CN104478708B - One step prepares the method for salicylic acid compounds - Google Patents
One step prepares the method for salicylic acid compounds Download PDFInfo
- Publication number
- CN104478708B CN104478708B CN201510015887.6A CN201510015887A CN104478708B CN 104478708 B CN104478708 B CN 104478708B CN 201510015887 A CN201510015887 A CN 201510015887A CN 104478708 B CN104478708 B CN 104478708B
- Authority
- CN
- China
- Prior art keywords
- structural formula
- salicylic acid
- acid compounds
- catalyzer
- oxygenant
- 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
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 150000005172 methylbenzenes Chemical class 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 9
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical class [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/305—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with sulfur or sulfur-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of method that a step prepares salicylic acid compounds, is that catalyzer ML and the structural formula of I is that the methylbenzenes of V drops into solvent, then adds structural formula oxygenant, be obtained by reacting finished product; The structural formula I of described catalyzer ML is
wherein M is Fe, Cu, Ni, Mn or Co; Described structural formula V is
Description
Technical field
The present invention relates to a kind of preparation method of salicylic acid compounds.
Background technology
Whitfield's ointment is a kind of fat-soluble organic acid, has a wide range of applications in fields such as rubber, makeup and biological medicines.Current salicylic preparation method's many employings phenol and liquid caustic soda make sodium phenylate salts solution, vacuum-drying, at 100 DEG C, then slowly pass into dry carbonic acid gas, when pressure reaches 0.7 ~ 0.8MPa, stop logical carbonic acid gas, are warming up to 140 ~ 180 DEG C; Add clear water after completion of the reaction, carry out decolouring, filtering after salicylic acid sodium salt is dissolved, then add sulfuric acid acidation, namely separate out Whitfield's ointment, after filtration, wash, be drying to obtain finished product.It is more that existing method prepares desired raw material kind, and step is comparatively loaded down with trivial details.
Summary of the invention
For solving above technical problem, a kind of methylbenzenes that adopts is the object of the present invention is to provide to be the method that raw material one step obtains salicylic acid compounds.
The object of the present invention is achieved like this:
One step prepares a method for salicylic acid compounds, and its key is: by structural formula be I catalyzer ML and structural formula be that the methylbenzenes of V drops into solvent, then add oxygenant, be obtained by reacting finished product;
The structural formula I of described catalyzer ML is
wherein M is Fe, Cu, Ni, Mn or Co;
Described structural formula V is
wherein R is positioned at position or contraposition between methyl.
In order to better realize the object of the invention:
Structure above is that in V, R is any one in H, halogen, alkyl, substituted alkyl, aryl or substituted aryl.
In structure above I, Ra is H, alkyl, halogen, nitro or amino.
Above-mentioned solvent be for the one in water, ethanol, acetone and chloroform, two kinds, three kinds or four kinds.
After adding above-mentioned oxygenant, controlling temperature of reaction is 20 ~ 100 DEG C, and the reaction times is 4-48h, obtains finished product finally by filtration, separation.
Above-mentioned oxygenant is oxygen, hydrogen peroxide, Peracetic Acid or Potassium Persulphate.
A step of the present invention prepares the method for salicylic acid compounds, is undertaken by following reaction formula:
Beneficial effect: adopt a step of the present invention to prepare the method for salicylic acid compounds, desired raw material is less, preparation method is simple, and only needing to carry out single step reaction can obtain salicylic acid compounds by methylbenzenes, and required temperature of reaction is also lower.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
An a kind of step prepares the method for salicylic acid compounds:
By structural formula be I catalyzer ML and structural formula be that the methylbenzenes of V drops into solvent, then add oxygenant, controlling temperature of reaction is 20 DEG C, and the reaction times is 4h, finally by filtration, is separated and obtains finished product;
The structural formula I of described catalyzer ML is
wherein M is Fe; Ra is H.
Described structural formula V is
wherein R is positioned at position or contraposition between methyl, and R is H.
Described solvent is any one in water, ethanol, acetone and chloroform.
Described oxygenant is oxygen.
The structural formula of the finished product that the present embodiment obtains is
Embodiment 2:
An a kind of step prepares the method for salicylic acid compounds:
By structural formula be I catalyzer ML and structural formula be that the methylbenzenes of V drops into solvent, then add oxygenant, controlling temperature of reaction is 100 DEG C, and the reaction times is 48h, finally by filtration, is separated and obtains finished product;
The structural formula I of described catalyzer ML is
wherein M is Cu; Ra is alkyl.
Described structural formula V is
wherein R is positioned at position or contraposition between methyl, and R is any halogens.
Described solvent is the mixture for any two kinds in water, ethanol, acetone and chloroform.
Described oxygenant is hydrogen peroxide.
The structural formula of the finished product that the present embodiment obtains is
Embodiment 3:
An a kind of step prepares the method for salicylic acid compounds:
By structural formula be I catalyzer ML and structural formula be that the methylbenzenes of V drops into solvent, then add oxygenant, controlling temperature of reaction is 80 DEG C, and the reaction times is 24h, finally by filtration, is separated and obtains finished product;
The structural formula I of described catalyzer ML is
wherein M is Ni; Ra is halogen.
Described structural formula V is
wherein R is positioned at position or contraposition between methyl, and R is any alkyl or substituted alkyl.
Described solvent is the mixture for any three kinds in water, ethanol, acetone and chloroform.
Described oxygenant is Peracetic Acid.
The structural formula of the finished product that the present embodiment obtains is
Embodiment 4:
An a kind of step prepares the method for salicylic acid compounds:
By structural formula be I catalyzer ML and structural formula be that the methylbenzenes of V drops into solvent, then add oxygenant, controlling temperature of reaction is 60 DEG C, and the reaction times is 12h, finally by filtration, is separated and obtains finished product;
The structural formula I of described catalyzer ML is
wherein M is Mn; Ra is nitro.
Described structural formula V is
wherein R is positioned at position or contraposition between methyl, and R is any aryl.
Described solvent is the mixture for any three kinds in water, ethanol, acetone and chloroform.
Described oxygenant is Peracetic Acid.
The structural formula of the finished product that the present embodiment obtains is
Embodiment 5:
An a kind of step prepares the method for salicylic acid compounds:
By structural formula be I catalyzer ML and structural formula be that the methylbenzenes of V drops into solvent, then add oxygenant, controlling temperature of reaction is 40 DEG C, and the reaction times is 36h, finally by filtration, is separated and obtains finished product;
The structural formula I of described catalyzer ML is
wherein M is Co; Ra is amino.
Described structural formula V is
wherein R is positioned at position or contraposition between methyl, and R is any substituted aryl.
Described solvent is the mixture for water, ethanol, acetone and chloroform.
Described oxygenant is Potassium Persulphate.
The structural formula of the finished product that the present embodiment obtains is
Finally it should be noted that; foregoing description is only the preferred embodiments of the present invention; those of ordinary skill in the art is under enlightenment of the present invention; under the prerequisite without prejudice to present inventive concept and claim; can make like multiple types and representing, such conversion all falls within protection scope of the present invention.
Claims (3)
1. a step prepares a method for salicylic acid compounds, it is characterized in that: by structural formula be I catalyzer ML and structural formula be that the methylbenzenes of V drops into solvent, then add oxygenant, be obtained by reacting finished product;
The structural formula I of described catalyzer ML is
wherein M is Fe, Cu, Ni, Mn or Co;
Described structural formula V is
wherein R is positioned at position or contraposition between methyl;
In described structural formula V, R is H or halogen;
In described structural formula I, Ra is H, halogen, nitro or amino;
Described oxygenant is oxygen, hydrogen peroxide, Peracetic Acid or Potassium Persulphate.
2. a step according to claim 1 prepares the method for salicylic acid compounds, it is characterized in that: described solvent be for the one in water, ethanol, acetone and chloroform, two kinds, three kinds or four kinds.
3. a step according to claim 1 prepares the method for salicylic acid compounds, it is characterized in that: after adding described oxygenant, and controlling temperature of reaction is 20 ~ 100 DEG C, and the reaction times is 4-48h, obtains finished product finally by filtration, separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510015887.6A CN104478708B (en) | 2015-01-13 | 2015-01-13 | One step prepares the method for salicylic acid compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510015887.6A CN104478708B (en) | 2015-01-13 | 2015-01-13 | One step prepares the method for salicylic acid compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104478708A CN104478708A (en) | 2015-04-01 |
| CN104478708B true CN104478708B (en) | 2016-01-13 |
Family
ID=52753344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510015887.6A Expired - Fee Related CN104478708B (en) | 2015-01-13 | 2015-01-13 | One step prepares the method for salicylic acid compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104478708B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613270A (en) * | 2009-07-30 | 2009-12-30 | 浙江大学 | A kind of salicylic preparation method |
| CN102627530A (en) * | 2012-03-19 | 2012-08-08 | 天津大学 | Method for preparing phenol and dihydroxybenzene by catalytic hydroxylation of benzene |
| CN103193631A (en) * | 2013-03-15 | 2013-07-10 | 北京工业大学 | Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-cresol with metalloporphyrin and metal salt compound as catalyst |
-
2015
- 2015-01-13 CN CN201510015887.6A patent/CN104478708B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613270A (en) * | 2009-07-30 | 2009-12-30 | 浙江大学 | A kind of salicylic preparation method |
| CN102627530A (en) * | 2012-03-19 | 2012-08-08 | 天津大学 | Method for preparing phenol and dihydroxybenzene by catalytic hydroxylation of benzene |
| CN103193631A (en) * | 2013-03-15 | 2013-07-10 | 北京工业大学 | Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-cresol with metalloporphyrin and metal salt compound as catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Iron-Promoted ortho- and/or ipso-Hydroxylation of Benzoic Acids with H2O2;Olga V. Makhlynets et al.;《Chem. Eur. J.》;20091028;第15卷;13171-13180 * |
| 苯羟基化合成苯酚的研究进展;闫肃 等;《化学世界》;20141231(第5期);301-306,320 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104478708A (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102276663B (en) | Preparation method of glucosamine sulfate | |
| CN104877042B (en) | A kind of preparation method of heparan | |
| CN105218728A (en) | A kind of preparation method of strong-basicity styrene series macroporous anion exchange resin | |
| CN104370680A (en) | Method for extracting lycopene from tomatoes | |
| CN102964270B (en) | Method for reducing hydrazine synthesized by diazonium salt by utilizing sodium sulphite | |
| CN104478708B (en) | One step prepares the method for salicylic acid compounds | |
| CN102516971A (en) | Block polyether zwitterionic heavy oil emulsified viscosity reducer and preparation method thereof | |
| CN103880717B (en) | The preparation method of two (3-allyl group-4-hydroxy phenyl) sulfones and derivative thereof | |
| CN105777599A (en) | Method for preparing canthaxanthin through oxidation | |
| CN104496785A (en) | Salicylic acid compound preparation method | |
| CN103396292A (en) | Method for industrially producing A,A'-dihydroxy-1,3-diisobutylbenzene | |
| CN105362300A (en) | Method for using seaweed to prepare concentrated solution rich in seaweed polyphenols | |
| AU2013345925B2 (en) | Method for recovering Ru complex dye from used dye solution | |
| CN1970530A (en) | Method for separating and purifying capsaicin compound using membrane separation technology | |
| CN102887848A (en) | Method for preparing lutein crystals from marigold ointment by catalytic saponification | |
| MX2013006954A (en) | Process for preparing divinylarene oxides. | |
| CN103288878B (en) | For magnesium salts precipitation agent and the method for purification of (R)-9-[2-(diethoxy phosphatidyl methoxy) propyl group] VITAMIN B4 of purifying | |
| CN106831655B (en) | A method of epoxidized soybean oil is catalyzed and synthesized under the conditions of no carboxylic acid | |
| CN104558059A (en) | Copper-zinc double coordination polymer | |
| CN103224452B (en) | 2-bromine-4,6-dichloroaniline preparation method | |
| CN104447506A (en) | Preparation method of 2-acetyl-9-alkyl carbazole | |
| CN104230747B (en) | A kind of preparation method of asymmetry aromatic azo-compound | |
| CN104743722B (en) | Comprehensive treatment method for high-concentration sodium sulfate wastewater generated in dicumyl peroxide production | |
| CN103435503B (en) | Preparation process of phenylephrine key intermediate 3-hydroxyl-alpha-(methylamine ethyl)-phenylcarbinol (dextro-laevo isomer) | |
| CN102584688B (en) | Preparing method of 2,6-dichloro-3-nitropyridine |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211224 Address after: Room 7-2, building 8, Jiuxi international, No. 6, Asia Pacific Road, Nan'an District, Chongqing 400060 Patentee after: Chongqing Mulan Environmental Protection Engineering Co.,Ltd. Address before: 401120 Chongqing Yubei District (Airport) Taoyuan Avenue 1000 Patentee before: CHONGQING INDUSTRY POLYTECHNIC College |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160113 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |