CN101948382B - Synthetic method of 2-(4-alkyl substituted benzoyl) phenylformic acid - Google Patents
Synthetic method of 2-(4-alkyl substituted benzoyl) phenylformic acid Download PDFInfo
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- CN101948382B CN101948382B CN 201010288705 CN201010288705A CN101948382B CN 101948382 B CN101948382 B CN 101948382B CN 201010288705 CN201010288705 CN 201010288705 CN 201010288705 A CN201010288705 A CN 201010288705A CN 101948382 B CN101948382 B CN 101948382B
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- Prior art keywords
- fluoroform sulphonate
- alkyl substituted
- phthalic anhydride
- substituted benzene
- formyl radical
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 title abstract 3
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 75
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 50
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 150000003863 ammonium salts Chemical class 0.000 claims description 24
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- -1 diphenylamine fluoroform Chemical compound 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 13
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229960001701 chloroform Drugs 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 7
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 38
- 239000002904 solvent Substances 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YWVYZMVYXAVAKS-UHFFFAOYSA-N pyridin-1-ium;trifluoromethanesulfonate Chemical compound C1=CC=[NH+]C=C1.[O-]S(=O)(=O)C(F)(F)F YWVYZMVYXAVAKS-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- QSIFOTQDNVCTTM-UHFFFAOYSA-N 3-methyl-1h-imidazol-3-ium;trifluoromethanesulfonate Chemical compound CN1C=CN=C1.OS(=O)(=O)C(F)(F)F QSIFOTQDNVCTTM-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BILZTADTIZWOIH-UHFFFAOYSA-N quinoline;trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.N1=CC=CC2=CC=CC=C21 BILZTADTIZWOIH-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of 2-(4-alkyl substituted benzoyl) phenylformic acid with a structure represented by a formula (I). The 2-(4-alkyl substituted benzoyl) phenylformic acid is prepared by reacting phthalic anhydride with a structure represented by a formula (II) with alkylbenzene with a structure represented by a formula (III) in a reaction solvent, wherein the phthalic anhydride and the alkylbenzene are used as raw materials. The synthetic method is characterized in that trifluoromethanesulfonic salt is used as a catalyst; and a feeding mol ratio of the organic amine trifluoromethanesulfonic salt to the phthalic anhydride is 1-50% :1. The organic amine trifluoromethanesulfonic salt catalyst is used to replace the traditional alchlor catalyst, and the organic amine trifluoromethanesulfonic salt has high water solubility, water stability and lower cost and is easy to obtain and prepare. The method has the advantages of greatly reduced consumption of the organic amine trifluoromethanesulfonic salt, no waste acid generation, high reaction yield, mild reaction condition, safe and simple operation, few three wastes and larger implementation value.
Description
(1) technical field
The present invention relates to take Tetra hydro Phthalic anhydride, alkyl substituted benzene class material as the synthetic benzoic method of 2-(4-alkyl substituted benzene formyl radical) of raw material.
(2) background technology
2-(4-alkyl substituted benzene formyl radical) phenylformic acid is a kind of important organic synthesis key intermediate.It is the important intermediate of synthetic substituted anthraquinone as 2-(4-alkyl substituted benzene formyl radical) phenylformic acid.2-ethyl-anthraquinone (2-amyl anthraquinone) is main raw material and the intermediate of hydrogen dioxide solution production by anthraquinone process, sensitive materials, dyestuff and degradative resin.
Before the present invention provides, the synthetic benzoic industrial applications method of 2-(4-alkyl substituted benzene formyl radical) of existing bibliographical information be (EP 451714,1991,90%; Jiangxi Normal University's journal, 2000,24 (2), 152-154,85%):
Take Tetra hydro Phthalic anhydride and alkylbenzene as raw material, chlorobenzene (or alkylbenzene self) is solvent, and the above aluminum chloride of twice equivalent prepares target product as catalyzer.The method exist catalyst levels large, can't reclaim, aftertreatment produces the problems such as a large amount of hydrogenchloride, equipment is had larger corrosion, and environment is unfriendly.
(3) summary of the invention
The objective of the invention is to overcome the shortcoming of prior art; substitute the aluminum chloride of existing technique with the louis catalyst of easy recovery, aftertreatment, the benzoic synthetic method of the 2-that a kind of technique is reasonable, production safety is reliable, reaction yield is good, cost is low, the three wastes are few (4-alkyl substituted benzene formyl radical) is provided.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of composite structure is suc as formula the benzoic method of the 2-shown in (I) (4-alkyl substituted benzene formyl radical), to react as raw material suc as formula the alkylbenzene shown in (III) suc as formula the Tetra hydro Phthalic anhydride shown in (II) and structure take structure to make in reaction solvent, described reaction is take the organic amine fluoroform sulphonate as catalyzer, and the molar ratio of described organic amine fluoroform sulphonate and Tetra hydro Phthalic anhydride is 1～50%: 1;
In formula (III), R is alkyl, and the alkyl of preferred C1～C6 is as methyl, ethyl, n-propyl, sec.-propyl, amyl group etc.
Further, organic amine fluoroform sulphonate of the present invention can be selected from one of following:
Arylamines fluoroform sulphonate, substituted aryl amine fluoroform sulphonate, nitrogenous fragrant heterocycle trifluoromethanesulfacid acid ammonium salt, alkylamine fluoroform sulphonate, substituted alkylamine fluoroform sulphonate, Cycloalkyl amine fluoroform sulphonate etc.Described organic amine can be primary amine, secondary amine or tertiary amine.
further, organic amine fluoroform sulphonate of the present invention can be one of following: the tri-n-butyl amine fluoroform sulphonate, the diphenylamine fluoroform sulphonate, the dicyclohexylamine fluoroform sulphonate, the triethylene diamine fluoroform sulphonate, the vulkacit H fluoroform sulphonate, proline trifluoromethanesulfacid acid ammonium salt, the diphenylamine fluoroform sulphonate, pentafluorophenyl group amine fluoroform sulphonate, two-(pentafluorophenyl group) amine fluoroform sulphonates, the trifluoromethanesulfonic acid pyridinium salt, the trifluoromethanesulfonic acid quinolinium, trifluoromethanesulfonic acid two-(2-pyridyl) ammonium salt, trifluoromethanesulfonic acid N-methylimidazole salt, trifluoromethanesulfonic acid N, N-lutidine salt etc.
Further, organic amine fluoroform sulphonate of the present invention is preferred one of following: tri-n-butyl amine fluoroform sulphonate, diphenylamine fluoroform sulphonate, dicyclohexylamine fluoroform sulphonate, proline trifluoromethanesulfacid acid ammonium salt, pentafluorophenyl group amine fluoroform sulphonate etc.
Further again, one of organic amine fluoroform sulphonate of the present invention is preferred following: tri-n-butylamine fluoroform sulphonate, proline trifluoromethanesulfacid acid ammonium salt, diphenylamine fluoroform sulphonate.
Organic amine fluoroform sulphonate of the present invention is the ammonium salt that is formed by trifluoromethanesulfonic acid and corresponding organic amine, can be prepared according to existing bibliographical information method.
Further, reaction of the present invention, can substituted benzene self as reaction solvent, also can add organic solvent as reaction solvent, of the present inventionly add the mixture that organic solvent is following one or more arbitrary proportions: the halohydrocarbon of C1～C4, the aliphatic hydrocarbon of C4～C7, tetrahydrofuran (THF), dioxane, acetonitrile, Nitromethane 99Min. or oil of mirbane.
Further, the described mixture that adds one or several preferred following arbitrary proportion of organic solvent: methylene dichloride, trichloromethane, tetracol phenixin, 1,1-ethylene dichloride, 1,2-ethylene dichloride, 1,1,1-trichloroethane, vinyl trichloride, tetrahydrofuran (THF), dioxane, acetonitrile, hexanaphthene, normal butane, Nitromethane 99Min., oil of mirbane etc.
Further again, of the present invention to add organic solvent preferred one of following: trichloromethane, acetonitrile, hexanaphthene, methylene dichloride, oil of mirbane or 1,2-ethylene dichloride.
Further, reaction of the present invention is carried out under the temperature condition of 10～120 ℃.
Further, preferred reaction of the present invention is carried out under the temperature condition of 30～100 ℃.
The present invention follows the tracks of reaction process with TLC, and the reaction times is generally at 2～24 hours.
Further, the molar ratio of Tetra hydro Phthalic anhydride of the present invention and alkylbenzene is 1: 1～20, be preferably 1: 1～and 10.
Further, the molar ratio of organic amine fluoroform sulphonate of the present invention and Tetra hydro Phthalic anhydride is preferably 10～30%: 1.
Further, it is 1～20 times of Tetra hydro Phthalic anhydride quality that the present invention recommends the quality consumption of described reaction solvent, preferred 2～10 times.
The concrete benzoic method of described synthetic 2-(4-alkyl substituted benzene formyl radical) of recommending of the present invention, comprise the steps: Tetra hydro Phthalic anhydride and catalyzer organic amine fluoroform sulphonate are dissolved in reaction solvent, add alkylbenzene under stirring, fully reaction under the temperature condition of 30～100 ℃, react complete after, add the water extracting catalyst, then filter, filter cake is product 2-(4-alkyl substituted benzene formyl radical) phenylformic acid after the washing evaporate to dryness, filtrate is recyclable catalyzer through simple aftertreatment; The molar ratio of described Tetra hydro Phthalic anhydride and alkylbenzene, trifluoromethanesulfonic acid organic amine salt is 1: 1～20: 0.1～0.3, and it is one of following that described organic amine fluoroform sulphonate is selected from: tri-n-butyl amine fluoroform sulphonate, diphenylamine fluoroform sulphonate, dicyclohexylamine fluoroform sulphonate, proline trifluoromethanesulfacid acid ammonium salt, pentafluorophenyl group amine fluoroform sulphonate; Described reaction solvent is alkylbenzene self or is trichloromethane, acetonitrile, oil of mirbane, hexanaphthene, methylene dichloride or 1,2-ethylene dichloride.The simple aftertreatment of described filtrate can be adopted following method: if in filtrate, organic solvent and water do not dissolve each other, first divide water-yielding stratum then evaporate to dryness be recyclable catalyzer; If in filtrate, organic solvent and water dissolve each other, directly evaporate to dryness is recyclable catalyzer.
The present invention compared with prior art, its beneficial effect is embodied in:
The present invention with highly water-soluble, water stability, easily obtain, easily preparation, organic amine trifluoromethanesulfonic acid salt catalyst that price is cheaper substitute traditional aluminum trichloride catalyst, and consumption reduces greatly, produce without spent acid, the present invention has got rid of the use of poisonous reagent chlorobenzene, reaction yield is high, reaction conditions is gentle, safety simple to operate, the three wastes are few, have larger implementary value.
(4) embodiment:
Below with specific embodiment, technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
Embodiment 1
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 1, the amount of Tetra hydro Phthalic anhydride is 37g (0.25mol), the amount of methylene chloride is 5 times of amounts of Tetra hydro Phthalic anhydride, and the consumption of catalyzer tri-n-butylamine trifluoromethanesulfacid acid ammonium salt is Tetra hydro Phthalic anhydride 10mol%.
in thermometer and churned mechanically 250mL there-necked flask are housed, add methylene chloride, add again Tetra hydro Phthalic anhydride 0.25mol (37g), catalyzer tri-n-butylamine trifluoromethanesulfacid acid ammonium salt 0.025mol (8.4g), drip ethylbenzene 0.25mol (26.5g), dropwise and continue to stir 5h under 30 ℃, then add distilled water 20mL to continue to stir 10min, then suction filtration, with 10mL * 2 water washing filter cakes, after draining, filter cake is thrown into 80 ℃ of stirring 0.5h in 150mL water, remove the complete raw material Tetra hydro Phthalic anhydride of unreacted, take advantage of heat filtering, obtaining white filter cake is 2-(4-ethylamino benzonitrile acyl group) phenylformic acid crude product, the product of oven dry weighing is 60.3g, product yield 91.5%, purity 98.0%.Crude product or can drop into next step operation without hot wash and directly use.Filtrate is reclaimed water layer by standing demix, and the evaporate to dryness water layer is the recyclable catalyzer that obtains both.
Embodiment 2
The molar ratio Tetra hydro Phthalic anhydride feeds intake: toluene=1: 2, and get 1,2-ethylene dichloride 80g and make solvent, getting diphenylamine trifluoromethanesulfacid acid ammonium salt 10mol% is catalyzer, reacts 4h under 40 ℃.
Other operate with embodiment 1, product yield 74.3%, purity 96.5%.
Embodiment 3
The molar ratio Tetra hydro Phthalic anhydride feeds intake: isopropyl benzene=1: 3, and hexanaphthene 80g makes solvent, and getting dicyclohexylamine trifluoromethanesulfacid acid ammonium salt 10mol% is catalyzer, reacts 3.5h under 40 ℃.
Other operate with embodiment 1, product yield 82.4%, purity 97.8%.
Embodiment 4
The molar ratio Tetra hydro Phthalic anhydride feeds intake: n-amylbenzene=1: 2.5, and acetonitrile 80g makes solvent, and getting proline trifluoromethanesulfacid acid ammonium salt 20mol% is catalyzer, reacts 2h under 50 ℃.
Other operate with embodiment 1, product yield 76.2%, purity 98.2%.Filtrate is the acetonitrile water liquid that dissolves each other, and evaporate to dryness solution obtains to reclaim catalyzer.
Embodiment 5
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 5, trichloromethane 100g are as organic solvent, and adding triethylene diamine trifluoromethanesulfacid acid ammonium salt 30mol% is catalyzer, react 10h under 100 ℃.
Other operate with embodiment 1, product yield 80.5%, purity 93.8%.
Embodiment 6
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 7, and self makes solvent ethylbenzene, and adding triethylene diamine trifluoromethanesulfacid acid ammonium salt 1mol% is catalyzer, reacts 24h under 20 ℃.
Other operate with embodiment 1, product yield 48.2%, purity 94.6%.
Embodiment 7
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 2, methylene dichloride are solvent, and consumption is 10 times of Tetra hydro Phthalic anhydride, and adding proline trifluoromethanesulfacid acid ammonium salt 50mol% is catalyzer, react 1h under 70 ℃.
Other operate with embodiment 1, product yield 79.5%, purity 98.5%.
Embodiment 8
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 10, and self makes solvent ethylbenzene, and adding vulkacit H trifluoromethanesulfacid acid ammonium salt 10mol% is catalyzer, reacts 5h under 30 ℃.
Other operate with embodiment 1, product yield 75.4%, purity 97.9%.
Embodiment 9
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 20, and self makes solvent ethylbenzene, and adding pentanoic trifluoromethanesulfacid acid ammonium salt 5mol% is catalyzer, reacts 8h under 50 ℃.
Other operate with embodiment 1, product yield 89.2%, purity 98.5%.
Embodiment 10
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 5, and self makes solvent ethylbenzene, and adding proline trifluoromethanesulfacid acid ammonium salt 30mol% is catalyzer, reacts 10h under 50 ℃.
Other operate with embodiment 1, product yield 93.5%, purity 97.4%.
Embodiment 11
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 10, and self makes solvent ethylbenzene, and adding proline trifluoromethanesulfacid acid ammonium salt 10mol% is catalyzer, reacts 5h under 100 ℃.
Other operate with embodiment 1, product yield 84.0%, purity 96.9%.
Embodiment 12
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 2, and chloroform give solvent, consumption are 5 times of Tetra hydro Phthalic anhydride, adding proline trifluoromethanesulfacid acid ammonium salt 50mol% is catalyzer, reacts 8h under reflux conditions.
Other operate with embodiment 1, product yield 79.0%, purity 97.5%.
Embodiment 13
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 2, and Nitromethane 99Min. is made solvent, and consumption is 5 times of Tetra hydro Phthalic anhydride, and adding proline trifluoromethanesulfacid acid ammonium salt 50mol% is catalyzer, reacts 8h under reflux conditions.
Other operate with embodiment 1, product yield 70.0%, purity 94.8%.
Embodiment 14
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 2, and chloroform give solvent, consumption are 10 times of Tetra hydro Phthalic anhydride, adding proline trifluoromethanesulfacid acid ammonium salt 50mol% is catalyzer, reacts 8h under reflux conditions.
Other operate with embodiment 1, product yield 73.0%, purity 95.9%.
Embodiment 15
The molar ratio Tetra hydro Phthalic anhydride feeds intake: ethylbenzene=1: 5, and ethylbenzene is made solvent, and adding trifluoromethanesulfonic acid pyridinium 0mol% is catalyzer, reacts 8h under reflux conditions.
Other operate with embodiment 1, product yield 76.0%, purity 97.2%.
Claims (9)
1. a composite structure benzoic method of 2-(4-alkyl substituted benzene formyl radical) as shown in the formula (I), to react in reaction solvent as raw material and make take structure Tetra hydro Phthalic anhydride and structure alkylbenzene as shown in the formula (III) as shown in the formula (II), it is characterized in that described reaction take the organic amine fluoroform sulphonate as catalyzer, the molar ratio of described organic amine fluoroform sulphonate and Tetra hydro Phthalic anhydride is 1～50%:1; Described organic amine fluoroform sulphonate is one of following: tri-n-butyl amine fluoroform sulphonate, diphenylamine fluoroform sulphonate, dicyclohexylamine fluoroform sulphonate, triethylene diamine fluoroform sulphonate, vulkacit H fluoroform sulphonate, proline trifluoromethanesulfacid acid ammonium salt, penta fluoro benzene amine fluoroform sulphonate, two-(five fluorine) phenyl amine fluoroform sulphonate;
Wherein, R is alkyl.
2. the benzoic method of synthetic 2-as claimed in claim 1 (4-alkyl substituted benzene formyl radical) is characterized in that described reaction carries out under the temperature condition of 10 ~ 120 ℃.
3. the benzoic method of synthetic 2-as claimed in claim 2 (4-alkyl substituted benzene formyl radical) is characterized in that described reaction carries out under the temperature condition of 30 ~ 100 ℃.
4. the benzoic method of synthetic 2-as claimed in claim 1 (4-alkyl substituted benzene formyl radical); it is characterized in that described reaction solvent is substituted benzene self or for adding organic solvent, adds the mixture that organic solvent is following one or more arbitrary proportions: the halohydrocarbon of C1～C4, the aliphatic hydrocarbon of C4～C7, tetrahydrofuran (THF), dioxane, acetonitrile, Nitromethane 99Min., oil of mirbane.
5. the benzoic method of synthetic 2-as claimed in claim 4 (4-alkyl substituted benzene formyl radical); it is characterized in that the described mixture that organic solvent is following one or several arbitrary proportion that adds: methylene dichloride, trichloromethane, tetracol phenixin, 1; 1-ethylene dichloride, 1; 2-ethylene dichloride, 1; 1; 1-trichloroethane, vinyl trichloride, tetrahydrofuran (THF), dioxane, acetonitrile, hexanaphthene, normal butane, Nitromethane 99Min. or oil of mirbane.
6. the benzoic method of synthetic 2-as claimed in claim 1 (4-alkyl substituted benzene formyl radical), the molar ratio that it is characterized in that described Tetra hydro Phthalic anhydride and alkylbenzene is 1:1～20.
7. the benzoic method of synthetic 2-as claimed in claim 1 (4-alkyl substituted benzene formyl radical), the molar ratio that it is characterized in that described organic amine fluoroform sulphonate and Tetra hydro Phthalic anhydride is 10～30%:1.
8. the benzoic method of synthetic 2-as claimed in claim 1 (4-alkyl substituted benzene formyl radical), is characterized in that described R is selected from the alkyl of C1 ~ C6.
9. the benzoic method of synthetic 2-as claimed in claim 1 (4-alkyl substituted benzene formyl radical), it is characterized in that described method comprises the steps: Tetra hydro Phthalic anhydride and catalyzer organic amine fluoroform sulphonate are dissolved in reaction solvent, add alkylbenzene under stirring, fully reaction under the temperature condition of 30～100 ℃, react complete after, add the water extracting catalyst, then filter, filter cake is product 2-(4-alkyl substituted benzene formyl radical) phenylformic acid after the washing evaporate to dryness, filtrate is recyclable catalyzer through simple aftertreatment; The molar ratio of described Tetra hydro Phthalic anhydride and alkylbenzene, organic amine fluoroform sulphonate is 1:1～20:0.1 ~ 0.3, described reaction solvent is alkylbenzene self or is trichloromethane, acetonitrile, oil of mirbane, hexanaphthene, methylene dichloride or 1,2-ethylene dichloride; It is one of following that described organic amine fluoroform sulphonate is selected from: tri-n-butyl amine fluoroform sulphonate, diphenylamine fluoroform sulphonate, dicyclohexylamine fluoroform sulphonate, proline trifluoromethanesulfacid acid ammonium salt, pentafluorophenyl group amine fluoroform sulphonate.
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Citations (2)
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|---|---|---|---|---|
| US5136089A (en) * | 1990-04-12 | 1992-08-04 | Basf Aktiengesellschaft | Acylation of alkyl aromatic hydrocarbons |
| CN101648893A (en) * | 2009-09-11 | 2010-02-17 | 浙江工业大学 | Dicyclohexyl trifluoromethanesulfonate ammonium salt and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136089A (en) * | 1990-04-12 | 1992-08-04 | Basf Aktiengesellschaft | Acylation of alkyl aromatic hydrocarbons |
| CN101648893A (en) * | 2009-09-11 | 2010-02-17 | 浙江工业大学 | Dicyclohexyl trifluoromethanesulfonate ammonium salt and application thereof |
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| 刘山等.水合2-苯甲酰基苯甲酸的合成及其晶体结构.《南京工业大学学报》.2006,第28卷(第4期),第57-60页. |
| 康晓丽等.苯酐法合成蒽醌固体酸催化剂的进展.《精细化工中间体》.2005,第35卷(第4期),第4-7页. |
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| 苯酐法合成蒽醌固体酸催化剂的进展;康晓丽等;《精细化工中间体》;20050831;第35卷(第4期);第4-7页 * |
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