CN1696092A - Method for chemical synthesizing compound in symmetric bi-aromatic base ketone group - Google Patents
Method for chemical synthesizing compound in symmetric bi-aromatic base ketone group Download PDFInfo
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- CN1696092A CN1696092A CN 200410018221 CN200410018221A CN1696092A CN 1696092 A CN1696092 A CN 1696092A CN 200410018221 CN200410018221 CN 200410018221 CN 200410018221 A CN200410018221 A CN 200410018221A CN 1696092 A CN1696092 A CN 1696092A
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Abstract
A process for chemically synthesizing symmetrical diarylketone compound includes reaction between aromatic compound and bis-trichloromethyl carbonate in organic solvent under the action of yttarbium trifluoromethane sulfonate, filtering, separating filtered cake, and purifying.
Description
(1) technical field
The present invention relates to a kind of chemical synthesis process of symmetrical two aromatic base ketone compounds.
(2) technical background
Symmetry two aromatic base ketone compounds are widely used in the synthetic of agricultural chemicals, medicine and dyestuff, have very high practical value.
In the prior art, the chemical synthesis process of symmetrical two aromatic base ketone compounds is to prepare with hypertoxic phosgene as catalyzer with traditional Lewis acid.Traditional Lewis acid such as aluminum chloride can improve reaction efficiency as catalyzer under the condition of gentleness, existing application widely in organic synthesis, however the shortcoming of this production technique is that catalyzer aluminum chloride consumption is big.Because traditional mostly Lewis acid is met water decomposition and was lost efficacy, reaction will be strict controlled under the anhydrous condition, and for nitrogenous or imine compound, nitrogen-atoms can suppress lewis acidic catalytic activity, need big consumption could satisfy reaction, this method also exists quantity of three wastes big simultaneously, aftertreatment difficulty, shortcoming such as product yield and purity are lower.In addition, hypertoxic phosgene is because its operational difficulty and aftertreatment trouble also are not suitable for suitability for industrialized production.
(3) summary of the invention
Problem for the preparation method who solves traditional Lewis acid photoreactive gas exists the invention provides fluoroform sulphonate-Ytterbiumtriflate [Yb (OTf) that the novel catalyzer of a kind of usefulness is the lanthanide rare metal
3] substitute traditional Lewis acid such as aluminum chloride, be used in that relatively stable and two trichloromethyl carbonates (BTC) that easily transport and operate replace hypertoxic phosgene in the air, prepare the chemical synthesis process of symmetrical two aromatic base ketone compounds.
Symmetrical two aromatic base ketone compounds of the present invention are suc as formula the compound shown in (I), the chemical synthesis process of symmetrical two aromatic base ketone compounds of the present invention comprises following steps: reacted 1～24 hour in 0～150 ℃ in the presence of the catalyzer Ytterbiumtriflate in organic solvent suc as formula the aromatic compound shown in (II) and two trichloromethyl carbonates (BTC), reaction product is filtered, and the filter cake separation and purification is got symmetrical two aromatic base ketone compounds;
Wherein: in formula (I) and the formula (II), Ar is an aromatic group, and described aromatic group is one of following: furyl; Thienyl; Pyrryl; N-methylpyrrole base; Phenyl; Chloro-phenyl-; Bromophenyl; Iodophenyl; Tolyl; The ethylbenzene base; Xylyl; Propyl phenyl; Benzofuryl; Benzothienyl; The benzopyrrole base; Naphthyl; N, N '-dialkyl phenyl organic.
Reaction formula is as follows:
The molar ratio of aromatic compound of the present invention, BTC, Ytterbiumtriflate is 1～20: 1: 0.02～1.0, be preferably 1～10: 1: 0.02～0.2; The weight ratio of described organic solvent and BTC is 1～100: 1, is preferably 5～50: 1; Above-mentioned chemical reaction temperature of reaction is preferably 50～80 ℃, and the reaction times is preferably 5～12 hours.
Above-mentioned organic solvent can be following one of in all kinds of or the mixture of arbitrary proportion: 1. carbonatoms is 1～4 halohydrocarbon; 2. carbonatoms is 1～7 ester class; 3. carbonatoms is 3～6 ketone; 4. carbonatoms is 2～6 ethers, as can being one of following or its mixture: methylene dichloride; Trichloromethane; Tetracol phenixin; 1, the 1-ethylene dichloride; 1, the 2-ethylene dichloride; 1; Vinyl trichloride; Methyl acetate; Ethyl acetate; Propyl acetate; Butylacetate; Isopropyl acetate; Isobutyl acetate; Pentyl acetate; Isoamyl Acetate FCC; Methyl propionate; Ethyl propionate; Propyl propionate; Butyl propionate; Amyl propionate; Acetone; Butanone; Pimelinketone etc.; Ether; Propyl ether; Isopropyl ether; Butyl ether; Dithiocarbonic anhydride; Nitromethane 99Min.; Oil of mirbane.One of above-mentioned organic solvent is more preferably following or its mixture: 1. methylene dichloride 2. 1, and the 2-ethylene dichloride is 4. 5. 6. oil of mirbane of ethyl acetate of dithiocarbonic anhydride of tetracol phenixin 3..
When the aromatic compound described in the present invention was liquid, described organic solvent can be an aromatic compound itself.At this moment, the molar ratio of described aromatic compound, BTC, Ytterbiumtriflate is 5～100: 1: 0.05～1.0, and being preferably is 5～50: 1: 0.05～0.2.
The recyclable utilization of catalyzer that the present invention is used, recovery method are reaction to be finished the gained filtrate decompression concentrate, washing, and thermal dehydration under vacuum promptly gets white Ytterbiumtriflate crystal, and the rate of recovery can reach 95%.That is to say that the catalyzer Ytterbiumtriflate can be concentrated by the reaction product filtrate filtered, washing, thermal dehydration makes under vacuum.
The chemical synthesis process of symmetrical two aromatic base ketone compounds of the present invention, specifically can carry out as follows:
A. be 1～10 with molar ratio: 1: 0.02～0.2 aromatic compound, BTC, Ytterbiumtriflate join in the methylene dichloride that consumption is 5～50 times of BTC quality and dissolve;
B. be warmed up to 50～80 ℃ of temperature of reaction, reacted 5～12 hours;
C. boil off solvent, the cooling, with frozen water to reaction solution to remove remaining BTC, filter to such an extent that filter cake is a product.
When above-mentioned aromatic compound was liquid state, described synthetic method also can be carried out as follows:
A. be 10～40 with molar ratio: 1: 0.05～0.2 aromatic liquid compound, BTC, Ytterbiumtriflate mixed dissolution;
B. be warmed up to 50～80 ℃ of temperature of reaction, reacted 5～12 hours;
C. boil off solvent, the cooling, with frozen water to reaction solution to remove remaining BTC, filter to such an extent that filter cake is a product.
The chemical synthesis process that the present invention sends out the symmetry two aromatic base ketone compounds of stating has following beneficial effect:
1. reaction yield height (generally more than 80%), production cost are low;
2. operational path advanced person, reaction conditions gentleness;
3. the few and recyclable utilization of catalyst levels, there are not three wastes substantially;
4. easy to operate, safety.
(4) embodiment
Embodiment 1
The molar ratio of benzene, BTC, Ytterbiumtriflate is 6: 1: 0.05, and methylene dichloride is as organic solvent, and its consumption is 10 times of BTC quality.
In thermometer, reflux condensing tube and churned mechanically 50ml four-hole boiling flask are housed, add benzene 4.68g (60mmol), with methylene dichloride 15g dissolving.In addition 2.97g BTC and 0.31g Ytterbiumtriflate are dissolved in the 15g methylene dichloride, and slowly join above-mentioned solution in the four-hole bottle, finish, reaction is 1 hour under the room temperature, is warming up to 40 ℃ again, and 40 ℃ of reactions 4 hours, boil off solvent, the ice bath cooling slowly adds the 20ml frozen water down, constantly stir 10min, filter.
Filtrate decompression concentrates, washing, 190 ℃ of following thermal dehydrations of vacuum 4 hours, white Ytterbiumtriflate crystal 0.30g, the rate of recovery 95%.
The white filter cake is the product benzophenone, gets pure product 4.64g through recrystallization, 45 ℃ of fusing points, yield 85%, purity 99.8%.
Embodiment 2
The molar ratio of aromatic compound, BTC, Ytterbiumtriflate is 6: 1: 0.1, and aromatic compound is a benzene, and consumption is 4.68g; The Ytterbiumtriflate consumption is 0.62g, and the BTC consumption is 2.97g; Methylene dichloride is as organic solvent, and its consumption is 10 times of BTC quality, and other is operated with embodiment 1.
The result gets product benzophenone 4.8g, yield 88%, purity 99.6%, 45.5 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.58g, the rate of recovery 94%.
Embodiment 3
The molar ratio of aromatic compound, BTC, Ytterbiumtriflate is 6: 1: 0.2, and aromatic compound is a benzene, and consumption is 4.68g; The BTC consumption is 2.97g; Methylene dichloride is as organic solvent, and its consumption is 10 times of BTC quality; The Ytterbiumtriflate consumption is 1.24g, and other is operated with embodiment 1.
The result gets product benzophenone 4.86g, yield 89%, purity 99.1%, 46 ℃ of fusing points; Reclaim Ytterbiumtriflate 1.14g, the rate of recovery 92%.
Embodiment 4
The molar ratio of aromatic compound, BTC, Ytterbiumtriflate is 15: 1: 0.05, and aromatic compound is a benzene, and consumption is 11.7g; The BTC consumption is 2.97g; Methylene dichloride is as organic solvent, and its consumption is 20 times of BTC quality; The Ytterbiumtriflate consumption is 0.31g, and other is operated with embodiment 1.
The result gets product benzophenone 4.8g, yield 88%, purity 99.4%, 46 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 91%.
Embodiment 5
The molar ratio of aromatic compound, BTC, Ytterbiumtriflate is 1: 1: 0.05, and aromatic compound is a benzene, and consumption is 0.78g; The BTC consumption is 2.97g; Methylene dichloride is as organic solvent, and its consumption is 30 times of BTC quality; The Ytterbiumtriflate consumption is 0.31g, and other is operated with embodiment 1.
The result gets product benzophenone 0.81g, yield 89%, purity 99.7%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 95%.
Embodiment 6
The molar ratio of aromatic compound, BTC, Ytterbiumtriflate is 6: 1: 0.05, and aromatic compound is a thiophene, and consumption is 5.0g; The BTC consumption is 2.97g; Methylene dichloride is as organic solvent, and its consumption is 40 times of BTC quality; The Ytterbiumtriflate consumption is 0.31g, and other is operated with embodiment 1.
The result gets product 5g, yield 86%, purity 99.4%, 86 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 94.5%.
Embodiment 7
The molar ratio of aromatic compound, BTC, Ytterbiumtriflate is 6: 1: 0.05, and aromatic compound is the N-methylpyrrole, and consumption is 4.86g; The BTC consumption is 2.97g; Methylene dichloride is as organic solvent, and its consumption is 50 times of BTC quality; The Ytterbiumtriflate consumption is 0.31g, and other is operated with embodiment 1.
The result gets product 4.74g, yield 84%, purity 99.4%, 24 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 92.5%.
Embodiment 8
Organic solvent is a methylene dichloride, and consumption is 20 times of BTC quality.Other operation is with embodiment 1.
The result gets product 4.62g, yield 82%, purity 99.4%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 90%.
Embodiment 9
Organic solvent is a methylene dichloride, and consumption is 50 times of BTC quality.Other operation is with embodiment 1.
The result gets product 4.37g, yield 80%, purity 99.1%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 90%.
Embodiment 10
Organic solvent changes Nitromethane 99Min. into, and consumption is 10 times of BTC quality.Other operation together
Embodiment 1.
The result gets product 4.63g, yield 83%, purity 99.4%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 93%.
Embodiment 11
Organic solvent changes oil of mirbane into, and consumption is 10 times of BTC quality.Other operation is with embodiment 1.
The result gets product 4.62g, yield 82%, purity 99.6%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 92%.
Embodiment 12
Temperature of reaction changes 20 ℃ into, and other is operated with embodiment 1.
The result gets product 4.1g, yield 75%, purity 99.1%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 92%.
Embodiment 13
Temperature of reaction changes 80 ℃ into, and other is operated with embodiment 1.
The result gets product 4.91g, yield 90%, purity 99.3%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 93%.
Embodiment 14
Reaction times changes 8 hours into, and other is operated with embodiment 1.
The result gets product 4.8g, yield 88%, purity 99.6%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 93%.
Embodiment 15
Reaction times changes 24 hours into, and other is operated with embodiment 1.
The result gets product 4.86g, yield 89%, purity 99.4%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 93%.
Embodiment 16
Aromatic compound: BTC: the Ytterbiumtriflate molar ratio is 10: 1: 0.05, and aromatic compound is a benzene.
In thermometer, reflux condensing tube and churned mechanically 50ml four-hole boiling flask are housed, add BTC 2.97g with benzene 7.8g dissolving, at room temperature slowly add Ytterbiumtriflate 0.31g, finish, reaction is 1 hour under the room temperature, be warming up to 40 ℃ again, and, boil off solvent 40 ℃ of reactions 4 hours, the ice bath cooling down, slowly add the 20ml frozen water, constantly stir 10min, filter.
Filtrate decompression concentrates, washing, 190 ℃ of thermal dehydrations are 4 hours under vacuum, white Ytterbiumtriflate crystal 0.29g, the rate of recovery 94%.
The white filter cake is the product benzophenone, gets pure product 4.6g through recrystallization, 45 ℃ of fusing points, yield 85%, purity 99.8%.
Embodiment 17
The benzene consumption is 15.6g (a BTC mole number 20 times), and other is operated with embodiment 16.
The result gets product 4.8g, yield 88%, purity 99.1%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 92%.
Embodiment 18
The benzene consumption is 31.2g (a BTC mole number 40 times), and other is operated with embodiment 16.
The result gets product 4.7g, yield 86%, purity 99.4%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 90%.
Embodiment 19
Aromatic compound changes thiophene into, and consumption is 10 times of BTC mole number, and other operation together
Embodiment 16.
The result gets product 5g, yield 86%, purity 99.4%, 86 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.29g, the rate of recovery 94%.
Embodiment 20
Aromatic compound changes the N-methylpyrrole into, and consumption is 10 times of BTC mole number, and other is operated with embodiment 16.
The result gets product 4.85g, yield 99.4%, purity 99.4%, 24 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 90%.
Embodiment 21
The Ytterbiumtriflate consumption changes 0.16g into, and other is operated with embodiment 16.
The result gets product 4.86g, yield 89%, purity 99.8%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.14g, the rate of recovery 88%.
Embodiment 22
The Ytterbiumtriflate consumption changes 1.55g into, and other is operated with embodiment 16.
The result gets product 4.97g, yield 91%, purity 99.5%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 1.40g, the rate of recovery 90%.
Embodiment 23
Temperature of reaction changes 0 ℃ into, and other is operated with embodiment 16.
The result gets product 4.4g, yield 81%, purity 99.1%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 90%.
Embodiment 24
Temperature of reaction changes 80 ℃ into, and other is operated with embodiment 16.
The result gets product 5.1g, yield 94%, purity 99.6%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 90%.
Embodiment 25
Reaction times changes 8 hours into, and other is operated with embodiment 16.
The result gets product 4.9g, yield 90%, purity 99.2%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 90%.
Embodiment 26
Temperature of reaction changes 24 hours into, and other is operated with embodiment 16.
The result gets product 5.25g, yield 96%, purity 99.8%, 45 ℃ of fusing points; Reclaim Ytterbiumtriflate 0.28g, the rate of recovery 90%.
Claims (12)
1, a kind of chemical synthesis process of symmetrical two aromatic base ketone compounds, it is characterized in that described symmetrical two aromatic base ketone compounds are suc as formula shown in (I), synthetic method comprises following steps: reacted 1～24 hour in 0～150 ℃ in the presence of the catalyzer Ytterbiumtriflate in organic solvent suc as formula the aromatic compound shown in (II) and two trichloromethyl carbonates, reaction product is filtered, and the filter cake separation and purification is got symmetrical two aromatic base ketone compounds;
(I) (II) wherein: in formula (I) and the formula (II), Ar is an aromatic group, and described aromatic group is one of following: furyl; Thienyl; Pyrryl; N-methylpyrrole base; Phenyl; Chloro-phenyl-; Bromophenyl; Iodophenyl; Tolyl; The ethylbenzene base; Xylyl; Propyl phenyl; Benzofuryl; Benzothienyl; The benzopyrrole base; Naphthyl; N, N '-dialkyl phenyl organic.
2, the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 1, the molar ratio that it is characterized in that described aromatic compound, two trichloromethyl carbonate, Ytterbiumtriflate is 1～20: 1: 0.02～1.0.
3, the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 2, it is characterized in that the described organic solvent and the weight ratio of two trichloromethyl carbonates are 1～100: 1, described organic solvent is following one of in all kinds of or the mixture of arbitrary proportion: 1. carbonatoms is 1～4 halohydrocarbon; 2. carbonatoms is 1～7 ester class; 3. carbonatoms is 3～6 ketone; 4. carbonatoms is 2～6 ethers.
4, the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 3 is characterized in that described organic solvent is one of following or its mixture: methylene dichloride; Trichloromethane; Tetracol phenixin; 1, the 1-ethylene dichloride; 1, the 2-ethylene dichloride; 1; Vinyl trichloride; Methyl acetate; Ethyl acetate; Propyl acetate; Butylacetate; Isopropyl acetate; Isobutyl acetate; Pentyl acetate; Isoamyl Acetate FCC; Methyl propionate; Ethyl propionate; Propyl propionate; Butyl propionate; Amyl propionate; Acetone; Butanone; Pimelinketone; Ether; Propyl ether; Isopropyl ether; Butyl ether etc.; Dithiocarbonic anhydride; Nitromethane 99Min.; Oil of mirbane.
5, the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 4, it is characterized in that described organic solvent is one of the following or its mixture: 1. methylene dichloride 2. 1, and the 2-ethylene dichloride is 4. 5. 6. oil of mirbane of ethyl acetate of dithiocarbonic anhydride of tetracol phenixin 3..
6,, it is characterized in that the described organic solvent and the weight ratio of two trichloromethyl carbonates are 5～50: 1 as the chemical synthesis process of the described symmetrical two aromatic base ketone compounds of one of claim 3～5.
7, the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 1, when it is characterized in that described aromatic compound for liquid state, described organic solvent is an aromatic compound, and the molar ratio of described aromatic compound, two trichloromethyl carbonate, Ytterbiumtriflate is 5～100: 1: 0.05～1.0.
8, the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 7, the molar ratio that it is characterized in that described aromatic compound, two trichloromethyl carbonate, Ytterbiumtriflate is 5～50: 1: 0.05～0.2.
9, as the chemical synthesis process of claim 3 or 7 described symmetrical two aromatic base ketone compounds, it is characterized in that described temperature of reaction is 50～80 ℃, the reaction times is 5～12 hours.
10, as the chemical synthesis process of claim 3 or 7 described symmetrical two aromatic base ketone compounds, it is characterized in that described catalyzer Ytterbiumtriflate is concentrated by described reaction product filtrate filtered, washing, thermal dehydration makes under vacuum.
11. the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 3 is characterized in that described synthetic method is to carry out as follows:
A. be 1～10 with molar ratio: 1: 0.02～0.2 aromatic compound, two trichloromethyl carbonate, Ytterbiumtriflate join in the methylene dichloride of consumption for 5～50 times of two trichloromethyl carbonate quality and dissolve;
B. be warmed up to 50～80 ℃ of temperature of reaction, reacted 5～12 hours;
C. boil off solvent, the cooling, with frozen water to reaction solution to remove remaining pair of trichloromethyl carbonate, filter to such an extent that filter cake is a product.
12. the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 7 is characterized in that described synthetic method is to carry out as follows:
A. be 10～40 with molar ratio: 1: 0.05～0.2 aromatic liquid compound, two trichloromethyl carbonate, Ytterbiumtriflate mixed dissolution;
B. be warmed up to 50～80 ℃ of temperature of reaction, reacted 5～12 hours;
C. boil off solvent, the cooling, with frozen water to reaction solution to remove remaining pair of trichloromethyl carbonate, filter to such an extent that filter cake is a product.
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| CN105418396A (en) * | 2015-12-28 | 2016-03-23 | 湖北师范学院 | Synthetic method of ultraviolet ray absorber BP-2 |
| CN105418396B (en) * | 2015-12-28 | 2016-08-17 | 湖北师范学院 | A kind of synthetic method of UV absorbent BP-2 |
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