CN1603293A - Process for preparing 4-tert-butoxy-chlorobenzene - Google Patents
Process for preparing 4-tert-butoxy-chlorobenzene Download PDFInfo
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- CN1603293A CN1603293A CN 200410041580 CN200410041580A CN1603293A CN 1603293 A CN1603293 A CN 1603293A CN 200410041580 CN200410041580 CN 200410041580 CN 200410041580 A CN200410041580 A CN 200410041580A CN 1603293 A CN1603293 A CN 1603293A
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Abstract
This invention relates to a preparation method of 4-t butoxy chlorbenzene. P chlorophenol and isobutene are main reaction materials and catalyst is brimstone acid with deepness is 30~98Wt% and season ammonia salt is assistant, then the 4-t butoxy chlorbenzene is prepared through etherealization. The reaction is done under normal temperature and solvents are benzene, toluene, dimethyl benzene etc. petrochemicals that easy to get, and the solid material p chlorophenol and gas material isobutene are easy dissolve in the several kind of reaction solvents. The whole reaction belongs to homogeneous reaction process and easy to control. The remnant materials after reaction are easy to dissolve in sodium hydroxide solution and the product is easy to separate and purify. Good catalysis effect is got by using triethyl ammonia chloride in selecting the season ammonia. Comparing to exist technology, reaction time is shortened efficiently, product yield and purity are better than the best value of the exist technology in this invention.
Description
Technical field
The present invention relates to the preparation method of 4-tert.-butoxy chlorobenzene, relating in particular to para-chlorophenol and iso-butylene is starting raw material, prepares the method for 4-tert.-butoxy chlorobenzene by etherification reaction.
Background technology
P-hydroxyphenylethanol is a kind of important medicine intermediate and spices intermediate.With 4-tert.-butoxy chlorobenzene is raw material, and preparing p-hydroxyphenylethanol by grignard reaction is a kind of simple, method that yield is higher, and the product purity that obtains is also high.So the preparation method of 4-tert.-butoxy chlorobenzene is the problem that people relatively are concerned about and study.
Mainly containing two big class methods at present and prepare 4-tert.-butoxy chlorobenzene, that is: is starting raw material with 4-tertiary butyl phenylate 1., adopts " chlorination process " to prepare; 2. be starting raw material with the para-chlorophenol, adopt " etherification method " to prepare.For " chlorination process ", mainly be to use the manganic compound catalyzer on phenyl ring, to make the chlorine atom replace hydrogen atom and (see J.Chem.Res.Synop.1998, (10), 662～663), though can obtain 4-tert.-butoxy chlorobenzene, in the hydrogen atom process on the chlorine atom substituted benzene ring, can replace simultaneously at 1 and 4 inevitably, cause the by-products content height, bring difficulty for the separation Purification of back." etherification method " has three kinds of methods more again, and it is catalyzer as etherifying reagent, with nickel that document 1 (Synthesis, 1982, (3), 186～188) adopts tert-butyl chloride, and product yield only is 32%; Document 2 (J.Chem.Res.Synop, 2000, (5), 252～253) also adopts tert-butyl chloride as etherifying reagent, is zinc powder but catalyzer uses, and the product yield that obtains is not high yet, about about 65%; Document 3 (Japanese Patent JP2001,151,718) adopts iso-butylene to make catalyzer as etherifying reagent, methyl sulfate, and product yield is brought up to about 75.1%.In this method, the iso-butylene raw material obtains easily, but the catalyst sulfuric acid methyl esters that uses does not have ready-made supply, needs preparation; Secondly, reaction is solvent with the chlorobenzene, and is convenient not as directly adopting the petrochemical complex solvent; And the long reaction time of this method needs 26 hours; In addition, need to use thermokalite in this method, also not too convenient in the operation.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of 4-tert.-butoxy chlorobenzene, this method adopts " etherification method " response path, with iso-butylene as etherifying reagent, select new catalyzer and reaction solvent, on the basis that keeps the prior art advantage, overcome all deficiencies of prior art, the preparation process of 4-tert.-butoxy chlorobenzene is easilier carried out, product yield is higher, the reaction times is shorter.
Purpose of the present invention is achieved through the following technical solutions:
A kind of method for preparing 4-tert.-butoxy chlorobenzene is the main reaction raw material with para-chlorophenol and iso-butylene, generates 4-tert.-butoxy chlorobenzene through etherification reaction, is prepared successively according to following steps:
1. para-chlorophenol and sulfuric acid are joined in the organic solvent according to 100: 0.2～5 weight ratio, mix para-chlorophenol is dissolved fully, para-chlorophenol is 1: 1.5～5 with the ratio of the weight of organic solvent;
2. slowly feed isobutene gas at normal temperatures in the solution of preparation, the mol ratio of iso-butylene and para-chlorophenol is 1～2: 1;
3. after ventilation finished, normal temperature was incubated 1～6 hour down;
4. with after the sodium hydroxide solution washing, extremely neutral with the sodium chloride solution washing again;
5. the organic solution underpressure distillation after will washing, the Fractional Collections cut obtains reclaiming solvent and 4-tert.-butoxy chlorobenzene product.
Purpose of the present invention can also further realize by following optimal technical scheme:
The aforesaid method for preparing 4-tert.-butoxy chlorobenzene wherein also adds the quaternary amine contain benzyl in step in 1., and it with the ratio of vitriolic weight is: 0.5～5: 1.
The aforesaid method for preparing 4-tert.-butoxy chlorobenzene, wherein said quaternary amine is a benzyltriethylammoinium chloride.
The aforesaid method for preparing 4-tert.-butoxy chlorobenzene, wherein said vitriolic concentration expressed in percentage by weight is 30～98%.
The aforesaid method for preparing 4-tert.-butoxy chlorobenzene, wherein step 1. in used organic solvent be benzene, toluene or dimethylbenzene, more preferably benzene.
2. and 3. the aforesaid method for preparing 4-tert.-butoxy chlorobenzene, wherein in the process, the solution bulk temperature is no more than 30 ℃ to step.
The aforesaid method for preparing 4-tert.-butoxy chlorobenzene, wherein step 4. in the concentration expressed in percentage by weight of used sodium hydroxide solution be 20～40%, used sodium chloride solution is the saturated solution of sodium-chlor, is 2～4 times with the washing times of sodium hydroxide solution.
The aforesaid method for preparing 4-tert.-butoxy chlorobenzene, wherein step is when 5. underpressure distillation is carried out under the 8mmHg absolute pressure, and the cut of collecting 73～75 ℃ of scopes can obtain 4-tert.-butoxy chlorobenzene product.
The outstanding substantive distinguishing features and the obvious improvement of technical solution of the present invention is mainly reflected in:
(1) adopts sulfuric acid or sulfuric acid to mix use with quaternary amine, carry out the catalyzer of etherification reaction as para-chlorophenol and iso-butylene.Especially sulfuric acid mixes use with benzyltriethylammoinium chloride, and catalytic effect is better;
(2) can adopt the most common petroleum chemicals such as benzene, toluene or dimethylbenzene as reaction solvent, cost is low, and is less relatively to the pollution of environment, and aftertreatment and recycling are comparatively convenient;
(3) reaction process is the homogeneous reaction process, and carries out at normal temperatures, easy handling control, and reacted various raw materials are easy to separate with product;
(4) reaction times compared with prior art shortens greatly, only needs about 6 hours;
(5) product that obtains is the purity height not only, and yield has raising again than prior art best-case.
Embodiment
The present invention is the main reaction raw material with para-chlorophenol and iso-butylene, chooses the sulfuric acid of 30～98Wt% concentration and is aided with doped quaternary ammonium salt as catalyzer, prepares 4-tert.-butoxy chlorobenzene through etherification reaction.Reaction is to carry out at normal temperatures, reaction solvent adopts the most common petrochemical complex solvents such as benzene,toluene,xylene, participate in the solid material para-chlorophenol and the gas raw material iso-butylene of reaction, all be soluble in this several reaction solvents, thereby entire reaction is the homogeneous reaction process, is easy to operate and control.Reacted surplus stock is soluble in sodium hydroxide solution again, and the product that makes reaction obtain is easy to separate and purifies.In the middle of the selection of various quaternary amines, the present invention especially uses benzyltriethylammoinium chloride, has obtained better catalytic effect.Compared with prior art, total reaction times of technical solution of the present invention effectively shortens, and product yield and purity all are better than the prior art optimum value.
Be several the specific exampless of using technical solution of the present invention below, they only provide as an example, are not considered as application limitations of the present invention.All operational conditions be equal to replacement, all drop within protection scope of the present invention.
Embodiment 1:
The four neck round-bottomed flasks of a 500ml have mechanical stirring, thermometer, ventpipe, prolong and device for absorbing tail gas.Adding 1mol para-chlorophenol, 300ml benzene, 0.5g concentration are dilute sulphuric acid and the 0.3g benzyltriethylammoinium chloride of 30Wt% in flask, are stirred to the transparent clarification of feed liquid, feed the 1.2mol isobutene gas down in normal temperature, and control ventilation temperature is no more than 30 ℃.After ventilation in 4 hours finishes, continue to stir insulation 2 hours again.With 150ml concentration is that the sodium hydroxide solution of 30Wt% drips the washing feed liquid at twice, washs feed liquid at twice to neutral with the 200ml saturated aqueous common salt again.Be to distill under the vacuum of 8mmHg in absolute pressure with feed liquid, the cut of collecting 73～75 ℃ gets 4-tert.-butoxy chlorobenzene 145.5g, and yield is 78.6%.High performance liquid chromatography (HPLC) analysis revealed, 4-tert.-butoxy chlorobenzene content is 99.8% in the product.
Embodiment 2:
The four neck round-bottomed flasks of a 500ml have mechanical stirring, thermometer, ventpipe, prolong and device for absorbing tail gas.Adding 1mol para-chlorophenol, 300ml benzene and 0.5g concentration in flask is the dilute sulphuric acid of 30Wt%, is stirred to the transparent clarification of feed liquid, feeds the 1mol isobutene gas down in normal temperature, and control ventilation temperature is no more than 30 ℃.After ventilation in 4 hours finishes, continue to stir insulation 6 hours again.With 150ml concentration is that the sodium hydroxide solution of 30Wt% drips the washing feed liquid at twice, wash feed liquid at twice to neutral with the 200ml saturated aqueous common salt again, feed liquid is distilled under the vacuum of absolute pressure 8mmHg, the cut of collecting 73～75 ℃ gets 4-tert.-butoxy chlorobenzene 153g, yield is 82.9%, and HPLC analysis revealed purity is 99.8%.
Embodiment 3:
The four neck round-bottomed flasks of a 500ml have mechanical stirring, thermometer, ventpipe, prolong and device for absorbing tail gas.Adding 1mol para-chlorophenol, 300ml toluene and 0.5g concentration in flask is the dilute sulphuric acid of 30Wt%, is stirred to the transparent clarification of feed liquid, feeds the 2mol isobutene gas down in normal temperature, and control ventilation temperature is no more than 30 ℃.After ventilation in 4 hours finishes, continue again to stir in normal temperature insulation 2 hours.With 150ml concentration is that the sodium hydroxide solution of 30Wt% washs feed liquid at twice, wash feed liquid at twice to neutral with the 200ml saturated aqueous common salt again, be to distill under the vacuum of 8mmHg feed liquid in absolute pressure, the cut of collecting 73～75 ℃ gets 4-tert.-butoxy chlorobenzene 146g, yield is 79.1%, and HPLC analysis revealed purity is 99.8%.
Embodiment 4:
The four neck round-bottomed flasks of a 500ml have mechanical stirring, thermometer, ventpipe, prolong and device for absorbing tail gas.Adding 1mol para-chlorophenol, 300ml benzene, 0.5g concentration are dilute sulphuric acid and the 0.5g benzyltriethylammoinium chloride of 30Wt% in flask, are stirred to the transparent clarification of feed liquid, feed the 1mol isobutene gas down in normal temperature, and control ventilation temperature is no more than 50 ℃.After ventilation in 4 hours finishes, continue to be stirred in 45 ℃ of insulations 2 hours again.With 150ml concentration is that the sodium hydroxide solution of 30Wt% drips the washing feed liquid at twice, wash feed liquid at twice to neutral with the 200ml saturated aqueous common salt again, be to distill under the vacuum of 8mmHg feed liquid in absolute pressure, the cut of collecting 73～75 ℃ gets 4-tert.-butoxy chlorobenzene 126g, yield is 68.3%, and HPLC analysis revealed purity is 99.5%.
Embodiment 5:
The four neck round-bottomed flasks of a 500ml have mechanical stirring, thermometer, ventpipe, prolong and device for absorbing tail gas.Adding 1mol para-chlorophenol, 300ml benzene, 0.5g concentration are dilute sulphuric acid and the 0.3g benzyltriethylammoinium chloride of 30Wt% in flask, are stirred to the transparent clarification of feed liquid, slowly feed the 2mol isobutene gas down in normal temperature, control the temperature of ventilating and are no more than 30 ℃.After ventilation in 4 hours finishes, continue again to stir in 25 ℃ of insulations 2 hours.With 150ml concentration is that the sodium hydroxide solution of 30Wt% washs feed liquid at twice, wash feed liquid at twice to neutral with the 200ml saturated aqueous common salt again, be to distill under the vacuum of 8mmHg feed liquid in absolute pressure, the cut of collecting 73～75 ℃ gets 4-tert.-butoxy chlorobenzene 148g, yield is 80.2%, and HPLC analysis revealed purity is 99.8%.
Embodiment 6:
The four neck round-bottomed flasks of a 500ml have mechanical stirring, thermometer, ventpipe, prolong and device for absorbing tail gas.Adding 1mol para-chlorophenol, 300ml benzene, 0.8g concentration are sulfuric acid and the 0.3g benzyltriethylammoinium chloride of 98Wt% in flask, are stirred to the transparent clarification of feed liquid, feed the 1mol isobutene gas down in normal temperature, and control ventilation temperature is no more than 30 ℃.After ventilation in 4 hours finishes, continue to stir insulation 2 hours again.With 150ml concentration is that the sodium hydroxide solution of 30Wt% drips the washing feed liquid at twice, wash feed liquid at twice to neutral with the 200ml saturated aqueous common salt again, be to distill under the vacuum of 8mmHg feed liquid in absolute pressure, the cut of collecting 73～75 ℃ gets 4-tert.-butoxy chlorobenzene 139g, yield is 75.3%, and HPLC analysis revealed purity is 99.5%.
Claims (9)
1. a method for preparing 4-tert.-butoxy chlorobenzene is the main reaction raw material with para-chlorophenol and iso-butylene, generates 4-tert.-butoxy chlorobenzene through etherification reaction, it is characterized in that: be prepared successively according to following steps,
1. para-chlorophenol and sulfuric acid are joined in the organic solvent according to 100: 0.2～5 weight ratio, mix para-chlorophenol is dissolved fully, para-chlorophenol is 1: 1.5～5 with the ratio of the weight of organic solvent;
2. slowly feed isobutene gas at normal temperatures in the solution of preparation, the mol ratio of iso-butylene and para-chlorophenol is 1～2: 1;
3. after ventilation finished, normal temperature was incubated 1～6 hour down;
4. with after the sodium hydroxide solution washing, extremely neutral with the sodium chloride solution washing again;
5. the organic solution underpressure distillation after will washing, the Fractional Collections cut obtains reclaiming solvent and 4-tert.-butoxy chlorobenzene product.
2. by the described method that prepare 4-tert.-butoxy chlorobenzene of claim 1, it is characterized in that: step 1. in also adding contain the quaternary amine of benzyl, it with the ratio of vitriolic weight is: 0.5～5: 1.
3. by the described method for preparing 4-tert.-butoxy chlorobenzene of claim 2, it is characterized in that: described quaternary amine is a benzyltriethylammoinium chloride.
4. by claim 1, the 2 or 3 described methods that prepare 4-tert.-butoxy chlorobenzene, it is characterized in that: described vitriolic concentration expressed in percentage by weight is 30～98%.
5. by claim 1, the 2 or 3 described methods that prepare 4-tert.-butoxy chlorobenzene, it is characterized in that: step 1. in used organic solvent be benzene, toluene or dimethylbenzene.
6. by the described method for preparing 4-tert.-butoxy chlorobenzene of claim 5, it is characterized in that: described organic solvent is a benzene.
2. and 3. 7. by claim 1, the 2 or 3 described methods that prepare 4-tert.-butoxy chlorobenzene, it is characterized in that: in the process, the solution bulk temperature is no more than 30 ℃ to step.
8. by claim 1, the 2 or 3 described methods that prepare 4-tert.-butoxy chlorobenzene, it is characterized in that: step 4. in the concentration expressed in percentage by weight of used sodium hydroxide solution be 20～40%, used sodium chloride solution is the saturated solution of sodium-chlor, is 2～4 times with the washing times of sodium hydroxide solution.
9. by claim 1, the 2 or 3 described methods that prepare 4-tert.-butoxy chlorobenzene, it is characterized in that: step 5. underpressure distillation is carried out under the 8mmHg absolute pressure, and the cut of collecting 73～75 ℃ of scopes promptly gets 4-tert.-butoxy chlorobenzene product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976885A (en) * | 2012-12-24 | 2013-03-20 | 三门峡奥科化工有限公司 | Synthesis method of 4-tert-butyl-1-chlorobenzene |
| CN108285409A (en) * | 2018-03-07 | 2018-07-17 | 上海博栋化学科技有限公司 | A method of the Styrene and its derivatives of synthesis tert-butoxy substitution |
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2004
- 2004-08-02 CN CN 200410041580 patent/CN1256313C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976885A (en) * | 2012-12-24 | 2013-03-20 | 三门峡奥科化工有限公司 | Synthesis method of 4-tert-butyl-1-chlorobenzene |
| CN102976885B (en) * | 2012-12-24 | 2015-10-21 | 三门峡奥科化工有限公司 | To the synthetic method of tertiary butyl chlorobenzene |
| CN108285409A (en) * | 2018-03-07 | 2018-07-17 | 上海博栋化学科技有限公司 | A method of the Styrene and its derivatives of synthesis tert-butoxy substitution |
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| CN1256313C (en) | 2006-05-17 |
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