CN100497280C - Para phenyl phenol preparation method - Google Patents
Para phenyl phenol preparation method Download PDFInfo
- Publication number
- CN100497280C CN100497280C CNB200610049123XA CN200610049123A CN100497280C CN 100497280 C CN100497280 C CN 100497280C CN B200610049123X A CNB200610049123X A CN B200610049123XA CN 200610049123 A CN200610049123 A CN 200610049123A CN 100497280 C CN100497280 C CN 100497280C
- Authority
- CN
- China
- Prior art keywords
- biphenyl
- reaction
- preparation
- phenyl phenol
- temperature
- 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
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000004927 fusion Effects 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 9
- XDTYUYVIGLIFCW-UHFFFAOYSA-N 4-phenylbenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=CC=C1 XDTYUYVIGLIFCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 6
- 239000004305 biphenyl Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- PXWYZLWEKCMTEZ-UHFFFAOYSA-N 1-ethyl-2-nitrobenzene Chemical compound CCC1=CC=CC=C1[N+]([O-])=O PXWYZLWEKCMTEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 abstract 3
- 239000002585 base Substances 0.000 abstract 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 230000003340 mental effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XAWCLWKTUKMCMO-UHFFFAOYSA-N 2-nitroethylbenzene Chemical class [O-][N+](=O)CCC1=CC=CC=C1 XAWCLWKTUKMCMO-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- -1 tetracol phenixin Chemical compound 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation method of p-phenylphenol, which belongs to the technical field of a compound preparation method. The present invention is characterized in that the prepaThe invention relates to a method for preparing phenyl phenol in the field of compound preparing method technology. It comprises the following steps: using sulfonyl chloride to do sulfonation biphenylration method has the following procedures: under the condition of 0DEG. C to 180DEG. C of the temperature, chlorosulfonic acid is used for sulfonating biphenyl in organic solvent, and biphenyl-4-sulf in the organic solution at the reacting temperature 0-180 deg., filtering and drying to obtain the biphenyl-4-sulfonation; mixing the biphenyl-4-sulfonation and the base mental hydroxide (1:2-30 moleonic acid is obtained though filtration and dryness; the prepared biphenyl-4-sulfonic acid and alkali metal hydroxide of which the molar ratio is 1: 2 to 30 are mixed in the organic solvent, and under rate) in the organic solution and preparing the phenyl phenol on the condition of PH value >=13; the temperature 160-340 deg.; the pressure 0-1.5 MPa; reclaiming the solvent form the base fusion matt the conditions that a pH value is not less than 13, temperature is 160DEG. C to 340DEG. C, and pressure is 0MPa to 1.5MPa, the p-phenylphenol is prepared through alkali fusion; solvent is reclaimed fer and separating the phenyl phenol and other fenol compounds during the course. rom prepared alkali fusion substances, and the p-phenylphenol and other phenolic compounds are separated during the process. The preparation method has a simple manufacturing process, and little pollution; side products which are generated in the preparation method are far less than the side products which are generated by using sulfuric acid sulfonation; the purity of a sulphonation product is so high that the highly-purified p-phenylphenol can be directly prepared through the alkali fusion without refining, and the present invention has low cost.
Description
Technical field
The invention belongs to the compounds process for production thereof technical field, be specially a kind of preparation method's technical field of p-phenyl phenol.
Background technology
The p-phenyl phenol purposes is very extensive, is mainly used in: the preparation heat sensitive dye; Preparation hot melt ink, classified papers impact paper; Synthetic have extremely strong weather resistance and weather resisteant resin, coating; Synthesizing hydrophobic fiber promotor can be improved dyeing kinetics and colour fastness greatly; Synthetic red, green sensitizing dye; Be widely used in novel pesticide, the new pharmaceutical of preparation high-efficiency low-toxicity; Can synthesize various monomers.General biphenyl and the sulfuric acid of adopting carries out sulfonation reaction in the prior art, preparation biphenyl-4-sulfonic acid, then hydro-oxidation sodium at high temperature and under the condition of long-time reaction alkali fusion prepare p-phenyl phenol.Also have by replacing sodium hydroxide to reduce the technology of alkali fusion temperature with potassium hydroxide.All these methods all produce a large amount of acid waste water in the processing of sulfonated bodies, the purity of sulfonated bodies is not high, and temperature of reaction is higher during alkali fusion.The inertia organic medium or the water that also will add high boiling point sometimes carry out alkali fusion.The easy contaminate environment of acid waste water that produces must can be discharged through handling, and has increased production cost.
Summary of the invention
The present invention is for overcoming the above-mentioned problems in the prior art, design provides a kind of preparation method's of new p-phenyl phenol technical scheme, the by product that its reaction generates is few, sulfonated bodies purity height, and just not needing to make with extra care directly, alkali fusion prepares highly purified p-phenyl phenol.
The preparation method of described a kind of p-phenyl phenol is characterized in that comprising the steps:
1) biphenyl is dissolved in the organic solvent, adds chlorsulfonic acid and carry out sulfonation reaction, temperature of reaction is 0～180 ℃, and reaction finishes after-filtration, drying, makes biphenyl-4-sulfonic acid;
2) biphenyl-4-sulfonic acid that makes is mixed with alkali metal hydroxide, organic solvent, under 160～340 ℃ of temperature, carry out the alkali fusion reaction;
3) after reaction finished, with the water diluted reaction mixture, separating suspension reclaimed solvent, and reaction solution carries out neutralization reaction with mineral acid, to pH be 4～6.5, filtration, cleaning, dry p-phenyl phenol.
The preparation method of described a kind of p-phenyl phenol is characterized in that the described organic solvent of step 1) is a kind of in the straight-chain paraffin (n 〉=2) of o-nitroethylbenzene, Ortho Nitro Toluene, tetracol phenixin, chloroform, chloride atom.
The preparation method of described a kind of p-phenyl phenol is characterized in that step 2) described organic solvent is a kind of in hydrogenated terphenyl or the straight chain alcohol compounds, described straight chain alcohol compounds is methyl alcohol, ethanol, butanols, Virahol etc.
The preparation method of described a kind of p-phenyl phenol is characterized in that the temperature of reaction described in the step 1) is: 10～80 ℃.
The preparation method of described a kind of p-phenyl phenol is characterized in that step 2) described in temperature of reaction be 280～320 ℃.
The preparation method of described a kind of p-phenyl phenol is characterized in that step 2) described in biphenyl-40-sulfonic acid and the mol ratio of alkali metal hydroxide be 1:6～12.
The preparation method of described a kind of p-phenyl phenol is characterized in that mineral acid described in the step 3) is sulfuric acid or hydrochloric acid.
The preparation method of described a kind of p-phenyl phenol is characterized in that the described drying process of step 3) is 100 ℃ of following vacuum-dryings, and then the purification that distils.
Among the above-mentioned preparation method, step 1) also can adopt the segmentation reaction, as: reacted 10-20 minute down at 30～50 ℃, be warming up to 60～80 ℃ then, kept 0.5-4 hour, be generally 1-3 hour, be preferably 2-3 hour.
Among the above-mentioned preparation method, step 2) the insulation reaction time is 5-20 hour, is generally 12-18 hour, is preferably 14-16 hour, and reaction finishes postcooling and enters down step process to 180-220 ℃.
Alkali fusion is reflected in the Inconel(nickel alloys) autoclave and carries out among the above-mentioned preparation method, and when reacting under air-tight state, the pressure-controlling that reaction mass self produces generally is controlled at 0.2-1.5Mpa below 5.0Mpa, be preferably 0.5-1.5Mpa.
The preparation method of above-mentioned a kind of p-phenyl phenol, technology is simple, and the by product that reaction generates is few; sulfonated bodies purity height does not need the direct alkali fusion of refining just energy prepare highly purified p-phenyl phenol, has reduced production cost; can not produce a large amount of acid waste water, help environment protection.
Embodiment
Below by embodiment the present invention is described in further detail.
31.2 gram (0.2 mole) biphenyl are dissolved in 200 milliliters of o-nitroethylbenzenes, and temperature is controlled at 30～40 ℃, slow Dropwise 35 gram chlorsulfonic acid, and this thermotonus 10 to 15 minutes, then reaction mixture is heated to 80 ℃ and kept 2 hours.Be cooled to room temperature, filter, dry that dry product weighs 49.2 gram biphenyl-4-sulfonic acid content 98.5%.In the Inconel(nickel alloys) autoclave, add 100 milliliters of above-mentioned sulfonation material and hydrogenated terphenyls, 96% sodium hydroxide 167 grams (4 moles), airtight autoclave.Start stirring and be warming up to 280 ℃, insulation reaction 15 hours, pressure rises to 0.8～1.5MPa.After insulation was finished, reaction mixture was cooled to 200 ℃, pumps into 300 ml waters, and suspended substance shifts out from autoclave, and water flushing autoclave.Reactant and wash water cumulative volume are told hydrogenated terphenyl with separating funnel for 1600 milliliters and are applied mechanically next time, the water of telling with in 30% sulfuric acid and the pH value be 4.5～6.0.Sedimentary product filters with B, and with the clear water washing, wet product 100 ℃ of dryings under vacuum are used the pure system of subliming method again.Product yield 83% (in biphenyl), p-phenyl phenol purity 99.9%.The used organic solvent of the present invention leaches the later recycled for a long time of product, does not have the waste water output.
Claims (3)
1, a kind of preparation method of p-phenyl phenol is characterized in that comprising the steps:
1) biphenyl is dissolved in the o-nitroethylbenzene, add chlorsulfonic acid and carry out sulfonation reaction, described sulfonation reaction was reacted 10-15 minute under 30～40 ℃ of conditions earlier, then reaction mixture was heated to 80 ℃ and kept 2 hours, reaction finishes after-filtration, drying, makes biphenyl-4-sulfonic acid;
2) biphenyl-4-sulfonic acid that makes is mixed with alkali metal hydroxide, organic solvent, under 160～340 ℃ of temperature, carry out the alkali fusion reaction, described organic solvent is a kind of in hydrogenated terphenyl or the straight chain alcohol compounds, and the mol ratio of described biphenyl-4-sulfonic acid and alkali metal hydroxide is 1:6～12;
3) after reaction finished, with the water diluted reaction mixture, separating suspension reclaimed solvent, and reaction solution carries out neutralization reaction with sulfuric acid or hydrochloric acid, to pH be 4～6.5, filtration, cleaning, dry p-phenyl phenol.
2, the preparation method of a kind of p-phenyl phenol as claimed in claim 1 is characterized in that step 2) described in temperature of reaction be 280～320 ℃.
3, the preparation method of a kind of p-phenyl phenol as claimed in claim 1 is characterized in that the described drying process of step 3) is 100 ℃ of following vacuum-dryings, and then the purification that distils.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610049123XA CN100497280C (en) | 2006-01-17 | 2006-01-17 | Para phenyl phenol preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610049123XA CN100497280C (en) | 2006-01-17 | 2006-01-17 | Para phenyl phenol preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1800126A CN1800126A (en) | 2006-07-12 |
| CN100497280C true CN100497280C (en) | 2009-06-10 |
Family
ID=36810385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610049123XA Expired - Fee Related CN100497280C (en) | 2006-01-17 | 2006-01-17 | Para phenyl phenol preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100497280C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739449B (en) * | 2013-12-30 | 2016-05-04 | 青岛双桃精细化工（集团）有限公司 | A kind of preparation method of 1,5-dihydroxy naphthlene |
| CN114853575A (en) * | 2022-06-13 | 2022-08-05 | 连云港市三联化工有限公司 | Production process of p-phenylphenol for mother liquor recycling |
| CN117945857A (en) * | 2023-12-27 | 2024-04-30 | 浙江工业大学 | Synthesis method for fusing sulfonated alkali into 4-hydroxy biphenyl by solvent method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US424822A (en) * | 1890-04-01 | pokoeny | ||
| US4467123A (en) * | 1982-02-06 | 1984-08-21 | Bayer Aktiengesellschaft | Process for the preparation of alkali metal diphenylates and free hydroxydiphenyls |
| US4633024A (en) * | 1982-04-23 | 1986-12-30 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for producing aromatic hydroxy compound |
| CN1566053A (en) * | 2003-07-04 | 2005-01-19 | 江西麒麟化工有限公司 | Process for producing para phenyl phenol |
-
2006
- 2006-01-17 CN CNB200610049123XA patent/CN100497280C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US424822A (en) * | 1890-04-01 | pokoeny | ||
| US4467123A (en) * | 1982-02-06 | 1984-08-21 | Bayer Aktiengesellschaft | Process for the preparation of alkali metal diphenylates and free hydroxydiphenyls |
| US4633024A (en) * | 1982-04-23 | 1986-12-30 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for producing aromatic hydroxy compound |
| CN1566053A (en) * | 2003-07-04 | 2005-01-19 | 江西麒麟化工有限公司 | Process for producing para phenyl phenol |
Non-Patent Citations (2)
| Title |
|---|
| 联苯衍生物的磺化反应. 邹友思等.合成化学，第4卷第3期. 1996 |
| 联苯衍生物的磺化反应. 邹友思等.合成化学，第4卷第3期. 1996 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1800126A (en) | 2006-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109369430A (en) | A method of preparing 6-aminocaprolc acid | |
| CN100497280C (en) | Para phenyl phenol preparation method | |
| CN105435706A (en) | Sulfonate-type anion dimeric surfactant and preparation method thereof | |
| CN107915644A (en) | A kind of method that p-aminophenyl ether is prepared using paranitrochlorobenzene as raw material | |
| CN107935875B (en) | Method for synthesizing melphalan | |
| CN102614919B (en) | Sulfonated cross-linked chitosan resin type solid acid catalyst and preparation method thereof | |
| CN113698276B (en) | Synthesis method of 2, 6-dihydroxytoluene | |
| CN111187152A (en) | Method for synthesizing pseudo ionone under catalysis of alkaline immobilized ionic liquid | |
| CN102942463A (en) | Preparation method for benzophenone compound | |
| CN106117168A (en) | A kind of preparation method of furosemide | |
| CN101830820B (en) | Method for preparing 2,5-diparamethylaniline terephthalic acid (DTTA) | |
| CN102659579A (en) | preparation method of p-chlorine methyl cinnamate | |
| CN110511182B (en) | Method for synthesizing 7-nitro-1,2,3,4-tetrahydroquinoline by continuous flow reaction | |
| CN114213283A (en) | One-pot method for the preparation of [2-[1-(Fmoc-amino)ethoxy]ethoxy]acetic acid | |
| US4275002A (en) | Process for preparing polymeric colorants having a poly(vinylamine) backbone | |
| CN108546232B (en) | Preparation method of mono-substituted or di-substituted benzoate compound | |
| CN101844996B (en) | Method for preparing 2,5-di(p-chloroanilino)-terephthalic acid (DpCTA) | |
| CN112142579A (en) | Preparation process of 2-hydroxy-4-methoxybenzophenone | |
| CN101823978B (en) | Method for preparing 2, 5-diphenyl amino acid DATA | |
| CN118405972B (en) | Preparation method of 5-fluoro salicylic acid | |
| CN111848510A (en) | Synthesis method of montelukast sodium | |
| CN104230747B (en) | A kind of preparation method of asymmetry aromatic azo-compound | |
| CN113801152B (en) | Synthesis method of 3-carboxyl-5-hydroxyphenylboric acid | |
| CN112759562B (en) | Preparation method of high-purity hydrobromic acid vortioxetine | |
| CN104262332A (en) | Preparation method of olmesartan medoxomil |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090610 Termination date: 20190117 |