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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- butyl
- tert
- hydroxybenzoic acid
- methanol
- reaction
- 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.)
- Pending
Links
- UPVYFJALDJUSOV-UHFFFAOYSA-N 3,5-Bis(1,1-dimethylethyl)-4-hydroxy-benzoic acid ethyl ester Chemical compound COC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 UPVYFJALDJUSOV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- YEXOWHQZWLCHHD-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1O YEXOWHQZWLCHHD-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- LCQXXVFFJHBYME-UHFFFAOYSA-N 2-butyl-4-hydroxybenzoic acid Chemical group CCCCC1=CC(O)=CC=C1C(O)=O LCQXXVFFJHBYME-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- -1 methyl 3,5-di-tert-butyl-4-hydroxybenzoate compound Chemical class 0.000 abstract description 12
- 238000005406 washing Methods 0.000 abstract description 11
- 239000012047 saturated solution Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 239000003963 antioxidant agent Substances 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 238000003828 vacuum filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610732086.6A CN106349066A (en) | 2016-08-26 | 2016-08-26 | Synthesis method of methyl 3,5-di-tert-butyl-4-hydroxybenzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610732086.6A CN106349066A (en) | 2016-08-26 | 2016-08-26 | Synthesis method of methyl 3,5-di-tert-butyl-4-hydroxybenzoate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106349066A true CN106349066A (en) | 2017-01-25 |
Family
ID=57855138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610732086.6A Pending CN106349066A (en) | 2016-08-26 | 2016-08-26 | Synthesis method of methyl 3,5-di-tert-butyl-4-hydroxybenzoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106349066A (en) |
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》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3848357B1 (en) | Reactive benzotriazole uv absorber and use thereof | |
| CN110105201B (en) | Preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid | |
| CN109721548A (en) | A kind of preparation method of Fluoxastrobin | |
| CN102816324B (en) | Method for synthesis of polyethylene glycol monoricinoleate by borate method | |
| CN104860872A (en) | Bis-(3R,4R)-1-benzyl-N,4-dimethyl piperidin-3-amine L-di-p-toluyl tartrate synthesis method | |
| CN106349066A (en) | Synthesis method of methyl 3,5-di-tert-butyl-4-hydroxybenzoate | |
| CN103435456B (en) | Preparation method for 9-fluorenone | |
| CN113354695A (en) | Continuous production process of emamectin benzoate B1/B2 | |
| CN104311493A (en) | Azoxystrobin synthesis method | |
| CN107722042B (en) | A kind of synthetic method of Flomoxef parent nucleus | |
| CN107434772A (en) | A kind of N, N are double（2 hydroxyethyls）The preparation method of Methacrylamide | |
| CN114315575B (en) | Preparation method and application of photoinitiator intermediate | |
| CN103467264B (en) | A kind of method being prepared 9-Fluorenone by Industrial fluorene | |
| CN110713439A (en) | Preparation method of cyclohexane-1, 2-dicarboxylate environment-friendly plasticizer | |
| CN113087740B (en) | Preparation method and application of organotin ionic liquid catalyst | |
| US20240425371A1 (en) | Working solution for producing hydrogen peroxide through anthraquinone process and solvent system thereof | |
| CN109535041B (en) | Method for producing polyester modifier SIPE (styrene-isoprene-styrene) by using composite catalyst | |
| CN116283514A (en) | A kind of preparation method of 2-tert-butyl-4-hydroxyanisole | |
| CN104876822B (en) | A kind of preparation method of pentaerythritol acrylate | |
| CN111116567A (en) | Intermediates of zanamivir and lanamivir and their synthetic methods | |
| CN111072450B (en) | Synthesis method of allyl alcohol derivative | |
| CN102675148A (en) | Preparation method of hydroxybenzyl cyanide | |
| CN116730841A (en) | Preparation method for synthesizing bisphenol monoacrylate antioxidant with low cost and high selectivity | |
| CN105732969B (en) | High-molecular antioxidant and antistatic bifunctional compound, and synthesis method and application thereof | |
| CN114478315B (en) | Method for catalytic reduction of irosartan biphenyl waste residues by using halogen-modified Pd/C catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170125 |