CN1179428A - Process for preparing tri (meta-sulfonate phenyl) phosphine - Google Patents
Process for preparing tri (meta-sulfonate phenyl) phosphine Download PDFInfo
- Publication number
- CN1179428A CN1179428A CN 96120055 CN96120055A CN1179428A CN 1179428 A CN1179428 A CN 1179428A CN 96120055 CN96120055 CN 96120055 CN 96120055 A CN96120055 A CN 96120055A CN 1179428 A CN1179428 A CN 1179428A
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- China
- Prior art keywords
- triphenylphosphine
- phosphine
- sulfuric acid
- reaction
- product
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Abstract
A process for preparing 3 -(meta -sulfonate phenyl) phosphine includes such technological steps as adding triphenyl phosphine to 100% sulfuric acid or fuming sulfuric acid while stirring, addition of SO3, sulonating reaction at 15-30 deg. C for 15-35 hr under the existance of B2O3 (0.05-5 Wt.%), neutralization with alkali solution, and separating product. The mole ratio is 10-20 for SO3 to triphenyl phosphine or 6-20 for sulfuric acid to triphenyl phosphine. Its advantages are short reaction period and low content of oxide as by-product.
Description
The invention relates to the preparation method of organic phosphine, the preparation method of (-sulfonate phenyl) phosphine of more specifically saying so about three.
Three (-sulfonate phenyl) phosphine is mainly used in and transition metal forms water-soluble complexes, for example can form with rhodium have better water miscible title complex, and this title complex is the catalyzer that a kind of good alkene formylation prepares aldehyde.
According to J.Chem.Soc.276～288,1958 and BP 1,066,261 disclosed methods, with triaryl phosphine oleum sulfonation, the alkaline derivant with metal M neutralizes the organic phosphine compound that can obtain being shown below then:
Ar wherein
1, Ar
2And Ar
3Can be the same or different, represent aryl; Y
1, Y
2And Y
3Can be the same or different, representative contains the straight or branched alkyl of 1～4 carbon atom, the alkoxyl group that contains 1～4 carbon atom, halogen atom or hydroxyl etc.; M represents inorganic or organic ion, m
1, m
2And m
3Can be the same or different, represent 0～5 numerical value; n
1, n
2And n
3Can be the same or different, represent 0～3 numerical value, one of them is more than or equal to 1 at least.For example, with triphenylphosphine in 20% oleum after the sulfonation, with NaOH neutralization (-sodium sulfonate phenyl) phosphine (TPPTS) that can obtain three.During with this method preparation three (-sulfonate phenyl) phosphine, contain more single sulfonation, two sulfonated products and corresponding oxide compound (OTPPTS) in the product, the complex compound solvability in water that forms because of single sulfonation and two sulfonated products and rhodium is relatively poor and difficultly remove from product, and oxide compound does not possess ligancy, can not form title complex with rhodium, thereby require the growing amount of above-mentioned by product in the product to lack as far as possible.
EP 0,133, and 410 are dissolved in triphenylphosphine (TPP) in 100% sulfuric acid, and adds SO
320～22 ℃ of sufficiently long times of reaction, all generate three sulfonated products with the TPP that guarantees to add, and then with alkali neutralization (-sulfonate phenyl) phosphine of preparing three, avoided the generation of single sulfonation and two sulfonated products with this method, but the content of oxide byproducts is still higher in the product, and the reaction times is longer, for example, according to the description of the example 1, at SO
3/ TPP=12 (mol ratio), SO
3/ (SO
3+ H
2SO
4+ TPP)=0.34 under the condition of (weight ratio), in 22 ℃ of reactions 72 hours, TPPTS accounted for 91 moles of % in the products therefrom, and OTPPTS accounts for 9 moles of %; Improve SO
3Consumption can shorten the reaction times, but the also corresponding increase of oxide content in the product for example, according to the description of the example 2, is worked as SO
3/ (SO
3+ H
2SO
4+ TPP)=0.43 when (weight ratio), 22 ℃ of reactions got final product in 52 hours sulfonated products, but TPPTS accounts for 88.7 moles of % and oxide compound OTPPTS is increased to 11.3 moles of % in the product.
The objective of the invention is to overcome the shortcoming that oxide content in the prior art sulfonated products is higher and the reaction times is long, providing a kind of can shorten the reaction times, can reduce the preparation method of new three (-sulfonate phenyl) phosphine of oxide content in the product again.
Method provided by the invention comprises under agitation triphenylphosphine is added in 100% sulfuric acid or the oleum, and adds SO
3Carry out sulfonation reaction, use the alkaline solution neutralization reaction product, Separation and Recovery product three (-the sulfonate phenyl) phosphine, its key is, has also added the B that accounts for total reactant weight 0.05～5% in reaction system
2O
3, SO in the reaction system
3With the mol ratio of triphenylphosphine be 10～20, the mol ratio of sulfuric acid and triphenylphosphine is 6～20, the temperature of sulfonation reaction is 15～30 ℃, the time of sulfonation reaction is 15～35 hours.
Wherein, the hydroxide solution of described alkaline solution preferred as alkali or ammonia soln, described basic metal is selected from one or more in lithium, sodium, potassium, rubidium, the caesium, and described alkaline solution is the aqueous solution of sodium hydroxide, potassium hydroxide or ammonia more preferably.
Described B
2O
3Can be under 0～30 ℃ temperature and triphenylphosphine, SO
3Together or successively join in 100% sulfuric acid or the oleum, described each raw material adds mode preferably earlier with B
2O
3Add in 100% sulfuric acid or the oleum, under 0～10 ℃ temperature, add triphenylphosphine more in batches, add SO at last
3B
2O
3Consumption preferably account for 0.1～2.0 heavy % of total reactant.
Described SO
3Be difficult to guarantee that the triphenylphosphine that adds all is converted into three sulfonated products with the mol ratio of triphenylphosphine being lower than at 10 o'clock, thereby SO in the reaction system
3With the mol ratio of triphenylphosphine should be greater than 10, preferred 10～20, best 12～17;
The mol ratio of described sulfuric acid and triphenylphosphine is lower than at 6 o'clock, is difficult to guarantee the triphenylphosphine that adds all by protonated and be not easy to oxidizedly, thereby the mol ratio of sulfuric acid and triphenylphosphine should be greater than 6, and is preferred 6～20, and more preferably 6～15.
When the temperature of described sulfonation reaction was lower than 15 ℃, sulfonation reaction speed was slower, and when temperature of reaction is higher than 30 ℃, oxide content will significantly increase in the product, thereby the sulfonation reaction temperature should be controlled at 15～30 ℃, best 20～30 ℃.
The time of described sulfonation reaction can not guarantee that the triphenylphosphine that adds all is converted into three sulfonated products when being less than 15 hours, and the reaction times, long meeting increased energy consumption.Thereby the time of sulfonation reaction should be controlled at best 15～30 hours 15～35 hours.
The described alkaline solution neutralization reaction product of using, separated product three (-the sulfonate phenyl) phosphine employing usual method, promptly earlier with dilution heat of sulfuric acid or water, preferably 20～50 weigh the excessive SO of % sulphuric acid soln hydrolysis
3, with alkaline solution neutralization, remove by filter the vitriol of separating out again, the aqueous solution concentrated and add ethanol, residual vitriol is separated out, filter, with aqueous solution evaporate to doing, (-sulfonate phenyl) the phosphine product that promptly gets three.Wherein, with in the alkaline solution and after, when removing by filter vitriol, the B in the system
2O
3To together be removed, and can not contain B in the final product
2O
3
Method provided by the invention has not only shortened the time of sulfonation reaction greatly, and the content of oxide compound also significantly reduces in the product, the yield of (-sulfonate phenyl) phosphine that improved three simultaneously, for example, adopt method provided by the invention when the sulfonation reaction temperature is 22～28 ℃, reaction times only is under 20～28 hours the condition, oxide content only is 2～6 moles of % in three (-sodium sulfonate phenyl) phosphine product of preparing, and the yield of three (-sodium sulfonate phenyl) phosphine is up to 85～94.5 heavy %.
The following examples will the present invention will be further described, but not thereby limiting the invention.
Example 1
In being housed, churned mechanically 250 milliliters of three-necked bottles add 174.0 grams, 20% oleum (chemical pure, chemical reagent factory in Chengdu produces) and 5.0 gram B
2O
3(chemical pure, chemical reagent factory in Chengdu produces) is cooled to 5 ℃, under stirring fast 30.0 gram triphenylphosphines (chemical pure, chemical reagent one factory in Shanghai produces) added in 70 minutes in the three-necked bottle in batches, adds 112.0 gram SO
3(technical pure, Chengdu soapless soap factory produces) temperature is risen to 24 ℃, reacted 24 hours, be cooled to 0 ℃, under stirring fast, reaction product is added in the 60 milliliter 50 heavy % aqueous sulfuric acid, drip 10N sodium hydroxide neutralization reaction product to neutral, separate out a large amount of solids, filter, collect mother liquor, be evaporated to 100 milliliters, add 100 milliliters of ethanol, be placed to and no longer include the precipitation generation, remove by filter the solid of separating out, and, filtrate evaporated under reduced pressure is extremely done, under vacuum with 30 milliliter 50 heavy % aqueous ethanolic solution washing solid, in 80 ℃ of dryings 4 hours, get white solid 55.4 grams, yield 85 heavy % use
31PNMR measures in the product three (-sodium sulfonate phenyl) 96.0 moles of % of phosphine content, 4 moles of % of oxide content.
Example 2
Press the described method preparation three of example 1 (-sodium sulfonate phenyl) phosphine, each raw material consumption is: 20% oleum, 174.0 grams, B
2O33.0 gram, triphenylphosphine 30.0 grams, SO
3112.0 gram, 24 ℃ of temperature of reaction, 28 hours reaction times, white solid product 59.2 gram, yield 90.5 heavy %, (-sodium sulfonate phenyl) 98.0 moles of % of phosphine content in the product three, 2.0 moles of % of oxide content.
Example 3
Press the described method preparation three of example 1 (-sodium sulfonate phenyl) phosphine, each raw material consumption is: 20% oleum, 196.0 grams, B
2O
30.5 gram, triphenylphosphine 50.0 grams, SO
3170.0 gram, 22 ℃ of temperature of reaction, 28 hours reaction times, white solid product 102.5 gram, yield 94.5 heavy %, (-sodium sulfonate phenyl) 96.0 moles of % of phosphine content in the product three, 4 moles of % of oxide content.
Example 4
Press the described method preparation three of example 1 (-sodium sulfonate phenyl) phosphine, each raw material consumption is: 20% oleum, 50.0 grams, B
2O
30.9 gram, triphenylphosphine 10.0 grams, SO
330.0 gram, 28 ℃ of temperature of reaction, 20 hours reaction times, white solid product 19.4 gram, yield 89.4 heavy %, (-sodium sulfonate phenyl) 94.0 moles of % of phosphine content in the product three, 6.0 moles of % of oxide content.
Example 5
Press the described method preparation three of example 1 (-sodium sulfonate phenyl) phosphine, each raw material consumption is: 20% oleum, 30.0 grams, B
2O
30.1 gram, triphenylphosphine 10.0 grams, SO
342.0 gram, 22 ℃ of temperature of reaction, 24 hours reaction times, white solid product 19.6 gram, yield 90.3 heavy %, (-sodium sulfonate phenyl) 94.0 moles of % of phosphine content in the product three, 6.0 moles of % of oxide content.
Claims (8)
1. the preparation method of one kind three (-sulfonate phenyl) phosphine comprises under agitation triphenylphosphine is added in 100% sulfuric acid or the oleum, and adds SO
3Carry out sulfonation reaction, with the alkaline solution neutralization, the Separation and Recovery product is characterized in that also having added in the reaction system B that accounts for total reactant 0.05～5 heavy %
2O
3, SO in the reaction system
3With the mol ratio of triphenylphosphine be 10～20, the mol ratio of sulfuric acid and triphenylphosphine is 6～20, the temperature of sulfonation reaction is 15～30 ℃, the time of sulfonation reaction is 15～35 hours.
2. according to the described method of claim 1, it is characterized in that B
2O
3Consumption be 0.1～2.0 heavy %.
3. according to claim 1 or 2 described methods, it is characterized in that described alkaline solution refers to be selected from one or more alkali-metal hydroxide solution or the ammonia soln in lithium, sodium, potassium, rubidium, the caesium.
4. according to the described method of claim 3, it is characterized in that described alkaline solution refers to the aqueous solution of sodium hydroxide, potassium hydroxide or ammonia.
5. according to claim 1 or 2 described methods, it is characterized in that the adding mode of described each raw material is: in 100% sulfuric acid or oleum, add B earlier
2O
3, under 0～10 ℃ temperature, add triphenylphosphine more in batches, add SO at last
3
6. according to claim 1 or 2 described methods, it is characterized in that SO
3With the mol ratio of triphenylphosphine be 12～17.
7. according to claim 1 or 2 described methods, the mol ratio that it is characterized in that sulfuric acid and triphenylphosphine is 6～15.
8. according to claim 1 or 2 described methods, the temperature that it is characterized in that sulfonation reaction is 20～30 ℃, and the time of sulfonation reaction is 15～30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120055A CN1046530C (en) | 1996-10-15 | 1996-10-15 | Process for preparing tri (meta-sulfonate phenyl) phosphine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120055A CN1046530C (en) | 1996-10-15 | 1996-10-15 | Process for preparing tri (meta-sulfonate phenyl) phosphine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1179428A true CN1179428A (en) | 1998-04-22 |
| CN1046530C CN1046530C (en) | 1999-11-17 |
Family
ID=5126103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120055A Expired - Fee Related CN1046530C (en) | 1996-10-15 | 1996-10-15 | Process for preparing tri (meta-sulfonate phenyl) phosphine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046530C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328284C (en) * | 2004-11-17 | 2007-07-25 | 南京大学 | Stabilized silver sulfonate complex of organo-phosphine, method for synthesizing and use thereof |
| CN103254232A (en) * | 2013-05-27 | 2013-08-21 | 成都欣华源科技有限责任公司 | Preparation method of water-soluble tri(m-sulfonate phenyl)phosphine |
| CN112724170A (en) * | 2020-12-24 | 2021-04-30 | 南京恒远科技开发有限公司 | Preparation method of trisulfonated triphenylphosphine TPPTS |
| CN117777194A (en) * | 2024-02-23 | 2024-03-29 | 江苏集萃分子工程研究院有限公司 | Method for preparing triphenylphosphine tri-m-sodium sulfonate by using sulfur trioxide polysulfonation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2550202B1 (en) * | 1983-08-03 | 1986-03-21 | Rhone Poulenc Rech | PROCESS FOR THE PREPARATION OF SOR (M-SULFOPHENYL) PHOSPHINE |
| FR2561650B1 (en) * | 1984-03-26 | 1987-10-23 | Rhone Poulenc Rech | IMPROVEMENT IN THE PROCESS FOR THE PREPARATION OF SORF (M-SULFOPHENYL) PHOSPHINE BY CONTROLLED HYDROLYSIS AND DILUTION OF SULFONATE |
-
1996
- 1996-10-15 CN CN96120055A patent/CN1046530C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328284C (en) * | 2004-11-17 | 2007-07-25 | 南京大学 | Stabilized silver sulfonate complex of organo-phosphine, method for synthesizing and use thereof |
| CN103254232A (en) * | 2013-05-27 | 2013-08-21 | 成都欣华源科技有限责任公司 | Preparation method of water-soluble tri(m-sulfonate phenyl)phosphine |
| CN103254232B (en) * | 2013-05-27 | 2016-05-18 | 成都欣华源科技有限责任公司 | The preparation method of water-soluble three (m-sulfonate phenyl) phosphine |
| CN112724170A (en) * | 2020-12-24 | 2021-04-30 | 南京恒远科技开发有限公司 | Preparation method of trisulfonated triphenylphosphine TPPTS |
| CN112724170B (en) * | 2020-12-24 | 2022-04-15 | 南京恒远科技开发有限公司 | Preparation method of trisulfonated triphenylphosphine TPPTS |
| CN117777194A (en) * | 2024-02-23 | 2024-03-29 | 江苏集萃分子工程研究院有限公司 | Method for preparing triphenylphosphine tri-m-sodium sulfonate by using sulfur trioxide polysulfonation |
| CN117777194B (en) * | 2024-02-23 | 2024-05-14 | 江苏集萃分子工程研究院有限公司 | Method for preparing triphenylphosphine tri-m-sodium sulfonate by using sulfur trioxide polysulfonation |
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| Publication number | Publication date |
|---|---|
| CN1046530C (en) | 1999-11-17 |
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Granted publication date: 19991117 Termination date: 20091116 |