CN103073586A - Double (3-sulfonic acid-4-chlorophenyl)-3'-sulfoacid phenyl phosphine oxide and preparation method of salt thereof - Google Patents
Double (3-sulfonic acid-4-chlorophenyl)-3'-sulfoacid phenyl phosphine oxide and preparation method of salt thereof Download PDFInfo
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Abstract
The invention discloses a double (3-sulfonic acid-4-chlorophenyl)-3'-sulfoacid phenyl phosphine oxide and a preparation method of a salt thereof. The method comprises the steps as follow: mixing double (4-chlorophenyl) phenyl phosphine oxide and fuming sulphuric acid in a molar ratio of 1:(4.0-8.0), pouring a reaction solution into ice after the reaction, adding alkali, regulating the pH value to be neutral, conducting azeotropy, evaporating water, filtering insoluble substances, drying the solvent, and recrystallizing water and isopropanol to obtain a white product. The preparation method can be operated conveniently, and salting-out, butanone extraction and a column chromatography manner are not required in a separation and purification process for the product, so that an aftertreatment flow is simplified greatly, the preparation period is shortened, and the double (3-sulfonic acid-4-chlorophenyl)-3'-sulfoacid phenyl phosphine oxide is more suitable for large-scale industrial production.
Description
Technical field
The invention belongs to technical field of polymer materials, the preparation method who relates to the required important sulfonated monomers of synthetic polyether aromatic phosphine phosphine oxide family macromolecule polymkeric substance, the specifically high efficiency preparation method of two (3-sulfonic acid-4-halobenzene base)-3 '-sulphenyl phosphine oxides and salt thereof.
Background technology
The introducing of sulfonic acid group can improve permeability rate, contamination resistance and the proton conductivity of mould material, can not reduce its mechanical property again simultaneously.At present, sulfonic acid group extensively is incorporated on the multiple aromatic polymer, such as polyether-ether-ketone, polyethersulfone, polyimide etc.The polymer materials stable chemical nature, high temperature resistant that contains the phosphono structural unit, extensive application in the preparation of fire-retardant material; Materials is stronger to the mineral compound adhesive capacity, also exists wide application prospect in the Proton Exchange Membrane Fuel Cells field.Generally believe, keying action has been played in the raising of stronger interaction partners material property between the phosphono group.This class material can by the copolyreaction of the monomers such as two (4-fluorophenyl)-phenyl phosphine oxides (BFPPO) or two (4-hydroxy phenyl)-phenyl phosphine oxides (BOHPPO), be incorporated into the phosphine oxide structure in the macromolecular chain.Wherein adopt two (4-fluorophenyl)-phenyl phosphine oxide monomers of sulfonation; not only can obtain main chain all is the sulfonated polymer material (CN101712756A) of phosphine oxide-ether structure; from and so that the effect of phosphono group maximization; simultaneously; because two (4-fluorophenyl)-phenyl phosphine oxides (BFPPO) but have the position of three sulfonation in the structure; can obtain the different sulfonated monomers of sulfonation degree, thereby so that the density of the sulfonic acid group in the macromolecular material that will form and distribution are controlled.
Two (3-sulfonic acid-4-halobenzene base)-3 '-sulphenyl phosphine oxides and salt monomer thereof can make (CN101168548) by two (4-halobenzene base) phenylphosphine oxide and oleum reaction.Although reaction yield can reach 73%, its separation and purification need through saltout, butanone extraction and column chromatography process, do not possess the feasibility of economy and scale operation.
Summary of the invention
For overcoming above-mentioned deficiency and shortcoming, the invention provides the high efficiency preparation method of two (3-sulfonic acid-4-halobenzene base)-3 '-sulphenyl phosphine oxides and salt thereof, it is characterized in that being undertaken by following step:
（Ⅰ）
Wherein, X=fluorine or chlorine; M=hydrogen, lithium, sodium, potassium, caesium and ammonium ion;
(1) with two (4-halobenzene base) the phenyl phosphine oxides of raw material and oleum according to certain mixed in molar ratio, at a certain temperature, react certain hour;
(2) reaction solution is poured in the ice, added the adjusting PH with base value to neutral;
(3) add aprotic polar solvent and toluene, reflux water-dividing boils off toluene, filters, and filtrate is spin-dried for, and water and Virahol recrystallization obtain white products (I) again.
Among the preparation method of the present invention, wherein said two (4-halobenzene base) phenyl phosphine oxides are two (4-fluorophenyl) phenyl phosphine oxides or two (4-chloro-phenyl-) phenyl phosphine oxide.
Among the preparation method of the present invention, wherein the concentration of oleum is: 15-35%.
Among the preparation method of the present invention, the mol ratio of two (4-halobenzene base) phenyl phosphine oxides and oleum is 1:4.0-8.0.
Among the preparation method of the present invention, wherein temperature of reaction is 90-150 ℃.
Among the preparation method of the present invention, wherein the reaction times is 4-24 hour.
Among the preparation method of the present invention, wherein alkali is MOH or NR
1R
2R
3, M=Li wherein, Na, K, Cs; R
1, R
2, R
3=H or C
1-3Alkyl.
Among the preparation method of the present invention, wherein aprotic polar solvent is N,N-dimethylacetamide, DMF, methyl-sulphoxide or N-Methyl pyrrolidone.
Among the preparation method of the present invention, wherein the solvent of recrystallization is water and Virahol, and volume ratio is 1:1-20.
Two (3-sulfonic acid-4-halobenzene base)-3 '-sulphenyl phosphine oxide and salt thereof of the present invention, typical compound representative wherein is as follows:
(1) two (3-sodium sulfonate-4-fluorophenyl)-3 '-sodium sulfonate phenyl phosphine oxide
(2) two (3-sodium sulfonate-4-chloro-phenyl-)-3 '-sodium sulfonate phenyl phosphine oxide
(3) two (3-Sulfonic Lithium-4-fluorophenyl)-3 '-Sulfonic Lithium phenyl phosphine oxide
(4) two (3-potassium sulfonate-4-fluorophenyl)-3 '-potassium sulfonate phenyl phosphine oxide
(5) two (3-sulfonic acid caesium-4-fluorophenyl)-3 '-sulfonic acid caesium phenyl phosphine oxide
(6) two (3-ammonium sulphonate-4-fluorophenyl)-3 '-ammonium sulphonate phenyl phosphine oxide
(7) two (3-sulfonic acid-4-fluorophenyl)-3 '-sulphenyl phosphine oxide
The positively effect that the high efficiency preparation method of two (3-sulfonic acid-4-halobenzene base)-3 '-sulphenyl phosphine oxide of the present invention and salt thereof compared with prior art has is: preparation method of the present invention need not through oversalting, butanone extraction and column chromatography means; so that the aftertreatment flow process is greatly simplified; shortened preparation cycle; reduced the consumption (consumption of column chromatography) of organic solvent, so that large-scale production becomes possibility.
Embodiment
For simple and purpose clearly, hereinafter appropriate omission the description of known technology, in order to avoid the impact of unnecessary details is to the description of the technical program.The present invention is described further below in conjunction with comparative example.Two (4-fluorophenyl) phenyl phosphine oxides or two (4-chloro-phenyl-) phenyl phosphine oxide reference literature make (with reference to Journal of Organic Chemistry, 60 (11), 3499-508; 1995 and DE3727423).Hydrogen 1 nuclear magnetic resonance spectrum (
1HNMR), phosphorus 31 nuclear magnetic resonance spectrums (
31P NMR), carbon-13 magnetic resonance spectrum (
13C NMR) all at deuterated dimethyl sulfoxide (DMSO-d
6) in record.
Comparative example:
(50%, 6ml), reaction is 3 hours under 0 to 90 ℃, reacts respectively under 110 and 130 ℃ subsequently 4 hours and 9 hours with oleum for two (4-fluorophenyl) phenyl phosphine oxide (3g, 9.55mmol).In the rear impouring frozen water of reaction solution cooling, separate out light red oily matter with sodium chloride salt, the butanone extraction, remove solvent, sodium hydroxide neutralization, activated carbon decolorizing is spin-dried for the thick product that obtains and carries out column chromatography for separation with the mixed solvent of methyl alcohol and ethyl acetate, obtain two (3-sodium sulfonate-4-fluorophenyl)-the 3 '-sodium sulfonate phenyl phosphine oxides of product, productive rate 73%.
1HNMR?(DMSO-d
6),?δ:?8.01~8.06(m,?2H),?7.96~7.99(d,?
J=?12.0Hz,?1H),?7.89~7.91(d,?
J=?7.6Hz,?1H),?7.47~7.61(m,?4H),?7.37~7.40(t,?
J=?8.8Hz,?2H);?
31PNMR?(DMSO-d
6):?δ?=?24.75ppm;?
13CNMR(100?MHz,?DMSO-d6),?δ:?117.16,?126.86,?128.39,?129.48,?131.16,?131.67,?132.29,?134.74,?135.47,?148.22,?159.66,?162.21。
Embodiment 1:
Two (4-fluorophenyl) phenyl phosphine oxide (30.0g, 93.6mmol) and oleum (20%, 150ml, 0.375 mole) 90 ℃ of lower reactions 4 hours, reacted respectively under 110 and 130 ℃ 3 hours and 10 hours subsequently.During impouring is iced after the reaction solution cooling, transfer pH to neutral with sodium hydroxide, add 200mlN, N-N,N-DIMETHYLACETAMIDE (DMAc), reflux water-dividing filters, be spin-dried for and reclaim solvent DMAc, the crude product water that obtains and Virahol (volume ratio 1:10) recrystallization obtain two (3-sodium sulfonate-4-fluorophenyl)-the 3 '-sodium sulfonate phenyl phosphine oxide 58.0g of white products, yield 98%.
1HNMR?(DMSO-d
6),?δ:?8.00~8.05(m,?2H),?7.95~7.98(d,?
J=?12.0Hz,?1H),?7.88~7.90(d,?
J=?7.6Hz,?1H),?7.46~7.60(m,?4H),?7.36~7.40(t,?
J=?8.8Hz,?2H)?;
?31PNMR?(DMSO-d
6):?δ?=?24.73ppm;
?13CNMR(100?MHz,?DMSO-d6),?δ:?117.18,?126.87,?128.40,?129.50,?131.16,?131.69,?132.29,?134.74,?135.48,?148.21,?159.67,?162.20;?HRMS(ESI):
?m/z?[M+Na]
+?calcd?for?C
18H
10F
2Na
4O
10PS
3:?642.8727;?found:?642.8725。
Embodiment 2:
Two (4-fluorophenyl) phenyl phosphine oxide (30.0g, 93.6mmol) and oleum (20%, 300ml, 0.75 mole) 90 ℃ of lower reactions 4 hours, reacted respectively under 110 and 130 ℃ 3 hours and 10 hours subsequently.During impouring is iced after the reaction solution cooling, transfer pH to neutral with sodium hydroxide, add 300mlN, N-N,N-DIMETHYLACETAMIDE (DMAc), reflux water-dividing filters, be spin-dried for and reclaim solvent DMAc, the crude product water that obtains and Virahol (volume ratio 1:10) recrystallization obtain two (3-sodium sulfonate-4-fluorophenyl)-the 3 '-sodium sulfonate phenyl phosphine oxide 56.2g of white products, yield 95%.
Embodiment 3:
Two (4-fluorophenyl) phenyl phosphine oxide (30.0g, 93.6mmol) and oleum (20%, 150ml, 0.375 mole) 90 ℃ of lower reactions 4 hours, reacted respectively under 110 and 130 ℃ 3 hours and 10 hours subsequently, 150 ℃ of lower reactions 2 hours.During impouring is iced after the reaction solution cooling, transfer pH to neutral with sodium hydroxide, add 200mlN, N-N,N-DIMETHYLACETAMIDE (DMAc), reflux water-dividing filters, be spin-dried for and reclaim solvent DMAc, the crude product water that obtains and Virahol (volume ratio 1:10) recrystallization obtain two (3-sodium sulfonate-4-fluorophenyl)-the 3 '-sodium sulfonate phenyl phosphine oxide 57.6g of white products, yield 97%.
Embodiment 4:
Two (4-fluorophenyl) phenyl phosphine oxide (30.0g, 93.6mmol) and oleum (20%, 150ml, 0.375 mole) 90 ℃ of lower reactions 4 hours, reacted respectively under 110 and 130 ℃ 3 hours and 24 hours subsequently.During impouring is iced after the reaction solution cooling, transfer pH to neutral with sodium hydroxide, add 200mlN, N-N,N-DIMETHYLACETAMIDE (DMAc), reflux water-dividing filters, be spin-dried for and reclaim solvent DMAc, the crude product water that obtains and Virahol (volume ratio 1:10) recrystallization obtain two (3-sodium sulfonate-4-fluorophenyl)-the 3 '-sodium sulfonate phenyl phosphine oxide 57.3g of white products, yield 97%.
Embodiment 5:
Two (4-fluorophenyl) phenyl phosphine oxide (30.0g, 93.6mmol) and oleum (20%, 150ml, 0.375 mole) 90 ℃ of lower reactions 4 hours, reacted respectively under 110 and 130 ℃ 3 hours and 10 hours subsequently.During impouring is iced after the reaction solution cooling, transfer pH to neutral with sodium hydroxide, add 200mlN-methyl-2-pyrrolidone (NMP), reflux water-dividing, filter, be spin-dried for and reclaim solvent NMP, the crude product water that obtains and Virahol (volume ratio 1:10) recrystallization, obtain two (3-sodium sulfonate-4-fluorophenyl)-the 3 '-sodium sulfonate phenyl phosphine oxide 56.1g of white products, yield 95%.
Embodiment 6:
Two (4-fluorophenyl) phenyl phosphine oxide (30.0g, 93.6mmol) and oleum (20%, 150ml, 0.375 mole) 90 ℃ of lower reactions 4 hours, reacted respectively under 110 and 130 ℃ 3 hours and 10 hours subsequently.During impouring is iced after the reaction solution cooling, transfer pH to neutral with sodium hydroxide, add 200mlN, N-N,N-DIMETHYLACETAMIDE (DMAc), reflux water-dividing filters, be spin-dried for and reclaim solvent DMAc, the crude product water that obtains and Virahol (volume ratio 1:20) recrystallization obtain two (3-sodium sulfonate-4-fluorophenyl)-the 3 '-sodium sulfonate phenyl phosphine oxide 37.8g of white products, yield 64%.
Embodiment 7:
(20%, 50ml), reaction is 4 hours under 90 ℃, reacts respectively under 110 and 130 ℃ subsequently 3 hours and 10 hours with oleum for two (4-chloro-phenyl-) phenyl phosphine oxide (11.0g, 31.8mmol).During impouring is iced after the reaction solution cooling, transfer pH to neutral with sodium hydroxide, add 200mlN, N-N,N-DIMETHYLACETAMIDE (DMAc), reflux water-dividing filters, be spin-dried for and reclaim solvent DMAc, the crude product water that obtains and Virahol (volume ratio 1:10) recrystallization obtain two (3-sodium sulfonate-4-chloro-phenyl-)-the 3 '-sodium sulfonate phenyl phosphine oxide 18.9g of white products, yield 91%.
1H?NMR?(DMSO-d
6),?δ:?7.99~8.04(m,?2H),?7.94~7.96(d,?
J=?12.0Hz,?1H),?7.87~7.91(d,?
J=?7.6Hz,?1H),?7.46~7.60(m,?4H),?7.38~7.42(t,?
J=?8.8Hz,?2H)?;?
31P?NMR?(DMSO-d
6):?δ?=?24.70ppm;?
13CNMR(100?MHz,?DMSO-d6),?δ:?117.17,?126.86,?128.40,?129.50,?131.18,?131.67,?132.28,?134.74,?135.47,?148.22,?159.67,?162.22.。
Embodiment 8:
(20%, 50ml), reaction is 4 hours under 90 ℃, reacts respectively under 110 and 130 ℃ subsequently 3 hours and 10 hours with oleum for two (4-fluorophenyl) phenyl phosphine oxide (10.0g, 31.8mmol).During impouring is iced after the reaction solution cooling, transfer pH to neutral with potassium hydroxide, add 200mlN, N-N,N-DIMETHYLACETAMIDE (DMAc), reflux water-dividing filters, be spin-dried for and reclaim solvent DMAc, the crude product water that obtains and Virahol (volume ratio 1:8) recrystallization obtain two (3-potassium sulfonate-4-fluorophenyl)-the 3 '-potassium sulfonate phenyl phosphine oxide 19.3g of white products, yield 91%.
1H?NMR?(DMSO-d
6),?δ:?8.02~8.07(m,?2H),?7.97~7.99(d,?
J=?12.0Hz,?1H),?7.90~7.92(d,?
J=?7.6Hz,?1H),?7.48~7.62(m,?4H),?7.38~7.43(t,?
J=?8.8Hz,?2H)?;?
31PNMR?(DMSO-d
6):?δ?=?24.74ppm;?
13CNMR(100?MHz,?DMSO-d6),?δ:?117.19,?126.88,?128.42,?129.51,?131.16,?131.69,?132.29,?134.75,?135.49,?148.23,?159.69,?162.23。
Embodiment 9:
(20%, 50ml), reaction is 4 hours under 90 ℃, reacts respectively under 110 and 130 ℃ subsequently 3 hours and 10 hours with oleum for two (4-fluorophenyl) phenyl phosphine oxide (10.0g, 31.8mmol).During impouring is iced after the reaction solution cooling, transfer pH to neutral with triethylamine, add 200mlN, N-N,N-DIMETHYLACETAMIDE (DMAc), reflux water-dividing filters, be spin-dried for and reclaim solvent DMAc, the crude product water that obtains and Virahol (volume ratio 1:20) recrystallization get two (3-sulfonic acid triethyl hydrogen ammonium-4-fluorophenyl)-the 3 '-sulfonic acid triethyl hydrogen ammonium phenyl phosphine oxide 25.0g of white products, yield 92%.
1H?NMR?(DMSO-d
6),?δ:?8.01~8.05(m,?2H),?7.95~7.98(d,?
J=?12.0Hz,?1H),?7.89~7.92(d,?
J=?7.6Hz,?1H),?7.46~7.61(m,?4H),?7.37~7.41(t,?
J=?8.8Hz,?2H),?2.89~3.15(m,?18H),?1.25~1.36(m,?27H);?
31P?NMR?(DMSO-d
6):?δ?=?24.72ppm;
?13CNMR(100?MHz,?DMSO-d6),?δ:?117.18,?126.89,?128.40,?129.52,?131.18,?131.70,?132.29,?134.74,?135.45,?148.23,?159.67,?162.19,?54.60,?13.73。
Embodiment 10:
Get product 10.0 grams that embodiment 1 obtains, add the 20ml water dissolution, add the 100ml concentrated hydrochloric acid, use the 50ml chloroform extraction three times again, merge organic layer, calcium chloride is dry, be spin-dried for desolventizing and obtain two (3-sulfonic acid-4-fluorophenyl)-3 '-sulphenyl phosphine oxide 7.3 grams of white solid, yield: 81%.
1HNMR?(DMSO-d
6),?δ:?8.00~8.04(m,?2H),?7.93~7.96(d,?
J=?12.0Hz,?1H),?7.87~7.89(d,?
J=?7.6Hz,?1H),?7.48~7.61(m,?4H),?7.37~7.40(t,?
J=?8.8Hz,?2H)?;?
31PNMR?(DMSO-d
6):?δ?=?24.72ppm;?
13CNMR(100?MHz,?DMSO-d6),?δ:?117.17,?126.86,?128.40,?129.50,?131.15,?131.69,?132.28,?134.74,?135.46,?148.21,?159.67,?162.18。
After the preferred embodiment that describes in detail, being familiar with this technology personage can be well understood to, can carry out various variations and modification not breaking away under above-mentioned claim and the spirit, all foundations technical spirit of the present invention all belongs to the scope of technical solution of the present invention to any simple modification, equivalent variations and modification that above embodiment does.And the present invention also is not subjected to the restriction of the embodiment that gives an actual example in the specification sheets.
Claims (7)
1. the preparation method of two (3-sulfonic acid-4-halobenzene base)-3 '-sulphenyl phosphine oxides and salt thereof is characterized in that being undertaken by following step:
（Ⅰ）
Wherein, X=fluorine or chlorine; M=hydrogen, lithium, sodium, potassium, caesium and ammonium ion;
(1) with the two 4-halobenzene bases of raw material) phenyl phosphine oxide and oleum be according to certain mixed in molar ratio, at a certain temperature, reacts certain hour; The mol ratio of described two (4-halobenzene base) phenyl phosphine oxide and oleum is 1:4.0-8.0;
(2) reaction solution is poured in the ice, added the adjusting PH with base value to neutral;
(3) add aprotic polar solvent and toluene, reflux water-dividing boils off toluene, filters, and filtrate is spin-dried for, and water and Virahol recrystallization obtain white products (I) again; Wherein aprotic polar solvent is N,N-dimethylacetamide, DMF, methyl-sulphoxide or N-Methyl pyrrolidone.
2. preparation method claimed in claim 1, wherein said two (4-halobenzene base) phenyl phosphine oxides be pair (4-fluorophenyl) phenyl phosphine oxides or two (4-chloro-phenyl-) phenyl phosphine oxide.
3. preparation method claimed in claim 1, wherein the concentration of oleum is: 15-35%.
4. preparation method claimed in claim 1, wherein temperature of reaction is 90-150 ℃.
5. preparation method claimed in claim 1, wherein the reaction times is 4-24 hour.
6. preparation method claimed in claim 1, wherein alkali is MOH or NR
1R
2R
3, M=Li wherein, Na, K, Cs; R
1, R
2, R
3=H or C
1-3Alkyl.
7. preparation method claimed in claim 1, wherein the solvent of recrystallization is water and Virahol, volume ratio is 1:1-20.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292453A (en) * | 2014-09-09 | 2015-01-21 | 天津师范大学 | Multi-sulfonated polyaromatic ether phosphine oxide high-molecular materials and preparation method and application thereof |
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|---|---|---|---|---|
| US4623490A (en) * | 1984-08-29 | 1986-11-18 | Ruhrchemie Aktiengesellschaft | Process for the purification of sulfonated aryl phosphines |
| CN1101360A (en) * | 1993-08-24 | 1995-04-12 | 拜尔公司 | Stabilised, flame resistant polycarbonate moulding compounds |
| CN101168548A (en) * | 2007-11-29 | 2008-04-30 | 上海交通大学 | Sulfonated compound containing phosphinyl structure and preparation method thereof |
| CN101186623A (en) * | 2007-12-06 | 2008-05-28 | 上海交通大学 | Di(halogenated phenyl)-3-nitrophenyloxyphosphine containing sodium sulphonate and preparation method thereof |
-
2013
- 2013-01-11 CN CN2013100102547A patent/CN103073586A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4623490A (en) * | 1984-08-29 | 1986-11-18 | Ruhrchemie Aktiengesellschaft | Process for the purification of sulfonated aryl phosphines |
| CN1101360A (en) * | 1993-08-24 | 1995-04-12 | 拜尔公司 | Stabilised, flame resistant polycarbonate moulding compounds |
| CN101168548A (en) * | 2007-11-29 | 2008-04-30 | 上海交通大学 | Sulfonated compound containing phosphinyl structure and preparation method thereof |
| CN101186623A (en) * | 2007-12-06 | 2008-05-28 | 上海交通大学 | Di(halogenated phenyl)-3-nitrophenyloxyphosphine containing sodium sulphonate and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292453A (en) * | 2014-09-09 | 2015-01-21 | 天津师范大学 | Multi-sulfonated polyaromatic ether phosphine oxide high-molecular materials and preparation method and application thereof |
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Application publication date: 20130501 |