CN104177407A - Preparation process of bis (diphenylphosphino) alkane - Google Patents
Preparation process of bis (diphenylphosphino) alkane Download PDFInfo
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- CN104177407A CN104177407A CN201410433201.0A CN201410433201A CN104177407A CN 104177407 A CN104177407 A CN 104177407A CN 201410433201 A CN201410433201 A CN 201410433201A CN 104177407 A CN104177407 A CN 104177407A
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- alkane
- diphenylphosphine
- diphenylphosphino
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Abstract
The invention relates to a preparation process of bis (diphenylphosphino) alkane and belongs to the technical field of synthesis of organic matters. The preparation process comprises the following steps of generating (diphenylphosphino) lithium by reaction of metal lithium and triphenylphosphine in an organic solvent; generating (diphenylphosphino) alkane by reaction of (diphenylphosphino) lithium and water; preparing bis (diphenylphosphino) alkane by reaction of (diphenylphosphino) alkane and dichloroalkane in the presence of an alkaline reagent. The process is simple to operate, the cost of raw materials is low, the yield is high and the process can meet the requirements of industrial production.
Description
Technical field
The present invention designs a kind of preparation technology of catalyst ligand precursor, the preparation technology of a kind of pair of diphenylphosphine alkane of special design.
Background technology
Two diphenylphosphine alkane are metallo-chelates of the industrial widespread use of a class, can be used as the part of homogeneous catalyst.It is an organophosphorus compounds, contains two phosphorus atom, and each phosphorus atom can be used as and join atom and provide lone electron pair to transition metal, is bidentate phosphine ligands.Thereby two transition metal atoms can be coupled together, form double-core bridged complex, make two metal latch in in-plant ligand system.Bidentate phosphine ligands is the optimal ligand of two low-oxidation-state transition metal atoms of bridging.Can be used as the part of metal catalyst, make reaction from the heterogeneous homogeneous phase that changes into, simultaneously with certain selectivity.Two (diphenylphosphino) alkane can with the metal reaction such as nickelous chloride or Palladous chloride, be prepared into homogeneous catalyst, be widely used in the hydrogenating reduction, olefin oxidation, grignard reagent of hydrogenation, the oil of mirbane of industrial catalyzed alkene and coupling of halohydrocarbon etc. and react.
Known two diphenylphosphine alkane comprise at present: 1, two (diphenylphosphine) ethane of 2-, two diphenylphosphine methane, 1, two (diphenylphosphine) propane of 3-, Isosorbide-5-Nitrae-bis-(diphenylphosphine) butane, 1, two (diphenylphosphine) hexanes of 3-etc.
The synthetic method of two diphenylphosphine alkane has:
By metallic lithium and triphenylphosphine reaction, generate diphenylphosphino lithium and phenyl lithium, then low temperature dropping tert-butyl chloride, to decompose phenyl lithium.After sufficient reacting, low temperature drips corresponding two enparas.Generate final product.The method need to be controlled low temperature, need expensive solvent, and reaction yield is very low, and cost is high.Be not to be applicable to the method that industrialization is amplified.
Summary of the invention
This patent provides a kind of new two diphenylphosphine alkane preparation methods, does not use tert-butyl chloride, and yield is high, and cost is low.
Specifically comprise the following steps:
(1) first metallic lithium and triphenylphosphine are reacted in solvent, need to protect under nitrogen atmosphere, after sufficient reacting carries out.In reaction solution, drip pure water, add half an hour, generates diphenylphosphine alkane.
(2) decompression and solvent recovery.
(3) configuration alkaline solution, slowly adds in above-mentioned recovery raffinate.
(4) in this reaction solution, drip two enparas again, be heated to 30 degree～80 degree, be incubated 1 hour, react complete.
(5) filter, and water making beating, wash inorganic salt off
(6) recrystallization obtains product.
This route, by adding water, changes phenylbenzene lithium into diphenylphosphine alkane, avoids using tert-butyl chloride.Alkaline solution can be aqueous sodium hydroxide solution, can be also potassium hydroxide aqueous solution, or lithium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical.
Reaction equation involved in the present invention:
Yield of the present invention is high, and reaction conditions is easy, is easy to industrialization and amplifies.
Embodiment
Can further describe the present invention by the following examples, but the enforcement being not limited to below of the present invention, these embodiment are limit value scope of the present invention never in any form.Some change that those skilled in the art has done within the scope of the claims and adjust and also should think and belong to scope of the present invention.
Embodiment 1
In reaction flask, logical nitrogen, adds 75 milliliters of dry tetrahydrofuran (THF)s, takes 14 grams of lithium sheets, drops in bottle.And then add 26.2 grams of triphenylphosphines.Stirring reaction 3 hours.Solution is scarlet.
Cooling, drips 5.4 grams of water.Within 30 minutes, drip and finish.In solution, adularescent crystallization occurs.Air distillation THF.While being concentrated into 1/3rd volumes, be cooled to room temperature, by 13.75 grams of massfraction 56% potassium hydroxide aqueous solutions, drip into solution, within 15 minutes, drip off.
Drip 4 milliliter 1,2-ethylene dichloride, drips off for 15 minutes, is heated to 50 DEG C, is incubated 1 hour.Cooling adds water 100 milliliters.Stir, filter, dry.
With the mixed solvent recrystallization of toluene ethanol, obtain 18 grams of white crystals.HPLC purity > 98%
Fusing point: 138 DEG C～140 DEG C
Embodiment 2:
In reaction flask, logical nitrogen, adds 80 milliliters of dry tetrahydrofuran (THF)s, takes 14 grams of lithium sheets, drops in bottle.And then add 26.2 grams of triphenylphosphines.Stirring reaction 3 hours.Solution is scarlet.
Cool to 0 DEG C, drip 5.4 grams of water.Within 30 minutes, drip and finish.In solution, adularescent crystallization occurs.Air distillation THF.While being concentrated into 1/3rd volumes, be cooled to room temperature, by 14 grams of massfraction 56% potassium hydroxide aqueous solutions, drip into solution, within 15 minutes, drip off.
Drip 4.8 milliliter 1,3-propylene dichloride, drips off for 15 minutes, is heated to 50 DEG C, is incubated 2 hours.Cooling adds water 100 milliliters.Stir, filter, dry.
With the mixed solvent recrystallization of toluene ethanol, obtain 17.4 grams of white crystals.HPLC purity > 98%
Fusing point: 63 DEG C-65 DEG C
Embodiment 3:
In reaction flask, logical nitrogen, adds 80 milliliters of dry tetrahydrofuran (THF)s, takes 14 grams of lithium sheets, drops in bottle.And then add 26.2 grams of triphenylphosphines.Stirring reaction 3 hours.Solution is scarlet.
Cool to 0 DEG C, drip 5.4 grams of water.Within 30 minutes, drip and finish.In solution, adularescent crystallization occurs.Air distillation THF.While being concentrated into 1/3rd volumes, be cooled to room temperature, by 14 grams of massfraction 56% potassium hydroxide aqueous solutions, drip into solution, within 15 minutes, drip off.
Drip 5.6 milliliters of Isosorbide-5-Nitrae-dichlorobutane, within 15 minutes, drip off, be heated to 50 DEG C, be incubated 3 hours.Cooling adds water 100 milliliters.Stir, filter, dry.
By re-crystallizing in ethyl acetate, obtain 17.8 grams of white crystals.HPLC purity > 98%
130℃——137℃。
Claims (5)
1. the synthesis technique of two (diphenylphosphine) alkane, its step is as follows:
(1) metallic lithium reacts in organic solvent with triphenyl phosphorus, generates diphenylphosphino lithium
(2) diphenylphosphino lithium reacts with water and generates diphenylphosphine alkane
(3) diphenylphosphine alkane makes two (diphenylphosphine) base alkane of formula (2) under the existence of alkaline reagents with the dichloro alkane reaction of formula (1)
Formula (1) Cl-R-Cl
Formula (2)
Wherein R is the alkyl that contains 1-6 carbon atom.
2. the synthesis technique of two (diphenylphosphine) base alkane according to claim 1, is characterized in that the preparation of diphenylphosphine alkane in above-mentioned steps (2), and reagent used is water.
3. the synthesis technique of two (diphenylphosphine) base alkane according to claim 1, it is characterized in that the alkaline reagents selection sodium hydroxide in above-mentioned steps (3), potassium hydroxide, lithium hydroxide, salt of wormwood, sodium carbonate, triethylamine, any one in Trimethylamine 99 is as reaction reagent.
4. alkaline reagents according to claim 3, is characterized in that alkaline reagents is configured to the certain density aqueous solution and uses.
5. according to claim 4, the mass concentration that it is characterized in that this aqueous solution is 20%-80%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111235A (en) * | 2015-08-14 | 2015-12-02 | 张玉清 | Alkyl diphenylphosphine and method for preparing alkyl diphenylphosphine with co-production of alkylbenzene |
| CN110041363A (en) * | 2019-05-08 | 2019-07-23 | 天津格林泰格科技有限公司 | A kind of preparation process of double diphenylphosphine alkane |
| CN112321639A (en) * | 2020-11-10 | 2021-02-05 | 河南省科学院化学研究所有限公司 | Preparation method of aryl diphenylphosphine derivative |
| WO2023017841A1 (en) | 2021-08-11 | 2023-02-16 | 国立研究開発法人科学技術振興機構 | Novel method for producing compound, novel compound, and metal catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020674A (en) * | 2009-09-12 | 2011-04-20 | 陈琪 | Process for synthesizing bis(diphenylphosphino)-alkane |
-
2014
- 2014-08-29 CN CN201410433201.0A patent/CN104177407A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020674A (en) * | 2009-09-12 | 2011-04-20 | 陈琪 | Process for synthesizing bis(diphenylphosphino)-alkane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111235A (en) * | 2015-08-14 | 2015-12-02 | 张玉清 | Alkyl diphenylphosphine and method for preparing alkyl diphenylphosphine with co-production of alkylbenzene |
| CN105111235B (en) * | 2015-08-14 | 2017-04-19 | 张玉清 | Alkyl diphenylphosphine and method for preparing alkyl diphenylphosphine with co-production of alkylbenzene |
| CN110041363A (en) * | 2019-05-08 | 2019-07-23 | 天津格林泰格科技有限公司 | A kind of preparation process of double diphenylphosphine alkane |
| CN112321639A (en) * | 2020-11-10 | 2021-02-05 | 河南省科学院化学研究所有限公司 | Preparation method of aryl diphenylphosphine derivative |
| WO2023017841A1 (en) | 2021-08-11 | 2023-02-16 | 国立研究開発法人科学技術振興機構 | Novel method for producing compound, novel compound, and metal catalyst |
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Application publication date: 20141203 |