CN106432074B - A method of 4- aryl -2- quinolinone is prepared by carbon dioxide - Google Patents
A method of 4- aryl -2- quinolinone is prepared by carbon dioxide Download PDFInfo
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- CN106432074B CN106432074B CN201610813950.5A CN201610813950A CN106432074B CN 106432074 B CN106432074 B CN 106432074B CN 201610813950 A CN201610813950 A CN 201610813950A CN 106432074 B CN106432074 B CN 106432074B
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- carbon dioxide
- quinolinone
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000018044 dehydration Effects 0.000 claims abstract description 22
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 22
- 150000002940 palladium Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 42
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 22
- 238000004440 column chromatography Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 230000020477 pH reduction Effects 0.000 claims description 21
- 239000012264 purified product Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 4
- 229910052763 palladium Inorganic materials 0.000 claims 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000006452 multicomponent reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003379 elimination reaction Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 238000010523 cascade reaction Methods 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000010930 lactamization Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 38
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 24
- 239000000843 powder Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical group INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- -1 benzoxazine ketone compound Chemical class 0.000 description 12
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 11
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- MIXFDFCKBMCLGN-SSZFMOIBSA-N 4-methyl-n-[(z)-1-phenylethylideneamino]benzenesulfonamide Chemical compound C=1C=CC=CC=1C(/C)=N\NS(=O)(=O)C1=CC=C(C)C=C1 MIXFDFCKBMCLGN-SSZFMOIBSA-N 0.000 description 7
- 150000001448 anilines Chemical group 0.000 description 7
- 150000007529 inorganic bases Chemical class 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010490 three component reaction Methods 0.000 description 4
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 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 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NAMDIHYPBYVYAP-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound COCCOCCOC.COCCOCCOC NAMDIHYPBYVYAP-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 description 1
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 1
- WRXGEZLZGNKKGJ-UHFFFAOYSA-N 3-methyl-4-phenyl-1h-quinolin-2-one Chemical compound C12=CC=CC=C2NC(=O)C(C)=C1C1=CC=CC=C1 WRXGEZLZGNKKGJ-UHFFFAOYSA-N 0.000 description 1
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 1
- SNFOXOPKANOMBH-UHFFFAOYSA-N 4-(2-methoxyphenyl)-1h-quinolin-2-one Chemical compound COC1=CC=CC=C1C1=CC(=O)NC2=CC=CC=C12 SNFOXOPKANOMBH-UHFFFAOYSA-N 0.000 description 1
- HAYNUPISMMZZDS-UHFFFAOYSA-N 4-(2-methylphenyl)-1H-quinolin-2-one Chemical compound Cc1ccccc1-c1cc(=O)[nH]c2ccccc12 HAYNUPISMMZZDS-UHFFFAOYSA-N 0.000 description 1
- FHZCFLYJSPEEGK-UHFFFAOYSA-N 4-(4-methoxyphenyl)-1h-quinolin-2-one Chemical compound C1=CC(OC)=CC=C1C1=CC(=O)NC2=CC=CC=C12 FHZCFLYJSPEEGK-UHFFFAOYSA-N 0.000 description 1
- HBIOIQZVPMAPSZ-UHFFFAOYSA-N 4-(4-methylphenyl)-1h-quinolin-2-one Chemical compound C1=CC(C)=CC=C1C1=CC(=O)NC2=CC=CC=C12 HBIOIQZVPMAPSZ-UHFFFAOYSA-N 0.000 description 1
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 1
- TWTWWQDWKPRWFI-UHFFFAOYSA-N 4-methyl-n-(1-phenylpropylideneamino)benzenesulfonamide Chemical compound C=1C=CC=CC=1C(CC)=NNS(=O)(=O)C1=CC=C(C)C=C1 TWTWWQDWKPRWFI-UHFFFAOYSA-N 0.000 description 1
- HPZLOXJGOVVEFU-UHFFFAOYSA-N 6-phenyl-1h-quinolin-2-one Chemical compound C=1C=C2NC(=O)C=CC2=CC=1C1=CC=CC=C1 HPZLOXJGOVVEFU-UHFFFAOYSA-N 0.000 description 1
- LDPRNNJZMNKZOX-UHFFFAOYSA-N 7,8-dihydro-5H-benzo[k]phenanthridin-6-one Chemical compound C1=CC=CC=2NC(C=3CCC4=C(C=3C1=2)C=CC=C4)=O LDPRNNJZMNKZOX-UHFFFAOYSA-N 0.000 description 1
- MBHZHSKXZYGYNF-UHFFFAOYSA-N 7,8-dihydrobenzo[k]phenanthridine Chemical class C1=CC=C2CCC3=CN=C(C=CC=C4)C4=C3C2=C1 MBHZHSKXZYGYNF-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- YFPJHMQGTRFVAV-UHFFFAOYSA-N FN1C(C=C(C2=CC=CC=C12)C1=CC=CC=C1)=O Chemical compound FN1C(C=C(C2=CC=CC=C12)C1=CC=CC=C1)=O YFPJHMQGTRFVAV-UHFFFAOYSA-N 0.000 description 1
- BGWHUEITMZDQPN-UHFFFAOYSA-N N-[1-(2-methoxyphenyl)ethylideneamino]-4-methylbenzenesulfonamide Chemical compound COC1=CC=CC=C1C(C)=NNS(=O)(=O)C1=CC=C(C)C=C1 BGWHUEITMZDQPN-UHFFFAOYSA-N 0.000 description 1
- XGWPPLYSQFLVLE-UHFFFAOYSA-N N-[1-(4-cyanophenyl)ethylideneamino]-4-methylbenzenesulfonamide Chemical compound C=1C=C(C#N)C=CC=1C(C)=NNS(=O)(=O)C1=CC=C(C)C=C1 XGWPPLYSQFLVLE-UHFFFAOYSA-N 0.000 description 1
- SSXCSHDSASIKDO-UHFFFAOYSA-N N-iodo-4-nitroaniline Chemical compound [O-][N+](=O)C1=CC=C(NI)C=C1 SSXCSHDSASIKDO-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- JAGRBVUQNWAXFU-UHFFFAOYSA-N [Li].C(CCC)O Chemical compound [Li].C(CCC)O JAGRBVUQNWAXFU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KQNWJQOEQKMDHH-UHFFFAOYSA-N n-(3,4-dihydro-2h-naphthalen-1-ylideneamino)-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NN=C1C2=CC=CC=C2CCC1 KQNWJQOEQKMDHH-UHFFFAOYSA-N 0.000 description 1
- LKESOLUTWZJVJP-UHFFFAOYSA-N n-chloro-2-iodoaniline Chemical compound ClNC1=CC=CC=C1I LKESOLUTWZJVJP-UHFFFAOYSA-N 0.000 description 1
- NEOLWKPYXMBCON-UHFFFAOYSA-N n-fluoro-2-iodoaniline Chemical compound FNC1=CC=CC=C1I NEOLWKPYXMBCON-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/227—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of methods for preparing 4- aryl -2- quinolinone by carbon dioxide, belong to Utilization of Carbon Dioxide technical field, the specific process steps are as follows: in the Schlenk pipe handled through dehydration and deoxidation, N- Tosylhydrazone, adjacent halogenated aniline, under the catalyst system effect being made of palladium salt, alkali, with the CO under condition of normal pressure2Tandem reactions, the reaction solutions such as Cabbeen migration insertion/β-hydrogen elimination/lactamization occurs to terminate via dilute hydrochloric acid solution, obtains 4- aryl -2- quinolinone compounds.The present invention uses the multi-component reaction of transition metal-catalyzed N- Tosylhydrazone, adjacent halogenated aniline, carbon dioxide for the first time, prepares 4- aryl -2- quinolinone compounds.And have reaction raw materials and catalyst simple and easy to get, the advantages that reaction condition is mild, and reaction substrate universality is wide, and the reaction time is short, the high income of target product, operation and simple last handling process.
Description
Technical field
The present invention relates to Utilization of Carbon Dioxide technical fields, and in particular to be transition metal-catalyzed carbon dioxide
Chemistry is fixed and converts.
Background technique
In recent years, it is carbonyl source using carbon dioxide, carbonyl containing compound is constructed by multi-component reaction and is increasingly caused
People's note that with it is traditional using toxic carbon monoxide, phosgene etc. compared with the carbonylation of carbonyl source, the method tool
It is cheap and easily-available, nontoxic there is carbon dioxide, and advantageously reduces in atmosphere the concentration of " greenhouse effects " gas.
Such as: Kunai et al. is reported, and under the action of potassium fluoride, 18- crown- 6, utilizes generated in-situ benzyne chemical combination
Object, imines and CO2Three component reactions, construct a series of benzoxazine ketone compound.(referring to: H.Yoshida,
H.Fukushima, J.Ohshita, A.Kunai, J.Am.Chem.Soc.2006,128,11040.) Kobayashi is reported,
Generated in-situ benzyne, Terminal Acetylenes and the CO of mantoquita catalysis2Three component reactions, construct a series of lactone compound.(ginseng
See: W.-J.Yoo, T.Nguyen, S.Kobayashi, Angew.Chem.Int.Ed.2014,53,10213.) in the recent period, Biju etc.
People reports, generated in-situ benzyne, isonitrile and the CO that cesium fluoride promotes2Three component reactions, construct a series of benzene
Adjacent dicarboximide compound.(referring to: T.Kaicharla, M.Thangaraj, A.Biju, Org.Lett.2014,16,
1728.) professor Li reports the aromatic aldehyde, fatty amine, fragrant Terminal Acetylenes, CO of ketone catalysis2Four component reactions, and construct a system
The oxazoline compound of column.(referring to: W.-J.Yoo, C.-J.Li, Adv.Synth.Catal.2008,350,1503.) Jiang
Seminar reports, Tosylhydrazone, the amine, CO of inorganic base promotion2Three component reactions, and construct a series of amino
Formic acid ester compound.(referring to: C.Qi, H.Jiang, L.Huang, G.Yuan, Y.Ren, Org.Lett.2011,13,5520.)
Although the multi-component reaction that carbon dioxide participates in, has been achieved for certain progress.However, further development utilization is simple and easy to get
Starting material, different types of heterocyclic compound containing carbonyl is constructed by multi-component reaction, still research valence with higher
Value.
On the other hand, in recent years, the reaction that N- Tosylhydrazone participates in has obtained great development, has developed one
Series is the reaction of synthon based on N- Tosylhydrazone.Such as: halogenated hydrocarbons can be with N- Tosylhydrazone, Ke Yitong
Cross migration insertion/β-hydrogen elimination reaction of Cabbeen, available a series of substituted olefine compound.Wherein, adjacent amido aryl
The reaction that halogenated hydrocarbons participates in, available o- (1- styryl) aniline, and this compound can be used as and a kind of prepare 2- quinoline
The precursor of quinoline ketone compound.Such as: recently, Yu seminar reports, sodium tert-butoxide promote o- (1- styryl) aniline with
CO2Reaction, and then a series of 4- aryl -2- quinolinone compounds have been prepared.(referring to: Z.Zhang, L.-L.；
Liao,S.-S.Yan,L.Wang,Y.-Q.He,J.-H.Ye,J.Li,Y.-G.Zhi,D.-G.Yu,
Angew.Chem.Int.Ed.2016,55,7068.).However the above method also suffers from certain drawbacks, the starting used is former
Expect that o- (1- styryl) aniline needs to be prepared by aniline and expensive substitutedphenylethynyl, and needs multistep
Separation can just obtain required target compound.Therefore, develop a kind of using cheap and easily-available starting material, pass through " one kettle way "
4- aryl -2- quinolinone compounds are prepared, undoubtedly there is biggish scientific research and practical application value.
In view of this, the present invention has developed one kind in a mild condition, N- Tosylhydrazone is utilized, replaces adjacent halogeno-benzene
Amine, carbon dioxide are starting material, under palladium salt, the facilitation of inorganic base, with higher yield and selectivity, are prepared
A series of 4- aryl -2- quinolinone compounds.
Summary of the invention
The present invention is directed to develop the method that a kind of activation of carbon dioxide is fixed and is converted into useful fine chemicals, the party
The spies such as method has required raw material, catalyst simple and easy to get, and reaction condition is mild, and post-reaction treatment is simple and convenient and reaction yield is high
Point.
The present invention utilizes the catalyst system that is made of palladium salt, inorganic base, the N- benzenesulfonyl hydrazone of catalysis, adjacent halogenated aniline with
Carbon dioxide reaction prepares the reaction of 4- aryl -2- quinolinone compounds.
Synthesis technology reaction equation is as follows:
To achieve the above object of the invention, intend being achieved through the following technical solutions:
A method of 4- aryl -2- quinolinone is prepared by carbon dioxide, is carried out as steps described below:
(1) in the Schlenk pipe (Schlenk pipe) handled through dehydration and deoxidation, N- tolysulfonyl is added by a certain percentage
Above-mentioned Schlenk pipe is placed in oil bath under 0.1MPa carbon dioxide atmosphere by hydrazone, adjacent halogenated aniline, palladium salt, alkali and solvent
Middle heating stirring 24 hours.
(2) reaction is terminated, acidification is carried out to reaction solution using the hydrochloric acid solution of 1M first, then be extracted with ethyl acetate
Then organic phase in system out is dried to obtain 4- aryl -2- quinolinone chemical combination finally by column chromatography for separation purified product
Object.
Wherein: the step (1) is firstly added 0.30mmol N- p-toluenesulfonyl hydrazone, 0.20mmol neighbour's halogenated aniline,
It is subsequently added into the palladium salt (relative to adjacent halogenated aniline) of 10%mmol, the inorganic base (relative to adjacent halogenated aniline) of 6 equivalents, then it is past
About 3.0mL solvent is added in reaction tube.
Wherein: the temperature setting polymerizeing in the step (1) is 100~140 DEG C, and is no more than the boiling point of solvent；Catalysis
In system, CO2Pressure be 0.1MPa, the dosage of inorganic base is 6 equivalents (relative to adjacent halogenated aniline).The alkali are as follows: uncle
One of butanol lithium, sodium tert-butoxide；Solvent for use is one of diethylene glycol dimethyl ether, 1,4- dioxane.
Wherein: the N- Tosylhydrazone, chemical structural formula are as follows:
Wherein, the substituent R on aromatic ring1, R2Selected from H, Cl, Br, CF3, OMe, CN, one or both of Me etc., carbochain
Length n be 1-5.
Wherein: the preparation method of N- benzenesulfonyl hydrazone is based on document (Xiao, Q.；Xia,Y.；Li,H.；Zhang,Y.；
Wang, J.Angew.Chem., Int.Ed.2011,50,1114.) disclosed in synthetic method.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
A kind of method for fixing and being converted into useful fine chemicals of carbon dioxide disclosed by the invention, used for the first time
The multi-component reaction for crossing metal catalytic N- Tosylhydrazone, adjacent halogenated aniline, carbon dioxide, prepares 4- aryl -2- quinolinone
Compound.And having reaction raw materials and catalyst simple and easy to get, reaction condition is mild, and reaction substrate universality is wide, when reaction
Between it is short, the advantages that the high income of target product, operation and simple last handling process.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1: preparation 4- phenyl -2- (1H)-quinolinone (4-phenylquinolin-2 (1H)-one)
Method 1: in the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added acetophenone Tosylhydrazone
(0.30mmol, 86.4mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 33.2mg, yield 75% finally by column chromatography for separation purified product.It is molten
Point: 264-265 DEG C.Nuclear magnetic data:1H NMR(DMSO-d6 400MHz):δ11.89(brs,1H),7.50-7.56(m,4H),
7.45-7.47 (m, 2H), 7.35-7.41 (m, 2H), 7.10-7.14 (t, J=7.4Hz, 1H), 6.39 (s, 1H)13C NMR
(DMSO-d6 100MHz):δ115.8,118.3,121.2,121.8,126.1,128.6,128.7,130.5,136.7,
139.3,151.5,161.3. (referring to: Z.Zhang, L.-L.；Liao,S.-S.Yan,L.Wang,Y.-Q.He,J.-H.Ye,
J.Li,Y.-G.Zhi,D.-G.Yu,Angew.Chem.Int.Ed.2016,55,7068.)
Method 2: in the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added acetophenone Tosylhydrazone
(0.30mmol, 86.4mg), o-bromoaniline (0.2mmol, 34.2mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 30.9mg, yield 70% finally by column chromatography for separation purified product.
Method 3: in the Schlenk pipe that 20mL is handled through dehydration and deoxidation, acetophenone method 2: is firstly added to toluene sulphur
Acylhydrazone (0.30mmol, 86.4mg), adjacent Iodoaniline (0.2mmol, 43.8mg), palladium acetate (0.02mmol, 4.5mg), triphenyl
Phosphine (0.04mmol, 10.4mg), sodium tert-butoxide (1.2mmol, 115.2mg), 3.0mL diethylene glycol dimethyl ether (diglyme), most
The CO of 0.1MPa is injected into reaction tube afterwards2.It is small that the reaction tube being sealed is placed in heating stirring about 24 in 140 DEG C of oil bath pan
Shi Hou.Acidification is carried out to reaction solution using the hydrochloric acid solution that 1.5mL concentration is 1M, then is extracted with ethyl acetate (4mL × 5)
It takes, merges organic phase finally by column chromatography for separation purified product and be then dried to obtain white solid powder solid 31.9mg,
Yield 72%.
Method 4: in the Schlenk pipe that 20mL is handled through dehydration and deoxidation, acetophenone method 2: is firstly added to toluene sulphur
Acylhydrazone (0.30mmol, 86.4mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), tert-butyl alcohol lithium (1.2mmol, 96mg), 3.0mL diethylene glycol dimethyl ether (diglyme) are finally infused into reaction tube
Enter the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.Use 1.5mL
The hydrochloric acid solution that concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic phase, most
Afterwards by column chromatography for separation purified product, it is then dried to obtain white solid powder solid 25.6mg, yield 58%.
Method 5: in the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added acetophenone Tosylhydrazone
(0.30mmol, 86.4mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), Isosorbide-5-Nitrae-dioxane of sodium tert-butoxide (1.2mmol, 115.2mg), 3.0mL are finally injected into reaction tube
The CO of 0.1MPa2.The reaction tube being sealed is placed in 100 DEG C of oil bath pan after heating stirring about 24 hours.It is dense using 1.5mL
The hydrochloric acid solution that degree is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic phase, finally
By column chromatography for separation purified product, it is then dried to obtain white solid powder solid 27.0mg, yield 61%.
Embodiment 2: preparation 4- (p-methylphenyl) -2- (1H)-quinolinone (4- (4-Me-phenyl) quinolin-2 (1H) -
one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added melilotal Tosylhydrazone
(0.30mmol, 90.6mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 34.3mg, yield 73% finally by column chromatography for separation purified product.It is molten
Point: 248-249 DEG C.Nuclear magnetic data:1H NMR(CDCl3 400MHz):δ12.88(brs,1H),7.50-7.60(m,3H),
7.31-7.39(m,4H),7.14-7.18(m,1H),6.70(s,1H),2.46(s,3H).13C NMR(CDCl3 100MHz):δ
21.3,116.7,119.6,120.5,122.4,126.7,128.8,129.3,130.6,134.2,138.8,138.9,153.5,
164.3. (referring to: a) G.Battistuzzi, R.Bernini, S.Cacchi, I.Salve, G.Fabrizia,
Adv.Synth.Catal.2007,349,297；b)J.Wu,S.Xiang,J.Zeng,M.Leow,X.-W.Liu,
Org.Lett.2015,17,222.)
Embodiment 3: preparation 4- (p-methoxyphenyl) -2- (1H)-quinolinone (4- (4-OMe-phenyl) quinolin-2
(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added acetanisole Tosylhydrazone
(0.30mmol, 95.4mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 35.2mg, yield 70% finally by column chromatography for separation purified product.It is molten
Point: 264-265 DEG C.Nuclear magnetic data:1H NMR(CDCl3400MHz): δ 12.82 (brs, 1H), 7.62 (d, J=8.1Hz, 1H),
7.50-7.56 (m, 2H), 7.42 (d, J=8.7Hz, 2H), 7.15-7.19 (m, 1H), 7.04 (d, J=8.7Hz, 2H), 6.69
(s,1H),3.90(s,3H).13C NMR(CDCl3 100MHz):δ55.4,114.1,116.7,119.7,120.4,122.4,
126.7,129.4,130.2,130.6,139.0,153.1,160.1,164.3. (referring to: a) G.Battistuzzi,
R.Bernini,S.Cacchi,I.Salve,G.Fabrizia,Adv.Synth.Catal.2007,349,297；b)J.Wu,
S.Xiang,J.Zeng,M.Leow,X.-W.Liu,Org.Lett.2015,17,222.)
Embodiment 4: preparation 4- (o-tolyl) -2- (1H)-quinolinone (4- (o-Me-phenyl) quinolin-2 (1H) -
one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added o-methyl-benzene ethyl ketone Tosylhydrazone
(0.30mmol, 90.6mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 27.3mg, yield 58% finally by column chromatography for separation purified product.It is molten
Point: 235-236 DEG C.Nuclear magnetic data:1H NMR(DMSO-d6 300MHz):δ11.91(brs,1H),7.48-7.53(m,1H),
7.29-7.40(m,4H),7.18-7.20(m,1H),7.05-7.10(m,1H),6.90-6.93(m,1H),6.32(s,1H),
2.04(s,3H).13C NMR(CDCl3 100MHz):δ19.8,116.6,120.0,120.8,122.7,125.9,126.6,
128.6,128.9,130.2,130.7,135.6,136.6,138.5,153.6,164.4. mass spectrometric data: MS (EI): 235 (M+)；HRMS(ESI-TOF)m/z[M+Na]+Theoretical value: [C16H13NNaO]+258.0889 experiment value 258.0889.
Embodiment 5: preparation 4- (o-methoxyphenyl) -2- (1H)-quinolinone (4- (o-OMe-phenyl) quinolin-2
(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added o-methoxyacetophenone Tosylhydrazone
(0.30mmol, 95.4mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 30.6mg, yield 61% finally by column chromatography for separation purified product.It is molten
Point: 258-260 DEG C.Nuclear magnetic data:1H NMR(CDCl3 300MHz):δ12.89(brs,1H),7.44-7.55(m,3H),
7.24-7.28(m,2H),7.03-7.13(m,3H),6.70(s,1H),3.74(s,3H).13C NMR(CDCl3 75MHz):δ
55.5,110.0,116.5,120.0,120.7,121.5,122.2,126.0,126.8,130.2,130.3,130.5,138.4,
151.0,156.5,164.5. mass spectrometric data: MS (EI): 251 (M+)；HRMS(ESI-TOF)m/z[M+Na]+Theoretical value
[C16H13NNaO2]+274.0838 calculated value 274.0836.
Embodiment 6: preparation 4- (2- naphthalene) -2- (1H)-quinolinone (4- (naphthalen-2-yl) quinolin-2
(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added 2- acetonaphthone Tosylhydrazone
(0.30mmol, 101.4mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 24.9mg, yield 46% finally by column chromatography for separation purified product.It is molten
Point: 274-275 DEG C.Nuclear magnetic data:1H NMR(DMSO-d6 300MHz):δ11.93(brs,1H),8.01-8.09(m,4H),
7.52-7.62(m,4H),7.41-7.44(m,2H),7.11-7.17(m,1H),6.51(s,1H).13C NMR(DMSO-d6
75MHz):δ115.9,118.5,121.6,122.0,126.3,126.5,126.8,126.9,127.7,127.9,128.2,
128.3,130.7,132.7,132.8,134.3,139.4,151.5,161.4. mass spectrometric data: MS (EI): 271 (M+)；HRMS
(ESI-TOF)m/z[M+Na]+Theoretical value [C19H13NNaO]+294.0889 experiment value 294.0883.
Embodiment 7: preparation 4- (rubigan) -2- (1H)-quinolinone (4- (p-Cl-phenyl) quinolin-2 (1H) -
one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added parachloroacetophenone Tosylhydrazone
(0.30mmol, 96.6mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 31.6mg, yield 62% finally by column chromatography for separation purified product.It is molten
Point: 236-237 DEG C.Nuclear magnetic data:1H NMR(DMSO-d6 400MHz):δ11.91(brs,1H),7.58-7.60(m,2H),
7.49-7.55 (m, 3H), 7.39-7.41 (m, 1H), 7.33-7.35 (m, 1H), 7.13 (t, J=7.3Hz 1H), 6.41 (s,
1H).13C NMR(DMSO-d6 100MHz):δ115.8,118.1,121.5,122.0,126.0,128.7,130.6,130.7,
133.6,135.5,139.3,150.2,161.2. (referring to: a) G.Battistuzzi, R.Bernini, S.Cacchi,
I.Salve,G.Fabrizia,Adv.Synth.Catal.2007,349,297；b)J.Wu,S.Xiang,J.Zeng,M.Leow,
X.-W.Liu,Org.Lett.2015,17,222.)
Embodiment 8: preparation 4- (to cyano-phenyl) -2- (1H)-quinolinone (4- (p-CN-phenyl) quinolin-2
(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added 4-Acetylbenzonitrile Tosylhydrazone
(0.30mmol, 96.6mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 34.9mg, yield 71% finally by column chromatography for separation purified product.It is molten
Point: 252-254 DEG C.Nuclear magnetic data:1H NMR(DMSO-d6300MHz): δ 11.98 (brs, 1H), 8.02 (d, J=8.3Hz,
2H), 7.70 (d, J=8.4Hz, 2H), 7.52-7.55 (m, 1H), 7.41 (d, J=7.6Hz, 1H), 7.27 (d, J=7.1Hz,
1H),7.12-7.17(m,1H),6.46(s,1H).13C NMR(DMSO-d6 75MHz):δ111.6,115.9,117.8,
118.6,121.8,122.1,125.9,129.9,130.9,132.7,139.3,141.4,14 9.8,161.1. (referring to:
K.Inamoto,T.Saito,K.Hiroya,T.Doi,J.Org.Chem.2010,75,3900.)
Embodiment 9: preparation 3- methyl -4- (phenyl) -2- (1H)-quinolinone (3-Me-4-phenylquinolin-2
(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added propiophenone Tosylhydrazone
(0.30mmol, 90.6mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 33.4mg, yield 71% finally by column chromatography for separation purified product.It is molten
Point: 238-240 DEG C.Nuclear magnetic data:1H NMR(CDCl3 300MHz):δ12.60(brs,1H),7.42-7.56(m,5H),
7.24-7.28(m,2H),7.03-7.10(m,2H),2.10(s,3H).13C NMR(CDCl3 75MHz):δ14.3,115.9,
121.0,122.1,126.7,127.4,127.9,128.6,128.8,129.2,137.0,13 7.1,148.8,164.6. (ginseng
See: (a) K.Park, J.Lee, Tetrahedron 2004,60,2993；b)K.Kim,H.Lee,J.Kim Tetrahedron
Lett.2009,50,1249.)
Embodiment 10: preparation 3,4- diphenyl -2- (1H)-quinolinone (3,4-diphenylquinolin-2 (1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added diphenylethan Tosylhydrazone
(0.30mmol, 109.2mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 33.3mg, yield 56% finally by column chromatography for separation purified product.It is molten
Point: 249-251 DEG C.Nuclear magnetic data:1H NMR(DMSO-d6 300MHz):δ12.09(brs,1H),7.48-7.54(m,1H),
7.39-7.42(m,1H),7.25-7.33(m,3H),7.06-7.17(m,8H),6.99-7.00(m,1H).13C NMR(DMSO-
d6 75MHz):δ115.2,119.9,121.8,126.6,126.9,127.1,127.5,128.0,129.5,130.2,130.7,
132.0,135.7,136.1,138.3,148.1,161.2. mass spectrometric data: MS (EI): 297 (M+)；HRMS(ESI-TOF)m/z
[M+Na]+Theoretical value [C21H15NNaO]+320.1046 experiment value 320.1044.
Embodiment 11: preparation 7,8- dihydrobenzo [k] phenanthridines -6- (5H) ketone (7,8-dihydrobenzo [k]
phenanthridin-6(5H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added 1-tetralone Tosylhydrazone
(0.30mmol, 94.2mg), adjacent Iodoaniline (0.2mmol, 43.8mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 29.6mg, yield 60% finally by column chromatography for separation purified product.It is molten
Point: 235-238 DEG C.Nuclear magnetic data:1H NMR(CDCl3300MHz): δ 12.65 (brs, 1H), 8.16 (d, J=8.1Hz, 1H),
7.85-7.87(m,1H),7.47-7.58(m,2H),7.33-7.42(m,3H),7.20-7.25(m,1H),2.82-2.93(m,
4H).13C NMR(CDCl3 75MHz):δ21.9,28.4,116.8,117.8,122.1,126.0,126.1,128.2,128.3,
129.0,129.2,129.4,131.8,138.1,140.3,142.5,163.5. mass spectrometric data: MS (EI): 247 (M+)；HRMS
(ESI-TOF)m/z[M+Na]+Theoretical value [C17H13NNaO]+270.0889 experiment value 270.0885.
Embodiment 12: preparation 6- methyl 4-phenyl -2- (1H)-quinolinone (6-methyl-4-phenylquinolin-2
(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added acetophenone Tosylhydrazone
(0.30mmol, 86.4mg), 2- iodine 4- methylaniline (0.2mmol, 46.6mg), bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 30.5mg, yield 65% finally by column chromatography for separation purified product.It is molten
Point: 238-241 DEG C.Nuclear magnetic data:1H NMR(CDCl3 300MHz):δ12.85(brs,1H),7.45-7.55(m,6H),
7.32-7.37(m,2H),6.68(s,1H),2.33(s,3H).13C NMR(CDCl3 75MHz):δ21.1,116.6,119.5,
120.7,126.1,128.6,128.7,128.8,132.1,132.2,136.9,137.3,15 3.2,164.1. mass spectrometric data: MS
(EI):235(M+)；HRMS(ESI-TOF)m/z[M+Na]+Theoretical value [C16H13NNaO]+258.0889 experiment value 258.0888.
Embodiment 13: preparation chloro- 4- phenyl -2- (1H)-quinolinone (7-chloro-4-phenylquinolin-2 of 7-
(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added acetophenone Tosylhydrazone
(0.30mmol, 86.4mg), the chloro- 2- Iodoaniline (0.2mmol, 50.6mg) of 5-, bis-triphenylphosphipalladium palladium dichloride (0.02mmol,
14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally into reaction tube
Inject the CO of 0.1MPa2.The reaction tube being sealed is placed in 140 DEG C of oil bath pan after heating stirring about 24 hours.It uses
The hydrochloric acid solution that 1.5mL concentration is 1M carries out acidification to reaction solution, then is extracted with ethyl acetate (4mL × 5), merges organic
Then phase is dried to obtain white solid powder solid 31.1mg, yield 61% finally by column chromatography for separation purified product.It is molten
Point: 225-227 DEG C.Nuclear magnetic data:1H NMR(CDCl3 300MHz):δ12.73(brs,1H),7.43-7.55(m,7H),
7.11-7.15(m,1H),6.69(s,1H).13C NMR(DMSO-d6 75MHz):δ114.9,117.3,121.5,122.0,
128.1,128.7,128.8,129.0,135.0,136.3,140.2,151.0,161.2. mass spectrometric data: MS (EI): 255 (M+)；HRMS(ESI-TOF)m/z[M+Na]+Theoretical value [C15H10ClNNaO]+278.0343 experiment value 278.0342.
Embodiment 14: preparation fluoro- 4- phenyl -2- (1H)-quinolinone (6-chloro-8-fluoro-4- of the chloro- 8- of 6-
phenylquinolin-2(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added acetophenone Tosylhydrazone
(0.30mmol, 86.4mg), the fluoro- 6- Iodoaniline (0.2mmol, 54.2mg) of the chloro- 2- of 4-, bis-triphenylphosphipalladium palladium dichloride
(0.02mmol, 14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally
The CO of 0.1MPa is injected into reaction tube2.The reaction tube being sealed is placed in heating stirring about 24 hours in 140 DEG C of oil bath pan
Afterwards.Acidification is carried out to reaction solution using the hydrochloric acid solution that 1.5mL concentration is 1M, then is extracted with ethyl acetate (4mL × 5),
Merge organic phase and is then dried to obtain white solid powder solid 29.5mg, yield finally by column chromatography for separation purified product
54%.Fusing point: 233-235 DEG C.Nuclear magnetic data:1H NMR(CDCl3 300MHz):δ10.84(brs,1H),7.52-7.55(m,
3H),7.41-7.44(m,2H),7.31-7.34(m,2H),6.73(s,1H).13C NMR(CDCl3 75MHz):δ116.5(d,J
=20.5Hz), 121.8 (d, J=3.3Hz), 122.0 (d, J=3.8Hz), 123.5,126.8 (d, J=8.4Hz), 127.0,
(128.6,128.9,129.4,135.9,149.5 d, J=248Hz), 151.8 (d, J=2.8Hz), 162.0. mass spectrometric data: MS
(EI):273(M+)；HRMS(ESI-TOF)m/z[M+Na]+Theoretical value [C15H9ClFNNaO]+296.0249, experiment value
296.0247.
Embodiment 15: preparation 6- nitro -4- phenyl -2- (1H)-quinolinone (6-nitro-4-phenylquinolin-2
(1H)-one)
In the Schlenk pipe that 20mL is handled through dehydration and deoxidation, it is firstly added acetophenone Tosylhydrazone
(0.30mmol, 86.4mg), the iodo- 4- nitroaniline (0.2mmol, 52.8mg) of 2-, bis-triphenylphosphipalladium palladium dichloride
(0.02mmol, 14.0mg), sodium tert-butoxide (1.2mmol, 115.2mg) 3.0mL diethylene glycol dimethyl ether (diglyme), finally
The CO of 0.1MPa is injected into reaction tube2.The reaction tube being sealed is placed in heating stirring about 24 hours in 140 DEG C of oil bath pan
Afterwards.Acidification is carried out to reaction solution using the hydrochloric acid solution that 1.5mL concentration is 1M, then is extracted with ethyl acetate (4mL × 5),
Merge organic phase and is then dried to obtain white solid powder solid 23.9mg, yield finally by column chromatography for separation purified product
45%.Fusing point: 261-263 DEG C.Nuclear magnetic data:1H NMR(DMSO-d6300MHz): δ 12.47 (brs, 1H), 8.36 (dd, J=
2.5Hz, J=9.1Hz, 1H), 8.19 (d, J=2.5Hz, 1H), 7.51-7.61 (m, 6H), 6.59 (s, 1H)13C NMR
(DMSO-d6 75MHz):δ116.9,117.9,122.4,123.0,125.4,128.8,129.0,129.4,135.5,141.5,
143.8,151.1,161.4. mass spectrometric data: MS (EI): 266 (M+)；HRMS(ESI-TOF)m/z[M+Na]+Theoretical value
[C15H10N2NaO3]+289.0584 experiment value 289.0577.
Claims (3)
1. a kind of method for preparing 4- aryl -2- quinolinone by carbon dioxide, it is characterised in that carry out as steps described below:
(1) in the reaction tube handled through dehydration and deoxidation, N- Tosylhydrazone, adjacent halogenated aniline, palladium are added by a certain percentage
Above-mentioned reaction tube is placed in heating stirring 24 hours in oil bath under 0.1 MPa carbon dioxide atmosphere by salt, alkali and solvent；
(2) reaction is terminated, acidification is carried out to reaction solution using the hydrochloric acid solution of 1 M first, then be extracted with ethyl acetate out
Then organic phase in system is dried to obtain 4- aryl -2- quinolinone compounds finally by column chromatography for separation purified product；
The N- Tosylhydrazone, chemical structural formula are as follows:
；
Wherein, the substituent R on aromatic ring1, R2Selected from H, Cl, Br, CF3, OMe, CN, one of Me, the length n of carbochain be 1 ~
5；
The adjacent halogenated aniline, its structural features are as follows:
；
Wherein, the substituent R on aromatic ring is selected from F, Cl, OMe, CN, NO2, one of Me；X is selected from I, one of Br；
The palladium salt is palladium acetate, bis-triphenylphosphipalladium palladium dichloride, palladium chloride, tetra-triphenylphosphine palladium, bis- (dibenzyl subunits third
One of ketone) palladium；
The alkali is one of tert-butyl alcohol lithium, sodium tert-butoxide；
Solvent for use is diethylene glycol dimethyl ether, one of Isosorbide-5-Nitrae-dioxane.
2. a kind of method for preparing 4- aryl -2- quinolinone by carbon dioxide according to claim 1, it is characterised in that:
In reaction system, the dosage of palladium salt is 10 mmol% relative to adjacent halogenated aniline；The dosage of alkali is relative to adjacent halogenated aniline 6
Equivalent.
3. a kind of method for preparing 4- aryl -2- quinolinone by carbon dioxide according to claim 1, it is characterised in that:
The pressure of carbon dioxide is 0.1 MPa；Reaction temperature is 100~140 DEG C, and is no more than the boiling point of solvent；The dosage of solvent is 3
mL。
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| CN105524108A (en) * | 2016-01-20 | 2016-04-27 | 北京大学 | Preparation method of 1,1,3-tri-substituted divinyl dimethyl phosphate compound |
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| CN105524108A (en) * | 2016-01-20 | 2016-04-27 | 北京大学 | Preparation method of 1,1,3-tri-substituted divinyl dimethyl phosphate compound |
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| Palladium-Catalyzed Multi-Component Reactions of N-Tosylhydrazones, 2-Iodoanilines and CO2 towards 4-Aryl-2-Quinolinones;Song Sun et al.;《Chem.Eur.J.》;20161117;第22卷;18729-18732 |
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