CN102476061B - Alkene double decomposition catalyst and preparation method thereof - Google Patents
Alkene double decomposition catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a prepariton method of an alkene double decomposition catalyst as shown in the formula (I), wherein each symbol is defined in the description. The method comprises the following steps of: (1) performing a reaction between unsubstituted or substituted benzaldehyde (a) and hydrazine hydrate to generate a diazonium compound (b); and (2) performing a reaction between the diazonium compound (b) obtained from the step (1) and metal salt M(L1)p(L2)q.
Description
Technical field
The present invention relates to a kind of preparation method of olefin metathesis catalyst.
Background technology
Along with the development of petrochemical industry, people begin to pay close attention to how to replace the petroleum base chemical raw material with the non-petroleum base chemical raw material, such as natural and transgenic seed oil are changed into the organic chemistry raw material with higher economic worth.Can make two kinds to form identical or different alkene by olefin metathesis reaction, react by fracture and the reorganization of carbon-carbon double bond, and generate one or more product alkene different with reactant olefin.When the composition of reactant olefin was identical, this method was called as " homogeneous phase double decomposition ".When the composition of reactant olefin not simultaneously, this method is called as " intersection double decomposition ".For example unsaturated fatty acid ester can with low-carbon alkene (C
2-10Alkene) under the effect of metathesis catalyst, intersect metathesis reaction, generate linear end group alkene and the beta-unsaturated esters of short chain.
The existing report of catalyst that is used for olefin metathesis reaction.The metal carbene compound is the metal alkylidene compound of the two keys (M=C) of a class containing metal-carbon, because their various types of olefin metathesis reactions of catalysis and receiving publicity effectively.In the metal carbene compound, the Grubbs catalyst is the important catalyst that is used for olefin metathesis reaction of a class.
WO96/04289 has introduced high activity and the stable metal carbene compound based on ruthenium or osmium, their preparation method and in olefin metathesis reaction as Application of Catalyst.Yet what the disclosed Preparation of catalysts of WO96/04289 adopted is to be raw material with the cycloolefin, and the reaction scheme more complicated.US Patent No. 2009088581A1 also discloses the preparation that is used for the metal carbene compound of olefin metathesis catalyst, and the raw material that adopts is aryl olefin, prepares catalyst by methods such as protonated or rearrangements.Document " J.Am.Chem.Soc., 1996,118 (1), 100-110 " discloses various metal carbene Catalysts and its preparation methods for olefin metathesis reaction.Yet the initiation material of its preparation catalyst is baroque acylhydrazone class, is difficult for preparation and cost height.
In view of the foregoing, need to simplify the Preparation of catalysts method, provide a kind of raw material to be easy to get, synthesize the easy method for preparing olefin metathesis catalyst, thereby a kind of approach that produces the useful industrial organic chemicals by the non-petroleum base raw material is provided.
Summary of the invention
The present invention relates to a kind of preparation method of olefin metathesis catalyst.More specifically, the invention provides a kind of preparation suc as formula the method for the olefin metathesis catalyst shown in (I):
Wherein M is ruthenium or osmium;
R is selected from hydrogen, C
1-20Alkyl, C
1-20Alkoxyl, C
6-20Aryl, nitro, at least one in amino and the halogen;
L
1Be selected from the anionic group independently of one another, for example halogen or nitrate anion;
L
2Be selected from neutral group independently of one another, can be selected from tricyclohexyl phosphine, triphenylphosphine, three (sulfonation phenyl) phosphine, nitrogen heterocyclic ring, amine, acid amides, ether and sulfoxide independently of one another;
M and n are 0～4 integer independently of one another, and wherein m and n are not 0 simultaneously, and the summation of m and n is 4;
Comprise the steps: that (1) makes the compound (a) (the not benzaldehyde that replaces or replace) and hydrazine hydrate (N of following general formula
2H
4H
2O) react, generate the compound (b) (diazonium compound) of following general formula:
Compound (a) compound (b)
Wherein R is suc as formula defining in (I);
(2) make by the compound (b) that obtains in the step (1) and slaine M (L
1)
p(L
2)
qReaction, the catalyst of production (I),
Wherein M, L
1And L
2Suc as formula defining in (I); P and q are 0～5 integer independently of one another, and p and q are not 0 simultaneously, and the summation of p and q is 5.
The method that the present invention prepares olefin metathesis catalyst adopt unsubstituted or the benzaldehyde that replaces as initiation material, can obtain catalyst for olefin metathesis reaction through two-step reaction, have that raw material is easy to get, synthetic easy advantage.
The specific embodiment
In the present invention, C
1-C
20Alkyl and C
1-C
20The alkyl structure of alkoxyl partly refers to have saturated straight chain or the branched hydrocarbyl radical of 1-20 carbon atom, preferred C
1-C
6Alkyl, methyl for example, ethyl, propyl group, the 1-Methylethyl, butyl, the 1-methyl-propyl, the 2-methyl-propyl, 1, the 1-dimethyl ethyl, amyl group, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1,1,2-trimethyl propyl group, 1,2,2-trimethyl propyl group, 1-ethyl-1-methyl-propyl, 1-ethyl-2-methyl-propyl.
C
1-C
20Alkoxyl refers to the straight chain with 1-20 carbon atom or the branching saturated hydrocarbyl via the oxygen atom connection, preferred C
1-C
6Alkoxyl, for example methoxyl group, ethyoxyl, OCH
2-C
2H
5, OCH (CH
3)
2, n-butoxy, OCH (CH
3)-C
2H
5, OCH
2-CH (CH
3)
2, OC (CH
3)
3N-pentyloxy, 1-methyl butoxy, 2-methyl butoxy, 3-methyl butoxy, 1,1-dimethyl propoxyl group, 1,2-dimethyl propoxyl group, 2,2-dimethyl-propoxyl group, 1-ethyl propoxyl group, just own oxygen base, 1-methyl amoxy, 2-methyl amoxy, 3-methyl amoxy, 4-methyl amoxy, 1,1-dimethyl butoxy, 1,2-dimethyl butoxy, 1,3-dimethyl butoxy, 2,2-dimethyl butoxy, 2,3-dimethyl butoxy, 3,3-dimethyl butoxy, 1-ethyl butoxy, 2-ethyl butoxy, 1,1,2-trimethyl propoxyl group, 1,2,2-trimethyl propoxyl group, 1-ethyl-1-methyl propoxyl group, 1-ethyl-2-methyl propoxyl group etc.
C
6-20Aryl is interpreted as referring to have monocycle or many rings of 6-20 carbon atom, and optional quilt is selected from halogen, C
1-6Alkyl, C
1-6The aromatic hydrocarbyl that the substituting group of alkoxyl and nitro replaces; Preferred C
6-10Aryl, for example phenyl, naphthyl or the phenyl that replaced by halogen such as fluorine, chlorine or bromine.
Halogen is selected from fluorine, chlorine, bromine and iodine, preferred chlorine and bromine.
Nitrogen heterocyclic ring is to contain one or more nitrogen-atoms as the monocycle of ring members or many ring (for example dicyclo), the saturated or undersaturated heterocycle of part, preferably contains 1 nitrogen-atoms as 5 Yuans or 6 Yuans bicyclic heterocycles, for example bipyridyls of ring members.
In the definition of the olefin metathesis catalyst shown in the formula (I), R is selected from hydrogen, C
1-20Alkyl, C
1-20Alkoxyl, C
6-20Aryl, nitro, at least one in amino and the halogen; Preferred hydrogen, C
1-6Alkyl, C
1-6Alkoxyl, C
6-10Aryl, at least one in nitro and the halogen; More preferably at least one in hydrogen, methyl, isopropoxy, phenyl, nitro and the chlorine.Preferred R is positioned at 2 and/or 4 of phenyl ring.
The anionic group L
1For example be halogen or nitrate anion, preferred halogen, more preferably chlorine and bromine.
Neutral group L
2Can be selected from tricyclohexyl phosphine, triphenylphosphine, three (sulfonation phenyl) phosphine, nitrogen heterocyclic ring, amine, acid amides, ether and sulfoxide independently of one another; More preferably tricyclohexyl phosphine, triphenylphosphine, three (sulfonation phenyl) phosphine and nitrogen heterocyclic ring; Further preferred tricyclohexyl phosphine, triphenylphosphine and bipyridyl.
Preferably, m is that 2, n is 2.
Preferably, p is that 2, q is 3.
In Preparation of catalysts method of the present invention, the reaction of step (1) can be carried out in the presence of organic solvent.Used organic solvent can be alcohol, ether or its mixture, for example methyl alcohol, ethanol, propyl alcohol, butanols, ether, oxolane etc. or its mixture; Particular methanol, ethanol or its mixture.The consumption of solvent gets final product to guarantee that reactant fully dissolves or disperses.
The reaction of step (1) can be in the presence of the catalyst or do not have to carry out in the presence of the catalyst.Possible catalyst is acid compounds, for example acetic acid, p-methyl benzenesulfonic acid etc.; Also can use strong absorptive catalyst such as molecular sieve, titanium tetrachloride etc.
Preferred 1: 0.5～1: 10 of the mol ratio of compound (a) and hydrazine hydrate in step (1), more preferably 1: 1～1: 5, most preferably 1: 1～1: 3.
Reaction in the step (1) can be carried out under 10-30 ℃, preferably carries out under room temperature (15-30 ℃).Preferred 0.5-5 of reaction time hour, more preferably 0.5-2 hour.
In Preparation of catalysts method of the present invention, the reaction of step (2) can be carried out in the presence of organic solvent, and used organic solvent can be hydrocarbon, halogenated hydrocarbons, ether or its mixture; For example pentane, n-hexane, cyclohexane, carrene, chloroform, tetrachloromethane, ether, oxolane etc. or its mixture; Preferred carrene, chloroform, pentane or its mixture.The consumption of solvent gets final product to guarantee that reactant fully dissolves or disperses.
Used slaine M (L in the step (2)
1)
p(L
2)
qBe preferably selected from three (triphenylphosphine) ruthenous chloride, three (tricyclohexyl phosphine) ruthenous chloride, three (triphenylphosphine) osmium dichlorides and three (bipyridyl) ruthenous chloride.
The reaction of step (2) is preferably at-100 ℃ to-30 ℃, more preferably-90 ℃ to-40 ℃, most preferably-80 ℃ carries out under-50 ℃.Reaction time is 10 minutes to 10 hours, preferred 20 minutes to 5 hours, and more preferably 0.5-2 hour.
In step (2), compound (b) and slaine M (L
1)
p(L
2)
qPreferred 1: 0.25～1: 4 of mol ratio, more preferably 1: 0.25～1: 2, most preferably 1: 0.25～1: 1.
Catalyst of the present invention can be according to this area when carrying out olefin metathesis reaction in method commonly used, adopt this area reaction condition commonly used to carry out.For example reaction temperature is 0-200 ℃, and reaction pressure is 0.1-6.0MPa.
Embodiment
The present invention is described in further detail by the following examples, and described embodiment only is the present invention is described and never limits the present invention.Used aldehyde, hydrazine hydrate is commercially available among the embodiment, analyzes pure; Slaine is analyzed pure from Beijing lark prestige reagent company.
The elementary analysis instrument is the CE-440 that U.S. Jia Lian Instr Ltd. produces.
The nmr analysis instrument is the AV400 type NMR that Switzerland Bruker company produces.
Embodiment 1
A: catalyst C
1Preparation
In the round-bottomed flask of 100mL, add benzaldehyde (1.06g, 10mmol) and hydrazine hydrate (1.0g 20mmol), adds 20mL ethanol, stirring at room reaction 1 hour.Reactant liquor extracts with pentane, and the organic phase anhydrous magnesium sulfate drying after the extraction revolves and obtains grease-diazonium compound (0.8g, 6.8mmol, productive rate 68%) after steaming desolventizing.
(0.24g 2mmol) is dissolved in the 5mL pentane, and after the ice bath cooling, adding is dissolved with three (triphenylphosphine) ruthenous chloride, and (0.95g in 10mL carrene 1mmol), cooled to mixture-78 ℃ of stirring reactions 0.5 hour with above-mentioned oily diazonium compound.Revolve the steaming desolventizing, residue is namely obtained catalyst C with carrene/pentane (volume ratio 1: 1) recrystallization
1(0.8g, 0.96mmol, productive rate 96%).
The elementary analysis data of product are C
43H
36Cl
2P
2Ru (measured value): C, 65.65 (65.57); H, 4.61 (4.80).The nucleus magnetic hydrogen spectrum data of product are
1H NMR (C
6D
6): (t, Ru=CH), 7.8-7.6 and 7.0-6.7 (are m, C to δ 19.6
6H
5And P (C
6H
5)
3).
B: catalyst C
1The metathesis reaction of catalyzed ethylene and methyl oleate
Adopt the 300mL stainless steel autoclave.With the autoclave heating, vacuumize the back with nitrogen replacement for several times, charged pressure is the ethene of 0.5MPa then, is cooled to 40 ℃.Atmospheric valve is opened, added rapidly and contain 5 μ mol catalyst C
1And the dehydrated toluene solution (100mL) of 20mmol methyl oleate.Close atmospheric valve, control reaction pressure 4.0MPa feeds ethene, reacts, and the reaction time is 1 hour.
After reaction is finished, reaction system is cooled to room temperature, liquid-phase product is collected in the conical flask, measure laggard circumstances in which people get things ready for a trip analysis of spectrum.It is as follows to record reaction result: the conversion ratio of methyl oleate is that the productive rate of 72%, 1-decene is that the productive rate of 62.3%, 9-decylenic acid methyl esters is 60.8%.
Embodiment 2 catalyst C
2Preparation
The preparation method is with embodiment 1, but benzaldehyde is replaced with o-chlorobenzaldehyde, makes catalyst C
2, its elementary analysis data are C
43H
35Cl
3P
2Ru (measured value): C, 62.90 (63.01); H, 4.30 (4.71).
Embodiment 3 catalyst C
3Preparation
The preparation method is with embodiment 1, but benzaldehyde is replaced with paranitrobenzaldehyde, makes catalyst C
3, its elementary analysis data are C
43H
35Cl
2NO
2P2Ru (measured value): C, 62.10 (62.05); H, 4.24 (4.59); N, 1.68 (1.52).
Embodiment 4 catalyst C
4Preparation
The preparation method is with embodiment 1, but benzaldehyde is replaced with o-methyl-benzene formaldehyde, makes catalyst C
4, its elementary analysis data are C
44H
38Cl
2P
2Ru (measured value): C, 60.00 (60.03); H, 4.78 (4.49).
Embodiment 5 catalyst C
5Preparation
The preparation method is with embodiment 1, but benzaldehyde is replaced with the 4-biphenylcarboxaldehyde, makes catalyst C
5, its elementary analysis data are C
49H
40Cl
2P
2Ru (measured value): C, 68.21 (68.16); H, 4.67 (4.89).
Embodiment 6 catalyst C
6Preparation
The preparation method is with embodiment 1, but three (triphenylphosphine) ruthenous chloride is replaced with three (tricyclohexyl phosphine) ruthenous chloride, makes catalyst C
6, its elementary analysis data are C
43H
72Cl
2P
2Ru (measured value): C, 62.76 (62.63); H, 8.82 (9.22).
Embodiment 7 catalyst C
7Preparation
The preparation method is with embodiment 1, but three (triphenylphosphine) ruthenous chloride is replaced with three (triphenylphosphine) osmium dichloride, makes catalyst C
7, its elementary analysis data are C
43H
36Cl
2P
2Os (measured value): C, 58.97 (58.92); H, 4.14 (4.22).
Embodiment 8 catalyst C
8Preparation
The preparation method is with embodiment 1, but three (triphenylphosphine) ruthenous chloride is replaced with three (bipyridyl) ruthenous chloride, makes catalyst C
8, its elementary analysis data are C
27H
22Cl
2N
4Ru (measured value): C, 56.45 (56.58); H, 3.86 (3.66); N, 9.75 (9.51).
Embodiment 9 catalyst C
1Preparation
The preparation method is with embodiment 1, and difference is to change the hydrazine hydrate consumption into 10mmol.The gross production rate 60% of target catalyst.The elementary analysis data are C
43H
36Cl
2P
2Ru (measured value): C, 65.65 (65.57); H, 4.61 (4.80).The nucleus magnetic hydrogen spectrum data of product are
1H NMR (C
6D
6): (t, Ru=CH), 7.8-7.6 and 7.0-6.7 (are m, C to δ 19.6
6H
5And P (C
6H
5)
3).
Embodiment 10 catalyst C
1Preparation
The preparation method is with embodiment 1, and difference is to change the hydrazine hydrate consumption into 30mmol.The gross production rate 66% of target catalyst.The elementary analysis data are C
43H
36Cl
2P
2Ru (measured value): C, 65.65 (65.57); H, 4.61 (4.80).The nucleus magnetic hydrogen spectrum data of product are
1H NMR (C
6D
6): (t, Ru=CH), 7.8-7.6 and 7.0-6.7 (are m, C to δ 19.6
6H
5And P (C
6H
5)
3).
Embodiment 11 catalyst C
1Preparation
The preparation method is with embodiment 1, and difference is to change the consumption of three (triphenylphosphine) ruthenous chloride into 0.5mmol.The gross production rate 58% of target catalyst.The elementary analysis data are C
43H
36Cl
2P
2Ru (measured value): C, 65.65 (65.57); H, 4.61 (4.80).The nucleus magnetic hydrogen spectrum data of product are
1H NMR (C
6D
6): (t, Ru=CH), 7.8-7.6 and 7.0-6.7 (are m, C to δ 19.6
6H
5And P (C
6H
5)
3).
Embodiment 12 catalyst C
1Preparation
The preparation method is with embodiment 1, and difference is to change the consumption of three (triphenylphosphine) ruthenous chloride into 2mmol.The gross production rate 61% of target catalyst.The elementary analysis data are C
43H
36Cl
2P
2Ru (measured value): C, 65.65 (65.57); H, 4.61 (4.80).The nucleus magnetic hydrogen spectrum data of product are
1H NMR (C
6D
6): (t, Ru=CH), 7.8-7.6 and 7.0-6.7 (are m, C to δ 19.6
6H
5And P (C
6H
5)
3).
Embodiment 13 catalyst C
1Preparation
The preparation method is with embodiment 1, and difference is that the reaction temperature in the step (2) is-50 ℃.The gross production rate 55% of target catalyst.The elementary analysis data are C
43H
36Cl
2P
2Ru (measured value): C, 65.65 (65.57); H, 4.61 (4.80).The nucleus magnetic hydrogen spectrum data of product are
1H NMR (C
6D
6): (t, Ru=CH), 7.8-7.6 and 7.0-6.7 (are m, C to δ 19.6
6H
5And P (C
6H
5)
3).
Claims (27)
1. method for preparing suc as formula the olefin metathesis catalyst shown in (I):
Wherein M is ruthenium or osmium;
R is selected from hydrogen, C
1-20Alkyl, C
1-20Alkoxyl, C
6-20Aryl, nitro, at least one in amino and the halogen;
L
1Be selected from the anionic group independently of one another;
L
2Be selected from neutral group independently of one another, can be selected from tricyclohexyl phosphine, triphenylphosphine, trisulfonated triphenylphosphine, nitrogen heterocyclic ring, amine, acid amides, ether and sulfoxide independently of one another;
M and n are 0～4 integer independently of one another, and wherein m and n are not 0 simultaneously, and the summation of m and n is 4;
Comprise the steps: that (1) makes the compound (a) and hydrazine hydrate reaction of following general formula, generates the compound (b) of following general formula:
Wherein R is suc as formula defining in (I);
(2) make by the compound (b) that obtains in the step (1) and slaine M (L
1)
p(L
2)
qReaction, the catalyst of production (I),
Wherein M, L
1And L
2Suc as formula defining in (I); P and q are 0～5 integer independently of one another, and p and q are not 0 simultaneously, and the summation of p and q is 5.
2. according to the preparation method of claim 1, anionic group L wherein
1Be selected from halogen or nitrate anion independently of one another.
3. according to the preparation method of claim 1, wherein R is selected from hydrogen, C
1-6Alkyl, C
1-6Alkoxyl, C
6-10Aryl, at least one in nitro and the halogen.
4. according to the preparation method of claim 1, wherein R is selected from least one in hydrogen, methyl, isopropoxy, phenyl, nitro and the chlorine.
5. according to each preparation method among the claim 1-4, wherein anionic group L
1Be selected from chlorine and bromine independently of one another.
6. according to each preparation method among the claim 1-4, wherein neutral group L
2Be selected from tricyclohexyl phosphine, triphenylphosphine, trisulfonated triphenylphosphine and nitrogen heterocyclic ring independently of one another.
7. according to the preparation method of claim 5, neutral group L wherein
2Be selected from tricyclohexyl phosphine, triphenylphosphine, trisulfonated triphenylphosphine and nitrogen heterocyclic ring independently of one another.
8. according to the preparation method of claim 7, neutral group L wherein
2Be selected from tricyclohexyl phosphine, triphenylphosphine and bipyridyl independently of one another.
9. according to each preparation method among the claim 1-4, wherein m is that 2, n is 2.
10. according to the preparation method of claim 7 or 8, wherein m is that 2, n is 2.
11. according to each preparation method among the claim 1-4, wherein p is that 2, q is 3.
12. according to the preparation method of claim 10, wherein p is that 2, q is 3.
13. according to each preparation method among the claim 1-4, wherein in step (1), compound (a) is 1: 0.5～1: 10 with the mol ratio of hydrazine hydrate.
14. according to the preparation method of claim 12, wherein in step (1), compound (a) is 1: 0.5～1: 10 with the mol ratio of hydrazine hydrate.
15. according to the preparation method of claim 14, wherein in step (1), compound (a) is 1: 1～1: 5 with the mol ratio of hydrazine hydrate.
16. according to the preparation method of claim 14, wherein in step (1), compound (a) is 1: 1～1: 3 with the mol ratio of hydrazine hydrate.
17. according to each preparation method among the claim 1-4, wherein being reflected under 10-30 ℃ of step (1) carried out.
18. according to each preparation method among the claim 14-16, wherein being reflected under 10-30 ℃ of step (1) carried out.
19. according to the preparation method of claim 18, wherein being reflected under 15-30 ℃ of step (1) carried out.
20. according to each preparation method among the claim 1-4, wherein in step (2), compound (b) and slaine M (L
1)
p(L
2)
qMol ratio be 1: 0.25～1: 4.
21. according to the preparation method of claim 19, wherein in step (2), compound (b) and slaine M (L
1)
p(L
2)
qMol ratio be 1: 0.25～1: 4.
22. according to the preparation method of claim 21, wherein in step (2), compound (b) and slaine M (L
1)
p(L
2)
qMol ratio be 1: 0.25～1: 2.
23. according to the preparation method of claim 21, wherein in step (2), compound (b) and slaine M (L
1)
p(L
2)
qMol ratio be 1: 0.25～1: 1.
24. according to each preparation method among the claim 1-4, wherein being reflected under-100 ℃ to-30 ℃ of step (2) carried out.
25. according to each preparation method among the claim 21-23, wherein being reflected under-100 ℃ to-30 ℃ of step (2) carried out.
26. according to the preparation method of claim 25, wherein being reflected under-90 ℃ to-40 ℃ of step (2) carried out.
27. according to the preparation method of claim 25, wherein being reflected under-80 ℃ to-50 ℃ of step (2) carried out.
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