CN102557894A - Synthesis process of 1, 2, 3-trimethoxy benzene - Google Patents
Synthesis process of 1, 2, 3-trimethoxy benzene Download PDFInfo
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- CN102557894A CN102557894A CN2012100099075A CN201210009907A CN102557894A CN 102557894 A CN102557894 A CN 102557894A CN 2012100099075 A CN2012100099075 A CN 2012100099075A CN 201210009907 A CN201210009907 A CN 201210009907A CN 102557894 A CN102557894 A CN 102557894A
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Abstract
The invention relates to a synthesis process of 1, 2, 3-trimethoxy benzene. The synthesis process comprises the following steps of: (1) putting guaiacol into a reaction kettle and then dripping acetylchloride; (2) after the reaction in the step (1) is finished, adding o-xylene and aluminium chloride into the reaction kettle; (3) after the reaction in the step (2) is finished, dripping process water for hydrolysis; (4) after the reaction in the step (3) is finished, standing for layering, desolventizing an organic layer and obtaining an intermediate, i.e., 2-hydroxyl-methoxyacetophenone; (5) putting the 2-hydroxyl-methoxyacetophenone, alkali and the process water obtained in the step (4) into the reaction kettle, stirring uniformly, then dripping hydrogen peroxide and obtaining 1, 2-dyhydroxyl-3-metoxybenzene; (6) after the reaction in the step (5) is finished, dripping dimethyl sulfate and alkali liquor simultaneously into the reaction kettle; (7) after the reaction in the step (6) is finished, standing for layering, and obtaining a crude product; and (8) putting the crude product into a distillation kettle for distillation and obtaining a product. The synthesis process has the advantages of mild condition, simple operation, low synthesis cost, good product quality and suitability for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic and preparation method of organic cpds, particularly a kind of 1,2, the synthesis technique of 3-trimethoxy-benzene.
Background technology
1,2,3-trimethoxy-benzene is widely used in organic synthesis and pharmaceutical industry field, and it is the important intermediate of producing multiple medicine.Producing this product in the past all utilizes traditional Chinese medicine Turkey-galls and import tower to draw powder production.Patented claim 200510018690.4 discloses a kind of employing pyrogallol preparation 1; 2; The method of 3-trimethoxy-benzene, patented claim 200610030549.0 disclose a kind of employing acer ginnala leaf and have produced 1,2; The method of 3-trimethoxy-benzene, patented claim 200810210575.0 disclose a kind of employing NSC 2150 through the methylated again working method of Dakin oxidation.Current also do not have industry to go up utilization methyl catechol (2-methoxyl group phenol) through acidylate, Fries rearrangement, the methylated again working method of Dakin (reaching gold) oxidation.
Summary of the invention
The object of the present invention is to provide that gentle, simple to operate, the synthetic cost of a kind of reaction conditions is low, good product quality 1,2, the synthesis technique of 3-trimethoxy-benzene.
For realizing above-mentioned purpose, the technical scheme that the present invention adopted is:
A kind of 1,2, the synthesis technique of 3-trimethoxy-benzene comprises the steps:
1. methyl catechol (2-methoxyl group phenol) is dropped in the reaction kettle, dripping acetyl chloride obtains adjacent acetoxyl group methyl-phenoxide again;
2. after 1. step reacts end, in reaction kettle, add o-Xylol, aluminum chloride (AlCl
3);
3. after 2. step reacts end, drip the process water hydrolysis;
4. after 3. step reacted end, standing demix, organic layer precipitation obtained midbody 2-hydroxy 3-methoxybenzene ethyl ketone;
5. the 2-hydroxy 3-methoxybenzene ethyl ketone that 4. step is obtained, alkali, process water drop in the reaction kettle, after stirring, drip ydrogen peroxide 50 again, obtain 1,2-dihydroxyl-3-anisole;
6. after 5. step reacts end, in reaction kettle, drip methyl-sulfate and alkali lye simultaneously;
7. after 6. step reacted end, standing demix obtained bullion;
8. bullion is dropped in the still kettle and distill, obtain product.
As the further setting of such scheme, the mass ratio between 1. middle methyl catechol of said step and the Acetyl Chloride 98Min. is 1:1.0 ~ 1.3; Said step 2., step 3. in mass ratio between the adjacent acetoxyl group methyl-phenoxide, o-Xylol, aluminum chloride, process water be 1:1.5 ~ 3.0:0.3 ~ 0.5:1.0 ~ 2.0; Mass ratio between the 5. middle 2-hydroxy 3-methoxybenzene ethyl ketone of said step, ydrogen peroxide 50, alkali, the process water is 1:3 ~ 3.5:0.2 ~ 0.5:1.0 ~ 1.5; Said step 6. in 1, the mass ratio between 2-dihydroxyl-3-anisole, methyl-sulfate, the alkali lye is 1:2 ~ 2.5:3 ~ 3.5.
1. in adding the Acetyl Chloride 98Min. process, reactor temperature is controlled at-5 ~ 20 ℃ to said step; Drip and finish, holding temperature is controlled at 0 ~ 30 ℃, soaking time 2 ~ 4 hours.
The 2. middle reactor temperature of said step is controlled at 100 ~ 150 ℃, insulation return time 2 ~ 5 hours.
Said step 3. in during hydrolysis reactor temperature be controlled at 30 ~ 50 ℃, hydrolysis time 1 ~ 3 hour, step 4. in during standing demix, temperature is controlled at 30 ~ 50 ℃, time of repose 1 ~ 2 hour, the precipitation temperature is controlled at 50 ~ 90 ℃, vacuum tightness is greater than-0.095Mpa.
The 5. middle reactor temperature of said step is controlled at 10 ~ 20 ℃, and system pH is controlled at 9 ~ 11.
When said step added methyl-sulfate, alkali lye in 6. simultaneously, reactor temperature was controlled at 30 ~ 45 ℃, and system pH is controlled at 9 ~ 10, reaction soaking time 1 ~ 2 hour, 70 ~ 80 ℃ of heating and heat preservation temperature, 1 ~ 2 hour heating and heat preservation time.
The 7. middle standing demix temperature of said step is controlled at 30 ~ 45 ℃, time of repose 1 ~ 2 hour.
Said step 8. in the interior temperature control of still kettle at 110 ~ 140 ℃, vacuum tightness is greater than-0.095Mpa.
Said step 2. in determining step 1. reaction end, step 3. in determining step 2. reaction end, step 4. in determining step 3. reaction end, step 6. in determining step 5. reaction end, step 7. in determining step 6. reaction end monitor through tlc (TLC).
The present invention is a kind of 1,2, the synthesis technique of 3-trimethoxy-benzene, and 1. its step in the reaction process, use the refrigerated water control reaction temperature, in case overtemperature will be carried out the absorption of HCl acid mist simultaneously;
1. reaction end is through tlc (TLC) monitoring for the 2. middle determining step of step, and developping agent is second eyeball/normal hexane of 1:1, is regarded as reacting completely until the completely dissolve of raw material point.Reaction must have in the reflux to be carried out;
2. reaction end is through tlc (TLC) monitoring for the 3. middle determining step of step, and developping agent is acetonitrile/ETHYLE ACETATE of 2:3, is regarded as reacting completely until the completely dissolve of raw material point.When adding process water, forbid the temperature in the kettle overtemperature;
3. reaction end is through tlc (TLC) monitoring for the 4. middle determining step of step, and developping agent is acetonitrile/ETHYLE ACETATE of 2:3, is regarded as reacting completely until the completely dissolve of raw material point;
The hydrogen peroxide concentration of step described in 5. is 10 ~ 35%, preferred 25%.Said alkali is sodium hydroxide or Pottasium Hydroxide, preferred Pottasium Hydroxide, and concentration is 20 ~ 60%, preferred 25%;
5. reaction end is through tlc (TLC) monitoring for the 6. middle determining step of step, and developping agent is ETHYLE ACETATE/normal hexane of 2:3.Be regarded as reacting completely until the completely dissolve of raw material point.Said alkali lye is sodium hydroxide or Pottasium Hydroxide, preferred sodium hydroxide, concentration preferred 30%;
6. reaction end is through tlc (TLC) monitoring for the 7. middle determining step of step, and developping agent is ETHYLE ACETATE/normal hexane of 2:3, is regarded as reacting completely until the completely dissolve of raw material point;
Step 8. in, during distillation, condensing surface must lead to 40 ~ 45 ℃ hot water cooling, in case blocking pipe.The distillation thermal source can adopt steam or thermal oil.
The present invention is a kind of 1,2, the synthesis technique of 3-trimethoxy-benzene, and involved correlated response formula comprises as follows:
The present invention is a kind of 1,2, and the synthesis technique of 3-trimethoxy-benzene has that raw material sources are extensive, reaction conditions is gentle, simple to operate, synthetic low, the good product quality of cost, is fit to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is further specified.Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1
In actual production, drop in the reaction kettle calculating 150 kilograms of good methyl catechol, 100 kilograms of Acetyl Chloride 98Min.s drop into header tank, stir slow dripping acetyl chloride down, along with dropping is carried out, note the absorption of tail gas HCl.Simultaneously, in the dripping acetyl chloride process, reactor temperature is controlled at-5 ℃; Drip and finish, holding temperature is controlled at 0 ℃, soaking time 4 hours, and to reacting completely, reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.After reacting completely, drop into 400 kilograms of o-Xylols, 160 kilograms in aluminum chloride, 100 ℃ of refluxed rearrangement reactions, insulation return time 5 hours.Reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.Reaction drips 250 kilograms of process water hydrolysis after accomplishing, and stirs, and reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.Wherein reactor temperature is controlled at 30 ℃, hydrolysis time 3 hours during hydrolysis.Reaction is controlled at 30 ℃ with temperature and carries out standing demix, time of repose 2 hours after finishing.The organic layer of telling carries out precipitation under the condition of 50 ℃ of temperature, vacuum tightness-0.095Mpa, obtain midbody 2-hydroxy 3-methoxybenzene ethyl ketone.Midbody 2-hydroxy 3-methoxybenzene ethyl ketone is put in the reaction kettle for 190 kilograms, added 200 kilograms of process waters, 52 kilograms of Pottasium Hydroxide simultaneously, after stirring, drip 600 kilograms in 25% ydrogen peroxide 50.Along with dropping is carried out, exothermic heat of reaction, with 10 ℃ of cooling water control temperature of reaction, the pH of reaction system keeps 9 ~ 10 simultaneously.Dropwise, insulation is to reacting completely.Reaction drips 450 kilograms of methyl-sulfates and 610 kilogram of 30% sodium hydroxide after accomplishing simultaneously, and the control rate of addition makes system pH keep 9 ~ 10, and keeps reactor temperature to be controlled at 30 ℃.Dropwise, insulation is 2 hours under this temperature, is warming up to 70 ℃ of insulations 2 hours again.Reaction finishes, and standing demix under 30 ℃ temperature condition leaves standstill and got 182 kilograms of bullions in 2 hours.Bullion is dropped in the still kettle, under the condition of 120 ℃ of interior temperature, vacuum tightness-0.095Mpa, obtain 154 kilograms of products (finished product), product appearance white is to faint yellow solid, and content is greater than 99%, yield 76% (calculating with methyl catechol).
Embodiment 2
In actual production, drop in the reaction kettle calculating 150 kilograms of good methyl catechol, 96 kilograms of Acetyl Chloride 98Min.s drop into header tank, stir slow dripping acetyl chloride down, along with dropping is carried out, note the absorption of tail gas HCl.Simultaneously, in the dripping acetyl chloride process, reactor temperature is controlled at 20 ℃; Drip and finish, holding temperature is controlled at 30 ℃, soaking time 2 hours, and to reacting completely, reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.After reacting completely, drop into 380 kilograms of o-Xylols, 155 kilograms in aluminum chloride, 150 ℃ of refluxed rearrangement reactions, insulation return time 2 hours.Reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.Reaction drips 220 kilograms of process water hydrolysis after accomplishing, and stirs, and reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.Wherein reactor temperature is controlled at 50 ℃, hydrolysis time 1 hour during hydrolysis.Reaction is controlled at 50 ℃ with temperature and carries out standing demix, time of repose 1 hour after finishing.The organic layer of telling carries out precipitation under the condition of 90 ℃ of temperature, vacuum tightness-0.095Mpa, obtain midbody 2-hydroxy 3-methoxybenzene ethyl ketone.Midbody 2-hydroxy 3-methoxybenzene ethyl ketone is put in the reaction kettle for 185 kilograms, added 150 kilograms of process waters, 50 kilograms of Pottasium Hydroxide simultaneously, after stirring, drip 550 kilograms in 25% ydrogen peroxide 50.Along with dropping is carried out, exothermic heat of reaction, with 20 ℃ of cooling water control temperature of reaction, the pH of reaction system keeps 9 ~ 10 simultaneously.Dropwise, insulation is to reacting completely.Reaction drips 430 kilograms of methyl-sulfates and 580 kilogram of 30% sodium hydroxide after accomplishing simultaneously, and the control rate of addition makes system pH keep 9 ~ 10, and keeps reactor temperature to be controlled at 45 ℃.Dropwise, insulation is 1 hour under this temperature, is warming up to 80 ℃ of insulations 1 hour again.Reaction finishes, and standing demix under 45 ℃ temperature condition leaves standstill and got 170 kilograms of bullions in 1 hour.Bullion is dropped in the still kettle, under the condition of 140 ℃ of interior temperature, vacuum tightness-0.098Mpa, obtain 146 kilograms of products (finished product), product appearance white is to faint yellow solid, and content is greater than 99%, yield 72% (calculating with methyl catechol).
Embodiment 3
In actual production, drop in the reaction kettle calculating 150 kilograms of good methyl catechol, the 105 kg Acetyl Chloride 98Min. drops into header tank, stirs slow dripping acetyl chloride down, along with dropping is carried out, notes the absorption of tail gas HCl.Simultaneously, in the dripping acetyl chloride process, reactor temperature is controlled at 10 ℃; Drip and finish, holding temperature is controlled at 15 ℃, soaking time 3 hours, and to reacting completely, reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.After reacting completely, drop into 450 kilograms of o-Xylols, 180 kilograms in aluminum chloride, 120 ℃ of refluxed rearrangement reactions, insulation return time 3 hours.Reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.Reaction drips 240 kilograms of process water hydrolysis after accomplishing, and stirs, and reaction end is judged through tlc (TLC), is regarded as reacting completely until the completely dissolve of raw material point.Wherein reactor temperature is controlled at 40 ℃, hydrolysis time 2 hours during hydrolysis.Reaction is controlled at 40 ℃ with temperature and carries out standing demix, time of repose 1.5 hours after finishing.The organic layer of telling carries out precipitation under the condition of 70 ℃ of temperature, vacuum tightness-0.098Mpa, obtain midbody 2-hydroxy 3-methoxybenzene ethyl ketone.Midbody 2-hydroxy 3-methoxybenzene ethyl ketone is put in the reaction kettle for 180 kilograms, added 210 kilograms of process waters, 60 kilograms of Pottasium Hydroxide simultaneously, after stirring, drip 750 kilograms in 25% ydrogen peroxide 50.Along with dropping is carried out, exothermic heat of reaction, with 16 ℃ of cooling water control temperature of reaction, the pH of reaction system keeps 9 ~ 10 simultaneously.Dropwise, insulation is to reacting completely.Reaction drips 480 kilograms of methyl-sulfates and 650 kilogram of 30% sodium hydroxide after accomplishing simultaneously, and the control rate of addition makes system pH keep 9 ~ 10, and keeps reactor temperature to be controlled at 40 ℃.Dropwise, insulation is 1.5 hours under this temperature, is warming up to 75 ℃ of insulations 1.5 hours again.Reaction finishes, and standing demix under 40 ℃ temperature condition leaves standstill and got 160 kilograms of bullions in 1.5 hours.Bullion is dropped in the still kettle, under the condition of 110 ℃ of interior temperature, vacuum tightness-0.098Mpa, obtain 142 kilograms of products (finished product), product appearance white is to faint yellow solid, and content is greater than 99%, yield 70% (calculating with methyl catechol).
The foregoing description only is used to the inventive concept of the present invention of explaining, but not to the qualification of rights protection of the present invention, allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should fall into protection scope of the present invention.
Claims (10)
1. one kind 1,2, the synthesis technique of 3-trimethoxy-benzene is characterized in that comprising the steps:
1. methyl catechol is dropped in the reaction kettle, dripping acetyl chloride obtains adjacent acetoxyl group methyl-phenoxide again;
2. after 1. step reacts end, in reaction kettle, add o-Xylol, aluminum chloride;
3. after 2. step reacts end, drip the process water hydrolysis;
4. after 3. step reacted end, standing demix, organic layer precipitation obtained midbody 2-hydroxy 3-methoxybenzene ethyl ketone;
5. the 2-hydroxy 3-methoxybenzene ethyl ketone that 4. step is obtained, alkali, process water drop in the reaction kettle, after stirring, drip ydrogen peroxide 50 again, obtain 1,2-dihydroxyl-3-anisole;
6. after 5. step reacts end, in reaction kettle, drip methyl-sulfate and alkali lye simultaneously;
7. after 6. step reacted end, standing demix obtained bullion;
8. bullion is dropped in the still kettle and distill, obtain product.
2. a kind of according to claim 11,2, the synthesis technique of 3-trimethoxy-benzene is characterized in that: said step 1. in mass ratio between methyl catechol and the Acetyl Chloride 98Min. be 1:1.0 ~ 1.3; Said step 2., step 3. in mass ratio between the adjacent acetoxyl group methyl-phenoxide, o-Xylol, aluminum chloride, process water be 1:1.5 ~ 3.0:0.3 ~ 0.5:1.0 ~ 2.0; Mass ratio between the 5. middle 2-hydroxy 3-methoxybenzene ethyl ketone of said step, ydrogen peroxide 50, alkali, the process water is 1:3 ~ 3.5:0.2 ~ 0.5:1.0 ~ 1.5; Said step 6. in 1, the mass ratio between 2-dihydroxyl-3-anisole, methyl-sulfate, the alkali lye is 1:2 ~ 2.5:3 ~ 3.5.
3. a kind of according to claim 11,2, the synthesis technique of 3-trimethoxy-benzene is characterized in that: 1. in the dripping acetyl chloride process, reactor temperature is controlled at-5 ~ 20 ℃ to said step; Drip and finish, holding temperature is controlled at 0 ~ 30 ℃, soaking time 2 ~ 4 hours.
4. a kind of according to claim 11,2, the synthesis technique of 3-trimethoxy-benzene is characterized in that: said step 2. in reactor temperature be controlled at 100 ~ 150 ℃, insulation return time 2 ~ 5 hours.
5. a kind of according to claim 11,2, the synthesis technique of 3-trimethoxy-benzene; It is characterized in that: said step 3. in during hydrolysis reactor temperature be controlled at 30 ~ 50 ℃, hydrolysis time 1 ~ 3 hour, step 4. in during standing demix; Temperature is controlled at 30 ~ 50 ℃; Time of repose 1 ~ 2 hour, precipitation temperature are controlled at 50 ~ 90 ℃, and vacuum tightness is greater than-0.095Mpa.
6. a kind of according to claim 11,2, the synthesis technique of 3-trimethoxy-benzene is characterized in that: said step 5. in reactor temperature be controlled at 10 ~ 20 ℃, system pH is controlled at 9 ~ 11.
7. a kind of according to claim 11,2, the synthesis technique of 3-trimethoxy-benzene; It is characterized in that: when said step drips methyl-sulfate, alkali lye in 6. simultaneously; Reactor temperature is controlled at 30 ~ 45 ℃, and system pH is controlled at 9 ~ 10, reaction soaking time 1 ~ 2 hour; 70 ~ 80 ℃ of heating and heat preservation temperature, 1 ~ 2 hour heating and heat preservation time.
8. a kind of according to claim 11,2, the synthesis technique of 3-trimethoxy-benzene is characterized in that: said step 7. in the standing demix temperature be controlled at 30 ~ 45 ℃, time of repose 1 ~ 2 hour.
9. a kind of according to claim 11,2, the synthesis technique of 3-trimethoxy-benzene is characterized in that: said step 8. in the interior temperature control of still kettle at 110 ~ 140 ℃, vacuum tightness is greater than-0.095Mpa.
10. a kind of according to claim 11; 2; The synthesis technique of 3-trimethoxy-benzene is characterized in that: said step 2. in determining step 1. reaction end, step 3. in determining step 2. reaction end, step 4. in determining step 3. reaction end, step 6. in determining step 5. reaction end, step 7. in determining step 6. reaction end monitor through tlc.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05148175A (en) * | 1991-11-07 | 1993-06-15 | Eisai Co Ltd | Production of p-dimethoxybenzene derivative |
| CN1340494A (en) * | 2000-08-31 | 2002-03-20 | 科学工业研究院 | Improved method for preparing 1-propyl-2,4,5-trimethoxy benzene |
| US20060035982A1 (en) * | 2004-08-06 | 2006-02-16 | Takasago International Corporation | Method for promoting blood stream |
| CN101665417A (en) * | 2008-09-02 | 2010-03-10 | 中化宁波（集团）有限公司 | One-pot process for synthesizing 1,2,3-trimethoxy-benzene by using o-vanillin |
-
2012
- 2012-01-13 CN CN201210009907.5A patent/CN102557894B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05148175A (en) * | 1991-11-07 | 1993-06-15 | Eisai Co Ltd | Production of p-dimethoxybenzene derivative |
| CN1340494A (en) * | 2000-08-31 | 2002-03-20 | 科学工业研究院 | Improved method for preparing 1-propyl-2,4,5-trimethoxy benzene |
| US20060035982A1 (en) * | 2004-08-06 | 2006-02-16 | Takasago International Corporation | Method for promoting blood stream |
| CN101665417A (en) * | 2008-09-02 | 2010-03-10 | 中化宁波（集团）有限公司 | One-pot process for synthesizing 1,2,3-trimethoxy-benzene by using o-vanillin |
Non-Patent Citations (2)
| Title |
|---|
| HENRY O. MOTTERN: "A New Vanillin Synthesis", 《JOURNAL OF THE AMERICAN SOCIETY》, vol. 56, 31 October 1934 (1934-10-31), pages 2107 - 2108 * |
| 鲁伶兰等: "4-乙基愈创木酚的合成研究", 《天津化工》, no. 6, 31 December 2000 (2000-12-31), pages 27 - 28 * |
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