CN112961019B - 一种合成芳香族烯烃衍生物的方法 - Google Patents
一种合成芳香族烯烃衍生物的方法 Download PDFInfo
- Publication number
- CN112961019B CN112961019B CN202110190896.4A CN202110190896A CN112961019B CN 112961019 B CN112961019 B CN 112961019B CN 202110190896 A CN202110190896 A CN 202110190896A CN 112961019 B CN112961019 B CN 112961019B
- Authority
- CN
- China
- Prior art keywords
- compound
- silane
- reaction
- solvent
- trifluoromethanesulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 aromatic olefin Chemical class 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 150000008365 aromatic ketones Chemical class 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000001893 nitrooxy group Chemical group [O-][N+](=O)O* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KEIFWROAQVVDBN-UHFFFAOYSA-N 1,2-dihydronaphthalene Chemical compound C1=CC=C2C=CCCC2=C1 KEIFWROAQVVDBN-UHFFFAOYSA-N 0.000 description 1
- LIGHOIDTGDLAKK-UHFFFAOYSA-N 1-bromo-4-prop-2-enylbenzene Chemical compound BrC1=CC=C(CC=C)C=C1 LIGHOIDTGDLAKK-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- ZJSKEGAHBAHFON-UHFFFAOYSA-N 1-ethenyl-3-fluorobenzene Chemical compound FC1=CC=CC(C=C)=C1 ZJSKEGAHBAHFON-UHFFFAOYSA-N 0.000 description 1
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical compound COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-UHFFFAOYSA-N 0.000 description 1
- CEWDRCQPGANDRS-UHFFFAOYSA-N 1-ethenyl-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C=C)C=C1 CEWDRCQPGANDRS-UHFFFAOYSA-N 0.000 description 1
- KWHSBYQFELZKKS-UHFFFAOYSA-N 1-ethenyl-4-iodobenzene Chemical compound IC1=CC=C(C=C)C=C1 KWHSBYQFELZKKS-UHFFFAOYSA-N 0.000 description 1
- BFMBTATYOXZSJD-UHFFFAOYSA-N 1-ethenyl-4-methylsulfonylbenzene Chemical compound CS(=O)(=O)C1=CC=C(C=C)C=C1 BFMBTATYOXZSJD-UHFFFAOYSA-N 0.000 description 1
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SFHOANYKPCNYMB-UHFFFAOYSA-N 2-ethenyl-1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1C=C SFHOANYKPCNYMB-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- SNTUCKQYWGHZPK-UHFFFAOYSA-N 4-ethenylbenzonitrile Chemical compound C=CC1=CC=C(C#N)C=C1 SNTUCKQYWGHZPK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UVDOIWXDCYNLJD-UHFFFAOYSA-N cyclopentylidenemethylbenzene Chemical compound C1CCCC1=CC1=CC=CC=C1 UVDOIWXDCYNLJD-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000008204 material by function Substances 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003281 rhenium Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种合成芳香族烯烃衍生物的方法,以含α氢芳香族酮类为原料,将酮羰基在三氟甲磺酸和硅氢烷的共同作用下经还原脱氧生成相应烯烃。本发明的方法具有出色的选择性和简易的操作流程,使用廉价的催化反应体系,收率良好,具有巨大应用潜力。
Description
技术领域
本发明属于烯烃制备技术领域,涉及一种合成芳香族烯烃衍生物的方法。
背景技术
芳香族烯烃类衍生物在有机精细化工领域,诸如药物合成、香精香料及有机功能材料开发方面上都有着巨大的应用价值。从廉价易得的芳香酮类化合物到芳香族烯烃的直接催化转化有着实际应用价值。当前,现有合成技术报道存在诸多问题,反应条件苛刻危险(需要高温高压条件),且大多数催化体系使用昂贵的金属配合物做催化剂。例如,2016年Ana C.Fernandes等利用铼配合物在170℃下催化异丙醇氢转移反应还原芳香酮化合物成相应烯烃化合物。2015年,Stephan课题组报道了缺电子的B(C6F5)3作为催化剂在H2(60atm)惰性气体氛围及无水条件下,甲苯溶液中加氢催化还原芳香酮类化合物生成相应烯烃化合物。综上,尽管当前有廉价芳香酮向芳香族烯烃合成转化领域取得了一些进步,但是目前的合成手段依然存在的操作条件苛刻,催化反应体系成本过高等问题,其适用的芳香酮类小分子也存在很大局限性。因此,进一步发展简易高效的方法进行芳香酮化合物转化合成芳香族烯烃仍需进一步发展探索。此外,一些重要芳香族烯烃化合物有着实际需求而缺乏有效的市面供应渠道,这也使得开发该类合成转化方法愈发重要。
发明内容
本发明的目的解决现有技术存在的催化体系成本高,反应条件苛刻,底物适用范围窄的问题,发明了一种的芳香族烯烃化合物合成方法。采用三氟甲磺酸/硅氢烷共催化转化芳香族酮类化合物,简便高效选择性地合成芳香族烯烃化合物。
本发明的技术方案为:
以含α氢芳香族酮类为原料,将酮羰基在三氟甲磺酸和硅氢烷的共同作用下经还原脱氧生成相应烯烃。
其中代表性的一种示例性反应式如:
反应式I:三氟甲磺酸/硅氢烷共催化芳香酮向芳香烯烃的转化
其中,所述含α氢芳香族酮类为芳香酮、含杂原子硫、氧、氮的杂环芳香族酮类化合物中的一种;所述α氢芳香族酮类的酮基的一侧具有取代或未被取代的吸电子基苯环;
优选的,所述含α氢芳香族酮类为上述化合物I;
其中,
n为1-5的整数,优选为1、2或3;
R1各自独立地为(即苯环或芳香杂环上连接的n个R1可以互不相同)H、卤素、醚基、烷基、卤代烷基、硝基、取代硝基、硝基氧基、取代的硝基氧基、磺酰基、取代磺酰基、氰基;优选为H、卤素C1-4的醚基、C1-4取代的烷基、C1-4取代的卤代烷基、硝基、C1-4取代的硝基烷基、C1-4取代的硝基氧基、磺酰基、C1-4取代的磺酰基、氰基;
R2为烷基、环烷基、取代烷基、取代环烷基、烷基苯基、取代烷基苯基;优选为C1-7的烷基、C1-7的环烷基、C1-7的取代烷基、C1-7的取代环烷基、C1-7的烷基苯基、C1-7的取代烷基苯基;
最优选的化合物I具有以下结构:
其中,所述硅氢烷为含有Si-H键且Si上具有至少一个C1-6取代基取代的化合物;优选为1,1,3,3-四甲基二硅氧烷、二苯基硅烷、苯基硅烷、三异丙基硅基硅烷;最优选为1,1,3,3-四甲基二硅氧烷;
其中,所述溶剂为有机溶剂,优选为四氢呋喃、1,4-二噁烷、乙醚中的一种,最优选为四氢呋喃。
其中,所述方法中,反应过程需要在惰性气体保护下,搅拌并加热20-70℃温度下进行,优选为35-70℃。
优选的,所述溶剂的浓度为0.2-0.5M,最优选为0.33-0.5M;反应时间为1-24h。
优选的,所述含α氢芳香族酮类化合物、三氟甲磺酸、硅氢烷的投料当量比为1:1.3:3。
其中,所述方法还包括后处理步骤,包括:用饱和碳酸氢钠溶液中和反应液,再用乙酸乙酯稀释并萃取,合并有机相,有无水硫酸钠干燥,减压浓缩去除溶剂得到残余物,再将残余物经硅胶柱层析分离,得到化合物II的目标烯烃产物。
相对于现有技术,本发明的有益效果如下:
本发明的方法具有出色的选择性和简易的操作流程,并且通过廉价的稳定含α氢芳香酮类化合物,可大量合成市面上昂贵的烯烃产物,使用廉价的催化反应体系,原料来源广泛、反应条件温和、操作简便、产物选择性高,收率良好,具有巨大应用潜力。
以其中一种反应示例为例,本发明的反应机理如下:
本发明中,选取的含α氢芳香族酮类化合物具有吸电子基团,在还原过程中更容易受到超强酸和小位阻硅氢烷的共同催化作用,同时一步脱水,使反应更加偏向烯烃选择性,目标反应物产率高。
具体实施方式
以下结合具体实施例,对本发明做进一步详述。在下文中,如无特殊说明,所述方法均为本领域常规方法,所使用得试剂均可通过商业途径购买获得。
实施例1-8反应条件典型实验
以下式1所示酮类化合物,探讨了不同反应条件下,对溴苯乙酮1a转化为相应对溴苯乙烯目标产物式2a的产率变化。见以下代表性的实施例1-8
反应式1如下:
实施例1
由表1所示选用不同的溶剂在30℃下,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol)和三氟甲磺酸(1.2equiv.,0.6mmol),该混合物在0.5M有机溶液中于氮气保护下反应5h。具体反应结果如表1:
表1
实施例2
由表2所示,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol)和三氟甲磺酸(1.2equiv.,0.6mmol)。在30℃条件下下,该混合物在不同浓度的四氢呋喃溶液(基于1a)中于氮气保护下反应5h。具体反应结果如表2:
表2
实施例3
在30℃下,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol)和酸(1.3equiv.,0.6mmol),该混合物在四氢呋喃(1.5mL)溶液中于氮气保护下反应5h。具体反应结果如表3:
表3
实施例4
选用不同剂量的三氟甲磺酸来测试反应效果,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol)和三氟甲磺酸,该混合物在0.33M四氢呋喃溶液中于30℃氮气保护下反应5h。反应结果如表4所示:
表4
实施例5
选用不同的硅氢烷与三氟甲磺酸催化转化1a成烯烃2a。25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),硅氢烷(3.0equiv.,1.5mmol)和三氟甲磺酸(1.3equiv.,0.65mmol),该混合物在0.33M四氢呋喃溶液中于30℃氮气保护下反应5h。结果如表5所示:
表5
实施例6
选用不同浓度1,1,3,3-四甲基二硅氧烷来实验反应效果,25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷和三氟甲磺酸(1.3equiv.,0.65mmol),该混合物在0.3M四氢呋喃溶液中于30℃氮气保护下反应5h。结果如表6所示:
表6
实施例7
不同的温度下,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol),三氟甲磺酸(1.2equiv.,0.6mmol),该混合物在0.3M四氢呋喃溶液中于氮气保护下反应5h。结果如表7所示:
表7
实施例8
检测反应的最佳时间条件,于25mL Schlenk反应管中加入对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol),三氟甲磺酸(1.2equiv.,0.6mmol),该混合物在0.3M四氢呋喃溶液中于氮气保护下反应。结果如表8所示:
表8
由实施例1-8可以看出最佳溶剂式四氢呋喃(0.3M),最佳的催化剂式三氟甲磺酸(1.2equiv.,0.6mmol),最佳硅氢烷是1,1,3,3-四甲基二硅氧烷(3.0equiv.,1.5mmol),最佳温度是35℃,最佳芳香酮原料1a,三氟甲磺酸及1,1,3,3-四甲基二硅氧烷的配比是1:1.3:3。
通过以上实施例,最佳溶剂式四氢呋喃,最佳的催化剂是三氟甲磺酸,最佳硅氢烷是1,1,3,3-四甲基二硅氧烷,最佳温度是35℃,最佳原料与磺酸硅氢烷的配比是1:1.3:3为例,本发明的典型操作如下:
向25mL Schlenk反应管中加入式1所示的对溴苯乙酮1a(0.5mmol,99.5mg),1,1,3,3-四甲基二硅氧烷(3equiv.,1.5mmol)四氢呋喃(1.5mL,0.33M)三氟甲磺酸(1.3equiv.,0.65mmol),随后使用双排管将反应器内气氛用氮气置换并将反应溶液在35℃下搅拌,经TLC,GC检测原料完全消耗的时间为(5小时),即反应完全。该反应混合液冷却后用乙酸乙酯(10ml)稀释,加入饱和碳酸氢钠溶液至混合液不再有气泡产生(PH≈7-8)。使用分液漏斗萃取得到有机相溶液(乙酸乙酯溶液,合并有机相并用无水硫酸钠干燥,减压浓缩得到残余物经硅胶柱层析分离(洗脱剂为石油醚)即得到式1所示的目标产物2a:
4-溴苯乙烯(2a)
1H NMR(400MHz,CDCl3):δ7.41(d,J=8.0Hz,2H),7.23(d,J=8.0Hz,2H),6.62(dd,J=10.3,6.2Hz,1H),5.71(d,J=16.4,1H),5.24(d,J=10.3Hz,1H)ppm.
反应底物扩展实验:
在获得最佳反应条件的基础上,发明人进一步对该催化反应条件下,对不同结构第五的适应性进行了研究。
实施例1b-q芳香酮类化合物的适应性研究,对应的芳香烯烃产物如下:
化合物2b-2n的数据表征如下:
(2-methylprop-1-en-1-yl)benzene(2b)
2b:1H NMR(400MHz,CDCl3):δ7.30(d,J=7.5Hz,2H),7.24-7.16(m,3H),6.27(s,1H),1.90(s,3H),1.86(s,3H)ppm.
(E)-1,2-diphenylethene(2c)
2c:1H NMR(400MHz,CDCl3):δ7.53-7.29(m,10H),7.13(s,2H)ppm.
1,2-dihydronaphthalene(2d)
2d:1H NMR(400MHz,CDCl3):δ7.10-7.01(m,3H),6.95-6.91(m,1H),6.38(d,J=9.6Hz,1H),5.98-5.91(m,1H),2.72(t,J=8.2Hz,2H),2.24(tdd,J=8.0,4.4,1.8Hz,2H)ppm.
(cyclopentylidenemethyl)benzene(2e)
2i:1HNMR(400MHz,CDCl3):δ7.35-7.34(m,4H),7.22-7.17(m,1H),6.41-6.39(m,1H),2.61-2.57(m,2H),2.55-2.51(m,2H),1.86-1.79(m,2H),1.74-1.67(m,2H)ppm.
1-allyl-4-bromobenzene(2f)
2f:1H NMR(400 MHz,CDCl3):δ7.40(t,J=8.4 Hz,2H),7.05(d,J=8.4 Hz,2H),5.87-5.97(m,1H),5.03-5.09(m,2H),3.33(d,J=6.8 Hz,2H)ppm.
1-methoxy-3-vinylbenzene(2g)
2g:1H NMR(400 MHz,CDCl3):δ7.29-7.25(m,1H),7.04(d,J=7.6 Hz,1H),6.98(s,1H),6.86-6.83(m,1H),6.76-6.69(m,1H),5.77(d,J=17.6 Hz,1H),5.28(d,J=10.8 Hz,1H),3.84(s,3H)ppm.
1-fluoro-3-vinylbenzene(2h)
2h:1H NMR(400 MHz,CDCl3):δ7.56(s,1H),7.40-7.31(m,2H),7.22-7.18(m,1H),6.69-6.61(m,1H),5.76(d,J=17.6 Hz,1H),5.31(d,J=10.8 Hz,1H)ppm.
1-chloro-4-vinylbenzene(2i)
2i:1H NMR(400 MHz,CDCl3):δ7.35-7.28(m,4H),6.71-6.64(m,1H),5.73(d,J=17.6 Hz,1H),5.28(d,J=10.8 Hz,1H)ppm.
1-iodo-4-vinylbenzene(2j)
2j:1H NMR(400 MHz,CDCl3)δ7.65(d,J=8.2 Hz,1H),7.15(d,J=8.2 Hz,1H),6.63(dd,J=17.6,10.9 Hz,1H),5.75(d,J=17.6 Hz,1H),5.27(d,J=10.9 Hz,1H)ppm.
2-iodo-4-vinylbenzene(2k)
2k:1H NMR(400 MHz,CDCl3)d 7.84(dd,J=7.6,1.6 Hz,1H),7.52(dd,J=7.6,1.6Hz,1H),7.32(dd,J=7.6,7.6 Hz,1H),6.95(ddd,J=7.6,7.6,1.6 Hz,1H),6.88(dd,J=17.4,10.8 Hz,1H),5.63(d,J=17.4 Hz,1H),5.32(d,J=10.8 Hz,1H)ppm.
1-(trifluoromethyl)-4-vinylbenzene(2l)
2l:1H NMR(400 MHz,CDCl3):δ7.60-7.49(m,4H),6.79-6.72(m,1H),5.86(d,J=17.6 Hz,1H),5.39(d,J=10.8 Hz,1H)ppm.
1-(methylsulfonyl)-4-vinylbenzene(2m)
2m:1H NMR(400 MHz,CDCl3):δ7.90(d,J=8.2 Hz,2H),7.58(d,J=8.1 Hz,2H),6.77(dd,J=17.5,11.0 Hz,1H),5.92(d,J=17.6 Hz,1H),5.47(d,J=10.9 Hz,1H),3.05(s,3H)ppm.
1,3-difluoro-2-vinylbenzene(2n)
2n:1H NMR(400 MHz,CDCl3):δ7.16(dq,J=6.3,2.0 Hz,1H),6.89-6.85(m,2H),6.73(dd,J=18.0,11.9 Hz,1H),6.04(d,J=18.0 Hz,1H),5.58(dd,J=11.9,1.0 Hz,1H)ppm.
3,5-dichloro-2-vinylbenzene(2o)
2o:1H NMR(400 MHz,CDCl3):δ7.27(d,J=1.8 Hz,2H),7.24(t,J=1.8 Hz,1H),6.59(dd,J=17.5,10.8 Hz,1H),5.78(d,J=17.5 Hz,1H),5.36(d,J=10.8 Hz,1H)ppm.
1-nitro-4-vinylbenzene(2p)
2p:1H NMR(400MHz,CDCl3):δ8.28–8.11(m,2H),7.64–7.47(m,2H),6.78(dd,J=17.6,10.9Hz,1H),5.93(d,J=17.6Hz,1H),5.50(d,J=10.9Hz,1H)ppm.
4-vinylbenzonitrile(2q)
2q:1H NMR(400MHz,CDCl3):δ7.62-7.60(m,2H),7.49-7.47(m,2H),6.76-6.69(m,1H),5.87(d,J=17.6Hz,1H),5.45(d,J=10.8Hz,1H)ppm.
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (11)
3.根据权利要求1所述的方法,其特征在于,所述硅氢烷为含有Si-H键且Si上具有至少一个C1-6取代基取代的化合物。
4.根据权利要求1所述的方法,其特征在于,所述硅氢烷为1,1,3,3-四甲基二硅氧烷、二苯基硅烷、苯基硅烷、三异丙基硅基硅烷中的一种。
5.根据权利要求1所述的方法,其特征在于,所述溶剂为四氢呋喃、1,4-二噁烷、乙醚中的一种。
6.根据权利要求1所述的方法,其特征在于,所述方法中,反应过程需要在惰性气体保护下,搅拌并加热20-70℃温度下进行。
7.根据权利要求1所述的方法,其特征在于,所述方法中,反应过程需要在惰性气体保护下,搅拌并加热35-70℃温度下进行。
8.根据权利要求1所述的方法,其特征在于,所述化合物I在溶剂中的浓度为0.2-0.5M;反应时间为1-24h。
9.根据权利要求1所述的方法,其特征在于,所述化合物I在溶剂中的浓度为0.33-0.5M;反应时间为1-24h。
10.根据权利要求1所述的方法,其特征在于,所述含α氢芳香族酮类化合物、三氟甲磺酸、硅氢烷的投料当量比为1:1.3:3。
11.根据权利要求1所述的方法,其特征在于,还包括后处理步骤,包括:用饱和碳酸氢钠溶液中和反应液,再用乙酸乙酯稀释并萃取,合并有机相,由无水硫酸钠干燥,减压浓缩去除溶剂得到残余物,再将残余物经硅胶柱层析分离,得到化合物II的目标烯烃产物。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110190896.4A CN112961019B (zh) | 2021-02-19 | 2021-02-19 | 一种合成芳香族烯烃衍生物的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110190896.4A CN112961019B (zh) | 2021-02-19 | 2021-02-19 | 一种合成芳香族烯烃衍生物的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112961019A CN112961019A (zh) | 2021-06-15 |
CN112961019B true CN112961019B (zh) | 2022-08-26 |
Family
ID=76285159
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110190896.4A Expired - Fee Related CN112961019B (zh) | 2021-02-19 | 2021-02-19 | 一种合成芳香族烯烃衍生物的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112961019B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109400518A (zh) * | 2018-11-21 | 2019-03-01 | 湘潭大学 | 多取代6-芳基苯并[a]咔唑及衍生物及其合成方法 |
-
2021
- 2021-02-19 CN CN202110190896.4A patent/CN112961019B/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109400518A (zh) * | 2018-11-21 | 2019-03-01 | 湘潭大学 | 多取代6-芳基苯并[a]咔唑及衍生物及其合成方法 |
Also Published As
Publication number | Publication date |
---|---|
CN112961019A (zh) | 2021-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Highly enantioselective phenylacetylene addition to aldehydes catalyzed by a chiral N, O-ferrocene ligand | |
Donthiri et al. | NaOH‐Catalyzed Imine Synthesis: Aerobic Oxidative Coupling of Alcohols and Amines | |
Menges et al. | Catalyst-free hydrogenation of alkenes and alkynes with hydrazine in the presence of oxygen | |
CN111205279A (zh) | 一种多取代苯并二氢呋喃并杂环类化合物及其制备方法和应用 | |
Zolfigol et al. | A simple and efficient route for the synthesis of di and tri (bis (indolyl) methanes) as new triarylmethanes | |
Han et al. | A catalyst-controlled switchable reaction of β-keto acids to silyl glyoxylates | |
Santoro et al. | Oxidation of alkynes in aqueous media catalyzed by diphenyl diselenide | |
CN112961019B (zh) | 一种合成芳香族烯烃衍生物的方法 | |
CN115710287B (zh) | 一种无金属催化下环丙烷类化合物开环硼化的反应方法 | |
CN107382741B (zh) | 催化炔烃和胺的分子间氢胺化反应的方法 | |
CN113173859B (zh) | 一种合成手性α-胺基醇化合物的方法 | |
CN110734354B (zh) | 一种由醇类化合物制备联芳烃类化合物的方法 | |
Rinaldi et al. | Synthesis of (±)‐epi‐Jungianol by the Gold (I)‐Catalyzed Propargyl Claisen Rearrangement/Hydroarylation Cascade Reaction of Propargyl Vinyl Ethers | |
Wu et al. | Phenylazoalkanes from reaction of nitrosobenzene with alkylamines | |
CN111574569B (zh) | 铑的配位化合物及其制备方法和应用 | |
CN114133373A (zh) | 一种合成维兰特罗中间体的前驱体的方法 | |
CN103694182A (zh) | 一种喹喔啉类化合物的制备方法 | |
CN113024340A (zh) | 一种镍催化水为氢源还原炔烃为烯烃的方法 | |
CN111018779B (zh) | 一种2-(3-异喹啉基)-丙酸乙酯衍生物及合成方法 | |
Hui et al. | Copper (II) bromide catalyzed novel preparation of propargylic ethers and sulfides by Sn1-type substitution between propargylic alcohols and alcohols or thiols | |
CN105669598A (zh) | 一种α-蒎烯烯丙位选择性氧化方法及其产品 | |
Padmaja et al. | Highly regioselective α-alkylation of α, β, γ, δ-unsaturated aldehydes | |
CN111039968A (zh) | 一种催化2,3-二氢苯并呋喃衍生物选择性发生硼化反应的方法 | |
CN112125843B (zh) | 一种3-羟甲基-4-苯基-3,4-二氢喹啉酮化合物的制备方法 | |
Zhao et al. | Highly Regioselective Rhenium‐Catalyzed Hydrosilylation of Styrenes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220826 |