CN104230675A - Preparation method of 4-bromoanisole - Google Patents
Preparation method of 4-bromoanisole Download PDFInfo
- Publication number
- CN104230675A CN104230675A CN201410439286.3A CN201410439286A CN104230675A CN 104230675 A CN104230675 A CN 104230675A CN 201410439286 A CN201410439286 A CN 201410439286A CN 104230675 A CN104230675 A CN 104230675A
- Authority
- CN
- China
- Prior art keywords
- preparation
- bromoanisole
- product
- oxidizing gas
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 4-bromoanisole. The preparation method comprises the following steps: under an oxidizing gas atmosphere, dissolving methoxybenzene and liquid bromine into 1-butyl-3-methylimidazole nitrate, and reacting for more than 1h under closed conditions at 25-100 DEG C to obtain a 4-bromoanisole product. The preparation method disclosed by the invention has the advantages that (1) almost all of bromination reagents and raw materials adopted in the preparation method are transformed into the product, and wastes such as hydrobromic acid and the like can be hardly produced; (2) the preparation method is simple in reaction operation, and adopted solvents are hard to volatilize, so that the volatile pollution of organic solvents can be reduced; and (3) the 4-bromoanisole product prepared by using the preparation method is good in purity and high in raw material conversion rate, so that the product quality can be effectively improved, and the production cost can be reduced.
Description
Technical field
The present invention relates to industrial chemicals preparing technical field, be specifically related to a kind of preparation method of 4-bromoanisole.
Background technology
4-bromoanisole is the synthesis material of multiple organic chemicals, such as can be used for synthesis and avoid injured skin, Octyl methoxycinnamate UV light absorber (chemistry and the biotechnology of prevention skin carcinoma, 2012,29,47), can be used for medicinal intermediates (Chinese patent, the patent No.s: 201210498870.7) such as preparation 4-methoxyphenethylamine.The bromination reaction of methyl-phenoxide is one of the effective ways of synthesis 4-bromoanisole (Chemical Industry in Guangzhou, 2006,33,12).Based on this bromination reaction, the major technique of exploitation is as follows both at home and abroad: the method (Adv.Synth.Catal.2013,355,337) that (1) is bromide reagent with Bromonium ion Equivalent.This method is general comparatively effective, but the higher (J.Am.Chem.Soc. 2012 of bromide reagent cost such as the bromo-succinimide used, 134,8298), and the atom utilization of bromide reagent is not high, a lot of waste can be produced after bromine is utilized, not meet the Atom economy principle of contemporary chemical requirements.(2) with the method (Green Chem.2012,14,1125) that bromine salt/oxygenant is bromide reagent system.Also there is the not high problem of the atom utilization of bromide reagent in this method; Not only waste raw material, and can industrial cost be increased.(3) take molecular bromine as the method (Guangxi science, 2000,7,200) of bromide reagent.In this approach, only the bromine of half is utilized, and second half bromine is converted into the strong Hydrogen bromide of corrodibility, thus causes the waste of raw material and the increase of industrial cost.Therefore add oxygenant, be the molecular bromine that can participate in reacting Hydrogen bromide in-situ oxidation, thus improve the utilization ratio in bromine source, avoid hydrobromic generation to be necessary.
Summary of the invention
The object of the invention is the deficiency for solving the problems of the technologies described above, a kind of preparation method of 4-bromoanisole is provided, using 1-butyl-3-methylimidazolium nitrate as solvent and catalyzer, methyl-phenoxide is utilized to prepare 4-bromoanisole, overcome the waste produced in existing method many, the problem that comprehensive cost is high.
The present invention is the deficiency solved the problems of the technologies described above, the technical scheme adopted is: a kind of preparation method of 4-bromoanisole, under oxidizing gas atmosphere, methyl-phenoxide and bromine are dissolved in 1-butyl-3-methylimidazolium nitrate, under 25-100 DEG C of temperature condition and air tight condition, react more than 1h, obtain 4-bromoanisole product.
4-bromoanisole structural formula of compound is as follows:
Synthetic route is as follows:
Described oxidizing gas is oxygen or air.
Described oxidizing gas is air.
Described reaction raw materials methyl-phenoxide and Br
2the ratio of amount of substance be 1:0.5.
The temperature of described confined reaction is 80 DEG C.
The time of described confined reaction is 24h.
beneficial effect
(1), in preparation method of the present invention nearly all bromide reagent and raw material have all been transformed in product, and product yield is high, produce Hydrogen bromide the like waste hardly.
(2), preparation method's operation of the present invention is simple, and the solvent of use is non-volatile, avoids the pollution caused because organic solvent volatilization.
(3), the 4-bromoanisole product purity that obtains of preparation method of the present invention is high, thus effectively improves quality product, reduces production cost.
accompanying drawing illustrates:
Fig. 1 is the product 4-bromoanisole of embodiment 1
1h-NMR schemes.
Fig. 2 is the product 4-bromoanisole of embodiment 1
13c-NMR schemes.
Fig. 3 is the mass spectrum of the product 4-bromoanisole of embodiment 1.
embodiment:
Be below specific embodiments of the invention, but protection scope of the present invention is not limited thereto:
embodiment 1
In reaction tubes, add magneton, the 1-butyl-3-methylimidazolium nitrate of 1ml, the methyl-phenoxide of 0.5mmol and the Br of 0.25mmol successively
2(not removing the air in reaction tubes).Then sealed reaction test tube, 80
oc lower magnetic force stirs 24h.After question response terminates, cooling reaction system, to room temperature, adds 3ml distilled water, extracts (3 × 10mL) product with methylene dichloride.Merge organic phase, utilize gas chromatograph to carry out quantitative analysis, show that the gas phase interior mark productive rate of product is 86%.Utilize column chromatography to carry out separating-purifying to product, obtain 4-bromoanisole product.Utilize
1h-NMR,
3c-NMR and
1mass spectrum determination product structure is shown in Fig. 1-3.
embodiment 2
Reaction atmosphere in embodiment 1 is replaced by the oxygen of normal pressure, other conditions are constant, show that the gas phase interior mark productive rate of product is 87%.
embodiment 3-7
Temperature of reaction in embodiment 1 is become 25 respectively
oc, 40
oc, 60
oc, 80
oc, 100
oc, other conditions are constant, show that the GC interior mark productive rate of product is respectively 54%, 72%, 81%, 86%, 91%.
embodiment 8-17
Reaction times in embodiment 1 is become 1h, 3h, 5h, 8h, 10h, 13h, 15h, 20h, 24h, 30h respectively, other conditions are constant, show that the GC interior mark productive rate of product is respectively 85%, 97%, 87%, 90%, 92%, 93%, 97%, 95%, 86%, 85%.
Claims (6)
1. a preparation method for 4-bromoanisole, is characterized in that: under oxidizing gas atmosphere, methyl-phenoxide and bromine is dissolved in 1-butyl-3-methylimidazolium nitrate, at 25-100 DEG C of temperature and air tight condition, reacts more than 1h, obtain 4-bromoanisole product.
2. the preparation method of a kind of 4-bromoanisole as claimed in claim 1, is characterized in that: described oxidizing gas is oxygen or air.
3. the preparation method of a kind of 4-bromoanisole as claimed in claim 2, is characterized in that: described oxidizing gas is air.
4. the preparation method of a kind of 4-bromoanisole as claimed in claim 1, is characterized in that: described reaction raw materials methyl-phenoxide and Br
2the ratio of amount of substance be 1:0.5.
5. the preparation method of a kind of 4-bromoanisole as claimed in claim 1, is characterized in that: the temperature of described confined reaction is 80 DEG C.
6. the preparation method of a kind of 4-bromoanisole as claimed in claim 1, is characterized in that: the time of described confined reaction is 24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410439286.3A CN104230675A (en) | 2014-09-01 | 2014-09-01 | Preparation method of 4-bromoanisole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410439286.3A CN104230675A (en) | 2014-09-01 | 2014-09-01 | Preparation method of 4-bromoanisole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104230675A true CN104230675A (en) | 2014-12-24 |
Family
ID=52219690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410439286.3A Pending CN104230675A (en) | 2014-09-01 | 2014-09-01 | Preparation method of 4-bromoanisole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104230675A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403452A (en) * | 2022-10-12 | 2022-11-29 | 锦州四海生物化学有限公司 | Preparation method of p-methoxyphenol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471502A (en) * | 2000-10-10 | 2004-01-28 | ������˹��Ů����ѧ | Oxidative halogenation of aromatic compound |
| CN101857518A (en) * | 2010-06-10 | 2010-10-13 | 浙江工业大学 | Green synthesizing method of aryl bromide |
| CN102030706A (en) * | 2010-12-22 | 2011-04-27 | 江苏食品职业技术学院 | Method for preparing 6-hydroxy-2(1H)-quinolone in ionic liquid by using one-pot method |
| CN102260127A (en) * | 2011-06-16 | 2011-11-30 | 华东师范大学 | Method for preparing halogenated aryl compounds through oxidation and halogenation |
| CN102351815A (en) * | 2011-11-04 | 2012-02-15 | 合肥工业大学 | Synthesis method of 5-bromo-2-furaldehyde |
-
2014
- 2014-09-01 CN CN201410439286.3A patent/CN104230675A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471502A (en) * | 2000-10-10 | 2004-01-28 | ������˹��Ů����ѧ | Oxidative halogenation of aromatic compound |
| CN101857518A (en) * | 2010-06-10 | 2010-10-13 | 浙江工业大学 | Green synthesizing method of aryl bromide |
| CN102030706A (en) * | 2010-12-22 | 2011-04-27 | 江苏食品职业技术学院 | Method for preparing 6-hydroxy-2(1H)-quinolone in ionic liquid by using one-pot method |
| CN102260127A (en) * | 2011-06-16 | 2011-11-30 | 华东师范大学 | Method for preparing halogenated aryl compounds through oxidation and halogenation |
| CN102351815A (en) * | 2011-11-04 | 2012-02-15 | 合肥工业大学 | Synthesis method of 5-bromo-2-furaldehyde |
Non-Patent Citations (5)
| Title |
|---|
| SUBHAS CHANDRA ROY ET AL.: "An efficient chemo and regioselective oxidative nuclear bromination of activated aromatic compounds using lithium bromide and ceric ammonium nitrate", 《TETRAHEDRON LETTERS》, vol. 42, 31 December 2001 (2001-12-31), pages 6941 - 6942, XP004317813, DOI: doi:10.1016/S0040-4039(01)01412-5 * |
| 乐长高: "离子液体在选择性有机反应中的应用研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 8, 15 December 2005 (2005-12-15), pages 014 - 7 * |
| 汪旭轮: "芳烃氧化溴代反应及芳烃与炔烃的反应", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 11, 15 November 2010 (2010-11-15), pages 014 - 39 * |
| 邵艳等: "对溴苯甲醚合成的研究", 《广东化工》, vol. 33, no. 8, 31 December 2006 (2006-12-31) * |
| 陈巍: "氧化溴代反应的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 01, 15 January 2007 (2007-01-15), pages 014 - 26 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403452A (en) * | 2022-10-12 | 2022-11-29 | 锦州四海生物化学有限公司 | Preparation method of p-methoxyphenol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Transition-metal-free aerobic oxidation of primary alcohols to carboxylic acids | |
| Liu et al. | Transition‐Metal‐Free Coupling of Alkynes with α‐Bromo Carbonyl Compounds: An Efficient Approach towards β, γ‐Alkynoates and Allenoates | |
| CN101928309B (en) | 3,2',6'-tri-N-acetyl gentamicin C1asynthesis method | |
| CN103641722B (en) | A kind of production method of adjacent nitro bromobenzyl | |
| CN104447271A (en) | Method for synthesizing benzoic acid through alcohol catalysis under condition of illumination | |
| CN103664656A (en) | Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid | |
| CN103214328B (en) | Synthesis method for alpha-bromo-aromatic ketone compounds | |
| CN108558916B (en) | Synthesis process of p-phenylbutoxy benzoic acid | |
| CN104230675A (en) | Preparation method of 4-bromoanisole | |
| CN104892426A (en) | Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst | |
| Luo et al. | Oxidation of alcohols to carbonyl compounds with molecular iodine in the presence of potassium tert-butoxide | |
| CN103804105A (en) | Synthesis method for biphenyl compounds | |
| CN106995362A (en) | The preparation method of seven fluorine cyclopentene | |
| CN103539766A (en) | Preparation method of furfural | |
| CN101717949B (en) | Method for preparing p-vinyl phenylacetic acid | |
| CN103497138B (en) | A kind ofly utilize zinc chloride, method that POTASSIUM BOROHYDRIDE prepares cis-hexahydroisoindoline | |
| CN114293210B (en) | Method for continuously electrosynthesis of benzopyran-4-ketone by using micro-reaction device | |
| CN104209086B (en) | Can be used to separate the adsorption separating agent and separation method of hexafluoropropene and HFPO mixed gas | |
| CN107417659A (en) | A kind of method using carbon dioxide atmospheric synthesis carbonic ester | |
| CN109134538B (en) | Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof | |
| CN102040527A (en) | Preparation method of N,N-benzyl diphenylamine | |
| CN104610064A (en) | Process for preparing dimethyl carbonate through taking carbonate as catalyst by one-pot method | |
| CN105622351A (en) | Method for preparing benzenediol | |
| CN107382895B (en) | A kind of synthetic method of 2- phenyl benzoxazoles class compound | |
| CN104311456A (en) | Preparation method of guaiacol potassium sulfoacid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141224 |