CN101195641A - Novel phosphine ligand, production and uses in catalytic reaction thereof - Google Patents
Novel phosphine ligand, production and uses in catalytic reaction thereof Download PDFInfo
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- CN101195641A CN101195641A CNA2007101999361A CN200710199936A CN101195641A CN 101195641 A CN101195641 A CN 101195641A CN A2007101999361 A CNA2007101999361 A CN A2007101999361A CN 200710199936 A CN200710199936 A CN 200710199936A CN 101195641 A CN101195641 A CN 101195641A
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Abstract
The invention relates to two new phosphine ligands, a relative preparation method, and an application in catalysis particularly in halogenated aromatic compound refining process, wherein the phosphine ligands as formulas Ia and Ib are represented as (adamantine)nP(alkyl)mIa, (adamantine)o(alkyl)qP(alkylene')P(adamantine)r(alkyl)sIb, n is 1-3 and m is 0-2, n+m=3, o and r are 1 or 2, q and s are o or 1, o+q=2 and r+s=2.
Description
Technical field
The present invention relates to novel phosphine part, their preparation and their purposes in the particularly refining halogenated aromatic compound of catalyzed reaction.
Background technology
Halogenated aromatic compound comprises that especially chlorinated aromatic compound is an intermediate, and described intermediate has multiple application and is used as the precursor of preparation agrochemicals intermediate, medicine, dyestuff, material etc. in chemical industry.Vinyl halide also is important intermediate, and it is as the precursor of polymerization single polymerization monomer and above-mentioned product.
Be commonly used for halogenated aromatic compound or vinyl halide functionalized be palladium and nickel catalyzator with those catalyzer of obtaining fragrant alkene or diene (Heck reaction, Stille reaction), biaryl (Suzuki reaction), alkynes (Sonogashira reaction), carboxylic acid derivative (Heck carbonylation) and amine (Buchwald-Hartwig reaction).The range that palladium catalyst is used with regard to coupling matrix usually and make peace that mask has superiority below some situation of catalyst activity, and nickel catalyzator has advantage aspect the conversion field of chlorinated aromatic compound and vinyl halide and the metal price.
Although known palladium (0)/nickel (0) compound is present catalysts, be used for activating and the palladium and the nickel catalyzator of refining halogenated aromatic compound are palladium (II) and/or nickel (II) and palladium (0) and/or nickel (0) complex compound.Especially, according to documents and materials, with the donor part for example the phosphine undersaturated 14-electronics of cooperation and 16-electronics palladium (0)/nickel (0) complex compound that carry out stabilization be confirmed as reactive specy.
Also might be when in linked reaction, using iodide without the phosphine part as educt.But aryl and vinyl iodate thing are very expensive initial compounds, produce stoichiometric salt compounded of iodine refuse in addition.Be reflected at educt more to one's profit on the cost for Heck, for example aryl bromide or aryl chloride require to use stabilization and activatory part to become effective in catalytic production.
Often have only with uneconomic starting raw material for example iodo aromatic compound and activatory bromo aromatic compound, the catalyst system of describing at alkylene, ethynylation, carbonylation, arylation, amination and similar reaction just has satisfied catalytic conversion number (TON).Otherwise, under the situation of chlorinated aromatic compound under the situation of the bromo aromatic compound of passivation and particularly, need to add a large amount of catalyzer-usually usually greater than the yield (＞90%) of 1mol%-to reach industrial practicality.In addition, because the complicacy of reaction mixture, simple catalyst recovery is impossible, therefore reclaim catalyzer also cause expensive, the obstacle that this normally realizes on technical scale.In addition, particularly in preparation active substance or active substance precursor, do not expect to use a large amount of catalyzer because stay the cause of the catalyst residue in the product.Nearest active catalyst system is based on phosphine (W.A.Herrmann, C.Brossmer, K. fele, the C.-P.Reisinger of the ring palladiumization of palladium salt or palladium complex, T.Priermeier, M.Beller, H.Fischer, Angew.Chem.1995,107,1989; Angew.Chem.Int.Ed.Engl.1995,34,1844) or space accurate aryl phosphine mixture (J.P.Wolfe, S.L.Buchwald, Angew.Chem.1999,111,2570; Angew.Chem.Int.Ed.Engl.1999,38,2413) or three-tertiary butyl phosphine (A.F.Littke, G.C.Fu, Angew.Chem.1998,110,3586; Angew.Chem.Int.Ed.Engl.1998,37,3387).
Yet, even use these catalyzer, from the industrial point of view halogenated aromatic compound calculated of activating cost, the i.e. turnover number of catalyzer (TON)＜10,000 and catalyst activity (TOF)＜1000h satisfactorily usually
-1Therefore, for obtaining high yield, need to use a large amount of relatively and therefore expensive catalysts very.Thereby, for example prepare a kgMW and be 200 organic intermediate, under current precious metal price with the catalyzer cost of 1mol% palladium catalyst greater than 100US$, therefore very clearly need to improve catalyst production.Therefore, although catalyzer is in development in recent years, the industrialization reaction of arylation that minority is used for chlorinated aromatic compound, carbonylation, alkylene etc. is only disclosed up to now.
Summary of the invention
Based on described reason, the objective of the invention is to satisfy the great demand of novel, more voluminous catalyst system, this system has simple part and does not show the deficiency of known catalysis process, described system is applicable to large-scale commercial production, it is converted into separately coupled product with high yield with the chlorinated aromatic compound calculated on the cost and bromo aromatic compound and corresponding vinyl compound, has high catalyst production and high purity coupling simultaneously.
This purpose is to be that the phosphine part of Ia and Ib novelty reaches according to the present invention by the research general formula:
(adamantyl)
nP (alkyl)
mIa
(adamantyl)
o(alkyl)
qP (alkylene ') P (adamantyl)
r(alkyl)
sIb
Wherein adamantyl is the adamantyl group (IIa, IIb) at 1-or 2-position connection phosphorus atom:
Alkyl is C
1To C
18Alkyl group and
Alkylene ' be methylene radical, ethylene, trimethylene, tetramethylene, pentamethylene or the hexamethylene bridge, 1 of bridging, 2-diphenylene, 2,1 of 2 '-replacement, 1 '-binaphthylyl or ferrocenyl derivative,
Wherein said alkyl, alkylene ' and adamantyl can have maximum 10 substituting groups except hydrogen atom independently of each other, described substituting group is C independently of each other
1To C
8Alkyl, O-alkyl (C
1-C
8), OH, OCO-alkyl (C
1-C
8), O-phenyl, phenyl, aryl, fluorine, NO
2, Si-alkyl (C
1-C
8)
3, CN, COOH, CHO, SO
3H, NH
2, NH-alkyl (C
1-C
8), N-alkyl (C
1-C
8)
2, P (alkyl (C
1-C
8))
2, P (aryl)
2, SO
2-alkyl (C
1-C
6), SO-alkyl (C
1-C
6), CF
3, NHCO-alkyl (C
1-C
4), COO-alkyl (C
1-C
8), CONH
2, CO-alkyl (C
1-C
8), NHCHO, NHCOO-alkyl (C
1-C
4), CO-phenyl, COO-phenyl, CH=CH-CO
2-alkyl (C
1-C
8), CH=CHCOOH, PO (phenyl)
2, PO (alkyl (C
1-C
4))
2, PO
3H
2, PO (O-alkyl (C
1-C
6))
2Or SO
3(alkyl (C
1-C
4)), aryl is the aromatic compound with 5 to 14 ring carbon atoms, and its one or more available ring carbon atoms are replaced obtaining the assorted aromatic compound that contains ring carbon atom of 1-to 13-unit by nitrogen, oxygen and/or sulphur atom,
Wherein n is the numeral that is selected from 1-3, and m is the numeral that is selected from 0-2, and need satisfy condition n+m=3 and
Wherein o and r are numerals 1 or 2, and q and s are numerals 0 or 1, and need satisfy condition o+q=2 and r+s=2.
Used phosphine part is meant that especially general formula is the compound of Ia and Ib according to the present invention, and wherein adamantyl is that adamantyl group (IIa, IIb) and the alkyl that connects phosphorus atom in 1-or 2-position is C
1To C
12Alkyl.Alkylene ' ethylene, trimethylene or the tetramethylene bridge, 1 of preferably bridging, 2-diphenylene, 2,2 '-replace 1,1 '-binaphthylyl or ferrocenyl derivative.
Preferably, alkyl group, alkylene ' group and adamantyl group can have maximum 5 substituting groups except hydrogen atom independently of each other, and described substituting group is C independently of each other
1To C
8Alkyl, O-alkyl (C
1-C
8), OH, OCO-alkyl (C
1-C
8), O-phenyl, phenyl, aryl, fluorine, Si-alkyl (C
1-C
8)
3, COOH, SO
3H, NH
2, NH-alkyl (C
1-C
8), the N-alkyl
2(C
1-C
8), P (alkyl (C
1-C
8))
2, P (phenyl)
2, CF
3, NHCO-alkyl (C
1-C
4), COO-alkyl (C
1-C
8), CONH
2, CO-alkyl (C
1-C
8), COO-phenyl, PO (phenyl)
2, PO (alkyl (C
1-C
4))
2, PO
3H
2Or PO (O-alkyl (C
1-C
6))
2, aryl is to have the aromatic compound of 5 to 14 ring carbon atoms and heteroatoms that its one or more available ring carbon atoms are selected from nitrogen, oxygen and/or sulphur replaces to obtain having the assorted aromatic compound of 4 to 13 ring carbon atoms.
Assorted aromatic base for example can have the ring of 5-unit at least, and it comprises 1 to 13 ring carbon atom and maximum 4 nitrogen-atoms and/or maximum 2 Sauerstoffatoms or sulphur atom.Preferred assorted aromatize thing aromatic base comprises one or two nitrogen heteroatom or oxygen heteroatom or sulfur heteroatom or nitrogen heteroatom and oxygen heteroatom or sulfur heteroatom.
The compound that particularly preferred phosphine part according to the present invention is general formula I a and Ib, wherein adamantyl is that alkyl is C at the adamantyl group (IIa, IIb) of 1-or 2-position connection phosphorus atom
1To C
12Alkylene among alkyl and the general formula I b ' be the ethylene, 1 of bridging, 3-propylidene or 1,4-butylidene bridge, wherein alkyl group, alkylene ' group and adamantyl group can have maximum 3 substituting groups except hydrogen atom independently of each other, and described substituting group is C independently of each other
1To C
8Alkyl, O-alkyl (C
1-C
8), OH, OCO-alkyl (C
1-C
8), O-phenyl, phenyl, COOH, SO
3H, NH
2, P (alkyl (C
1-C
8))
2, P (phenyl)
2, COO-alkyl (C
1-C
8), CONH
2Or PO (phenyl)
2
The present invention also provides the preparation method of phosphine part that should novelty.Their the synthetic known synthetic route that is similar to alkylphosphines.Houben-Weyl for example, Methoden derorganischen Chemie, 1963, volume XII, 1, such synthetic route has been described in p.33..Normally, the phosphine part for preparing novelty described herein by dihalo adamantyl phosphine or halo two adamantyl phosphines and organometallic reagent (for example lithium alkylide, alkyl magnesium, zinc alkyl(s) or alkyl Tong Shiji) reaction.Specially suitable halo adamantyl phosphine is the corresponding chlorinated compound.Another synthetic route of preparation part according to the present invention is basic metal adamantyl phosphide or basic metal two adamantyl phosphides and organic electrophilic reagent for example alkyl halide or pseudohalide, aldehyde or epoxide reaction.
Normally, can synthesize two adamantyl alkylphosphines according to following explanation:
Dropwise add THF or the hexane solution of 18mmol R-M in 250ml contains the anhydrous THF solution of 15mmol two adamantyl phosphonium chlorides, M is lithium or MgHal, and Hal is chlorine, bromine or iodine.This mixture two hours refluxes.This mixture is at room temperature handled with the aqueous ammonium chloride solution and the diethyl ether of the degassing.Distill solvent, resistates distills under high vacuum or separates with chromatography on silica gel 60 with the hexane/ethyl acetate mixture.
These explanations can be used for preparation example such as following preferred part:
Two (1-adamantyl) methylphosphine,
Two (1-adamantyl) sec.-propyl phosphine,
Two (1-adamantyl) normal-butyl phosphine,
Two (1-adamantyl) tertiary butyl phosphine,
Two (1-adamantyl) n-hexyl phosphine,
Two (1-adamantyl) cyclohexyl phosphine,
Two (1-adamantyl) benzyl phosphine,
Two (1-adamantyl) pentafluoroethyl group phosphine,
Two (3-aminoadamantan base-1-yl) n-Butyl Lithium,
Two (3-acetyl adamantane base-1-yl) normal-butyl phosphine,
Two [3-(p-hydroxybenzene) adamantyl-1-yl] methylphosphine,
Two (2-adamantyl) sec.-propyl phosphine,
Two (2-adamantyl) normal-butyl phosphine,
Two (2-adamantyl) tertiary butyl phosphine,
Two (2-adamantyl) cyclohexyl phosphine.
Normally, can be according to following explanation synthesizing adamantane base dialkyl phosphine:
Contain the THF solution that dropwise adds 15mmol dialkyl group phosphonium chloride in the anhydrous THF of 35mmol adamantyl-M or the hexane solution to 400ml, M is lithium or MgHal, and Hal is a chlorine or bromine.This mixture four hours refluxes.This mixture is at room temperature handled with the aqueous ammonium chloride solution and the diethyl ether of the degassing.Distill solvent, resistates distills under high vacuum or separates with chromatography on silica gel 60 with the hexane/ethyl acetate mixture.
These explanations can be used for preparation example such as following preferred part:
(1-adamantyl) two-tertiary butyl phosphine,
(1-adamantyl) dicyclohexylphosphontetrafluoroborate,
(2-adamantyl) di-n-butyl phosphine.
Normally, can synthesize two (two adamantyl phosphino-s) alkane according to following explanation:
Dropwise add THF or the hexane solution of 15mmol M-alkylene-M in 400ml contains the anhydrous THF solution of 33mmol two adamantyl phosphonium chlorides, M is lithium or MgHal, and Hal is chlorine, bromine or iodine.This mixture four hours refluxes.This mixture is at room temperature handled with degassing aqueous ammonium chloride solution and diethyl ether.Distill solvent, resistates distills under high vacuum or separates with chromatography on silica gel 60 with the hexane/ethyl acetate mixture.
These explanations can be used for preparation example such as following preferred part:
1,2-two [two (1-adamantyl) phosphino-] ethane,
1,4-two [two (1-adamantyl) phosphino-] butane,
2,3-two [two (1-adamantyl) phosphino-] butane,
4,5-two [two (1-adamantyl) phosphinomethyl]-2,2-dimethyl-1, the 3-dioxolane,
1,2-two [two (1-adamantyl) phosphino-] benzene.
According to the present invention, phosphine part that this is novel and period of element Table VIII subgroup, for example the transition metal complex of palladium, nickel, platinum, rhodium, iridium, ruthenium or cobalt or transition metal salt binding are as catalyzer.Normally, can original position join in the suitable transition metal precursors compound and according to part of the present invention and be used for catalytic applications with this form.
Used transistion metal compound is preferably palladium or nickel compound and preferred especially palladium compound.
Sometimes earlier the list of the defined described transition metal of preparation-, two-, three-or the tetraphosphine complex compound these complex compounds to be used for catalyzed reaction again can be favourable.
Preferred palladium and the nickel catalyzator that contains with good grounds phosphine of the present invention that use.
The preferred especially palladium catalyst that contains with good grounds part of the present invention that uses.The common original position of part according to the present invention joins in palladium (II) salt or palladium (II) or palladium (0) complex compound.But preparation is directly according to the palladium (0) of phosphine of the present invention-or palladium (II)-phosphine complex compound and then these complex compounds are used for catalytic applications can be favourable.This has increased initial catalyst activity in some cases.
The example of the palladium component that can use with part according to the present invention is palladium (II), Palladous chloride (II), palladium bromide (II), the sour lithium of tetrachloro palladium (II), acetopyruvic acid palladium (II), palladium (0)-diphenylmethylene acetone complex compound, tetrakis triphenylphosphine palladium (0), two (three-o-tolyl phosphine) palladiums (0), propionic acid palladium (II), two (triphenylphosphine) palladium chloride (II), palladium (0)-diallyl ether complexes, Palladous nitrate (II), two (acetonitrile) Palladous chloride (II), two (benzonitrile) Palladous chloride (II) and other palladium (0) and palladium (II) complex compound.
Normally, use for catalyzer, the phosphine part of use is excessive with respect to transition metal.The ratio of transition metal and part is preferably 1: 1 to 1: 1000.The ratio of preferred especially transition metal and part is 1: 1 to 1: 100.The accurate ratio of the transition metal/part that uses depends on the amount of concrete application and used catalyzer.Therefore normally, generally uses and compare at low-down transiting metal concentration low under the situation of transiting metal concentration as the transition metal 0.5-0.01mol% (＜0.01mol%) transition metal/part ratio under the situation.
This novel phosphine part is very heat-staple.Therefore can temperature of reaction reach 250 ℃ or more relative superiority or inferiority use catalyst according to the invention.Preferably under 20 to 200 ℃ temperature, use this catalyzer; Verified in a lot of situations 30 to 180 ℃ of temperature, be favourable under preferred 40 to the 160 ℃ temperature.This part can also use in compressive reaction and not lose activity, and working pressure can reach 100 crust usually, but preferably in the normal pressure scope that is not higher than 60 crust.
The phosphine part of identity basis the present invention preparation prepares the part component particularly advantageous of alpha-aromatic ketone and amine as catalytic preparation arylation alkene (Heck reaction), biaryl (Suzuki reaction), from aryl halide or vinyl halides.Yet, clearly the catalyzed reaction of other transition metal for those skilled in the art, the metathesis or the hydrogenation of for example two keys or carbonyl compound, particularly the carbonylation of palladium catalysis and the catalytic aryl halide of nickel, with the ethynylation (Sonogashira coupling) of alkynes with the cross-coupling of organometallic reagent (zincon, tin reagent etc.), also can be with this novel catalyst system catalysis.
For some catalytic applications, carbonylation for example may be favourable with the phosphine part of chelating, and the chelating phosphine part of particularly important is that those have aliphatics C
2To C
6Carbon bridge or have the part of fragrant bridge (1,2-phenylene, ferrocenyl, xenyl).
A special advantage according to part of the present invention is a high reactivity, wherein said part cause on cost calculate but be the activation of inert chlorinated aromatic compound.Shown as embodiment, the palladium catalyst with novel adamantyl phosphine is with respect to existing best existing catalyst system (J.P.Wolfe, S.L.Buchwald, Angew.Chem.1999,111,2570 among the Buchwald; Angew.Chem.Int.Ed.Engl.1999,38,2413) and Fu (A.F.Littke, G.C.Fu, Angew.Chem.1998,110,3586; Angew.Chem.Int.Ed.Engl.1998,37,3387) be very outstanding.Therefore, use the catalyst according to the invention system, with the chlorination aromatic compound as the turnover number of matrix even can reach＞10,000 rank and with the bromination aromatic compound as the TON of initial substance can reach＞500,00, make desired catalyzer and ligand system be applicable to the heavy industrialization target.
The character of adamantyl phosphine is wondrous especially.Although people understand the adamantyl group already in organic chemistry, also do not recognize the importance of the phosphine part that contains the adamantyl group.Thereby, the alkyl adamantane phosphine is not also described up to now as catalytic applications.We are surprised to find, in specific catalytic applications, the adamantyl part with respect to all other known phosphine part outstanding in the extreme.For example, in the coupling of 4-toluene(mono)chloride and aryl boric acid, use known best palladium catalyst up to now, using the resulting product yield of a spot of catalyzer (0.005mol%) is 16 to 46%, and uses the resulting yield of part according to the present invention＞90%.
Phosphine prepared in accordance with the present invention can be used for preparing aryl olefin, diene, diaryl, benzoic acid derivative, acrylic acid derivative, aromatic yl paraffin, alkynes and amine.In this way Zhi Bei compound also can be used as the intermediate of UV absorption agent, pharmacy and agrochemicals, the ligand precursor of metalloscene catalyst, perfume, active substance and polymer structure unit.
Embodiment
Embodiment:
Following embodiment is used for illustrating the present invention and does not mean that restriction the present invention.
General introduction: prepare adamantyl phosphine part down at shielding gas (argon gas).
The ordinary method of synthetic phosphine:
The mixture of 100g (0.73mol) diamantane, 105g (0.79mol) aluminum chloride (III) and 300ml phosphorus chloride (III) was refluxed 5 hours.Distill excessive phosphorus chloride (III), stay the reddish-brown viscous substance.This material is suspended in 1 liter of chloroform, uses 1 liter of frozen water hydrolysis subsequently.In dry organic phase on the sodium sulfate and under vacuum (0.1 millibar), be concentrated into dried.Output: 130g (0.37mol, 93%) two (1-adamantyl) phosphinyl chlorine (fusing point: 195 ℃).
40g two adamantyl phosphinyl chlorine (0.11mol) are placed the 600ml anhydrous tetrahydro furan, this mixture is cooled to-14 ℃, in 60 minutes, add 10g (0.26mol) lithium aluminum hydride continuously with frozen water/sodium chloride cools down mixture.At room temperature stirred this mixture subsequently 16 hours and used the hydrolysis of 200ml 1N HCl solution down at-14 ℃.In dry organic phase on the sodium sulfate and under vacuum (0.1 millibar), be concentrated into dried.Output: 30g (0.10mol, 94%) two (1-adamantyl) phosphine.
31P NMR(162.0MHz，CDCl
3)：δ＝18.2
Contain 23g (76mmol) two (1-adamantyl) phosphine and 14.5g (9.5mmol) 1 to 600ml, dropwise add the anhydrous toluene solution of 60g 20% carbonyl chloride in the toluene solution of 8-diazabicyclo [5.4.0] 11-7-alkene (DBU), and heat this mixture to room temperature and stirred subsequently 16 hours.Filtration also distills solvent under vacuum.Output: 23g (68mmol, 90%) two adamantyl phosphonium chlorides.
31P NMR(162.0MHz，CDCl
3)：δ＝138.4
Embodiment 1
Two (1-adamantyl) normal-butyl phosphine (n-BuPAd
2) (variant 1):
The hexane solution that in 250ml contains the anhydrous tetrahydrofuran solution of 5.0g (15mmol) two adamantyl phosphonium chlorides, dropwise adds 11ml 1.6M n-Butyl Lithium (18mmol).This solution was refluxed 1 hour.Under vacuum,, under vacuum, distill resistates except that after desolvating.
Obtain 2.6g (7.3mmol, 49%) two adamantyl normal-butyl phosphines.
Two (1-adamantyl) normal-butyl phosphine (n-BuP (1-Ad)
2) (variant 2):
4.6g (15mmol) two (1-adamantyl) phosphine is placed the 50ml di-n-butyl ether, add the toluene solution of 20ml 2.5M n-BuLi (50mmol).This mixture was refluxed 1 hour and cooling, and dropwise add 4.1g (30mmol) 1-butyl bromide.This mixture was refluxed 30 minutes, and cooling and with saturated ammonium chloride solution washing (3x) separates organic phase and dry and under reduced pressure distill solvent on sodium sulfate.
Output: 4.6g (13mmol, 85%) two (1-adamantyl) normal-butyl phosphine.This product can be from di-n-butyl ether recrystallization (102 ℃ of fusing points).
31P{
1H}NMR(162.0MHz，C
6D
6，297K)：δ＝24.6
MS(E.I.，70eV)：m/z：358(M
+，12％)；135(Ad
+，100％)
MS (C.I., iso-butylene): m/z:359 (M
++ H, 100%)
Two (1-adamantyl) normal-butyl phosphine (n-BuP (1-Ad)
2) (variant 3):
1.5g (4.5mmol) two (1-adamantyl) phosphonium chloride is placed the anhydrous THF of 40ml, stir the hexane solution that adds 5ml 1.6M n-BuLi (8mmol) down with syringe.This mixture was refluxed 2 hours, distill solvent and distillation residue in bulb under the decompression.Output: 0.77g (2.1mmol, 48%) two (1-adamantyl) normal-butyl phosphine.
Two (1-adamantyl) normal-butyl phosphine (n-BuP (1-Ad)
2) (variant 4):
4.6g (15mmol) two (1-adamantyl) phosphine is placed the 50ml di-n-butyl ether, add the toluene solution of 20ml 2.5M n-BuLi (50mmol).This solution was refluxed 1 hour and cooling, and dropwise add 2.8g (30mmol) 1-Butyryl Chloride.This mixture was refluxed 30 minutes, and cooling and with saturated ammonium chloride solution washing (3x) separates organic phase and dry and under reduced pressure distill solvent on sodium sulfate.Under high vacuum, pass through bulb distillation purifying product.Output: 4.6g (13mmol, 85%) two (1-adamantyl) normal-butyl phosphine.
Embodiment 2
Two (1-adamantyl) methylphosphine (MeP (1-Ad)
2) (variant 1):
The hexane solution that in 250ml contains the anhydrous tetrahydrofuran solution of 5.0g (15mmol) two adamantyl phosphonium chlorides, dropwise adds 11ml 1.6M lithium methide (18mmol).This solution was refluxed 1 hour.After distilling solvent under the vacuum, distillation residue under the vacuum.
Obtain 2.3g (7.3mmol, 49%) two adamantyl methylphosphine.
Two (1-adamantyl) methylphosphine (MeP (1-Ad)
2) (variant 2):
2.0g (6.0mmol) two (1-adamantyl) phosphonium chloride is placed the anhydrous THF of 50ml, stir the diethyl ether solution that adds 5ml 1.6M MeLi (8mmol) down with syringe.This mixture was refluxed 2 hours, distill solvent and distillation residue in bulb under the decompression.Output: 0.85g (2.7mmol, 45%) two (1-adamantyl) methylphosphine (fusing point: 143 ℃).
Ultimate analysis: measured value (calculated value): C:79.52% (79.70%); H:10.60% (10.51%); P:9.78% (9.79%)
31P{
1H}NMR(162.0MHz，C
6D
6，297K)：δ＝7.8
MS(E.I.，70eV)：m/z：316(M
+，36％)；135(Ad
+，100％)
Embodiment 3
Two (1-adamantyl) n-hexyl phosphine (HexP (1-Ad)
2) (variant 1):
(18mmol) places the 150ml anhydrous tetrahydro furan with the 0.45g magnesium chips, under agitation adds 3.0g hexyl bromide 1 bromohexane (18mmol), causes the ether heating.After this mixture is cooled to room temperature, dropwise add the 100ml anhydrous tetrahydrofuran solution of 5.0g two adamantyl phosphonium chlorides (15mmol), and this mixture was refluxed 1 hour.After distilling solvent under the vacuum, (0.01 millibar) distillation residue under the high vacuum.Output: 2.0g (5.2mmol, 35%) two adamantyl n-hexyl phosphines.
Two (1-adamantyl) n-hexyl phosphine (HexP (1-Ad)
2) (variant 2):
5.5g (18mmol) two (1-adamantyl) phosphine is placed the 60ml di-n-butyl ether, and add the toluene solution of 20ml 2.5M n-BuLi (50mmol).This mixture was refluxed 45 minutes and cooling, dropwise add 3.0g (18mmol) hexyl bromide 1 bromohexane.This mixture was refluxed 30 minutes, cooling and with saturated ammonium chloride solution washing (3x), it is also dry on sodium sulfate to separate organic phase, and under reduced pressure distills solvent.Output: 4.9g (13mmol, 70%) two (1-adamantyl) n-hexyl phosphine.This product can be from di-n-butyl ether recrystallization.
31P{
1H}NMR(162.0MHz，C
6D
6，297K)：δ＝24.6
MS:386.31062 (C
26H
43The calculated value of P: 386.31024)
Embodiment 4
Two (two adamantyl phosphino-s) butane (butylidene (PAd
2)
2):
(18mmol) places the 150ml anhydrous tetrahydro furan with the 0.45g magnesium chips, under agitation adds 2.0g 1, and 4-dibromobutane (9.3mmol) causes the ether heating.After this mixture was cooled to room temperature, the 100ml anhydrous tetrahydrofuran solution that dropwise adds 5.0g two adamantyl phosphonium chlorides (15mmol) also refluxed this mixture 1 hour.After distilling solvent under the vacuum, (0.01 millibar) distillation residue under the high vacuum.Output: 1.0g (1.5mmol, 10%) two (two adamantyl phosphino-s) butane.
Embodiment 5
Two (1-adamantyl)-3-dimethylaminopropyl phosphines:
5.1g (17mmol) two (1-adamantyl) phosphine is placed the 50ml di-n-butyl ether, and add the toluene solution of 20ml 2.5M n-BuLi (50mmol).This mixture refluxed 1 hour and cooling and under the ice-water bath cooling, add 5.0g (31mmol) 3-dimethylaminopropyl villaumite acidulants.This mixture was refluxed 30 minutes, cooling and with saturated ammonium chloride solution washing (3x), it is also dry on sodium sulfate to separate organic phase, and under reduced pressure distills solvent.Output: 4.6g (12mmol, 70%) two (1-adamantyl)-3-dimethylaminopropyl base phosphines.This product can be from di-n-butyl ether recrystallization (fusing point: 138 ℃).
Ultimate analysis: measured value (calculated value): C:77.46% (77.47%); H:11.09% (10.92%); N:3.47% (3.61%); P:7.78% (7.99%)
31P{
1H}NMR(162.0MHz，C
6D
6，297K)：δ＝24.5
MS:387.30528 (C
25H
42The calculated value of NP: 387.30548)
Embodiment 6
Two (1-adamantyl) benzyl phosphine:
4.0g (13mmol) two (1-adamantyl) phosphine is placed the 50ml di-n-butyl ether, and add the toluene solution of 18ml 2.5M n-BuLi (45mmol).This solution backflow 30 minutes and cooling are also dropwise added 3.2g (19mmol) bromotoluene.This mixture was refluxed 30 minutes, cooling and with saturated ammonium chloride solution washing (3x), it is also dry on sodium sulfate to separate organic phase, and under reduced pressure distills solvent.Output: 4.6g (12mmol, 90%) two (1-adamantyl) benzyl phosphine.This product can be from di-n-butyl ether recrystallization (fusing point: 182 ℃).
31P{
1H}NMR(162.0MHz，C
6D
6，297K)：δ＝29.8
MS:392.26420 (C
27H
37The calculated value of P: 392.26328)
Embodiment 7 to 20
The routine operation explanation of Heck reaction:
In penstock (can derive from for example Aldrich), under argon atmosphere, in the anhydrous two alkane of 5ml, add 5mmol aryl halide, 6mmol alkene, 6mmol alkali, appropriate amount of ligands and palladium (0)-dba complex compound and 500mg glycol ether di-n-butyl ether (as the interior mark of GC analysis).With this seal of tube and be suspended in 120 ℃ the silicone oil bath.After 24 hours it is taken away and be cooled to room temperature.Solid is dissolved in 5ml methylene dichloride and the 5ml 2N hydrochloric acid.Use the gc analysis organic phase.By the distillation, from the methanol/acetone mixture recrystallization or column chromatography (silica gel, hexane/ethyl acetate mixture) separated product.
| Table 1: parachlorotoluene and cinnamic Heck reaction; N-BuPAd 2As part | |||||||
| Sequence number | Alkali | Temperature (℃) | Catalyst concn (mol%) | L∶Pd | Transformation efficiency (%) | Yield (%) | TON |
| 7 | K 3PO 4 | 100 | 1.0 | 1∶1 | 42 | 38 | 38 |
| 8 | K 3PO 4 | 100 | 1.0 | 2∶1 | 39 | 25 | 25 |
| 9 | K 3PO 4 | 120 | 0.1 | 2∶1 | 27 | 20 | 200 |
| 10 | K 3PO 4 | 120 | 1.0 | 2∶1 | 98 | 98 | 98 |
| 11 | K 3PO 4 | 120 | 0.1 | 4∶1 | 25 | 11 | 110 |
| 12 | K 2CO 3 | 120 | 1.0 | 2∶1 | 78 | 68 | 68 |
| 13 | K 3PO 4 | 140 | 0.1 | 4∶1 | 88 | 81 | 810 |
| Show 2:120 ℃ of following chlorobenzene and cinnamic Heck reaction; L: Pd=2: 1 | |||||
| Sequence number | Alkali | Catalyst concn (mol%) | Transformation efficiency (%) | Yield (%) | TON |
| 14 | K 2CO 3 | 1.0 | 71 | 63 | 63 |
| 15 | K 3PO 4 | 2.0 | 46 | 33 | 17 |
Embodiment 21 to 40
The routine operation explanation of Suzuki reaction:
In penstock (can derive from for example Aldrich), under argon atmosphere, with 3mmol aryl halide, 4.5mmol phenyl-boron dihydroxide, 6mmol alkali, appropriate amount of ligands and palladium (II) (P: Pd=2: 1) and 100mg n-Hexadecane (the interior mark of analyzing as GC) be dissolved in the 6ml dry toluene.With this seal of tube and be suspended in 100 ℃ the silicone oil bath.After 20 hours it is taken away and be cooled to room temperature.Solid is dissolved in the rare sodium hydroxide solution of 10ml methylene dichloride and 10ml.Use the gc analysis organic phase.By crystallization or column chromatography from the methanol/acetone mixture (silica gel, hexane/ethyl acetate mixture) separated product.
| Table 4: part is to 4-toluene(mono)chloride and the influence of phenyl-boron dihydroxide link coupled | ||||
| Sequence number | PR 3 | Pd(OAc) 2(mol％) | Yield (%) | TON |
| 21 | PPh 3 | 0.1 | 5 | 50 |
| 22 | PhPCy 2 | 0.1 | 23 | 230 |
| 23 [a] | (o-tol)PCy 2 | 0.1 | 49 | 490 |
| 24 [a] | (o-anisyl) PCy 2 | 0.1 | 42 | 420 |
| 25 | (o-biph)PCy 2 | 0.01 | 47 | 4700 |
| 26 | PCy 3 | 0.1 | 23 | 230 |
| 27 | P tBu 3 | 0.01 | 92 | 9200 |
| 28 | P tBu 3 | 0.005 | 41 | 8200 |
| 29 | BuPAd 2 | 0.01 | 94 | 9400 |
| 30 | BuPAd 2 | 0.005 | 87 | 17,400 |
[a]P∶Pd＝4∶1
| Table 5: multiple aryl halide (R-C 6H 4-Cl) and phenyl-boron dihydroxide at 0.005mol%Pd (OAc) 2/2BuPAd 2Suzuki coupling under existing | |||
| Sequence number | R | Yield (%) | TON |
| 31 | 4-Me | 87 | 17,400 |
| 32 [a] | 4-Me | 74 | 14,800 |
| 33 | 2-Me | 85 | 17,000 |
| 34 | 2，6-Me 2 | 68 | 13,600 |
| 35 | H | 80 | 16,000 |
| 36 | 2-F | 96 | 19,200 |
| 37 | 4-MeO | 64 | 12,800 |
| 38 | 3-MeO | 58 | 11,600 |
| 39 | 2-CN | 100 | 20,000 |
| 40 | “3-N” [b] | 99 | 19,800 |
[a] replaced 20 hours in 4 hours; [b] 3-chloropyridine
Embodiment 41 to 54
The routine operation explanation of Study on Catalytic Amination of Alcohols:
In penstock (can derive from for example Aldrich), under argon atmosphere, in the 5ml dry toluene, add 5mmol aryl halide, 6mmol amine, 6mmol sodium tert-butoxide and appropriate amount of ligands and palladium (0)-dibenzalacetone complex compound.With this seal of tube and be suspended in 120 ℃ the silicone oil bath.After 20 hours it is taken away and be cooled to room temperature.Solid is dissolved in 5mlCH
2Cl
2In 5ml 2N hydrochloric acid, and add 500mg glycol ether di-n-butyl ether as marking in the GC.Use the gc analysis organic phase.By the distillation, from the methanol/acetone mixture crystallization or column chromatography (silica gel, hexane/ethyl acetate mixture) separated product.
| Table 6: the Study on Catalytic Amination of Alcohols of aryl halide; 0.5mol%Pd (dba) 2，n-BuPAd 2 | ||||
| Sequence number | Aryl halide | Amine | Product | Yield [%] |
| 41 | 2-chloro-m-xylene | 2, the 6-xylidine | Two (2, the 6-3,5-dimethylphenyl) amine | 84 |
| 42 | 2-chloro-m-xylene | 2, the 6-diisopropyl aniline | 2,6-3,5-dimethylphenyl-2 ', 6 '-diisopropyl aniline | 70 |
| 43 | 2-chlorine fluoro-benzene | 2, the 6-diisopropyl aniline | 2-fluorophenyl-2 ', 6 '-diisopropyl aniline | 70 |
| 44 | 2-chloro-m-xylene | The 1-adamantanamines | N-(1-adamantyl)-2, the 6-xylidine | 84 |
| 45 | 2-chloro-m-xylene | Tert-butylamine | N-(tertiary butyl)-2, the 6-xylidine | 93 |
| 46 | Chlorobenzene | Diethylamide | N, the N-Diethyl Aniline | 44 |
| 47 | Chlorobenzene | Di-n-butyl amine | N, N-di-n-butyl aniline | 72 |
| 48 | The 3-toluene(mono)chloride | Diethylamide | N, N-diethyl-meta-aminotoluene | 49 |
| 49 | The 3-chloroneb | Diethylamide | N, N-diethyl-m-anisidine | 58 |
| 50 | The 4-toluene(mono)chloride | Diethylamide | N, N-diethyl-para-totuidine | 40 |
| 51 | Chlorobenzene | Piperidines | The N-Phenylpiperidine | 76 |
| 52 | Chlorobenzene | Morpholine | N-phenyl-morpholine | 87 |
| 53 | O-chloro-anisole | 2, the 6-xylidine | 2-p-methoxy-phenyl-2, the 6-xylidine | 100 |
| 54 | O-chloro-anisole | 2, the 6-diisopropyl aniline | 2-p-methoxy-phenyl-2, the 6-diisopropyl aniline | 88 |
Embodiment 55 to 59
The catalysis alpha-aromaticization of ketone.
In penstock (can derive from for example Aldrich), under argon atmosphere, in the 5ml dry toluene, add 5mmol aryl halide, 6mmol ketone, 6mmol sodium tert-butoxide and appropriate amount of ligands and palladium (II).With this seal of tube and be suspended in 80 ℃ the silicone oil bath.After 20 hours it is taken away and be cooled to room temperature.Solid is dissolved in 5ml CH
2Cl
2In 5ml 2N hydrochloric acid, and add 500mg glycol ether di-n-butyl ether as marking in the GC.Use the gc analysis organic phase.By the distillation, from the methanol/acetone mixture crystallization or column chromatography (silica gel, hexane/ethyl acetate mixture) separated product.
Embodiment 60 to 79
The further analysis embodiment of the alpha-aromaticization of ketone:
In penstock (can derive from for example Aldrich), under argon atmosphere, in the anhydrous two alkane of 5ml, add 5mmol aryl halide, 6mmol ketone, 6mmol Tripotassium phosphate and appropriate amount of ligands and palladium (II).With this seal of tube and be suspended in 100 ℃ the silicone oil bath.After 20 hours it is taken away and be cooled to room temperature.Solid is dissolved in 5ml CH
2Cl
2In 5ml 2N hydrochloric acid, and add 500mg glycol ether di-n-butyl ether as marking in the GC.Use the gc analysis organic phase.By the distillation, from the methanol/acetone mixture crystallization or column chromatography (silica gel, hexane/ethyl acetate mixture) separated product.
A) yield per-cent is based on the aryl halide of introducing in the product
Embodiment 80
With organic zinc compound coupling aryl halide:
Under 0 ℃, in the 40ml THF of 50mmol ethynyl lithium-quadrol complex compound, add 50mmol Zinc Chloride Anhydrous (being dissolved in 40ml THF) in the suspension.After being heated to room temperature half an hour, again this solution is cooled to 0 ℃, and adds 40mmol 4-chlorine anisole, 0.05mol%Pd (OAc)
2With 0.1mol% butyl two adamantyl phosphines.25-50 ℃ is stirred this reaction mixture down until conversion fully.In this reaction soln, add 2M HCl solution subsequently.After the ether extraction, washing ether is also distillation mutually, obtains 76% p-methoxyphenyl acetylene.
Embodiment 81
Use the alkynes coupling:
In the 40ml diethylamine solution of the mixture of 12mmol trimethyl silyl acetylene and 10mmol 4-chloronitrobenzene, add 0.005mol%Pd (OAc)
2, 0.01mol% hexyl two adamantyl phosphines and 1mol%Cu (I) I.Reflux and stir this mixture down until transforming fully.Under vacuum, remove volatile components subsequently.Be dissolved in resistates in the toluene and wash with water.After stratographic analysis on the silica gel, obtain 1-(4-nitrophenyl)-2-trimethyl silyl acetylene of 89%.
Embodiment 82
With ethene Heck coupling:
50mmol 6-methoxyl group-2-bromonaphthalene and 60mmol salt of wormwood are dissolved among the 40ml NMP, and add 0.001mol%Pd (OAc)
2With 0.004mol% butyl two adamantyl phosphines.It is under the ethene of 20 crust that this mixture is placed pressure, and stirs until conversion fully down at 130 ℃.After filtering out soluble component,, obtain 6-methoxyl group-2-vinylnaphthalene of 92% with alkaline solution washing and distillation.
Embodiment 83
Carbonylation reaction:
20mmol 6-methoxyl group-2-bromonaphthalene and 30mmol triethylamine are dissolved in the 30ml 1-butanols, and add 0.05ol%Pd (OAc)
2With 0.1mol% butyl two adamantyl phosphines.It is that stirring is complete until conversion down down and at 130 ℃ for 3 CO that cling to that this mixture is placed pressure.After filtering out soluble component,, obtain 6-methoxyl group-2-naphthyl butyl carboxylate of 94% with alkaline solution washing and distillation.
Claims (16)
1. general formula is the phosphine part of the novelty of Ia and Ib:
(adamantyl)
nP (alkyl)
mIa
(adamantyl)
o(alkyl)
qP (alkylene ') P (adamantyl)
r(alkyl)
sIb
Wherein adamantyl is the adamantyl group (IIa, IIb) that is connected to phosphorus atom in 1-or 2-position:
Alkyl is C
1To C
18Alkyl group and
Alkylene ' be methylene radical, ethylene, trimethylene, tetramethylene, pentamethylene or the hexamethylene bridge, 1 of bridging, 2-diphenylene, 2,1 of 2 '-replacement, 1 '-binaphthylyl or ferrocenyl bridge,
Wherein said alkyl, described alkylene ' and described adamantyl can have maximum 10 substituting groups except hydrogen atom independently of each other, described substituting group is C independently of each other
1To C
8Alkyl, O-alkyl (C
1-C
8), OH, OCO-alkyl (C
1-C
8), O-phenyl, phenyl, aryl, fluorine, NO
2, Si-alkyl (C
1-C
8)
3, CN, COOH, CHO, SO
3H, NH
2, NH-alkyl (C
1-C
8), N-alkyl (C
1-C
8)
2, P (alkyl (C
1-C
8))
2, P (aryl)
2, SO
2-alkyl (C
1-C
6), SO-alkyl (C
1-C
6), CF
3, NHCO-alkyl (C
1-C
4), COO-alkyl (C
1-C
8), CONH
2, CO-alkyl (C
1-C
8), NHCHO, NHCOO-alkyl (C
1-C
4), CO-phenyl, COO-phenyl, CH=CH-CO
2-alkyl (C
1-C
8), CH=CHCOOH, PO (phenyl)
2, PO (alkyl (C
1-C
4))
2, PO
3H
2, PO (O-alkyl (C
1-C
6))
2Or SO
3(alkyl (C
1-C
4)), aryl is the aromatic compound with 5 to 14 ring carbon atoms, and its one or more available ring carbon atoms are replaced obtaining having the assorted aromatic compound of 1 to 13 ring carbon atom by nitrogen, oxygen and/or sulphur atom,
Wherein n is that numeral and the m that is selected from 1-3 is the numeral that is selected from 0-2, and need satisfy condition n+m=3 and
Wherein o and r are numerals 1 or 2, and q and s are numerals 0 or 1, and need satisfy condition o+q=2 and r+s=2.
2. the phosphine part of novelty according to claim 1, wherein adamantyl is the adamantyl group (IIa, IIb) that is connected in 1-or 2-position on the phosphorus atom, alkyl is C
1To C
12Alkyl group and alkylene ' be ethylene, trimethylene or the tetramethylene bridge, 1 of bridging, 2-diphenylene, 2,2 '-replace 1,1 '-binaphthylyl or ferrocenyl derivative,
Wherein said alkyl, alkylene ' and adamantyl can have maximum 5 substituting groups except hydrogen atom independently of each other, described substituting group is C independently of each other
1To C
8Alkyl, O-alkyl (C
1-C
8), OH, OCO-alkyl (C
1-C
8), O-phenyl, phenyl, aryl, fluorine, Si-alkyl (C
1-C
8)
3, COOH, SO
3H, NH
2, NH-alkyl (C
1-C
8), the N-alkyl
2(C
1-C
8), P (alkyl (C
1-C
8))
2, P (phenyl)
2, CF
3, NHCO-alkyl (C
1-C
4), COO-alkyl (C
1-C
8), CONH
2, CO-alkyl (C
1-C
8), COO-phenyl, PO (phenyl)
2, PO (alkyl (C
1-C
4))
2, PO
3H
2Or PO (O-alkyl (C
1-C
6))
2, aryl is to have the aromatic compound of 5 to 14 ring carbon atoms and heteroatoms that its one or more available ring carbon atoms are selected from nitrogen, oxygen and sulphur atom to replace obtaining having the assorted aromatic compound of 1 to 13 ring carbon atom,
Wherein n be the numeral 1 or 2 and m be the numeral 1 or 2, and need satisfy condition n+m=3 and
Wherein o and r are numerals 1 or 2, and q and s are numerals 0 or 1, and need satisfy condition o+q=2 and r+s=2.
3. the phosphine part of novelty according to claim 1 and 2, wherein adamantyl is the adamantyl group (IIa, IIb) that is connected in 1-or 2-position on the phosphorus atom, alkyl is C
1To C
12Alkyl group and alkylene ' be ethylene, trimethylene or the tetramethylene bridge of bridging,
Wherein said alkyl group, described alkylene ' group and described adamantyl group can have maximum 3 substituting groups except hydrogen atom independently of each other, and described substituting group is C independently of each other
1To C
8Alkyl, O-alkyl (C
1-C
8), OH, OCO-alkyl (C
1-C
8), O-phenyl, phenyl, COOH, SO
3H, NH
2, P (alkyl (C
1-C
8))
2, P (aryl)
2, COO-alkyl (C
1-C
8), CONH
2Or PO (phenyl)
2,
Wherein n be the numeral 1 or 2 and m be the numeral 1 or 2, and need satisfy condition n+m=3 and
Wherein o and r are 1 or 2, and q and s are numerals 0 or 1, and need satisfy condition o+q=2 and r+s=2.
4. according to the preparation method of the phosphine part of a described novelty in the claim 1 to 3, it is characterized in that reacting the phosphine part for preparing described novelty by dihalo adamantyl phosphine or halo two adamantyl phosphines and organometallic reagent.
5. according to the preparation method of the phosphine part of a described novelty in the claim 1 to 3, it is characterized in that for example alkyl halide or pseudohalide, aldehyde or epoxide reaction prepare the phosphine part of described novelty by basic metal adamantyl phosphide or basic metal two adamantyl phosphides and organic electrophilic reagent.
6. according to the transition metal complex of the phosphine part of a described novelty in the aforementioned claim and period of element Table VIII subgroup or transition metal salt binding purposes as catalyzer, wherein, common described part original position is joined in the suitable transition metal precursors compound or with described part directly is used as transition metal phosphine complex compound.
7. purposes according to claim 6 is characterized in that used transition metal is palladium metal, nickel, platinum, rhodium, iridium, ruthenium and cobalt.
8. according to claim 6 or 7 described purposes, it is characterized in that used transistion metal compound is palladium or nickel compound, preferred palladium compound.
9. purposes according to claim 6, it is characterized in that with the list of previously prepared transition metal according to claim 7 or 8-, two, three-or the tetraphosphine complex compound be used for catalyzed reaction.
10. according to the described purposes of claim 6 to 9, it is characterized in that described part component be used for catalytic preparation diene or aromatize alkene (Heck reaction), biaryl (Suzuki reaction), from aryl halide or vinyl halide catalytic preparation alpha-aromatic ketone and/or amine.
11. according to the described purposes of claim 6 to 9, it is characterized in that described part component be used for the catalyzed carbonylation of aryl halide, with the ethynylation (Sonogashira coupling) of alkynes with the cross-coupling of organometallic reagent.
12., it is characterized in that described phosphine part is used for the preparation of aryl olefin, diene, diaryl, benzoic acid derivative, acrylic acid derivative, aromatic yl paraffin, alkynes and amine according to the described purposes of claim 6 to 9.
13., it is characterized in that under 20 to 200 ℃ temperature, using described part according to an aforementioned described purposes of claim.
14. purposes according to claim 13 is characterized in that described temperature remains on 30 to 180 ℃, preferred 40 to 160 ℃.
15., it is characterized in that in described catalytic applications, the described phosphine part of use is excessive with respect to described transition metal according to an aforementioned described purposes of claim, the ratio of described transition metal and described part is 1: 1 to 1: 1000.
16. purposes according to claim 15, the ratio that it is characterized in that transition metal and part are 1: 1 to 1: 100.
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