarbons, for example alkanes, in particular, cycloalkanes, active oxygen, such as molecular oxygen or air, to obtain the corresponding(s) of product(s) reaction - alcohol, ketone and/or acid - was for many years the subject of research activity because of the usefulness and benefits of reactions for the chemical industry from the point of view of environmental protection.

It was, in particular, it is proved that the oxidation of alkanes is a difficult reaction, for which usually tough conditions, and/or as a result of its exercise of the observed low degree of transformation of parent compounds and/or low selectivity for the desired reaction products. For example, it is known from literature, the oxidation of alkane such as cyclohexane with air in the presence of cobalt catalyst. However, for the reaction and activation of oxygen necessary high temperature and pressure. In addition, under specified conditions to obtain acceptable selectivity of the products, the degree of conversion or transformation of parent compounds must be reduced to values less than the example is about 10%. Alternative reaction includes the implementation of the oxidation macrocyclic alkane, such as cyclododecane, molecular oxygen in the presence of stoichiometric amount of boric acid, metaboric acid or boric anhydride to obtain alkylboronic reaction products. These reaction products hydrolyzing at a later stage to obtain the corresponding alcohol and boric acid. However, the degree of transformation of the parent compound, which represents a macrocyclic alkane, typically is still low, and therefore the total outputs of the desired reaction products, as a rule, small.

Another catalytic system described in EP-A-824962. This document disclosed a catalytic oxidation system, including below the N-hydroxyphthalimide compound of formula (I) and socialization, which is described as a system, accelerating the effective oxidation of the substrate at relatively mild conditions. For example, the oxidation of cyclohexane using N-hydroxyphthalimide and socializaton type manganese (II) described as a process carried out at atmospheric pressure (1 ATM) and a temperature of 100°obtaining carboxylic acid, with the formation of intermediate compounds ketone and alcohol is not observed.

Formula 1

Additional reaction is Oia, presented in this document represents the oxidation of cyclododecane in the presence of N-hydroxyphthalimide, socializaton type cobalt (II) and oxygen at atmospheric pressure and the reaction temperature 100°C.

Although catalytic oxidation system proposed in EP-A-824962, compared to the previously presented methods, provides to some extent the possibility of the reaction of catalytic oxidation of alkanes, especially cycloalkanes, under conditions from relatively mild to moderate, there is still a need for new catalysts, which show enhanced catalytic activity, and thus, compared with the catalysts of the prior art are effective even at low temperatures.

Additionally or alternatively, the new catalysts in contrast to the known catalysts usually show increased selectivity and/or the degree of transformation.

The invention

In one aspect the invention provides a method for the catalytic oxidation of alkane, comprising contacting the alkane with a source of oxygen in the presence of a catalyst comprising a compound of the following formula:

Formula 2

in which R1and R2independently represent a hydrogen atom, halogen atom, alkylen the th group, aryl group, cycloalkyl group, hydroxyl group, CNS group, carboxyl group, alkoxycarbonyl group or acyl group, or R1and R2may together form a double bond or aromatic or non-aromatic ring; Y represents an oxygen atom or a sulfur atom; X represents an oxygen atom or a hydroxyl group; m denotes an integer from 0 to 4; and n means an integer from 1 to 3.

Used in this description, the term "selectivity" means the relative share of each of the reaction products, that is usually ketone and alcohol, in moles, expressed as a percentage of the number of moles of the starting compound, converted into a specific reaction of catalytic oxidation.

Alkane

Catalytic oxidation of alkane involves getting as the corresponding reaction product of the alcohol, ketone or carboxylic acid or mixtures thereof.

Preferably alkane is cycloalkane, when used in this description, the term "cycloalkane" should be understood as including macrocyclic cycloalkanes having carbon ring, consisting of 8 or more members and up to 25 members, and simple cycloalkanes having carbon ring, consisting of less than 8 members, but more than 4 members, such as cyclopentane, cyclohexane.

Typically the qi is loakan is 5-C20-membered ring.

Cycloalkanes, suitable for use in the method presented in this description, include, for example, cyclopentane, cyclohexane, Cycloheptane, cyclooctane, cyclonona, cyclodecane, cyclodecane, cyclododecane, cycletrader, collaterality, cyclopentadecane, cyclohexadecane, cyclooctadiene, cyclododecene, cycloalkane, cyclodecane or collateralised.

Usually cycloalkyl may be substituted or unsubstituted. Preferably, cycloalkyl is unsubstituted. However, suitable substituted cycloalkanes include, for example, cycloalkanes, each of which has a hydroxyl group (for example, cyclohexanol, cyclooctanol, cyclodecane, cyclohexanol, cyclododecanol, cyclomethycaine, cycloartenol), cycloalkanes, each of which has oxoprop (for example, Cyclopentanone, cyclohexanone, methylcyclohexanone, dimethylcyclohexane, cyclohexadien, Cyclopentanone, cyclooctane, cyclooctadiene, ciclesonide, cyclodecane, cycloundecanone, cyclododecane, cyclomethycaine, cyclooctadiene, cycloalkane), cycloalkanes, each of which has an alkyl group (for example, methylcyclohexane, 1,2-dimethylcyclohexane, isopropylcyclohexane, Methylcyclopentane).

Additional alkanes suitable for use in the method in accordance with this is Subramaniam, represent linear alkanes, which may be unsubstituted or substituted, for example benzyl alkanes, such as ethylbenzene, or allyl alkanes.

The compounds of formula (2)

The compounds of formula (2) are cyclic, where m denotes an integer from 0 to 4, and preferably, it is equal to 0.

In the compounds represented by formula (2), R1and R2can be a halogen atom such as iodine atom, bromine, chlorine or fluorine. The alkyl group may be a straight chain or branched chain, containing from 1 to 10 carbon atoms which may be substituted by one or more substituents, or may be unsubstituted. Examples of suitable alkyl groups include, for example, methyl, ethyl, sawn, ISO-propyl, boutelou, isobutylene, second-boutelou, tributylin, pentelow, hexeline, heptylene, octillo, nonalloy or decile groups. The alkyl group preferably represents an alkyl group containing from 1 to 6 carbon atoms, and more preferably, a lower alkyl group containing from 1 to 4 carbon atoms.

Suitable aryl groups include, for example, phenyl group or naftalina group. Examples of suitable cycloalkyl groups include cyclopentyloxy, tsiklogeksilnogo and cyclooctyl group. Suitable alkoxy is performance communications group include, for example, metaxylene, amoxilina, propoxyimino, isopropoxyphenol, betaxolol, isobutoxide, tertbutoxide, pentyloxy, hexyloxy and other CNS group, each of which has 1 to 10 carbon atoms. Of these groups, preferred CNS group having from 1 to 6 carbon atoms, especially lower CNS group having from 1 to 4 carbon atoms.

Examples of suitable alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxyethanol, tertbutoxycarbonyl, ventilatsioonile, hexyloxyphenol and other alkoxycarbonyl group having CNS fragment from 1 to 10 carbon atoms. Preferred alkoxycarbonyl groups include from 1 to 6 carbon atoms in the CNS fragment of which is generally preferable are lower alkoxycarbonyl group having CNS fragment from 1 to 4 carbon atoms.

Examples of suitable acyl groups include, for example, formyl, acetyl, propionyl, butyryloxy, isobutyryloxy, valerino, isovaleryl, pivaloyl and other acyl groups having from 1 to 6 carbon atoms.

R1and R2may be the same or different.

In soy is Ananiah, represented by formula (2), R1and R2may together form a double bond or aromatic or non-aromatic ring. Preferred aromatic or non-aromatic ring may present With5-C12-membered ring, in particular With6-C10-membered ring and more preferably6-membered ring. Suitable ring may include a heterocyclic ring or a condensed heterocyclic ring hydrocarbon ring, such as non-aromatic alicyclic rings (e.g., cyclohexane ring or other cycloalkane ring, which may optionally have one or more substituents, cyclohexenone ring or other cycloalkene ring, which optionally can be substituted), non-aromatic ring with the internal bridge (custom made) (for example, 5-norbornene ring or other optionally substituted hydrocarbon ring with an internal bridge), aromatic rings such as benzene ring, naphthalene ring or other aromatic ring which may be optionally substituted. Almost ring may include an aromatic ring.

It is assumed that the substituents R1and R2the compounds of formula (2) is not involved in catalytic alkane oxidation. This is because IU is aNISM reactions of N-hydroxyphthalimide (NHPI) of the catalyst according to EP-A-824962, illustrated, for example, in: Ishii et al., Chem. Commun., 2000, 163-164, shows that the hydrogen atom of hydroxyl group in the NHPI is subtracted oxygen or complex socialization/oxygen with formation of an intermediate radical PINO, after the accession of a hydrogen atom is removed from the alkane to the radical PINO education again NHPI. Thus, R1and R2do not participate in the activation of oxygen, and is essentially the nature of these groups as such has nothing to do with the mechanism of action useful in the present invention compounds of formula (2). Therefore, R1and R2can be selected from a wide range of the above substituents.

Suitable in this invention catalysts include compounds shown by the following formulas: (2A)to(2g).

where R3, R4, R5, R6, R7, R8, R9, R10, R11and R12independently represent a hydrogen atom, alkyl group, hydroxyl group, CNS group, carboxyl group, alkoxycarbonyl group, acyl group, a nitrogroup, cyano, amino group or halogen atom; the bond between the nitrogen atom "N" and X is a simple bond or double bond; and R1and R2have the same values that are indicated in the above, and n, X and Y have the values listed below.

As for the substituents R3, R4, R5, R6, R7, R8, R9, R10, R11and R12they can represent the above alkyl group and preferably an alkyl group having from 1 to 6 carbon atoms. CNS group may be such as is indicated above, particularly suitable is the lowest CNS group having from 1 to 4 carbon atoms. Examples of suitable alkoxycarbonyl groups include those mentioned above, especially lower alkoxycarbonyl group having CNS fragment from 1 to 4 carbon atoms. As for the acyl group, there may be mentioned acyl group, presented above, in particular acyl group having from 1 to 6 carbon atoms. Examples of suitable halogen atoms include fluorine atoms, chlorine and bromine. Each of the substituents R3, R4, R5, R6, R7, R8, R9, R10, R11and R12may practice independently represent hydrogen atoms, lower alkyl groups having from 1 to 4 carbon atoms, carboxyl group, nitro group or halogen atoms.

Y represents an oxygen atom or a sulfur atom, and preferably an oxygen atom.

X represents an oxygen atom or hydroxyl group, and preferred is sustained fashion hydroxyl group. The relationship between the nitrogen atom N and X as such preferably represents a simple link.

In addition, n means an integer from 1 to 3, preferably 1 or 2, and more preferably 1.

For catalysis of the oxidation reaction can be used one or more compounds represented by formula (2).

In the preferred embodiment of this invention R1and R2together form an aromatic, unsubstituted With6-membered ring, that is, each of R3, R4, R5and R6formula (2C) independently represents a hydrogen atom; n is 1; Y is Oh and X represents a hydroxyl group. Therefore, in this particular embodiment, the preferred catalyst is N-hydroxycoumarin (also known as 1,1-dioxide, 2-hydroxy-1,2-benzisothiazol-3-(2H)-it", which for simplicity and brevity may be referred to in this description as "NHS") and which can be obtained in accordance with the method described in: Nagasawa et al. (J.Med. Chem., 1995, 38, 1865-1871).

The compounds of formula (2) can be usually obtained from Sultangaliev connection process limitirovaniya, well known to specialists in this field.

It was found that the compounds of the formula (2) possess high catalytic properties and are able to activate the source of oxygen and accelerate the oxidation of alkane even when bolenski temperatures of reaction, than the temperature, which apply when using the N-hydroxyphthalimide catalysts disclosed in EP-A-824962.

Normally, the amount of compounds of formula (2)used in the reaction for the catalytic oxidation of alkane, choose from a wide range from about 0.001 to 1 mol (from 0.01 to 100 mol.%), preferably from about 0.001 to 0.5 mol (from 0.1 to 50 mol.%), more preferably from about 0.01 to 0.30 mol and most preferably from about 0.01 to 0.25 mol per 1 mol of alkane.

A catalyst comprising a compound of the formula (2)may be any homogeneous system or a heterogeneous system. The oxidation catalyst or catalytic oxidation system may be a solid catalyst containing a catalytic component on a substrate or carrier. As the substrate in practice, there may be used a substrate made of activated carbon, zeolite, silica, silica - alumina, bentonite, or other porous substrates. In the solid catalyst, the amount of the catalytic component, which is the substrate may be such that the corresponding ratio of the compounds of formula (2) to 100 parts by weight of the substrate ranged from about 0.1 to 50 parts by weight, preferably from about 0.5 to 30 parts by weight and more preferably from about 1 to 20 parts by mass.

In the presence of the source of the ICA oxygen and a catalyst, comprising the compound of the formula (2)presented in this description, the alkane is subjected to the reaction of catalytic oxidation to a convenient way to obtain the reaction products, comprising a ketone, in particular monoketone, with access from moderate to high. This reaction occurs even when the alkane is the macrocyclic cycloalkane with 8-membered ring or a ring with a large number of carbon atoms, in particular 9-membered ring or a ring with a large number of carbon atoms (for example, C10-C25-membered ring), such alkanes typically have low activity in the oxidation. In this description of the way cycloalkane can be oxidized under mild conditions with high conversion and selectivity with obtaining a ketone, in particular macrocyclic monoketone, such as cycloalkanes. This ketone can be a useful precursor in obtaining, for example, long chain dicarboxylic acids, which can be used as feedstock to produce complex polyester, polyamide or plasticizer.

Acetalization

The catalyst used in the oxidation of alkane may optionally include, in addition to the compounds of formula (2), acetalization or its mixture.

Used in this invention an appropriate socket the catalysts usually have oxidizing properties. Usually socializaton include a metal complex of a metal or compound of the metal, where the metal may represent a transitional metal or alkaline-earth metal. Alternatively, socialization can be a compound that includes an element, such as boron, or other compounds containing an element of group 3B of the Periodic table of elements, such as aluminum.

Examples of suitable alkaline earth metals include magnesium Mg, calcium Ca, strontium Sr and barium Ba from the group 2A elements of the Periodic table of elements.

As examples of suitable transition metals can be named, for example, the elements of the group 3A of the Periodic table of elements (e.g., scandium Sc, yttrium Y, and lanthanum La, cerium CE, samarium Sm and other lanthanide elements, anemone Ac and other actinide elements), elements of group 4A of the Periodic table of elements (e.g., titanium Ti, zirconium Zr, hafnium Hf), elements of group 5A (for example, vanadium V, niobium Nb, tantalum Ta), the elements of group 6A (for example, chromium Cr, molybdenum Mo, tungsten W), elements group 7A (for example, manganese (Mn), technetium, Tc, re, Re), the elements of group 8 (e.g., iron Fe, ruthenium Ru, osmium Os, cobalt, rhodium Rh, iridium Ir, Nickel Ni, palladium Pd, platinum Pt), elements of group 1B (for example, copper Cu, silver Ag, gold Au) and the elements of group 2B (for example, zinc (Zn), cadmium Cd).

The high oxidizing the activity can be particularly demonstrated when the compound of the formula (2) is used in combination with a compound containing Ti, Zr, or other elements of the groups 4A, V, or other elements of group 5A, Cr, Mo, W, or other elements of group 6A, Mn, Tc, Re, or other elements of group 7A, Fe, Ru, Co, Rh, Ni, or other elements of group 8 or Cu, or other elements of group 1B.

As the boron compounds can be named, for example, boron hydride (for example, DIBORANE, tetraboron, pentaborane, decaborane), boric acid (e.g., orthoboric acid, metaboric acid, tetraborate acid), borate (for example, Nickel borate, magnesium borate, manganese borate), B2O3and other oxides of boron, borazan, brazen, burazin, boron amide, imide boron and other nitrogen-containing compounds of boron, BF3, BCl3tetrafluoroborate and other halides, esters of boric acid (for example, metalpart, phenylboric), etc. are Preferred for use in this invention, the boron compound includes boron hydrides, orthoboric acid and other boric acid or their salts, which preferably can be used boric acid. These socializaton can be used individually or in combination.

Suitable metal joining as socializaton can include a metal hydroxide, a metal oxide, comprising a double oxide which does not cause oxygen-containing acid, the halide of the metal salt of organic acid, salt of inorganic acid coordination compound (complex metal) or policycato, for example, heteroalicyclic or isopoliteia, or its salt, which contains the element of metal.

Suitable for use in this invention hydroxides metal typically include, for example, Mn(OH)2, MnO(OH), Fe(OH)2and Fe(OH)3.

Examples of suitable metal oxides are described in EP-A-824962 included in this description by reference. As examples of the double oxide or salts of oxygen-containing acids can be named, for example, MnAl2O4, MnTiO3, LaMnO3, K2Mn2O5,CaO·xMnO2(x= 0,5, 1, 2, 3, 5) and other salts of manganese, given by way of example in EP-A-824962.

Examples of suitable metal halides is presented in EP-A-824962 and include, for example, FeCl3and CuCl2and complex halides, such as M1MnCl3M12MnCl5M12MnCl6where M1represents a monovalent metal.

Examples of suitable salts of organic acids include cobalt acetate, manganese acetate, propionate, cobalt, manganese propionate, cobalt naphthenate, manganese naphthenate, cobalt stearate, manganese stearate, and other salts of fatty acids With2-20, manganese thiocyanate and relevant is the following salts of Ce, Ti, Zr, V, Cr, Mo, Fe, Ru, Ni, Pd, Cu and Zn.

Examples of suitable salts of inorganic acids include, for example, nitrate, sulfate, phosphate and carbonate salts of Co, Fe, Mn, Ni and Cu (for example, cobalt sulfate, iron phosphate, manganese carbonate, iron perchlorate).

Coordination (or complex) connection, suitable for use in this invention typically comprises a transition metal element and one or more ligands.

Examples of suitable ligands, which can be complex, include a hydroxyl group, metaxylene, amoxilina, propoxyimino, betaxolol and other CNS group, acetyl, propionyl and other acyl groups, methoxycarbonyl (acetate), ethoxycarbonyl and other alkoxycarbonyl group, acetylacetonato (ASAS), cyclopentadienyls group, halogen atom, CO, CN and their derivatives, an oxygen atom, H2O, NH3(ammine), NO, NO2(nitro), NO3(nitrate), Ethylenediamine, Diethylenetriamine, phenanthrolin and other nitrogen-containing compounds. In complexes or complex salts of the same or different ligands may be coordinated individually or in combination with transition metals.

The ligand is, for example, acyl group, alkoxycarbonyl group, acetylacetonato, halogen atom, CN and CR is spodnie and H 2O (akvo).

Examples of complexes suitable for use in this invention are described in EP-A-824962 and include, for example, acetylacetonate complexes (for example, acetylacetonate complexes of Fe, Co or Cu) and acetyl complexes (for example, cobalt acetate and copper acetate).

Policestate (isomaltulose or heteroalicyclic) typically includes at least one member selected from elements of group 5A or elements of group 6A of the Periodic table of elements, such as V (vanadium acid), Mo (molybdenum acid) or W (tungsten acid). However, the type of the element is metal not imposed special restrictions, and it can be used any of the metals shown and described in EP-A-824962. As explanatory examples of heteroalicyclic can be called cobalt molybdate, cobalt tungstate, tungstate, molybdenum, manganese molybdate, tungstate manganese tungstate manganese and molybdenum, vanadomolybdophosphoric, manganese molybdate and vanadium, phosphovanadomolybdate vanadium and molybdenum or phosphovanadomolybdate acid and margaretvenablesbingo. In socializaton constituting the catalytic oxidation system of the present invention, the preferred policestate is ecopolitical.

Typical functions of a specific socializaton depend on R is of Noventa of socializaton and are as such which are described in EP-A-824962 included in this description by reference.

Effective socialization designed for use in this invention in the case when the alkane is cycloalkane, usually represents a compound containing at least an element of group 8 of the Periodic table of elements (e.g., Co). Another effective socialization can include a combination of compounds containing an element of group 7A of the Periodic table of elements (e.g., Mn), with a compound containing an element of group 8 of the Periodic table of elements (e.g., Fe).

Another effective socialization designed for use in this invention is a compound of divalent transition metal, i.e., the compound of divalent cobalt, such as cobalt acetylacetonate Co(ASAS)2or a compound of divalent manganese, which usually ensures cycloalkanones from the respective cycloalkane with a significantly improved selectivity and yield. The use of this socializaton can also suppress the formation of side product diketone.

Preferred socializaton, useful in this invention can be selected from one or more socialization, including Co(acac)2, Co(OAc)2·4H2O, Cu(OAc) 2·4H2O, Cu(acac)2, Ru(CH3CN)4Cl2, Fe(acac)3or Co(ASAS)3.

The ratio of socializaton (socieites), in his presence, to alkane can be freely selected from the range not having a harmful effect on the activity and selectivity and usually it is from about 0.0001 mol (0.1 mol%) to 0.7 mol (70 mol.%), preferably from about 0.0001 to 0.5 mol, and more preferably from about 0.001 to 0.3 mol relative to one mol of alkane. Socialization practically used in the ratio of from 0.0005 to 0.1 mol, preferably from about 0.005 to 0.1 mol per 1 mol of alkane.

The corresponding ratio of socializaton, in his presence, to the compound of formula (2) can be selected from a range that will have no adverse effect on the reaction rate and selectivity, and usually it is, for example, from about 0.001 to 10 mol, preferably from about 0.005-5 mol and more preferably from about 0.01 to 3 mol relative to one mol of the compounds of formula (2). Acetalization can be practically used in an amount of from 0.01 to 5 mol (in particular from 0.001 to 1 mol relative to one mol of the compounds of formula (2).

Incidentally, the activity of the compounds of formula (2) can sometimes worsen with the increase in the share of socializaton. Therefore, to maintain high catalytic activity with the system of oxidation, the preferred ratio of socializaton relative to one mole of the compounds of formula (2) should be not less than the efficient amount of not more than 0.1 mol (for example, from about 0.001 to 0.1 mol, preferably from about 0.005 to 0.08 mol, and more preferably from about 0.01 to 0.07 mol).

If socialization is located on the substrate, the ratio of socializaton on the substrate is usually from about 0.1 to 30 parts by weight, preferably from about 0.5 to 25 parts by weight and more preferably from about 1 to 20 parts by weight relative to 100 parts by weight of the substrate.

When as socializaton used policestate (isomaltulose or heteroalicyclic) or its salt, the ratio of the polyacid is usually from 0.1 to 25 parts by weight, preferably from about 0.5 to 10 parts by weight and more preferably from about 1 to 5 parts by weight relative to 100 parts by weight of alkane.

The oxidation reaction

Source oxidation used in catalytic alkane oxidation, can be a source containing active oxygen, for example, hydrogen peroxide, perborate, percolate, percarbonate, molecular oxygen, but usually economically advantageous to use molecular oxygen. Usually the type of molecular oxygen, which can be advantageously used, not imposed limiting the Oia, and can be used any gas of pure gaseous oxygen or oxygen diluted with an inert gas, such as nitrogen, helium, argon or carbon dioxide. From the point of view of manipulation and security can also be used on the air. The reaction is preferably carried out in an atmosphere of molecular oxygen, such as air or gaseous oxygen.

The amount of oxygen that can be used in this description of the method of catalytic oxidation is typically in the range of 0.5 mole or more (e.g. 1 mol or more, preferably from about 1 to 100 mol, and more preferably from about 2 to 50 moles relative to 1 mole of alkane. For practical purposes, the oxygen is usually used in excess relative to the number of moles of alkane.

The catalytic oxidation reaction is usually carried out in a solvent, usually in an inert organic solvent. Suitable organic solvents include, for example, acetic acid and other organic carboxylic acids or hydroxycarboxylic acids, acetonitrile, benzene and other aromatic hydrocarbons, including triptorelin, and mixtures of these solvents. Preferred for use in the present invention organic solvents include acetic acid and triptorelin. Alternate is but as the reaction solvent can be used alkane and usually, if it is used in excess.

The reaction can be optionally carried out in the presence of a proton acid, which contributes to the smooth alkane oxidation. In addition, carrying out the reaction in the presence of this acid usually gives the desired oxidized compound with high selectivity and high yield. Proton acid can also be used as the reaction solvent. Examples of suitable proton acids include organic acids such as formic acid, acetic acid, propionic acid and other organic carboxylic acids, oxalic acid, succinic acid, tartaric acid and other hydroxycarboxylic acids, methansulfonate acid, econsultancy acid and other alkylsulfonate acid, benzolsulfonat acid, p-toluensulfonate acid and other arylsulfonate acid and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid.

The method in accordance with the present invention is characterized by the fact that usually the oxidation reaction proceeds smoothly to obtain the desired(s) of product(s) of the reaction even at relatively mild conditions, including room temperature. Usually the reactions the catalytic oxidation is carried out at a temperature, e.g. in the range from about 0 to 300°C, preferably from about 20 to 250°S, more preferably from about 20 to 150°and almost from about 20 to about 100°C. As mentioned above, the oxidation reaction can proceed smoothly even at relatively low temperatures, such as room temperature.

The reaction may be carried out at the ambient pressure (atmospheric pressure or at elevated pressures. The reaction is preferably carried out at atmospheric pressure. When the reaction is carried out at elevated pressure, the pressure is typically from about 1.5 to 100 ATM, preferably from about 2 to 70 MPa and more preferably from about 5 to 50 ATM. The reaction time can be freely selected in the range from about 30 minutes to 48 hours, preferably from about 1 to 36 hours and more preferably from about 2 to 24 hours depending on the reaction temperature and pressure.

The reaction can be performed in a conventional device, such as a batch reactor, the reactor properities actions or reactor continuous action, in the presence of active oxygen, usually of molecular oxygen or molecular oxygen. After completion of the reaction, the reaction product can be easily isolated and purified by one or more traditional methods, such as fil the walkie-talkie, condensation, distillation, extraction, crystallization, recrystallization, column chromatography or other means of selection.

Alternatively, if the product of the oxidation reaction contains a hydrophilic group, it can be isolated from the reaction mixture in accordance with the method described in EP-A-825165, in which the use of an aqueous solvent and non-aqueous solvent in the reaction mixture promotes the distribution of hydrophilic products of the oxidation reaction in the layer of aqueous solvent, and catalyst - layer non-aqueous solvent. Because of the above, this method is a convenient way enables efficient extraction of the reaction products of the oxidation and extraction of the catalyst, so the latest (catalyst) can be re-used in further reactions.

The invention is illustrated in the following examples of inorganic

In examples 2-6 presents the degree of conversion and selectivity are determined by gas chromatography (GC) (GC) using as internal standard 1,2,4-trichlorobenzene. In each of these examples to each reaction mixture as a standard was added 1,2,4-trichlorobenzene.

The GC conditions used in the analyses in the following examples:

GC:Varian Star 600, equipped with autopromotion (Varian 8200)
Column:CB CP Sil 50 m x 0.53 mm; outer diameter of 0.70 mm; df 1.00 micron; 133
Carrier gas:Nitrogen
Temperature program:
Injector:70°C for 0.1 min, then 150°C/min to 300°C, holding for 0.5 minutes at 300°
Detector:300°
Oven:70°C for 2 minutes, then 10°C/min to 300°C, holding for 10 minutes at 300°C.

Example 1 to Obtain N-hydroxycoumarin

N-hydroxycoumarin received in accordance with the following reaction scheme:

Synthesis of 2-(etoxycarbonyl)benzosulfimide ammonium(2)

Anhydride 2-sulfobenzoic acid (1; 50,2 g; 0,270 mol) in 160 ml of absolute ethanol was stirred overnight. After adding 60 ml of 7n methanolic ammonia solution and the mixture was stirred for another 2 hours and formed a thick white reaction mixture was osvetleni by adding 160 ml of methanol. The solution was diluted simple ether (1.1 l) before the termination of the deposition of solid particles and the product was collected by filtration and the whole night was dried in the air to receive to 60.6 g of compound (2) (yield 91%).

1H NMR (D2O) δ to 1.35 (t, 3H, CH3 ), and 4.40 (q, 2H, CH2), 7,56 (m, 3H, Ar-H), of 7.90 (m, 1H, Ar-H).

The obtained product was used in the next stage without further purification.

Synthesis of ethyl 2-(chlorosulfonyl)benzoate(3)

The above compound 2 (10.0 g, 0.040 mol) is suspended in dimethylformamide (7 ml) was added dropwise thionyl chloride (54 ml). The reaction mixture was heated under reflux overnight and then cooled in a bath with ice and carefully added to crushed ice (600 g). The cold mixture was immediately extracted with dichloromethane (I ml). The organic layer is washed with 5% NaHCO3(100 ml) and then water (100 ml) and dried over MgSO4.After evaporation of solvent received light transparent oil (quantitative yield 10 g). The product was used in the next stage without additional purification.

Rf: hexane/EtOAc (3/1) (silicate chromagen; 60F254available from Merck): 0,35.

1H NMR (CDCl3): δ of 1.43 (t, 3H, CH3), to 4.46 (q, 2H, och2), 7,72 for 7.78 (m, 3H, Harene.), 8,16 (m, 1H, Harene.).

13With NMR (CDCl3): δ 13,8 (CH3), 62,9 (CH2), 129,0, 130,2, 131,4, 132,7, 135,2 and 141,5 (6arene.), 165,9 (C=O).

Synthesis of ethyl 2-[(N-hydroxyamino)sulfonyl]benzoate(4)

To a solution of ethyl 2-(chlorosulfonyl)benzoate (3; 10.0 g, with 40.2 mmol) in tetrahydrofuran (130 ml) was added a solution of hydroxylamine hydrochloride (ceiling of 5.60 g of 80.1 mmol) in water 37 ml). The mixture was cooled in a bath with a mixture of ethanol and dry ice to a temperature of from -10°-15°and under stirring for 1 hour was added dropwise 10% NaHCO3(135 ml, 160,5 mmol). After stirring for another one hour two layers were separated. The aqueous bottom layer twice was extracted with dichloromethane (I ml and h ml) and the combined organic extracts were added to the upper layer THF. The combined solution (cloudy) and washed with water (75 ml) and the organic layer was dried (MgSO4) and evaporated to obtain compound (4) in the form of a clear yellow solid (6.50 g, yield 66%). The product was used in the next stage without additional purification.

1H NMR (CDCl3): δ of 1.42 (t, 3H, CH3), of 4.45 (q, 2H, och2), to 7.67-7,71 (m, 2H, Harene.), a 7.85-7,89 (1H, Harene.), 8,17 to 8.2 (m, 1H, Harene.), and 8.6 (s, 1H, NH).

13With NMR (CDCl3): δ 14,0 (CH3), 63,0 (CH2), 130,9, 131,5, 131,6, 132,7, 133,6 and 135,3 (6arene.), 167,5 (C=O).

Synthesis of ethyl 2-[[N-tetrahydropyranyloxy)amino]sulfonyl]benzoate(5)

To a solution of (4) (6.50 g, of 26.5 mmol) in dichloromethane (125 ml) was added dihydropyran (4,80 ml, 52,3 mmol) and monohydrate p-toluensulfonate acid (100 mg). The reaction mixture was stirred at room temperature for 1 hour and the dark reaction mixture is evaporated to obtain dark-colored oil. The oil was purified count the night flash chromatography on Kieselgel 6 (kieselgel 6) using as an eluting solvent mixture of EtoAc:hexane (1:6), when it got to 8.70 g of compound (5) as a pale yellow oil (quantitative yield).

Rf: hexane/EtOAc (2/1) (silicate chromagen; 60F254available from Merck): 0,3.

1H NMR (CDCl3): δ 1,3-2,0 (m, N, CH2TNR and CH3), 3,4-3,9 (m, 2H, och2TNR), 4.4 to 4.5 (m, 2H, och2), 5,1-of 5.15 (m, 1H, O-CH-AU TNR), of 7.4 to 8.2 (m, 4H, Harene.), 8,9 (m, 1H, NH).

Synthesis of 2-[{N-(tetrahydropyranyloxy)amino]sulfonyl]benzoic acid(6)

The solution of the above compound (5) (8,70 g of 26.4 mmol) in dioxane (82 ml) omilami addition of 6M NaOH (128 ml) and water (70 ml) and the mixture was heated under reflux for 2 hours. The reaction mixture was cooled (<10°C) and then was extracted with EtOAc (g ml). The combined EtOAc extracts were washed with water (135 ml) and the rinse was added to the original aqueous solution. The aqueous solution was covered with EtOAc (400 ml) and acidified using 6N HCl (135 ml). The phases were separated and the aqueous phase was again extracted with EtOAc (135 ml). The combined extracts were washed with water (I ml), dried (MgSO4and the solution volume was reduced. Formed precipitate was filtered and then dried in vacuum to obtain 3.03 g of compound (6) in the form of a white powder (yield 49% after taking into account 1,90 g extracted the source material).

1H NMR (CDCl3): δ 1,4-1,8 (m, 6N, CH2TNR), of 3.5-3.9 (m, 2H, och2TNR), a 5.1 (m, 1H, O-CH-AU TNR), of 7.6 to 7.8 (m, 2H, Harene./sub> ), 7,9-to 7.95 (m, 1H, Harene.), 8,05 to 8.1 (m, 1H, Harene.), and 9.1 (s, 1H, NH)

Synthesis of 1,1-dioxide, 2-(tetrahydropyranyloxy)-1,2-benzisothiazol-3(2H)she(N-(tetrahydropyranyloxy)saccharin7)

The mixed solution of the compound (6) (2,87 g, 9.50 mmol) in dry distilled tetrahydrofuran (40 ml) was cooled in an atmosphere of nitrogen in a bath with a mixture of ethanol and dry ice to a temperature of from -10°-15°and added isobutylparaben (1.70 ml, 13,10 mmol) and then triethylamine (of 1.85 ml, 13,30 mmol). After 5 minutes, bath with dry ice was removed and upon reaching room temperature, the precipitate of triethylamine hydrochloride was collected by filtration and the filtrate evaporated to obtain 2.67 g of light yellow powder. The product was recrystallized from EtOAc (18 ml) to give 2.00 g of the compound (7) in the form of white crystals (yield 78%).

1H NMR (CDCl3): δ 1,6-2,2 (m, 6N, CH2TNR and CH3), 3,8-4,2 (m, 2H, CH2-AU TNR), the 5.45 (s, 1H, O-CH-AU TNR), is 7.9 to 8.1 (m, 4H, Harene.)

13With NMR (CDCl3): δ 17,7, 24,8, 27,7, (CH2TNR), 62,4 (O-CH2), 104,9 (O-SN-O), 121,6, 125,5, 125,8, 134,8, 135,5, 136,4 (6Sarene.), 158,5 (C=O)

Synthesis of 1,1-dioxide, 2-hydroxy-1,2-benzisothiazol-3(2H)she(N-hydroxycoumarin8)

Obtained, as indicated above, the compound (7) (1.90 g, 6,70 mmol) was dissolved in tetrahydrofuran (14 ml) by heating on a water bath at 45°With, then added water (3.5 ml), PEFC is what was added triperoxonane acid (0.1 ml). The solution was stirred at 45-50°C for 7.5 hours, and after adding water (7 ml) the mixture was evaporated to small volume. Resulting solid suspension was collected and washed with water and then recrystallized using cold diethyl ether. After air drying, the solid is recrystallized from a mixture of EtOAc/hexane to obtain 980 mg of crystalline compound (8) (yield 73%).

1H NMR (DMSO): δ of 7.9 to 8.1 (m, 4H, Harene.), and 11.2 (user., 1H, NOH)

13With NMR (DMSO): δ 121,5, 125,1, 125,8, 134,7, 135,2, 135,7 (6 Witharene.), 157,5 (C=O)

Example 2 - alkane Oxidation in the presence of N-hydroxycoumarin

Example A

To 7.5 ml of acetic acid was added 504 mg (3.0 mmol) of cyclododecane and 60 mg (0.3 mmol) N-hydroxycoumarin. Formed mixture was stirred under oxygen atmosphere at a temperature of 100°C for 8 hours. The reaction was repeated several times and the products of each reaction mixture were analyzed by gas chromatography. The results were averaged, and they showed that cyclododecane turned with an average degree of transformation from 19.7% to 34.4% in cyclododecanone (average selectivity ranged from 56.7% to 80,8%) and cyclododecanol (average selectivity 26,1%).

Example A

To 7.5 ml of acetic acid was added 504 mg (3.0 mmol) of cyclododecane and 60 mg (0.3 mmol) N-hydroxycoumarin. Formed mixture stirred the atmosphere of oxygen at a temperature of 100° With in 24 hours. The reaction was repeated several times and the products of each reaction mixture were analyzed by gas chromatography. The results were averaged, and they showed that cyclododecane turned with an average degree of transformation from 50,0% to 69.8% in cyclododecanone (average selectivity ranged from 31.9% to 52%) and cyclododecanol (average selectivity of 1.2%).

Example 3 - Comparison of efficiency of N-hydroxycoumarin and N-hydroxyphthalimide (EP-A-824962) at different temperatures

Examples A-A

To 7.5 ml of acetic acid was added 504 mg (3.0 mmol) of cyclododecane, 60 mg (0.3 mmol) N-hydroxycoumarin and 3.9 mg (0.015 mmol) of acetylacetonate With(ASAS)2. Formed mixture was stirred under oxygen atmosphere at a temperature of either 100°or 75°s or 50°within the time period specified below in table 1. Then, each reaction mixture was analyzed by gas chromatography to determine the degree of conversion of cyclododecane and selectivity of the reaction with respect to the products of cyclododecanone and cyclododecanol. The results are shown below in table 1.

Examples 3A4-A

To 7.5 ml of acetic acid was added 504 mg (3.0 mmol) of cyclododecane, for 48.9 mg (0.3 mmol) N-hydroxyphthalimide (in this description for simplicity and brevity marked "NHPT) and 3.9 mg (0.015 mmol) of acetylacetonate With(ASAS)2. Formed mesh was stirred under oxygen atmosphere at a temperature of either 100° With or 75°s or 50°within the time period specified below in table 1. Each reaction mixture was analyzed as described above and the results are presented in table 1.

Table 1
ExampleCatalystTemperature/ reaction timeThe degree of transformationThe selectivity for C1The selectivity for C2With1+C2
A100°S, 6 h64%31%5,5%36,5%
ANHS75°C, 8 hours43%45%12%57%
A50°C, 24 hour41,5%46,5%12,5%59%
3A4100°C, 4 h57%29%7%36%
ANHPI75°C, 8 hours35%42%8%50%
A50°C, 24 hour0%///
With1is cyclododecanone
With2is cyclododecanol

As shown in the above example 3, the degree of transformation of cyclododecane in the presence of N-gidroksistearinovoj catalyst is higher than in the presence of N-hydroxyphthalimide (EP-A-824962) at 100°and 75°and is respectively 64% and 57% at 100°and 43% and 36% at 75°C. it has Been found that when the oxidation reaction is carried out in the presence of N-hydroxyphthalimide at 50°it does not occur. Conversely, when the reaction was carried out in the presence of N-hydroxycoumarin, watched the degree of transformation of cyclododecane of 41.5%.

Example 4 - alkane Oxidation in the presence of N-hydroxycoumarin and socializaton

Examples A-E show the effect of temperature on the degree of conversion and selectivity of the reaction when using as socializaton of acetylacetonate With(ASAS)2.

Examples A-E show the change in the degree of conversion and selectivity, when as socializaton instead of With(ASAS)2use Co(OAc)2·4H2O.

The results are shown below in table 2.

Table 2
ExampleT

(°)
Time

(h)
With Epen transformation

(%)
With1< / br>
(%)
With2< / br>
(%)
With3< / br>
(%)
With1+C2+C3< / br>
(%)
A100664315,52a 38.5
A758434512259
A6010354312,5156,5
A502041,546,512,5261
A100663,532,552,540
A7585042,59253,5
A5024455211265
With1is cyclododecanone
With2is cyclododecanol
With3is cyclododecene

Example A

the 7.5 ml of acetic acid was added 504 mg (3.0 mmol) of cyclododecane and 60 mg (0.3 mmol) N-hydroxycoumarin and 3.9 mg (0.015 mmol) of acetylacetonate With(ASAS) 2. Formed mixture was stirred under oxygen atmosphere at a temperature of 100°C for 6 hours. Contained in the reaction mixture were analyzed by gas chromatography, and in accordance with the analysis, it was found that cyclododecane turned with a degree of conversion of 64% in cyclododecanone (selectivity of 31%, a yield of 20%), cyclododecanol (selectivity of 5.5%, the yield of 3.5%) and cyclododecene (selectivity of 2%, the yield of 1.5%).

Example A

The reaction was carried out, following in General the procedure of example A, except that the reaction was carried out at 75°C for 8 hours instead of 100°C for 6 hours. The analysis method GC of the reaction mixture showed that cyclododecane turned with a degree of conversion of 43% in cyclododecanone (selectivity of 45%, the yield of 19.5%), cyclododecanol (selectivity 12%, 5%) and cyclododecene (selectivity 2%, 1%).

Example A

The reaction was carried out, following in General the procedure of example A, except that the reaction was carried out at 60°C for 10 hours instead of 100°C for 6 hours. GC-analysis of reaction mixture showed that cyclododecane turned with a degree of conversion of 35% in cyclododecanone (selectivity 43%, exit 15%), cyclododecanol (selectivity of 12.5%, the yield of 4.5%) and cyclododecene (selectivity of 1%, the yield of 0.5%).

Example A

The reaction was carried out, following in General is yodice example A, except that the reaction was carried out at 50°C for 20 hours instead of 100°C for 6 hours. GC-analysis of reaction mixture showed that cyclododecane turned with the degree of transformation of 41.5% in cyclododecanone (selectivity 46,5%, the yield of 19.5%), cyclododecanol (selectivity of 12.5%, 5%) and cyclododecene (selectivity 2%, 1%).

Example A

The reaction was carried out, following in General the procedure of example A, using 3.7 mg (0.015 mmol) of Co(OAc)2·4H2O instead of With(ASAS)2. GC-analysis of reaction mixture showed that cyclododecane turned with the degree of transformation of 63.5% in cyclododecanone (selectivity of 32.5%, the yield of 20.5%), cyclododecanol (selectivity of 5%, 3%) and cyclododecene (selectivity of 2.5%, the yield of 1.5%).

Example A

The reaction was carried out, following in General the procedure of example A, using 3.7 mg (0.015 mmol) of Co(OAc)2·4H2O instead of With(ASAS)2and the reaction was carried out at 75°C for 8 hours instead of 100°C for 6 hours. The analysis method GC of the reaction mixture showed that cyclododecane turned with a degree of conversion of 50% in cyclododecanone (selectivity 42,5%, the yield of 21.5%), cyclododecanol (selectivity of 9%, the yield of 4.5%) and cyclododecene (selectivity 2%, 1%).

Example A

The reaction was carried out, following in General the procedure of example A, using as the of socializaton 3.7 mg (0.015 mmol) of Co(OAc) 2·4H2O and the reaction was carried out at 50°C for 24 hours. GC-analysis of reaction mixture showed that cyclododecane turned with a degree of conversion of 45% in cyclododecanone (selectivity of 52%, the yield of 23.5%), cyclododecanol (selectivity 11%, 5%) and cyclododecene (selectivity 2%, 1%).

Examples A-E show the degree of conversion and selectivity obtained in the oxidation of cyclododecane in the presence of N-hydroxycoumarin and various metal socialization. The results are shown below in table 3.

Table 3
ExampleT

(°)
Time

(h)
AcetalizationThe degree of conversion

(%)
With1< / br>
(%)
With2< / br>
(%)
With3< / br>
(%)
With1+C2+C3< / br>
(%)
A1008Cu(OAc)2.4H2O55326341
4A97510Cu(OAc)2.4H2O2834186,558,5
4A101006 Cu(acac)244,53111,5244,5
4A111002Ru(CH3CN)4Cl22131,5151056,5
4A12752Ru(CH3CN)4Cl22435,514,58,558,5
4A131006Fe(acac)33132,523,5258
4A147520Fe(acac)323,537,532,52,572,5
4A151005Co(acac)364306339
4A166024Co(acac)335,54319264
4A175024Co(acac)32248262,576,5
With1is cyclododecanone
With2is cyclododecanol
With3is cyclododecene

Example A

The reaction was carried out, following in General the procedure of example A using 2,9 mg (0.015 mmol) of Cu(OAc)2·4H2O instead of Co(ASAS)2in the reaction cyclododecane turned with a degree of conversion of 55% in cyclododecanone (selectivity of 32%, the yield of 17.5%), cyclododecanol (selectivity of 6%, the yield of 3.5%) and cyclododecene (selectivity of 3%, the yield of 1.5%).

Example A

The reaction was carried out, following in General the procedure of example A, using as socializaton of 2.9 mg (0.015 mmol) of Cu(OAc)2·4H2O and the reaction was carried out at 75°C for 10 hours. The analysis method GC of the reaction mixture showed that cyclododecane turned with a degree of conversion of 28% in cyclododecanone (selectivity 34%, the yield of 9.5%), cyclododecanol (selectivity 18%, 5%) and cyclododecene (selectivity of 6.5%, the yield of 2%).

Example A

The reaction was carried out, following in General the procedure of example A, using 4.0 mg (0.015 mmol) of Cu(ASAS)2instead With(ASAS)2in the reaction cyclododecane turned with a degree of conversion of 44.5% in cyclododecanone (selectivity 31%, yield 14%), cyclododecanol (selectivity of 11.5%, 5%) and cyclododecene (selek is Yunosti 2%, output 1%).

Example A

The reaction was carried out, following in General the procedure of example A, using 4.0 mg (0.015 mmol) of Ru(CH3CN)4Cl2instead With(ASAS)2. After 2 hours, watched the absence of transformation and termination reactions. The analysis method GC of the reaction mixture showed that cyclododecane turned with a degree of conversion of 21% in cyclododecanone (selectivity of 31.5%, the yield of 6.5%), cyclododecanol (selectivity of 15%, yield 3%) and cyclododecene (selectivity 10%, the yield of 2%).

Example A

The reaction was carried out, following in General the procedure of example A, using 4.0 mg (0.015 mmol) of Ru(CH3CN)4Cl2at 75°C for 2 hours instead of With(ASAS)2at 100°C for 6 hours. After 2 hours, watched the absence of transformation and termination reactions. The analysis method GC of the reaction mixture showed that under these conditions, cyclododecane turned with a degree of conversion of 24% in cyclododecanone (selectivity of 35.5%, the yield of 8.5%), cyclododecanol (selectivity of 14.5%, the yield of 3.5%) and cyclododecene (selectivity of 8.5%, the yield of 2%).

Example A

The reaction was carried out, following in General the procedure of example A, using 5.3 mg (0.015 mmol) of Fe(ASAS)3instead With(ASAS)2in the reaction cyclododecane turned with a degree of conversion of 31% in cyclododecanone (selectivity with 32.5%output 10%), cyclododecanol (electively 23,5%, the output of 7.5%) and cyclododecene (selectivity of 2%, the yield of 0.5%).

Example A

The reaction was carried out, following in General the procedure of example A, using as socializaton 5.3 mg (0.015 mmol) of Fe(ASAS)3and the reaction was carried out at 75°C for 20 hours. The analysis method GC of the reaction mixture showed that cyclododecane turned with the degree of transformation of 23.5% in cyclododecanone (selectivity of 37.5%, yield 9%), cyclododecanol (selectivity of 32.5%, the yield of 7.5%) and cyclododecene (selectivity of 2.5%, the yield of 0.5%).

Example A

The reaction was carried out, following in General the procedure of example A, using 5.3 mg (0.015 mmol) Co(ASAS)3instead of Co(ASAS)2in the reaction cyclododecane turned with a degree of conversion of 64% in cyclododecanone (selectivity of 30%, the yield of 19.5%), cyclododecanol (selectivity 6%, 4%) and cyclododecene (selectivity of 3%, the yield of 2%).

Example A

The reaction was carried out, following in General the procedure of example A, using as socializaton 5.3 mg (0.015 mmol) Co(ASAS)3and the reaction was carried out at 60°C for 24 hours. The analysis method GC of the reaction mixture showed that cyclododecane turned with a degree of conversion of 35.5% in cyclododecanone (selectivity 43%, the yield of 15.5%), cyclododecanol (selectivity of 19%, yield 7%), cyclododecene (selectivity of 2%, the yield of 0.5%) and dodecandioic the GTC (selectivity of 18.5%, exit 4%).

Example A

The reaction was carried out, following in General the procedure of example A, using as socializaton 5.3 mg (0.015 mmol) Co(ASAS)3and the reaction was carried out at 50°C for 24 hours. The analysis method GC of the reaction mixture showed that cyclododecane turned with a degree of conversion of 22% in cyclododecanone (selectivity 48%, yield 11%), cyclododecanol (selectivity 26%, the yield of 5.5%), cyclododecene (selectivity of 2.5%, the yield of 0.5%) and dodekanisou (selectivity of 18.5%, 4%).

The results show that when using socializaton containing elemental copper (see examples A-A), instead of the complex Co (II) examples A-E, obtained the degree of conversion is lower and selectivity comparable to selectively obtained with the use of a complex of cobalt (II), or just above them. When the oxidation reaction is carried out in the presence of Fe(ASAS)3implemented the average degree of transformation of cyclododecane with high selectivity for the formation of products of the oxidation reaction as at 100°and at 75°C. in Addition, from the results shown in table 3, it follows that at 100°With the degree of conversion and selectivity obtained in the presence of a complex of cobalt (III) (Co(ASAS)3)similar to those obtained in the presence of complexes of cobalt (II). At low the Arturo cobalt (III) results in lower degrees of conversion in comparison with cobalt (II) and a higher selectivity with respect to the education of cyclododecanone, cyclododecanol and cyclododecanone.

Examples A-A

Examples A-E show the degree of conversion of the reaction and the selectivity obtained using different solvents.

The results are shown below in table 4.

Table 4
ExampleSolventT°)AcetalizationTime

(h)
The degree of conversion

(%)
With1< / br>
(%)
With2< / br>
(%)
With4< / br>
(%)
In General

(%)
ACH3CN85°With(ASAS)2222834,514nd.48,5
APhCl100°With(ASAS)282452,526,5nd.79
APhCF3100°With(ASAS)224325420nd.74
APhCF380°With(ASAS)24824 5821nd.79
APhCF3100°With(ASAS)3434,56416,5585,5
APhCF380°With(ASAS)3102472of 17.50to 89.5
APhCF3100°With(SLA)224264930nd.79
APhCF3100°Cu(ASAS)2831,5of 60.59,5nd.70
APhCF3100°Fe(ASAS)382058,537nd.95,5
With1is cyclododecanone
With2is cyclododecanol
With4is dodekanisou
In General = 1+With2+C4
nd. means "not determined"

Example A

To 7.5 ml of acetonitrile was added 504 mg (3.0 mmol) of cyclododecane, 60 mg (0.3 mmol) N-hydroxycoumarin and 3.9 mg (0.015 mmol) of acetylacetonate Co(ASAS)2. Formed mixture was stirred under oxygen atmosphere at a temperature of 85°C for 22 hours. Contained in the reaction mixture were analyzed by gas chromatography, it was found that cyclododecane turned with a degree of conversion of 28% in cyclododecanone (selectivity of 34.5%, the yield of 9.5%) and cyclododecanol (selectivity 14%, 4%).

Example A

The reaction was carried out, following in General the procedure of example A, except that the reaction was carried out at 100°in chlorobenzene for 8 hours. Under these conditions, cyclododecane turned with a degree of conversion of 24% in cyclododecanone (selectivity 52,5%, the yield of 12.5%) and cyclododecanol (selectivity of 26.5%, the yield of 6.5%).

Example A

The reaction was carried out, following in General the procedure of example A, except that the reaction was carried out at 100°in triptoreline (9 ml) for 24 hours. Under these conditions, cyclododecane turned with a degree of conversion of 32% in cyclododecanone (selectivity of 54%, the yield of 17.5%) and cyclododecanol (selectivity of 20%, the yield of 6.5%).

Example A

The reaction was carried out, following in General the procedure of example A, for which the conclusion of the addition, the reaction was carried out at 80°in triptoreline (9 ml) for 48 hours. Under these conditions, cyclododecane turned with a degree of conversion of 24% in cyclododecanone (selectivity of 58%, yield 14%) and cyclododecanol (selectivity 21%, 5%).

Example A

To 9 ml of triptoreline added 504 mg (3.0 mmol) of cyclododecane, 60 mg (0.3 mmol) N-hydroxycoumarin and 5.3 mg (0.015 mmol) of acetylacetonate Co(ASAS)3. Formed mixture was stirred under oxygen atmosphere at a temperature of 100°C for 4 hours. Contained in the reaction mixture were analyzed by gas chromatography, it was found that cyclododecane turned with the degree of transformation of 34.5% in cyclododecanone (selectivity of 64%, yield 22%), cyclododecanol (selectivity of 16.5%, the yield of 5.5%) and dodekanisou (selectivity of 5%, the yield of 2%).

Example A

The reaction was carried out, following in General the procedure of example A, except that the reaction was carried out at 80°C for 10 hours instead of 100°C for 4 hours. Under these conditions, cyclododecane turned with a degree of conversion of 24% in cyclododecanone (selectivity of 72%, the yield of 17.5%) and cyclododecanol (selectivity of 17.5%, 4%).

Example A

The reaction was carried out, following in General the procedure of example A, using 3.7 mg (0.015 mmol) of Co(OAc)2·4H2O instead of With(and the AC) 2. Under these conditions, cyclododecane turned with a degree of conversion of 26% in cyclododecanone (selectivity 49%, yield 13%) and cyclododecanol (selectivity of 30%, yield 8%).

Example A

The reaction was carried out, following in General the procedure of example A, using 3.9 mg (0.015 mmol) of Cu(ASAS)2instead With(ASAS)2. After 8 hours reaction cyclododecane turned with a degree of conversion of 31.5% in cyclododecanone (selectivity of 60.5%, yield 19%) and cyclododecanol (selectivity of 9.5%, yield 3%).

Example A

The reaction was carried out, following in General the procedure of example A, using 5.3 mg (0.015 mmol) of Fe(ASAS)3instead With(ASAS)2. After 8 hours reaction cyclododecane turned with a degree of conversion of 20% in cyclododecanone (selectivity 58,5%, the yield of 11.5%) and cyclododecanol (selectivity of 37%, the yield of 7.5%). The results show that triptorelin is an effective solvent for the oxidation reaction.

Examples A-A

Examples A-E show the degree of conversion and selectivity obtained in the oxidation of cyclooctene in the presence of N-hydroxycoumarin and various metal socialization. The results are shown below in table 5.

Table 5
ExampleT

(°)
Time

(h)
katalysator The degree of conversion(%)With5< / br>
(%)
With6< / br>
(%)
With7< / br>
(%)
With8< / br>
(%)
In General

(%)
A1006With(ASAS)28842311,51874,5
A509With(ASAS)23448,524,54,51996,5
A508With(SLA)2.4H2About43,543,5184,52389
A7524Fe(ASAS)35633,51672177,5
A6024With(ASAS)377,5446,572178,5
A5024With(ASAS)353of 17.516120,555
A100 1,5With(ASAS)33054,52202298,5
A808With(ASAS)3404510,501974,5
With5is cyclooctane
With6is cyclooctanol
With7represents 1,4-cyclooctadiene
With8is octanedionato
In General=5+C6+C7+C8

Example A

To 7.5 ml of acetic acid was added 336 mg (3.0 mmol) of cyclooctene, 60 mg (0.3 mmol) N-hydroxycoumarin and 3.9 mg (0.015 mmol) of acetylacetonate With(ASAS)2. Formed mixture was stirred under oxygen atmosphere at a temperature of 100°C for 6 hours. Contained in the reaction mixture were analyzed by gas chromatography, it was found that cycloocten turned with a degree of conversion of 88% in cyclooctane (selectivity 42%, yield 37%), cyclooctanol (selectivity of 3%, the yield of 2.5%), 1,4-cyclooctadiene (selectivity 11.5%output 10%) and octanedionato (selectivity 18%, yield 16%).

Example A

The reaction is s spent, following in General the procedure of example A, except that the reaction was carried out at 50°C for 9 hours instead of 100°C for 6 hours. Under these conditions, cyclooctane turned with a degree of conversion of 34% in cyclooctane (selectivity 48.5%, and the yield of 16.5%), cyclooctanol (selectivity of 24.5%, the yield of 8.5%), 1,4-cyclooctadiene (selectivity of 4.5%, a yield of 1.5%) and octanedionato (selectivity of 19%, the yield of 6.5%).

Example A

To 27.5 ml of acetic acid was added 336 mg (3.0 mmol) of cyclooctene, 60 mg (0.3 mmol) N-hydroxycoumarin and 3.7 mg (0.015 mmol) With(SLA)2·4H2O. Formed mixture was stirred under oxygen atmosphere at a temperature of 50°C for 9 hours. Contained in the reaction mixture were analyzed by gas chromatography, it was found that cycloocten turned with the degree of transformation of 43.5% in cyclooctane (selectivity of 43.5%, yield 19%), cyclooctanol (selectivity 18%, yield 8%), 1,4-cyclooctadiene (selectivity of 4.5%, the yield of 2%) and octanedionato (selectivity 23%, yield 10%).

Example A

To 7.5 ml of acetic acid was added 336 mg (3.0 mmol) of cyclooctene, 60 mg (0.3 mmol) N-hydroxycoumarin and 5.3 mg (0.015 mmol) of Fe(ASAS)3. Formed mixture was stirred under oxygen atmosphere at a temperature of 75°C for 24 hours. Contained in the reaction mixture were analyzed by gas chromium is ografia, in the result, it was found that cycloocten turned with a degree of conversion of 56% in cyclooctane (selectivity 33.5%, yield 19%), cyclooctanol (selectivity 16%, yield 9%), 1,4-cyclooctadiene (selectivity 7%, 4%) and octanedionato (selectivity 21%, yield 12%).

Example A

To 7.5 ml of acetic acid was added 336 mg (3.0 mmol) of cyclooctene, 60 mg (0.3 mmol) N-hydroxycoumarin and 5.3 mg (0.015 mmol) With(ASAS)3. Formed mixture was stirred under oxygen atmosphere at a temperature of 60°C for 24 hours. Contained in the reaction mixture were analyzed by gas chromatography, it was found that cycloocten turned with the degree of transformation of 77.5% in cyclooctane (selectivity 44%, yield 34%), cyclooctanol (selectivity of 6.5%, 5%), 1,4-cyclooctadiene (selectivity of 7%, the yield of 5.5%) and octanedionato (selectivity 21%, yield 16%).

Example A

To 7.5 ml of acetic acid was added 336 mg (3.0 mmol) of cyclooctene, 60 mg (0.3 mmol) N-hydroxycoumarin and 5.3 mg (0.015 mmol) With(ASAS)3. Formed mixture was stirred under oxygen atmosphere at a temperature of 50°C for 24 hours. Contained in the reaction mixture were analyzed by gas chromatography, it was found that cycloocten turned with a degree of conversion of 53% in cyclooctane (selectivity of 17.5%, the yield of 9.5%), cyclooctane the (selectivity 16%, the output of 8.5%), 1,4-cyclooctadiene (selectivity of 1%, the yield of 0.5%) and octanedionato (selectivity of 20.5%, yield 11%).

Example A

To 9 ml of triptoreline was added 336 mg (3.0 mmol) of cyclooctene, 60 mg (0.3 mmol) N-hydroxycoumarin and 5.3 mg (0.015 mmol) of acetylacetonate With(ASAS)3. Formed mixture was stirred under oxygen atmosphere at a temperature of 100°C for 1.5 hours. Contained in the reaction mixture were analyzed by gas chromatography, it was found that cycloocten turned with a degree of conversion of 30% in cyclooctane (selectivity of 54.5%, the yield of 16.5%), cyclooctanol (selectivity of 22%, the yield of 6.5%) and octanedionato (selectivity of 22%, the yield of 6.5%).

Example A

The reaction was carried out, following in General the procedure of example A, except that the reaction was carried out at 80°C for 8 hours instead of 100°C for 1.5 hours. Under these conditions, cyclooctane turned with a degree of conversion of 40% in cyclooctane (selectivity of 45%, yield 18%), cyclooctanol (selectivity 10.5%, 4%) and octanedionato (selectivity of 19%, the yield of 7.5%).

1. Method for the catalytic oxidation of alkane, comprising contacting the alkane with a source of oxygen in the presence of a catalyst comprising a compound of the following formula:

in which R1and R21and R2may together form a double bond or aromatic or non-aromatic ring; Y represents an oxygen atom and X represents an oxygen atom or a hydroxyl group; m indicates an integer of 1 or 2; n is 1.

2. The method according to claim 1, where R1and R2together form an aromatic or nonaromatic ring.

3. The method according to claim 1, where R1and R2together form an aromatic or non-aromatic ring, m=1.

4. The method according to claim 1, where R1and R2together form an aromatic C6-membered ring, m=1.

5. The method according to any of the preceding paragraphs, where X represents a hydroxyl group.

6. The method according to claim 1, where m is equal to 1.

7. The method according to any one of claims 1 or 6, where R1and R2together form an aromatic ring.

8. The method according to claim 1, where R1and R2together form an aromatic C6-membered ring.

9. The method according to any of the preceding paragraphs, in which the catalyst is N-hydroxycoumarin.

10. The method according to any of the preceding paragraphs, in which the alkane is C5-C25-cycloalken.

11. The method according to claim 10, in which cycloalkyl is C5-C20-membered also.

12. The method according to any one of claims 1 to 9, in which the alkane is a linear alkane, benzyldimethyl alkane or allylamine alkane.

13. The method according to any of the preceding paragraphs, in which the reaction of catalytic oxidation is carried out at a temperature in the range from 20 to 100°C.

14. The method according to any of the preceding paragraphs, in which the catalyst additionally includes socialization or mixtures thereof.



 

Same patents:

The invention relates to a method for producing monocyclic ketones7-C20

The invention relates to a method of obtaining a mixture containing cyclic saturated alkane and the corresponding alkanol

The invention relates to an improved process for the preparation of methanol by direct oxidation of hydrocarbon gas, comprising the sequential feeding site mixing of the reactor, which is located in the upper part of the reactor, the heated hydrocarbon gas and compressed air, followed by direct oxidation of the hydrocarbon gas, cooling the reaction mixture and separation, in which the cooled reaction mixture is separated into exhaust gases and liquid products, and regeneration obtained in the process of separation of methanol, with the release of methanol and exhaust gas discharge, and the oxidation of the hydrocarbon gas is carried out in two stages: homogeneous oxidation of the tubular part of the reactor and subsequent heterogeneous oxidation in the shell side of the reactor using a two-layer catalyst at a temperature 390-4900C and a pressure of 8.0 MPa, and cooling the reaction mixture is performed first in the heat exchanger “gas-gas”, then in the air cooler gas
The invention relates to a method for oxidation of hydrocarbons in the presence of a mixture of hydrogen and oxygen on the catalyst containing 0.5-10 wt.% silver and titanium containing medium, characterized in that the catalyst contains: a) a titanium containing media, such as titansilver, titanium dioxide or mixed oxides of silicon and titanium, or mixed oxides of silicon, aluminum and titanium, (b) silver particles with an average particle size of from 0.3 to 100 nm

The invention relates to a method for producing methanol, which is used for gas production

The invention relates to organic chemistry, in particular to methods of producing methanol by direct oxidation of natural gas, and can be used in the chemical industry for the production of methanol used, for example, as a component of motor fuel or feedstock for production of synthetic gasoline and other motor fuels

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to catalytic oxidation of saturated hydrocarbons with oxygen-containing gas. Process according to invention comprises contacting alkane with oxygen source in presence of catalyst including compound of general formula: , where R1 and R2 independently represent hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxy, alkoxy, carboxyl, alkoxycarbonyl, or acyl, or R1 and R2 can together form double bond or aromatic or non-aromatic ring; Y represents oxygen atom; X oxygen atom to hydroxyl group; m is integer 1 or 2; and n = 1. Process is conducted at 20 to 100°C. Advantageously, catalyst includes cocatalyst.

EFFECT: increased efficiency of catalytic system.

14 cl, 5 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of oxidation of hydrocarbons using oxygen in trifluoroacetic acid and can be used particularly for oxidation of alkanes, cycloalkanes, alkylaromatic hydrocarbons, alkenes, cycloalkenes. The method involves saturation of trifluoroacetic acid with oxygen, after which, the initial hydrocarbon is added to the obtained reaction medium and is kept until depletion of bound oxygen with obtaining the corresponding oxygen containing compound.

EFFECT: invention allows carrying out a process of selective partial catalytic oxidation of hydrocarbons with obtaining different oxygen containing organic compounds without use of high temperature and traditional catalyst systems based on transition metals.

1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of continuous oxidation of saturated cyclic hydrocarbons using oxygen, into a mixture of hydroperoxide, alcohol and ketones. The method involves feeding into the lower part of a column and in parallel flow, a stream of oxidisable liquid hydrocarbon and a gas stream containing oxygen, and degassing the liquid phase in the upper part of the column by forming a gas dome and extraction of the degassed liquid phase. The gas containing oxygen is let into different compartments of the column, and into the dome and/or liquid phase at the level of the degassing zone, or directly above. A stream of non-oxidising gas with output sufficient for maintaining concentration of oxygen in the gas layer at the level of volume concentration, less than or equal to the upper limiting concentration of oxygen is supplied.

EFFECT: possibility of implementing a method with high selectivity on an explosion safe level.

9 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: method involves partial oxidation of an alkane contained in a gaseous crude stream, which contains an alkane, with oxygen contained in an oxygen-containing crude stream. Said method involves: forming a reactor system, having a back-mixing reaction chamber with injection mixing, which is connected to a tubular flow reactor, wherein said back-mixing reaction chamber with injection mixing ensures dwell time from about 0.05 s to about 1.5 s; feeding said crude stream containing alkanes and said oxygen-containing crude stream into said back-mixing reaction chamber with injection mixing; initiating formation of alkyl free radicals in said back-mixing reaction chamber with injection mixing to obtain a product stream from the back-mixing reaction chamber with injection mixing, containing oxygen, said alkane and at least a portio of said alkyl free radicals; feeding the product stream obtained in the back-mixing reaction chamber with injection mixing into the tubular flow reactor; and converting said product stream obtained in the back-mixing reaction chamber with injection mixing into said alkyl oxygenate in said tubular flow reactor; where said alkane is selected from group consisting of methane, ethane, propane and butane.

EFFECT: invention enables to obtain the end product using an efficient and cheap method without using a catalyst.

34 cl, 2 ex, 36 dwg

FIELD: chemistry.

SUBSTANCE: Invention relates to methanol production plant and to method of methanol production by oxidising methane-containing gas at said plant. Proposed plant comprises plant for integrated gas treatment, reactor gas-phase methane-containing gas oxidation consisting of gas-to-gas heat exchanger of reaction zone and gas-to-water heat exchanger of cooling zone, refrigerator-condenser, rectification unit, ecological system and gas burner. Note here that reaction mix maximum heat zone accommodates extra reactor made up of cylindrical tube with feeder of extra portion of cold methane-containing gas including natural gas, refrigerator-condenser communicated via injector with one of gas burner inlets.

EFFECT: higher yield of methanol per 1 m3 of methane in single cycle.

1 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for direct conversion of lower C1-C4 paraffins to oxygenates such as alcohols and aldehydes, which are valuable intermediate products of organic synthesis and can be used as components of engine fuel and/or starting material for producing synthetic gasoline and other engine fuels. The method involves passing a mixture consisting of a lower paraffin or oxygen, diluted with an inert gas or air or pure oxygen, through a catalyst bed at temperature not higher than 350°C. The catalyst used is a catalyst system for heterogeneous reactions, which contains microfibre of a high-silica support and at least one active element, the active element being in form of either a MeOxHalv composite or a EwMezOxHaly composite, wherein the element Me in both composites is selected from a group which includes transition metals of groups 5-12 and periods 4 and 5, or elements of lanthanum or lanthanide groups or, preferably, ruthenium; element Hal is one of the halogens: fluorine, chlorine, bromine, iodine, but preferably chlorine; element E in the EwMezOxHaly composite is selected from a group which includes alkali, alkali-earth elements, or hydrogen, and indices w, z, x and y are weight fractions of elements in given composites and can vary in the following ranges: z - from 0.12 to 0.80, x - from 0.013 to 0.34, y - from 0.14 to 0.74, w - from 0 to 0.50.

EFFECT: method enables to achieve high degree of conversion of starting reactants and high selectivity of formation of alcohols.

4 cl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 1,3,5-trihydroxyadamantane. The method includes oxidising 1-adamantanol with molecular oxygen in the presence of N-hydroxyphthalimide in molar ratio of 1:0.05-0.2 with respect to 1-adamantanol, cobalt (II) acetylacetonate in molar ratio of 1:0.0025-0.02 with respect to 1-adamantanol and manganese dioxide in molar ratio of 1:0.01-0.1 with respect to 1-adamantanol at 50-118°C in a medium of glacial acetic acid for 10-40 hours.

EFFECT: method enables to obtain an end product with high output using readily available material using a simple method.

13 ex

FIELD: oil and gas industry.

SUBSTANCE: invention is referred to conversion process of associated and natural gases with high content of heavy methane homologs by direct partial oxidation of hydrocarbon gas and further carbonylation of the received products. At that hydrocarbons gas is mixed up with oxygen or oxygen-containing gas with mole ratio of hydrocarbon in heavy components: oxygen of 10-1:1 and selective oxidation of heavy components is made at temperature of 350-420°C and pressure of 10-40 bar and the received products are subjected to processing in presence of carbonylation catalysts with production of liquid products of carboxylic acids and their ethers and dry fuel gas purified from heavy components and enriched with methane.

EFFECT: method is the simplest and the most economically feasible for processing of associated oil gas and natural gas with high content of methane homologs with production of dry gas and a range of valuable liquid products.

3 ex

FIELD: oil and gas industry.

SUBSTANCE: invention refers to oil and gas industry, namely to utilisation and processing methods for associated and natural gas with high methane homologue content to obtain oil products. Processing method for natural and associated gas with high content of heavy methane homologues by selective oxidation of hydrocarbon gas and further carbonylation of products obtained involves mixing of hydrocarbon gas with oxygen or oxygen-containing gas at molar ratio of heavy carbon components to oxygen 5÷0.2:1, and selective oxidation of heavy components at air or near-air pressure and temperature of 500-800°C, and products obtained are processed in the presence of carbonylation catalysts containing compounds of VIII group metals and phosphine (arsinic) ligands, at 80-120°C and air pressure to obtain liquid products such as aldehydes, carbonic acids, diethyl ketone, polyketones, and dry fuel gas saturated with methane and purified from heavy components.

EFFECT: solution to the problem of associated oil gas utilisation, common to all oil companies.

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to catalytic oxidation of saturated hydrocarbons with oxygen-containing gas. Process according to invention comprises contacting alkane with oxygen source in presence of catalyst including compound of general formula: , where R1 and R2 independently represent hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxy, alkoxy, carboxyl, alkoxycarbonyl, or acyl, or R1 and R2 can together form double bond or aromatic or non-aromatic ring; Y represents oxygen atom; X oxygen atom to hydroxyl group; m is integer 1 or 2; and n = 1. Process is conducted at 20 to 100°C. Advantageously, catalyst includes cocatalyst.

EFFECT: increased efficiency of catalytic system.

14 cl, 5 tbl, 6 ex

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