CN110483223A - 吡啶钯高效催化制备二芳基酮化合物的方法 - Google Patents
吡啶钯高效催化制备二芳基酮化合物的方法 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 77
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- -1 diaryl ketone compound Chemical class 0.000 title claims abstract description 39
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 38
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 12
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 239000011630 iodine Substances 0.000 claims abstract description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 150000008424 iodobenzenes Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
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- 239000003446 ligand Substances 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 3
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- 239000003480 eluent Substances 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 2
- IHMWJDNMIIEDDN-UHFFFAOYSA-N (4-methoxyphenyl)-(4-methylphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(C)C=C1 IHMWJDNMIIEDDN-UHFFFAOYSA-N 0.000 description 2
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 2
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- DEGIYCMFDIWAKC-UHFFFAOYSA-N (4-methoxyphenyl)-naphthalen-1-ylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC2=CC=CC=C12 DEGIYCMFDIWAKC-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- IGZGUYVVBABKOY-UHFFFAOYSA-N 1-iodo-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1I IGZGUYVVBABKOY-UHFFFAOYSA-N 0.000 description 1
- FNRMMDCDHWCQTH-UHFFFAOYSA-N 2-chloropyridine;3-chloropyridine;4-chloropyridine Chemical compound ClC1=CC=NC=C1.ClC1=CC=CN=C1.ClC1=CC=CC=N1 FNRMMDCDHWCQTH-UHFFFAOYSA-N 0.000 description 1
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- HHOXWPCTCQMHNN-UHFFFAOYSA-N C1(=CC=CC=C1)I.[F] Chemical compound C1(=CC=CC=C1)I.[F] HHOXWPCTCQMHNN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- YHKDMJOYMRUGBQ-UHFFFAOYSA-N bis[4-(trifluoromethyl)phenyl]methanone Chemical compound C1=CC(C(F)(F)F)=CC=C1C(=O)C1=CC=C(C(F)(F)F)C=C1 YHKDMJOYMRUGBQ-UHFFFAOYSA-N 0.000 description 1
- OOPSAZSKOMIGFX-UHFFFAOYSA-N boric acid;toluene Chemical compound OB(O)O.CC1=CC=CC=C1 OOPSAZSKOMIGFX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZOQCZTRFTARYGJ-UHFFFAOYSA-N chlorooxy(phenyl)borinic acid Chemical compound ClOB(O)C1=CC=CC=C1 ZOQCZTRFTARYGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DWYFUJJWTRPARQ-UHFFFAOYSA-N phenyl(thiophen-2-yl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CS1 DWYFUJJWTRPARQ-UHFFFAOYSA-N 0.000 description 1
- OHTYZZYAMUVKQS-UHFFFAOYSA-N phenyl-[4-(trifluoromethyl)phenyl]methanone Chemical compound C1=CC(C(F)(F)F)=CC=C1C(=O)C1=CC=CC=C1 OHTYZZYAMUVKQS-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种吡啶钯高效催化制备二芳基酮化合物的方法，以芳基苯硼酸、碘苯类化合物和一氧化碳作为原料，碳酸钾或氢氧化钾为碱、吡啶钯或3‑氯吡啶钯为催化剂，高效、高产率制备二芳基化合物。本发明所用催化剂用量少和催化活性高、对空气稳定，操作简单，反应时间短，原子经济性高，为二芳基酮化合物物的制备开辟了低成本的且绿色高效的途径，具有广阔的应用前景。
Description
技术领域
本发明属于二芳基酮化合物合成技术领域，具体涉及一种吡啶钯高效催化制备二芳基酮化合物的方法。
背景技术
二芳基酮是构成大量天然产物和生物活性小分子的结构基元。这种结构也是制备抗炎药中和农用化学品的关键组分。这种结构模板是核心支架，广泛存在于药品、先进的有机材料和光敏剂中。
二芳基酮它们通常是由取代芳香化合物的付克酰化制得的。传统的付克酰化的主要缺点是过量使用Lewis酸，限制了对位的区域选择性。其他的合成二芳基酮的方法包括过渡金属介导的三组分交叉偶联反应，芳基金属试剂、一氧化碳和芳基酸酐。这些羰基化反应由于一氧化碳未能插入而形成了二芳基的副产物，特别是与缺电子芳基卤化物的反应是有局限性的。
另一种合成二芳基酮的有效方法是钯催化的羰基化Suzuki-Miyaura偶联反应，即芳基卤化物与芳基硼酸的偶联反应，CO为碳源。CO是一种用途广泛、成本效益很高的化工原料，很容易由天然气体、煤、生物质等产生。并且芳基硼酸通常是无毒的和耐热的，在空气和水分是稳定的。
近年来，N杂环卡宾(NHC)作为过渡金属的有效配体在均相催化中得到了广泛关注。因为其与过渡金属的各种氧化态有效结合。与膦配体相比，N-杂环卡宾配体具有很高的离解能。因此，NHC和过渡金属之间的结合要强得多，在化学和热上都比其他配合物更难分解。在催化反应中，NHC配体具有较高的σ供给量，可防止非活性钯黑的形成。这是因为N杂环卡宾配体能够为各种催化应用提供高活性和稳定的金属配合物。另外，吡啶和3-氯吡啶为中心的钯具有强有力的、使用友好的、高反应活性的特性，并且钯配合物的吡啶部分在整个反应中能够提升催化前体的制备、稳定性及引发反应，对于合成一系列吡啶钯越来越重要。
发明内容
本发明的目的是克服现有二芳基酮类化合物制备方法存在的缺点，提供一种条件温和、操作简单、反应时间短，反应产物单一、底物适用性好、高效制备二芳基酮化合物的方法。
针对上述目的，本发明所采用的技术方案是：将式I所示的碘苯类化合物和式 II所示的芳基苯硼酸、吡啶钯或3-氯吡啶钯、无机碱加入有机溶剂中，并通入CO 气体，在CO压力为3～6atm下60～100℃反应6～8小时，分离纯化产物，得到式Ш所示的二芳基酮化合物。
式中，R1代表H、卤素、C1～C4烷氧基、三氟甲基、噻吩基中的任意一种，具体如 H、甲氧基、F、Cl、Br、三氟甲烷基、噻吩基等；R2代表H、卤素、C1～C4烷基中的任意一种，具体如H、甲基、Cl等。
上述吡啶钯的结构式如下所示：
上述3-氯吡啶钯的结构式如下所示：
上述吡啶钯或3-氯吡啶钯的制备方法为：将式A化合物与二氯化钯、碳酸钾按摩尔比1:1:2溶解于吡啶或间氯吡啶中，在40℃下反应5小时，反应结束后，用硅藻土辅助过滤，旋蒸溶剂后用乙腈和正己烷体积比为1:3的混合液重结晶，得到吡啶钯或3-氯吡啶钯，合成方程式如下：
上述方法中，优选在CO压力为5atm下80～100℃反应8小时。
上述方法中，所述碘苯类化合物与芳基苯硼酸的摩尔比为1:1～1.5；所述吡啶钯的加入量为碘苯类化合物摩尔量的0.1％～0.2％；所述的无机碱为碳酸钾或氢氧化钾，无机碱的加入量为碘苯类化合物摩尔量的1.5～2.0倍；所述有机溶剂为1,4- 二氧六环或甲苯。
本发明以芳基苯硼酸、碘苯类化合物和一氧化碳作为原料，碳酸钾或氢氧化钾为碱、吡啶钯或3-氯吡啶钯为催化剂，可高效、高产率制备二芳基酮化合物。本发明所用催化剂用量少、对空气稳定，时间短，操作简单，原子经济性高，为二芳基酮化合物的制备开辟了新的低成本且绿色高效的途径，具有广阔的应用前景。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明所要保护的范围不仅限于这些实施例。
实施例1
制备结构式如下的二苯甲酮
向20mL反应瓶中加入0.2040g(1mmol)碘苯、0.1829g(1.5mmol)苯硼酸、 0.0005g(0.001mmol)吡啶钯(R＝H)、0.2764g(2mmol)碳酸钾、3mL1,4-二氧六环，并通入CO气体，在CO压力为5atm下80℃搅拌反应8小时，停止反应，自然降至室温，旋转蒸发除去1,4-二氧六环，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到二苯甲酮，其产率为95％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.71(dd,J＝8.2,1.2Hz,4H),7.49(t,J＝7.4Hz, 2H),7.39(t,J＝7.7Hz,4H)；13C NMR(600MHz,CDCl3)δ195.68(s),136.57(s), 131.37(s),129.01(s),127.24(s).
实施例2
制备结构式如下的4-甲氧基二苯甲酮
本实施例中，用等摩尔对甲氧基碘苯替换实施例1中的碘苯，其他步骤与实施例1相同，得到4-甲氧基二苯甲酮，其产率为97％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.74(d,J＝8.8Hz,2H),7.69-7.63(m,2H),7.47 (t,J＝7.4Hz,1H),7.38(t,J＝7.7Hz,2H),6.87(d,J＝8.8Hz,2H),3.79(s,3H)；13C NMR(151MHz,CDCl3)δ195.57(s),163.25(s),138.31(s),132.57(s),131.90(s), 130.17(s),129.73(s),128.20(s),113.58(s),55.50(s).
实施例3
制备结构式如下的(4-甲氧基苯基)(对甲苯基)甲酮
向20mL反应瓶中加入0.2340g(1mmol)对甲氧基碘苯、0.2039(1.5mmol) 对甲基苯硼酸、0.0005g(0.001mmol)吡啶钯(R＝H)、0.2764g(2mmol)碳酸钾、 mL 1,4-二氧六环，并通入CO气体，在CO压力为5atm下100℃搅拌反应小8小时，停止反应，自然降至室温，旋转蒸发除去1,4-二氧六环，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到(4-甲氧基苯基)(对甲苯基)甲酮，其产率为96％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.72(d,J＝8.8Hz,2H),7.58(d,J＝8.1Hz,2H), 7.18(d,J＝7.6Hz,2H),6.86(d,J＝8.8Hz,2H),3.78(s,3H),2.34(s,3H)；13C NMR(151 MHz,CDCl3)δ195.34(s),163.06(s),142.61(s),135.54(s),132.43(s),130.50(s), 130.00(s),128.89(s),113.50(s),55.48(s),21.61(s).
实施例4
制备结构式如下的(4-甲氧基苯基)(对氯苯基)甲酮
本实施例中，用等摩尔对氯苯硼酸替换实施例3中的对甲基苯硼酸，其他步骤与实施例3相同，得到(4-甲氧基苯基)(对氯苯基)甲酮，其产率为93％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.69(d,J＝8.8Hz,2H),7.60(d,J＝8.4Hz,2H), 7.34(d,J＝8.4Hz,2H),6.86(d,J＝8.8Hz,2H),3.78(s,3H)；13C NMR(151MHz, CDCl3)δ194.20(s),163.41(s),138.27(s),136.57(s),132.44(s),131.15(s),129.81(s), 128.52(s),113.70(s),55.52(s).
实施例5
制备结构式如下的(4-甲氧基苯基)(萘-1-基)甲酮
本实施例中，用等摩尔1-萘硼酸替换实施例3中的对甲基苯硼酸，洗脱剂是二氯甲烷与石油醚的体积比为1:10的混合液，其他步骤与实施例3相同，得到(4-甲氧基苯基)(萘-1-基)甲酮，其产率为98％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.91(dd,J＝13.4,8.2Hz,2H),7.83(d,J＝8.1Hz, 1H),7.80-7.74(m,2H),7.48-7.35(m,4H),6.92-6.78(m,2H),3.79(s,3H)；13C NMR (151MHz,CDCl3)δ196.73(s),163.83(s),137.08(s),133.69(s),132.80(s),131.12(s), 130.91(s),130.65(s),128.36(s),127.02(s),126.82(s),126.37(s),125.75(s),124.45(s), 113.72(s),55.54(s).
实施例6
制备结构式如下的4-氟二苯甲酮
本实施例中，用等摩尔对氟碘苯替换实施例1中的碘苯，在CO压力为5atm下100 ℃搅拌反应8小时，其他步骤与实施例1相同，得到4-氟二苯甲酮，其产率为96％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.76(dd,J＝8.8,5.5Hz,2H),7.71-7.66(m,2H), 7.51(dd,J＝10.6,4.3Hz,1H),7.40(t,J＝7.7Hz,2H),7.07(t,J＝8.6Hz,2H)；13C NMR (151MHz,CDCl3)δ195.25(s),166.25(s),137.53(s),133.82(s),132.68(d,J＝9.2Hz), 132.48(s),129.88(s),128.37(s),115.39(s).
实施例7
制备结构式如下的4-氯二苯甲酮
本实施例中，用等摩尔对氯碘苯替换实施例1中的碘苯，在CO压力为5atm 下100℃搅拌反应8小时，其他步骤与实施例1相同，得到4-氯二苯甲酮，其产率为96％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.79-7.73(m,4H),7.59(dd,J＝10.6,4.3Hz,1H), 7.51-7.44(m,4H)；13C NMR(151MHz,CDCl3)δ195.46(s),138.90(s),137.27(s), 135.90(s),132.65(s),131.47(s),129.94(s),128.65(s),128.42(s).
实施例8
制备结构式如下的苯基(4-(三氟甲基)苯基)甲酮
本实施例中，用等摩尔对三氟甲基碘苯替换实施例1中的碘苯，在CO压力为 5atm下100℃搅拌反应8小时，其他步骤与实施例1相同，得到苯基(4-(三氟甲基) 苯基)甲酮，其产率为96％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.89(d,J＝8.1Hz,2H),7.80(dd,J＝8.2,1.2Hz, 2H),7.75(d,J＝8.2Hz,2H),7.65-7.60(m,1H),7.50(t,J＝7.8Hz,2H)；13C NMR(151 MHz,CDCl3)δ195.49(s),140.76(s),136.76(s),133.62(s),133.08(s),130.12(d,J＝5.5 Hz),128.53(s),125.35(q,J＝3.7Hz),124.60(s),122.79(s).
实施例9
制备结构式如下的苯基-2-噻吩基甲酮
本实施例中，用等摩尔2-碘代噻吩替换实施例1中的碘苯，用等摩尔3-氯吡啶钯替换实施例1中的吡啶钯，其他步骤与实施例1相同，得到苯基-2-噻吩基甲酮，其产率为95％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.87(d,J＝7.3Hz,2H),7.72(d,J＝4.8Hz,1H), 7.65(d,J＝3.7Hz,1H),7.59(t,J＝7.4Hz,1H),7.50(t,J＝7.7Hz,2H),7.18-7.13(m, 1H)；13C NMR(151MHz,CDCl3)δ188.24(s),143.67(s),138.18(s),134.85(s),134.21 (s),132.28(s),129.19(s),128.43(s),127.97(s).
实施例10
制备结构式如下的4-溴二苯甲酮
本实施例中，用等摩尔对溴碘苯替换实施例1中的碘苯，用等摩尔3-氯吡啶钯替换实施例1中的吡啶钯，其他步骤与实施例1相同，得到4-溴二苯甲酮，其产率为85％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(600MHz,CDCl3)δ7.77(dd,J＝8.1,1.1Hz,2H),7.69-7.66(m,2H), 7.64-7.61(m,2H),7.59(d,J＝7.5Hz,1H),7.49(t,J＝7.8Hz,2H)；13C NMR(151MHz, CDCl3)δ195.62(s),137.20(s),136.34(s),132.68(s),131.60(d,J＝8.7 Hz),129.95(s), 128.43(s),127.52(s)。
Claims (7)
1.一种吡啶钯高效催化制备二芳基酮化合物的方法，其特征在于：将式I所示的碘苯类化合物和式II所示的芳基苯硼酸、吡啶钯或3-氯吡啶钯、无机碱加入有机溶剂中，并通入CO气体，在CO压力为3～6atm下60～100℃反应6～8小时，分离纯化产物，得到式Ш所示的二芳基酮化合物；
式中，R1代表H、卤素、C1～C4烷氧基、三氟甲基、噻吩基中的任意一种；R2代表H、卤素、C1～C4烷基中的任意一种；
上述吡啶钯的结构式如下所示：
上述3-氯吡啶钯的结构式如下所示：
上述的无机碱为碳酸钾或氢氧化钾。
2.根据权利要求1所述的吡啶钯高效催化制备二芳基酮化合物的方法，其特征在于：所述R1代表H、甲氧基、F、Cl、Br、三氟甲烷基、噻吩基中任意一种；R2代表H、甲基、Cl中任意一种。
3.根据权利要求1或2所述的吡啶钯高效催化制备二芳基酮化合物的方法，其特征在于：在CO压力为5atm下80～100℃反应8小时。
4.根据权利要求1或2所述的吡啶钯高效催化制备二芳基酮化合物的方法，其特征在于：所述碘苯类化合物与芳基苯硼酸的摩尔比为1:1～1.5。
5.根据权利要求1或2所述的吡啶钯高效催化制备二芳基酮化合物的方法，其特征在于：所述吡啶钯的加入量为碘苯类化合物摩尔量的0.1％～0.2％。
6.根据权利要求1或2所述的吡啶钯高效催化制备二芳基酮化合物的方法，其特征在于：所述无机碱的加入量为碘苯类化合物摩尔量的1.5～2.0倍。
7.根据权利要求1或2所述的吡啶钯高效催化制备二芳基酮化合物的方法，其特征在于：所述有机溶剂为1,4-二氧六环或甲苯。
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| CN112110817A (zh) * | 2020-09-21 | 2020-12-22 | 陕西师范大学 | 一种吡啶钯高效催化制备二芳基酯类化合物的方法 |
| CN114950558A (zh) * | 2021-02-22 | 2022-08-30 | 陕西师范大学 | 联哌啶骨架四齿含氮锰催化剂及其催化碳氢分子苄基位选择性氧化的方法 |
| CN115322081A (zh) * | 2022-01-05 | 2022-11-11 | 南京工业大学 | 一种烷基烯基酮的合成方法 |
| CN115385765A (zh) * | 2022-01-05 | 2022-11-25 | 南京工业大学 | 一种烷基芳基酮的合成方法 |
| CN115448809A (zh) * | 2022-10-18 | 2022-12-09 | 陕西师范大学 | 一种三嗪卡宾钯催化合成二芳基化合物的方法 |
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| CN112110817A (zh) * | 2020-09-21 | 2020-12-22 | 陕西师范大学 | 一种吡啶钯高效催化制备二芳基酯类化合物的方法 |
| CN114950558A (zh) * | 2021-02-22 | 2022-08-30 | 陕西师范大学 | 联哌啶骨架四齿含氮锰催化剂及其催化碳氢分子苄基位选择性氧化的方法 |
| CN114950558B (zh) * | 2021-02-22 | 2023-08-11 | 陕西师范大学 | 联哌啶骨架四齿含氮锰催化剂及其催化碳氢分子苄基位选择性氧化的方法 |
| CN115322081A (zh) * | 2022-01-05 | 2022-11-11 | 南京工业大学 | 一种烷基烯基酮的合成方法 |
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| CN115385765B (zh) * | 2022-01-05 | 2023-11-10 | 南京工业大学 | 一种烷基芳基酮的合成方法 |
| CN115448809A (zh) * | 2022-10-18 | 2022-12-09 | 陕西师范大学 | 一种三嗪卡宾钯催化合成二芳基化合物的方法 |
| CN115448809B (zh) * | 2022-10-18 | 2023-09-19 | 陕西师范大学 | 一种三嗪卡宾钯催化合成二芳基化合物的方法 |
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