CN108659054A - A kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums - Google Patents
A kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums Download PDFInfo
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- CN108659054A CN108659054A CN201810779111.5A CN201810779111A CN108659054A CN 108659054 A CN108659054 A CN 108659054A CN 201810779111 A CN201810779111 A CN 201810779111A CN 108659054 A CN108659054 A CN 108659054A
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- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
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Abstract
The preparation method of 4 dimethylaminophenyl phosphine palladium of dichloro di-t-butyl disclosed by the invention, includes the following steps：Step 1, using raw material N, N dimethyl prepares Grignard Reagent to halobenzene amine and magnesium chips；Step 2, it takes Grignard Reagent and cools down, reacted after catalyst then is added, then di-t-butyl phosphorus chloride is added dropwise, reaction is to obtain 4 dimethylamino phenyl phosphine of di-t-butyl after heating；Step 3, to 4 dimethylamino phenyl phosphine purification process of di-t-butyl；Step 4, bis- (acetonitrile) palladium chlorides is taken to carry out complex reaction with 4 dimethylamino phenyl phosphine of di-t-butyl after purification to get to target product.The preparation method of the present invention to 4 dimethylamino phenyl phosphine of di-t-butyl by carrying out purification process, it is reacted with bis- (acetonitrile) palladium chlorides with the 4 dimethylamino phenyl phosphine of di-t-butyl of high-purity, greatly reduce the yield losses of precious metal palladium, so that manufacturing cost is greatly reduced, there is good practical value.
Description
Technical field
The invention belongs to phosphine palladium preparation method technical fields, and in particular to a kind of dichloro di-t-butyl -4- dimethylaminos
The preparation method of Phenylphosphine palladium.
Background technology
Dichloro di-t-butyl-(4- dimethylaminophenyls) phosphine palladium plays important in current organic synthesis practical application
Effect is used in C-C, C-N coupling reaction mainly as catalyst, in chemical raw material, liquid crystalline monomeric material, optical function material
There is extremely wide application in the synthesis of equal substances.In the synthesis of these compounds, the dichloro di-t-butyl-of high-quality
(4- dimethylaminophenyls) phosphine palladium has extremely efficient catalytic action.
Currently, dichloro di-t-butyl-(4- dimethylaminophenyls) phosphine palladium of high-quality in order to obtain, there has been proposed permitted
The preparation method of more dichloro di-t-butyl-(4- dimethylaminophenyls) phosphine palladiums is attempted.Document report：It is prepared with one-step method
Obtain, obtain di-t-butyl -4- dimethylamino phenyl Phosphine ligands, handle without further purification directly with (1,5- cyclo-octadiene) dichloro
Change palladium to be complexed to obtain product；The route reaction step is few, is easier to control, but the disadvantage is that because ligand without purification process,
The loss of palladium is caused to increase, and product purity is low, poor quality；Moreover, in synthetic ligands di-t-butyl -4- dimethylamino phenyl phosphines
During, the tris(dibenzylideneacetone) dipalladium of noble metal catalyst containing palladium is used, the consumption of precious metal palladium is increased.
The catalyst synthetic ligands di-t-butyl -4- dimethylamino phenyls not used containing precious metal palladium separately are documented
Phosphine, but with n-BuLi or the murther lithium reagent of tert-butyl lithium one kind, be not suitable for large-scale industrial production.
Therefore, it develops safety, high precious metal palladium yield, be suitble to large-scale production high-quality dichloro di-t-butyl-(4- bis-
Methylamino phenyl) new process of phosphine palladium is a technical problem to be solved urgently.
Invention content
The object of the present invention is to provide a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums, solutions
In existing dichloro di-t-butyl-(4- dimethylaminophenyls) phosphine palladium preparation process of having determined, the consumption of precious metal palladium is big, uses lithium
The problem that reagent raw material danger coefficient is high, synthesis cost is high.
The technical solution adopted in the present invention is a kind of preparation of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums
Method includes the following steps：
Step 1, using raw material N, N- dimethyl prepares Grignard Reagent to halobenzene amine and magnesium chips, spare；
Step 2, it takes Grignard Reagent in step 1 and cools down, reacted after catalyst then is added, then di-t-butyl chlorination is added dropwise
Phosphorus, reaction is to obtain di-t-butyl -4- dimethylamino phenyl phosphines after heating；
Step 3, by the di-t-butyl -4- dimethylamino phenyl phosphine purification process of step 2；
Step 4, bis- (acetonitrile) palladium chlorides are taken and are added in anhydrous tetrahydro furan, under nitrogen protection, step 3 are added
After di-t-butyl -4- dimethylamino phenyl phosphines after purification are stirred to react 25min-35min, yellow solid to be had is formed, and is continued
It is stirred to react no less than 8h at room temperature, stops reaction, filtering, filter cake is dried in vacuo after being embathed with anhydrous tetrahydro furan, obtains Huang
Color crystalline powder, i.e. dichloro di-t-butyl -4- dimethylaminophenyls phosphine palladium.
It is of the invention to be further characterized in that,
The preparation process of Grignard Reagent in step 1：
Step 1.1, the initiation of grignard reaction
Under the protective effect of nitrogen, magnesium chips is added, the anhydrous tetrahydro furan for not having magnesium chips just is then added, is then dripping
N, N- dimethyl is added to cause to the anhydrous tetrahydrofuran solution of halobenzene amine, addition iodine grain, heating stirring, grignard reaction, stop adding
Heat；
Step 1.2, continue that N is added dropwise in the solution of step 1.1, N- dimethyl is molten to the anhydrous tetrahydro furan of halobenzene amine
Liquid is added dropwise and keeps temperature and react to be no less than 1h；
Step 1.3, it detects
The solution that step 1.2 is put into is taken to carry out GC detections, as N in solution, N- dimethyl is little to halobenzene amine residual mass
When the 0.1% of total system, prepared by Grignard Reagent completes.
N in step 1.1 and step 1.2, N- dimethyl are a concentration of to the anhydrous tetrahydrofuran solution of halobenzene amine：Every liter of nothing
The N of 160g-210g, N- dimethyl parachloroanilinum are added in water tetrahydrofuran；
Iodine grain quality is 0.1-0.5g in step 1.1；
- 55 DEG C of temperature 45 C is warming up in step 1.1；
In step 1.2, N is added dropwise, N- dimethyl is to the speed of the anhydrous tetrahydrofuran solution of halobenzene amine to maintain reactant
It is temperature at 50 DEG C -65 DEG C.
N in step 1, N- dimethyl are specially N to halobenzene amine, and N- dimethyl parachloroanilinum or N, N- dimethyl are to bromobenzene
Amine or N, N- dimethyl paraiodoanilines.
N in step 1, N- dimethyl are 1 to the molar ratio of halobenzene amine and magnesium chips:1-1.5.
Catalyst is cuprous halide, specially stannous chloride or cuprous bromide or cuprous iodide in step 2.
It is -90 DEG C -0 DEG C that temperature is cooled in step 2；
The reaction time is 8min-12min after catalyst is added；
Be warming up to temperature be 50 DEG C -60 DEG C, after heating the reaction time be no less than 3h.
N in step 1, N- dimethyl are to di-t-butyl phosphorus chloride molar ratio 1 in halobenzene amine and step 2:0.9-1.2；
Molar ratio 1 of N in step 1, the N- dimethyl to catalyst in halobenzene amine and step 2:0.01-0.1.
The purification process of step 3 is specially：
Under nitrogen protection, the di-t-butyl -4- dimethylamino phenyl phosphine reaction liquid of step 2 is down to 0 DEG C hereinafter, then
Addition saturated aqueous ammonium chloride is quenched, upper organic phase precipitation is evaporated under reduced pressure by liquid separation, and 120 DEG C -140 DEG C of collection evaporates
Point, obtain di-t-butyl -4- dimethylamino phenyl phosphines after purification.
The molar ratio 1 of (acetonitrile) palladium chlorides bis- in step 4 and di-t-butyl -4- dimethylamino phenyl phosphines after purification:
2-2.5。
The advantageous effect of preparation method of the present invention is：
(1) preparation method of the invention first carries out purification process to di-t-butyl -4- dimethylamino phenyl Phosphine ligands, with subtracting
The method of pressure distillation obtains ligand after purification, then is complexed with bis- (acetonitrile) palladium chlorides, to obtain high quality, high yield,
Dichloro di-t-butyl-(4- dimethylaminophenyls) phosphine palladium product of high-purity；
(2) preparation method of the invention is using inexpensive copper salt catalyst, among the ligand for producing low cost, high-quality
Body obtains the ligand production technology that is produced on a large scale；It avoids and uses precious metal palladium of high cost in the synthesis process, or use danger
The problem of dangerous chemical raw material, unsuitable large-scale production.
Description of the drawings
Fig. 1 is a kind of reaction mechanism figure of dichloro di-t-butyl -4- dimethylaminophenyls phosphine palladium preparation method of the present invention；
Fig. 2 is dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums prepared by the present invention1H-NMR spectrum；
Fig. 3 is dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums prepared by the present invention31P-NMR spectrograms.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
It is found in for a long time to the synthesis of dichloro di-t-butyl-(4- dimethylaminophenyls) phosphine palladium and application study：Due to
Ligand di-t-butyl -4- dimethylamino phenyl phosphines easily aoxidize, it is more difficult to high-purity sterling are obtained, so easily causing in synthesis target
The loss of palladium increases when compound, and the purity for obtaining target compound is relatively low.And it has been investigated that, it is depressurized and is steamed by high vacuum
The ligand of high-purity can be obtained by evaporating, then is complexed with bis- (acetonitrile) palladium chlorides, obtained dichloro di-t-butyl-(4- dimethyl
Aminophenyl) phosphine palladium is yellow crystalline powder, high income, purity are high, and catalytic activity is high, quality is good.
As shown in Figure 1, for a kind of reaction of dichloro di-t-butyl -4- dimethylaminophenyls phosphine palladium preparation method of the present invention
Mechanism figure, specifically includes following steps：
Step 1, using material molar ratio 1:The N of 1-1.5, N- dimethyl prepare Grignard Reagent to halobenzene amine and magnesium chips.
Step 1.1, the initiation of grignard reaction
Under the protective effect of nitrogen, magnesium chips is added, the anhydrous tetrahydro furan for not having magnesium chips just is then added, is then dripping
N, N- dimethyl is added (N, N- of 160g-210g to be added in every liter of anhydrous tetrahydro furan to the anhydrous tetrahydrofuran solution of halobenzene amine
Dimethyl parachloroanilinum), 0.1-0.5g iodine grains are added, are warming up to 45 DEG C of -55 DEG C of stirrings, grignard reaction causes, and stops heating；
Step 1.2, continue that N is added dropwise in the solution of step 1.1, N- dimethyl is molten to the anhydrous tetrahydro furan of halobenzene amine
N is added dropwise in liquid, and N- dimethyl is to the speed of the anhydrous tetrahydrofuran solution of halobenzene amine to maintain temperature of reaction system at 50 DEG C -65
DEG C, it is added dropwise and keeps temperature and react to be no less than 1h；
Step 1.3, it detects
The solution that step 1.2 is put into is taken to carry out GC detections, as N in solution, N- dimethyl is little to halobenzene amine residual mass
When the 0.1% of total system, prepared by Grignard Reagent completes；If more than 0.1%, continue to keep reaction to reaching requirement.
N, N- dimethyl are specially N, N- dimethyl parachloroanilinum or N, N- dimethylatedρ-bromoaniline or N to halobenzene amine,
N- dimethyl paraiodoanilines.
Step 2, it takes Grignard Reagent in step 1 and is cooled to -90 DEG C -0 DEG C, be then stirred to react after addition catalyst
8min-12min, then di-t-butyl phosphorus chloride is added dropwise, during dropwise addition, stringent controlling reaction temperature is no more than 0 DEG C, is warming up to 50
Reaction is no less than 3h to get to di-t-butyl -4- dimethylamino phenyl phosphines after DEG C -60 DEG C.
Catalyst is cuprous halide, specially stannous chloride or cuprous bromide or cuprous iodide.
Wherein N, N- dimethyl are to halobenzene amine and di-t-butyl phosphorus chloride molar ratio 1:0.9-1.2；N, N- dimethyl are to halogen
The molar ratio 1 of aniline and catalyst:0.01-0.1.
Step 3, by the di-t-butyl -4- dimethylamino phenyl phosphine purification process of step 2, specially：
Under nitrogen protection, di-t-butyl -4- dimethylamino phenyl phosphine reaction liquid is down to 0 DEG C hereinafter, being then added full
Be quenched with aqueous ammonium chloride solution, stratification, liquid separation, upper organic phase precipitation under nitrogen protection obtains residue decompression and steams
Evaporate, under control vacuum degree 0.3-0.5mmHg, collect 120 DEG C -140 DEG C of fraction, obtain purity not less than 97% after purification
Ligand di-t-butyl -4- dimethylamino phenyl phosphines.
Step 4, bis- (acetonitrile) palladium chlorides are taken and are added in anhydrous tetrahydro furan, under nitrogen protection, step 3 are added
After di-t-butyl -4- dimethylamino phenyl phosphines after purification are stirred to react 25min-35min, yellow solid to be had is formed, and is continued
It is stirred to react no less than 8h at room temperature, stops reaction, filtering, filter cake is dried in vacuo after being embathed with anhydrous tetrahydro furan, obtains Huang
Color crystalline powder, i.e. dichloro di-t-butyl -4- dimethylaminophenyls phosphine palladium, wherein bis- (acetonitrile) palladium chlorides with after purification
The molar ratio 1 of di-t-butyl -4- dimethylamino phenyl phosphines:2-2.5.
Dichloro di-t-butyl -4- dimethylaminophenyl phosphine the palladiums being prepared are tested for the property, obtain such as Fig. 2 and
It is shown in Fig. 31H-NMR spectrum and31P-NMR spectrograms.
Embodiment 1
Tetra- mouthfuls of reaction bulbs of dry 10L are taken, is sufficiently displaced from through drying nitrogen and under dry nitrogen air-flow protection, addition has removed
The magnesium chips 150g of surface oxide layer is removed, anhydrous tetrahydro furan 200mL is then added and did not had magnesium chips, then N is added dropwise, N- dimethyl is to chlorine
(the wherein N of 800g, N- dimethyl parachloroanilinum are dissolved in the anhydrous tetrahydrochysene furans of 5L to the anhydrous tetrahydrofuran solution 50-80mL of aniline
In muttering)；Then 0.5g iodine grains are added, stirring is warming up to 50 DEG C, after grignard reaction initiation, stops heating；Continue that N, N- is added dropwise
The anhydrous tetrahydrofuran solution of dimethyl parachloroanilinum, rate of addition is to maintain temperature of reaction system at 60 DEG C, after being added dropwise
Keep 60 DEG C of reaction 1h, the surplus of sample detection raw material N, N- dimethyl parachloroanilinum, N, N- dimethyl parachloroanilinum residue
Quality is less than 0.1%, then Grignard Reagent preparation finishes.
Reaction system is cooled to -30 DEG C, and under nitrogen stream protection, the catalyst stannous chloride of vacuum dried water removal is added
It is stirred to react 10min after powder 10.2g, then di-t-butyl phosphorus chloride 930g is added dropwise, process control reaction temperature is added dropwise at -30 DEG C
Hereinafter, be added dropwise, 50 DEG C of reaction 3h are warming up to get to di-t-butyl -4- dimethylamino phenyl phosphines.
Reaction system is cooled to -30 DEG C again, while stirring dropwise addition saturated aqueous ammonium chloride 1.5L, quiet after stirring 0.5h
Layering is set, under nitrogen stream protection, liquid separation, upper organic phase precipitation concentration obtains clear yellow viscous object and carries out high vacuum decompression steaming
It evaporates, vacuum degree 0.3-0.5mmHg, collects 120 DEG C -140 DEG C of fraction, be off-white powder, as two uncle of ligand after cooling
Butyl -4- dimethylamino phenyl phosphines, yield 1145-1160g, purity are not less than 97%, and yield is 81.5%~85.0%.
It takes in tri- mouthfuls of reaction bulbs of dry 10L, drying nitrogen is sufficiently displaced from and under nitrogen stream protection, 5.5L anhydrous four is added
Hydrogen furans stirs and adds bis- (acetonitrile) palladium chloride 540g, the ligand di-t-butyl -4- Dimethylaminobenzenes added
Base phosphine reaction 30min, there is yellow solid precipitation, and after the reaction was continued at room temperature 9h, filtering, filter cake is embathed with anhydrous tetrahydro furan
Afterwards, it drains and in 60 DEG C of dryings in vacuum drying oven, obtains yellow crystalline powder shape target product, i.e. dichloro di-t-butyl-(4-
Dimethylaminophenyl) phosphine palladium, yield 1440g~1445g, elemental analyser analysis, product content is more than 98.0%, palladium content
More than 15.0%, yield is calculated as 97.7%~98.1% with palladium.
Embodiment 2
Tetra- mouthfuls of reaction bulbs of dry 10L are taken, is sufficiently displaced from through drying nitrogen and under dry nitrogen air-flow protection, addition has removed
The magnesium chips 150g of surface oxide layer is removed, anhydrous tetrahydro furan 200mL is then added and did not had magnesium chips, then N is added dropwise, N- dimethyl is to bromine
(the wherein N of 1028.5g, N- dimethylatedρ-bromoaniline are dissolved in the anhydrous tetrahydrochysenes of 5L to the anhydrous tetrahydrofuran solution 50-80mL of aniline
In furans)；Then 0.3g iodine grains are added, stirring is warming up to 45 DEG C, after grignard reaction initiation, stops heating；Continue that N is added dropwise,
The anhydrous tetrahydrofuran solution of N- dimethylatedρ-bromoanilines, rate of addition are added dropwise with maintaining temperature of reaction system at 50 DEG C
50 DEG C of reaction 1h of holding, the surplus of sample detection raw material N, N- dimethylatedρ-bromoaniline, N, N- dimethylatedρ-bromoanilines are surplus afterwards
Remaining quality is less than 0.1%, then Grignard Reagent preparation finishes.
Reaction system is cooled to -60 DEG C, and under nitrogen stream protection, the catalyst cuprous bromide of vacuum dried water removal is added
It is stirred to react 8min after powder 14.8g, then di-t-butyl phosphorus chloride 930g is added dropwise, process control reaction temperature is added dropwise at -60 DEG C
Hereinafter, be added dropwise, 55 DEG C of reaction 4h are warming up to get to di-t-butyl -4- dimethylamino phenyl phosphines.
Reaction system be cooled to again -60 DEG C hereinafter, while stirring be added dropwise saturated aqueous ammonium chloride 1.5L, stir 0.5h
Stratification afterwards, the liquid separation under nitrogen stream protection, the concentration of upper organic phase precipitation obtain clear yellow viscous object and carry out high vacuum decompression
Distillation, vacuum degree 0.3-0.5mmHg collect 120 DEG C -140 DEG C of fraction, are off-white powder after cooling, are two uncle of ligand
Butyl -4- dimethylamino phenyl phosphines, yield 1145-1160g, purity are not less than 97%, and yield is 81.5%~85.0%.
It takes in tri- mouthfuls of reaction bulbs of dry 10L, drying nitrogen is sufficiently displaced from and under nitrogen stream protection, 5.5L anhydrous four is added
Hydrogen furans stirs and adds bis- (acetonitrile) palladium chloride 540g, the ligand di-t-butyl -4- Dimethylaminobenzenes added
Base phosphine reaction 25min, there is yellow solid precipitation, and after the reaction was continued at room temperature 8h, filtering, filter cake is embathed with anhydrous tetrahydro furan
Afterwards, it drains and in 60 DEG C of dryings in vacuum drying oven, obtains yellow crystalline powder shape target product, i.e. dichloro di-t-butyl-(4-
Dimethylaminophenyl) phosphine palladium, yield 1440g~1445g, elemental analyser analysis, product content is more than 98.0%, palladium content
More than 15.0%, yield is calculated as 97.7%~98.1% with palladium.
Embodiment 3
Tetra- mouthfuls of reaction bulbs of dry 10L are taken, is sufficiently displaced from through drying nitrogen and under dry nitrogen air-flow protection, addition has removed
The magnesium chips 150g of surface oxide layer is removed, anhydrous tetrahydro furan 200mL is then added and did not had magnesium chips, then N is added dropwise, N- dimethyl is to iodine
(the wherein N of 1270.0g, N- dimethyl paraiodoaniline are dissolved in the anhydrous tetrahydrochysenes of 5L to the anhydrous tetrahydrofuran solution 50-80mL of aniline
In furans)；Then 0.5g iodine grains are added, stirring is warming up to 50 DEG C, after grignard reaction initiation, stops heating；Continue that N is added dropwise,
The anhydrous tetrahydrofuran solution of N- dimethyl paraiodoanilines, rate of addition are added dropwise with maintaining temperature of reaction system at 50 DEG C
50 DEG C of reaction 1h of holding, the surplus of sample detection raw material N, N- dimethyl paraiodoaniline, N, N- dimethyl paraiodoanilines are surplus afterwards
Remaining quality is less than 0.1%, then Grignard Reagent preparation finishes.
Reaction system is cooled to 0 DEG C, and under nitrogen stream protection, the catalyst cuprous iodide powder of vacuum dried water removal is added
Be stirred to react 12min after last 19.64g, then di-t-butyl phosphorus chloride 930g be added dropwise, be added dropwise process control reaction temperature 0 DEG C with
Under, it is added dropwise, is warming up to 60 DEG C of reaction 3h to get to di-t-butyl -4- dimethylamino phenyl phosphines.
Reaction system be cooled to again -60 DEG C hereinafter, while stirring be added dropwise saturated aqueous ammonium chloride 1.5L, stir 0.5h
Stratification afterwards, the liquid separation under nitrogen stream protection, the concentration of upper organic phase precipitation obtain clear yellow viscous object and carry out high vacuum decompression
Distillation, vacuum degree 0.3-0.5mmHg collect 120 DEG C -140 DEG C of fraction, are off-white powder after cooling, are two uncle of ligand
Butyl -4- dimethylamino phenyl phosphines, yield 1145-1160g, purity are not less than 97%, and yield is 81.5%~85.0%.
It takes in tri- mouthfuls of reaction bulbs of dry 10L, drying nitrogen is sufficiently displaced from and under nitrogen stream protection, 5.5L anhydrous four is added
Hydrogen furans stirs and adds bis- (acetonitrile) palladium chloride 540g, the ligand di-t-butyl -4- Dimethylaminobenzenes added
Base phosphine reaction 30min, there is yellow solid precipitation, and after the reaction was continued at room temperature 9h, filtering, filter cake is embathed with anhydrous tetrahydro furan
Afterwards, it drains and in 60 DEG C of dryings in vacuum drying oven, obtains yellow crystalline powder shape target product, i.e. dichloro di-t-butyl-(4-
Dimethylaminophenyl) phosphine palladium, yield 1440g~1445g, elemental analyser analysis, product content is more than 98.0%, palladium content
More than 15.0%, yield is calculated as 97.7%~98.1% with palladium.
The nuclear-magnetism of product dichloro di-t-butyl-(4- dimethylaminophenyls) the phosphine palladium prepared through embodiment 1-3 characterizes knot
Fruit sees below shown in attached drawing 1, attached drawing 2, it can thus be appreciated that：Preparation method of the present invention has obtained the target compound of high-purity, high-quality,
While being suitble to large-scale production, it is greatly reduced synthesis cost.
Claims (10)
1. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums, which is characterized in that including following step
Suddenly：
Step 1, using raw material N, N- dimethyl prepares Grignard Reagent to halobenzene amine and magnesium chips, spare；
Step 2, it takes Grignard Reagent in step 1 and cools down, reacted after catalyst then is added, then di-t-butyl phosphorus chloride is added dropwise,
Reaction obtains di-t-butyl -4- dimethylamino phenyl phosphines after heating；
Step 3, by the di-t-butyl -4- dimethylamino phenyl phosphine purification process of step 2；
Step 4, bis- (acetonitrile) palladium chlorides are taken and are added in anhydrous tetrahydro furan, under nitrogen protection, step 3 purifying are added
After di-t-butyl -4- dimethylamino phenyl phosphines afterwards are stirred to react 25min-35min, yellow solid to be had is formed, and continues room temperature
Under be stirred to react no less than 8h, stop reaction, filtering, filter cake is dried in vacuo after being embathed with anhydrous tetrahydro furan, obtains yellow knot
Crystalline flour end, i.e. dichloro di-t-butyl -4- dimethylaminophenyls phosphine palladium.
2. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums according to claim 1, special
Sign is, the preparation process of Grignard Reagent in the step 1：
Step 1.1, the initiation of grignard reaction
Under the protective effect of nitrogen, magnesium chips is added, the anhydrous tetrahydro furan for not having magnesium chips just is then added, N then is being added dropwise,
Iodine grain, heating stirring is added to the anhydrous tetrahydrofuran solution of halobenzene amine in N- dimethyl, and grignard reaction causes, and stops heating；
Step 1.2, continue that N is added dropwise in the solution of step 1.1, N- dimethyl is to the anhydrous tetrahydrofuran solution of halobenzene amine, drop
It adds to finish and keeps temperature and react to be no less than 1h；
Step 1.3, it detects
The solution that step 1.2 is put into is taken to carry out GC detections, as N in solution, N- dimethyl is to halobenzene amine residual mass no more than total
System 0.1% when, Grignard Reagent prepare complete.
3. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums according to claim 2, special
Sign is, N in the step 1.1 and step 1.2, and N- dimethyl is a concentration of to the anhydrous tetrahydrofuran solution of halobenzene amine：Often
Rise the N that 160g-210g is added in anhydrous tetrahydro furan, N- dimethyl parachloroanilinum；
Iodine grain quality is 0.1-0.5g in the step 1.1；
- 55 DEG C of temperature 45 C is warming up in the step 1.1；
In the step 1.2, N is added dropwise, N- dimethyl is to the speed of the anhydrous tetrahydrofuran solution of halobenzene amine to maintain reactant
It is temperature at 50 DEG C -65 DEG C.
4. according to a kind of preparation side of any dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums of claim 1-3
Method, which is characterized in that N in the step 1, N- dimethyl are specially N, N- dimethyl parachloroanilinum or N, N- bis- to halobenzene amine
Methyl para-bromoaniline or N, N- dimethyl paraiodoanilines.
5. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums according to claim 1, special
Sign is that N in the step 1, N- dimethyl is 1 to the molar ratio of halobenzene amine and magnesium chips:1-1.5.
6. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums according to claim 1, special
Sign is that catalyst is cuprous halide, specially stannous chloride or cuprous bromide or cuprous iodide in the step 2.
7. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums according to claim 1, special
Sign is that it is -90 DEG C -0 DEG C that temperature is cooled in the step 2；
The reaction time is 8min-12min after catalyst is added；
Be warming up to temperature be 50 DEG C -60 DEG C, after heating the reaction time be no less than 3h.
8. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums according to claim 1, special
Sign is that N in the step 1, N- dimethyl is to di-t-butyl phosphorus chloride molar ratio 1 in halobenzene amine and step 2:0.9-1.2；
Molar ratio 1 of N in step 1, the N- dimethyl to catalyst in halobenzene amine and step 2:0.01-0.1.
9. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums according to claim 1, special
Sign is that the purification process of the step 3 is specially：
Under nitrogen protection, the di-t-butyl -4- dimethylamino phenyl phosphine reaction liquid of step 2 is down to 0 DEG C hereinafter, being then added
Saturated aqueous ammonium chloride is quenched, upper organic phase precipitation is evaporated under reduced pressure by liquid separation, collects 120 DEG C -140 DEG C of fraction, obtains
To di-t-butyl -4- dimethylamino phenyl phosphines after purification.
10. a kind of preparation method of dichloro di-t-butyl -4- dimethylaminophenyl phosphine palladiums according to claim 1,
It is characterized in that, mole of (acetonitrile) palladium chlorides bis- in the step 4 and di-t-butyl -4- dimethylamino phenyl phosphines after purification
Than 1:2-2.5.
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Cited By (4)
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| CN110669079A (en) * | 2019-11-11 | 2020-01-10 | 西安凯立新材料股份有限公司 | Preparation method of 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride |
| CN111909217A (en) * | 2020-08-20 | 2020-11-10 | 昆明贵金属研究所 | Bis (di-tert-butyl-4-dimethylaminophenylphosphine) tetrabromobiladalladium (II) compound and preparation method and application thereof |
| CN112194685A (en) * | 2020-10-27 | 2021-01-08 | 西安凯立新材料股份有限公司 | Preparation method of [ (S) - (-) -2,2 '-bis (diphenylphosphino) -1,1' -binaphthyl ] palladium dichloride |
| CN114907415A (en) * | 2022-05-10 | 2022-08-16 | 浙江微通催化新材料有限公司 | Preparation method of bis (di-tert-butyl-4-dimethylaminophenylphosphine) palladium chloride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669079A (en) * | 2019-11-11 | 2020-01-10 | 西安凯立新材料股份有限公司 | Preparation method of 1,1' -bis (di-tert-butylphosphino) ferrocene palladium dichloride |
| CN111909217A (en) * | 2020-08-20 | 2020-11-10 | 昆明贵金属研究所 | Bis (di-tert-butyl-4-dimethylaminophenylphosphine) tetrabromobiladalladium (II) compound and preparation method and application thereof |
| CN111909217B (en) * | 2020-08-20 | 2023-05-02 | 昆明贵金属研究所 | Bis (di-tert-butyl-4-dimethylaminophenylphosphine) tetrabromodipalladium (II) compound and preparation method and application thereof |
| CN112194685A (en) * | 2020-10-27 | 2021-01-08 | 西安凯立新材料股份有限公司 | Preparation method of [ (S) - (-) -2,2 '-bis (diphenylphosphino) -1,1' -binaphthyl ] palladium dichloride |
| CN114907415A (en) * | 2022-05-10 | 2022-08-16 | 浙江微通催化新材料有限公司 | Preparation method of bis (di-tert-butyl-4-dimethylaminophenylphosphine) palladium chloride |
| CN114907415B (en) * | 2022-05-10 | 2023-12-19 | 浙江微通催化新材料有限公司 | Preparation method of bis (di-tert-butyl-4-dimethylaminophenylphosphine) palladium chloride |
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