CN110330528A - A kind of preparation method of bis- (triphenylphosphine) palladium bromides - Google Patents
A kind of preparation method of bis- (triphenylphosphine) palladium bromides Download PDFInfo
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- CN110330528A CN110330528A CN201910608462.4A CN201910608462A CN110330528A CN 110330528 A CN110330528 A CN 110330528A CN 201910608462 A CN201910608462 A CN 201910608462A CN 110330528 A CN110330528 A CN 110330528A
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- triphenylphosphine
- palladium
- bis
- preparation
- bromides
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- -1 bis- (triphenylphosphine) palladium bromides Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 64
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 34
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 32
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000013019 agitation Methods 0.000 claims abstract description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910002666 PdCl2 Inorganic materials 0.000 abstract description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 3
- WGXZDYPGLJYBJW-UHFFFAOYSA-N chloroform;propan-2-ol Chemical compound CC(C)O.ClC(Cl)Cl WGXZDYPGLJYBJW-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of bis- (triphenylphosphine) palladium bromides, this method comprises: one, palladium chloride dissolved with hydrochloric acid solution, sodium bromide is then added, is stirred to react；Two, triphenylphosphine dissolved is obtained into isopropanol/chloroform soln of triphenylphosphine in the in the mixed solvent of isopropanol and chloroform；Three, the reaction solution after being stirred to react in step 1 is added dropwise in isopropanol/chloroform soln of triphenylphosphine described in step 2 under agitation, it is stirred to react rear cold filtration, solid is washed with dehydrated alcohol, it is dry, obtain bis- (triphenylphosphine) palladium bromides of target product.The present invention is directly with PdCl2, triphenylphosphine and NaBr be raw material, one-step synthesis obtains target product PdBr2(PPh3)2, eliminate intermediate products PdCl2(PPh3)2Synthesis process, reaction process is simple, and synthesis cycle is short, and production cost is low, product yield be greater than 95%, purity be greater than 98%.
Description
Technical field
The invention belongs to organic catalysis, medical synthesis noble metal catalyst preparation technical field, and in particular to Yi Zhongshuan
The preparation method of (triphenylphosphine) palladium bromide.
Background technique
Bis- (triphenylphosphine) palladium bromide [PdBr2(PPh3)2] it is a kind of important catalyst in chemical reaction, organic
It is widely used in catalysis and medicine synthesis, for example, being coupling reaction, aryl is combined to biaryl, formyl is combined to formyl
Amine, oxidation of alkanes at the reactions such as alcoxyl alkene, decarboxylation of fatty acids end alkene effective catalyst.
The synthetic method of current bis- (triphenylphosphine) palladium bromides is to synthesize bis- (triphenylphosphine) palladium chloride [PdCl first2
(PPh3)2] finished product, PdCl is then used again2(PPh3)2It is reacted with NaBr, synthesizes target product PdBr2(PPh3)2.This method is passed through
Two-step reaction, preparation process is comparatively laborious, and production cost is higher.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of bis- (triphenyls
Phosphine) palladium bromide preparation method.This method is directly with PdCl2, triphenylphosphine (PPh3) and NaBr be raw material, one-step synthesis obtains
Target product PdBr2(PPh3)2, eliminate intermediate products PdCl2(PPh3)2Synthesis process, reaction process is simple, synthesis week
Phase is short, and production cost is low, and reaction condition is mild, and product is precipitated with crystal form, and yield is greater than 95%, and purity is greater than 98%.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of system of bis- (triphenylphosphine) palladium bromides
Preparation Method, which comprises the following steps:
Step 1: palladium chloride is dissolved with hydrochloric acid solution, sodium bromide is then added, is 45 DEG C~60 DEG C conditions in temperature
Under be stirred to react 2h~3h；
Step 2: triphenylphosphine dissolved is obtained the different of triphenylphosphine in the in the mixed solvent of isopropanol and chloroform
Propyl alcohol/chloroform soln；
Step 3: the reaction solution after being stirred to react in step 1 is added dropwise to triphen described in step 2 under agitation
In isopropanol/chloroform soln of base phosphine, it is stirred to react 2h~3h under conditions of temperature is 55 DEG C~60 DEG C, reaction terminates
Cold filtration afterwards washs solid with dehydrated alcohol, dry, obtains bis- (triphenylphosphine) palladium bromides of target product.
The preparation method of above-mentioned bis- (triphenylphosphine) palladium bromides of one kind, which is characterized in that palladium chloride described in step 1
Quality and the ratio between the volume of hydrochloric acid solution be 1:(25~30), wherein the unit of quality is g, and the unit of volume is mL.
The preparation method of above-mentioned bis- (triphenylphosphine) palladium bromides of one kind, which is characterized in that hydrochloric acid described in step 1 is molten
The concentration of liquid is 0.5mol/L~0.8mol/L.
The preparation method of above-mentioned bis- (triphenylphosphine) palladium bromides of one kind, which is characterized in that palladium chloride described in step 1
Mass ratio with sodium bromide is 1:(4.6~5.8).
The preparation method of above-mentioned bis- (triphenylphosphine) palladium bromides of one kind, which is characterized in that triphenyl described in step 2
The quality of phosphine is 3.1~3.4 times of palladium chloride quality in step 1.
The preparation method of above-mentioned bis- (triphenylphosphine) palladium bromides of one kind, which is characterized in that triphenyl described in step 2
The ratio between volume of the quality of phosphine, the volume of isopropanol and chloroform is 1:(4~4.4): (2.4~3), the wherein list of quality
Position is g, and the unit of volume is mL.
The preparation method of above-mentioned bis- (triphenylphosphine) palladium bromides of one kind, which is characterized in that drying described in step 3
Temperature is 60 DEG C~80 DEG C, and the dry time is 4h~6h.
Compared with the prior art, the present invention has the following advantages:
1, the present invention is directly with PdCl2, triphenylphosphine (PPh3) and NaBr be raw material, one-step synthesis obtains target product
PdBr2(PPh3)2, eliminate intermediate products PdCl2(PPh3)2Synthesis process, reaction process is simple, and synthesis cycle is short, production
It is at low cost.
2, reaction condition of the present invention is mild, and product is precipitated with crystal form, and yield is greater than 95%, and purity is greater than 98%.
Below by embodiment, technical scheme of the present invention will be described in further detail.
Specific embodiment
Embodiment 1
Step 1: then sodium bromide is added in the hydrochloric acid solution stirring and dissolving of the 20g palladium chloride 0.5mol/L of 600mL
92g is stirred to react 3h under the conditions of 45 DEG C；
Step 2: 68g triphenylphosphine dissolved is obtained in the in the mixed solvent of 300mL isopropanol and 200mL chloroform
Isopropanol/chloroform soln of triphenylphosphine；
Step 3: the reaction solution after being under agitation stirred to react step 1 is added dropwise to triphenyl described in step 2
In isopropanol/chloroform soln of phosphine, it is stirred to react 2h under conditions of temperature is 60 DEG C, after reaction cold filtration,
Solid is washed with dehydrated alcohol, 60 DEG C of dry 6h obtain bis- (triphenylphosphine) the palladium bromide 84.8g of target product, yield 95.1%,
Product purity is 98.9%.
The elemental analysis result of complex manufactured in the present embodiment is C54.34%, H3.91%, Pd13.31%；It is theoretical
Value is C54.68%, H3.82%, Pd13.46%.
Embodiment 2
Step 1: then sodium bromide is added in the hydrochloric acid solution stirring and dissolving of the 20g palladium chloride 0.8mol/L of 500mL
116g is stirred to react 2h under the conditions of 60 DEG C；
Step 2: 62g triphenylphosphine dissolved is obtained in the in the mixed solvent of 250mL isopropanol and 150mL chloroform
Isopropanol/chloroform soln of triphenylphosphine；
Step 3: the reaction solution after being under agitation stirred to react step 1 is added dropwise to triphenyl described in step 2
In isopropanol/chloroform soln of phosphine, it is stirred to react 3h under conditions of temperature is 55 DEG C, after reaction cold filtration,
Solid is washed with dehydrated alcohol, 80 DEG C of dry 4h obtain bis- (triphenylphosphine) the palladium bromide 86.2g of target product, yield 96.7%,
Product purity is 98.6%.
The elemental analysis result of complex manufactured in the present embodiment is C54.49%, H3.69%, Pd13.27%；It is theoretical
Value is C54.68%, H3.82%, Pd13.46%.
Embodiment 3
Step 1: then sodium bromide is added in the hydrochloric acid solution stirring and dissolving of the 20g palladium chloride 0.6mol/L of 550mL
100g is stirred to react 2.5h under the conditions of 55 DEG C；
Step 2: 65g triphenylphosphine dissolved is obtained in the in the mixed solvent of 280mL isopropanol and 170mL chloroform
Isopropanol/chloroform soln of triphenylphosphine；
Step 3: the reaction solution after being under agitation stirred to react step 1 is added dropwise to triphenyl described in step 2
In isopropanol/chloroform soln of phosphine, it is stirred to react 2.5h under conditions of temperature is 58 DEG C, it is cooled after reaction
Filter, washs solid with dehydrated alcohol, 70 DEG C of dry 5h obtain bis- (triphenylphosphine) the palladium bromide 85.6g of target product, yield
96.0%, product purity 98.3%.
The elemental analysis result of complex manufactured in the present embodiment is C54.41%, H3.73%, Pd13.23%；It is theoretical
Value is C54.68%, H3.82%, Pd13.46%.
The above is only presently preferred embodiments of the present invention, not does any restrictions to the present invention, all according to invention skill
Art any simple modification substantially to the above embodiments, change and equivalent structural changes, still fall within the technology of the present invention
In the protection scope of scheme.
Claims (7)
1. a kind of preparation method of bis- (triphenylphosphine) palladium bromides, which comprises the following steps:
Step 1: palladium chloride is dissolved with hydrochloric acid solution, sodium bromide is then added, is stirred under the conditions of temperature is 45 DEG C~60 DEG C
React 2h~3h；
Step 2: by triphenylphosphine dissolved in the in the mixed solvent of isopropanol and chloroform, obtain the isopropanol of triphenylphosphine/
Chloroform soln；
Step 3: the reaction solution after being stirred to react in step 1 is added dropwise to triphenylphosphine described in step 2 under agitation
Isopropanol/chloroform soln in, temperature be 55 DEG C~60 DEG C under conditions of be stirred to react 2h~3h, it is cold after reaction
But it filters, washs solid with dehydrated alcohol, it is dry, obtain bis- (triphenylphosphine) palladium bromides of target product.
2. the preparation method of bis- (triphenylphosphine) palladium bromides of one kind according to claim 1, which is characterized in that in step 1
The ratio between quality and the volume of hydrochloric acid solution of the palladium chloride are 1:(25~30), wherein the unit of quality is g, the unit of volume
For mL.
3. the preparation method of bis- (triphenylphosphine) palladium bromides of one kind according to claim 1, which is characterized in that in step 1
The concentration of the hydrochloric acid solution is 0.5mol/L~0.8mol/L.
4. the preparation method of bis- (triphenylphosphine) palladium bromides of one kind according to claim 1, which is characterized in that in step 1
The mass ratio of the palladium chloride and sodium bromide is 1:(4.6~5.8).
5. the preparation method of bis- (triphenylphosphine) palladium bromides of one kind according to claim 1, which is characterized in that in step 2
The quality of the triphenylphosphine is 3.1~3.4 times of palladium chloride quality in step 1.
6. the preparation method of bis- (triphenylphosphine) palladium bromides of one kind according to claim 1, which is characterized in that in step 2
The ratio between volume of the quality of the triphenylphosphine, the volume of isopropanol and chloroform is 1:(4~4.4): (2.4~3), wherein
The unit of quality is g, and the unit of volume is mL.
7. the preparation method of bis- (triphenylphosphine) palladium bromides of one kind according to claim 1, which is characterized in that in step 3
The temperature of the drying is 60 DEG C~80 DEG C, and the dry time is 4h~6h.
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| CN201910608462.4A CN110330528A (en) | 2019-07-08 | 2019-07-08 | A kind of preparation method of bis- (triphenylphosphine) palladium bromides |
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ID=68143188
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786551A (en) * | 2012-08-08 | 2012-11-21 | 陕西瑞科新材料股份有限公司 | Preparation method of bis-triphenylphosphine palladium dichloride |
| CN102794199A (en) * | 2012-08-08 | 2012-11-28 | 陕西瑞科新材料股份有限公司 | Preparation method of phosphine ligand palladium catalyst |
| CN106243151A (en) * | 2016-09-26 | 2016-12-21 | 天津师范大学 | A kind of improvement synthetic method of palladium complex |
-
2019
- 2019-07-08 CN CN201910608462.4A patent/CN110330528A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786551A (en) * | 2012-08-08 | 2012-11-21 | 陕西瑞科新材料股份有限公司 | Preparation method of bis-triphenylphosphine palladium dichloride |
| CN102794199A (en) * | 2012-08-08 | 2012-11-28 | 陕西瑞科新材料股份有限公司 | Preparation method of phosphine ligand palladium catalyst |
| CN106243151A (en) * | 2016-09-26 | 2016-12-21 | 天津师范大学 | A kind of improvement synthetic method of palladium complex |
Non-Patent Citations (1)
| Title |
|---|
| 刘桂华等: "反式-双(三苯基膦)二氯合钯(Ⅱ)的合成及其结构表征", 《云南化工》 * |
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Application publication date: 20191015 |