CN116283520A - Preparation method of aryl ketone, alpha-hydroxy ketone and alpha-amino ketone - Google Patents
Preparation method of aryl ketone, alpha-hydroxy ketone and alpha-amino ketone Download PDFInfo
- Publication number
- CN116283520A CN116283520A CN202111564404.XA CN202111564404A CN116283520A CN 116283520 A CN116283520 A CN 116283520A CN 202111564404 A CN202111564404 A CN 202111564404A CN 116283520 A CN116283520 A CN 116283520A
- Authority
- CN
- China
- Prior art keywords
- alpha
- catalyst
- trifluoromethanesulfonate
- ketone compound
- methanesulfonate
- 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.)
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- -1 aryl ketone Chemical class 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 47
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims abstract description 22
- 150000001555 benzenes Chemical class 0.000 claims abstract description 16
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 claims abstract description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- CMWINYFJZCARON-UHFFFAOYSA-N 6-chloro-2-(4-iodophenyl)imidazo[1,2-b]pyridazine Chemical compound C=1N2N=C(Cl)C=CC2=NC=1C1=CC=C(I)C=C1 CMWINYFJZCARON-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 6
- JKHXWQFLCQONBH-UHFFFAOYSA-K [Sc+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O Chemical compound [Sc+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O JKHXWQFLCQONBH-UHFFFAOYSA-K 0.000 claims abstract description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 6
- HIYUMYXSGIKHHE-UHFFFAOYSA-M bismuth trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F HIYUMYXSGIKHHE-UHFFFAOYSA-M 0.000 claims abstract description 6
- MNMKEULGSNUTIA-UHFFFAOYSA-K bismuth;methanesulfonate Chemical compound [Bi+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O MNMKEULGSNUTIA-UHFFFAOYSA-K 0.000 claims abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 6
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 6
- 239000011592 zinc chloride Substances 0.000 claims abstract description 6
- 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 claims abstract description 6
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims abstract description 6
- MKRZFOIRSLOYCE-UHFFFAOYSA-L zinc;methanesulfonate Chemical compound [Zn+2].CS([O-])(=O)=O.CS([O-])(=O)=O MKRZFOIRSLOYCE-UHFFFAOYSA-L 0.000 claims abstract description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 21
- 229920001230 polyarylate Polymers 0.000 claims description 19
- 238000007142 ring opening reaction Methods 0.000 claims description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 230000026030 halogenation Effects 0.000 claims description 10
- 238000005658 halogenation reaction Methods 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 4
- 125000000068 chlorophenyl group Chemical group 0.000 claims description 4
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000005561 phenanthryl group Chemical group 0.000 claims description 4
- 125000001725 pyrenyl group Chemical group 0.000 claims description 4
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- VXVVUHQULXCUPF-UHFFFAOYSA-N cycloheptanamine Chemical compound NC1CCCCCC1 VXVVUHQULXCUPF-UHFFFAOYSA-N 0.000 claims description 3
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 238000007086 side reaction Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- CCNMTCHDGVNKBI-UHFFFAOYSA-K aluminum;methanesulfonate Chemical compound [Al+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O CCNMTCHDGVNKBI-UHFFFAOYSA-K 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 59
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000003599 detergent Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 125000005037 alkyl phenyl group Chemical group 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000005695 dehalogenation reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 150000008365 aromatic ketones Chemical class 0.000 description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000002140 halogenating effect Effects 0.000 description 3
- 125000005322 morpholin-1-yl group Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- SXWIAEOZZQADEY-UHFFFAOYSA-N 1,3,5-triphenylbenzene Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=C1 SXWIAEOZZQADEY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- FKOASGGZYSYPBI-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)alumanyl trifluoromethanesulfonate Chemical compound [Al+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 FKOASGGZYSYPBI-UHFFFAOYSA-K 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
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Abstract
The invention discloses a preparation method of aryl ketone, alpha-hydroxy ketone and alpha-amino ketone, belonging to the field of organic chemistry. The preparation method of the aryl ketone compound comprises the following steps: under the catalysis of a catalyst, carrying out Friedel-crafts acylation reaction on substituted benzene and acyl chloride to obtain aryl ketone compounds; the catalyst comprises: a polyaryl three-dimensional network polymer, an active component supported on the polyaryl three-dimensional network polymer; the active component comprises AlX 3 At least one of ferric trichloride, bismuth trichloride, gallium trichloride, boron trifluoride, titanium tetrachloride, tin tetrachloride, zinc chloride, zinc methanesulfonate, aluminum methanesulfonate, bismuth methanesulfonate, scandium methanesulfonate, zinc trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, scandium trifluoromethanesulfonate, and ferric oxide, wherein X comprises chlorine, bromine, iodine, methanesulfonate, or trifluoromethanesulfonate. The catalyst has the advantages of higher catalytic activity, high reaction efficiency, less side reaction, safety and environmental protection.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a preparation method of aryl ketone, alpha-hydroxy ketone and alpha-amino ketone.
Background
Friedel-Crafts Acylation (Friedel-Crafts reaction), also known as Friedel-Crafts reaction or F-C reaction, is widely used for synthesizing aromatic ketone compounds, and the aromatic ketone compounds are used as a common chemical intermediate and are commonly used for preparing alpha-hydroxy ketone compounds or alpha-amino ketone photoinitiators.
The related technology adopts the following mode to prepare alpha-hydroxyketone or alpha-aminoketone: friedel-crafts acylation reaction is carried out on substituted benzene and acyl chloride under the catalysis of a catalyst to generate aryl ketone, halogenating is carried out on tertiary hydrogen on alpha position of the aryl ketone to obtain halogenated product, dehalogenation is carried out on the halogenated product to obtain epoxy product, and ring opening is carried out on the epoxy product under the action of acid/alkali to obtain alpha-hydroxy ketone or alpha-amino ketone. Wherein, the catalyst used in Friedel-crafts acylation reaction is Lewis acid.
However, lewis acids have at least the following technical problems in catalyzing friedel-crafts acylation reactions: large dosage, multiple side reactions, irrecoverability, long reaction time, difficult separation after reaction and easy generation of a large amount of wastewater after post-treatment.
Disclosure of Invention
In view of the above, the embodiments of the present invention provide a method for preparing aryl ketone, α -hydroxy ketone and α -amino ketone, which can solve the above-mentioned technical problems.
Specifically, the method comprises the following technical scheme:
in one aspect, a method for preparing an aromatic ketone compound is provided, which includes: under the catalysis of a catalyst, carrying out Friedel-crafts acylation reaction on substituted benzene and acyl chloride to obtain aryl ketone compounds;
wherein the catalyst comprises: a polyarylate three-dimensional network polymer, an active component supported on the polyarylate three-dimensional network polymer;
the active component comprises AlX 3 At least one of ferric trichloride, bismuth trichloride, gallium trichloride, boron trifluoride, titanium tetrachloride, tin tetrachloride, zinc chloride, zinc methanesulfonate, aluminum methanesulfonate, bismuth methanesulfonate, scandium methanesulfonate, zinc trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, scandium trifluoromethanesulfonate, and ferric oxide, wherein X comprises chlorine, bromine, iodine, methanesulfonate, or trifluoromethanesulfonate.
In some possible implementations, the polyarylate three-dimensional network polymer has the chemical structural formula:
wherein Ar comprises at least one of phenyl, tolyl, phenol, chlorophenyl, biphenyl, 1,3, 5-triphenylphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, furyl, thienyl and pyrrolyl.
In some possible implementations, the active component is AlX 3 。
In some possible implementations, the mass ratio of the substituted benzene to the catalyst is 1000:1-50.
In another aspect, a method for preparing an α -hydroxyketone compound is provided, the method comprising:
preparing an aryl ketone compound, wherein the aryl ketone compound is prepared by adopting the method;
carrying out halogenation treatment on the aryl ketone compound to obtain a halogenated product;
dehalogenating the halogenated product to obtain an epoxy product;
and (3) carrying out ring opening treatment on the epoxy product in an acidic environment to obtain the alpha-hydroxy ketone compound.
In some possible implementations, the acidic environment is provided by hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, or phosphoric acid.
In some possible implementations, the chemical structural formula of the α -hydroxyketone compound is as follows:
Wherein R is 1 At least one of C10-C14 linear monoalkyl groups;
R 2 、R 3 each independently is methyl or ethyl;
R 4 is cyclopentyl, cyclohexyl or cycloheptyl;
Z 1 is hydroxyl.
In still another aspect, a method for preparing an α -aminoketone compound is provided, the method comprising:
preparing an aryl ketone compound, wherein the aryl ketone compound is prepared by adopting the method;
carrying out halogenation treatment on the aryl ketone compound to obtain a halogenated product;
dehalogenating the halogenated product to obtain an epoxy product;
and (3) carrying out ring opening treatment on the epoxy product in an alkaline environment to obtain the alpha-aminoketone compound.
In some possible implementations, the alkaline environment is provided by cyclopentylamine, cyclohexylamine, cycloheptylamine, morpholine, piperazine, or N-methylpiperazine.
In some possible implementations, the chemical structural formula of the α -aminoketone compound is as follows:
wherein R is 1 At least one of C10-C14 linear monoalkyl groups;
R 2 、R 3 each independently is methyl or ethyl;
Z 2 is cyclopentylamino, cyclohexylamino, cycloheptylamino, morpholino, piperazino, or N-methylpiperazino.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
according to the preparation method of the aryl ketone compound, provided by the embodiment of the invention, the catalyst for loading the active component on the polyaryl three-dimensional network polymer is used, and the polyaryl three-dimensional network polymer has a rich micropore structure and a higher specific surface area, so that the active component has high dispersity and high loading capacity. When the catalyst is used for preparing the aryl ketone compound through Friedel-crafts acylation reaction, the catalyst has the advantages of higher catalytic activity, high reaction efficiency, less side reaction, safety and environmental protection, can be easily separated from a product system through a simple solid-liquid separation means, and avoids a large amount of wastewater problems caused by post-treatment.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Friedel-Crafts Acylation (Friedel-Crafts reaction), also known as Friedel-Crafts reaction or F-C reaction, is widely used for synthesizing aromatic ketone compounds, and the aromatic ketone compounds are used as a common chemical intermediate and are commonly used for preparing alpha-hydroxy ketone compounds.
The related technology adopts the following mode to prepare alpha-hydroxyketone or alpha-aminoketone: friedel-crafts acylation reaction is carried out on substituted benzene and acyl chloride under the catalysis of a catalyst to generate aryl ketone, halogenating is carried out on tertiary hydrogen on alpha position of the aryl ketone to obtain halogenated product, dehalogenation is carried out on the halogenated product to obtain epoxy product, and ring opening is carried out on the epoxy product under the action of acid/alkali to obtain alpha-hydroxy ketone or alpha-amino ketone. Wherein, the catalyst used in Friedel-crafts acylation reaction is Lewis acid. However, lewis acids have at least the following technical problems in catalyzing friedel-crafts acylation reactions: large dosage, multiple side reactions, irrecoverability, long reaction time, difficult separation after reaction and easy generation of a large amount of wastewater after post-treatment.
The embodiment of the invention provides a preparation method of an aromatic ketone compound, which comprises the following steps: under the catalysis of the catalyst, the substituted benzene and acyl chloride undergo Friedel-crafts acylation reaction to obtain the aryl ketone compound.
In particular, the catalyst used for the friedel-crafts acylation reaction comprises: polyaryl three-dimensional network polymer, active component loaded on polyaryl three-dimensional network polymer. Wherein the active component comprises AlX 3 (X comprises at least one of chlorine, bromine, iodine, methanesulfonate or trifluoromethanesulfonate), ferric trichloride, bismuth trichloride, gallium trichloride, boron trifluoride, titanium tetrachloride, tin tetrachloride, zinc chloride, zinc methanesulfonate, aluminum methanesulfonate, bismuth methanesulfonate, scandium methanesulfonate, zinc trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, scandium trifluoromethanesulfonate, and ferric oxide.
According to the preparation method of the aryl ketone compound, provided by the embodiment of the invention, the catalyst for loading the active component on the polyaryl three-dimensional network polymer is used, and the polyaryl three-dimensional network polymer has a rich micropore structure and a higher specific surface area, so that the active component has high dispersity and high loading capacity. Thus, when the catalyst is applied to the reaction process, the dispersity of the catalyst in the solvent is higher, so that the contact area between the active component and the reactant is larger, which is beneficial to improving the catalytic activity, reducing the dosage and reducing the reaction time. Since the polyaryl three-dimensional network polymer includes a plurality of aryl groups, the rigid three-dimensional skeleton of the polyaryl three-dimensional network polymer is formed by using a plurality of rigid aryl structural units, so that the active component is stably confined in the mesh thereof, i.e., the active component is stably supported on the polyaryl three-dimensional network polymer, so that the active component is not easily combined with the reaction product, which is advantageous in reducing side reactions, and further ensures catalytic activity. When the catalyst is used for preparing the aryl ketone compound through Friedel-crafts acylation reaction, the catalyst has the advantages of higher catalytic activity, high reaction efficiency, less side reaction, safety and environmental protection, can be easily separated from a product system through a simple solid-liquid separation means, and avoids a large amount of wastewater problems caused by post-treatment.
The active component includes AlX 3 (X comprises at least one of chlorine, bromine, iodine, methanesulfonate or trifluoromethanesulfonate), ferric trichloride, bismuth trichloride, gallium trichloride, boron trifluoride, titanium tetrachloride, tin tetrachloride, zinc chloride, zinc methanesulfonate, aluminum methanesulfonate, bismuth methanesulfonate, scandium methanesulfonate, zinc trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, scandium trifluoromethanesulfonate, and ferric oxide. For example, alX 3 May be aluminum trichloride or aluminum tris (trifluoromethanesulfonate). The active component may include any one of the above, or may include two or more of the above.
In particular, the active component is AlX 3 When the catalyst is used, the catalyst shows more excellent catalytic activity than other active components in the Friedel-crafts acylation reaction for preparing aryl ketone compounds.
The catalyst according to the embodiment of the invention is based on the use of the polyarylate three-dimensional network polymer as a carrier, so that the loading of the active component is sufficiently large, and in some examples, 1.5mmol to 1.7mmol of the active component is included in each gram of the catalyst, for example, the loading of the active component in each gram of the catalyst is 1.5mmol, 1.55mmol, 1.6mmol, 1.65mmol, 1.7mmol, and the like.
The chemical structural formula of the polyaryl three-dimensional network polymer suitable for the embodiment of the invention is shown as follows:
wherein Ar is an aromatic hydrocarbon group, and a wavy line represents a connecting site of the group.
In some examples, ar includes at least one of phenyl (Ph), tolyl (To), phenol (Po), chlorophenyl (Lp), biphenyl (Dp), 1,3, 5-triphenylphenyl (Tp), naphthyl (Na), anthryl (An), phenanthryl (Pn), pyrenyl (Pe), furanyl (Fn), thienyl (Th), pyrrolyl (Py). For example, the aromatic hydrocarbon group Ar is phenyl or tolyl.
The polyaryl three-dimensional network polymer with the chemical structure has rich micropore structure and higher specific surface area.
The embodiment of the invention also provides a preparation method of the catalyst, which comprises the following steps:
polyarylate three-dimensional network polymers and active components are provided. Stirring the polyaryl three-dimensional network polymer and the active component in a first solvent for a first set time to load the active component on the polyaryl three-dimensional network polymer, thereby obtaining the catalyst.
The objective of supporting the active component on the polyarylate three-dimensional network polymer is achieved by thoroughly stirring the polyarylate three-dimensional network polymer and the active component in the first solvent.
Illustratively, suitable first solvents for use in the loading process described above include, but are not limited to: at least one of dichloromethane, 1, 2-dichloroethane, carbon disulfide, nitrobenzene, benzene, toluene, xylene, chlorobenzene, bromobenzene, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, propionitrile, methyl tert-butyl ether, isopropyl ether, dioxane, ethylene glycol dimethyl ether, methanol, ethanol, isopropanol, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane.
For the amount of first solvent used, in some examples, the mass to volume ratio of the polyarylate three-dimensional network polymer to the first solvent is from 1:1 to 10, further from 1:1 to 5, such as 1:1, 1:2, 1:3, 1:4, 1:5, and the like. Wherein the mass to volume ratio is the ratio of the unit mass of the polyarylate three-dimensional network polymer to the unit volume of the first solvent.
Illustratively, the polyarylate three-dimensional network polymer and the active component are stirred in the first solvent for a first set time, and the first set time is from 12 hours to 36 hours, at a temperature of from-20 ℃ to 150 ℃.
For example, the above stirring temperature may further be from 0 ℃ to 100 ℃, including but not limited to: 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, etc.
The above stirring time may further be 12 hours to 24 hours, including but not limited to: 12 hours, 15 hours, 17 hours, 19 hours, 20 hours, etc.
Further, in order to obtain a catalyst with high purity and high yield, the preparation method of the catalyst provided by the embodiment of the invention further comprises the following steps: after the active component is loaded on the polyaryl three-dimensional network polymer, the obtained first product system is sequentially filtered, extracted and decompressed and dried to obtain the catalyst.
For example, the extraction may be performed in a Soxhlet extractor using an extraction solvent such as acetonitrile or the like, and the temperature of the above-mentioned reduced pressure drying may be 40℃to 80℃or the like.
In some examples, specific operational steps of the catalyst preparation method are as follows:
under the anhydrous and anaerobic condition, the polyaryl three-dimensional network polymer, the active component and the first solvent are mixed according to the proportion of the polyaryl three-dimensional network polymer and the active component, and the obtained mixture is stirred for 12 to 36 hours at the temperature of between 20 ℃ below zero and 150 ℃. Wherein the molar ratio of the polyaryl three-dimensional network polymer to the active component is 1:1-3.
And cooling the obtained first product system to room temperature, filtering, taking a filter cake, washing the filter cake in a Soxhlet extractor by using acetonitrile for 20-30 hours, and then drying the washed product at 40-80 ℃ under reduced pressure for 20-30 hours to obtain the catalyst.
In some examples, the polyarylate three-dimensional network polymer has the chemical structural formula:
wherein Ar is An aromatic hydrocarbon group, and Ar comprises at least one of phenyl (Ph), tolyl (To), phenol (Po), chlorophenyl (Lp), biphenyl (Dp), 1,3, 5-triphenylphenyl (Tp), naphthyl (Na), anthryl (An), phenanthryl (Pn), pyrenyl (Pe), furyl (Fn), thienyl (Th) and pyrrolyl (Py).
Correspondingly, the chemical structural formula of the catalyst is shown as follows:
wherein M is the active component.
The above-described catalysts are particularly suitable for friedel-crafts acylation reactions and have at least the following advantages: the reaction efficiency is high; the usage amount is low; the side reaction is less; the reaction condition is mild and controllable; is easily separated from the product; can be recovered through simple solid-liquid separation; can be reused after being recovered; safety, energy conservation and environmental protection; no waste water and the like are generated.
After the Friedel-crafts acylation reaction is carried out by using the catalyst, the catalyst can be recovered by a conventional solid-liquid separation method, and the quality, activity and selectivity of the recovered catalyst are not obviously changed compared with those before the reaction.
The chemical equation of the catalyst prepared by using the polyarylate three-dimensional network polymer and the active component M is as follows:
for the polyarylate three-dimensional network polymer, the preparation method of the polyarylate three-dimensional network polymer is as follows:
under the catalysis of the catalyst, triphenylphosphine and aromatic hydrocarbon react in a second solvent. And after the reaction is finished, sequentially filtering, extracting and decompressing and drying the obtained second product system to obtain the polyaryl three-dimensional network polymer.
The chemical equation for preparing the polyaryl three-dimensional network polymer is shown as follows:
illustratively, the second solvent suitable for preparing the polyaryl three-dimensional network polymer is selected from at least one of dichloromethane, 1, 2-dichloroethane, carbon disulfide, nitrobenzene, for example, the second solvent is 1, 2-dichloroethane.
Illustratively, a catalyst suitable for preparing the polyarylate three-dimensional network polymer is selected from at least one of aluminum trichloride, iron trichloride, bismuth trichloride, gallium trichloride, boron trifluoride, titanium tetrachloride, tin tetrachloride, zinc chloride, zinc methanesulfonate, aluminum methanesulfonate, bismuth methanesulfonate, scandium methanesulfonate, zinc trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, scandium trifluoromethanesulfonate, active ferric oxide, for example, the catalyst is aluminum trichloride or ferric trichloride.
Illustratively, the aromatic hydrocarbon is at least one selected from benzene, toluene, phenol, chlorobenzene, biphenyl, 1,3, 5-triphenylbenzene, naphthalene, anthracene, phenanthrene, pyrene, furan, thiophene, pyrrole, and is benzene or toluene, for example.
In some examples, the molar ratio between triphenylphosphine, aromatic hydrocarbon, dimethoxymethane, and catalyst is 1 (1-5): 1-10, and further may be 1 (1-5): 1-5, to obtain high reaction efficiency and high product yield.
In some examples, reacting triphenylphosphine, an aromatic hydrocarbon in a second solvent under anhydrous oxygen-free conditions comprises:
and stirring the mixture of triphenylphosphine, aromatic hydrocarbon, dimethoxymethane, catalyst and the second solvent for 0.5-2 hours at-20-room temperature to obtain a reaction raw material liquid with uniform texture.
Stirring the reaction raw material liquid at 0-60 ℃ for reaction for 5-15 hours to form a cross-linked intermediate, wherein the cross-linked intermediate has a basic cross-linked network.
And (3) continuously stirring and reacting the product system containing the cross-linked intermediate for 24-84 hours at 65-100 ℃ to form the polyaryl three-dimensional network polymer.
Further, cooling a product system containing the polyaryl three-dimensional network polymer to room temperature, filtering, taking a filter cake, washing the filter cake for 20-30 hours by using methanol in a Soxhlet extractor, and then drying the washed product at 40-80 ℃ under reduced pressure for 20-30 hours to obtain the polyaryl three-dimensional network polymer.
For the above reaction, the content of triphenylphosphine in the product system can be detected by high performance liquid chromatography (High Performance Liquid Chromatography, HPLC) to determine the reaction endpoint and prevent insufficient reaction or reaction transition.
The above description is given by way of example of the composition of the catalyst and its preparation method, and the following description is given by way of example of the use of the catalyst in the preparation of aromatic ketone compounds:
in some examples, the corresponding chemical equations for the preparation of aromatic ketones are shown below:
wherein R is 1 Is at least one of C10-C14 linear monoalkyl groups.
R 2 、R 3 Each independently is methyl or ethyl.
In other examples, the corresponding chemical equations for the preparation of aromatic ketones are shown below:
wherein R is 1 Is at least one of C10-C14 linear monoalkyl groups.
R 4 Is cyclopentyl, cyclohexyl or cycloheptyl.
In some examples, the molar ratio of substituted benzene to acid chloride is 1:1 to 2, further 1:1 to 1.2, including but not limited to: 1:1.05, 1:1.07, 1:1.08, 1:1.09, 1:1.1, etc. By slightly exceeding the amount of the acid chloride, on the one hand, a sufficiently complete reaction of the substituted benzene can be ensured, and on the other hand, the substituted benzene can be prevented from exceeding.
In some examples, the mass ratio of substituted benzene to catalyst is 1000:1 to 50, further 1000:1 to 30, such as 1000:1 to 10, including but not limited to: 1000:1, 1000:5, 1000:10, 1000:15, 1000:20, 1000:25, 1000:30, etc. By setting the ratio of the substituted benzene to the catalyst, not only can the substituted benzene be reacted sufficiently completely, but also an excess of the substituted benzene can be prevented.
In some examples, the friedel-crafts acylation reaction has a reaction temperature of-20 ℃ to 150 ℃, further 0 ℃ to 100 ℃, such as 60 ℃ to 80 ℃, including but not limited to: 60 ℃, 62 ℃, 65 ℃, 67 ℃, 70 ℃, 75 ℃, 78 ℃, 80 ℃ and the like. In this temperature range, not only can the reaction be ensured to be sufficient and complete, but also the occurrence of side reactions can be prevented, avoiding the occurrence of undesirable impurities.
In preparing the aromatic ketone compound, the substituted benzene is reacted with the acid chloride in a third solvent, which may be, for example, methylene chloride, 1, 2-dichloroethane, or a mixture of both.
After the Friedel-crafts acylation reaction is finished, the catalyst can be obtained through separation by a conventional solid-liquid separation means, wherein only a little first solvent is remained, so that the catalyst can be directly used in a new Friedel-crafts acylation reaction without any post-treatment, the energy is fully facilitated, and the catalyst is more energy-saving and environment-friendly. The solid-liquid separation means include, but are not limited to: decantation, filtration, centrifugation, and the like.
On the other hand, the embodiment of the invention also provides a preparation method of the alpha-hydroxyketone compound, which comprises the following steps:
the aromatic ketone compound is prepared by adopting any one of the preparation methods of the aromatic ketone compound.
And carrying out halogenation treatment on the aryl ketone compound to obtain a halogenated product.
Dehalogenating the halogenated product to obtain an epoxy product.
And (3) ring-opening treatment is carried out on the epoxy product in an acidic environment to obtain the alpha-hydroxy ketone compound.
The ring-opening treatment in the acidic environment is an acidolysis reaction based on an acid, the acid may be in the form of an aqueous solution of an acid, and the acid may be an inorganic acid such as at least one of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, and phosphoric acid.
Illustratively, the molar ratio of epoxy product to acid is 1:1 to 10, further 1:1 to 5, further 1:2 to 3. The reaction temperature corresponding to the ring opening treatment in the acidic environment can be between-20 ℃ and 150 ℃, and further between 10 ℃ and 40 ℃.
The solvent used for the ring-opening treatment in the acidic environment is an organic solvent, and is at least one of aromatic hydrocarbon benzene, toluene, xylene, chlorobenzene, and chlorinated aliphatic hydrocarbon (methylene chloride, 1, 2-dichloroethane, etc.).
The chemical structural formula of the alpha-hydroxy ketone compound is shown in the following example:
Wherein R is 1 At least one of C10-C14 linear monoalkyl groups;
R 2 、R 3 each independently is methyl or ethyl;
R 4 is cyclopentyl, cyclohexyl or cycloheptyl;
Z 1 is hydroxyl.
In still another aspect, the embodiment of the present invention further provides a method for preparing an α -aminoketone compound, where the method for preparing an α -aminoketone compound includes:
the aromatic ketone compound is prepared by adopting any one of the preparation methods of the aromatic ketone compound.
And carrying out halogenation treatment on the aryl ketone compound to obtain a halogenated product.
Dehalogenating the halogenated product to obtain an epoxy product.
And (3) ring-opening treatment is carried out on the epoxy product in an alkaline environment to obtain the alpha-aminoketone compound.
The ring opening treatment under alkaline conditions described above is a base-based alkaline hydrolysis reaction, and in some examples the base used may be at least one of cyclopentylamine, cyclohexylamine, cycloheptylamine, morpholine, piperazine, N-methylpiperazine, for example one of them, which provides an alkaline environment. The molar ratio of the epoxy product to the alkali is 1:1-2, and further 1:1-1.1.
In some examples, the chemical structural formula of the α -aminoketone compound is as follows:
wherein R is 1 At least one of the linear mono-alkyl radicals having a formula of C10-C14, i.e. CH 3 C n H 2n N is an integer of 9 to 13.
R 2 、R 3 Each independently is methyl or ethyl;
Z 2 is cyclopentylamino, cyclohexylamino, cycloheptylamino, morpholino, piperazino, or N-methylpiperazino.
In some examples, the chemical equations corresponding to the halogenation treatments in the methods of preparing the α -hydroxy ketones and α -amino ketones are shown below:
for the halogenation treatment step, the aromatic ketone compound and the chlorinating agent are reacted to obtain a halogenated product, and the molar ratio of the aromatic ketone compound to the chlorinating agent is, illustratively, 1:1 to 5, further 1:1 to 2, further 1:1 to 1.2.
Illustratively, the corresponding reaction temperature for the halogenation treatment is from-20℃to 150℃such as from 0℃to 100℃and further from 30℃to 80℃
The halogenating agent used in the halogenation treatment may be at least one of chlorine, bromine, iodine and sulfonyl chloride, and may be, for example, sulfonyl chloride.
In some examples, the chemical equations corresponding to dehalogenation in the methods of preparing the α -hydroxy ketones and α -amino ketones are shown below:
for the dehalogenation treatment step, the halogenated product and sodium alkoxide are dehalogenated to obtain an epoxy product, and the molar ratio of the halogenated product to sodium alkoxide is, illustratively, 1:1 to 5, further 1:1 to 2, further 1:1 to 1.1. The sodium alkoxide may be at least one of sodium methoxide, sodium ethoxide, and sodium tert-butoxide.
The solvent used for the dehalogenation treatment may be a small molecule alcohol, such as at least one of methanol, ethanol, isopropanol. The corresponding reaction temperature for dehalogenation treatment is-20℃to 150℃and, for example, 20℃to 60 ℃.
In some examples, the chemical equations corresponding to the ring opening treatment in the methods of preparing the α -hydroxyketone compounds and the α -aminoketone compounds are shown below (wherein Z represents Z, respectively 1 Or Z is 2 )：
The alpha-hydroxy ketone compound and the alpha-amino ketone compound prepared by the method provided by the embodiment of the invention can be used as photoinitiators and have excellent photoinitiation characteristics.
Some specific implementations of embodiments of the present invention will be described in more detail below. While specific embodiments of the invention are described below, it should be understood that embodiments of the invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
This example 1 provides a catalyst having the chemical structural formula shown below:
the preparation steps of the catalyst are as follows:
step (1): 156 g of benzene, 525 g of triphenylphosphine, 456 g of dimethoxymethane, 975 g of anhydrous ferric trichloride and 3 l of 1, 2-dichloroethane are mixed and stirred for 1 hour under anhydrous oxygen-free and room temperature conditions, then heated to 45 ℃ and stirred for reaction for 10 hours at that temperature, then heated to 80 ℃ and stirred for reaction for 72 hours.
Step (2): and (3) cooling the temperature of the product system obtained in the step (1) to room temperature, filtering, taking a filter cake, washing the filter cake in a Soxhlet extractor by utilizing methanol for 24 hours, and then drying the washed product under reduced pressure at 60 ℃ for 24 hours to obtain the polyaryl three-dimensional network polymer. Wherein the polyarylate three-dimensional network polymer has a mass of 720 g and a yield of 96%, and the polyarylate three-dimensional network polymer has a light brown color.
Step (3): 700 g of polyaryl three-dimensional network polymer, 250 g of anhydrous aluminum trichloride and 2 liters of 1, 2-dichloroethane are mixed under anhydrous and anaerobic conditions, stirred at 60 ℃ for 24 hours, and the product system is cooled to room temperature after the reaction is finished.
Step (4): filtering the product system obtained in the step (3), taking a filter cake, washing the filter cake in a Soxhlet extractor by acetonitrile for 24 hours, and then drying the washed product under reduced pressure at 60 ℃ for 24 hours to obtain the catalyst of the embodiment 1.
The catalyst was tested to weigh 889 grams in 93% yield and appeared light brown in color. The active component AlCl in the catalyst 3 Is 1.6mmol AlCl 3 /g catalyst.
Example 2
Examples 2 to 0
Example 2-0 1- (4-Soft detergent alkylphenyl) -2-methyl-propan-1-one was prepared and the chemical structural formula of this 1- (4-Soft detergent alkylphenyl) -2-methyl-propan-1-one is shown below:
the preparation steps are as follows:
(1) 100 g of soft detergent alkylbenzene (for example, a liquid mixture consisting of monoalkylbenzene having a linear chain R of 10 to 14 carbon atoms), 65 g of isobutyryl chloride and 5 g of the catalyst prepared in example 1 are mixed under anhydrous and anaerobic conditions, and the mixture is stirred at 75 to 80℃for 20 to 24 hours. During the reaction, the reaction end point was monitored by TLC, and the spot of the soft detergent alkylbenzene was substantially disappeared, which was regarded as the completion of the reaction.
(2) Cooling the reaction product system to room temperature, filtering to obtain filter cake, recovering the filter cake, and distilling the filtrate at 40-50 deg.c under reduced pressure to recover excessive isobutyryl chloride. Then the mixture was depressurized at 70 to 80 ℃ to remove trace volatiles to give 1- (soft detergent alkylphenyl) -2-methyl-propan-1-one as an oil, weighing 128 g and the total purity of the mixed components was 98.6% by HPLC test.
Example 2-1
The catalyst recovered in example 2-0 was used again for the preparation of 1- (2-soft detergent alkylphenyl) -2-methyl-propan-1-one, and the amount and operation were the same as in example 2-0.
Example 2-2
The catalyst recovered in example 2-1 was used again for the preparation of 1- (2-soft detergent alkylphenyl) -2-methyl-propan-1-one, and the amount and operation were the same as in example 2-0.
Examples 2 to 3
The catalyst recovered in example 2-2 was used again for the preparation of 1- (2-soft detergent alkylphenyl) -2-methyl-propan-1-one, and the amount and operation were the same as in example 2-0.
Examples 2 to 4
And so on, the catalyst recovered in example 2-3 was used.
Examples 2 to 5
And so on, the catalysts recovered in examples 2-4 were used.
Examples 2 to 6
And so on, the catalyst recovered in examples 2-5 was used.
Examples 2 to 7
And so on, the catalysts recovered in examples 2-6 were used.
Examples 2 to 8
And so on, the catalysts recovered in examples 2-7 were used.
The relevant parameters for examples 2-0 to 2-8 above are shown in Table 1 below:
TABLE 1
As can be seen from table 1, after the catalyst provided in example 1 was repeatedly recovered and used 8 times, the activity of the catalyst and the reaction of friedel-crafts acylation by the catalyst were not significantly affected.
Example 3-example 5
Other aromatic ketones were prepared by the same procedure as in examples 2-0, respectively, except that the starting materials involved in the reaction were different, and the relevant parameters are shown in Table 2:
TABLE 2
According to tests, when the aromatic ketone compounds are prepared, the catalyst provided by the embodiment of the invention is used, so that the preparation process of the aromatic ketone compounds has at least the following advantages: the reaction efficiency is high; the catalyst usage amount is low; the side reaction is less; the reaction condition is mild and controllable; the catalyst can be easily separated from the product and can be recovered by simple solid-liquid separation; can be reused after being recovered; safety, energy conservation and environmental protection; no waste water and the like are generated.
Example 6
Example 6 an alpha-hydroxy ketone compound, in particular 1- (4-soft detergent alkylphenyl) -2-methyl-2-hydroxy-propan-1-one, was prepared having the chemical structural formula shown below:
the preparation steps of the 1- (4-soft detergent alkylphenyl) -2-methyl-2-hydroxy-propan-1-one are as follows:
(1) 70 g of sulfonyl chloride was slowly and uniformly mixed with 128 g of the 1- (4-soft detergent alkylphenyl) -2-methyl-propan-1-one prepared in example 2-0 and 200 ml of toluene at 40℃to 45℃under stirring, and stirring was continued for 3 hours at 45 ℃. And cooling the obtained product system to room temperature, washing with water, washing with sodium bicarbonate aqueous solution with the mass concentration of 5%, and then evaporating volatile matters such as toluene under reduced pressure at 50-60 ℃ to obtain about 142 g of chlorinated product.
(2) 22 g of sodium methoxide was added in batches to a mixture of 142 g of the above-mentioned chlorinated product, 100 ml of methanol and 200 ml of toluene at 40℃to 45℃with stirring, and the reaction was continued with stirring at 45℃for 3 hours. And cooling the obtained product system to room temperature, filtering to remove salt, and evaporating volatile matters such as toluene and the like from filtrate under reduced pressure at 50-60 ℃ to obtain about 140 g of epoxy product.
(3) 65 ml of 37% strength by mass hydrochloric acid are added dropwise, at 30℃to 35℃with stirring, to a mixture of 140 g of the abovementioned epoxide product, 100 ml of methanol, 100 ml of water and 200 ml of toluene, and stirring is continued for 3 hours at 35 ℃. Cooling the obtained product system to room temperature, standing and layering for 30 minutes, discarding a water phase, washing an organic phase sequentially by water, washing by sodium bicarbonate water solution with the mass concentration of 5%, washing by water, and evaporating volatile matters such as toluene under reduced pressure at 50-60 ℃ to obtain 130 g of 1- (4-soft detergent alkylphenyl) -2-methyl-2-hydroxy-propan-1-one.
Example 7-example 9
Examples 7-9 were prepared separately by following the same procedure as example 6 except for the starting materials, and the relevant parameters referred to are shown in Table 3:
TABLE 3 Table 3
Example 10
Example 10 prepared an α -aminoketone compound, specifically 1- (4-soft detergent alkylphenyl) -2-methyl-2- (morpholin-1-yl) -propan-1-one, having the chemical structural formula shown below:
the preparation method of the 1- (4-soft detergent alkylphenyl) -2-methyl-2- (morpholin-1-yl) -propan-1-one is shown as follows:
a mixture of 100 g of the epoxy product prepared in step (2) of example 6, 25 g of morpholine and 100 ml of xylene was refluxed with stirring under anhydrous and anaerobic conditions for 18 hours.
The resulting product system was cooled to 70℃to 80℃and volatiles such as xylene were distilled off under reduced pressure at this temperature to give 115 g of 1- (4-soft detergent alkylphenyl) -2-methyl-2- (morpholin-1-yl) -propan-1-one.
Example 11-example 15
Other α -aminoketones were prepared separately by following the same procedure as in example 10, except for the starting materials, examples 11-15, wherein the relevant parameters are referred to in table 4:
TABLE 4 Table 4
Therefore, the aromatic ketone compound prepared by using the catalyst provided by the embodiment of the invention can be used as a chemical intermediate, and various types of alpha-hydroxy ketone compounds and alpha-amino ketone compounds can be effectively prepared.
The foregoing description is only for the convenience of those skilled in the art to understand the technical solution of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the aromatic ketone compound is characterized by comprising the following steps of: under the catalysis of a catalyst, carrying out Friedel-crafts acylation reaction on substituted benzene and acyl chloride to obtain aryl ketone compounds;
wherein the catalyst comprises: a polyarylate three-dimensional network polymer, an active component supported on the polyarylate three-dimensional network polymer;
the active component comprises AlX 3 Ferric trichloride, bismuth trichloride, gallium trichloride, boron trifluoride, titanium tetrachloride, tin tetrachloride, zinc chloride, zinc methanesulfonate, and methylAt least one of aluminum sulfonate, bismuth methanesulfonate, scandium methanesulfonate, zinc trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, scandium trifluoromethanesulfonate and ferric oxide, wherein X comprises chlorine, bromine, iodine, methanesulfonate or trifluoromethanesulfonate.
2. The method for preparing an aromatic ketone compound according to claim 1, wherein the polyaryl three-dimensional network polymer has a chemical structural formula as follows:
wherein Ar comprises at least one of phenyl, tolyl, phenol, chlorophenyl, biphenyl, 1,3, 5-triphenylphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, furyl, thienyl and pyrrolyl.
3. The method for producing an aromatic ketone compound according to claim 1 or 2, wherein the active ingredient is AlX 3 。
4. The method for producing an aromatic ketone compound according to any one of claims 1 to 3, wherein the mass ratio of the substituted benzene to the catalyst is 1000:1 to 50.
5. The preparation method of the alpha-hydroxyketone compound is characterized by comprising the following steps of:
preparing an aryl ketone compound, wherein the aryl ketone compound is prepared by the method of any one of claims 1-4;
carrying out halogenation treatment on the aryl ketone compound to obtain a halogenated product;
dehalogenating the halogenated product to obtain an epoxy product;
and (3) carrying out ring opening treatment on the epoxy product in an acidic environment to obtain the alpha-hydroxy ketone compound.
6. The method for preparing alpha-hydroxy ketones according to claim 5, wherein the acidic environment is provided by hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid or phosphoric acid.
7. The method for preparing an alpha-hydroxy ketone compound according to claim 6, wherein the chemical structural formula of the alpha-hydroxy ketone compound is as follows:
Wherein R is 1 At least one of C10-C14 linear monoalkyl groups;
R 2 、R 3 each independently is methyl or ethyl;
R 4 is cyclopentyl, cyclohexyl or cycloheptyl;
Z 1 is hydroxyl.
8. The preparation method of the alpha-aminoketone compound is characterized by comprising the following steps of:
preparing an aryl ketone compound, wherein the aryl ketone compound is prepared by the method of any one of claims 1-4;
carrying out halogenation treatment on the aryl ketone compound to obtain a halogenated product;
dehalogenating the halogenated product to obtain an epoxy product;
and (3) carrying out ring opening treatment on the epoxy product in an alkaline environment to obtain the alpha-aminoketone compound.
9. The method for preparing an alpha-aminoketone compound according to claim 8, wherein the basic environment is provided by cyclopentylamine, cyclohexylamine, cycloheptylamine, morpholine, piperazine, or N-methylpiperazine.
10. The method for preparing an alpha-aminoketone compound according to claim 9, wherein the chemical structural formula of the alpha-aminoketone compound is as follows:
wherein R is 1 At least one of C10-C14 linear monoalkyl groups;
R 2 、R 3 each independently is methyl or ethyl;
Z 2 is cyclopentylamino, cyclohexylamino, cycloheptylamino, morpholino, piperazino, or N-methylpiperazino.
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