CN109305873A - 烷基苯的制备方法 - Google Patents
烷基苯的制备方法 Download PDFInfo
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- CN109305873A CN109305873A CN201710704673.9A CN201710704673A CN109305873A CN 109305873 A CN109305873 A CN 109305873A CN 201710704673 A CN201710704673 A CN 201710704673A CN 109305873 A CN109305873 A CN 109305873A
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- Prior art keywords
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- alkylbenzene
- starting material
- furan
- trifluoromethanesulfonic acid
- Prior art date
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- 150000004996 alkyl benzenes Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 21
- 239000007858 starting material Substances 0.000 claims abstract description 25
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- -1 alkylfuran Chemical compound 0.000 claims abstract description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000003377 acid catalyst Substances 0.000 claims description 12
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 6
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- MRVDPBDPQPBGMS-UHFFFAOYSA-N trifluoromethanesulfonic acid;yttrium Chemical compound [Y].OS(=O)(=O)C(F)(F)F MRVDPBDPQPBGMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- COOICNPQYBXPGE-UHFFFAOYSA-M indium(3+);trifluoromethanesulfonate Chemical compound [In+3].[O-]S(=O)(=O)C(F)(F)F COOICNPQYBXPGE-UHFFFAOYSA-M 0.000 claims description 3
- RJFSDTDWWBECIL-UHFFFAOYSA-N trifluoro(methyl)-$l^{4}-sulfane Chemical compound CS(F)(F)F RJFSDTDWWBECIL-UHFFFAOYSA-N 0.000 claims description 3
- NGOCMUBXJDDBLB-UHFFFAOYSA-N trifluoromethanesulfonic acid;zinc Chemical compound [Zn].OS(=O)(=O)C(F)(F)F NGOCMUBXJDDBLB-UHFFFAOYSA-N 0.000 claims description 3
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 claims description 2
- AABTWRKUKUPMJG-UHFFFAOYSA-N 2,4-dimethylfuran Chemical compound CC1=COC(C)=C1 AABTWRKUKUPMJG-UHFFFAOYSA-N 0.000 claims description 2
- QUJLPICXDXFRSN-UHFFFAOYSA-N scandium;trifluoromethanesulfonic acid Chemical compound [Sc].OS(=O)(=O)C(F)(F)F QUJLPICXDXFRSN-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims 2
- 238000007259 addition reaction Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 14
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract description 2
- 150000005673 monoalkenes Chemical class 0.000 abstract 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 56
- 239000000203 mixture Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+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 NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+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 HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 2
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+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 JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 description 2
- RCIGPOBMYPKFBY-UHFFFAOYSA-N 2-methoxynaphthalene-1-carboximidamide Chemical compound C1=CC=CC2=C(C(N)=N)C(OC)=CC=C21 RCIGPOBMYPKFBY-UHFFFAOYSA-N 0.000 description 1
- KOSPTJXKUHNQST-UHFFFAOYSA-N 2-methylfuran Chemical compound CC=1OC=CC1.CC=1OC=CC1 KOSPTJXKUHNQST-UHFFFAOYSA-N 0.000 description 1
- RUVLFILVRAZVIZ-UHFFFAOYSA-N CC1=C(OC=C1)C.CC1=C(OC=C1)C Chemical compound CC1=C(OC=C1)C.CC1=C(OC=C1)C RUVLFILVRAZVIZ-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- FEFJVLNQNOCBJQ-UHFFFAOYSA-N gold;trifluoromethanesulfonic acid Chemical compound [Au].OS(=O)(=O)C(F)(F)F FEFJVLNQNOCBJQ-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KVRSDIJOUNNFMZ-UHFFFAOYSA-L nickel(2+);trifluoromethanesulfonate Chemical compound [Ni+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F KVRSDIJOUNNFMZ-UHFFFAOYSA-L 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ITAKKORXEUJTBC-UHFFFAOYSA-L vanadium(ii) chloride Chemical compound Cl[V]Cl ITAKKORXEUJTBC-UHFFFAOYSA-L 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
- B01J31/0232—Halogen-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0228
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/867—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an aldehyde or a ketone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
- B01J2531/004—Ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/025—Sulfonic acids
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- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
一种烷基苯的制备方法，包含以下步骤：步骤(a)，提供一个起始原料，选自于呋喃、烷基呋喃、2,5‑己二酮，或上述任意的组合；步骤(b)，使该起始原料与单烯在三氟甲磺酸金属盐催化剂及无溶剂的存在下进行环加成反应，以产生烷基苯。
Description
技术领域
本发明涉及一种烷基苯的制备方法，特别是涉及一种在三氟甲磺酸金属盐催化剂及无溶剂的存在下制备烷基苯的方法。
背景技术
美国专利公告第9260359号揭示一种对二甲苯产率高的制备对二甲苯的方法。该方法为在有溶剂或无溶剂的操作下，将2,5-二甲基呋喃及乙烯在路易斯酸的存在下于150℃至300℃进行环加成反应并于该环加成反应后进行脱水反应，而形成对二甲苯。在有溶剂的操作下，该路易斯酸例如AlCl3、Bi(OTf)3、CuCl2、Cu(OTf)2、CoCl2、CrCl3、Fe(OTf)2、Gd(OTf)3、InCl3、In(OTf)3、NiCl2、Ni(OTf)2、MnCl2、SnCl2、TiCl4、VCl2、Y(OTf)3，或P2O5。在无溶剂的操作下，该路易斯酸例如醋酸、醋酸酐、氯醋酸，或氯醋酸酐。
美国专利公开第2014296600A1号揭示一种高产率及高选择性的制备对二甲苯的方法。该方法为将2,5-二甲基呋喃及乙烯在酸性异质催化剂(acidic heterogeneouscatalyst)及溶剂的存在下于100℃以上进行1小时以上的环加成反应并于该环加成反应后进行脱水反应，而形成对二甲苯。该酸性异质催化剂例如沸石分子筛、活性碳、二氧化硅、氧化铝，或非沸石的分子筛等。
美国专利公告第8889938号揭示一种对二甲苯产率高的制备对二甲苯的方法。该方法为将起始原料及乙烯在催化剂及溶剂的存在下于150℃至300℃进行环加成反应并于该环加成反应后进行脱水反应，而形成对二甲苯。该起始原料为2,5-二甲基呋喃或2,5-己二酮。该催化剂例如AlCl3、AlBr3、Al(OTf)3、BiCl3、BiBr3、Bi(OTf)3、CuCl2、CuBr2，或Cu(OTf)2等。
虽所述专利案的方法皆可制备出对二甲苯，然而，所述专利案需在溶剂的存在下进行，导致生产成本高，且于反应后需将对二甲苯自溶剂中取出，导致存在有生产程序的繁琐且工时及成本过高的问题，再者，该溶剂无法直接再利用，而存在有产生大量的废弃溶剂的问题，继而衍生出废弃物处理费用。此外，美国专利公告第9260359号还存在有在无溶剂的操作下对二甲苯的产率及2,5-二甲基呋喃的转化率不佳的问题。
美国专利公告第8314267号揭示一种对二甲苯产率高的制备对二甲苯的方法。该方法为将2,5-二甲基呋喃及乙烯在催化剂及无溶剂的存在下于100℃至300℃进行1小时至48小时的环加成反应并于该环加成反应后进行脱水反应，而形成对二甲苯。该催化剂例如活性碳、沸石，或非沸石的分子筛等。虽该方法可用来制备对二甲苯，然而，该方法在对二甲苯的产率及2,5-二甲基呋喃的转化率的方面上仍不佳而无法满足业界需求。
美国专利公开第20160115113A1号揭示一种在制备对苯二甲酸二甲酯(dimethylterephthalate)的过程中形成对二甲苯的方法。该方法为在有溶剂或无溶剂的操作下，将2,5-二甲基呋喃及乙烯在催化剂的存在下于100℃至300℃进行1小时至48小时的环加成反应，并于该环加成反应后进行脱水反应，而形成对二甲苯。该催化剂例如沸石或活性碳等。虽该方法可用来制备对二甲苯，然而，该方法也存在有上述专利案所存在的问题。
发明内容
本发明的目的在于提供一种能够克服现有技术的缺点的烷基苯的制备方法。
本发明烷基苯的制备方法，包含以下步骤：步骤(a)，提供一个起始原料，选自于呋喃、烷基呋喃、2,5-己二酮(2,5-hexanedione，简称HD)，或上述任意的组合；步骤(b)，使该起始原料与单烯(monoene)在三氟甲磺酸金属盐催化剂(metal triflate catalyst)及无溶剂的存在下进行环加成反应(cycloaddition reaction)，以产生烷基苯。
本发明的烷基苯的制备方法中，该烷基呋喃选自于2-甲基呋喃、2,3-二甲基呋喃、2,4-二甲基呋喃、2,5-二甲基呋喃，或上述任意的组合。
本发明的烷基苯的制备方法中，该三氟甲磺酸金属盐催化剂选自于三氟甲磺酸铜(II)、三氟甲磺酸锌、三氟甲磺酸钪、三氟甲磺酸钇、三氟甲磺酸钇水合物、三氟甲磺酸铟(III)，或上述任意的组合。
本发明的烷基苯的制备方法中，在该步骤(b)中，该三氟甲磺酸金属盐催化剂与该起始原料的摩尔比例范围为1:100至1:100000。
本发明的烷基苯的制备方法中，在该步骤(b)中，该三氟甲磺酸金属盐催化剂与该起始原料的摩尔比例范围为1:5000至1:30000。
本发明的烷基苯的制备方法中，该单烯选自于乙烯、丙烯、1-己烯、环己烯，或上述任意的组合。
本发明的烷基苯的制备方法中，该起始原料选自于2,5-二甲基呋喃或2,5-己二酮，且该单烯为乙烯。
本发明的烷基苯的制备方法中，该起始原料在该步骤(b)中为液态。
本发明的烷基苯的制备方法中，该环加成反应是在压力范围为1000psi至2000psi且温度范围为200℃至300℃下进行。
本发明的烷基苯的制备方法中，该步骤(b)包括一个初始阶段及一个最终阶段；该初始阶段的温度是控制在大于200℃至小于270℃且在该温度范围下30分钟至60分钟；该最终阶段的温度控制在270℃至300℃且在该温度范围下4小时至10小时。
本发明的有益效果在于：通过使用三氟甲磺酸金属盐催化剂并搭配在无溶剂条件下，使得本发明烷基苯的制备方法具有低成本、低污染及高产率的效果。此外，当以相同总体积量进行该环加成反应时，相较于有使用溶剂的条件下，本发明烷基苯的制备方法在无溶剂条件下还具有产能效益提升的效果。
以下将就本发明内容进行详细说明。
<<步骤a>>
<起始原料>
该烷基呋喃中的烷基选自于C1至C8的直链烷基。该烷基呋喃可单独一种使用或混合多种使用，且该烷基呋喃例如但不限于2-甲基呋喃(2-methylfuran)、2,3-二甲基呋喃(2,3-dimethylfuran)、2,4-二甲基呋喃(2,4-dimethylfuran)或2,5-二甲基呋喃(2,5-dimethylfuran，简称DMF)等。较佳地，该起始原料选自于2,5-二甲基呋喃或2,5-己二酮。
<<步骤b>>
为使本发明烷基苯的制备方法能在一定的产率下具有更低的成本的效果，较佳地，在该步骤(b)中，该三氟甲磺酸金属盐催化剂与该起始原料的摩尔数比例范围为1:100至1:100000。为使本发明烷基苯的制备方法能在低成本下具有更高的产率，更佳地，在该步骤(b)中，该三氟甲磺酸金属盐催化剂与该起始原料的摩尔数比例范围为1:5000至1:30000。为更利于该起始原料与该单烯有效地接触及混合以进行环加成反应，较佳地，该起始原料在该步骤(b)中为液态。
<单烯>
该单烯例如总碳数范围为2至18的单烯。该单烯可单独一种使用或混合多种使用，且该单烯例如但不限于乙烯、丙烯、1-己烯，或环己烯等。较佳地，该单烯为乙烯。
<三氟甲磺酸金属盐催化剂>
该三氟甲磺酸金属盐催化剂可单独一种使用或混合多种使用，且该三氟甲磺酸金属盐催化剂例如但不限于三氟甲磺酸铜(II)[copper(II)trifluoromethanesulfonate，简称Cu(OTf)2]、三氟甲磺酸锌[zinc trifluoromethanesulfonate，简称Zn(OTf)2]、三氟甲磺酸钪[scandium trifluoromethanesulfonate，简称Sc(OTf)2]、三氟甲磺酸钇[yttriumtrifluoromethanesulfonate，简称Y(OTf)2]、三氟甲磺酸钇水合物[yttriumtrifluoromethanesulfonate hydrate，简称Y(OTf)2hydrate]，或三氟甲磺酸铟(III)[indium(III)trifluoromethanesulfonate，简称In(OTf)2]等。
<环加成反应>
为更利于该起始原料与该单烯有效地接触及混合以进行环加成反应，较佳地，该环加成反应是在压力范围为1000psi至2000psi，且温度范围为200℃至300℃下进行。较佳地，该环加成反应的操作时间范围为大于4小时至11小时以下。
较佳地，该步骤(b)中的该环加成反应包括一个初始阶段及一个最终阶段。该初始阶段的温度是控制在大于200℃至小于270℃且在该温度范围下30分钟至60分钟。该最终阶段的温度控制在270℃至300℃且在该温度范围下4小时至10小时。
具体实施方式
本发明将就以下实施例来作进一步说明，但应了解的是，该实施例仅为例示说明用，而不应被解释为本发明实施的限制。
实施例1
将90克的2,5-二甲基呋喃置于一个高压反应器内，此时总体积量为100mL。将0.051克的三氟甲磺酸铜(II)加入，并将该反应器内的空气置换成氮气，且共进行三次置换。接着，于室温下导入乙烯，并使该反应器内的压力被建构在520psi。然后，将温度升至250℃反应0.5小时，接着，再将温度升至270℃反应4.5小时，形成包含对二甲苯的混合物，其中，于整个反应过程中该反应器内的压力由1600psi渐渐降至1200psi。将温度降至室温，并释放该反应器内的压力。将该反应器内的混合物倒出，且该混合物的颜色呈黄褐色。
实施例2至11
实施例2至11是以与实施例1相同的步骤来制备对二甲苯，不同的地方在于：改变原料的种类及其使用量，如表1所示。
比较例1
将8克的2,5-二甲基呋喃及221毫升的四氢呋喃(tetrahydrofuran，简称THF)置于一个高压反应器内，此时总体积量为230mL。将0.045克的三氟甲磺酸铜(II)加入，并将该反应器内的空气置换成氮气，且共进行三次置换。接着，于室温下导入乙烯，并使该反应器内的压力被建构在520psi。然后，将温度升至270℃反应5小时，形成一包含对二甲苯的混合物，其中，于整个反应过程中该反应器内的压力由1600psi渐渐降至1200psi。将温度降至室温，并释放该反应器内的压力。将该反应器内的混合物倒出，且该混合物的颜色呈黄褐色。
比较例2至13
比较例2至13是以与比较例1相同的步骤来制备对二甲苯，不同的地方在于：改变原料的种类及其使用量，如表2所示。
比较例14
将57.6克的2,5-二甲基呋喃及35毫升的四氢呋喃置于一个高压反应器内，此时总体积量为100mL。将0.007克的三氟甲磺酸铜(II)加入，并将该反应器内的空气置换成氮气，且共进行三次置换。接着，于室温下导入乙烯，并使该反应器内的压力被建构在520psi。然后，将温度升至250℃反应0.5小时，接着，再将温度升至270℃反应4.5小时，形成包含对二甲苯的混合物，其中，于整个反应过程中该反应器内的压力由1600psi渐渐降至1200psi。将温度降至室温，并释放该反应器内的压力。将该反应器内的混合物倒出，且该混合物的颜色呈黄褐色。
评价项目
对二甲苯的产率(单位：％)量测：将实施例1至11及比较例1至14所获得的包含对二甲苯的混合物利用高效液相层析仪(high performance liquid chromatography)分析，获得对二甲苯于该混合物中的含量。该高压液相层析法分析的设备包含作为固定相的C18管柱、作为移动相的0.05wt％的磷酸水溶液(包含磷酸及水)与乙腈，及光二极管阵列侦测器(diodearraydetector)，其中，该移动相采梯度冲提法。该梯度冲提法为先使用0.05wt％的磷酸水溶液以流速为1.0mL/min进行冲提，然后，以相同流速进行冲提并在30分钟内缓慢增加乙腈的比例达到100％，及降低0.05wt％的磷酸水溶液的比例到0％。依据一个公式计算该对二甲苯的产率，且该公式为(对二甲苯的摩尔数/起始原料的摩尔数)×100％。
起始原料的转化率(单位：％)的计算：[1-(反应后起始原料的摩尔数/反应前起始原料的摩尔数)]×100％。
对二甲苯选择率(单位：％)的计算：(对二甲苯的产率/起始原料的转化率)×100％。
表1
表2
综上所述，通过使用三氟甲磺酸金属盐催化剂并搭配在无溶剂条件下，使得本发明烷基苯的制备方法具有低成本、低污染及高产率的效果，此外，当以相同总体积量进行该环加成反应时，相较于有使用溶剂的条件下，本发明烷基苯的制备方法在无溶剂条件下还具有产能效益提升的效果，所以确实能达成本发明的目的。
Claims (10)
1.一种烷基苯的制备方法，其特征在于包含以下步骤：
步骤(a)，提供一个起始原料，选自于呋喃、烷基呋喃、2,5-己二酮，或上述任意的组合；
步骤(b)，使该起始原料与单烯在三氟甲磺酸金属盐催化剂及无溶剂的存在下进行环加成反应，以产生烷基苯。
2.根据权利要求1所述的烷基苯的制备方法，其特征在于：该烷基呋喃选自于2-甲基呋喃、2,3-二甲基呋喃、2,4-二甲基呋喃、2,5-二甲基呋喃，或上述任意的组合。
3.根据权利要求1所述的烷基苯的制备方法，其特征在于：该三氟甲磺酸金属盐催化剂选自于三氟甲磺酸铜(II)、三氟甲磺酸锌、三氟甲磺酸钪、三氟甲磺酸钇、三氟甲磺酸钇水合物、三氟甲磺酸铟(III)，或上述任意的组合。
4.根据权利要求3所述的烷基苯的制备方法，其特征在于：在该步骤(b)中，该三氟甲磺酸金属盐催化剂与该起始原料的摩尔比例范围为1:100至1:100000。
5.根据权利要求4所述的烷基苯的制备方法，其特征在于：在该步骤(b)中，该三氟甲磺酸金属盐催化剂与该起始原料的摩尔比例范围为1:5000至1:30000。
6.根据权利要求1所述的烷基苯的制备方法，其特征在于：该单烯选自于乙烯、丙烯、1-己烯、环己烯，或上述任意的组合。
7.根据权利要求1所述的烷基苯的制备方法，其特征在于：该起始原料选自于2,5-二甲基呋喃或2,5-己二酮，且该单烯为乙烯。
8.根据权利要求1所述的烷基苯的制备方法，其特征在于：该起始原料在该步骤(b)中为液态。
9.根据权利要求1所述的烷基苯的制备方法，其特征在于：该环加成反应是在压力范围为1000psi至2000psi且温度范围为200℃至300℃下进行。
10.权利要求9所述的烷基苯的制备方法，其特征在于：该步骤(b)包括一个初始阶段及一个最终阶段；该初始阶段的温度是控制在大于200℃至小于270℃且在该温度范围下30分钟至60分钟；该最终阶段的温度控制在270℃至300℃且在该温度范围下4小时至10小时。
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| CN111004078A (zh) * | 2019-12-24 | 2020-04-14 | 北京化工大学 | 一种生物基对二甲苯的制备方法 |
| CN111004078B (zh) * | 2019-12-24 | 2021-03-26 | 北京化工大学 | 一种生物基对二甲苯的制备方法 |
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| TW201910300A (zh) | 2019-03-16 |
| TWI630192B (zh) | 2018-07-21 |
| US20190031579A1 (en) | 2019-01-31 |
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