CN101234955B - Method for preparing 3-methoxyl-4-t-butyltoluene - Google Patents
Method for preparing 3-methoxyl-4-t-butyltoluene Download PDFInfo
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- CN101234955B CN101234955B CN2008100545968A CN200810054596A CN101234955B CN 101234955 B CN101234955 B CN 101234955B CN 2008100545968 A CN2008100545968 A CN 2008100545968A CN 200810054596 A CN200810054596 A CN 200810054596A CN 101234955 B CN101234955 B CN 101234955B
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- butyltoluene
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- 238000000034 method Methods 0.000 title claims abstract description 24
- NFDFEFJTYRAHEM-UHFFFAOYSA-N 1-tert-butyl-2-methoxy-4-methylbenzene Chemical compound COC1=CC(C)=CC=C1C(C)(C)C NFDFEFJTYRAHEM-UHFFFAOYSA-N 0.000 title abstract 4
- -1 -tert-butyl metacresol Chemical compound 0.000 claims abstract description 18
- 229940100630 metacresol Drugs 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical group COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 238000003908 quality control method Methods 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000012267 brine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WWGQWWMMZBUFEV-UHFFFAOYSA-N COC=1C=C(C)C=CC1.C1(=CC=CC=C1)COC Chemical compound COC=1C=C(C)C=CC1.C1(=CC=CC=C1)COC WWGQWWMMZBUFEV-UHFFFAOYSA-N 0.000 description 1
- SUAUILGSCPYJCS-UHFFFAOYSA-N Musk ambrette Chemical compound COC1=C([N+]([O-])=O)C(C)=C([N+]([O-])=O)C=C1C(C)(C)C SUAUILGSCPYJCS-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000006209 tert-butylation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 3-methoxyl-4-tert-butyl toluene. Under the existence of quaternary ammonium salt type phase transfer catalysts, 6-tert-butyl metacresol reacts with dimethyl sulphate and water solution of hydroxides or carbonates of alkali metals at 20-50 DEG C, and 3-methoxyl-4-tert-butyl toluene can be produced with high yield. Post treatment of the reaction mixture is very simple and 3-methoxyl-4-tert-butyl toluene with a content of higher than 99.2 percent can be obtained after only two water washing operations. The method has the advantages of simple process, easy product quality control, low cost, low environment pollution and safe production and is suitable for industrialized application.
Description
Technical field
The present invention relates to a kind ofly prepare the method for 3-methoxyl group-4-4-tert-butyltoluene, belong to the chemical industry technical field of organic synthesis from 6-tertiary butyl meta-cresol.
Background technology
In the chemical industry technical field of organic synthesis, 3-methoxyl group-4-4-tert-butyltoluene is an important organic synthesis intermediate, is widely used in the production of spices (as the preparation musk ambrette) and oxidation inhibitor industry.In the prior art, the operational path of preparation 3-methoxyl group-4-4-tert-butyltoluene can be divided into two classes according to the difference of use raw material.Article one, produce route and be between methyl phenylmethylether (3-methoxy toluene) set out, in the presence of catalyzer (as sulfuric acid), carry out liquid phase alkylation reaction with tert-butylation agent (as: trimethyl carbinol, chlorination uncle butane) and prepare.The employed raw material of this a route-methyl phenylmethylether price is higher, 3-methoxyl group-4-4-tert-butyltoluene content in crude product that reaction is generated is lower, need to obtain qualified product after further washing, alkali cleaning, layering and the rectifying, product yield lower (～60%), and in last handling process, to produce a large amount of dilute sulphuric acid waste water solutions, cause very big environmental problem.Therefore this route is not suitable for suitability for industrialized production.Another produces route is to set out from 6-tertiary butyl meta-cresol, in the presence of phase-transfer catalyst (as: tetrabutylammonium chloride) or resin catalyst (as: squama resin or ammonium resin), 6-tertiary butyl meta-cresol and excessive methyl chloride carry out solution-air mutually the O-alkylated reaction generate 3-methoxyl group-4-4-tert-butyltoluene, productive rate is near quantitatively (referring to Chem.Pharm.Bull.
29(8), 2246-50 (1981)).Because this route has used excessive inflammable, explosive methyl chloride (gas), therefore from security standpoint, equally be not suitable for suitability for industrialized production yet.
Summary of the invention
The object of the invention provides that a kind of technology is simple, the method for preparing 3-methoxyl group-4-4-tert-butyltoluene of good quality of product, with low cost and production safety.
In order to realize purpose of the present invention, the inventor has conscientiously studied the method that forefathers prepare 3-methoxyl group-4-4-tert-butyltoluene, shortcoming at forefathers institute using method, through concentrating on studies for many years, proposed the method for a kind of suitable preparation of industrialization 3-methoxyl group-4-4-tert-butyltoluene, and in suitability for industrialized production, achieved success.Particularly, the technical scheme of the inventive method is: in the presence of phase-transfer catalyst, 6-tertiary butyl meta-cresol and methyl-sulfate, alkali-metal oxyhydroxide or carbonate carry out the O-alkylated reaction and generate 3-methoxyl group-4-4-tert-butyltoluene.Above-mentioned these basic cpds are first-selected (for example) with sodium hydroxide, and then its reaction formula is as follows:
After reaction finishes, in reaction mixture, add an amount of water, in order to the methyl sulfate list sodium salt that generates in the solubilizing reaction and the further sodium sulfate that generated of hydrolysis.Layering then, and wash, can be met after the layering the qualified 3-methoxyl group-4-4-tert-butyltoluene of processing requirement once more, product purity＞99%, productive rate reaches 96.2%.
Reaction mass is 6-tertiary butyl meta-cresol, methyl-sulfate and alkali-metal oxyhydroxide or carbonate.In above-mentioned these basic cpds, from cost consideration: be preferably sodium hydroxide.
The methyl-sulfate feed ratio is too small, and then reaction is incomplete, and by product increases, and the temperature of reaction that needs is higher; Otherwise feed ratio is excessive, and then cost increases, and increases the difficulty of last handling process simultaneously, and 6-tertiary butyl meta-cresol: the ratio of the amount of substance that feeds intake of methyl-sulfate is generally 1: (0.95～1.5) is preferably 1: (1.05～1.2).Alkali-metal oxyhydroxide or carbonate feed ratio are too small, then incomplete, the reaction times prolongation of reaction; Otherwise feed ratio is excessive, and then cost increases, and washing times increases during aftertreatment.For ease of operation, above-mentioned these basic cpds feed intake with aqueous solution form, and the massfraction of its aqueous solution is generally 10%～50%, is preferably 40%～45%.6-tertiary butyl meta-cresol: the ratio of the amount of substance that feeds intake of alkali-metal oxyhydroxide or carbonate is generally 1: (0.95～1.5) is preferably 1: (1.1～1.25).
In the reaction, the almost not influence of the adding of each reaction mass or dropping time ordered pair reaction result, during industrial implementation, can adopt following two kinds of feed way as required neatly:
First kind of feed way: in reactor, add the aqueous solution, phase-transfer catalyst and the 6-tertiary butyl meta-cresol of alkali-metal oxyhydroxide or carbonate, then, drip methyl-sulfate down in stirring.
Second kind of feed way: in reactor, add 6-tertiary butyl meta-cresol, phase-transfer catalyst and methyl-sulfate, then, in stirring the aqueous solution that drips alkali-metal oxyhydroxide or carbonate down.
In the reaction, the catalyzer that is adopted is generally the phase-transfer catalyst of quaternary ammonium form, wherein better with the quaternary alkylammonium halides effect, the charging capacity of catalyzer is 0.005～0.02mol by the catalyzer charging capacity that the 6-tertiary butyl meta-cresol 1mol that drops into calculates, be preferably 0.01～0.015mol, best catalyzer is: Tetrabutyl amonium bromide, tetrabutylammonium chloride.
Temperature of reaction is generally 20～50 ℃, is preferably 25～40 ℃, is preferably 33～38 ℃.Reaction temperature is spent low, and the reaction times is long; Temperature of reaction is too high, and then side reaction increases, and product purity reduces.
Rate of addition by exterior cooling and change reaction mass (aqueous solution of methyl-sulfate or alkali-metal oxyhydroxide or its carbonate) comes control reaction temperature.
After dripping reaction mass (aqueous solution of methyl-sulfate or alkali-metal oxyhydroxide or its carbonate), restir reaction for some time, be generally 0.5～2hr., be preferably 1hr, then stopped reaction.
The post processing mode of reaction solution is very simple, the water, stirring, the hydrolysis washing that in reaction mixture, add certain volume, remove salt, leave standstill the branch oil-yielding stratum, resulting oil reservoir is used again the water of certain volume, stir, wash, leave standstill the branch oil-yielding stratum, just obtain 3-methoxyl group-4-4-tert-butyltoluene finished product.When necessary, then can obtain more highly purified product by underpressure distillation.But＞99%, be enough to satisfy the requirement that successor is produced by the purity of the resultant product of previous methods.The water consumption of twice water washing process is generally 0.5～2 times of reaction mixture volume, is preferably 0.8～1.2 times.
The positively effect that the present invention obtains is: preparation method's technology of the present invention is simple, and process cost is low, and quality product is easy to control, and productive rate is higher, and environmental pollution is little, and production safety is suitable for industrial applications.
Embodiment
The following examples are used to illustrate the present invention.It may be noted that following examples are not construed as limiting the invention.
Embodiment 1
The 6-tertiary butyl meta-cresol, 3.9g (12mmol) Tetrabutyl amonium bromide that in the 1000mL four-hole round-bottomed flask that has reflux exchanger, thermometer, constant pressure funnel and mechanical stirrer, add 153g (0.93mol) content＞99.5% successively, stir after 1～2 minute, add 105mL (～139.5g, 1.11mol) methyl-sulfate again.Under the ice-water bath cooling and stirring, in 2～3hr., in said mixture, drip the aqueous sodium hydroxide solution of 109.3g (1.16mol) concentration 42.5% (wt%).By the control rate of addition, the interior temperature of keeping the dropping process is 35 ± 2 ℃.After dripping off, keep said temperature, continue stirring reaction 0.5hr. again.After reaction finishes, stop to stir, add 200g water in flask, mix 0.5hr., stop to stir, standing demix divides water-yielding stratum.Oil reservoir stirs washing, standing demix with 300g water again, thereby obtains 157g 3-methoxyl group-4-4-tert-butyltoluene, and GC analysed preparation purity is 99.5%, productive rate 95%.
Embodiment 2
Except adopting 3.4g (12.3mol) tetrabutylammonium chloride to replace the Tetrabutyl amonium bromide in the example, other operation is all identical with embodiment 1, thereby obtains 152g 3-methoxyl group-4-4-tert-butyltoluene, and GC analysed preparation purity is 99.2%, productive rate 91.2%.
Embodiment 3
The aqueous sodium hydroxide solution that in the 2000L stirred autoclave, adds 407kg (4.324kmol) concentration 42.5% (wt%) successively, the 6-tertiary butyl meta-cresol of 570kg (3.476kmol) content＞99.5% and 14.55kg (45.19mol) Tetrabutyl amonium bromide, open and stir, in reacting kettle jacketing, feed cool brine, in 6～8hr., in the methyl-sulfate test tank, in said mixture, drip 393L (522kg, 4.14kmol) methyl-sulfate, by the rate of addition of control methyl-sulfate and the flow of cool brine, keeping the material in reactor temperature is 36～38 ℃.Drip after the methyl-sulfate (in the above-mentioned reaction, the mol ratio that feeds intake is: 6-tertiary butyl meta-cresol: methyl-sulfate: sodium hydroxide: Tetrabutyl amonium bromide=1: 1.192: 1.244: 0.013 (mol: mol)), keep said temperature and continue stirring reaction 1hr. again.After reaction finishes, in reactor, add water of 600L, mix 0.5hr., standing demix is emitted after lower floor's water, oil phase is put to outdoor washing still, add water of 1000L again, stir washing 0.5hr., standing demix, emit after lower floor's water, oil reservoir is 3-methoxyl group-4-4-tert-butyltoluene.Output: 601kg, GC purity: 99.2%, productive rate: 96.2%.
Embodiment 4～6
The aqueous sodium hydroxide solution in the aqueous solution (its concentration (wt%) and quantity see the following form) the replacement embodiment 1 that adopts potassium hydroxide, salt of wormwood, yellow soda ash, other operation is all identical with embodiment 1.Experimental result is listed in the table below
| Embodiment | Alkali-metal oxyhydroxide or carbonate solution feed intake | Product purity | Productive rate | ||
| Title | Concentration | Quantity (g)/mol number | |||
| 4 5 6 | Potassium hydroxide salt of wormwood yellow soda ash | 45％ 40％ 20％ | 150g/1.20mol 363g/1.05mol 557g/1.05mol | 99.5％ 99.2％ 99.5％ | 96.0％ 92.5％ 92％ |
Claims (7)
1. method for preparing 3-methoxyl group-4-4-tert-butyltoluene, it is characterized in that: in the presence of the quaternary phase-transfer catalyst, 20～50 ℃ of control reaction temperature, 6-tertiary butyl meta-cresol and methyl-sulfate and alkali-metal oxyhydroxide or carbonate reaction 0.5～2hr., reaction mixture adds suitable quantity of water and is hydrolyzed, layering then, and wash once more, obtain 3-methoxyl group-4-4-tert-butyltoluene product after the layering.
2. by the described method for preparing 3-methoxyl group-4-4-tert-butyltoluene of claim 1, it is characterized in that the ratio of the amount of substance of starting raw material is: 6-tertiary butyl meta-cresol: methyl-sulfate: alkali-metal oxyhydroxide or carbonate=1: (0.95～1.5): (0.95～1.5).
3. by the described method for preparing 3-methoxyl group-4-4-tert-butyltoluene of claim 1, it is characterized in that said quaternary phase-transfer catalyst is Tetrabutyl amonium bromide or tetrabutylammonium chloride.
4. by claim 1 or the 3 described methods that prepare 3-methoxyl group-4-4-tert-butyltoluene, it is characterized in that the catalyzer charging capacity of calculating by the 6-tertiary butyl meta-cresol 1mol that drops into is 0.005～0.02mol.
5. by the described method for preparing 3-methoxyl group-4-4-tert-butyltoluene of claim 1, it is characterized in that temperature of reaction is 33～38 ℃.
6. by the described method for preparing 3-methoxyl group-4-4-tert-butyltoluene of claim 1, the water consumption that it is characterized in that twice washing of last handling process is 0.5～2 times of reaction mixture volume.
7. by the described method for preparing 3-methoxyl group-4-4-tert-butyltoluene of claim 1, it is characterized in that alkali-metal oxyhydroxide is potassium hydroxide, sodium hydroxide, alkali-metal carbonate is salt of wormwood and yellow soda ash, and the massfraction of its aqueous solution is 10%～50%.
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| CN103833553B (en) * | 2010-12-21 | 2015-06-10 | 浙江九洲药业股份有限公司 | Midbody for preparing agomelatine and preparation method thereof |
| CN107417537A (en) * | 2017-06-02 | 2017-12-01 | 天津市安凯特科技发展有限公司 | A kind of synthetic method of Musk ambrette |
| CN112624922A (en) * | 2020-11-26 | 2021-04-09 | 青岛科技大学 | Method for alkylation reaction by phase transfer catalysis |
| CN113402437B (en) * | 2021-06-29 | 2023-07-14 | 河北维达康生物科技有限公司 | A new method for the synthesis of the dietary supplement melatonin |
| CN117105789A (en) * | 2023-09-06 | 2023-11-24 | 濮阳市元泰精细化工有限公司 | Preparation and refining method of musk with sunflower seeds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762949A (en) * | 2005-09-23 | 2006-04-26 | 云南科恩生物工程有限公司 | 3,4,5-trimethoxytoluene preparation process |
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| CN1762949A (en) * | 2005-09-23 | 2006-04-26 | 云南科恩生物工程有限公司 | 3,4,5-trimethoxytoluene preparation process |
Non-Patent Citations (2)
| Title |
|---|
| YASUMASA HAMADA NOBUHARU KATO et al..A Resin-promoted Williamson＇s Alkyl Ether Synthesis.Methylation of 2-tert-Butyl-5-methylphenol with Methyl Chloride.Chem. Pharm.Bull.29 8.1981,2246-2250. |
| YASUMASA HAMADA NOBUHARU KATO et al..A Resin-promoted Williamson＇s Alkyl Ether Synthesis.Methylation of 2-tert-Butyl-5-methylphenol with Methyl Chloride.Chem. Pharm.Bull.29 8.1981,2246-2250. * |
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