CN104250207A - Method for preparing 2-methyl-1-[4-(t-butyl)phenyl]-1-acetone - Google Patents
Method for preparing 2-methyl-1-[4-(t-butyl)phenyl]-1-acetone Download PDFInfo
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- CN104250207A CN104250207A CN201310273318.2A CN201310273318A CN104250207A CN 104250207 A CN104250207 A CN 104250207A CN 201310273318 A CN201310273318 A CN 201310273318A CN 104250207 A CN104250207 A CN 104250207A
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- butylbenzene
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- phenyl
- acetone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
Abstract
The invention relates to a method for preparing highly pure 2-methyl-1-[4-(t-butyl)phenyl]-1-acetone. The method comprises the following steps: carrying out a Friedel-Crafts reaction on raw materials comprising t-butylbenzene and isobutyryl chloride, hydrolyzing, washing by water, desolventizing, and carrying out reduced pressure distillation to obtain a final product. The method has the advantages of reduction of the generation of impurities through later dropwise addition of t-butylbenzene, high yield, safe post-treatmetn operation, industrial application value, and high purity of the 2-methyl-1-[4-(t-butyl)phenyl]-1-acetone product.
Description
Technical field
The present invention relates to the preparation method of a kind of chemical intermediate 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone.
Background technology
2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone (formula II) is a kind of important chemical intermediate, prepares alcohol ketone photoinitiator 2-hydroxy-2-methyl-1-[4-(tertiary butyl) phenyl]-1-acetone (formula III) by halogenating reaction, hydrolysis reaction.
The synthesis of 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone (formula II), document (1) Chemical Communications (Cambridge, United Kingdom), 2012,48 (56), 7034-7036, document (2) Organic Letters, 2012,14 (12), 3044-3047 and document (3) Journal of the American Chemical Society, 1986,108 (2), 245-247 have report.
Document (1) discloses two kinds of synthetic methods, 2-iodopropane respectively with 4-p t butylbenzoic acid (formula IV) and 4-p t butylbenzoic acid anhydride reactant, yield is respectively up to 91% and 96%, but reaction process uses expensive catalyzer bathophenanthroline and two (1,5-cyclooctadiene) nickel, reaction process drops into a large amount of magnesium chlorides and zinc, and post-processing difficulty is large, and these two kinds of synthetic methods are all without commercial viability.
To be 4-tert-butyl benzoyl chloride (formula V) react with 2-iodopropane the synthetic method that document (2) is reported, reaction yield 76%, exists and problem that in document (1), synthetic method is same, without industry amplification value simultaneously.
The synthetic method of report in document (3), with tert.-butylbenzene (formula I) for raw material, through being obtained by reacting 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone (formula II) with isobutyryl chloride.Its reaction process is shown below:
The method prepares 2, the process of 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone (formula II) is: 0.42mol isobutyryl chloride is added drop-wise to aluminum trichloride (anhydrous) (0.28mol) with the mixture of tert.-butylbenzene (1.27mol), stopped reaction after system is released without hydrogen chloride gas, mixture is poured in frozen water and is used extracted with diethyl ether, organic phase anhydrous sodium sulfate drying, after steaming ether, rectification under vacuum obtains 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone (formula II) of content 95%.
The present inventor finds in proof procedure, although the method raw material is easy to get, but the feed way dripping isobutyryl chloride in aluminum trichloride (anhydrous) and tert-butylbenzene mixtures can cause a large amount of impurity to generate, reaction yield only 70 ~ 75%, and post-processing operation uses extracted with diethyl ether, dangerous large, commercial viability is restricted.
Experimental result shows, prepare high yield, 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-product acetone of high-content, there is larger difficulty, also a large amount of impurity can be generated while generation product, these impurity have no idea to be removed by simple post-treating method, have both affected the yield of main products, have also affected the content of product.By a large amount of experiments, the present inventor has found the reason of a large amount of impurity of generation, mainly under reaction raw materials situation about existing at aluminum chloride and higher temperature conditions, the migration of alkyl can be there is, cause the generation of a series of impurity, thus causing the effective content of product on the low side, the yield of product reduces.For this situation, the present inventor adopts and changes the method for feeding mode and decrease the chance that raw material contacts with aluminum chloride, and reduce the method for temperature of reaction, the generation of minimizing impurity, achieves good result, complete the present invention simultaneously.
Summary of the invention
The object of the present invention is to provide one with tert.-butylbenzene (formula I) for raw material, process and isobutyryl chloride are obtained by reacting the preparation method of 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone (formula II).This preparation method changes order of addition(of ingredients) into rear dropping tert.-butylbenzene by the rear dropping isobutyryl chloride of document (3); Meanwhile, aftertreatment does not re-use dangerous large ether and extracts.Improve with tert.-butylbenzene is that the industrial applications that raw material prepares light trigger 2-hydroxy-2-methyl-1-[4-(tertiary butyl) phenyl]-1-acetone (formula III) by friedel-crafts reaction, chlorination and Basic fluxing raction is worth.
It is raw material that the present invention to be prepared in the method for 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone with tert.-butylbenzene, and concrete technology comprises the following steps:
(1) in reaction flask, add isobutyryl chloride, auxiliary agent and solvent successively, add the tert.-butylbenzene with isobutyryl chloride equimolar amount ,-20 ~ 0 DEG C of reaction, stopped reaction when no longer increasing to 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone.
(2) material carries out aftertreatment, obtains 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone, i.e. structural formula II compound.
Auxiliary agent in above-mentioned steps (1) is aluminum trichloride (anhydrous).
The consumption of the auxiliary agent aluminum trichloride (anhydrous) in above-mentioned steps (1) is 1.1 ~ 1.5 times of tert.-butylbenzene molar weight.
In above-mentioned steps (1), the feed way of tert.-butylbenzene is: after adding isobutyryl chloride, auxiliary agent and solvent, drip tert.-butylbenzene.
The temperature adding tert.-butylbenzene in above-mentioned steps (1) is-20 ~ 0 DEG C.
The time adding tert.-butylbenzene in above-mentioned steps (1) is 2 ~ 4h.
Solvent in above-mentioned steps (1) is 1,2-ethylene dichloride.
In above-mentioned steps (1), solvent 1,2-ethylene dichloride consumption is 5 ~ 10 times of tert.-butylbenzene quality.
Post-processing operation in above-mentioned steps (2) is: 10% dilute hydrochloric acid is hydrolyzed, layering, organic phase washing after steam solvent, steam the material rectification under vacuum after solvent.
The present inventor finds in research process, use 1,2-ethylene dichloride is solvent, take aluminum trichloride (anhydrous) as auxiliary agent, at-20 ~ 0 DEG C, the reaction of tertiary butyl benzo is dripped after adding isobutyryl chloride, aftertreatment uses 10% dilute hydrochloric acid to be hydrolyzed to reaction mass, washes, precipitation, rectification under vacuum, prepare product, yield can reach 90 ~ 95%.
Outstanding feature of the present invention is: adopt the feed way dripping tert.-butylbenzene after adding isobutyryl chloride, auxiliary agent and solvent, 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-product acetone content of preparation is high, reaction yield is high, and with hydrochloric acid reaction mass be hydrolyzed, wash, precipitation, rectification under vacuum post-processing operation safety, there is good industrial applications and be worth.
Embodiment
Just enforcement example of the present invention illustrates below.
Embodiment 1
In 1000ml reaction flask, add 53.3g(0.5mol) isobutyryl chloride, 73.3g(0.55mol) aluminum trichloride (anhydrous), 1, 2-ethylene dichloride 340g, stir cooling, remain on-20 ~ 0 DEG C and drip tert.-butylbenzene 67.1g(0.5mol), time for adding 2h, drip tert.-butylbenzene-20 ~ 0 DEG C reaction 10h, stop reaction, material joins in 10% hydrochloric acid of 500g and is hydrolyzed, layering obtains organic phase, organic phase washes precipitation rectification under vacuum after neutrality, obtain 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone that 92.6g purity is 98.5%, yield 90.6%.
1hNMR(CDCl
3, 400MHz) characterize: δ 1.21(d, 6H, CH
3), δ 1.46(s, 9H, CH
3), δ 3.62(m, 1H, CH), δ 7.63(d, 2H, fragrance-H), δ 7.80(d, 2H, fragrance-H).
Embodiment 2
In 1000ml reaction flask, add 53.3g(0.5mol) isobutyryl chloride, 80.0g(0.60mol) aluminum trichloride (anhydrous), 1, 2-ethylene dichloride 420g, stir cooling, remain on-20 ~ 0 DEG C and drip tert.-butylbenzene 67.1g(0.5mol), time for adding 2.5h, drip tert.-butylbenzene-20 ~ 0 DEG C reaction 8h, stop reaction, material joins in 10% hydrochloric acid of 500g and is hydrolyzed, layering obtains organic phase, organic phase washes precipitation rectification under vacuum after neutrality, obtain 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone that 93.2g purity is 98.2%, yield 91.2%.
1hNMR(CDCl
3, 400MHz) characterize: δ 1.21(d, 6H, CH
3), δ 1.46(s, 9H, CH
3), δ 3.62(m, 1H, CH), δ 7.63(d, 2H, fragrance-H), δ 7.80(d, 2H, fragrance-H).
Embodiment 3
In 1000ml reaction flask, add 53.3g(0.5mol) isobutyryl chloride, 86.7g(0.65mol) aluminum trichloride (anhydrous), 1, 2-ethylene dichloride 500g, stir cooling, remain on-20 ~ 0 DEG C and drip tert.-butylbenzene 67.1g(0.5mol), time for adding 3h, drip tert.-butylbenzene-20 ~ 0 DEG C reaction 6h, stop reaction, material joins in 10% hydrochloric acid of 500g and is hydrolyzed, layering obtains organic phase, organic phase washes precipitation rectification under vacuum after neutrality, obtain 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone that 95.5g purity is 97.9%, yield 93.5%.
1hNMR(CDCl
3, 400MHz) characterize: δ 1.21(d, 6H, CH
3), δ 1.46(s, 9H, CH
3), δ 3.62(m, 1H, CH), δ 7.63(d, 2H, fragrance-H), δ 7.80(d, 2H, fragrance-H).
Embodiment 4
In 1000ml reaction flask, add 53.3g(0.5mol) isobutyryl chloride, 93.3g(0.70mol) aluminum trichloride (anhydrous), 1, 2-ethylene dichloride 580g, stir cooling, remain on-20 ~ 0 DEG C and drip tert.-butylbenzene 67.1g(0.5mol), time for adding 3.5h, drip tert.-butylbenzene-20 ~ 0 DEG C reaction 5h, stop reaction, material joins in 10% hydrochloric acid of 500g and is hydrolyzed, layering obtains organic phase, organic phase washes precipitation rectification under vacuum after neutrality, obtain 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone that 96.7g purity is 98.0%, yield 94.7%.
1hNMR(CDCl
3, 400MHz) characterize: δ 1.21(d, 6H, CH
3), δ 1.46(s, 9H, CH
3), δ 3.62(m, 1H, CH), δ 7.63(d, 2H, fragrance-H), δ 7.80(d, 2H, fragrance-H).
Embodiment 5
In 1000ml reaction flask, add 53.3g(0.5mol) isobutyryl chloride, 100.0g(0.75mol) aluminum trichloride (anhydrous), 1, 2-ethylene dichloride 670g, stir cooling, remain on-20 ~ 0 DEG C and drip tert.-butylbenzene 67.1g(0.5mol), time for adding 4h, drip tert.-butylbenzene-20 ~ 0 DEG C reaction 6h, stop reaction, material joins in 10% hydrochloric acid of 500g and is hydrolyzed, layering obtains organic phase, organic phase washes precipitation rectification under vacuum after neutrality, obtain 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone that 97.0g purity is 97.8%, yield 95.0%.
1hNMR(CDCl
3, 400MHz) characterize: δ 1.21(d, 6H, CH
3), δ 1.46(s, 9H, CH
3), δ 3.62(m, 1H, CH), δ 7.63(d, 2H, fragrance-H), δ 7.80(d, 2H, fragrance-H).
Claims (9)
1. prepare the method for 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone, it is characterized in that, be raw material with tert.-butylbenzene, through following steps:
Isobutyryl chloride, auxiliary agent, solvent and the tert.-butylbenzene with isobutyryl chloride equimolar amount is added in reaction flask,-20 ~ 0 DEG C of reaction, stopped reaction when no longer increasing to 2-methyl isophthalic acid-[4-(tertiary butyl) phenyl]-1-acetone, material carries out aftertreatment, obtains structural formula II compound.
2. according to the process of claim 1 wherein that described auxiliary agent is aluminum trichloride (anhydrous).
3., according to the method for claim 2, wherein said auxiliary agent aluminum trichloride (anhydrous) consumption is 1.1 ~ 1.5 times of tert.-butylbenzene molar weight.
4., according to the method for claim 1, the feed way of tert.-butylbenzene is: after adding isobutyryl chloride, auxiliary agent and solvent, drip tert.-butylbenzene.
5., according to the method for claim 4, the temperature of described dropping tert.-butylbenzene is-20 ~ 0 DEG C.
6., according to the method for claim 5, the time dripping tert.-butylbenzene is 2 ~ 4h.
7. according to the process of claim 1 wherein that described solvent is 1,2-ethylene dichloride.
8., according to the method for claim 7, wherein said solvent 1,2-ethylene dichloride consumption is 5 ~ 10 times of tert.-butylbenzene quality.
9. according to the process of claim 1 wherein that described post-processing operation is: with 10% dilute hydrochloric acid be hydrolyzed, layering, organic phase washing after steam solvent, steam the material rectification under vacuum after solvent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310273318.2A CN104250207A (en) | 2013-06-30 | 2013-06-30 | Method for preparing 2-methyl-1-[4-(t-butyl)phenyl]-1-acetone |
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| CN201310273318.2A CN104250207A (en) | 2013-06-30 | 2013-06-30 | Method for preparing 2-methyl-1-[4-(t-butyl)phenyl]-1-acetone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872216A (en) * | 2019-12-06 | 2020-03-10 | 南京恒道医药科技有限公司 | Method and device for producing (2-chloro-5-iodophenyl) -4-fluorobenzyl ketone by reaction separation coupling |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2808459A1 (en) * | 1977-05-17 | 1979-08-30 | Merck Patent Gmbh | Substd. hydroxyalkyl-phenone cpds. for use as photosensitisers - esp. in photopolymerisation, and as UV hardeners in printing inks |
| US4347111A (en) * | 1977-05-17 | 1982-08-31 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Photosensitive hydroxyalkylphenones |
| CN103012317A (en) * | 2012-12-23 | 2013-04-03 | 惠州市华泓新材料有限公司 | Alkyl phenyl derivative and application of alkyl phenyl derivative as photoinitiator |
-
2013
- 2013-06-30 CN CN201310273318.2A patent/CN104250207A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2808459A1 (en) * | 1977-05-17 | 1979-08-30 | Merck Patent Gmbh | Substd. hydroxyalkyl-phenone cpds. for use as photosensitisers - esp. in photopolymerisation, and as UV hardeners in printing inks |
| US4347111A (en) * | 1977-05-17 | 1982-08-31 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Photosensitive hydroxyalkylphenones |
| CN103012317A (en) * | 2012-12-23 | 2013-04-03 | 惠州市华泓新材料有限公司 | Alkyl phenyl derivative and application of alkyl phenyl derivative as photoinitiator |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872216A (en) * | 2019-12-06 | 2020-03-10 | 南京恒道医药科技有限公司 | Method and device for producing (2-chloro-5-iodophenyl) -4-fluorobenzyl ketone by reaction separation coupling |
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Application publication date: 20141231 |