CN106349066A - Synthesis method of methyl 3,5-di-tert-butyl-4-hydroxybenzoate - Google Patents
Synthesis method of methyl 3,5-di-tert-butyl-4-hydroxybenzoate Download PDFInfo
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- CN106349066A CN106349066A CN201610732086.6A CN201610732086A CN106349066A CN 106349066 A CN106349066 A CN 106349066A CN 201610732086 A CN201610732086 A CN 201610732086A CN 106349066 A CN106349066 A CN 106349066A
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- butyl
- tert
- hydroxybenzoic acid
- methanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention discloses a synthesis method of an antioxidant methyl 3,5-di-tert-butyl-4-hydroxybenzoate, belonging to the field of organic chemical synthesis. The method comprises the following steps: by using methanol as both the raw material and reaction solvent for esterification and sodium methoxide or p-toluenesulfonic acid as a catalyst, carrying out reaction on 3,5-di-tert-butyl-4-hydroxybenzoic acid and the methanol in a mole ratio of 1.0:2.0-1.0:15.0 at 60-80 DEG C under reflux for 8-14 hours, evaporating to remove the solvent, washing the solid with a sodium carbonate or sodium bicarbonate saturated solution, washing with distilled water to a neutral state, carrying out vacuum filtration, and drying to obtain the pure product methyl 3,5-di-tert-butyl-4-hydroxybenzoate compound. The method has the advantages of simple technique, mild reaction conditions, no use of toxic solvents and lower cost, and is beneficial to the environment. The obtained product has the advantages of higher yield and high purity, and thus, has favorable industrial application prospects.
Description
Technical field
The present invention relates to a kind of synthetic method of 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester, belong to organic chemistry and close
One-tenth field.
Background technology
3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester are a kind of Hinered phenols antioxidants, as important interpolation auxiliary agent
Be widely used in plastics, rubber, fiber Polymer material processing in.Hydroxyl due to Hinered phenols antioxidant is subject to space bit
Resistance impact, the hydrogen on hydroxyl easily comes off from molecule, with oxygen radical, such as alkyl peroxy radical (roo), alkyl certainly
Combined by base (ro), hydroxyl radical free radical (ho) etc., be allowed to lose activity, so that the chain reaction of deterioration by oxidation terminates, suppression
System or the autoxidation preventing product, improve thermostability, extend the life-span.In addition, 3,5- di-tert-butyl-4-hydroxybenzoic acid first
Ester and light stabilizer can work in coordination with use, the living radical in capture macromolecule, suppress photo-oxidation process, the light improving product is steady
Qualitative, product colour fastness rate and brightness.3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester is alternatively arranged as medium and participates in high score
The synthesis of sub- liquid crystal material, improves the serviceability of LCD product.
3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester molecular formula is: c16h24o3, structural formula is as follows:
The domestic report of study on the synthesis with regard to 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester is little.Abroad use the tertiary fourth of 2,6- bis-
Base phenol, carbon dioxide, methanol are raw material, and oxolane is solvent, and boron trifluoride is catalyst, synthesis 3,5- di-t-butyl-
4-HBA methyl ester, this method yield is relatively low, is only capable of reaching 10%.Separately have with benzene as solvent, triethylamine synthesizes for catalyst,
And benzene is highly toxic substance, seriously polluted.
Content of the invention
The purpose of the present invention is for problems of the prior art, provides a kind of high efficiency, high yield, nontoxic no dirt
The synthetic method of the easily controllable 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester of dye, reaction.
The method that the present invention synthesizes 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester, with 3,5- di-t-butyl -4- hydroxy benzeness
Formic acid is raw material, and with excessive methanol as solvent, p-methyl benzenesulfonic acid or Feldalat NM are catalyst, are obtained by back flow reaction.
Methanol both raw material as esterification in the reaction, also serves as reaction dissolvent it is therefore desirable to excess.Experiment table
Bright, 3,5 di-tert-butyl-4-hydroxybenzoic acids control in the range of 1.0:2.0 ~ 1.0:15.0 with the mol ratio of methanol, ability
Ensure being smoothed out of reaction.
The consumption of catalyst sodium methoxide or p-methyl benzenesulfonic acid be 3,5- di-tert-butyl-4-hydroxybenzoic acid quality 2% ~
15%.
Described back flow reaction is back flow reaction 8 ~ 14h at 60 ~ 80 DEG C；Solvent is evaporated off, sodium carbonate first used by solid after reaction
Or saturated solution of sodium bicarbonate washing, then it is washed to neutrality, sucking filtration, purification with distillation, it is dried, obtain sterling 3, the tertiary fourth of 5- bis-
Base -4-HBA methyl ester.
In order to improve reaction yield, at interval of 1.5 ~ 2h during back flow reaction, in system water and methanol mixed is evaporated off
Compound, then add methanol to the amount needing, then proceed to back flow reaction.
Described vacuum drying is to carry out at 30 ~ 60 DEG C.
The product of present invention synthesis detects through melting point apparatus, infrared spectrum, nuclear magnetic spectrogram, mass spectrum etc., is defined as 3,5- bis- uncle
Butyl -4-HBA methyl ester.
The present invention compared with prior art has the advantage that
1st, the present invention is with 3,5- di-tert-butyl-4-hydroxybenzoic acid for Material synthesis 3,5- di-tert-butyl-4-hydroxybenzoic acid first
Ester, in reaction, methanol is esterification raw material and solvent, not only process is simple, and reaction condition is gentle, and makes reaction
Easily controllable；Avoid the use of the toxic solvents such as oxolane, benzene simultaneously, reduce the toxic and side effects in reaction, safely may be used
Lean on, environmental protection；
2nd, the high income (reaching 82%) of the synthesis final product of the present invention, purity height (reaching 99%), effectively increase synthesis 3,5- bis-
The efficiency of tertiary butyl-4-hydroxy essence of Niobe；
3rd, the raw material that the present invention uses is cheap and easy to get, synthesizes low cost, has preferable prospects for commercial application.
Specific embodiment
Below by specific experiment example to the synthesis of 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester of the present invention and characterize into
Row describes in detail.
Embodiment 1
Weigh 3,5- di-tert-butyl-4-hydroxybenzoic acid (25g, 0.1mol), methanol (32g, 10.0mol), be added to 250ml tri-
In mouth flask, it is heated with stirring to 70 DEG C, so that 3, the 5- di-tert-butyl-4-hydroxybenzoic acid in system is dissolved, add Feldalat NM
(2.5g, 0.0463 mol), back flow reaction 12h.After reaction terminates, solvent be evaporated off, Deca saturated solution of sodium carbonate agitator treating,
Add water washing to neutrality, sucking filtration obtains white solid；It is vacuum dried at 60 DEG C, obtain sterling 3,5- di-t-butyl -4- hydroxy benzeness first
Sour methyl compound.Calculated yield of weighing is 76.9%, 160.9 ~ 163.2 DEG C of fusing point.
The characterize data of product:
ir (neat) ν: 3577, 2959,2911,2873,1700,1601,1427,1304,1238,1140,1120,995,
776 cm-1. anal. calcd for c16h24o3.1h nmr (400 mhz, dmso)δ: 1.4612 (18h,-ch3),
3.8760 (3h, -o-ch3), 5.6735 (1h ,-oh), 7.8997(2h,-arh). esi+-ms( 35 ev, m/z):
265.1850[m +h]+.
Embodiment 2
Weigh 3,5- di-tert-butyl-4-hydroxybenzoic acid (25g, 0.1mol), methanol (32g, 10.0mol), be added to 250ml tri-
In mouth flask, it is heated with stirring to 70 DEG C, so that 3, the 5- di-tert-butyl-4-hydroxybenzoic acid in system is dissolved, add Feldalat NM
(2.5g, 0.0463 mol), back flow reaction 12h.Period, divide exactly the mixture of first alcohol and water at interval of 2h, add methanol 25g,
Continue reaction.After reaction terminates, solvent is evaporated off, plus saturated solution of sodium carbonate agitator treating, add water washing to neutrality, sucking filtration obtains
White solid；It is vacuum dried at 60 DEG C, obtain sterling 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl compound.Calculating of weighing is received
Rate is 78.5%, 161.9 ~ 163.5 DEG C of fusing point.
The characterize data of product is with example 1.
Embodiment 3
Weigh 3,5- di-tert-butyl-4-hydroxybenzoic acid (25g, 0.1mol), methanol (32g, 1.0mol), be added to 250ml tri-
In mouth flask, it is heated with stirring to 70 DEG C, so that 3, the 5- di-tert-butyl-4-hydroxybenzoic acid in system is dissolved, add to toluene sulphur
Sour (1.25g, 0.00726mol), back flow reaction 12h.Period, the mixture dividing exactly first alcohol and water at interval of 2h, add methanol
25g, continues reaction.After reaction terminates, solvent, Deca saturated solution of sodium carbonate agitator treating are evaporated off, add water washing to neutrality,
Sucking filtration obtains white solid, is dried, obtains sterling 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl compound.Calculated yield of weighing is
81.2%, 164.3 ~ 164.5 DEG C of fusing point.
The sign of product is with embodiment 1.
Embodiment 4
Weigh 3,5- di-tert-butyl-4-hydroxybenzoic acid (25g, 0.1mol), methanol (6.4g, 0.2mol), 50ml toluene adds
To in 250ml there-necked flask, agitating heating, so that 3, the 5- di-tert-butyl-4-hydroxybenzoic acid in system is dissolved, add to toluene
Sulfonic acid (2.0g, 0.0116mol), back flow reaction 10h.After reaction terminates, partial solvent is evaporated off, Deca saturated solution of sodium carbonate is stirred
Mix washing, add water washing to neutrality, sucking filtration obtains white solid；It is vacuum dried at 60 DEG C, obtain sterling 3,5- di-t-butyl -4- hydroxyl
Yl benzoic acid methyl compound.Calculated yield of weighing is 79.0%, 164.2 ~ 164.4 DEG C of fusing point.
The sign of product is with embodiment 1.
Embodiment 5
Weigh 3,5- di-tert-butyl-4-hydroxybenzoic acid (250g, 1mol), methanol (320g, 10mol), be added to 1000ml tri-
In mouth flask, it is heated with stirring to 70 DEG C, so that 3, the 5- di-tert-butyl-4-hydroxybenzoic acid in system is dissolved, add to toluene sulphur
Sour (20g, 0.116 mol), back flow reaction 13h.Period, divide exactly the mixture of first alcohol and water at interval of 2h, add methanol 250g,
Continue reaction.After reaction terminates, solvent, Deca saturated solution of sodium carbonate agitator treating are evaporated off, add water washing to neutral, sucking filtration
Obtain white solid, be dried, obtain sterling 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl compound.Calculated yield of weighing is
81.6%, 164.9 ~ 165.2 DEG C of fusing point.
The sign of product is with embodiment 1.
Embodiment 6
Weigh 3,5- di-tert-butyl-4-hydroxybenzoic acid (300g, 1.2mol), methanol (420g, 13.125mol), be added to
In 1000ml there-necked flask, it is heated with stirring to 75 DEG C, so that 3, the 5- di-tert-butyl-4-hydroxybenzoic acid in system is dissolved, add
P-methyl benzenesulfonic acid (30g, 0.1744 mol), back flow reaction 9h.Period, the mixture dividing exactly first alcohol and water at interval of 2h, add
Methanol 328g, continues reaction.After reaction terminates, solvent, Deca saturated solution of sodium carbonate agitator treating are evaporated off, add water washing extremely
Neutrality, sucking filtration obtains white solid, is vacuum dried, obtains sterling 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl compound at 60 DEG C.
Calculated yield of weighing is 80.7%, 164.5 ~ 164.8 DEG C of fusing point.
The sign of product is with embodiment 1.
Embodiment 7
Weigh 3,5- di-tert-butyl-4-hydroxybenzoic acid (250g, 1.0mol), methanol (278g, 0.869mol), be added to
In 1000ml there-necked flask, it is heated with stirring to 65 DEG C, so that 3, the 5- di-tert-butyl-4-hydroxybenzoic acid in system is dissolved, add
P-methyl benzenesulfonic acid (32g, 0.186 mol), back flow reaction 11h.Period, the mixture dividing exactly first alcohol and water at interval of 2h, add
Methanol 328g, continues reaction.After reaction terminates, solvent, Deca saturated solution of sodium carbonate agitator treating are evaporated off, add water washing extremely
Neutrality, sucking filtration obtains white solid, is dried, obtains sterling 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl compound.Calculating of weighing is received
Rate is 81.3%, 164.4 ~ 164.6 DEG C of fusing point.
The sign of product is with embodiment 1.
Claims (6)
1. one kind 3, the synthetic method of 5- di-tert-butyl-4-hydroxybenzoic acid methyl ester, is with 3,5- di-t-butyl -4- hydroxy benzeness first
Acid is raw material, and with excessive methanol as solvent, p-methyl benzenesulfonic acid or Feldalat NM are catalyst, are obtained by back flow reaction.
2. 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester as claimed in claim 1 synthetic method it is characterised in that: 3,5 two
Tertiary butyl-4-hydroxy benzoic acid is 1.0:2.0 ~ 1.0:15.0 with the mol ratio of methanol.
3. 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester as claimed in claim 1 synthetic method it is characterised in that: catalysis
The consumption of agent Feldalat NM or p-methyl benzenesulfonic acid is the 2% ~ 15% of 3,5- di-tert-butyl-4-hydroxybenzoic acid quality.
4. 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester as claimed in claim 1 synthetic method it is characterised in that: described
Back flow reaction is back flow reaction 8 ~ 14h at 60 ~ 80 DEG C；Solvent is evaporated off, solid first uses sodium carbonate or sodium bicarbonate to satisfy after reaction
Wash with solution, then be washed to neutrality, sucking filtration with distillation, be dried, obtain sterling 3,5- di-tert-butyl-4-hydroxybenzoic acid first
Ester.
5. as described in claim 1-4 any 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester synthetic method, its feature
It is: the mixture of in system water and methanol during back flow reaction, is evaporated off at interval of 1.5 ~ 2h, then adds methanol to needs
Amount, then proceed to back flow reaction.
6. 3,5- di-tert-butyl-4-hydroxybenzoic acid methyl ester as claimed in claim 1 synthetic method it is characterised in that: described
Drying is vacuum drying at 30 ~ 60 DEG C.
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| CN201610732086.6A CN106349066A (en) | 2016-08-26 | 2016-08-26 | Synthesis method of methyl 3,5-di-tert-butyl-4-hydroxybenzoate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3029276A (en) * | 1958-06-25 | 1962-04-10 | Bayer Ag | Process for the production of 3, 5-disubstituted-4-hydroxy benzoic acids and their esters |
| CN105541613A (en) * | 2015-12-31 | 2016-05-04 | 浙江师范大学 | Preparing method for 3,5-bis(tertiary butyl)-4-hydroxybenzoic acid hexadecane alkyl ester |
-
2016
- 2016-08-26 CN CN201610732086.6A patent/CN106349066A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3029276A (en) * | 1958-06-25 | 1962-04-10 | Bayer Ag | Process for the production of 3, 5-disubstituted-4-hydroxy benzoic acids and their esters |
| CN105541613A (en) * | 2015-12-31 | 2016-05-04 | 浙江师范大学 | Preparing method for 3,5-bis(tertiary butyl)-4-hydroxybenzoic acid hexadecane alkyl ester |
Non-Patent Citations (1)
| Title |
|---|
| STEPHEN D. PASTOR AND EDWARD T. HESSELL: "Nucleophilic substitution at silicon: synthesis of sterically-hindered bis(2,6-di-tert-butylaryloxy)silanes", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
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Application publication date: 20170125 |