CN108276258A - A kind of synthetic method of terephthaldehyde's ether - Google Patents
A kind of synthetic method of terephthaldehyde's ether Download PDFInfo
- Publication number
- CN108276258A CN108276258A CN201810268650.2A CN201810268650A CN108276258A CN 108276258 A CN108276258 A CN 108276258A CN 201810268650 A CN201810268650 A CN 201810268650A CN 108276258 A CN108276258 A CN 108276258A
- Authority
- CN
- China
- Prior art keywords
- product
- terephthaldehyde
- steamed
- synthetic method
- 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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
-
- 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
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of terephthaldehyde's ether, a kind of synthetic method of terephthaldehyde's ether specifically includes following steps：（1）Using hydroquinone and dimethyl suflfate as raw material, fully reacted in alkaline medium；（2）After completion of the reaction, crystal evaporate is steamed using rectifier unit, until water has all steamed；（3）Then distilling apparatus is used, product is distilled to receiving flask and is collected；（4）By product cooling solidification at solid, required finished product is obtained.The product elder generation rectifying water outlet that the present invention will obtain after reaction, redistillation go out product, the product moisture-free steamed, without carrying out the processes such as dewatered drying again, direct cooling solidification can be obtained solid articles, this isolation and purification method products obtained therefrom appearance color is white, purity is high, and moisture is low；And the water steamed in distillation process can recycle；It is easy to operate, production cost is reduced, the production cycle is shortened, improves production efficiency.
Description
Technical field
The invention belongs to technical field of chemical synthesis, and in particular to a kind of synthetic method of terephthaldehyde's ether.
Background technology
Title：Terephthaldehyde's ether,
Alias：1,4- dimethoxy benzenes；Hydroquinone dimethyl ether；Hydroquinone dimethyl ether；Paradimethoxybenzene
Structural formula：
Molecular formula：C8H10O2
Molecular weight：138.16
CAS NO.：150-78-8
Purposes：1. GB 2,760 1 96 is defined as the flavorant for allowing to use.It is mainly used for preparing nut fruits essence；2. should
Product are organic synthesis intermediate, for producing drug methoxamine hydrochloride, dyestuff black salt ANS etc..Fixastive is also served as, is used for
Household chemicals, synthetic food, flavouring essence for tobacco；Be alternatively arranged as plastics, weather-proof dose of coating；3. as among organic chemical industry
Body also serves as fixastive for producing drug methoxamine hydrochloride, dyestuff black salt ANS etc.；4. can also be used for the conjunction of fragrance
At.
Product quality indicator：
Documents CN200810200000.0 discloses the common commercial synthesis method of current terephthaldehyde's ether：With hydroquinone
It is raw material with dimethyl suflfate, replaces in alkaline medium and obtain product, uses distilling apparatus in the later stage of reaction, to be passed through water
Steam carries out steam distillation, reaction product is made to be distillated together with vapor, and intermediate product and raw material are further completely anti-
It answers, to improve reaction yield.The method has the drawback that：1. to there is water vapour to be passed through；2. distillation efficiency is low；3. the production steamed
Product will be dehydrated and dry；So production cost is high, the period is long, and efficiency is low.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of synthetic method of terephthaldehyde's ether,
The technical scheme is that：A kind of synthetic method of terephthaldehyde's ether, specifically includes following steps：
（1）Using hydroquinone and dimethyl suflfate as raw material, fully reacted in alkaline medium solution；
（2）After completion of the reaction, crystal evaporate is steamed using rectifier unit, until water has all steamed；
（3）Then distilling apparatus is used, product is distilled to receiving flask and is collected；
（4）By product cooling solidification at solid, required finished product is obtained.
Further, the alkaline medium solution is sodium hydroxide solution.
Further, the quality molar ratio of the hydroquinone, sodium hydroxide, water and dimethyl suflfate is 1:2.75:
18.35:1.3。
Further, the step（1）Reaction temperature be 95 ~ 100 DEG C, the reaction time be 5 hours.
Further, the step（2）Rectification temperature be 120 ~ 130 DEG C.
Further, the step（3）Vapo(u)rizing temperature be 240 ~ 250 DEG C.
Further, the step（4）Temperature be 55 DEG C or less.
Further, the step（2）The water that steams of rectifying can recycle.
Reaction equation is as follows：
At salt：
It methylates：
Wherein, step（2）The rectifying is to be detached water and product in rectifying column by rectifying column, and water is all steamed
Go out.
The beneficial effects of the invention are as follows：The product elder generation rectifying water outlet that will be obtained after reaction, redistillation go out product, the production steamed
Product moisture-free, without carrying out the processes such as dewatered drying again, direct cooling solidification can be obtained solid articles, this side of isolating and purifying
Method products obtained therefrom appearance color is white, and purity is high, and moisture is low；And the water steamed in distillation process can recycle；It does not need
Vapor is passed through, and directly distills out product by heating after rectifying water outlet, distillation efficiency is high, and impurity is few, and the product steamed is not required to
It is dehydrated and dries, easy to operate, production cost reduces about 8%-10%, and the production cycle shortens nearly 30%, improves production effect
Rate.
The present invention is compared with the conventional method that documents CN200810200000.0 is disclosed, and the comparison is as follows：
| Former technique | Present invention process | |
| 1 | Steam distillation needs steam generation facility, such as steam boiler equipment, and in use, needs Water in boiler is supplemented, there are secondary heating processes, extend the production cycle | Rectifying first steams water, and product stays in reaction kettle, has steamed Product is steamed after water again. |
| 2 | Steam distillation, distillate are the mixtures of water and product, and distillation efficiency is low, and the production cycle is long. | First water has all been steamed, then has steamed product, the production cycle It is short. |
| 3 | Distillate carries out dehydration and drying process, production cycle are long. | The product steamed is anhydrous, need not be dehydrated and dry Process. |
Specific implementation mode
Present disclosure is further elaborated with reference to specific embodiment, but embodiment is only of the invention
Better embodiment, therefore the equivalence changes that all features and principle according to described in present patent application range are done, are included in
Within the scope of present patent application.
Embodiment 1
To equipped with thermometer, stirs, 45g hydroquinones is added in the 500mL four-hole bottles of reflux condenser and constant pressure funnel,
45g sodium hydroxides, 135g water.Stirring is opened, after raw material all dissolving, is slowly added dropwise from constant pressure funnel into reaction bulb
67g dimethyl suflfates control rate of addition, and interior temperature is made to be no more than 80 DEG C.After being added dropwise, heating is opened, is kept the temperature at 95 DEG C anti-
It answers 5 hours.After the completion of reaction, reflux condenser is changed to rectifier unit, 120 DEG C is heated to and steams crystal evaporate, until water is whole
Until having steamed.Rectifier unit is changed to distilling apparatus again, is heated to 240 DEG C, product is distilled to receiving flask.Gained finished product cools down
To 50 DEG C, it is frozen into solid.
Embodiment 2
To equipped with thermometer, stirs, 90g hydroquinones is added in the 500mL four-hole bottles of reflux condenser and constant pressure funnel,
90g sodium hydroxides, 270g water.Stirring is opened, after raw material all dissolving, is slowly added dropwise from constant pressure funnel into reaction bulb
134g dimethyl suflfates control rate of addition, and interior temperature is made to be no more than 80 DEG C.After being added dropwise, heating is opened, is kept the temperature at 100 DEG C
Reaction 5 hours.After the completion of reaction, reflux condenser is changed to rectifier unit, 130 DEG C is heated to and steams crystal evaporate, until water is complete
Until portion has been steamed.Rectifier unit is changed to distilling apparatus again, is heated to 250 DEG C, product is distilled to receiving flask.Gained finished product drops
Temperature is frozen into solid to 52 DEG C.
Embodiment 3
It to equipped with thermometer, stirs, 67.5g is added in the 500mL four-hole bottles of reflux condenser and constant pressure funnel to benzene two
Phenol, 67.5g sodium hydroxides, 202.5g water.Stirring is opened, after raw material all dissolving, from constant pressure funnel into reaction bulb
100.5g dimethyl suflfates are slowly added dropwise, control rate of addition, interior temperature is made to be no more than 80 DEG C.After being added dropwise, heating is opened,
98 DEG C of insulation reactions 5 hours.After the completion of reaction, reflux condenser is changed to rectifier unit, 125 DEG C is heated to and steams crystal evaporate
Go out, until water has all steamed.Rectifier unit is changed to distilling apparatus again, is heated to 245 DEG C, product is distilled to receiving flask.
Gained finished product is cooled to 53 DEG C, is frozen into solid.
Embodiment 4
It to equipped with thermometer, stirs, 135g is added in the 500mL four-hole bottles of reflux condenser and constant pressure funnel to benzene two
Phenol, 135g sodium hydroxides, 405g water.Stirring is opened, it is slow into reaction bulb from constant pressure funnel after raw material all dissolving
201g dimethyl suflfates are added dropwise, control rate of addition, interior temperature is made to be no more than 80 DEG C.After being added dropwise, heating is opened, is protected at 98 DEG C
Temperature reaction 5 hours.After the completion of reaction, reflux condenser is changed to rectifier unit, 125 DEG C is heated to and steams crystal evaporate, until water
Until all having steamed.Rectifier unit is changed to distilling apparatus again, is heated to 245 DEG C, product is distilled to receiving flask.Gained finished product
53 DEG C are cooled to, solid is frozen into.
Embodiment 5
To equipped with thermometer, stirs, 45g hydroquinones is added in the 500mL four-hole bottles of reflux condenser and constant pressure funnel,
45g sodium hydroxides, 135g water.Stirring is opened, after raw material all dissolving, is slowly added dropwise from constant pressure funnel into reaction bulb
67g dimethyl suflfates control rate of addition, and interior temperature is made to be no more than 80 DEG C.After being added dropwise, heating is opened, is kept the temperature at 97 DEG C anti-
It answers 5 hours.After the completion of reaction, reflux condenser is changed to rectifier unit, 126 DEG C is heated to and steams crystal evaporate, until water is whole
Until having steamed.Rectifier unit is changed to distilling apparatus again, is heated to 244 DEG C, product is distilled to receiving flask.Gained finished product cools down
To 53 DEG C, it is frozen into solid.
Embodiment 6
To equipped with thermometer, stirs, 81g hydroquinones is added in the 500mL four-hole bottles of reflux condenser and constant pressure funnel,
81g sodium hydroxides, 243g water.Stirring is opened, after raw material all dissolving, is slowly added dropwise from constant pressure funnel into reaction bulb
120.6g dimethyl suflfates control rate of addition, and interior temperature is made to be no more than 80 DEG C.After being added dropwise, heating is opened, is kept the temperature at 99 DEG C
Reaction 5 hours.After the completion of reaction, reflux condenser is changed to rectifier unit, 128 DEG C is heated to and steams crystal evaporate, until water is complete
Until portion has been steamed.Rectifier unit is changed to distilling apparatus again, is heated to 248 DEG C, product is distilled to receiving flask.Gained finished product drops
Temperature is frozen into solid to 53 DEG C.
Embodiment 7
It to equipped with thermometer, stirs, 108g is added in the 500mL four-hole bottles of reflux condenser and constant pressure funnel to benzene two
Phenol, 108g sodium hydroxides, 324g water.Stirring is opened, it is slow into reaction bulb from constant pressure funnel after raw material all dissolving
160.8g dimethyl suflfates are added dropwise, control rate of addition, interior temperature is made to be no more than 80 DEG C.After being added dropwise, heating is opened, at 96 DEG C
Insulation reaction 5 hours.After the completion of reaction, reflux condenser is changed to rectifier unit, 128 DEG C is heated to and steams crystal evaporate, until
Until water has all steamed.Rectifier unit is changed to distilling apparatus again, is heated to 246 DEG C, product is distilled to receiving flask.Gained at
Product are cooled to 53 DEG C, are frozen into solid.
Embodiment 8
It to equipped with thermometer, stirs, 202.5g is added in the 500mL four-hole bottles of reflux condenser and constant pressure funnel to benzene two
Phenol, 202.5g sodium hydroxides, 486g water.Stirring is opened, after raw material all dissolving, is delayed from constant pressure funnel into reaction bulb
It is slow that 241.2g dimethyl suflfates are added dropwise, rate of addition is controlled, interior temperature is made to be no more than 80 DEG C.After being added dropwise, heating is opened, 97
DEG C insulation reaction 5 hours.After the completion of reaction, reflux condenser is changed to rectifier unit, 126 DEG C is heated to and steams crystal evaporate,
Until water has all steamed.Rectifier unit is changed to distilling apparatus again, is heated to 245 DEG C, product is distilled to receiving flask.Gained
Finished product is cooled to 53 DEG C, is frozen into solid.
The physical and chemical index parameter of terephthaldehyde's ether made from embodiment 1-8 see the table below.
The physical and chemical index parameter list of terephthaldehyde's ether
Assay method：
A. appearance
Range estimation takes appropriate test sample on filter paper, under natural light（Non-solar light direct beam）Its color, character are observed, and is recorded
As a result.
B. assay
High performance liquid chromatography.Sample is dissolved with methanol, and sample solution is injected chromatographic system using quantitative sample injection valve, passes through color
Spectrum column makes each component in sample solution detach, and is detected with ultraviolet absorption detector, and area normalization method calculates in sample to benzene two
Methyl ether content.
C. determination of moisture
The calibration of karl Fischer reagent:Chromatography methanol is added in reaction bulb, to flood electrode exposed end, is taken with karr
The moisture of solvent is to terminal not in reagent drop reaction bottle.Suitable quantity of water is added in reaction bulb（It is accurate to 0.0001 gram）, use
Karl Fischer reagent titrates to terminal, calculates water equivalent.
Determination of moisture:Accurately weigh test sample（About 0.3g）, add in reaction cup, end be titrated to karl Fischer reagent
It puts and calculates moisture.
Unless otherwise indicated, the percentage employed in the present invention is weight percent.
It can be seen that compared with other methods, the synthetic method of terephthaldehyde's ether provided by the invention is easy to operate, cost
Low, product purity is higher can to reach 99%, and appearance color is white, and moisture content is not higher than 0.5%, has a clear superiority.
In actual production, 450kg hydroquinones, 1237.5kg sodium hydroxides, 8257.5kg water and 585kg sulfuric acid two are put into
Methyl esters obtains finished product after reaction, rectifying, distillation and cooling, and the entire production cycle is 42h, compared to original reaction, is steamed
Evaporate, be dehydrated, dry after obtain the production cycle 60h of finished product, saving of time 30%.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (8)
1. a kind of synthetic method of terephthaldehyde's ether, which is characterized in that specifically include following steps：
（1）Using hydroquinone and dimethyl suflfate as raw material, fully reacted in alkaline medium solution；
（2）After completion of the reaction, crystal evaporate is steamed using rectifier unit, until water has all steamed；
（3）Then distilling apparatus is used, product is distilled to receiving flask and is collected；
（4）By product cooling solidification at solid, required finished product is obtained.
2. a kind of synthetic method of terephthaldehyde's ether according to claim 1, which is characterized in that the alkaline medium solution
For sodium hydroxide solution.
3. a kind of synthetic method of terephthaldehyde's ether according to claim 2, which is characterized in that the hydroquinone, hydrogen
The quality molar ratio of sodium oxide molybdena, water and dimethyl suflfate is 1:2.75:18.35:1.3.
4. a kind of synthetic method of terephthaldehyde's ether according to any one of claims 1 to 3, which is characterized in that the step
（1）Reaction temperature be 95 ~ 100 DEG C, the reaction time be 5 hours.
5. a kind of synthetic method of terephthaldehyde's ether according to any one of claims 1 to 3, which is characterized in that the step
（2）Rectification temperature be 120 ~ 130 DEG C.
6. a kind of synthetic method of terephthaldehyde's ether according to any one of claims 1 to 3, which is characterized in that the step
（3）Vapo(u)rizing temperature be 240 ~ 250 DEG C.
7. a kind of synthetic method of terephthaldehyde's ether according to any one of claims 1 to 3, which is characterized in that the step
（4）Temperature be 55 DEG C or less.
8. a kind of synthetic method of terephthaldehyde's ether according to claim 5, which is characterized in that the step（2）Essence
Evaporating the water steamed can recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810268650.2A CN108276258A (en) | 2018-03-29 | 2018-03-29 | A kind of synthetic method of terephthaldehyde's ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810268650.2A CN108276258A (en) | 2018-03-29 | 2018-03-29 | A kind of synthetic method of terephthaldehyde's ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108276258A true CN108276258A (en) | 2018-07-13 |
Family
ID=62810988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810268650.2A Pending CN108276258A (en) | 2018-03-29 | 2018-03-29 | A kind of synthetic method of terephthaldehyde's ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108276258A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096060A (en) * | 2018-09-08 | 2018-12-28 | 湖北荆洪生物科技股份有限公司 | A kind of synthetic method of alkyl -2- naphthyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348422A (en) * | 2008-09-17 | 2009-01-21 | 舒景林 | Novel synthetic process of p-phenylene dimethyl ether |
| CN205252575U (en) * | 2015-12-18 | 2016-05-25 | 杭州欣阳三友精细化工有限公司 | Dewatering rectifying column |
-
2018
- 2018-03-29 CN CN201810268650.2A patent/CN108276258A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348422A (en) * | 2008-09-17 | 2009-01-21 | 舒景林 | Novel synthetic process of p-phenylene dimethyl ether |
| CN205252575U (en) * | 2015-12-18 | 2016-05-25 | 杭州欣阳三友精细化工有限公司 | Dewatering rectifying column |
Non-Patent Citations (1)
| Title |
|---|
| XIAOCHENG WENG ET AL: "Synthesis and Biological Studies of Inducible DNA Cross-Linking Agents", 《ANGEW. CHEM. INT. ED》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096060A (en) * | 2018-09-08 | 2018-12-28 | 湖北荆洪生物科技股份有限公司 | A kind of synthetic method of alkyl -2- naphthyl ether |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101857545A (en) | Synthesis method of single-menthyl | |
| CN102351691B (en) | Method for synthesizing adipic acid monoethyl ester | |
| CN115010566A (en) | Method for producing deuterated compound by using tower equipment | |
| CN108276258A (en) | A kind of synthetic method of terephthaldehyde's ether | |
| CN104211584B (en) | A kind of method preparing dipropylene glycol methyl ether | |
| CN107935850B (en) | Synthesis method of stable isotope 18O-labeled nipagin ester | |
| CN109627226B (en) | Preparation method of 4-methyl-5-ethoxy oxazole | |
| CN203874490U (en) | Ethanol distillation system | |
| Ouyang et al. | Synthesis of a trimeric lignin model compound composed of α-O-4 and β-O-4 linkages under microwave irradiation | |
| CN100579955C (en) | Process for the manufacture of N-alkoxyoxaloalaninate | |
| CN106588837A (en) | Preparing method of 2,5-dimethyl-4-hydroxyl-3(2H) furanone | |
| CN109776314B (en) | Preparation method of cinnamate | |
| CN107954873B (en) | Polysubstituted olefine acid ester derivative and preparation method thereof | |
| US4191841A (en) | Process for manufacturing 4-hydroxy-3,5-dimethoxy benzoic acid from 3,4,5-trimethoxybenzoic acid | |
| CN114011461B (en) | Heterogeneous catalyst based on eutectic solvent and application thereof | |
| CN110698340A (en) | Process method for producing ethyl lactate by reactive distillation dividing wall tower technology | |
| US10550067B2 (en) | Levulinic acid compositions | |
| CN114437021B (en) | Agastache rugosa aroma compound and preparation method thereof | |
| CN109627144A (en) | A kind of low energy consumption methanol production equipment and technique | |
| JP2004010530A (en) | Method for producing high-purity butyl acetate | |
| CN113999138B (en) | Method for rapidly synthesizing citral by using methyl heptenone | |
| CN116332874B (en) | Separation and recovery method of waste solvent in pharmaceutical industry | |
| CN105837440B (en) | A kind of preparation process of the chloro- 2- acetyl group methoxy propane of 1,3- bis- | |
| RU2098404C1 (en) | Method of synthesis of monochloroacetic acid methyl ester | |
| CN208406125U (en) | For producing the continous way dehydration device of alkyl ketene dimer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200211 Address after: 043305 north of ban DUJIAGOU village, Qingjian street, Hejin City, Yuncheng City, Shanxi Province (limestone machine repair plant) Applicant after: Hejin Xingshen Pharmaceutical Co., Ltd Address before: 044000 Shanxi, Yuncheng, Hejin, Xuefu Road, North 209 National Road West Applicant before: Shanxi Jinjin Chemical Co., Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180713 |