CN102627668A - Preparation method of triphenylphosphine - Google Patents
Preparation method of triphenylphosphine Download PDFInfo
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- CN102627668A CN102627668A CN2012100747449A CN201210074744A CN102627668A CN 102627668 A CN102627668 A CN 102627668A CN 2012100747449 A CN2012100747449 A CN 2012100747449A CN 201210074744 A CN201210074744 A CN 201210074744A CN 102627668 A CN102627668 A CN 102627668A
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Abstract
The invention discloses a preparation of a compound, and concretely relates to a preparation method of triphenylphosphine. The preparation method comprises the following steps: reacting by adding potassium hydroxide or sodium hydroxide which is used as a solute to dimethyl sulfoxide which is used as a solvent, and reacting by inletting a phosphine gas to a reaction container; adding a chlorobenzene solution to the reaction container, and continuously reacting; and filtering reaction products after ending above reaction, and carrying out reduced pressure distillation on the resulting clear liquid to obtain triphenylphosphine. The preparation method of the invention has the advantages of realization of comprehensive utilization of above exhaust gas, simple entire process flow, safe production process, good benefit from economy, and high product purity.
Description
Technical field
The present invention relates to a kind of preparation method of compound, specifically be meant a kind of preparation method of triphenylphosphine.
Technical background
Triphenylphosphine is the basic material of rhodium phosphine complex catalyst, and wide purposes is arranged in the petrochemical complex at home.Triphenylphosphine also is applied to fields such as medicine industry, organic synthesis, analysis.Triphenylphosphine also can be used as glossing agent, the high molecular polymerization of dye technology, the oxidation inhibitor of colour film developing, gathers epoxidised stablizer, also can be used as analytical reagent.These article are colourless to faint yellow monoclinic crystal when being lower than room temperature, are colourless to faint yellow transparent oily liquid when being higher than room temperature, and irritating smell is arranged; Skin there is pungency, about 22 ℃ of m.p., b.p.360 ℃ (0.1MPa); ND 1.589; Specific density 1.184 (20 ℃) can be miscible with alcohol, ether, benzene and acetone and other organic solvent, water insoluble.
Present existing working method all is to add sodium or add the technology of magnesium with phosphorus trichloride; In addition, the method for producing triphenylphosphine has: Knut Fridell-Kerafyrm thatch method, with the direct back flow reaction of sulphur, phosphorus trichloride and benzene, generate triphenyl phosphine sulfide compound, and get triphenylphosphine through iron powder reducing again.
Bromobenzene carries out the phosphine reaction with phosphorus trichloride and obtains triphenyl phosphine behind grignard reaction.Its preparation method is to be raw material with phenol and phosphorus trichloride, after esterification, again through underpressure distillation, promptly obtains the product triphenyl phosphite.
3C6H5OH+PCl3[15～20℃]→(C3H5O)3P+3HCl
Concrete technology is divided two kinds of interrupter method and continuous processings.
(1) interrupter method
Phenol is added in the reactor drum, and warm fusing back adds phosphorus trichloride, begins reaction with phenol at 70～90 ℃, and after phosphorus trichloride adds, reaction mixture temperature will rise to about 150 ℃; Dissolved hydrogenchloride and unreacted phenol are removed in decompression at high temperature, promptly get product.
(2) adopt tower reactor
Phenol is got into from the condensing surface below, top of tower, and phosphorus trichloride gets into from the susceptor top, bottom of tower.The two reacts in tower, and product collection is in susceptor, and byproduct hydrogen chloride is introduced the absorption tower through upper end of condenser.Thick ester waits to handle through distillation and promptly gets product.
Yet; Produce problems such as pollution, process is complicated, reaction efficiency is not high in the aforesaid method production process; In the production process of phosphatization, producing a large amount of phosphuret-(t)ed hydrogen industrial gaseous wastees, generally is to absorb preparation phosphoric acid, the low and contaminate environment of added value through roasting kiln burning back water.
Summary of the invention
The objective of the invention is to the waste gas comprehensive utilization, technical process is simple, production process safety; Profitable; The method for preparing triphenylphosphine that product purity is high can replace original expensive starting raw material fully, and product cost is obviously reduced; Play the effect of administering environment simultaneously, the present invention directly makes with the chlorobenzene reaction with phosphine gas.
The present invention is achieved through following technical proposals:
A kind of preparation method of triphenylphosphine is characterized in that comprising the steps:
(1) with the DMSO 99.8MIN. is solvent, is that solute joins in the solvent with Pottasium Hydroxide or sodium hydroxide, and places sealed reaction vessel to solution; Use the inert gas replacement air then, or vacuumize;
(2) feeding phosphine gas in the reaction vessel reacts;
(3) in reaction vessel, add chlorobenzene solution more again, proceed reaction;
(4) after reaction finished, the filtering reaction thing carried out underpressure distillation with clear liquid, obtains triphenylphosphine.
As preferably, the solvent in the preparing method's of above-mentioned a kind of triphenylphosphine the step (1) and the mass ratio of solute are 8～12: 1.As better selection, wherein the mass ratio of solvent and solute is 9: 1.
As preferably; In the reaction vessel air of the preparing method's of above-mentioned a kind of triphenylphosphine step (1) and the mixed gas of rare gas element; The mass content of air is less than 2%; Rare gas element wherein is a nitrogen, mainly is for problem such as prevent that air and phosphine gas from can blast under certain condition, so come the air in the replacement(metathesis)reaction container through adding rare gas element.
As preferably, solution stirs earlier, heats up in the preparing method's of above-mentioned a kind of triphenylphosphine the step (1), and then feeds rare gas element or vacuumize; Wherein solution temperature is raised to 50 ℃～60 ℃.
As preferably; The quality that adds chlorobenzene in the preparing method's of above-mentioned a kind of triphenylphosphine the step (3) be in the step (1) solution quality 10%～25%, with continue in the reaction process, continue to keep feeding phosphine gas; Can make like this and react carry out more thorough, efficient is higher.For better realization response, 7 being reflected between 95 ℃～110 ℃ in step (3) are carried out, and keep reaction more than 4 hours; Stop to feed phosphine gas then, finish, and feed nitrogen phosphuret-(t)ed hydrogen discharge in the reaction vessel as reaction; Generally speaking, control is reflected at 4～8 hours and can have fully reacted, and this is also relevant with temperature etc. certainly; So in of the present invention step, adopted specific temperature can obtain better effect.
As preferably, the triphenylphosphine that obtains in the preparing method's of above-mentioned a kind of triphenylphosphine the step (4) put into toluene solution wash, again through underpressure distillation; Product after will distilling is again put into crystallization in the absolute ethyl alcohol, obtains the elaboration triphenylphosphine.This step is to reacting the treating process after the completion, can obtaining more high-quality product.Wherein clear liquid carries out the dimethyl sulfoxide solvent that underpressure distillation obtains and carries out reuse, though in DMSO 99.8MIN., contain solute, chlorobenzene etc., these are because content is less, thus can not have influence on the carrying out that reacts among the present invention, and yield of product; More main is that the present invention can realize environmental requirement, can not produce pollutents such as waste gas, waste liquid.
Beneficial effect: produce triphenylphosphine through the present invention, can realize the waste gas comprehensive utilization, and whole process flow is simple, production process safety, profitable in view of economy, product purity is high.
Embodiment
Specify in the face of enforcement of the present invention down:
Embodiment 1
500 milliliters of solvent DMSO 99.8MIN.s are joined in the flask with four necks,round bottom; Added for 60 gram Pottasium Hydroxide stirring reaction for some time again, feed nitrogen then, the air in the reaction vessel is discharged; Feed phosphine gas again in the reaction vessel and react certain hour; Add chlorobenzene solution again in the reaction soln and react for 100 milliliters, at last reactant is filtered, clear liquid is distilled promptly obtain triphenylphosphine bullion 59 grams.
Embodiment 2
500 milliliters of solvent DMSO 99.8MIN.s are joined in the flask with four necks,round bottom, added for 60 gram Pottasium Hydroxide stirring reaction half a hour again, be warming up to 50 ℃; Feed the nitrogen air in the flask of draining again; Mass content up to its air is lower than 2%; Feed phosphine gas again and add 100 milliliters of chlorobenzenes after half a hour, and be warming up to 100 ℃ and reacted 6 hours, stop to stir and turn off phosphine gas; Feed nitrogen unnecessary phosphine gas is discharged, reaction finishes; The reactant filtering separation is obtained clear liquid, and solids is that Repone K refilters for one time with 200 milliliters of DMSO 99.8MIN. washings, and solid obtains Repone K 73 grams of technical grade through oven dry; All clear liquids are put into 1000 milliliters of there-necked flask underpressure distillation; Add dimethyl sulfoxide solvent; Obtain bottle interior product 58 gram triphenylphosphines; Again triphenylphosphine is put in 500 ml flasks and added 170 milliliters of toluene agitator treatings again after the underpressure distillation, again the still bed material is put into crystallization in the flask that 200 milliliters of absolute ethyl alcohols are housed, obtained 48 gram triphenylphosphines; Analyzing content through gas chromatograph is 99.7%, has a small amount of chlorobenzene and Pottasium Hydroxide to remain in the dimethyl sulfoxide solvent and can be recycled.Do not influence production.
Embodiment 3
500 milliliters of solvent DMSO 99.8MIN.s are joined in the flask with four necks,round bottom, added for 60 gram sodium hydroxide stirring reaction half a hour again, be warming up to 60 ℃; Feed the nitrogen air in the flask of draining again; Mass content up to its air is lower than 2%; Feed phosphine gas again and add 110 milliliters of chlorobenzenes after half a hour, and be warming up to 110 ℃ and reacted 5 hours, stop to stir and turn off phosphine gas; Feed nitrogen unnecessary phosphine gas is discharged, reaction finishes; The reactant filtering separation is obtained clear liquid, and solids is that sodium-chlor refilters for one time with 220 milliliters of DMSO 99.8MIN. washings, and solid obtains sodium-chlor 72 grams of technical grade through oven dry; All clear liquids are put into 1000 milliliters of there-necked flask underpressure distillation; Add dimethyl sulfoxide solvent; Obtain bottle interior product 57 gram triphenylphosphines; Again triphenylphosphine is put in 500 ml flasks and added 180 milliliters of toluene agitator treatings again after the underpressure distillation, again the still bed material is put into crystallization in the flask that 200 milliliters of absolute ethyl alcohols are housed, obtained 47 gram triphenylphosphines; Analyzing content through gas chromatograph is 99.5%, has a small amount of chlorobenzene and Pottasium Hydroxide to remain in the dimethyl sulfoxide solvent and can be recycled.Do not influence production.
Embodiment 4
500 milliliters of solvent DMSO 99.8MIN.s are joined in the flask with four necks,round bottom, added for 65 gram Pottasium Hydroxide stirring reaction half a hour again, be warming up to 55 ℃; Feed the nitrogen air in the flask of draining again; Mass content up to its air is lower than 2%; Feed phosphine gas again and add 120 milliliters of chlorobenzenes after half a hour, and be warming up to 105 ℃ and reacted 6 hours, stop to stir and turn off phosphine gas; Feed nitrogen unnecessary phosphine gas is discharged, reaction finishes; The reactant filtering separation is obtained clear liquid, and solids is that Repone K refilters for one time with 200 milliliters of DMSO 99.8MIN. washings, and solid obtains Repone K 75 grams of technical grade through oven dry; All clear liquids are put into 1000 milliliters of there-necked flask underpressure distillation; Add dimethyl sulfoxide solvent; Obtain bottle interior product 60 gram triphenylphosphines; Again triphenylphosphine is put in 500 ml flasks and added 200 milliliters of toluene agitator treatings again after the underpressure distillation, again the still bed material is put into crystallization in the flask that 250 milliliters of absolute ethyl alcohols are housed, obtained 50 gram triphenylphosphines; Analyzing content through gas chromatograph is 99.7%, has a small amount of chlorobenzene and Pottasium Hydroxide to remain in the dimethyl sulfoxide solvent and can be recycled.Do not influence production.
Claims (9)
1. the preparation method of a triphenylphosphine is characterized in that comprising the steps:
(1) with the DMSO 99.8MIN. is solvent, is that solute joins in the solvent with Pottasium Hydroxide or sodium hydroxide, and places sealed reaction vessel to solution; Use the inert gas replacement air then, or vacuumize;
(2) feeding phosphine gas in the reaction vessel reacts;
(3) in reaction vessel, add chlorobenzene solution more again, proceed reaction;
(4) after reaction finished, the filtering reaction thing carried out underpressure distillation with clear liquid, obtains triphenylphosphine.
2. the preparation method of a kind of triphenylphosphine according to claim 1 is characterized in that solvent and the mass ratio of solute in the step (1) is 8～12: 1.
3. the preparation method of a kind of triphenylphosphine according to claim 2 is characterized in that solvent and the mass ratio of solute in the step (1) is 9: 1.
4. the preparation method of a kind of triphenylphosphine according to claim 1 is characterized in that the mass content of air is less than 2% in the mixed gas of reaction vessel air and rare gas element of step (1), and rare gas element wherein is a nitrogen.
5. the preparation method of a kind of triphenylphosphine according to claim 1 is characterized in that solution stirs earlier, heats up in the step (1), and then feeds rare gas element or vacuumize; Wherein solution temperature is raised to 50 ℃～60 ℃.
6. the preparation method of a kind of triphenylphosphine according to claim 1, the quality that it is characterized in that adding in the step (3) chlorobenzene be in the step (1) solution quality 10%～25%, with continue in the reaction process, continue to keep feeding phosphine gas.
7. the preparation method of a kind of triphenylphosphine according to claim 6; It is characterized in that being reflected between 95 ℃～110 ℃ in the step (3) carry out; Keep reaction more than 4 hours, stop to feed phosphine gas then, and feed nitrogen phosphuret-(t)ed hydrogen discharge in the reaction vessel.
8. the preparation method of a kind of triphenylphosphine according to claim 1, it is characterized in that the triphenylphosphine that obtains in the step (4) put into toluene solution wash, again through underpressure distillation; Product after will distilling is again put into crystallization in the absolute ethyl alcohol, obtains the elaboration triphenylphosphine.
9. the preparation method of a kind of triphenylphosphine according to claim 1 is characterized in that in the step (4) that clear liquid is carried out the dimethyl sulfoxide solvent that underpressure distillation obtains carries out reuse.
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| CN2012100747449A CN102627668A (en) | 2012-03-20 | 2012-03-20 | Preparation method of triphenylphosphine |
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| CN2012100747449A CN102627668A (en) | 2012-03-20 | 2012-03-20 | Preparation method of triphenylphosphine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910207A (en) * | 2015-02-12 | 2015-09-16 | 天津墨森科技有限公司 | Preparation method of di (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide |
| CN109553639A (en) * | 2018-12-11 | 2019-04-02 | 河南省科学院化学研究所有限公司 | A method of synthesis tri-tert-butylphosphine |
| CN109970789A (en) * | 2019-04-25 | 2019-07-05 | 大连理工大学 | A kind of preparation method of triaryl phosphine compound |
| CN113533591A (en) * | 2021-06-18 | 2021-10-22 | 山东罗欣药业集团恒欣药业有限公司 | GC analysis method for benzene and paraldehyde in cefprozil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268479A (en) * | 1991-12-14 | 1993-12-07 | Hoechst Aktiengesellschaft | Process for the preparation of tertiary phosphines |
-
2012
- 2012-03-20 CN CN2012100747449A patent/CN102627668A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268479A (en) * | 1991-12-14 | 1993-12-07 | Hoechst Aktiengesellschaft | Process for the preparation of tertiary phosphines |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910207A (en) * | 2015-02-12 | 2015-09-16 | 天津墨森科技有限公司 | Preparation method of di (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide |
| CN104910207B (en) * | 2015-02-12 | 2019-03-05 | 天津墨森科技有限公司 | The preparation method of bis(benzoylphenyl) phosphine oxide and benzoyl diphenyl phosphine oxide |
| CN109553639A (en) * | 2018-12-11 | 2019-04-02 | 河南省科学院化学研究所有限公司 | A method of synthesis tri-tert-butylphosphine |
| CN109553639B (en) * | 2018-12-11 | 2020-10-20 | 河南省科学院化学研究所有限公司 | Method for synthesizing tri-tert-butylphosphine |
| CN109970789A (en) * | 2019-04-25 | 2019-07-05 | 大连理工大学 | A kind of preparation method of triaryl phosphine compound |
| CN109970789B (en) * | 2019-04-25 | 2021-05-07 | 大连理工大学 | Preparation method of triarylphosphine compound |
| CN113533591A (en) * | 2021-06-18 | 2021-10-22 | 山东罗欣药业集团恒欣药业有限公司 | GC analysis method for benzene and paraldehyde in cefprozil |
| CN113533591B (en) * | 2021-06-18 | 2022-08-23 | 山东罗欣药业集团恒欣药业有限公司 | GC analysis method for benzene and paraldehyde in cefprozil |
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Application publication date: 20120808 |