A method of obtaining a lower saturated aliphatic or cyclic ketones and acid catalytic system for their production

 

(57) Abstract:

The inventive product is a lower aliphatic or cyclic ketones. Reagent 1: diolefin. Reagent 2: water. Reaction conditions: in the presence of a catalytic system which is a product of the interaction of the source metal, acid and ligand. 2 S. and 2 C. p. F.-ly, 1 table.

The invention relates to a method for producing ketones, in particular to a method for producing ketones using reaction paired diolefines and water, and thus obtained ketones.

Ketones are a technically versatile and valuable products and, as you know, are obtained by oxidation of secondary alcohols, hydrogenation of unsaturated ketones, decarboxylation of carboxylic acids and hydrogenation of alkynes with internal unsaturated bonds. Most of these reactions common that they use the original material, which in itself is a valuable connection, and often get ways that lead to severe conditions of reaction and/or require time-consuming methods of isolation of the final product.

Significant improvements in obtaining ketones can be achieved by using relatively the new phase at least5-paired diolefines with water in the presence of acid catalyst and use the ratio of water to the paired diene in the range of from 0.05:1 to 50:1. Thus, the output of ketone largely depends on and is proportional to the ratio of water: the diene, the weight ratio of water:Dien 41,5: 1 leads only to the output of the ketone of 48.7% (based on the feed isoprene, whereas a ratio of 2:1 gives output only 16% of the Requirement of substantial excess water in the way, which lead to the gas phase, making this method ineffective from the point of view of energy consumption. This requires a lot of energy as the evaporation of water and for the excretion of ketone from a very diluted mixture. Another disadvantage of this method is the restriction of its paired danami.

The objective of the invention is to develop a method of producing ketones, which does not have the above disadvantages.

As a result of research and experiments found that ketones can be obtained in the reaction of paired diolefines with water in the presence of catalytic systems based on metals.

Appropriate components of the catalyst (a) include themselves metals, their oxides, salts such as carboxylates, sulfates, x as a halogenated carboxylic acid, for example, triperoxonane acid, and halogenated sulfonic acid, for example, triftoratsetata, also complexes, such as phosphine complexes. Very good results were obtained with acetylacetone.

Component (b), which is based on the catalytic system of the invention, i.e., the source of protons is typically an acid with a PKand< 2 (measured at 25aboutWith a in aqueous solution). Suitable acid can be selected in a wide range of organic and inorganic acids, such as paratoluenesulfonyl acid, triftormetilfullerenov acid and percarboxylic acid.

As a ligand in the catalytic system for the method of the invention it is possible to use compounds of General formula

NC CN (II) where X and Y are the same or different organic bridging groups, each containing three or four atoms in the bridge, and at least two of them are carbon, more specifically, compounds containing at least two N-heterocyclic rings are connected to each other by one or more of the bridging groups, such as 2,2-biconical and its derivatives, such as 4,4'-dimethyl-2,2'-bipyridyl; 4,4'-dichloro-2,2'-train and its derivatives, such as 5-chloro-1,10-phenanthrolin. 4,7-diphenyl-1,10-phenanthroline; 4,7-dimethyl-1,10-phenanthroline; 2,9-dichloro-1,10-phenanthroline; 5,6-dimethyl-1,10-phenanthroline; 1,10-phenanthrolin-5-acid; 4,7-diphenyl-1,10-financialinstitution and sodium salt of 4,7-dimethyl-1,10-financialinstitution; 2,2'-beginopen; 2-(2-pyridyl)benzimidazole; 3-(2-pyridyl)-5,6-diphenyl - 1,2,4-triazine and 3-(2-pyridyl)5,6-diphenyl-1,2,4-triazine-pair-pair'-disulfonate sodium salt, 2-pyridyl-diphenylphosphine; 1,2-bis(phenylphosphino)ethane.

Preferred ligands for the method of the invention are bidentate ligands, the most preferred are ligands of General formula II, such as 2,2'-bipyridine and 1,10-phenanthroline.

Component of the ligand is preferably used in amount of 0.5-5 mol ligand per gram-atom of metal.

In the preferred catalytic system component (b) must be present in an amount that is sufficient to ensure the relationship in the range of 3.5-60 EQ N+per gram-atom of metal. If the specified catalytic system also includes a ligand hereinafter it will be called the component (C), you should be aware that any coordinational ligand can reduce the total acidity of the catalytic system is generowania ligand.

Irrelevant to the method of the invention using a catalytic system immobilized or deposited on a substrate ligand, i.e. a ligand, which is fixed on a material carrier, for example, silicon dioxide or aluminum oxide or polymeric material, it may be advantageous, for example, to facilitate the removal or recovery of the catalyst, or, for example, in the case of continuous reaction.

The catalytic system, which can be obtained with a combination of compounds of ruthenium, iridium and rhodium, acids with PKand< 2 (measured at 25aboutWith a in aqueous solution) and the ligand of General formula

NC CN where X and Y are the same or different organic bridging groups, each containing three or four atoms in the bridge, and at least two are carbon atoms, are new. Preferably, such catalytic systems were based on 1,10-phenanthroline or 2,2'-bipyridine due to their high activity.

A method of obtaining a secondary amine, which provides a catalytic system containing a source of cationic ruthenium, source cationic rhodium, aromatic N-heterocyclic ligand and istochniki, and the catalyst can be obtained in situ in the reaction mixture, adding the components (a) and (b) or (a), (b) and (C) separately. Components (a) and (b) or (a), (b) and (C) can be combined first and then enter into the reactor, before, simultaneously with or after the addition of one or more of the reagents. You can combine the components (a), (b) and (C) both in pure form and in a suitable solvent. Upon receipt of a catalytic system for use in the proposed method, the component (b) is usually used in such a quantity, which is at least sufficient to produce an acid catalytic system. It is preferable to use component (b) in a quantity sufficient to provide a ratio of 3.5 to 60 equivalents of N+per gram-atom of metal of group VIII in addition to the amount needed to prevent a possible effect of neutralizing any connection uncoordinated ligand.

Related diolefine that can be used as a starting material for the production of ketones by the method of the invention include 1,3-cyclohexadiene and 1,3-cyclopentadiene.

Preferred paired diolefine are those in which one of refinancinh groups paired >or R3are hydrogen. The most preferred paired diolefine are 1,3-butadiene and isoprene.

The proposed method is conveniently done by contacting the paired diolefin, water and catalyst in a suitable reactor at 60-220aboutWith, preferably in the range of 100-170aboutC, at a pressure of reaction.

The amount of catalyst relative to the reactants is not critical and can vary in a wide interval of values, and usually corresponds to the interval 10-7-10-1in gram-atom of metal per mole of conjugated diolefin, converted into a ketone, more specifically 10-5-10-2gram-atom of metal per mole of diolefin.

The ratio in which the conjugated diolefin and water can be used in the method of the invention, is not critical and can vary in a wide interval of values. You can use water in a molar excess relative to the paired diolefine. Given that diolefine not mixed with water, the reaction mixture may be a two-phase system, and this two-phase system can be transformed into a single-phase synthesis of ketone.

The method of the invention it is possible to describe what about the product of the reaction, you can also make this method in the presence of a solvent. Suitable solvents include hydrocarbon solvents such as n-decane, and the more polar solvents, such as dimethyl ether of diethylene glycol and the corresponding higher homologues.

When carrying out the method of the invention in a two-phase reaction medium, for example, in the absence of solvent or in the presence of apolar solvent, as already indicated previously, there has been a favourable effect on the receipt of the ketone when replacing the commonly used ligand for a more water-soluble ligand. Very good results were obtained for compounds of the type modified 1,10-phenanthroline, for example, sodium salt (4,7-diphenyl)1,10-phenanthrolin/dissolvability.

In the method of the invention the gradual addition of diolefines reagent in the reaction and not a full download of the entire diolefine in the reactor at the beginning of the reaction, has a beneficial effect on the receipt of the ketone. In a preferred variant of the method of the invention and in that case you can also use the gradual addition of diolefin, diolefin can be used in a mixture with other, usually carbon compounds containing diolefin, will win the same number of carbon atoms in the molecule, but they differ in the degree of unsaturation. Most preferred are4streams containing 1,3-butadiene, along with other4-compounds such as butane, isobutane and 2-butene (CIS - and TRANS-), and the corresponding5-the stream containing isoprene as diolefines connection. When using such paired diolefines fractions of cracking oil in the method of the invention can achieve 90% or higher percent conversion of diolefins to the corresponding ketone.

Note that the method, as shown earlier, which allows the use of multi-component feed mixture, and in which only one of the components of the raw material mixture is subjected to reaction and transformation in the target connection, for example, the ketone with high yield is great value as part of the integrated circuit process in which the interaction of various raw components and highlights the various components of the stream.

In the reaction of the invention the reaction product ketone can be successfully distinguished from the reaction mixture by known methods, such as distillation and extraction.

Used the following abbreviations:

MEK: methyl ethyl ketone;

hydroxy-2,2'-bipyridyl;

the ligand with: 1,10-phenanthroline;

the ligand o: 2,9-dimethyl-1,10-phenanthroline;

ligand e: 4,7-dimethyl-1,10-phenanthroline;

ligand f: 5,6-dimethyl-1,10-phenanthroline;

ligand g: 4,7-dimethyl-1,10-financialinstitution, sodium acid;

the ligand h: 2,2'-bis(4,5-dimethyl)imidazole;

the ligand j: 2,2'6'2"-terpyridyl;

the ligand l: 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine;

ligand m: 2,2'-(3,6-dithiocarbamate)biperiden;

the ligand n: 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine-pair, couple'-disulfonate;

the ligand R: 2-pyridyl-diphenylphosphine;

ligand q: 4.4'-dimethyl-2,2'-bipyridyl;

the ligand r: 2-(2-pyridyl)benzimidazole;

the ligand s: 1,2-bis(diphenylphosphino)ethane.

Diglyme: dimethyl ether of diethylene glycol.

P R I m e R s 1-23. The appropriate amount of water, solvent and catalyst are loaded into a 250 ml autoclave made of stainless steel (On telloy C), equipped with a magnetic stirrer. Then the reactor is pressurized and pumped, then download the conjugated diene, and the reactor is heated to the desired temperature under the pressure of the reaction. After 5 hours the reactor is cooled to room temperature (20aboutC). Then analyze content using gas chromatography (S. L. C.). Appropriate Analyt each example. The output of ketone calculated as the number of paired diolefin converted into the corresponding ketone.

P R I m e R 24. The following compounds is introduced into the reactor in the previously mentioned order: 25 ml Diglyme; 40 ml of water; 1 mmol EN/acac/3; 2 mmol of 1,10-phenanthroline; 7 mmol of paratoluenesulfonyl.

After the reactor is heated to 155aboutWith the pressure of the reaction, the reactor is injected 1,3-butadiene at a rate of 2 ml/h for 14 hours By the end of the first hour of adding 1,3-butadiene to the reactor temperature is reduced to 130aboutC. After the reaction time (16 h) the contents of the reactor is cooled to 20aboutC. Analysis by gas-liquid chromatography indicates the presence of 25 g of methyl ethyl ketone, which corresponds to 94% conversion of 1,3-butadiene in methyl ethyl ketone.

P R I m e R 25. Repeat the procedure of example 24 except using 25 ml of water, the temperature of the reactor support 155aboutWith, and 1,3-butadiene is used in the form of a mixture of the following composition, n-butane 6,1; TRANS-2-butene 19,3; CIS-2-butene 4,5; isobutene 26; 1,3-butadiene 39,1; which is injected into the reactor at a speed of 4 ml/hour for 2.5 hours After continuing the reaction for 4.5 hours the reactor is cooled to 20

P R I m e R 26. Repeat the procedure of example 25 except that use4-the stream containing 50% 1,3-butadiene, which is injected into the reactor at a rate of 2 ml/h for 15 hours in Addition, the reaction of lead without additional solvent. By the end of the reaction allocate 15 ml of MEK from the reaction mixture, which corresponds to a conversion of 84% 1,3-butadiene.

P R I m e R 27. Repeat the procedure of example 24, but using 0.5 mmol of Ru(acac)31 mmol of 1,10-phenanthroline, 45 ml diglyme, 5 ml of water and isoprene (supplied at a rate of 1 ml/h for 5 h), and the reaction time is 7 h at 155aboutC. This leads to the conversion of more than 95% of isoprene in methylisobutylketone.

1. A method of obtaining a lower saturated aliphatic or cyclic ketones in the interaction of paired diolefin with water in the presence of a catalyst, characterized in that the method is carried out in the liquid phase, as diolefin used as a compound of General formula

< / BR>
where R1, R2and R3the same or different, hydrogen, a lower alkyl group, or R1and R3together form an organic bridging group containing one or two who tion among ruthenium, rhodium or iridium, with the acid having a pKa < 2, 25oIn aqueous solution, taken in an amount to provide a ratio of 3.5 60 equivalents of N+1 g-atom of metal, and N,N-bidentate ligand of General formula

< / BR>
where X and Y are the same or different bridging groups containing three or four atoms in the bridge, two, three or four of which are carbon atoms, and any remaining atoms are nitrogen atoms,

the resulting structure can be substituted by substituents, selected from among pyridine, lower alkyl, lower alkoxy, phenyl, dioctyltin or residue sulfonic acid or 1,2-bis(diphenylphosphino)ethane or 2-pyridyl-diphenylphosphino as a ligand and the ligand used in quantities of 0.5 to 5.0 mol per 1 g-atom of metal.

2. The method according to p. 1, wherein the acid is selected among paratoluenesulfonyl acid, triftormetilfullerenov acid, percarbonic acid.

3. Acidic catalytic system for obtaining a lower saturated aliphatic or cyclic ketones of the paired diolefin and water, characterized in that is a reaction product of a source of metal selected from among ruthenium, rhodium or iridi the e 3,5 60 equivalents of N+1 g-atom of metal, and N, N-bidentate ligand of General formula

< / BR>
where X and Y are the same or different organic bridging group containing three or four atoms in the bridge, two, three or four of which are carbon atoms, and any remaining atoms are nitrogen atoms,

the resulting structure can be replaced by substituents selected among pyridyl, lower alkyl, lower alkoxy, phenyl, dioctyltin or residue sulfonic acid or 1,2-bis-(diphenylphosphino)ethane or 2-pyridylmethylamine as a ligand and the ligand used in quantities of 0.5 to 5.0 mol per 1 g-atom of metal.

4. The system under item 3, wherein the acid is selected among paratoluenesulfonyl acid, triftormetilfullerenov acid and percarbonic acid.

 

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7 cl, 1 dwg, 3 tbl, 8 ex

FIELD: main organic synthesis.

SUBSTANCE: proposed method is used for production of ketones, for example dimethyl ketone (CH3COCH3), methyl ethyl ketone (CH3COC2H5) by direct catalytic oxidation of respective alkenes, for example propylene, n-butenes, as well as catalysts for realization of this method. Oxidation of alkenes is performed in the presence of metallocomplex catalysts containing organic component where nitrogen oxide (I) is used as oxidant. Used for process is catalyst on base of peroxopolyoxo metallate complexes of terakis (oxo diperoxo metallate)-phosphate (3-) together with quaternary ammonium cationes having formula Q3{PO4[MeO(O2)2]4}, where Me-Mo, W,V; Q3 is quaternary ammonium catione containing alkyl chains C4-C8 or N-hexadecyl pyridinium.

EFFECT: enhanced selectivity of process.

10 cl, 14 ex

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