CN1285557C - 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
- Publication number
- CN1285557C CN1285557C CN 200410018221 CN200410018221A CN1285557C CN 1285557 C CN1285557 C CN 1285557C CN 200410018221 CN200410018221 CN 200410018221 CN 200410018221 A CN200410018221 A CN 200410018221A CN 1285557 C CN1285557 C CN 1285557C
- Authority
- CN
- China
- Prior art keywords
- symmetrical
- aromatic
- ytterbiumtriflate
- ketone compounds
- base ketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title abstract description 7
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 239000000126 substance Substances 0.000 title abstract 2
- 125000000468 ketone group Chemical group 0.000 title 1
- -1 ketone compound Chemical class 0.000 claims abstract description 32
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 claims description 58
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 33
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical class OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004799 bromophenyl group Chemical group 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- UDOUIRSXTJAWOV-UHFFFAOYSA-N ethyl acetate;propyl acetate Chemical compound CCOC(C)=O.CCCOC(C)=O UDOUIRSXTJAWOV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000006303 iodophenyl group Chemical group 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- 229940117955 isoamyl acetate Drugs 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000005023 xylyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 238000011084 recovery Methods 0.000 description 28
- 239000002585 base Substances 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for chemical synthesizing compounds in a symmetric bi-aromatic base ketone compound. The method comprises the following steps: aromatic compounds and bi-trichloromethyl carbonic acid ester react in organic solvent under the action of bi-trichloromethyl sulfonic acid used as a catalyst in the organic solvent for 1 to 24 hours at 0 to 150 DEG C; reaction products are filtered; and filter cakes are separated and purified to obtain the symmetrical bi-aromatic base ketone compound. The synthesizing method has the advantages of high reaction yield, low production cost, advanced technological lines, moderate reaction conditions, few catalyst dosage, reutilization, no three waste substantially, convenient operation and security.
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;
(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.
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; 5. Nitromethane 99Min.; 6. oil of mirbane.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; 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. oil of mirbane of ethyl acetate 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; 5. Nitromethane 99Min.; 6. oil of mirbane.
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; Nitromethane 99Min.; Oil of mirbane.
5, the chemical synthesis process of symmetrical two aromatic base ketone compounds as claimed in claim 4 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. oil of mirbane of ethyl acetate 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 aromatic compound shown in the described formula (II) for liquid state, described organic solvent is this aromatic compound itself, and the molar ratio of aromatic compound, two trichloromethyl carbonate, Ytterbiumtriflate is 5～100 shown in the described formula (II): 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410018221 CN1285557C (en) | 2004-05-11 | 2004-05-11 | Method for chemical synthesizing compound in symmetric bi-aromatic base ketone group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410018221 CN1285557C (en) | 2004-05-11 | 2004-05-11 | Method for chemical synthesizing compound in symmetric bi-aromatic base ketone group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1696092A CN1696092A (en) | 2005-11-16 |
| CN1285557C true CN1285557C (en) | 2006-11-22 |
Family
ID=35349006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410018221 Expired - Fee Related CN1285557C (en) | 2004-05-11 | 2004-05-11 | Method for chemical synthesizing compound in symmetric bi-aromatic base ketone group |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1285557C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8732608B2 (en) | 2003-12-29 | 2014-05-20 | Google Inc. | System and method for scrolling among categories in a list of documents |
| US8875030B1 (en) | 2003-12-29 | 2014-10-28 | Google Inc. | Color coding and selection highlighting of e-mail item listing |
| US9015603B1 (en) | 2003-12-29 | 2015-04-21 | Google Inc. | Secondary selection highlighting of e-mail item listing |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418396B (en) * | 2015-12-28 | 2016-08-17 | 湖北师范学院 | A kind of synthetic method of UV absorbent BP-2 |
-
2004
- 2004-05-11 CN CN 200410018221 patent/CN1285557C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8732608B2 (en) | 2003-12-29 | 2014-05-20 | Google Inc. | System and method for scrolling among categories in a list of documents |
| US8875030B1 (en) | 2003-12-29 | 2014-10-28 | Google Inc. | Color coding and selection highlighting of e-mail item listing |
| US9015603B1 (en) | 2003-12-29 | 2015-04-21 | Google Inc. | Secondary selection highlighting of e-mail item listing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1696092A (en) | 2005-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1886383A (en) | Process for the preparation of amorphous rosuvastatin calcium | |
| CN1709871A (en) | S-(-)-indolyl-2-carboxylic acid synthesizing method | |
| CN1914145A (en) | Method for producing aromatic carboxylic acid | |
| CN1723187A (en) | Continuous method for preparing ethyl lactate | |
| CN1880302A (en) | Method for synthesizing isorhodanate | |
| CN1095823C (en) | Process for synthesizing benzoic acids | |
| CN1285557C (en) | Method for chemical synthesizing compound in symmetric bi-aromatic base ketone group | |
| CN1680365A (en) | Novel synthesis and crystallization of piperazine ring-containing compounds | |
| CN1931839A (en) | Synthesis process of N-substituted pyrrole | |
| CN1923801A (en) | Preparation method of phenyl (S)-N-ethyl-N-methyl-3-[1-(dimethyamino)ethyl]-amidoformate (I) and tartrate thereof (II) | |
| CN1304381C (en) | Chemical synthesis method of 1,2,3,4-tetra nitroazole kind compound | |
| CN1960982A (en) | Method for producing 1,3-dioxolan-4,6-dione compound | |
| CN101050217A (en) | Method for synthesizing Vardenafil hydrochloric acid | |
| CN1100614C (en) | Solid catalyst for synthesizing glycol monoether acetate | |
| CN1751015A (en) | Method for producing aromatic carboxylic acid | |
| CN1803777A (en) | Chemical synthesis method of pyrimidine thioketone | |
| CN1227240C (en) | Process for producing 2-alkyl-4-isothiazoline-3-one | |
| CN1092624C (en) | Process for removal of heavy metals | |
| CN1074410C (en) | Process for preparation of 4,6-diaminoresorcinol | |
| CN1138027A (en) | Nitric esters from derivatives of 2-(2,6-dihalophenylamino) phenylacetoxyacetic acid and their preparation procedures | |
| CN1190429C (en) | Method for producing 2-chloro-5-chloromethyl-1,3-thiazole | |
| CN1786004A (en) | Synthesis of binuclear metal complex compound and its catalyzed copolymerization and cycloaddition reaction of carbon dioxide and epoxide | |
| CN1279035C (en) | Synthesis method of optical enantiomer 6-fluoro-3, 4-dihydro-2H-1-benzopyran-2-carboxylic acid and 6-fluoro-3, 4-dihydro-2H-1-benzopyran-2-carboxylic ester | |
| CN1252039C (en) | Chemical synthesis process of 2-hydrixy-5-amudo benzophenone compounds | |
| CN1944410A (en) | Chemically synthetic method for N-chloroformyl imino dibenzyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |