CN102079701A - Method for producing styrallyl acetate - Google Patents
Method for producing styrallyl acetate Download PDFInfo
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- CN102079701A CN102079701A CN2010105904108A CN201010590410A CN102079701A CN 102079701 A CN102079701 A CN 102079701A CN 2010105904108 A CN2010105904108 A CN 2010105904108A CN 201010590410 A CN201010590410 A CN 201010590410A CN 102079701 A CN102079701 A CN 102079701A
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- methyl phenyl
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Abstract
The invention discloses a spice synthesizing method in the technical field of chemical industry, and in particular relates to a method for synthesizing styrallyl acetate by using acetophenone as a raw material. The process comprises the steps of: (1) synthesizing alpha-phenethyl alcohol via catalytic hydrogenation by using acetophenone as a raw material; and (2) synthesizing styrallyl acetate by esterification of alpha-phenethyl alcohol. The invention has the advantages of repeated use of catalyst in process of hydrogenation, simple flow, short reaction time, high conversion rate and good selectivity and is suitable for industrialized production. The yield of the process product is greater than 95.0% and the purity is greater than 99.5%. The method provided by the invention can be widely used in spice enterprises.
Description
Technical field
The present invention relates to the spices synthetic method of chemical technology field, relating in particular to a kind of is the method for raw material synthesis of acetic acid styracin with the methyl phenyl ketone.
Technical background
Styroyl acetate formal name used at school: Alpha-Methyl phenylmethyl acetic acid ester, English name: Styralyl acetate, CA registration number [93-92-5].
Chemical structural formula is:
Styroyl acetate has intensive cape jasmine delicate fragrance fragrance, is applied to daily essences such as cape jasmine, Tuberose, jacinthe, Syringa oblata Lindl., jasmine, the lily of the valley mainly as throwing pastil, and also can uses by trace in food flavours such as apple, pineapple, apricot, peach.
The method of synthesis of acetic acid styracin mainly contains following two kinds at present:
(1) produces alpha-halogen ethylbenzene by the optical chlorinating reaction of ethylbenzene, chlorine, again with sodium-acetate reaction synthesis of acetic acid styracin.Reaction equation is as follows:
(2) substitution reaction of ethylbenzene and N-bromo-succinimide is again with sodium-acetate reaction synthesis of acetic acid styracin.Reaction equation is as follows:
More than two kinds of raw materials technology toxicity big, there is bigger potential safety hazard in reaction process, and productive rate is lower, generally 75%～85%.
Summary of the invention
The objective of the invention is to solve the deficiency of above-mentioned background technology, propose a kind of synthetic method of new styroyl acetate, this method technology is simple, safe and reliable, and the selectivity of conversion of raw material and product is all more than 99.0%.
For achieving the above object, the present invention adopts following proposal:
(1) preparation of methyl phenyl carbinol: with the methyl phenyl ketone is the synthetic methyl phenyl carbinol of raw material hydrogenation under the effect of solvent, catalyzer and alkali, and catalyst system therefor is palladium, nickel or the cobalt catalyst of carbon load.
(2) preparation of styroyl acetate: with the methyl phenyl carbinol and the aceticanhydride reaction synthesis of acetic acid styracin of above-mentioned preparation.
The preparation of methyl phenyl carbinol in the step of the present invention (1), reaction equation is as follows:
This reaction process is simple, the selectivity height, and production cost is low; The chromatogram content that reaction obtains the methyl phenyl carbinol crude product after filtration, obtains methyl phenyl carbinol behind neutralization and the recovery solvent more than 99.7%, and productive rate is more than 99.0%.
The preparation of styroyl acetate in the step of the present invention (2), reaction equation is as follows:
This reaction process is simple, need not catalyzer and solvent, and by product is few.Esterification finishes the back to the crude product washing that neutralizes, and rectification under vacuum at last obtains the styroyl acetate finished product, and product purity is more than 99.5%, and productive rate is more than 95.0%.
In the synthesis technique of above-mentioned styroyl acetate, the weight ratio of catalyzer described in the step (1) and methyl phenyl ketone is: 0.001～0.05: 1; Described hydrogenation temperature is controlled to be 30～150 ℃; Hydrogen pressure is controlled at 1.0～6.0MPa in the described hydrogenation reaction; The described hydrogenation reaction time is 2～15 hours.Described solvent is one or more in methyl alcohol, ethanol, the Virahol; Wherein the weight ratio of solvent and methyl phenyl ketone is 5.0～3.0: 1.Described alkali is one or more in solid potassium hydroxide, sodium hydroxide, the salt of wormwood; Wherein the weight ratio of solid alkali and methyl phenyl ketone is 0.005～0.05: 1.Wherein with sodium hydroxide as preferred.
In the synthesis technique of above-mentioned styroyl acetate, the weight ratio of aceticanhydride described in the step (2) and methyl phenyl carbinol is: 3.5～1.5: 1; The temperature of described esterification is controlled at 70～130 ℃; The time of described esterification was controlled at 4～10 hours.
The invention has the beneficial effects as follows: proposed a kind of synthesis technique of styroyl acetate, this technology is simple, and economic environmental protection is safe and reliable, and the reaction times is short, the transformation efficiency height, and selectivity is big, is fit to suitability for industrialized production.
Specific embodiments
By following specific examples, the present invention will be further described:
Embodiment 1:
In the 1L autoclave, add the 100.0g methyl phenyl ketone, 300.0mL ethanol, 0.5g potassium hydroxide, 10.0gPt/C catalyzer.With nitrogen replacement 3 times, use hydrogen exchange again 3 times.Feed the hydrogen control pressure at 2.0Mpa, slowly heat up, temperature is controlled at 50 ℃.React after 10 hours, stop hydrogenation, reduce to room temperature, discharging utilizes after catalyzer filters again, and filtrate is neutralized to neutrality with acetate, and normal pressure reclaims behind the etoh solvent again that underpressure distillation obtains methyl phenyl carbinol 98.5g, (GC content 99.3%), productive rate 96.8%.
Add the 98.5g methyl phenyl carbinol in the 500mL there-necked flask, drip the 100.0g aceticanhydride when still temperature is 90 ℃, dripped off in 2～3 hours, control still temperature is 100～110 ℃, and 3 hours afterreactions of back flow reaction finish.Be neutralized to neutrality with 10% sodium hydroxide solution after reducing to room temperature, repeatedly wash with salt solution again.Obtain styroyl acetate 128.8g (GC content 97.3%) after the crude product rectification under vacuum, productive rate 94.6%.
Embodiment 2:
In the 1L autoclave, add the 100.0g methyl phenyl ketone, 300.0mL ethanol, 0.5g potassium hydroxide, the 12.0gPt/C catalyzer.With nitrogen replacement 3 times, use hydrogen exchange again 3 times.Feed the hydrogen control pressure at 4.0Mpa, slowly heat up, temperature is controlled at 60 ℃.React after 8 hours, stop hydrogenation, reduce to room temperature, discharging utilizes after catalyzer filters again, and filtrate is neutralized to neutrality with acetate, and normal pressure reclaims behind the etoh solvent again that underpressure distillation obtains methyl phenyl carbinol 99.1g, (GC content 99.7%), productive rate 97.8%.
Add the 99.1g methyl phenyl carbinol in the 500mL there-necked flask, drip the 120.0g aceticanhydride when still temperature is 90 ℃, dripped off in 2～3 hours, control still temperature is 90～100 ℃, and 5 hours afterreactions of back flow reaction finish.Be neutralized to neutrality with 10% sodium hydroxide solution after reducing to room temperature, repeatedly wash with salt solution again.Obtain styroyl acetate 130.5g (GC content 97.5%) after the crude product rectification under vacuum, productive rate 95.5%.
Embodiment 3:
In the 1L autoclave, add the 100.0g methyl phenyl ketone, 400.0mL methyl alcohol, 1.0g sodium hydroxide, the 10.0g nickel catalyzator.With nitrogen replacement 3 times, use hydrogen exchange again 3 times.Feed the hydrogen control pressure at 5.0Mpa, slowly heat up, temperature is controlled at 80 ℃.React after 6 hours, stop hydrogenation, reduce to room temperature, discharging utilizes after catalyzer filters again, and filtrate is neutralized to neutrality with acetate, and normal pressure reclaims behind the etoh solvent again that underpressure distillation obtains methyl phenyl carbinol 97.5g, (GC content 99.7%), productive rate 96.2%.
Add the 97.5g methyl phenyl carbinol in the 500mL there-necked flask, drip the 130.0g aceticanhydride when still temperature is 90 ℃, dripped off in 2～3 hours, control still temperature is 70～80 ℃, and 7 hours afterreactions of back flow reaction finish.Be neutralized to neutrality with 10% sodium hydroxide solution after reducing to room temperature, repeatedly wash with salt solution again.Obtain styroyl acetate 129.6g (GC content 96.8%) after the crude product rectification under vacuum, productive rate 95.7%.
Embodiment 4:
In the 1L autoclave, add the 100.0g methyl phenyl ketone, 300.0mL methyl alcohol, 1.5g sodium hydroxide, the 14.0g nickel catalyzator.With nitrogen replacement 3 times, use hydrogen exchange again 3 times.Feed the hydrogen control pressure at 6.0Mpa, slowly heat up, temperature is controlled at 100 ℃.React after 4 hours, stop hydrogenation, reduce to room temperature, discharging utilizes after catalyzer filters again, and filtrate is neutralized to neutrality with acetate, and normal pressure reclaims behind the etoh solvent again that underpressure distillation obtains methyl phenyl carbinol 99.5g, (GC content 99.2%), productive rate 97.7%.
Add the 99.5g methyl phenyl carbinol in the 500mL there-necked flask, drip the 160.0g aceticanhydride when still temperature is 90 ℃, dripped off in 2～3 hours, control still temperature is 70～80 ℃, and 8 hours afterreactions of back flow reaction finish.Be neutralized to neutrality with 10% sodium hydroxide solution after reducing to room temperature, repeatedly wash with salt solution again.Obtain styroyl acetate 131.7g (GC content 96.5%) after the crude product rectification under vacuum, productive rate 95.0%.
Embodiment 5:
In the 1L autoclave, add the 100.0g methyl phenyl ketone, the 500.0mL Virahol, 1.5g salt of wormwood, the 10.0g cobalt catalyst.With nitrogen replacement 3 times, use hydrogen exchange again 3 times.Feed the hydrogen control pressure at 3.0Mpa, slowly heat up, temperature is controlled at 110 ℃.React after 4 hours, stop hydrogenation, reduce to room temperature, discharging utilizes after catalyzer filters again, and filtrate is neutralized to neutrality with acetate, and normal pressure reclaims behind the etoh solvent again that underpressure distillation obtains methyl phenyl carbinol 97.3g, (GC content 99.1%), productive rate 95.4%.
Add the 97.3g methyl phenyl carbinol in the 500mL there-necked flask, drip the 180.0g aceticanhydride when still temperature is 90 ℃, dripped off in 2～3 hours, control still temperature is 100～110 ℃, and 3 hours afterreactions of back flow reaction finish.Be neutralized to neutrality with 10% sodium hydroxide solution after reducing to room temperature, repeatedly wash with salt solution again.Obtain styroyl acetate 123.5g (GC content 98.5%) after the crude product rectification under vacuum, productive rate 93.0%.
Embodiment 6:
In the 1L autoclave, add the 100.0g methyl phenyl ketone, the 300.0mL Virahol, 0.5g salt of wormwood, the 12.0g cobalt catalyst.With nitrogen replacement 3 times, use hydrogen exchange again 3 times.Feed the hydrogen control pressure at 4.0Mpa, slowly heat up, temperature is controlled at 120 ℃.React after 3 hours, stop hydrogenation, reduce to room temperature, discharging utilizes after catalyzer filters again, and filtrate is neutralized to neutrality with acetate, and normal pressure reclaims behind the etoh solvent again that underpressure distillation obtains methyl phenyl carbinol 98.7g, (GC content 99.5%), productive rate 97.2%.
Add the 98.7g methyl phenyl carbinol in the 500mL there-necked flask, drip the 200.0g aceticanhydride when still temperature is 90 ℃, dripped off in 2～3 hours, control still temperature is 100～110 ℃, and 3 hours afterreactions of back flow reaction finish.Be neutralized to neutrality with 10% sodium hydroxide solution after reducing to room temperature, repeatedly wash with salt solution again.Obtain styroyl acetate 124.6g (GC content 93.7%) after the crude product rectification under vacuum, productive rate 87.9%.
Claims (6)
1. the production method of a styroyl acetate is characterized in that, may further comprise the steps:
(1) preparation of methyl phenyl carbinol: with the methyl phenyl ketone is the synthetic methyl phenyl carbinol of raw material hydrogenation under the effect of solvent, catalyzer and alkali, and catalyst system therefor is palladium, nickel or the cobalt catalyst of carbon load; Wherein said solvent is one or more in methyl alcohol, ethanol, the Virahol; Wherein the weight ratio of solvent and methyl phenyl ketone is 5.0～3.0: 1; Described alkali is one or more in solid potassium hydroxide, sodium hydroxide, the salt of wormwood; Wherein the weight ratio of solid alkali and methyl phenyl ketone is 0.005～0.05: 1;
(2) preparation of styroyl acetate: with the methyl phenyl carbinol and the aceticanhydride reaction synthesis of acetic acid styracin of above-mentioned preparation; The weight ratio of wherein said aceticanhydride and methyl phenyl carbinol is: 3.5～1.0: 1; The temperature of described esterification is controlled at 70～130 ℃; The time of described esterification was controlled at 4～10 hours.
2. the production method of styroyl acetate according to claim 1, the weight ratio that it is characterized in that catalyzer described in the step (1) and methyl phenyl ketone is 0.001～0.05: 1; The temperature of described hydrogenation reaction is controlled to be 30～150 ℃; Hydrogen pressure is controlled at 1.0～6.0MPa in the described hydrogenation reaction; The described hydrogenation reaction time is 2～15 hours.
3. the production method of styroyl acetate according to claim 1 is characterized in that the solvent in the step (1) is an ethanol.
4. the production method of styroyl acetate according to claim 1 is characterized in that the alkali in the step (1) is sodium hydroxide.
5. the production method of styroyl acetate according to claim 1 is characterized in that reacted filtrate is neutralized to neutrality with acetate in the step (1), carries out underpressure distillation again and gets methyl phenyl carbinol.
6. the production method of styroyl acetate according to claim 1 is characterized in that middle methyl phenyl carbinol of step (2) and aceticanhydride reaction back solution are neutralized to neutrality with 10% sodium hydroxide solution, again with the salt solution washing, after rectification under vacuum.
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| CN2010105904108A CN102079701A (en) | 2010-12-07 | 2010-12-07 | Method for producing styrallyl acetate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424650A (en) * | 2011-10-18 | 2012-04-25 | 黄山科宏科技发展有限公司 | Preparation technology of styrallyl acetate |
| CN106699507A (en) * | 2017-01-19 | 2017-05-24 | 浙江医药高等专科学校 | Preparation method for alpha-phenethanol |
| CN110090665A (en) * | 2018-01-31 | 2019-08-06 | 中国科学院大连化学物理研究所 | A kind of porous solid acid catalyst and its application in methyl phenyl carbinyl acetate synthesis |
| CN110357762A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院大连化学物理研究所 | A kind of preparation method of continuous production alpha-phenyl ethyl alcohol |
| CN112479879A (en) * | 2020-12-10 | 2021-03-12 | 万华化学集团股份有限公司 | Method for synthesizing styracin acetate from acetophenone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6511686B1 (en) * | 2000-05-19 | 2003-01-28 | International Flavors & Fragrances Inc. | Mixtures of optical isomers of styralyl alcohol or styralyl acetate, processes for preparing same and organoleptic uses thereof |
-
2010
- 2010-12-07 CN CN2010105904108A patent/CN102079701A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6511686B1 (en) * | 2000-05-19 | 2003-01-28 | International Flavors & Fragrances Inc. | Mixtures of optical isomers of styralyl alcohol or styralyl acetate, processes for preparing same and organoleptic uses thereof |
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| Title |
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| BRINDABAN C. RANU ET AL.: "Highly efficient acylation of alcohols, amines and thiols under solvent-free and catalyst-free conditions", 《GREEN CHEMISTRY》 * |
| MARIA GRAZIA MUSOLINOA ET AL.: "Aliphatic carbonyl reduction promoted by palladium catalysts under mild conditions", 《APPLIED CATALYSIS A: GENERAL》 * |
| 孙凌峰: "丙酸苏合香酯的合成", 《江西师范大学学报(自然科学版)》 * |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424650A (en) * | 2011-10-18 | 2012-04-25 | 黄山科宏科技发展有限公司 | Preparation technology of styrallyl acetate |
| CN102424650B (en) * | 2011-10-18 | 2014-04-30 | 黄山科宏生物香料股份有限公司 | Preparation technology of styrallyl acetate |
| CN106699507A (en) * | 2017-01-19 | 2017-05-24 | 浙江医药高等专科学校 | Preparation method for alpha-phenethanol |
| CN106699507B (en) * | 2017-01-19 | 2019-12-31 | 浙江医药高等专科学校 | Preparation method of alpha-phenethyl alcohol |
| CN110090665A (en) * | 2018-01-31 | 2019-08-06 | 中国科学院大连化学物理研究所 | A kind of porous solid acid catalyst and its application in methyl phenyl carbinyl acetate synthesis |
| CN110357762A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院大连化学物理研究所 | A kind of preparation method of continuous production alpha-phenyl ethyl alcohol |
| CN110357762B (en) * | 2018-04-10 | 2021-07-23 | 中国科学院大连化学物理研究所 | Preparation method for continuously producing alpha-phenethyl alcohol |
| CN112479879A (en) * | 2020-12-10 | 2021-03-12 | 万华化学集团股份有限公司 | Method for synthesizing styracin acetate from acetophenone |
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Application publication date: 20110601 |