CN103449997A - 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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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, important organic chemistry intermediate 1 specifically, the synthetic method of 3-diacetyl-4-hydroxyl-6-methylbenzene.
Two, background technology
The hydroxy acetophenone compounds is a kind of important chemical intermediate in Chemical Manufacture.It is documented, the synthetic of this compounds is raw material mainly with phenol, under aluminum chloride and hot conditions, by Fries, resets to realize.By comparative study, find, these synthetic methods all exist some drawbacks, for example: severe reaction conditions, cost of material is high, and the low and by product of product yield is more etc.According to the early literatures report, the synthetic method of 1,3-diacetyl-4-hydroxyl-6-methylbenzene is that methyl ethyl diketone refluxes and prepares this product in dimethyl sulfoxide (DMSO), this reaction yield extremely low (3.5%), 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 is to select new catalyzer to improve yield and to be suitable for industrialization.
The present invention be take methyl ethyl diketone as starting raw material, obtains the target product of high yield in next step condensation closed loop of organic solvent catalyst neutralisation existence condition.Chemical equation is as follows:
The present technique method be take methyl ethyl diketone as raw material, comprise synthetic, separation and purifying, difference with the prior art make described synthetic be methyl ethyl diketone in organic solvent and under copper complex catalyzer existence condition in 90-110 ℃ of reaction 7-9 hour, after reaction finishes, separate, purifying obtains target product.
Preferably 100 ℃ of temperature of reaction.
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 near the common agents of boiling point 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, the title complex that N ' N '-Tetramethyl Ethylene Diamine, EDTA or o-phenanthroline form.Preferred mantoquita and ammonia or N, N, the title complex that N ' N '-Tetramethyl Ethylene Diamine forms.
Above-mentioned copper complex all is disclosed in the database of crystallographic data center, Cambridge (CCDC).
Concrete operation step is as follows:
(1) methyl ethyl diketone joins in organic solvent, adds the copper complex catalyzer of proportional quantity under stirring, reaction 7-9 hour under 90-110 ℃;
(2) after reaction finishes, to reaction solution, add distilled water to stir, two be separated after, water is extracted with ethyl acetate twice, merges organic phase, washing once, anhydrous sodium sulfate drying;
(3) after extraction liquid filters, the pressure reducing and steaming solvent, residuum carries out column chromatography separation or recrystallization, obtain pure 1,3-diacetyl-4-hydroxyl-6-methylbenzene product.
The product that present method is synthetic, purity after purifying >=99%(HPLC measures), yield reaches 90%.Because technique is simple, thus can directly carry out industrial design on the laboratory work basis, and select the universalization construction equipment, realize very soon industrialization.
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 the 500mL round-bottomed flask, the title complex of copper sulfate and ammonia (5.0mmol) and toluene (100.0mL).Open and stir and heat up, under 100 ℃, reaction is 8 hours.Stop heating up, then add 100.0mL distilled water, two be separated after, water is extracted with ethyl acetate (100.0mL * 2) twice, merge organic phase, anhydrous sodium sulfate drying, filter, concentrating under reduced pressure, through column chromatography, (silica gel is the chromatographic column weighting agent to residuum, the sherwood oil that volume ratio is 5:1 is eluent with ethyl acetate) or recrystallization separate (adopt toluene and ethyl acetate mixed solvent), obtain colorless solid 5.78g, productive rate 90%, (the HPLC condition determination: moving phase is the isopropanol/hexane that volume ratio is 10/90 to product purity >=99%, 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。Product 1, the X-Ray single crystal diffraction result of 3-diacetyl-4-hydroxyl-6-methylbenzene is as accompanying drawing 1.
Embodiment 2: add methyl ethyl diketone (10.0g, 100.0mmol) in the 500mL round-bottomed flask, cupric nitrate and N, N, the title complex of N ' N '-Tetramethyl Ethylene Diamine (5.0mmol) and toluene (100.0mL).Open and stir and heat up, under 100 ℃, reaction is 8 hours.Stop heating up, then add 100.0mL distilled water, two be separated after, water is extracted with ethyl acetate (100.0mL * 2) twice, merge organic phase, anhydrous sodium sulfate drying, filter, concentrating under reduced pressure, through column chromatography, (silica gel is the chromatographic column weighting agent to residuum, the sherwood oil that volume ratio is 5:1 is eluent with ethyl acetate) or recrystallization separate (adopt toluene and ethyl acetate mixed solvent), obtain colorless solid 5.07g, productive rate 79%, (the HPLC condition determination: moving phase is the isopropanol/hexane that volume ratio is 10/90 to product purity >=99%, flow velocity is 1.0mL/min).
Claims (7)
1. one kind 1; the synthetic method of 3-diacetyl-4-hydroxyl-6-methylbenzene; take methyl ethyl diketone as raw material; comprise synthetic, separation and purifying; it is characterized in that: described synthesizing is that methyl ethyl diketone reacts 7-9 hour in 90-110 ℃ in organic solvent and under copper complex catalyzer existence condition; the consumption of catalyzer in mole, be the 3-8% of material quantity.
2. synthetic method according to claim 1, it is characterized in that: described organic solvent is selected from benzene,toluene,xylene, nitroethane or methylcyclohexane.
3. synthetic method according to claim 2, it is characterized in that: organic solvent is toluene.
4. synthetic method according to claim 1 is characterized in that:
Described catalyzer copper complex is selected from copper sulfate or cupric nitrate and part ammonia, quadrol, N, N, the title complex that N ' N '-Tetramethyl Ethylene Diamine, EDTA or o-phenanthroline form.
5. synthetic method according to claim 4 is characterized in that:
Described catalyzer is mantoquita and ammonia or N, N, the title complex that N ' N '-Tetramethyl Ethylene Diamine forms.
6. synthetic method according to claim 1, it is characterized in that: described temperature of reaction is 100 ℃.
7. according to the described synthetic method of claim 1 or 4, it is characterized in that: described catalyst levels in mole, be the 4-6% of material quantity.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110759820A (en) * | 2019-11-17 | 2020-02-07 | 安阳师范学院 | Preparation method of polysubstituted phenol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004080939A1 (en) * | 2003-03-11 | 2004-09-23 | Unilever Plc | Process for the preparation of a cosmetic active |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004080939A1 (en) * | 2003-03-11 | 2004-09-23 | Unilever Plc | Process for the preparation of a cosmetic active |
Non-Patent Citations (3)
| Title |
|---|
| LIAN-XU SHI等: "The synergistic effect of [WZn(VO)2(ZnW9O34)2]12- cores and peripheral metal sites in catalytic oxidative cyclization of acetylacetone", 《DALTON TRANS.》 * |
| 李邨等: "3-乙酰甲基-2,6-二乙酰基-5-甲基苯酚的合成和结构", 《有机化学》 * |
| 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）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110759820A (en) * | 2019-11-17 | 2020-02-07 | 安阳师范学院 | Preparation method of polysubstituted phenol |
| CN110759820B (en) * | 2019-11-17 | 2022-04-29 | 安阳师范学院 | Preparation method of polysubstituted phenol |
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