CN1034804C - Synthesis method of diphenyl sulfone tetracarboxylic acid - Google Patents
Synthesis method of diphenyl sulfone tetracarboxylic acid Download PDFInfo
- Publication number
- CN1034804C CN1034804C CN90109003A CN90109003A CN1034804C CN 1034804 C CN1034804 C CN 1034804C CN 90109003 A CN90109003 A CN 90109003A CN 90109003 A CN90109003 A CN 90109003A CN 1034804 C CN1034804 C CN 1034804C
- Authority
- CN
- China
- Prior art keywords
- diphenyl sulfone
- tetracid
- diphenyl
- hydrogen peroxide
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 title abstract description 9
- -1 diphenyl sulfone tetracarboxylic acid Chemical class 0.000 title description 2
- 238000001308 synthesis method Methods 0.000 title 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- CQKOHEPVNHWULI-UHFFFAOYSA-N C(=O)O.C(=O)O.C(=O)O.C(=O)O.C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1 Chemical compound C(=O)O.C(=O)O.C(=O)O.C(=O)O.C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1 CQKOHEPVNHWULI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010189 synthetic method Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000007800 oxidant agent Substances 0.000 claims abstract 2
- 101710171243 Peroxidase 10 Proteins 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ZNNSPZOSKINXHF-UHFFFAOYSA-N 5-sulfinylcyclohexa-1,3-diene Chemical compound O=S=C1CC=CC=C1 ZNNSPZOSKINXHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000006159 dianhydride group Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention belongs to a synthetic method of diphenyl sulfone tetraformic acid and its derivative. The invention uses excessive 30% hydrogen peroxide as oxidant and water as medium, under reflux temperature, diphenyl sulfide tetracid is directly made into diphenyl sulfone tetracid. The yield can reach more than 87 percent, and the purity is high.
Description
The invention belongs to the synthetic method of diphenyl sulfone tetraformic acid and derivative thereof.
Diphenyl sulfone tetraformic acid is the raw material of polyimide high-temperature polymer, also can be used as curing agent for epoxy resin etc.
The sulfobenzide tetracid can be made by corresponding tetramethyl diphenyl sulfone oxidation, also can be made by the oxidation of corresponding diphenyl sulfide tetracid.GE (US.APPL684,392) has reported with the diphenyl sulfide tetracid and prepared the sulfobenzide tetracid under 3% hydrogen peroxide effect, but product is the mixture of sulfobenzide tetracid and thionyl benzene tetracid.(US.4,609,712) have also been reported with excessive 5～15 equivalents, 30% hydrogen peroxide, the method for oxidation in the presence of acetic acid, and think that this oxidizing reaction undertaken by Peracetic Acid.
The shortcoming of next two kinds of methods is: product is impure, is the mixture of two kinds of tetracids, perhaps needs acetic acid to participate in reaction, and oxygenant is a peroxidation acetic acid, so need big excessive hydrogen peroxide.Simultaneously, because the existence of acetic acid is arranged, also make troubles for the separation of product.
The objective of the invention is with excessive 30% about one times hydrogen peroxide is oxygenant, and water is medium, under reflux temperature, directly makes high yield by the diphenyl sulfide tetracid, highly purified diphenyl sulfone tetraformic acid.
Synthesis step of the present invention is as follows:
Diphenyl thio-ether tetrformate can be 3.3 ', 4.4 '-2.2 ', 3.3 '-or 2.3 ', 3.4 '-isomer.
Only reaction conditions is: based on every gram diphenyl sulfide tetracid, and 3～5 milliliters in water, hydrogen peroxidase 10 .6～1.2 milliliter, return time is 20 minutes～1 hour.Product is purified with sublimation method.Productive rate can reach more than 87%.It is synthetic that this product can be directly used in polyimide.
Embodiments of the invention are as follows:
Embodiment 1:
With 15 grams, 3.3 ', 4.4 '-diphenyl sulfide returns acid and is dissolved in 50 milliliters of boiling water, adds 12 grams, 30% hydrogen peroxide, refluxed 1 hour, after the water evaporation, residue is at 340-360 ℃, and 0.01 mmhg distils down, get 13 gram diphenyl sulfone dianhydride, mp.292-294 ℃, yield 87.8%.
Embodiment 2:
Except the consumption of hydrogen peroxide is 10.5 milliliters, all the other conditions are with embodiment 1, mp288-294 ℃ of gained dianhydride, yield: 87.8%.
Embodiment 3:
With 15 the gram 3.3 ', 4.4 '-diphenyl sulfide tetracid and 12 milliliter of 30% hydrogen peroxide and 20 ml water reflux 30 minutes, filtered while hot is removed a small amount of insoluble substance, after the cooling, separate out white solid by filtrate, filter, after the drying, at 320-330 ℃, 0.01 mmhg is distillation down, yield 68.0%.
Embodiment 4:
With 15 grams 3.3 ', 4.4 '-hexichol sulfuric acid tetracid, 15 milliliter of 30% hydrogen peroxide stirred under the room temperature 24 hours in 20 ml waters, product still is unreacted diphenyl sulfide tetracid by analysis.
Embodiment 5:
With 12 the gram 2.2 ', 3.3 '-diphenyl sulfide tetracid is dissolved in 50 milliliters of boiling water, add 10 milliliter of 30% hydrogen peroxide, refluxed 1 hour, leach a small amount of insoluble impurity, filtrate being concentrated into separated out crystallization, leach solid after the cooling, with the washing of 3 * 20 ml waters, dry back is heated to 340-360 ℃ of distillation under 0.01 mmhg, get faint yellow crystallization 11.0 grams, yield: 83%.This dianhydride 340 ℃ begin the distillation, to 375 ℃ complete molten.
Claims (2)
1, a kind of synthetic method of diphenyl sulfone tetraformic acid is based on the diphenyl sulfide tetracid, adds excessive hydrogen peroxide, it is characterized in that, with excessive 30% about one times hydrogen peroxide as oxidant, water is medium, under reflux temperature, makes diphenyl sulfone tetraformic acid.
2, synthetic method as claimed in claim 1 is characterized in that, based on every gram diphenyl sulfide tetracid, and 3～5 milliliters in water, hydrogen peroxidase 10 .6～1.2 milliliter, return time is 20 minutes～1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90109003A CN1034804C (en) | 1990-11-05 | 1990-11-05 | Synthesis method of diphenyl sulfone tetracarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90109003A CN1034804C (en) | 1990-11-05 | 1990-11-05 | Synthesis method of diphenyl sulfone tetracarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1061219A CN1061219A (en) | 1992-05-20 |
| CN1034804C true CN1034804C (en) | 1997-05-07 |
Family
ID=4881238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90109003A Expired - Fee Related CN1034804C (en) | 1990-11-05 | 1990-11-05 | Synthesis method of diphenyl sulfone tetracarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1034804C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586297B (en) * | 2017-12-13 | 2021-02-19 | 广东省石油与精细化工研究院 | Method for preparing sulfoxide and sulfone by oxidizing thioether in water phase |
| CN111187187A (en) * | 2020-03-07 | 2020-05-22 | 桂林理工大学 | Preparation method of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU582660A1 (en) * | 1976-03-24 | 1978-06-25 | Институт Органической Химии Ан Украинской Сср | Method of obtaining pentachlorphenylalkylsulfone |
| US4625013A (en) * | 1984-12-20 | 1986-11-25 | General Electric Company | Aromatic sulfoxy compositions and method for their preparation |
-
1990
- 1990-11-05 CN CN90109003A patent/CN1034804C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU582660A1 (en) * | 1976-03-24 | 1978-06-25 | Институт Органической Химии Ан Украинской Сср | Method of obtaining pentachlorphenylalkylsulfone |
| US4625013A (en) * | 1984-12-20 | 1986-11-25 | General Electric Company | Aromatic sulfoxy compositions and method for their preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1061219A (en) | 1992-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ATE106380T1 (en) | PROCESS FOR THE PRODUCTION AND RECOVERY OF OXYDIPHTHALIC ANHYDRIDES. | |
| AU2001290367B2 (en) | Synthesis of ester linked long chain alkyl moieties | |
| CN1034804C (en) | Synthesis method of diphenyl sulfone tetracarboxylic acid | |
| AU2001290367A1 (en) | Synthesis of ester linked long chain alkyl moieties | |
| US4076728A (en) | Process for manufacturing crystal violet lactone | |
| EP0129449B1 (en) | Diniflumate of morpholinoethyl ester of niflumic acid, its preparation, and its use in analgesic and antiinflammatory pharmaceutical compositions | |
| CN115784894B (en) | Refining method of ultra-high purity sodium p-nitrophenolate | |
| EP0344737B1 (en) | Process for purifying alpha-substituted acetic acids | |
| CN112920036A (en) | Improved refining process of 1, 4-dihydroxy anthraquinone | |
| CN1066134C (en) | New process for synthetising m-nitrobenzoic | |
| CN1164572C (en) | Process for preparing dimethyl sulfone | |
| Depreux et al. | Synthesis of benzil from benzoin with copper (II) acetate | |
| CN1090177C (en) | Preparation of aromatic nitriles | |
| US3163675A (en) | Preparation of trans 1, 2-diamino-cyclohexane | |
| Gilbert | The synthesis of adamantane-2, 4-dione | |
| CN108299251A (en) | The preparation method of Glimepiride impurity | |
| CN1155566C (en) | Process for separating and purifying N-ethyl carbazole | |
| CN114181103A (en) | Method for synthesizing m-aminoacetanilide by taking m-phenylenediamine as raw material | |
| CN112028807A (en) | Refining method of glimepiride bulk drug | |
| FR2614298A1 (en) | PROCESS FOR PREPARING TRIFLUOROMETHYLBENZOIC ACID FROM HEXAFLUOROXYLENE | |
| KR20000053467A (en) | Process for recrystallizing 1,3-bis(aminophenoxy benzene) | |
| CN115784894A (en) | Refining method of ultra-high purity p-nitrophenol sodium | |
| CN87100039A (en) | Production method of carane aldehydic acid lactone | |
| JP2000072701A (en) | Production of cyclic dimer of p-isopropenylphenol | |
| JPH02172940A (en) | Production of p-hydroxybenzaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |