CN115611693A - 一种催化合成异色满-1-酮类或芳香酮类化合物的方法 - Google Patents
一种催化合成异色满-1-酮类或芳香酮类化合物的方法 Download PDFInfo
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- -1 aromatic ketone compounds Chemical class 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- HEBMCVBCEDMUOF-UHFFFAOYSA-N isochromane Chemical compound C1=CC=C2COCCC2=C1 HEBMCVBCEDMUOF-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 150000002596 lactones Chemical class 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000007036 catalytic synthesis reaction Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 93
- XVTAQSGZOGYIEY-UHFFFAOYSA-N 3,4-dihydroisocoumarin Chemical compound C1=CC=C2C(=O)OCCC2=C1 XVTAQSGZOGYIEY-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 150000001728 carbonyl compounds Chemical class 0.000 abstract description 3
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 14
- 238000010494 dissociation reaction Methods 0.000 description 13
- 230000005593 dissociations Effects 0.000 description 13
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- 239000000758 substrate Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- VTSAALCORKKACE-UHFFFAOYSA-N 3-methyl-3,4-dihydroisochromen-1-one Chemical compound C1=CC=C2C(=O)OC(C)CC2=C1 VTSAALCORKKACE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- BVZZDHFATCXUEL-UHFFFAOYSA-N 4-[(4-chlorophenyl)methoxy]pyridine Chemical compound C1=CC(Cl)=CC=C1COC1=CC=NC=C1 BVZZDHFATCXUEL-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- AVCXPCDTLAMANO-UHFFFAOYSA-N 5-methyl-3,4-dihydroisochromen-1-one Chemical compound O=C1OCCC2=C1C=CC=C2C AVCXPCDTLAMANO-UHFFFAOYSA-N 0.000 description 1
- PAMOJTCNFNGBLS-UHFFFAOYSA-N 7-bromo-3,4-dihydroisochromen-1-one Chemical compound C1COC(=O)C2=CC(Br)=CC=C21 PAMOJTCNFNGBLS-UHFFFAOYSA-N 0.000 description 1
- HXVLRASOFGXUDD-UHFFFAOYSA-N 7-fluoro-3,4-dihydroisochromen-1-one Chemical compound C1COC(=O)C2=CC(F)=CC=C21 HXVLRASOFGXUDD-UHFFFAOYSA-N 0.000 description 1
- CSYMRZLCEOMBAX-UHFFFAOYSA-N 7-methyl-3,4-dihydroisochromen-1-one Chemical compound C1COC(=O)C2=CC(C)=CC=C21 CSYMRZLCEOMBAX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- GCSHUYKULREZSJ-UHFFFAOYSA-N phenyl(pyridin-2-yl)methanone Chemical compound C=1C=CC=NC=1C(=O)C1=CC=CC=C1 GCSHUYKULREZSJ-UHFFFAOYSA-N 0.000 description 1
- SKFLCXNDKRUHTA-UHFFFAOYSA-N phenyl(pyridin-4-yl)methanone Chemical compound C=1C=NC=CC=1C(=O)C1=CC=CC=C1 SKFLCXNDKRUHTA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/106—Y-type faujasite
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- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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Abstract
本发明涉及催化合成技术领域,尤其涉及一种催化合成异色满‑1‑酮类或芳香酮类化合物的方法。所述方法将异色满类化合物或芳基烷烃类化合物、有机小分子催化剂兼溶剂在反应器内均匀混合,在常压下通入氧气,反应5~40 h,分离纯化产物后得到异色满‑1‑酮类化合物或芳香酮类化合物;有机小分子催化剂兼溶剂为C4~C6的内酯;该方法以绿色经济的分子氧为氧化剂,以C4~C6的内酯为催化剂兼溶剂,将芳基烷烃侧链C‑H键高效氧化得到相应的羰基化合物,以多相材料为助催化剂,将异色满及其衍生物选择性氧化得到异色满‑1‑酮类化合物。采用本发明的方法合成异色满‑1‑酮类和芳香酮类化合物,选择性好、收率高,助催化剂可重复使用,工艺流程简单易操作,具有很好的应用前景。
Description
技术领域
本发明涉及催化合成技术领域,具体涉及一种利用有机小分子催化合成异色满-1-酮类或芳香酮类化合物的方法。
背景技术
氧化是生物世界中普遍存在的一个过程,是许多生物学和化学的基础。而在现代有机合成化学中,芳烃侧链α-C(sp3)-H键的氧化是重点研究之一,可以从容易获得的前体中直接获得高价值的产物和重要的中间体,芳香酮和异色满-1-酮及其衍生物是组成具有生物活性的天然产物和药物分子的重要结构单元。鉴于这些化合物具有广泛的应用和重要意义,化学家们进行了大量的研究,但是早期的研究常用的反应条件需要使用贵金属、高价金属盐和强氧化剂等,这带来了成本高、安全性差和原子经济性低等问题。因此,近年来的相关研究使用的氧化剂是最丰富、廉价和绿色环保的分子氧,但是同时还需要添加过氧化物、NHPI等添加剂和高温高压的反应条件。还存在催化剂不能回收重复利用,活性低和选择性差等问题。
公开于该背景技术部分的信息仅仅旨在加深对本发明总体背景技术的理解,而不应当被视为承认或以任何形式暗示该信息构成本领域技术人员所公知的现有技术。
发明内容
本发明的目的在于开发一种高效的催化氧化合成异色满-1-酮类或芳香酮类化合物的方法,解决了现有体系中的需要加添加剂、催化剂不能回收和产率低等问题。
本发明为解决上述技术问题的不足,所采用的技术方案是:
一种催化合成异色满-1-酮类或芳香酮类化合物的方法,所述方法为将式I所示的异色满类化合物或式III所示的芳基烷烃类化合物、有机小分子催化剂兼溶剂在反应器内均匀混合,在常压下通入氧气,反应5~40h,分离纯化产物后得到式II所示的异色满-1-酮类化合物或式IV所示的芳香酮类化合物;
所述有机小分子催化剂兼溶剂为C4~C6的内酯;本发明中内酯既作为催化剂,又作为溶剂,解决了现有技术中催化剂不能回收的问题。
式I或式II中R1代表:H、F、Cl、Br、甲基、甲氧基、三氟甲基、硝基、乙酰基、叔丁基;R2代表:H、F、Cl、Br、甲基、甲氧基、三氟甲基、硝基、乙酰基、叔丁基;
式III或式IV中R3代表:苯基、4-氟苯基、4-氯苯基、4-甲基苯基、4-甲氧基苯基、4-三氟甲基苯基、4-联苯基、3-溴苯基、4-硝基苯基、2-溴苯基;R4代表:甲基、乙基、苯基、4-氟苯基、2-溴苯基、2-乙酰基苯基、4-吡啶基、2-吡啶基。
作为优选的,式I或式II中R1代表:H、F、Cl、Br、甲基;R2代表:H、甲基;由于强吸电子基团不利于反应的进行,为了提高目标产物的收率,因此本发明中的R1和R2优选为以上反应基团。
作为优选的,式III或式IV中R3代表:苯基、4-氟苯基、4-氯苯基、2-溴苯基;R4代表:苯基、4-氟苯基、2-溴苯基、2-乙酰基苯基、4-吡啶基、2-吡啶基。由于强吸电子基团不利于反应的进行,而反应位阻不影响,为了提高目标产物的收率,因此本发明中的R3和R4优选为以上反应基团。
本发明合成的反应机理如下所示(以γ-戊内酯/Ni2Al-LDH催化体系为例):
首先γ-戊内酯(I)在氧气条件下被氧化成自由基(II)和过氧自由基(III),在助催化剂Ni2Al-LDH条件下,Ni2Al-LDH提高了异色满1位和4位的C-H键的离解能,但是对4位的C-H键离解能提升程度要高于1位,因此底物异色满被II夺走一个氢原子主要生成自由基IV,在氧气条件下被氧化成过氧化自由基VI,再夺走底物的氢原子生成中间体VI′,分解生成目标产物异色满-1-酮。在无Ni2Al-LDH条件下,异色满1位和4位的C-H键的离解能差异不大,底物异色满被II夺走一个氢原子时,无选择性地生成自由基IV(60%)和V(40%),自由基IV同上反应路径,自由基V在氧气条件下被氧化成过氧化自由基VII,再夺走底物的氢原子生成中间体VII′,最后分解生成副产物异色满-4-酮。助催化剂的作用是改变异色满1位和4位的C-H键的离解能,从而使异色满选择性地生成异色满-1-酮。
进一步地,所述有机小分子催化剂兼溶剂为γ-戊内酯、1,4-丁内酯、ε-己内酯中的任意一种,即如下式(a)~(c)中的任意一种;下式中的小分子内酯可以引发自由基的生成,从而催化合成异色满-1-酮类或芳香酮类化合物。
进一步地,所述异色满类化合物或所述芳基烷烃类化合物在所述有机小分子催化剂兼溶剂里的浓度为0.2~3mol/L。当反应物浓度过高时,所述有机小分子催化剂兼溶剂氧化生成的自由基和过氧自由基含量减少,使得所述异色满类化合物或所述芳基烷烃类化合物失去氢原子生成自由基的反应不能充分实现,催化反应的效率明显降低;反应物浓度过低会降低反应体系的经济性。
进一步地,反应温度为80~140℃。作为优选的,所述异色满类化合物的反应温度为110℃;所述芳基烷烃类化合物的反应温度为140℃。由于助催化剂的加入会提高异色满类化合物两个α-位C-H键的离解能,反应温度高时,反应体系活性太高,导致异色满-1-酮选择性降低;反应温度低时,反应体系中的活性不足,不仅导致异色满-1-酮选择性低,而且降低了异色满的转化率。
进一步地,所述异色满类化合物的反应时间为5~40h;所述芳基烷烃类化合物的反应时间为24h。反应时间短,体系中的反应不能充分进行,导致目标产物的产率降低;反应时间过长,虽然对目标产物的产率影响不明显,但会降低反应体系的经济性。
进一步地,所述氧气通过氧气钢瓶连续输入,所述氧气与所述异色满类化合物或所述芳基烷烃类化合物摩尔比为10~100:1。氧气浓度过低,使得所述有机小分子催化剂兼溶剂不能氧化分解为足够的自由基和过氧自由基,使得异色满的转化率降低,影响反应效率;氧气浓度过高时,使得反应体系的催化活性过高,会降低异色满-1-酮的选择性。
进一步地,催化合成所述异色满-1-酮类化合物时,还包括助催化剂,所述助催化剂为类水滑石、分子筛、离子交换树脂中的任意一种。所述助催化剂的加入,表面的酸性位会与异色满结构中的氧原子作用,从而影响了异色满两个α-位C-H键的离解能,由于影响的程度是不同的,所以提高异色满-1-酮的选择性。
进一步地,所述类水滑石为Ni2Al-LDH、CuMgAl-LDH、Co2Al-LDH、Mg2Fe-LDH中的任意一种。类水滑石材料表面具有酸碱双功能性,是一种层状结构的材料,表面的酸性位与异色满结构中的氧原子作用而影响α-位C-H键的离解能,因此提高异色满-1-酮的选择性。
进一步地,所述分子筛为ZSM-5、NaY、13X、中的任意一种。分子筛是一种水合硅铝酸盐或天然沸石,有许多孔径均匀的孔道和孔穴,具有酸性、吸附性、离子交换性和催化性能。其表面酸性位和异色满结构中的氧原子作用,对不同反应位点的α-位C-H键的离解能影响小,所以提高异色满-1-酮的选择性略小于类水滑石。
进一步地,所述离子交换树脂为大孔弱酸性交换树脂、强碱性阴离子交换树脂、大孔强酸交换树脂、弱酸性苯乙烯交换树脂中的任意一种。离子交换树脂是一种带有官能团、具有网状结构、不溶性的高分子化合物。由于其所带官能团的不同分为酸性、碱性和离子型。其表面的酸性位和异色满结构中的氧原子作用而影响不同反应位点的α-位C-H键的离解能,提高异色满-1-酮的选择性。
进一步地,所述助催化剂与所述异色满类化合物或所述芳基烷烃类化合物的质量比50~200:100~670;助催化剂的用量少,对异色满两个α-位C-H键的离解能的影响程度小,生成异色满-4-酮的概率增大,导致异色满-1-酮的选择性降低;催化剂用量过多,由于其会过度提升两个α-位C-H键的离解能,所以导致异色满的转化率大幅度下降。
与现有技术比较,本发明的有益效果主要在于:
a)本发明以绿色经济的分子氧为氧化剂,以C4~C6的内酯为有机小分子催化剂兼溶剂,将芳基烷烃侧链C-H键高效氧化得到相应的羰基化合物;通过将C4~C6的内酯氧化活化生成活性的内酯自由基和过氧自由基,利用内酯自由基夺走异色满类化合物或芳基烷烃类化合物的氢原子,使得底物异色满类化合物或芳基烷烃类化合物经氢原子转移、过氧化、分解一系列反应,最终生成目标产物,本发明操作简单,反应条件温和,大大降低了经济和环境成本。
b)本发明以可循环利用的多相材料作为助催化剂,助催化剂表面的酸性位会与异色满结构中的氧原子作用,提升了异色满1位和4位的C-H键的离解能,尤其是针对异色满4位的C-H键的离解能,使得反应物有选择性地生成异色满-1-酮类化合物,提高了目标产物的收率和选择性,同时助催化剂可以重复使用,解决了现有体系中的需要加添加剂、催化剂不能回收和产率低等问题。与现有技术相比,本发明工艺流程简单易操作,合成方法绿色环保,具有很好的应用前景。
具体实施方式
下面通过具体实施方式对本发明作进一步说明,但本发明的保护范围并不限于此。
在本发明具体实施例中,各市售材料来源如下:
一、异色满氧化反应
实施例1
利用有机小分子催化异色满氧化的反应步骤如下:异色满1mmol,有机小分子催化剂兼溶剂γ-戊内酯2mL,助催化剂Ni2Al-LDH 100mg,加入反应器中,氧气:异色满摩尔比为50:1,在110℃条件下反应5h。采用气相色谱峰内标法分析反应液中原料异色满、产物异色满-1-酮的质量,联苯为内标物,经过计算得出,反应的转化率为98.8%,选择性为94%。
实施例2
利用有机小分子催化异色满氧化的反应步骤如下:异色满1mmol,有机小分子催化剂兼溶剂ε-己内酯2mL,助催化剂Ni2Al-LDH 100mg,加入反应器中,氧气:异色满摩尔比为50:1,在110℃条件下反应5h。采用气相色谱峰内标法分析反应液中原料异色满、产物异色满-1-酮的质量,联苯为内标物,经过计算得出,反应的转化率为85.0%,选择性为86.3%。
实施例3
利用有机小分子催化异色满氧化的反应步骤如下:异色满1mmol,有机小分子催化剂兼溶剂γ-戊内酯2mL,助催化剂NaY 100mg,加入反应器中,氧气:异色满摩尔比为50:1,在110℃条件下反应5h。采用气相色谱峰内标法分析反应液中原料异色满、产物异色满-1-酮的质量,联苯为内标物,经过计算得出,反应的转化率>99%,选择性为73.6%。
实施例4
利用有机小分子催化异色满氧化的反应步骤如下:异色满1mmol,有机小分子催化剂兼溶剂γ-戊内酯2mL,助催化剂大孔弱酸性交换树脂100mg,加入反应器中,氧气:异色满摩尔比为50:1,在110℃条件下反应5h。采用气相色谱峰内标法分析反应液中原料异色满、产物异色满-1-酮的质量,联苯为内标物,经过计算得出,反应的转化率为98.1%,选择性为75.7%。
二、底物拓展实验
以下列反应条件为基础,进一步拓展各种类型的反应底物,考察该方法对不同类型的反应底物的适应性,由于反应底物不同,其最适宜反应条件也会存在差异,因此本发明以下反应产率仅针对实施例5~实施例6的反应条件,并不代表本发明各反应底物的最佳效果。反应结果如下所示:
实施例5
在反应管中,加入1mmol的异色满及其衍生物(式(1-1)~(1-8))、100mg的Ni2Al-LDH和2mL的γ-戊内酯,用反应管帽密闭反应管,用空气泵检测反应管气密性和抽取管内空气,将反应管放入平行反应器上接通氧气并加热至110℃,反应5~40h。乙酸乙酯洗涤过滤,滤液减压蒸馏除去乙酸乙酯,然后用水和石油醚进行萃取除去γ-戊内酯,萃取液减压蒸馏除去石油醚,再进行柱层析分离,以乙酸乙酯/石油醚体积比1:20的混合液为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂即得异色满-1-酮类化合物(式(2-1)~(2-8))。
实施例6
在反应管中,加入1mmol的芳基烷烃类化合物(式(1-9)~(1-17))和2mL的γ-戊内酯,用反应管帽密闭反应管,用空气泵检测反应管气密性和抽取管内空气,将反应管放入平行反应器上接通氧气并加热至140℃,反应24h。乙酸乙酯洗涤过滤,滤液减压蒸馏除去乙酸乙酯,再进行柱层析分离,以乙酸乙酯/石油醚体积比1:10~100的混合液为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂即得芳香酮化合物(式(2-9)~(2-17))。
反应结果如表3所示:
表3不同底物的反应结果
产物表征如下:
异色满-1-酮(式(2-1)),分离收率为91%(134.7mg)。黄色油状物;1H NMR(500MHz,CDCl3)δ8.07(d,J=7.8Hz,1H),7.53(t,J=7.3Hz,1H),7.38(t,J=7.6Hz,1H),7.26(d,J=7.6Hz,1H),4.52(t,J=6.0Hz,2H),3.05(t,J=6.0Hz,2H).13C NMR(126MHz,CDCl3)δ165.2,139.6,133.7,130.3,127.7,127.3,125.3,67.4,27.8.
7-甲基异色满-1-酮(式(2-2)),分离收率为80.5%(130.5mg)。黄色油状物;1HNMR(500MHz,CDCl3)δ7.55(d,J=2.7Hz,1H),7.16(d,J=8.4Hz,1H),7.08(dd,J=8.4,2.7Hz,1H),4.49(t,J=6.0Hz,2H),3.82(s,3H),2.97(t,J=6.0Hz,2H).13C NMR(126MHz,CDCl3)δ165.2,159.0,131.9,128.5,126.0,121.5,113.0,67.7,55.6,27.0.
5-甲基异色满-1-酮(式(2-3)),分离收率为90.5%(146.8mg)。橘黄色油状物;1HNMR(500MHz,CDCl3)δ7.96(d,J=7.8Hz,1H),7.40(d,J=7.5Hz,1H),7.28(t,J=7.7Hz,1H),4.52(t,J=6.1Hz,2H),2.97(t,J=6.0Hz,2H),2.33(s,3H).13C NMR(126MHz,CDCl3)δ165.6,138.3,135.1,128.2,127.1,125.3,66.7,24.9,18.9.
3-甲基异色满-1-酮(式(2-4)),分离收率为82.5%(133.8mg)。黄色油状物;1HNMR(500MHz,CDCl3)δ8.03(d,J=7.8Hz,1H),7.49(t,J=7.5Hz,1H),7.33(t,J=7.6Hz,1H),7.20(d,J=7.6Hz,1H),4.65-4.60(m,1H),2.91-2.88(m,2H),1.47(d,J=6.3Hz,3H).13C NMR(126MHz,CDCl3)δ165.6,139.2,133.7,130.1,127.6,127.4,124.9,75.1,34.8,20.9.
7-氟异色满-1-酮(式(2-5)),分离收率为90.2%(149.9mg)。黄色油状物;1H NMR(500MHz,CDCl3)δ7.75(d,J=8.6Hz,1H),7.26(dt,J=8.0,4.8Hz,2H),4.54(t,J=6.0Hz,2H),3.04(t,J=6.0Hz,2H).13C NMR(126MHz,CDCl3)δ177.3,160.8,135.4,129.2,126.9,121.0,116.6,67.5,27.1.
7-氯异色满-1-酮(式(2-6)),分离收率为92.5%(168.9mg)。黄色固体;1H NMR(500MHz,CDCl3)δ7.97(s,1H),7.45(d,J=8.1Hz,1H),7.22(d,J=8.1Hz,1H),4.50(t,J=6.0Hz,2H),3.02(t,J=6.0Hz,2H).13C NMR(126MHz,CDCl3)δ163.9,137.9,133.7,133.5,129.9,128.9,126.7,67.3,27.2.
7-溴异色满-1-酮(式(2-7)),分离收率为90.9%(206.4mg)。黄色固体;1H NMR(500MHz,CDCl3)δ8.21(d,J=2.1Hz,1H),7.66(dd,J=8.1,2.1Hz,1H),7.18(d,J=8.1Hz,1H),4.54(t,J=6.0Hz,2H),3.03(t,J=6.0Hz,2H).13C NMR(126MHz,CDCl3)δ163.8,138.3,136.6,133.1,129.1,127.0,121.3,67.26(s),27.3.
4,5-二氢噻吩并[2,3-O]吡喃-7-酮(式(2-8)),分离收率为80.3%(123.8mg)。黄色油状物;1H NMR(500MHz,CDCl3)δ7.66(d,J=5.0Hz,1H),7.01(d,J=4.9Hz,1H),4.58(t,J=6.2Hz,2H),3.02(t,J=6.2Hz,2H).13C NMR(126MHz,CDCl3)δ161.3,147.6,134.5,126.6,122.5,68.4,21.1.
4,4′-二氟二苯甲酮(式(2-9)),分离收率为93.6%(204.2mg)。白色固体;1H NMR(500MHz,CDCl3)δ7.85-7.78(m,4H),7.20-7.13(m,4H).13C NMR(126MHz,CDCl3)δ193.7,166.4,164.4,133.7,132.5,115.6,115.5.
4-氯二苯甲酮(式(2-10)),分离收率为95.6%(207.1mg)。白色固体;1H NMR(500MHz,CDCl3)δ7.81-7.74(m,4H),7.63-7.58(m,1H),7.52-7.44(m,4H).13C NMR(126MHz,CDCl3)δ195.5,138.9,137.2,135.9,132.7,131.5,129.9,128.7,128.4.
2-苯甲酰吡啶(式(2-11)),分离收率为90.7%(166.2mg)。白色固体;1H NMR(500MHz,CDCl3)δ8.68-8.70(m,1H),7.93-8.05(m,3H),7.84(m,1H),7.48-7.56(m,4H).13CNMR(126MHz,CDCl3)δ194.3,149.9,145.1,133.8,132.6,129.7,128.8,123.4.
4-苯甲酰吡啶(式(2-12)),分离收率为96.2%(176.2mg)。白色固体;1H NMR(500MHz,CDCl3)δ8.83(d,J=5.8Hz,2H),7.89-7.80(m,2H),7.69-7.64(m,1H),7.60(dd,J=4.4,1.6Hz,2H),7.53(t,J=7.8Hz,2H).13C NMR(126MHz,CDCl3)δ195.2,150.3,144.5,135.9,133.6,130.2,128.7,122.9.
4-(4-氯苄氧基)吡啶(式(2-13)),分离收率为96.7%(210.5mg)。白色固体;1HNMR(500MHz,CDCl3)δ8.77(dd,J=4.3,1.6Hz,2H),7.75-7.69(m,2H),7.51(dd,J=4.3,1.6Hz,2H),7.46-7.41(m,2H).13C NMR(126MHz,CDCl3)δ193.8,150.4,143.9,140.1,134.1,131.5,129.0,122.7.
芴酮(式(2-14)),分离收率为97.6%(175.9mg)。黄色固体;1H NMR(500MHz,CDCl3)δ7.66(d,J=7.4Hz,2H),7.52-7.46(m,4H),7.32-7.27(m,2H).13C NMR(126MHz,CDCl3)δ193.9,144.4,134.7,134.1,129.1,124.3,120.3.
2-溴芴酮(式(2-15)),分离收率为90.6%(234.7mg)。黄色固体;1H NMR(500MHz,CDCl3)δ7.67(d,J=1.8Hz,1H),7.59(d,J=7.3Hz,1H),7.53(dd,J=7.9,1.9Hz,1H),7.45(ddd,J=16.6,11.5,4.1Hz,2H),7.29(ddd,J=8.6,5.2,1.5Hz,2H).13C NMR(126MHz,CDCl3)δ192.3,143.6,142.9,137.0,135.7,135.0,133.6,129.4,127.4,124.5,122.9,121.7,120.4.
2,2′-二溴芴酮(式(2-16)),分离收率为95%(321.1mg)。黄色固体;1H NMR(300MHz,CDCl3)δ7.76(d,J=1.6Hz,2H),7.64(d,J=1.9Hz,1H),7.61(d,J=1.9Hz,1H),7.40-7.36(m,2H).13C NMR(75MHz,CDCl3)δ191.0,142.3,137.5,135.3,127.9,123.3,121.9.
2-乙酰芴酮(式(2-17)),分离收率为97.8%(217.4mg)。黄色固体;1H NMR(500MHz,CDCl3)δ8.15-8.07(m,2H),7.66(d,J=7.3Hz,1H),7.58-7.49(m,3H),7.35(td,J=7.3,0.9Hz,1H),2.61(s,3H).13C NMR(126MHz,CDCl3)δ196.5,192.6,148.4,143.2,137.7,135.0,134.9,134.8,134.2,130.2,124.6,124.0,121.3,120.4,26.7.
三、对比实施例
对比例1
利用有机小分子催化异色满氧化的反应步骤如下:异色满1mmol,有机小分子催化剂兼溶剂γ-戊内酯2mL,加入反应器中,氧气:异色满摩尔比为50:1,在110℃条件下反应5h。采用气相色谱峰内标法分析反应液中原料异色满、产物异色满-1-酮的质量,联苯为内标物,经过计算得出,反应的转化率>99%,选择性为60.7%。
对比例2
利用有机小分子催化异色满氧化的反应步骤如下:异色满1mmol,有机小分子催化剂兼溶剂γ-戊内酯2mL,助催化剂Ni2Al-LDH 100mg,加入反应器中,通过空气泵连续输入空气,在110℃条件下反应5h。采用气相色谱峰内标法分析反应液中原料异色满、产物异色满-1-酮的质量,联苯为内标物,经过计算得出,反应的转化率为33.2%,选择性为91.9%。
对比例3
利用有机小分子催化异色满氧化的反应步骤如下:异色满1mmol,溶剂十二烷2mL,助催化剂Ni2Al-LDH100mg,加入反应器中,氧气:异色满摩尔比为50:1,在110℃条件下反应5h。采用气相色谱峰内标法分析反应液中原料异色满、产物异色满-1-酮的质量,联苯为内标物,经过计算得出,反应的转化率为1.6%,选择性为87%。
对比例4
利用有机小分子催化异色满氧化的反应步骤如下:异色满1mmol,溶剂二甲基亚砜2mL,助催化剂Ni2Al-LDH 100mg,加入反应器中,氧气:异色满摩尔比为50:1,在110℃条件下反应5h。采用气相色谱峰内标法分析反应液中原料异色满、产物异色满-1-酮的质量,联苯为内标物,经过计算得出,反应的转化率为2.3%,选择性为86.9%。
四、性能结果说明
由以上实施例1~6可以看出,本发明以绿色经济的分子氧为氧化剂,以C4~C6的内酯为有机小分子催化剂兼溶剂,催化合成异色满-1-酮类或芳香酮类化合物的方法,均具有较高的转化率、选择性和收率。通过底物拓展实验结果(表3)可以看出,本发明的催化方法,底物拓展性较好,适用范围广泛,助催化剂加入能提高异色满类化合物的选择性。
对比例1相对于实施例1,没有加入助催化剂,结果显示目标产物异色满-1-酮的选择性降低了33.3%,说明助催化剂尤其是Ni2Al-LDH的加入对异色满-1-酮的选择性有明显的优势,本发明中助催化剂表面的酸性位与异色满结构中的氧原子作用,降低了异色满1位和4位的C-H键的反应活性,尤其是异色满4位的C-H键的反应活性,使得反应物有选择性地生成异色满-1-酮类化合物,提高了目标产物的收率和选择性。
对比例2相对于实施例1,使用空气作为氧化剂,可知反应物的转化率降低了65.6%,说明分子氧作为氧化剂在氧化过程中起到了关键性作用,空气中氧气浓度变少,使得反应体系中有机小分子催化剂兼溶剂不能氧化分解为足够的自由基和过氧自由基,使得异色满的转化率降低,影响反应物的转化率。
对比例3相对于实施例1,没有加入催化剂,以十二烷作为溶剂,可知,异色满的转化率降至1.6%,说明本发明使用有机小分子内酯尤其是γ-戊内酯对异色满的转化率有明显的优势。本发明通过将C4~C6的内酯氧化分解,利用内酯自由基夺走异色满类化合物或芳基烷烃类化合物的质子氢,提高了反应物的转化率。
对比例4相对于实施例1,没有加入催化剂,以二甲基亚砜作为溶剂,可知,异色满的转化率降至2.3%,结合对比例3说明本发明使用有机小分子内酯作为催化剂兼溶剂效果显著,本发明以C4~C6的内酯为有机小分子催化剂兼溶剂,将芳基烷烃侧链C-H键高效氧化得到相应的羰基化合物,在反应体系中不可或缺。
申请人声明,以上所述仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,所属技术领域的技术人员应该明了,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种催化合成异色满-1-酮类或芳香酮类化合物的方法,其特征在于:将式I所示的异色满类化合物或式III所示的芳基烷烃类化合物、有机小分子催化剂兼溶剂在反应器内均匀混合,在常压下通入氧气,反应5~40h,分离纯化产物后得到式II所示的异色满-1-酮类化合物或式IV所示的芳香酮类化合物;所述有机小分子催化剂兼溶剂为C4~C6的内酯;
式I或式II中R1代表:H、F、Cl、Br、甲基、甲氧基、三氟甲基、硝基、乙酰基、叔丁基;R2代表:H、F、Cl、Br、甲基、甲氧基、三氟甲基、硝基、乙酰基、叔丁基;
式III或式IV中R3代表:苯基、4-氟苯基、4-氯苯基、4-甲基苯基、4-甲氧基苯基、4-三氟甲基苯基、4-联苯基、2-溴苯基、4-硝基苯基;R4代表:甲基、乙基、苯基、4-氟苯基、2-溴苯基、3-乙酰基苯基、4-吡啶基、2-吡啶基。
3.根据权利要求1或2所述的催化合成异色满-1-酮类或芳香酮类化合物的方法,其特征在于:所述异色满类化合物或所述芳基烷烃类化合物在所述有机小分子催化剂兼溶剂里的浓度为0.2~3mol/L。
4.根据权利要求1所述的催化合成异色满-1-酮类或芳香酮类化合物的方法,其特征在于:反应温度为80~140℃。
5.根据权利要求1所述的催化合成异色满-1-酮类或芳香酮类化合物的方法,其特征在于:所述氧气与所述异色满类化合物或所述芳基烷烃类化合物摩尔比为10~100:1。
6.根据权利要求1所述的催化合成异色满-1-酮类或芳香酮类化合物的方法,其特征在于:催化合成所述异色满-1-酮类化合物时,还包括助催化剂,所述助催化剂为类水滑石、分子筛、离子交换树脂中的任意一种。
7.根据权利要求6所述的催化合成异色满-1-酮类或芳香酮类化合物的方法,其特征在于:所述类水滑石为Ni2Al-LDH、CuMgAl-LDH、Co2Al-LDH、Mg2Fe-LDH中的任意一种。
9.根据权利要求6所述的催化合成异色满-1-酮类或芳香酮类化合物的方法,其特征在于:所述离子交换树脂为大孔弱酸性交换树脂、强碱性阴离子交换树脂、大孔强酸交换树脂、弱酸性苯乙烯交换树脂中的任意一种。
10.根据权利要求6~9任一项所述的催化合成异色满-1-酮类或芳香酮类化合物的方法,其特征在于:所述助催化剂与所述异色满类化合物或所述芳基烷烃类化合物的质量比50~200:100~670。
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