CN104470887A - Transition metal carbene complex catalysed method for producing carboxylic acid esters from alcohols under dehydration - Google Patents

Transition metal carbene complex catalysed method for producing carboxylic acid esters from alcohols under dehydration Download PDF

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CN104470887A
CN104470887A CN201380037308.7A CN201380037308A CN104470887A CN 104470887 A CN104470887 A CN 104470887A CN 201380037308 A CN201380037308 A CN 201380037308A CN 104470887 A CN104470887 A CN 104470887A
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uncle
alcohol
reaction
salt
mixture
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CN104470887B (en
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T·绍布
S·鲁德纳尔
D·施奈德
R·帕切洛
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/76—Dehydrogenation
    • B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

Abstract

The present invention relates to a method for producing carboxylic acid esters, comprising the reaction of at least one primary mono alcohol or a mixture of a primary mono alcohol and at least one alcohol differing from this in the presence of a transition metal carbene complex catalyst (K), which has as the central atom (M) at least one transition metal atom of group 8, 9 or 10 of the periodic table (IUPAC) and at least one monodentate N-heterocyclic carbene ligand, in the presence of a base, characterized in that the catalyst (K) is produced by reaction of a transition metal compound (V), which has at least one transition metal atom of group 8, 9 or 10 of the periodic table (IUPAC), but no carbene ligand, with an imidazolium salt in the presence of the primary mono alcohol and the base, wherein the reaction is a bulk reaction.

Description

Prepared the transition metal carbene complexes catalysis process of carboxylicesters by alcohol under dehydration
The present invention relates to by making the mixture of at least one uncle's single methanol or uncle's single methanol alcohol different from it with at least one react under the existence of transition metal carbene complexes catalyzer K and prepare the method for carboxylicesters.
Carboxylicesters is the important compound being such as used as solvent, softening agent and perfume compound and aromatoising substance.There is their method of multiple preparation, wherein the reaction of carboxylic acid and alcohol is the most frequently used:
Because this is acid catalyzed balanced reaction as a rule, water or carboxylicesters must be removed to realize high yield from reaction mixture.Particularly when lower boiling carboxylic acid and low-boiling point alcohol, in method, usually form undesired azeotropic mixture, which hinders separation.
The other method preparing carboxylicesters is the reaction of acid anhydrides and alcohol:
In the method, form the carboxylic acid of 1 equivalent, also must be separated.Also form azeotropic mixture herein, in addition, for 1 equivalent carboxylicesters, need 2 to work as quantity carboxylic acid.
The other method preparing carboxylicesters is the transition metal complex catalyzed reaction of alcohol, and dehydrogenation simultaneously, it is formed hereinafter referred to as direct ester., be raw materials usedly only alcohol herein, at least one wherein in two kinds of reactants must have uncle OH group, i.e. CH 2oH group:
R aCH 2OH+R bOH→R aCOOR b+2H 2
In this kind of carboxylicesters synthesis, do not need to use carboxylic acid, this is favourable, because have unjoyful smell especially compared with low-grade carboxylic acid.In addition, during reaction do not form water, this simplify the distillation aftertreatment of reaction mixture.In addition, this fact as mild as a dove can be kept by reaction conditions, only form a little by product.
Repeatedly describe in document and use transition metal complex catalysis that primary alconol is changed into carboxylicesters.
Tetrahedron Lett.1981,22,5327-5330 and J.Org.Chem.1987,52,4319-4327 describes the ruthenium complexe with phosphine part and is being prepared the purposes in carboxylicesters and lactone by primary alconol as catalyzer.
J.Organomet.Chem.1985,282, C7-C10 describe the catalyzer for using the ruthenium complexe with tetraphenylcyclopentadienone part to be prepared carboxylicesters by primary alconol.
Chem.Rev.2010,110,681-703 describe the various transition metal compound catalizers for being formed by the direct ester of primary alconol.
Organometallics 2011,30,2180-2188, Organometallics 2011,30,5716-5724 and J.Am.Chem.Soc.2005,127,10840-10841 describe the pincerlike title complex of ruthenium for the direct esterification of catalysis primary alconol.
The people such as M.Nielsen, Angew.Chem.2012,124 describe for by the ruthenium with multiple tooth organonitrogen and organophosphor ligand of ethanol synthesizing ethyl acetate and iridium complex catalyst.
Organometallics 2011,30,6044-6048 describes based on the N-heterocycle carbine base ruthenium complexe as catalyzer in being formed at the direct ester by primary alconol.Advantageously phosphoric acid salt is added in ruthenium complexe.
The shortcoming of the method for described synthesizing carboxylate is that transition metal compound catalizer used must be prepared by complicated synthesis and optionally must be separated.In addition, usually use oxidation-sensitive and the phosphine part of costliness, this forces and performs complicated reaction under inert conditions.In addition, this program is mainly carried out in the solvent added relatively in a large number, therefore, and must aftertreatment and space time yield reduce in a complex manner by reaction mixture.
The object of this invention is to provide the method formed by the direct ester of transition metal complex catalysis of the mixture of uncle's single methanol or uncle's single methanol alcohol different from it with at least one.
Surprisingly, this object of present discovery is realized by a kind of method, the mixture of uncle's single methanol or uncle's single methanol alcohol different from it with at least one is wherein made to react without dilution under the existence of alkali and at least one hereafter more transition metal carbene complexes catalyzer K of specific definition, described catalyzer has 8,9 or 10 group 4 transition metal atoms of the periodic table of elements (IUPAC), and wherein catalyzer K is by making suitable non-Cabbeen class transistion metal compound V and imidazoles salt uncle single methanol and alkali existence under reaction and prepare.
Therefore, the present invention relates to the method preparing carboxylicesters, described method comprises the reaction of mixture in the presence of base under the existence of transition metal carbene complexes catalyzer K of at least one uncle's single methanol or uncle's single methanol alcohol different from it with at least one, described catalyzer has 8 of at least one periodic table of elements (IUPAC), 9 or 10 group 4 transition metal atoms are as central atom M, with at least one monodentate N-heterocyclic carbene ligand, wherein catalyzer K is by making to have 8 of at least one periodic table of elements (IUPAC), 9 or 10 group 4 transition metal atoms, but not there is transistion metal compound V and the imidazoles of carbenes salt uncle single methanol and alkali existence under react, wherein said reaction is carried out without dilution.
Mainly mild reaction conditions, low by product are formed, simultaneously with high space time yield the advantage of the inventive method.In addition, can avoid like this must Kaolinite Preparation of Catalyst system dividually.Another advantage is the reaction mixture aftertreatment simplified, because perform without dilution owing to reacting, need not be separated solvent.In addition, the low oxidation sensitivity homologation reaction of catalyst system even performs under non-inert condition.In addition, this method avoid the use compared with low-grade carboxylic acid with unjoyful smell.
At least one is used to comprise the catalyzer K of 8, the 9 or 10 group 4 transition metal atoms of at least one periodic table of elements (IUPAC) in the methods of the invention.8,9 and 10 group 4 transition metals of the periodic table of elements (IUPAC) are particularly including iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.Preferably comprise the catalyzer K that at least one is selected from the transition metal atoms of ruthenium and iridium.Particularly preferred transition metal is ruthenium.
Catalyzer K has at least one, such as 1,2,3 or 4 N-heterocyclic carbene ligand.Suitable N-heterocyclic carbene ligand mainly imidazole ligands, the carbon wherein on 2 is Cabbeen class donor atom.These are particularly including those of formula (I):
Wherein:
R 1and R 4be C independently of each other 1-C 10alkyl, C 3-C 10cycloalkyl, have the 5-10 unit heteroaryl of 1,2 or 3 heteroatoms being selected from O, N and S as ring members, or an aryl, wherein last-mentioned four substituting groups are not substituted or can be selected from following substituting group and replace by one or more: halogen, C 1-C 10alkoxyl group, CN, C 1-C 10alkyl, C 3-C 10cycloalkyl, phenyl and naphthyl;
R 2and R 3be hydrogen or have about R independently of each other 1or R 4a kind of implication provided.
Herein and hereinafter, about the prefix " C that substituent definition uses p-C q" represent substituent possibility carbon atom number.
On the invention hereafter in, unless otherwise indicated, following general definition be applicable to about substituting group use term:
" C 1-C 10alkyl " for having the linear of 1-10 carbon atom or branched-alkyl.C 1-C 10the example of alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl (2-methyl-prop-2-base), n-pentyl (amyl group), 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1, 1-dimethyl propyl, 1, 2-dimethyl propyl, 2, 2-dimethyl propyl, 1-ethyl propyl, n-hexyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethyl-butyl, 2-ethyl-butyl, 1, 1, 2-thmethylpropyl, 1, 2, 2-thmethylpropyl, 1-ethyl-1-methyl-propyl, 1-Ethyl-2-Methyl propyl group, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl and constitutional isomer thereof.
" C 3-C 10cycloalkyl " for have the list of 3-10 carbon atom-, two-, three-or Fourth Ring alkyl.Example is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group and adamantyl.
Aryl " be possible substituted or unsubstituted aromatic hydrocarbyl.The example of unsubstituting aromatic yl is phenyl, 1-naphthyl, 2-naphthyl and 9-anthryl.Can by one or more C as hereinbefore defined 1-C 10the example of aryl that alkyl replaces be 2,6-bis-(sec.-propyl) phenyl, o-tolyl, a tolyl, p-methylphenyl and base.
" C 1-C 10alkoxyl group " be the alkyl with 1-10 carbon atom combined by Sauerstoffatom.Example is methoxyl group, oxyethyl group, positive propoxy, 1-methyl ethoxy (isopropoxy), n-butoxy, 1-methyl propoxy-(sec-butoxy), 2-methyl propoxy-(isobutoxy), 1, 1-dimethylethyloxy (tert.-butoxy), n-pentyloxy, 1-methylbutoxy group, 2-methylbutoxy group, 3-methylbutoxy group, 1, 1-dimethyl propoxy-, 1, 2-dimethyl propoxy-, 2, 2-dimethyl propoxy-, 1-ethylpropoxy, 2-ethylpropoxy, positive hexyloxy, 1-methyl pentyloxy, 2-methyl pentyloxy, 3-methyl pentyloxy, 4-methyl pentyloxy, 1-ethyl-butoxy, 2-ethyl-butoxy, 3-ethyl-butoxy, 1, 2-dimethyl butoxy, 1, 3-dimethyl butoxy, 2, 3-dimethyl butoxy, 1-Ethyl-2-Methyl propoxy-and 1-sec.-propyl propoxy-.
" 5-10 unit heteroaryl " is for having 1,2 or 3 heteroatoms being selected from O, N and S as the monocycle of ring members or two ring 5-10 unit aromatic ring.Example be thienyl, benzothienyl, 1-aphthothiophenes base, thianthrenyl, furyl, benzofuryl, pyrryl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indyl, pseudoindoyl, indazolyl, purine radicals, isoquinolyl, quinolyl, acridyl, naphthyridinyl, quinoxalinyl, quinazolyl, cinnolines base, piperidyl, carbolinyl, thiazolyl, azoles base, isothiazolyl and different azoles base.
" aliphatic olefin " is for having the linear of a usual 2-10 carbon atom or branching, list-or many unsaturated hydrocarbons.Example is ethene, propylene, 1-butylene, 2-butylene, 1,3-butadiene and 2-methyl-prop-1-alkene.
" cycloolefin " is for having the ring-type list-of a usual 4-10 carbon atom or many unsaturated hydrocarbons.Example is cyclobutene, cyclopentenes, tetrahydrobenzene and 1,5-cyclooctadiene.
" carbocyclic aromatic " is for having a usual 6-10 carbon atom and not being substituted or by alkyl list-or polysubstituted aromatic substance.Example is benzene, naphthalene and Paracymene.
" assorted aromatic hydrocarbons " is selected from the heteroatomic of O, N and S and is not substituted for having a usual 5-10 annular atoms and having at least one or replaces aromatic substance.Example be furans, pyrroles, thiophene, imidazoles, pyrazoles, azoles, different azoles and thiazole.
" aldehyde " is for having the linear of a usual 1-10 carbon atom or branching aldehyde.Example is formaldehyde, acetaldehyde and propionic aldehyde.
" ketone " is for having the linear of a usual 3-10 carbon atom or branching ketone.Example is acetone, butanone, 2 pentanone and propione.
" C 1-C 10carboxylate radical " for having 1-10, the particularly negatively charged ion of the saturated or unsaturated carboxylic acid of 1-4 carbon atom.C 1-C 10the example of carboxylate radical is formate, acetate moiety, propylene acid group, methacrylic acid group and propionate.
" C 1-C 10alkoxide " for having 1-10, the particularly group of the linear or branching alcohol of 1-4 carbon atom.Example is methylate, ethylate, propylate, propyl carbinol salt, 2-butanolate and tert butoxide.
In formula (I), variable R 1, R 2, R 3and R 4independently of each other, particularly there is following implication in combination:
In formula (I), R 1and R 4preferably be selected from C independently of each other 1-C 10alkyl, C 3-C 10the group of cycloalkyl, benzyl and phenyl, the phenyl ring wherein in last-mentioned two groups is unsubstituted or by C 1-C 3alkyl list-or polysubstituted, such as single-, two-or three to replace.Especially, R 1and R 4for C 1-C 10alkyl, especially C 1-C 6alkyl.
In formula (I), R 2and R 3preferably be selected from hydrogen, C independently of each other 1-C 10alkyl, C 3-C 10the group of cycloalkyl, benzyl and phenyl, the phenyl ring wherein in last-mentioned two groups is unsubstituted or by C 1-C 3alkyl list-or polysubstituted, such as single-, two-or three to replace.Especially, R 2and R 3for hydrogen or C 1-C 10alkyl, especially hydrogen or C 1-C 6alkyl, very especially hydrogen.
Except at least one monodentate N-heterocyclic carbene ligand, catalyzer K can have at least one other ligand L.Ligand L is preferably selected from CO, hydride, aliphatic olefin, cycloolefin, carbocyclic aromatic, particularly benzene, naphthalene and Paracymene, assorted aromatic hydrocarbons, particularly furans, pyrroles, imidazoles and pyrazoles, aldehyde, particularly formaldehyde, acetaldehyde and propionic aldehyde, ketone, particularly acetone, butanone, 2 pentanone and propione, halogenide, C 1-C 10carboxylate salt, metilsulfate, Methylsulfate, trifluoromethyl vitriol, tosylate, mesylate, prussiate, isocyanate, cyanate, thiocyanate, oxyhydroxide, C 1-C 10alkoxide, cyclopentadienide, pentamethylcyclopentadiene compound and five benzyl cyclopentadienide.Particularly preferred ligand L is Paracymene, muriate, CO, hydride, C 1-C 10alkoxide and C 1-C 10carboxylate salt.
Can be used for the imidazoles in the inventive method the imidazoles of salt mainly general formula (II) salt:
Wherein R 1, R 2, R 3and R 4there is above-mentioned implication, particularly herein as the implication preferably, especially or especially described,
A is H or COO -, and
X -for the Equivalent of negatively charged ion, particularly halogen, C 1-C 10carboxylate radical, benzoate anion, MeC 6h 4cOO -, tosylate, methanesulfonic root, trifluoromethayl sulfonic acid root, methanesulfonate, prussiate, isocyano, thiocyanate radical, tetrachloro aluminate, tetrabromo aluminate, tetrafluoroborate, hexafluoro-phosphate radical, hexafluoroantimonic anion, sulfate radical, hydroxide radical, two (trifluoromethane sulphonyl) imide or methylsulfate, condition is if A is COO -, then X -do not exist.
At particularly preferred formula (II) imidazoles in salt, variable X -, A, R 1, R 2, R 3and R 4separate, particularly there is following implication in combination:
X -be preferably chlorine, tosylate, methanesulfonic root, trifluoromethayl sulfonic acid root, methanesulfonate, tetrafluoroborate, hexafluoro-phosphate radical, hexafluoroantimonic anion, C 1-C 10carboxylate radical, sulfate radical or methylsulfate, particularly chlorine, methanesulfonic root or C 1-C 10carboxylate radical.
A is preferably hydrogen;
R 1and R 4preferably be selected from C independently of each other 1-C 10alkyl, C 3-C 10the group of cycloalkyl, benzyl and phenyl, the phenyl ring wherein in last-mentioned two groups is unsubstituted or by C 1-C 3alkyl list-or polysubstituted, such as single-, two-or three to replace.Especially, R 1and R 4for C 1-C 10alkyl, especially C 1-C 6alkyl.
R 2and R 3preferably be selected from hydrogen, C independently of each other 1-C 10alkyl, C 3-C 10the group of cycloalkyl, benzyl and phenyl, the phenyl ring wherein in last-mentioned two groups is unsubstituted or by C 1-C 3alkyl list-or polysubstituted, such as single-, two-or three to replace.Especially, R 2and R 3for hydrogen or C 1-C 10alkyl, especially hydrogen or C 1-C 6alkyl, very especially hydrogen.
Suitable formula (II) imidazoles the example of salt is 1,3-methylimidazole salt, 1-methyl-3-isopropylimdazole salt, 1,3-diethyl imidazolium salt, 1-methyl-3-n-propyl imidazoles salt, 1-methyl-4-butylimidazolium salt, 1,3,4,5-tetramethyl-imidazoles salt, 1,3-bis--n-propyl imidazoles salt, 1,3-di-isopropyl imidazoles salt, 1,3-di-n-butyl imidazoles salt, 1,3-bis--sec-butyl imidazoles salt, 1,3-bis--t-butyl imidazole salt, 1,3-dicyclohexyl imidazoles salt, 1,3-bis-adamantyl imidazoles salt, 1,3-diphenyl-imidazole salt, 1,3-xylyl imidazoles salt, 1,3-bis--xylyl imidazoles salt, 1,3-bis- base imidazoles salt, 1,3-two [2,6-bis-(sec.-propyl) phenyl] imidazoles salt, particularly their muriate, tosylate, methane sulfonates, trifluoro-methanyl sulfonate, mesylate, a tetrafluoro borate, hexafluorophosphate, hexafluoro antimonate, vitriol, C 1-C 10carboxylate salt and Methylsulfate, especially muriate, methane sulfonates and C 1-C 10carboxylate salt.
N-heterocycle carbine has and trialkyl-or the similar part performance of triaryl phosphine, but compared with phosphine, N-heterocycle carbine has this advantage: they are not oxidation-sensitives.N-heterocycle carbine based on 1,3-substituted imidazole is very easy to reach in synthesis, see such as W.A.Herrmann, Angew.Chem.2002, and 41,1290-1309; E.Peris, Top.Organomet.Chem.2007,21,83-116; The people such as T.N.Tekavec, Top.Organomet.Chem.2007,21,159-192; F.Glorius, Top.Organomet.Chem.2007,21,1-20, at this with reference to its full content.
N-heterocycle carbine based on imidazoles salt is commercially available and such as ionic liquid and known as solvent.
By imidazoles salt is prepared monodentate N-heterocyclic carbene ligand and is carried out under the existence of at least one alkali.
Suitable alkali is such as selected from alkali-metal hydride, oxyhydroxide, carbonate, alkoxide and acid amides, the hydride of alkaline-earth metal, oxyhydroxide, carbonate, alkoxide and acid amides, organic amine, aryl lithium compounds and alkyl lithium compounds.
Preferably, alkali is selected from:
B1 alkali metal hydroxide, particularly LiOH, NaOH or KOH
B2 alkaline earth metal hydroxides, particularly Ca (OH) 2
B3 alkalimetal hydride, particularly LiH, NaH, KH
B4 alkaline earth metal hydride, particularly CaH 2
B5 composite alkali aluminum hydride, particularly LiAlH 4
B6 alkali metal borohydride, particularly NaBH 4, LiBH 4
B7 alkaline carbonate, particularly Na 2cO 3, Li 2cO 3, K 2cO 3
B8 alkali metal phosphate, particularly K 3pO 4, Na 3pO 4
B9 alkyl lithium compounds, particularly n-Butyl Lithium, lithium methide, tert-butyl lithium
B10 aryl lithium compounds, particularly phenyl lithium
B11 alkali metal alcoholates, particularly lithium methoxide, lithium ethoxide, n-propyl alcohol lithium, isopropyl lithium alkoxide, propyl carbinol lithium, isobutyl lithium alkoxide, Pentyl alcohol lithium, n-hexyl alcohol lithium, n-Heptyl alcohol lithium, n-Octanol lithium, benzylalcohol lithium, phenol lithium, potassium methylate, potassium ethylate, n-propyl alcohol potassium, potassium isopropoxide, propyl carbinol potassium, isobutyl potassium alcoholate, Pentyl alcohol potassium, n-hexyl alcohol potassium, n-Heptyl alcohol potassium, n-Octanol potassium, potassium benzyl alcoholate, potassium phenylate, sodium methylate, sodium ethylate, n-propyl alcohol sodium, sodium isopropylate, propyl carbinol sodium, isobutyl sodium alkoxide, Pentyl alcohol sodium, n-hexyl alcohol sodium, n-Heptyl alcohol sodium, n-Octanol sodium, benzylalcohol sodium, sodium phenylate, and the constitutional isomer of described alkali metal alcoholates
B12 basic metal two (trimethyl silyl) acid amides, particularly two (trimethyl silyl) acid amides sodium, two (trimethyl silyl) acid amides lithium, two (trimethyl silyl) acid amides sodium
B13 formula R 5nH 2amine, wherein R 5for replacing or unsubstituted C 1-C 10alkyl, C 1-C 4alkyl-P (phenyl) 2, C 3-C 10cycloalkyl, C 3-C 10heterocyclic radical, wherein C 3-C 10heterocyclic radical comprises the heteroatoms that at least one is selected from N, O and S, C 5-C 14aryl or C 5-C 10heteroaryl, wherein C 5-C 10heteroaryl comprises the heteroatoms that at least one is selected from N, O and S,
B14 formula R 6r 7the amine of NH, wherein R 6and R 7independently of each other for replacing or unsubstituted C 1-C 10alkyl, C 1-C 4alkyl-P (phenyl) 2, C 3-C 10cycloalkyl, C 3-C 10heterocyclic radical, wherein C 3-C 10heterocyclic radical comprises the heteroatoms that at least one is selected from N, O and S, C 5-C 14aryl or C 5-C 10heteroaryl, wherein C 5-C 10heteroaryl comprises the heteroatoms that at least one is selected from N, O and S,
B15 formula R 8r 9r 10the amine of N, wherein R 8, R 9and R 10independently of each other for replacing or unsubstituted C 1-C 10alkyl, C 1-C 4alkyl-P (phenyl) 2, C 3-C 10cycloalkyl, C 3-C 10heterocyclic radical, wherein C 3-C 10heterocyclic radical comprises the heteroatoms that at least one is selected from N, O and S, C 5-C 14aryl or C 5-C 10heteroaryl, wherein C 5-C 10heteroaryl comprises the heteroatoms that at least one is selected from N, O and S.
Particularly preferably alkali metal hydroxide, especially potassium hydroxide, and alkaline earth metal hydroxides, and the alkali metal alcoholates of alcohol used in the inventive method, especially 3-methyl-propyl carbinol potassium and 2-methyl-propyl carbinol potassium.
Especially, potassium hydroxide is used as alkali.
Suitable transistion metal compound V is title complex and the salt of 8,9 and 10 group 4 transition metals of the periodic table of elements (IUPAC), the title complex of preferred ruthenium and iridium and salt, particularly preferably the title complex of ruthenium and salt.
Particularly preferably suitable transistion metal compound V has to be selected from the transition metal atoms of ruthenium and iridium and the compound of at least 2 parts, described part is selected from Paracymene, muriate, benzene, CO, 1,5-cyclooctadiene, allyl group, acetylacetonate, methyl-sulphoxide, cyclopentadienyl, pentamethylcyclopentadiene base, indenyl, cyclooctene, hydride, ethene and H 2o.
Suitable transistion metal compound V is such as [Ru (Paracymene) Cl 2] 2, [Ru (benzene) Cl 2] n, [Ru (CO) 2cl 2] n, wherein n is 1-100, [Ru (CO) under often planting situation 3cl 2] 2[Ru (1,5-cyclooctadiene) (allyl group)], RuCl 3h 2o, [Ru (acetylacetonate) 3], [Ru (methyl-sulphoxide) 4cl 2], [Ru (cyclopentadienyl) (CO) 2cl], [Ru (cyclopentadienyl) (CO) 2h], [Ru (cyclopentadienyl) (CO) 2] 2, [Ru (pentamethylcyclopentadiene base) (CO) 2cl], [Ru (pentamethylcyclopentadiene base) (CO) 2h], [Ru (pentamethylcyclopentadiene base) (CO) 2] 2, [Ru (indenyl) (CO) 2cl], [Ru (indenyl) (CO) 2h], [Ru (indenyl) (CO) 2] 2, ruthenocene, [Ru (1,5-cyclooctadiene) Cl 2] 2, [Ru (pentamethylcyclopentadiene base) (1,5-cyclooctadiene) Cl], [Ru 3(CO) 12], IrCl 3h 2o, KIrCl 4, K 3irCl 6, [Ir (1,5-cyclooctadiene) Cl] 2, [Ir (cyclooctene) 2cl] 2, [Ir (ethene) 2cl] 2, [Ir (cyclopentadienyl) Cl 2] 2, [Ir (pentamethylcyclopentadiene base) Cl 2] 2and [Ir (cyclopentadienyl) (CO) 2] and [Ir (pentamethylcyclopentadiene base) (CO) 2].
In the methods of the invention, the mixture reaction of uncle's single methanol or uncle's single methanol alcohol different from it with at least one is to obtain carboxylicesters.The use of alcohol mixture can cause forming mixed carboxylic acid's ester.React and illustrate by following two reaction equations:
2R aCH 2OH→R aCOOCH 2R a+2H 2
R aCH 2OH+R bOH→R aCOOR b+2H 2
If the mixture reaction of the alcohol that uncle's single methanol is different from it with at least one, then uncle's single methanol is preferably with the amount use based on the integral molar quantity of alcohol being at least 50 % by mole.
Uncle's single methanol suitable in the inventive method is generally all uncle's single methanols.Uncle's single methanol can be linearly, branching or ring-type.Uncle's single methanol has 3-10 carbon atom usually.Except a hydroxyl, uncle's single methanol does not have other functional group usually.Especially, uncle's single methanol is primary alkanol, the primary hydroxyl-C with a preferred 3-10 carbon atom 1-C 4alkylbenzene and primary hydroxyl-C 1-C 4alkyl-C 3-C 8naphthenic hydrocarbon.Especially, uncle's single methanol is for having the primary alkanol of preferred 3-10 a carbon atom, a particularly 3-6 carbon atom.Suitable uncle's single methanol is such as 1-propyl alcohol, n-butyl alcohol, 2-methyl-Pentyl alcohol, 1-amylalcohol, 3-methyl-propyl carbinol, 2-methyl-propyl carbinol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethyl-n-hexyl alcohol, 2-propyl group-n-Heptyl alcohol, 1-methylol hexanaphthene, benzylalcohol and 2-phenylethyl alcohol.Uncle's single methanol also can be used as mixture and uses.
Optionally can be aliphatic, alicyclic with the suitable alcohols used with the mixture of uncle's single methanol or aromatics, linearly or branching.They can be secondary alcohol or the tertiary alcohol.The alcohol being different from uncle's single methanol has 3-10 carbon atom usually.The alcohol being different from uncle's single methanol is preferably single methanol, and usually except a hydroxyl, does not have other functional group.Especially, the alcohol being different from uncle's single methanol is the second month in a season or the tertiary alkanol with a preferred 3-10 carbon atom, has the cycloalkanol of a preferred 5-10 carbon atom, secondary or tert-hydroxyl-C 1-C 4alkylbenzene and secondary or tert-hydroxyl-C 1-C 4alkyl-C 3-C 8naphthenic hydrocarbon.The example of this kind of alcohol is Virahol, 2-butanols, the trimethyl carbinol, cyclopentanol, hexalin, 1-phenylethyl alcohol, phenol or 1-methyl-propyl carbinol.
Also the mixture of the different alcohol obtained by fermentable sources can be used, the 3-methyl-propyl carbinol such as produced as by product in the technique preparation of bio-ethanol (so-called " potato spirit ") and the mixture of 2-methyl-propyl carbinol.
In addition, uncle's single methanol and optional other alcohol used with under the reaction conditions of the inventive method with the substituting group of inert way behavior, such as alkoxyl group, alkene oxygen base, dialkyl amido and halogen (F, Cl, Br, I).
In the present invention's specific embodiments, make the aliphatic C of uncle 3-C 10alcohol or the aliphatic C of uncle 3-C 10alcohol mixture, the particularly aliphatic C of uncle 4-C 6alcohol or the aliphatic C of uncle 4-C 6alcohol mixture reacts.
In the present invention one very specific embodiment, uncle's single methanol of reaction is the mixture of primary isoamyl alcohol or primary isoamyl alcohol and 2-methyl-propyl carbinol.
The inventive method is carried out under the existence of transition metal carbene complexes catalyzer K as hereinbefore defined.Prove that the catalytical active part of advantageously catalyzer K is present in liquid reaction medium with solubilized form at least in part.In a preferred embodiment, in method, the catalyzer K of used at least 90% is present in liquid reaction medium with solubilized form, and particularly preferably at least 95%, be very particularly preferably greater than 99%, based on the total amount in liquid reaction medium in often kind of situation.
According to the present invention, transition metal carbene complexes catalyzer K defined above is by making transistion metal compound V and imidazoles salt uncle single methanol and alkali existence under reaction and prepare.
Metal component in catalyzer, the amount of preferred ruthenium or iridium is generally 0.1-5000ppm (weight part), particularly 1-2000ppm, especially 50-1000ppm, based on the gross weight of liquid reaction mixture in often kind of situation.
Alkali is preferably with based on 1 equivalent imidazolium salt is the amount of 1-20 equivalent alkali, and particularly the amount of 1-5 equivalent alkali uses.
Imidazoles salt preferably uses with the amount of be 1-20 mole based on 1 mol of transition-metal in transistion metal compound V amount, particularly 1-6 mole.
According to the present invention, transition metal carbene complexes catalyzer K uncle single methanol and alkali existence under prepare.For this reason, program is usually directed to mixture, the imidazoles by uncle's single methanol or uncle's single methanol alcohol different from it with at least one salt, transistion metal compound V introduce in reaction compartment together with alkali, or first the mixture of uncle's single methanol or uncle's single methanol alcohol different from it with at least one and optional alkali are introduced in reaction compartment, and add the component that forms catalyzer and optional alkali wherein.
The reaction of the mixture of uncle's single methanol or uncle's single methanol alcohol different from it with at least one is carried out usually at the temperature of 20-250 DEG C.Preferred the inventive method, at 100-200 DEG C, is particularly preferably carried out at the temperature of 110-200 DEG C.
The reaction of the mixture of uncle's single methanol or uncle's single methanol alcohol different from it with at least one is carried out usually under the absolute total pressure of 0.1-20MPa, described pressure can be multiple or a kind of alcohol intrinsic pressure at the reaction temperatures, or gas is as the pressure of nitrogen, argon gas or hydrogen.Preferably, the inventive method is reaching under the absolute total pressure of 10MPa, particularly carries out reaching under the absolute total pressure of 1MPa.
According to the present invention, the reaction of the mixture of uncle's single methanol or uncle's single methanol alcohol different from it with at least one is carried out without dilution, is not namely added in reaction mixture by other solvent.Therefore, the solvent in reaction mixture, for being less than 10 % by weight, is preferably less than 5 % by weight, is particularly preferably less than 2 % by weight, is especially less than 1 % by weight.
Reaction times is usually by reactivity and the decision of required transformation efficiency of temperature of reaction, alcohol used.Usually, carry out the reaction of the reaction of uncle's single methanol or the mixture of uncle's single methanol alcohol different from it with at least one until transformation efficiency is at least 10% based on primary single methanol, particularly at least 20%, especially at least 25%.Prove advantageously to react and do not proceed to complete transformation efficiency (based on uncle's single methanol, 100%), but only proceed at the most 80%, particularly at the most 70% transformation efficiency.The required reaction times can be determined by routine experiment by those skilled in the art for this reason.It is generally 15 minutes to 100 hours, particularly 1-50 hour.
The esterification of the mixture of primary alconol or uncle's single methanol alcohol different from it with at least one is carried out along with the elimination of hydrogen (reaction equation see above) naturally.Prove advantageously from reactive system, to remove hydrogen.Transformation efficiency can be improved like this.This is by the unreacting alcohol stripping with boiling or carry out as nitrogen, carbonic acid gas or argon gas by introducing stripping gas.
Reaction can those skilled in the art become known for fluid-gas reaction conventional equipment and/or reactor in carry out, wherein catalyzer is present in liquid phase with the form of uniform dissolution.For the inventive method, all reactors of the gas-liquids reaction be substantially suitable at described temperature and described pressure can be used in principle.Such as K.D.Henkel is discussed at for gas-liquids with for the appropriate criteria reactor of Liquid-liquid reaction system, " Reactor Types and Their IndustrialApplications ", Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co.KGaA, 3.3rd chapter: in " Reactors for gas-liquidreactions ", at this with reference to the document.The example that can mention is stirred-tank reactor, tubular reactor or bubble-column reactor.Alcohol, transistion metal compound V, imidazoles the supply of salt and alkali can or be carried out apart from each other at this simultaneously.Herein, reaction with batch mode discontinuously or continuously, semi-continuously, can have or do not have recirculation and carry out.Mean residence time in reaction compartment is generally 15 minutes to 100 hours, particularly 1-50 hour.
After the reaction, usually preferably by distillation, carboxylicesters is separated from unreacted alcohol.Catalyzer K is retained in distillation bottom along with high boiling product and can re-uses.Unreacted alcohol can return in reaction.The thermal separation of one or more alcohol and carboxylicesters is by method known to those skilled in the art, and preferably carry out in vaporizer or in the water distilling apparatus comprising vaporizer and tower, described tower has multiple column plate, filler or obturator usually.
The present invention is set forth in more detail by following examples:
Embodiment 1:
[Ru (1, the 5-cyclooctadiene) Cl of 0.21g will be loaded in the 250ml three-necked flask with water separator and thermometer 2] 2, 0.7g 1-methyl-3-butylimidazolium 3-methyl-the propyl carbinol of muriate, 5g potassium hydroxide and 100g and the isomer mixture (product of distillation obtained by potato spirit of 2-methyl-propyl carbinol; 80 % by weight 3-methyl-propyl carbinols, 20 % by weight 2-methyl-propyl carbinols).Under the oil bath temperature of barometric point and 170 DEG C by mixture along with stirring (magnetic stirring apparatus) is heated 20 hours under reflux.At the end of reaction, the unreacting material mixture of 72.6% and the 27.1% carboxylicesters (isomer mixture formed by 3-methyl-propyl carbinol and 2-methyl-propyl carbinol; Transformation efficiency is measured by GC area %) be present in reaction mixture.46.3g (mixture of raw mixture and carboxylicesters) distills by (80 DEG C of oil bath temperatures, 20 millibars) from reaction discharge on the rotary evaporator.Catalyzer and alkali are retained in liquid residue and also can re-use.From the distillment of roughing out, be separated by alcohol mixture by carefully distilling with carboxylicesters, the purity obtaining 6.8g in thin distillation bottoms is the pure carboxylic acids ester (isomer mixture) of 99.2% (being measured by GC area %)
Embodiment 2:
[Ru (1, the 5-cyclooctadiene) Cl of 0.21g will be loaded in the 250ml three-necked flask with water separator and thermometer 2] 2, 0.7g 1-methyl-3-butylimidazolium muriate, 5g potassium hydroxide and 100g1-hexanol.Under the oil bath temperature of barometric point and 180 DEG C by mixture along with stirring (magnetic stirring apparatus) is heated 20 hours under reflux.At the end of reaction, the unreacting material of 44.1% and 39.5% carboxylicesters (hexyl hexanoate; Transformation efficiency is measured by GC area %) be present in reaction mixture.Can by the aftertreatment as described in Example 1 of reaction discharge.
Embodiment 3:
[Ru (1, the 5-cyclooctadiene) Cl of 0.21g will be loaded in the 250ml three-necked flask with water separator and thermometer 2] 2, 0.7g 1-methyl-3-butylimidazolium muriate, 5g potassium hydroxide and 100g benzylalcohol.Under the oil bath temperature of barometric point and 240 DEG C by mixture along with stirring (magnetic stirring apparatus) is heated 20 hours under reflux.At the end of reaction, the unreacting material of 10.4%, 4.7% phenyl aldehyde (intermediate of reaction) and 67.4% carboxylicesters (peruscabin; Transformation efficiency is measured by GC area %) be present in reaction mixture.Can by the aftertreatment as described in Example 1 of reaction discharge.

Claims (16)

1. prepare the method for carboxylicesters, it comprises the reaction of mixture in the presence of base under the existence of transition metal carbene complexes catalyzer K of at least one uncle's single methanol or uncle's single methanol alcohol different with it from least one, described catalyzer has 8 of at least one periodic table of elements (IUPAC), 9 or 10 group 4 transition metal atoms are as central atom M and at least one monodentate N-heterocyclic carbene ligand, wherein catalyzer K is by making to have 8 of at least one periodic table of elements (IUPAC), 9 or 10 group 4 transition metal atoms but not there is transistion metal compound V and the imidazoles of carbenes salt uncle single methanol and alkali existence under reaction and prepare, wherein said reaction is carried out without dilution.
2. method according to claim 1, wherein catalyzer K has ruthenium or iridium as central atom M.
3. the method any one of aforementioned claim, wherein catalyzer K has at least one, such as the N-heterocyclic carbene ligand of 1,2,3 or 4 formula (I):
Wherein:
R 1and R 4be C independently of each other 1-C 10alkyl, C 3-C 10cycloalkyl, have the 5-10 unit heteroaryl of 1,2 or 3 heteroatoms being selected from O, N and S as ring members, or an aryl, wherein last-mentioned four substituting groups are not substituted or can be selected from following substituting group and replace by one or more: halogen, C 1-C 10alkoxyl group, CN, C 1-C 10alkyl, C 3-C 10cycloalkyl, phenyl and naphthyl;
R 2and R 3be hydrogen or have about R independently of each other 1or R 4a kind of implication provided.
4. method according to claim 3, wherein except at least one N-heterocyclic carbene ligand, catalyzer K has at least one other ligand L, and other part described is selected from CO, hydride, aliphatic olefin, cycloolefin, carbocyclic aromatic, assorted aromatic hydrocarbons, aldehyde, ketone, halogenide, C 1-C 10carboxylate salt, metilsulfate, Methylsulfate, trifluoromethyl vitriol, tosylate, mesylate, prussiate, isocyanate, cyanate, thiocyanate, oxyhydroxide, C 1-C 10alkoxide, cyclopentadienide, pentamethylcyclopentadiene compound and five benzyl cyclopentadienide.
5. the method any one of aforementioned claim, wherein for the preparation of catalyzer K, uses the imidazoles of general formula (II) salt:
Wherein R 1, R 2, R 3and R 4there is the implication provided in claim 3,
A is H or COO -, and
X -for the Equivalent of negatively charged ion, particularly halogen, C 1-C 10carboxylate radical, benzoate anion, MeC 6h 4cOO -, tosylate, methanesulfonic root, trifluoromethayl sulfonic acid root, methanesulfonate, prussiate, isocyano, thiocyanate radical, tetrachloro aluminate, tetrabromo aluminate, tetrafluoroborate, hexafluoro-phosphate radical, hexafluoroantimonic anion, sulfate radical, hydroxide radical, two (trifluoromethane sulphonyl) imines or methylsulfate, condition is if A is COO -, then X -do not exist.
6. according to the method for claim 3 or 5, wherein in formula (I) and (II), variable R 1and R 4be C independently of each other 1-C 10alkyl, particularly branching C 3-C 10alkyl, especially sec.-propyl, R 2and R 3be hydrogen and A is hydrogen in often kind of situation.
7. the method any one of aforementioned claim, wherein alkali is selected from alkali-metal hydride, oxyhydroxide, carbonate, alkoxide and acid amides, the hydride of alkaline-earth metal, oxyhydroxide, carbonate, alkoxide and acid amides, organic amine, aryl lithium compounds and alkyl lithium compounds, particularly alkali metal hydroxide and alkali metal alcoholates.
8. the method any one of aforementioned claim, wherein alkali is with based on 1 equivalent imidazolium salt is that the amount of 1-20 equivalent alkali uses.
9. the method any one of aforementioned claim, wherein imidazoles salt uses with the amount being 1-20 mole based on 1 mol of transition-metal in transistion metal compound V
10. the method any one of aforementioned claim, wherein transistion metal compound V is selected from and does not have the ruthenium of carbenes or the title complex of iridium and salt, is especially selected from title complex and the salt of ruthenium.
11. methods according to claim 10, wherein transistion metal compound V has at least one transition metal atoms being selected from ruthenium and iridium and has at least 2 parts, described part is selected from Paracymene, muriate, benzene, CO, 1,5-cyclooctadiene, allyl group, acetylacetonate, methyl-sulphoxide, cyclopentadienyl, pentamethylcyclopentadiene base, indenyl, cyclooctene, hydride, ethene and H 2o.
12. methods according to claim 10, wherein transistion metal compound V is selected from [Ru (Paracymene) Cl 2] 2, [Ru (benzene) Cl 2] n, [Ru (CO) 2cl 2] n, wherein n is 1-100, [Ru (CO) under often planting situation 3cl 2] 2[Ru (1,5-cyclooctadiene) (allyl group)], RuCl 3h 2o, [Ru (acetylacetonate) 3], [Ru (methyl-sulphoxide) 4cl 2], [Ru (cyclopentadienyl) (CO) 2cl], [Ru (cyclopentadienyl) (CO) 2h], [Ru (cyclopentadienyl) (CO) 2] 2, [Ru (pentamethylcyclopentadiene base) (CO) 2cl], [Ru (pentamethylcyclopentadiene base) (CO) 2h], [Ru (pentamethylcyclopentadiene base) (CO) 2] 2, [Ru (indenyl) (CO) 2cl], [Ru (indenyl) (CO) 2h], [Ru (indenyl) (CO) 2] 2, ruthenocene, [Ru (1,5-cyclooctadiene) Cl 2] 2, [Ru (pentamethylcyclopentadiene base) (1,5-cyclooctadiene) Cl], [Ru 3(CO) 12], IrCl 3h 2o, KIrCl 4, K 3irCl 6, [Ir (1,5-cyclooctadiene) Cl] 2, [Ir (cyclooctene) 2cl] 2, [Ir (ethene) 2cl] 2, [Ir (cyclopentadienyl) Cl 2] 2, [Ir (pentamethylcyclopentadiene base) Cl 2] 2and [Ir (cyclopentadienyl) (CO) 2] and [Ir (pentamethylcyclopentadiene base) (CO) 2].
13. methods any one of aforementioned claim, wherein transistion metal compound V uses with the amount that the mixture based on uncle's single methanol of 1 weight part or uncle's single methanol alcohol different with it from least one is 0.1-5000ppm weight part.
14. methods any one of aforementioned claim, wherein make the aliphatic C of uncle 3-C 10alcohol or the aliphatic C of uncle 3-C 10alcohol mixture, the particularly aliphatic C of uncle 4-C 6alcohol or the aliphatic C of uncle 4-C 6alcohol mixture reacts.
15. methods according to claim 14, wherein make the mixture reaction of primary isoamyl alcohol or primary isoamyl alcohol and 2-methyl butanol.
16. methods any one of aforementioned claim, wherein the reaction of the mixture of at least one uncle's single methanol or uncle's single methanol alcohol different with it from least one is carried out at the temperature of 20-250 DEG C.
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WO2010058004A1 (en) * 2008-11-24 2010-05-27 Technical University Of Denmark Method for preparation of amides from alcohols and amines by extrusion of hydrogen
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