CN103449997B - Synthesis method for 1,3-diacetyl-4-hydroxyl-6-methyl benzene - Google Patents
Synthesis method for 1,3-diacetyl-4-hydroxyl-6-methyl benzene Download PDFInfo
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- CN103449997B CN103449997B CN201310367261.2A CN201310367261A CN103449997B CN 103449997 B CN103449997 B CN 103449997B CN 201310367261 A CN201310367261 A CN 201310367261A CN 103449997 B CN103449997 B CN 103449997B
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Abstract
The invention discloses a synthesis method for 1,3-diacetyl-4-hydroxyl-6-methyl benzene. Acetylacetone is used as a raw material. The synthesis method comprises synthesis, separation and purification, and is characterized in that the synthesis is that the acetylacetone reacts for 7-9 hours in an organic solvent at the temperature of 90-110 DEG C in the presence of a copper complex catalyst, wherein the using amount of the catalyst is 3-8 percent of the amount of the raw material in mole. The purity of a product synthesized by the method after purification is greater than or equal to 99 percent (HPLC (High Performance Liquid Chromatography) determination), and the yield reaches 90 percent. Since the process is simple, industrial design can be directly performed on the basis of laboratory work, universal chemical equipment is selected and used, and industrialization is quickly realized.
Description
One, technical field
The present invention relates to a kind of preparation method of fine chemicals hydroxy acetophenone, the synthetic method of specifically important organic chemical intermediates 1,3-diacetyl-4-hydroxyl-6-methylbenzene.
Two, background technology
Hydroxy acetophenone compounds is the important chemical intermediate of one in Chemical Manufacture.It is documented, the synthesis of this compounds is raw material mainly with phenol, is reset realize under aluminum chloride and hot conditions by Fries.Found by comparative study, these synthetic methods all also exist some drawbacks, and such as: severe reaction conditions, cost of material is high, and the low and by product of product yield is more etc.According to early literatures report, the synthetic method of 1,3-diacetyl-4-hydroxyl-6-methylbenzene is that methyl ethyl diketone refluxes and prepares this product, this reaction yield extremely low (3.5%) in dimethyl sulfoxide (DMSO), and purifying products is comparatively complicated, is not suitable for suitability for industrialized production.
Three, summary of the invention
The present invention is directed to the defect of prior art, aim to provide a kind of new synthetic method and prepare 1,3-diacetyl-4-hydroxyl-6-methylbenzene.Technical problem to be solved selects new catalyzer to improve yield and to be suitable for industrialization.
The present invention take methyl ethyl diketone as starting raw material, obtains the target product of high yield in organic solvent with next step condensation closed loop of catalyzer existence condition.Chemical equation is as follows:
This technological method take methyl ethyl diketone as raw material, comprise synthesis, abstraction and purification, difference with the prior art makes described synthesis be that methyl ethyl diketone reacts 7-9 hour in 90-110 DEG C in organic solvent with under copper complex catalyzer existence condition, and reaction terminates rear separation, purifying obtains target product.
Temperature of reaction preferably 100 DEG C.
Preferably 8 hours reaction times.
The consumption of catalyzer in mole, be the 3-8% of material quantity, preferred 4-6%.
Described organic solvent is selected from the common agents of boiling point near temperature of reaction, as benzene,toluene,xylene, nitroethane or methylcyclohexane etc., and preferred toluene.
Described copper complex is copper sulfate or cupric nitrate and part ammonia, quadrol, N, N, N ' title complex that formed of N '-Tetramethyl Ethylene Diamine, EDTA or o-phenanthroline.Preferred mantoquita and ammonia or N, N, N ' title complex that formed of N '-Tetramethyl Ethylene Diamine.
Above-mentioned copper complex is all disclosed in crystallographic data center, Cambridge (CCDC) database.
Concrete operation step is as follows:
(1) methyl ethyl diketone joins in organic solvent, adds the copper complex catalyzer of proportional quantity, react 7-9 hour at 90-110 DEG C under stirring;
(2) after reaction terminates, add distilled water to reaction solution and stir, after two-phase laminated flow, aqueous phase is extracted with ethyl acetate twice, merges organic phase, washes once, anhydrous sodium sulfate drying;
(3), after extraction liquid filters, pressure reducing and steaming solvent, residuum carries out pillar layer separation or recrystallization, obtains pure 1,3-diacetyl-4-hydroxyl-6-methylbenzene product.
The product of present method synthesis, after purifying, purity >=99%(HPLC measures), yield reaches 90%.Because technique is simple, so directly industrial design can be carried out on laboratory work basis, and selects universalization construction equipment, realize industrialization very soon.
Four, accompanying drawing explanation
Fig. 1 is this product X-ray single crystal diffraction figure.
Five, embodiment
Embodiment 1: add methyl ethyl diketone (10.0g, 100.0mmol) in 500mL round-bottomed flask, the title complex (5.0mmol) of copper sulfate and ammonia and toluene (100.0mL).Open and stir and heat up, react 8 hours at 100 DEG C.Stop heating up, then 100.0mL distilled water is added, after two-phase laminated flow, aqueous phase is extracted with ethyl acetate twice (100.0mL × 2), merge organic phase, anhydrous sodium sulfate drying, filter, concentrating under reduced pressure, through column chromatography, (silica gel is chromatographic column weighting agent to residuum, volume ratio is the sherwood oil of 5:1 is eluent with ethyl acetate) or recrystallization be separated (adopt toluene and ethyl acetate mixed solvent), obtain colorless solid 5.78g, productive rate 90%, product purity >=99% (HPLC condition determination: moving phase to be volume ratio be 10/90 isopropanol/hexane, flow velocity is 1.0mL/min).
1H NMR(400MHz,CDCl
3)：δ12.53(s,1H),8.16(s,1H),6.81(s,1H),2.66(s,3H),2.59(s,3H),2.57(s,3H);
13C NMR(100MHz，CDCl
3)：δ203.6,198.3,164.5,149.3,133.6,129.0,121.5,117.1,28.9,26.3,22.8。The X-Ray single crystal diffraction result of product 1,3-diacetyl-4-hydroxyl-6-methylbenzene is as accompanying drawing 1.
Embodiment 2: add methyl ethyl diketone (10.0g, 100.0mmol) in 500mL round-bottomed flask, cupric nitrate and N, N, N ' title complex (5.0mmol) of N '-Tetramethyl Ethylene Diamine and toluene (100.0mL).Open and stir and heat up, react 8 hours at 100 DEG C.Stop heating up, then 100.0mL distilled water is added, after two-phase laminated flow, aqueous phase is extracted with ethyl acetate twice (100.0mL × 2), merge organic phase, anhydrous sodium sulfate drying, filter, concentrating under reduced pressure, through column chromatography, (silica gel is chromatographic column weighting agent to residuum, volume ratio is the sherwood oil of 5:1 is eluent with ethyl acetate) or recrystallization be separated (adopt toluene and ethyl acetate mixed solvent), obtain colorless solid 5.07g, productive rate 79%, product purity >=99% (HPLC condition determination: moving phase to be volume ratio be 10/90 isopropanol/hexane, flow velocity is 1.0mL/min).
Claims (5)
1. one kind 1, the synthetic method of 3-diacetyl-4-hydroxyl-6-methylbenzene, take methyl ethyl diketone as raw material, comprise synthesis, abstraction and purification, it is characterized in that: described synthesis is that methyl ethyl diketone reacts 7-9 hour in 90-110 DEG C in organic solvent with under copper complex catalyzer existence condition, the consumption of catalyzer in mole, be the 3-8% of material quantity; Described catalyzer is mantoquita and ammonia or N, N, N
,, N
,the title complex that-Tetramethyl Ethylene Diamine is formed.
2. synthetic method according to claim 1, is characterized in that: described organic solvent is selected from benzene,toluene,xylene, nitroethane or methylcyclohexane.
3. synthetic method according to claim 2, is characterized in that: organic solvent is toluene.
4. synthetic method according to claim 1, is characterized in that: described temperature of reaction is 100 DEG C.
5. synthetic method according to claim 4, is characterized in that: described catalyst levels in mole, be the 4-6% of material quantity.
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| WO2004080939A1 (en) * | 2003-03-11 | 2004-09-23 | Unilever Plc | Process for the preparation of a cosmetic active |
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| WO2004080939A1 (en) * | 2003-03-11 | 2004-09-23 | Unilever Plc | Process for the preparation of a cosmetic active |
Non-Patent Citations (3)
| Title |
|---|
| 3-乙酰甲基-2,6-二乙酰基-5-甲基苯酚的合成和结构;李邨等;《有机化学》;19861231(第5期);第365-368页 * |
| The synergistic effect of [WZn(VO)2(ZnW9O34)2]12- cores and peripheral metal sites in catalytic oxidative cyclization of acetylacetone;Lian-Xu Shi等;《Dalton Trans.》;20101208;第40卷;第779-781页 * |
| 胥旋等.含铁硅钨杂多酸盐控制催化氧化环化乙酰丙酮.《浙江大学学报(理学版)》.2013,第40卷(第2期),166-170. * |
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