CN1705630A - Carbonylation process - Google Patents

Carbonylation process Download PDF

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CN1705630A
CN1705630A CN 200480001315 CN200480001315A CN1705630A CN 1705630 A CN1705630 A CN 1705630A CN 200480001315 CN200480001315 CN 200480001315 CN 200480001315 A CN200480001315 A CN 200480001315A CN 1705630 A CN1705630 A CN 1705630A
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compound
reaction
reactant
unsaturated
negatively charged
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M·J·格林
R·克劳斯
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Sasol Technology Pty Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

According to the present invention a carbonylation process comprises reacting at least one unsaturated reactant in the form of a compound having an aliphatic moiety with at least one unsaturated carbon-carbon bond; carbon monoxide; and a nucleophilic co-reactant in the presence of a Group VIII metal catalyst to produce a product containing a single unit of the unsaturated reactant in its reacted form. The catalyst is prepared by the reaction of a source of Group VIII metal a ligating compound to coordinate to the Group VIII metal, which ligating compound includes at least one atom selected from phosphorus, arsenic and antimony; and an anion or a source thereof of general formula (II) wherein R<1> and R<2> are the same or different and each comprises an organic group.

Description

Carbonylation method
Technical field
The present invention relates to the carbonylation method of unsaturated reactant that a kind of aliphatic series is partly with the compound form of at least one unsaturated C-C, being included in carbonylating catalyst exists down, with unsaturated reactant and carbon monoxide and nucleophilic co-reactant reaction, produce the product of the monobasic unsaturated reactant that contains its reaction back form.
Background technology
Unsaturated compound is known in the art such as the carbonylation reaction of olefinic or acetylenically unsaturated compound.In many European patents and patent application, the carbonylation of alkene has for example been described among EP-A-0495548, EP-A-0227160, EP-A-0495547, EP-A-0489472, EP-A-0282142, EP-A-04489472, EP-A-0106379 and the EP-A-0799180.In EP-A-0499329, EP-A-0441447 and WO 9515938, can find the example of the carbonylation of acetylenically unsaturated compound.
According to the character of co-reactant, described unsaturated compound can be converted into ester, acid, acid anhydride, monothioester and acid amides etc.At textbook " New Syntheses with Carbon Monoxide ", deeply discussed among the Ed.J.Falbe (Springer-Verlag 1980) and in the presence of VIII family metal catalyst, used nucleophilic compound carbonylation of olefin.It is believed that carbonylation reaction contain with one or more VIII family metallic cations of organic ligand complexing and suitable anionic active catalyst system effect under carry out.
That the organic ligand that is fit to is selected from usually is single-or bidentate ligand.
The negatively charged ion normally protonic acid of originating.Especially preferably non--or the weakly coordinating anion source.Because halide anion, especially cl anion are tending towards and palladium (VIII family metal) coordination quite doughtily, negatively charged ion is preferably derived by strong acid, except the haloid acid.
The main drawback of described carbonylation reaction is part, as the trend of organic phosphine and catalyst intermediate and/or reaction product and/or reactant and/or the blunt property phosphonium salt of reaction diluent reaction formation.For example, referring to R.P.Tooze et al.J.Chem.Soc., Dalton Trans.; (2000); 3441.Owing to reducing the catalyst activity and the stable loss that cause, the concentration of stablizing part makes that these reactions are disadvantageous from economic visual angle.
The object lesson of above-mentioned situation is hydrogenation and esterification reaction (unsaturated reactant with as the alcohol of nucleophilic co-reactant carbonylation reaction), wherein said sour promotor (being negative ion source) can with alcohol (pay close attention to most be that methyl alcohol is as co-reactant), make acid moieties esterified.The product that it is believed that this side reaction can be used as the potential alkylating reagent, immediately with solution in free ligand (pay close attention to most be three organophosphorus ligands) reaction form the Dun phosphonium salt of part.According to this mode, negatively charged ion and part are basically by losing in the reaction medium.This makes catalyst activity reduce, and matches with the time of losing because of the plating metallic palladium.
It is generally acknowledged, use bidentate ligand will partly reduce the formation of the inactive ligand that forms in the catalytic process, this is because than unidentate ligand, the lower in essence concentration of bidentate ligand that the stable metal positively charged ion needs.The example of the described bidentate ligand of aliphatic diphosphine form is disclosed in EP-A-0227160, EP-A-0495547, EP-A-0495548 and WO 9619434.
The problem of ligand loss can also reduce as negative ion source (also becoming promotor) by using weak carboxylic acids according to disclosed among the WO 97/03943 in the carbonylation reaction.Than strong acid promoter, such as methylsulfonic acid, the formation of Dun phosphonium salt reduces really, but total catalyst activity loses immediately.In order to overcome this shortcoming, disclose among the EP-A-0495547 and used sterically hindered carboxylic acid.Use large-substituent that deutero-negatively charged ion and metallic cation coordinate trend are minimized, thereby produce active higher catalyzer.But, weak acid trend towards than strong acid easier and irreversibly with nucleophilic co-reactant reaction, therefore the content of pollutent increase, and causes this scheme magnetism relatively poor.
EP-A-0121965 described contain VIII family metallic cation, bidentate ligand and pKa less than the carbonylating catalyst of 2 sour promotor in the presence of alkene and CO-copolymerization.Under this patent and the unexposed copolymerization conditions, any salt of formation part in the presence of as the strong acid of methylsulfonic acid and tosic acid.Use strong acid promoter that non-in essence coordination anion will be provided, this is regarded as forming the key of active carbonyl group catalyzer.Unfortunately,, contain with generation in the reaction of product of monobasic unsaturated reactant of its reaction back form, using such as these strong acid promoter and strengthening between the salify of part as if directly related at the unsaturated reactant carbonylation.
The boronic acid containing (as negative ion source) of particular types of having described use general formula (I) in EP 039 6268, EP 039 1579, EP 031 5318 and EP0314309 is as promotor, and is specifically related to prepare polyketone by alkene and carbon monoxide.Obviously, described polyketone comprises a plurality of unsaturated reactants unit (alkene) of its reaction back form.These boracic promotor are the strong acid that is enough to produce the high-activity palladium catalyzer.
Wherein R is the organic group that defines in these patents.
The inventor has been found that, if the known organic acid promotor (for example methylsulfonic acid) in the carbonylation reaction of the negatively charged ion of use following formula (I) replacement unsaturated reactant, contain the unitary product of single unsaturated reactant that is its reaction back form with generation, the formation of the inactive salts of free ligand reduces widely so.These negatively charged ion can activate the proper metal positively charged ion, form the higher relatively cationic complex of catalyst activity.Do not hint this advantage in the prior art, the result is very beat all.
Summary of the invention
According to the present invention, carbonylation reaction is included in VIII family metal catalyst and exists down, with at least a unsaturated reactant, carbon monoxide and nucleophilic co-reactant reaction, generation contains the unitary product of single unsaturated reactant that is its reaction back form, described unsaturated reactant is that the aliphatic series part has the form of the compound of at least one unsaturated C-C, and wherein catalyzer prepares by following substance reaction
I) VIII family source metal;
Ii) with the ligand compound of VIII family metal-complexing, wherein ligand compound comprises at least
An atom that is selected from phosphorus, arsenic and antimony;
The iii) negatively charged ion of general formula (II) or its source
R wherein 1And R 2Identical or different, comprise organic group respectively.
Negatively charged ion or its source
R in the formula (II) 1And R 2Can comprise alkyl or assorted alkyl respectively.
In a preferred embodiment of the invention, R 1And R 2At least one, but preferred two, comprise aromatic substance or heteroaromatics.In a preferred embodiment of the invention, R 1And R 2Can comprise respectively and be selected from C 1-C 6The part of alkylidene group, neighbour-phenylene, biphenylene, general formula (III), the part of general formula (IV)
Figure A20048000131500082
And the substitutive derivative of arbitrary described compound.Described substitutive derivative can comprise, for example one of above-claimed cpd of being replaced by for example halogen, alkyl, amine or nitro of at least one H wherein.Preferred R 1And R 2Identical.
In one embodiment of the invention, negatively charged ion can comprise compound (V)
Or its substitutive derivative.Described substitutive derivative can comprise, for example the above-claimed cpd that replaced by for example halogen, alkyl, amine or nitro of at least one H wherein.
In another embodiment of the present invention, negatively charged ion comprises compound (VI)
Or its substitutive derivative.Described substitutive derivative can comprise, for example the above-claimed cpd that replaced by for example halogen, alkyl, amine or nitro of at least one H wherein.
The preferred anionic source is anionic conjugate acid.
In one embodiment of the invention, negatively charged ion or its source can prepare on the spot.Can be by boric acid and R 1And R 2The condensation reaction preparation of suitable precursor.Under the situation of compound (V), R 1And R 2Precursor can be pyrocatechol.Under the situation of compound (VI), R 1And R 2Precursor can be Whitfield's ointment.
In another embodiment of the present invention, negative ion source can form in advance.
Carbonylation process and its reactant
In a preferred embodiment of the invention, carbonylation process can be used to prepare ester or carboxylic acid.In the case, nucleophilic co-reactant comprises source of hydroxyl groups.
Obviously, this moment is with the selective reaction condition, to form ester or carboxylic acid rather than polyketone.These appropriate reaction conditions are well known in the art, comprise the use unidentate ligand, as triphenylphosphine; Bidentate ligand, as 1, two (di-t-butyl phosphino-) propane of 3-, or its combination, perhaps wherein one or more.
In a preferred embodiment of the invention, this method can be used for preparing ester, and the nucleophilic co-reactant of this moment comprises alcohol.In these cases, reaction is known hydrogenation and esterification reaction.Can predict, can use any suitable alcohol, such as methyl alcohol, ethanol, propyl alcohol, glycol, polyvalent alcohol and phenol, but particular methanol.
Preferred ester comprises aliphatic ester.Ester can comprise non-branched product, and in a preferred embodiment of the invention, it comprises methyl propionate.In a preferred embodiment of the invention, this process comprises the process for preparing methyl propionate, and wherein unsaturated reactant comprises ethene, and alcohol comprises methyl alcohol.Obviously, this moment, methyl propionate contained an ethyl, and described ethyl is the unsaturated reactant of reaction back form.
Unsaturated reactant
At least a unsaturated reactant that nucleophilic is partly with at least one unsaturated C-C can comprise the olefin(e) compound of alkene form or contain alkene compound partly.In a preferred embodiment of the invention, olefin(e) compound comprises alkene.But can predict, olefin(e) compound can comprise the compound that contains the alkene part, and wherein said compound can comprise one or more functional groups such as ester, nitrous acid ester, alcohol, ether and hydroxyacetone.
Preferred at least a alkene only comprises a kind of alkene, and alkene can contain a two key.Alkene can comprise alpha-olefin, preferably includes ethene.
Carbon monoxide
Carbon monoxide can be from any suitable carbon monoxide source.
Catalyzer
VIII family metal catalyst preferably includes palladium catalyst.Catalyzer can be that all pre-formation or part are preformed.For example, can predict, the palladium source can be separately and the part reaction, to provide preformed precursor catalyst compound, its further situ reaction, preparation active catalyst.
In a preferred embodiment of the invention, palladium catalyst prepares on the spot.
Can predict, the non-halogen thing palladium source that is fit to can be with such as palladium salt (organic or inorganic), and for example the form of carboxylate salt and nitrate is used.In a preferred embodiment of the invention, the palladium source can comprise acid chloride.
Although prediction can be used bidentate ligand, in a preferred embodiment of the invention, part comprises unidentate ligand.Ligand compound can comprise the compound of band VA family central atom, for example organic phosphine, organic arsine and organic .Preferred ligand compound comprises organic phosphine.In one embodiment of the invention, the compound that comprises general formula (VII)
P(R 3R 4R 5)-------------(VII)
R wherein 3, R 4And R 5Identical or different, be respectively organic group.
In one embodiment of the invention, ligand compound comprises PPh 3
Solvent
Reaction is preferably carried out in solvent.Solvent can comprise alcohol, but also can use other solvent, especially water as co-reactant and situation as source of hydroxyl groups under.
Reaction conditions
The consumption of catalyst system is not strict usually, can change in wide region.For the preparation of catalyst system of the present invention, some is in excess in VIII family metal to the amount of part usually, represents with mole part/every mole of VIII family atoms metal.The amount of general such selection part, every mole metal (preferred palladium) atom, part exists in the scope of 1.5-500 mole.The amount of negative ion source can be in 1-500 mole/cationic scope of every mole metal.
Reaction of the present invention particularly 50 ℃-150 ℃, is carried out under more special 75 ℃-120 ℃ temperature preferably at 20 ℃-250 ℃.
Reaction can be carried out under the pressure of 5-70bar.Also can use higher pressure.
The present invention provides the negatively charged ion of general formula (II) or the purposes in its source on the other hand.
R wherein 1And R 2Identical or different, comprise organic group respectively;
In carbonylation method, being included in VIII family metal catalyst exists down, with at least a unsaturated reactant, carbon monoxide and nucleophilic co-reactant reaction, generation contains the unitary product of single unsaturated reactant that is its reaction back form, and described unsaturated reactant is that the aliphatic series part has the form of the compound of at least one unsaturated C-C; Wherein catalyzer prepares by following substance reaction
I) VIII family source metal;
Ii) with the ligand compound of VIII family metal-complexing, wherein ligand compound comprises at least
An atom that is selected from phosphorus, arsenic and antimony;
The iii) negatively charged ion of general formula (II) or its source;
Thereby the formation of ligand compound inactive salts is reduced.
The minimizing that the ligand compound inactive salts forms can with use strong acid, replace the same reaction under negative ion source or anionic the same terms suitable such as methylsulfonic acid.
Further describe the present invention below by following non-limiting example.
Embodiment
Embodiment 1
120ml methyl alcohol, 0.0538gPd (OAc) pack in a 300ml Hasteloy C autoclave 2(0.239mmol), 3.147g PPh 3(11.99mmol), 1.483g B (OH) 3(24mmol) with 6.629g Whitfield's ointment (48mmol).Reactor was heated to 110 ℃ through 20 minutes immediately, stirred with 1100rpm simultaneously.In case temperature-stable uses CO: C 2H 41: 1 mixture reactor is forced into the stagnation pressure of the highest 20bar.Subsequently gas feed is switched to the heavy disc type container (identical gaseous mixture) of 1L, and in heavy disc type container, continue reaction process by pressure drop.Observing initial speed of response is that every mole of palladium per hour forms 1020 moles of methyl propionates.After catalyzer moves about 1000 catalytic cycle, from the reactor sampling, and use (Bu) 3P (O) adopts as interior mark 31The amount of the quantitative methylsulphonic acid triphenyl phosphonium of P-NMR. 31The P-NMR wave spectrum shows, does not have methylsulphonic acid triphenyl phosphonium (passivity De phosphonium salt) in solution.The a small amount of triphenylphosphine oxidation thing that forms in total overall reaction is not separated as the phosphine branch and is phosphonium salt.Existing report before the stoichiometry reduction of acid chloride and the concomitant oxidation of triphenylphosphine.Referring to people Organometallics. such as C.Amatore; (1992); 11; 3009.).The GC analysis revealed of same sample of reaction mixture is 98% to the selectivity of methyl propionate.
Embodiment 2
Repeat embodiment 1, replace the B (OH) of adding respectively but in reaction mixture, add the preformed borosalicylic acid of 6.693g 3With salicylic amount.Observing initial speed of response is that every mole of palladium per hour forms 886 moles of methyl propionates.After catalyzer moves about 1000 catalytic cycle, from the reactor sampling, and use (Bu) 3P (O) adopts as interior mark 31The amount of the quantitative methylsulphonic acid triphenyl phosphonium of P-NMR. 31The P-NMR wave spectrum shows, does not have the methylsulphonic acid triphenyl phosphonium in solution.The GC analysis revealed of same sample of reaction mixture is 98% to the selectivity of methyl propionate.
In embodiment 1 and 2, the loss of ligand compound (triphenylphosphine) is reduced to the ester (methyl propionate) that 1% quality/every g forms.
Embodiment 3 (contrast)
In simultaneous test, repeat embodiment 1, replace borosalicylic acid but in reaction mixture, add 1.557ml methylsulfonic acid (24mmol).Observing initial speed of response is that every mole of palladium per hour forms 2144 moles of methyl propionates.After catalyzer moves about 1000 catalytic cycle, from the reactor sampling, and use (Bu) 3P (O) adopts as interior mark 31The amount of the quantitative methylsulphonic acid triphenyl phosphonium of P-NMR. 31The P-NMR wave spectrum shows that 72% triphenylphosphine is converted into the methylsulphonic acid triphenyl phosphonium in the solution.The GC analysis revealed of same sample of reaction mixture is 98% to the selectivity of methyl propionate.
Embodiment 4 (contrast)
In simultaneous test, repeat embodiment 1, replace borosalicylic acid but in reaction mixture, add 2.616g trifluoroacetic acid (24mmol).Observing initial speed of response is that every mole of palladium per hour forms 572 moles of methyl propionates.After catalyzer moves about 1000 catalytic cycle, from the reactor sampling, and use (Bu) 3P (O) adopts as interior mark 31The amount of the quantitative methylsulphonic acid triphenyl phosphonium of P-NMR. 31The P-NMR wave spectrum shows that 24% triphenylphosphine is converted into the methylsulphonic acid in the solution.The GC analysis revealed of same sample of reaction mixture is 90% to the selectivity of methyl propionate.
Embodiment 5 (contrast)
In simultaneous test, repeat embodiment 1, replace the 6.629g Whitfield's ointment but in reaction mixture, add 8.136g 5-chloro-Whitfield's ointment (24mmol).Observing initial speed of response is that every mole of palladium per hour forms 780 moles of methyl propionates.After catalyzer moves about 1000 catalytic cycle, from the reactor sampling, and use (Bu) 3P (O) adopts as interior mark 31The amount of the quantitative methylsulphonic acid triphenyl phosphonium of P-NMR. 31The P-NMR wave spectrum shows that 3% triphenylphosphine is converted into the methylsulphonic acid in the solution.The GC analysis revealed of same sample of reaction mixture is 98% to the selectivity of methyl propionate.
Obviously, can be in the change of carrying out under the situation that does not deviate from purport of the present invention on many details.

Claims (17)

1. carbonylation method, being included in VIII family metal catalyst exists down, with at least a unsaturated reactant, carbon monoxide and nucleophilic co-reactant reaction, generation contains the unitary product of single unsaturated reactant that is its reaction back form, described unsaturated reactant is that the aliphatic series part has the form of the compound of at least one unsaturated C-C, and wherein catalyzer prepares by following substance reaction
I) VIII family source metal;
Ii) with the ligand compound of VIII family metal-complexing, this ligand compound comprises that at least one is selected from the atom of phosphorus, arsenic and antimony; With
The iii) negatively charged ion of general formula (II) or its source
Figure A2004800013150002C1
R wherein 1And R 2Identical or different, comprise organic group respectively.
2. the process of claim 1 wherein R 1And R 2All comprise aromatic substance or heteroaromatics.
3. the process of claim 1 wherein R 1And R 2Comprise independently and be selected from C 1-C 6The compound of the part of alkylidene group, adjacent phenylene, biphenylene, formula (III), the part of formula (IV)
Figure A2004800013150003C1
And the substitutive derivative of arbitrary described compound.
4. the process of claim 1 wherein that negatively charged ion comprises compound (V)
Or its substitutive derivative.
5. the process of claim 1 wherein that negatively charged ion comprises compound (VI)
Figure A2004800013150003C3
Or its substitutive derivative.
6. aforesaid right requires each method, and wherein negatively charged ion or its source are by boric acid and R 1And R 2Suitable precursor between condensation reaction prepare on the spot.
7. aforesaid right requires each method, and wherein said carbonylation method is the method that is used to prepare ester, and this moment, nucleophilic co-reactant comprised alcohol.
8. the method for claim 7, it is used to prepare methyl propionate, and wherein unsaturated compound comprises ethene, and alcohol comprises methyl alcohol.
9. aforesaid right requires each method, and wherein VIII family metal comprises palladium.
10. the method for claim 9, wherein catalyzer prepares on the spot.
11. aforesaid right requires each method, wherein ligand compound comprises the compound of general formula (VII)
P(R 3R 4R 5)------------- (VII)
R wherein 3, R 4And R 5Identical or different, be organic group independently.
12. the method for claim 11, wherein ligand compound comprises PPh 3
13. aforesaid right requires each method, it carries out in solvent.
14. the negatively charged ion of general formula (II) or its source purposes in carbonylation method
R wherein 1And R 2Identical or different, comprise organic group respectively;
Described method is included in VIII family metal catalyst and exists down, with at least a unsaturated reactant, carbon monoxide and nucleophilic co-reactant reaction, generation contains the unitary product of single unsaturated reactant that is its reaction back form, described unsaturated reactant is that the aliphatic series part has the form of the compound of at least one unsaturated C-C, and wherein catalyzer prepares by following substance reaction
I) VIII family source metal;
Ii) with the ligand compound of VIII family metal-complexing, wherein ligand compound comprises that at least one is selected from the atom of phosphorus, arsenic and antimony;
The iii) negatively charged ion of general formula (II) or its source,
The formation of ligand compound inactive salts is reduced.
15. the purposes of claim 14, wherein the minimizing of ligand compound inactive salts formation and negative ion source or negatively charged ion are suitable by the same reaction under the displaced the same terms of methylsulfonic acid.
16. one kind basically according to the carbonylation method of the description of embodiment 1,2 and 5.
17. the purposes of negatively charged ion in the carbonylation methods of describing according to embodiment 1,2 and 5 basically.
CN 200480001315 2003-04-11 2004-03-31 Carbonylation process Pending CN1705630A (en)

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