CN102603811B - Synthetic method of [1,1'- bis-(diphenyl phosphine) ferrocene] palladium dichloride methylene dichloride complex - Google Patents
Synthetic method of [1,1'- bis-(diphenyl phosphine) ferrocene] palladium dichloride methylene dichloride complex Download PDFInfo
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- CN102603811B CN102603811B CN201210041027.6A CN201210041027A CN102603811B CN 102603811 B CN102603811 B CN 102603811B CN 201210041027 A CN201210041027 A CN 201210041027A CN 102603811 B CN102603811 B CN 102603811B
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- methylene dichloride
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Abstract
The invention discloses a synthetic method of a [1,1'- bis-(diphenyl phosphine) ferrocene] palladium dichloride methylene dichloride complex. The synthetic method comprises the following steps of: dissolving sodium chloropalladite to absolute ethyl alcohol to obtain an ethanol solution of the sodium chloropalladite; dissolving 1,1'- bis-(diphenyl phosphine) ferrocene to methylene dichloride to obtain a methylene dichloride solution of the 1,1'- bis-(diphenyl phosphine) ferrocene; and dropwise adding the ethanol solution of the sodium chloropalladite to the methylene dichloride solution of the 1,1'- bis-(diphenyl phosphine) ferrocene for stirring, reacting and filtering to obtain orange red [1,1'- bis-(diphenyl phosphine) ferrocene] palladium dichloride methylene dichloride complex crystal. In the synthetic method, the methylene dichloride is directly used as a solvent, a target product of the solvent complex is obtained through one-step synthesis, the reaction process is simple, the synthetic cycle is short, the production cost is low, the operation is easy, the reaction condition is mild, the product is precipitated in a crystal form, the purity is larger than 99%, and the yield is larger than 90%.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to the synthetic method of a kind of [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound.
Background technology
Take bidentate phosphine ligands as main various phosphine bridge transition dinuclear complexs are because its structure is special, have novel catalytic perfomance, thereby cause investigator's very big interest, ferrocene has also been subject to people's extensive concern with its special molecular structure.1,1 '-bis-(diphenylphosphine) ferrocene (dppf) is the Novel Ligands that organic bidentate phosphine ligands is combined with ferrocene, there is specific flexible back bone, can form various bimetals and multi-metal complex with another transition metal atoms.This class title complex is widely used in the reactions such as silicon hydrogen addition of catalytic hydrogenation, C-C coupling, ketone.
[1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound (Pd (dppf) Cl
2cH
2cl
2) be the bimetal solvent complex that Pd (II) and dppf form, for catalyzed carbonylation, cross-couplings and suzuki reaction etc.At present, the synthetic method of solvent complex compounds is generally: first synthetic presoma is (as PdCl
2(dppf)), then by presoma at corresponding solvent (as CH
2cl
2) in recrystallization obtain.The preparation process of this approach is more loaded down with trivial details, and production cost is higher.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, and the synthetic method of a kind of [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound is provided.The method directly be take methylene dichloride as solvent, and one-step synthesis obtains target product [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound of solvent complex thing, has saved presoma PdCl
2(dppf) building-up process, reaction process is simple, and synthesis cycle is short, and production cost is low, easy to operate, and reaction conditions is gentle, and product is separated out with crystalline form, and purity is greater than 99%, and yield is greater than 90%.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the synthetic method of a kind of [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound, it is characterized in that, and the method comprises the following steps:
Step 1, sodium chloropalladite is dissolved in dehydrated alcohol, obtains the ethanolic soln of sodium chloropalladite;
Step 2,1,1 '-bis-(diphenylphosphine) ferrocene is dissolved in methylene dichloride, obtains the dichloromethane solution of 1,1 '-bis-(diphenylphosphine) ferrocene;
Step 3, under agitation condition, the ethanolic soln of sodium chloropalladite described in step 1 is dripped in described in step 21, in the dichloromethane solution of 1 '-bis-(diphenylphosphine) ferrocene, in temperature, be stirring reaction 1h～4h under the condition of 25 ℃～35 ℃, reaction finishes rear filtering reacting liquid, obtain orange red [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound crystallization; The mol ratio of described sodium chloropalladite and 1,1 '-bis-(diphenylphosphine) ferrocene is 1: 1.1～1.2.
The synthetic method of above-mentioned [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound, the consumption of dehydrated alcohol described in step 1 is every gram of dehydrated alcohol of 10mL～20mL for sodium chloropalladite.
The synthetic method of above-mentioned [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound, the consumption of methylene dichloride described in step 2 is every gram 1,1 '-bis-(diphenylphosphines) 5mL～10mL methylene dichloride for ferrocene.
The present invention compared with prior art has the following advantages:
1, the present invention directly be take methylene dichloride as solvent, and one-step synthesis obtains target product [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound of solvent complex thing, has saved presoma PdCl
2(dppf) building-up process, reaction process is simple, and synthesis cycle is short, and production cost is low, easy to operate.
2, reaction conditions of the present invention is gentle, and product is separated out with crystalline form, and purity is greater than 99%, and yield is greater than 90%.
Below in conjunction with drawings and Examples, technical solution of the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is dppf, PdCl
2and synthetic [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound three's of the embodiment of the present invention 1 infrared spectrum (dppf).
Embodiment
Embodiment 1
Step 1,2.00 grams of sodium chloropalladites are dissolved in 30mL dehydrated alcohol, obtain the ethanolic soln of sodium chloropalladite;
Step 2,4.15 gram 1,1 '-bis-(diphenylphosphine) ferrocene is dissolved in 41mL methylene dichloride, obtains the dichloromethane solution of 1,1 '-bis-(diphenylphosphine) ferrocene;
Step 3, under agitation condition, the ethanolic soln of sodium chloropalladite described in step 1 is dripped in described in step 21, in the dichloromethane solution of 1 '-bis-(diphenylphosphine) ferrocene, in temperature, be stirring reaction 1h under the condition of 25 ℃, reaction finishes rear filtering reacting liquid, obtain 5.01 grams orange red [1,1 '-bis-(diphenylphosphine) ferrocene] crystallization of palladium chloride methylene dichloride complex compound, yield 90.46%.
The present embodiment directly be take methylene dichloride as solvent, and one-step synthesis obtains target product [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound of solvent complex thing, has saved presoma PdCl
2(dppf) building-up process, reaction process is simple, and synthesis cycle is short, easy to operate, and synthetic product purity reaches 99.4%, and yield reaches 90.46%.
Fig. 1 is part dppf (1,1 '-bis-(diphenylphosphine) ferrocene), title complex PdCl
2(dppf) ([1,1 '-bis-(diphenylphosphino) ferrocene] palladium chloride) and the synthetic PdCl of the present embodiment
2(dppf) CH
2cl
2the infrared spectrum of (i.e. [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound), 1479cm in figure
-1, 1165cm
-1and 745cm
-1belong to the absorption vibration peak of phenyl ring, 1434cm
-1and 828cm
-1belong to the substituent absorption vibration peak of cyclopentadienyl, with PdCl
2(dppf) compare, at 721cm
-1and 1269cm
-1there is absorption peak in place, belong to respectively C-Cl absorption peak and because of be close to that Cl strengthens-CH
2-wagging vibration absorption peak.
Embodiment 2
Step 1,2.00 grams of sodium chloropalladites are dissolved in 40mL dehydrated alcohol, obtain the ethanolic soln of sodium chloropalladite;
Step 2,4.52 gram 1,1 '-bis-(diphenylphosphine) ferrocene is dissolved in 45mL methylene dichloride, obtains the dichloromethane solution of 1,1 '-bis-(diphenylphosphine) ferrocene;
Step 3, under agitation condition, the ethanolic soln of sodium chloropalladite described in step 1 is dripped in described in step 21, in the dichloromethane solution of 1 '-bis-(diphenylphosphine) ferrocene, in temperature, be stirring reaction 1h under the condition of 25 ℃, reaction finishes rear filtering reacting liquid, obtain 5.02 grams orange red [1,1 '-bis-(diphenylphosphine) ferrocene] crystallization of palladium chloride methylene dichloride complex compound, yield 90.64%.
The present embodiment directly be take methylene dichloride as solvent, and one-step synthesis obtains target product [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound of solvent complex thing, has saved presoma PdCl
2(dppf) building-up process, reaction process is simple, and synthesis cycle is short, easy to operate, and synthetic product purity reaches 99.8%, and yield reaches 90.64%.
Embodiment 3
Step 1,2.00 grams of sodium chloropalladites are dissolved in 20mL dehydrated alcohol, obtain the ethanolic soln of sodium chloropalladite;
Step 2,4.15 gram 1,1 '-bis-(diphenylphosphine) ferrocene is dissolved in 21mL methylene dichloride, obtains the dichloromethane solution of 1,1 '-bis-(diphenylphosphine) ferrocene;
Step 3, under agitation condition, the ethanolic soln of sodium chloropalladite described in step 1 is dripped in described in step 21, in the dichloromethane solution of 1 '-bis-(diphenylphosphine) ferrocene, in temperature, be stirring reaction 2h under the condition of 25 ℃, reaction finishes rear filtering reacting liquid, obtain 5.20 grams orange red [1,1 '-bis-(diphenylphosphine) ferrocene] crystallization of palladium chloride methylene dichloride complex compound, yield 93.89%.
The present embodiment directly be take methylene dichloride as solvent, and one-step synthesis obtains target product [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound of solvent complex thing, has saved presoma PdCl
2(dppf) building-up process, reaction process is simple, and synthesis cycle is short, easy to operate, and synthetic product purity reaches 99.8%, and yield reaches 93.89%.
Embodiment 4
Step 1,2.00 grams of sodium chloropalladites are dissolved in 30mL dehydrated alcohol, obtain the ethanolic soln of sodium chloropalladite;
Step 2,4.15 gram 1,1 '-bis-(diphenylphosphine) ferrocene is dissolved in 41mL methylene dichloride, obtains the dichloromethane solution of 1,1 '-bis-(diphenylphosphine) ferrocene;
Step 3, under agitation condition, the ethanolic soln of sodium chloropalladite described in step 1 is dripped in described in step 21, in the dichloromethane solution of 1 '-bis-(diphenylphosphine) ferrocene, in temperature, be stirring reaction 1h under the condition of 35 ℃, reaction finishes rear filtering reacting liquid, obtain 5.32 grams orange red [1,1 '-bis-(diphenylphosphine) ferrocene] crystallization of palladium chloride methylene dichloride complex compound, yield 96.05%.
The present embodiment directly be take methylene dichloride as solvent, and one-step synthesis obtains target product [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound of solvent complex thing, has saved presoma PdCl
2(dppf) building-up process, reaction process is simple, and synthesis cycle is short, easy to operate, and synthetic product purity reaches 99.1%, and yield reaches 96.05%.
Embodiment 5
Step 1,2.00 grams of sodium chloropalladites are dissolved in 30mL dehydrated alcohol, obtain the ethanolic soln of sodium chloropalladite;
Step 2,4.15 gram 1,1 '-bis-(diphenylphosphine) ferrocene is dissolved in 30mL methylene dichloride, obtains the dichloromethane solution of 1,1 '-bis-(diphenylphosphine) ferrocene;
Step 3, under agitation condition, the ethanolic soln of sodium chloropalladite described in step 1 is dripped in described in step 21, in the dichloromethane solution of 1 '-bis-(diphenylphosphine) ferrocene, in temperature, be stirring reaction 4h under the condition of 25 ℃, reaction finishes rear filtering reacting liquid, obtain 5.26 grams orange red [1,1 '-bis-(diphenylphosphine) ferrocene] crystallization of palladium chloride methylene dichloride complex compound, yield 94.97%.
The present embodiment directly be take methylene dichloride as solvent, and one-step synthesis obtains target product [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound of solvent complex thing, has saved presoma PdCl
2(dppf) building-up process, reaction process is simple, and synthesis cycle is short, easy to operate, and synthetic product purity reaches 99.2%, and yield reaches 94.97%.
Embodiment 6
Step 1,20.00 grams of sodium chloropalladites are dissolved in 300mL dehydrated alcohol, obtain the ethanolic soln of sodium chloropalladite;
Step 2,41.5 gram 1,1 '-bis-(diphenylphosphine) ferrocene is dissolved in 415mL methylene dichloride, obtains the dichloromethane solution of 1,1 '-bis-(diphenylphosphine) ferrocene;
Step 3, under agitation condition, the ethanolic soln of sodium chloropalladite described in step 1 is dripped in described in step 21, in the dichloromethane solution of 1 '-bis-(diphenylphosphine) ferrocene, in temperature, be stirring reaction 4h under the condition of 35 ℃, reaction finishes rear filtering reacting liquid, obtain 53.14 grams orange red [1,1 '-bis-(diphenylphosphine) ferrocene] crystallization of palladium chloride methylene dichloride complex compound, yield 95.95%.
The present embodiment directly be take methylene dichloride as solvent, and one-step synthesis obtains target product [1,1 '-bis-(diphenylphosphine) ferrocene] the palladium chloride methylene dichloride complex compound of solvent complex thing, has saved presoma PdCl
2(dppf) building-up process, reaction process is simple, and synthesis cycle is short, easy to operate, and synthetic product purity reaches 99.2%, and yield reaches 95.95%.
The above; it is only preferred embodiment of the present invention; not the present invention is done to any restriction, every any simple modification of above embodiment being done according to invention technical spirit, change and equivalent structure change, and all still belong in the protection domain of technical solution of the present invention.
Claims (1)
1. the synthetic method of one kind [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound, is characterized in that, the method comprises the following steps:
Step 1, sodium chloropalladite is dissolved in dehydrated alcohol, obtains the ethanolic soln of sodium chloropalladite; The consumption of described dehydrated alcohol is every gram of dehydrated alcohol of 10mL～20mL for sodium chloropalladite;
Step 2,1,1 '-bis-(diphenylphosphine) ferrocene is dissolved in methylene dichloride, obtains the dichloromethane solution of 1,1 '-bis-(diphenylphosphine) ferrocene;
Step 3, under agitation condition, the ethanolic soln of sodium chloropalladite described in step 1 is dripped in described in step 21, in the dichloromethane solution of 1 '-bis-(diphenylphosphine) ferrocene, in temperature, be stirring reaction 1h～4h under the condition of 25 ℃～35 ℃, reaction finishes rear filtering reacting liquid, obtain orange red [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride methylene dichloride complex compound crystallization; The mol ratio of described sodium chloropalladite and 1,1 '-bis-(diphenylphosphine) ferrocene is 1: 1.1～1.2;
The consumption of methylene dichloride described in step 2 is every gram 1,1 '-bis-(diphenylphosphines) 5mL～10mL methylene dichloride for ferrocene.
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| CN110194781B (en) * | 2018-02-27 | 2023-12-08 | 上海奥普迪诗化学科技有限公司 | Preparation method of 1,1' -bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex |
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| CN101503428A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Method for preparing platinum complex |
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| US6248892B1 (en) * | 1998-07-11 | 2001-06-19 | Clariant Gmbh | Process for preparing arylpyridines |
| CN101503428A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Method for preparing platinum complex |
Non-Patent Citations (4)
| Title |
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| 1,1’-Bis[(alkyl/aryl)phosphino]ferrocenes: synthesis and metal complex formation-Crystal structure of three metal complexes of Fe(η5-C5H4PPh2)2;Ian R.Butler等,;《Organometallics》;19850630;第4卷(第6期);第972-980页，尤其是第973页右栏 * |
| Geraldo M. de Lima等,.Tin,palladium and platinum derivatives of 1,1’-bis(diphenylphosphine)ferrocene.Crystal and molecular structures of 1,1’-bis-(diphenylphosphine)ferrocenedichloropalladium(II) and of 1,1’-bis(diphenylphosphine)ferrocenedichloroplatinum(II).《Transition Met. Chem.》.1995,第20卷(第4期),第380-383页,尤其是第380页右栏第2段,第383页左栏图1. * |
| Ian R.Butler等,.1,1’-Bis[(alkyl/aryl)phosphino]ferrocenes: synthesis and metal complex formation-Crystal structure of three metal complexes of Fe(η5-C5H4PPh2)2.《Organometallics》.1985,第4卷(第6期),第972-980页，尤其是第973页右栏. |
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Address after: 710201 Xi'an Province Economic and Technological Development Zone, Jing Wei Jing Jing Road, West Road, No. 6, No. Patentee after: XI'AN CATALYST NEW MATERIALS CO., LTD. Address before: Weiyang road 710016 Shaanxi city of Xi'an province No. 96 Patentee before: Xi'An Catalyst Chemical Co., Ltd. |