CN108752299A - A kind of preparation method of 3- benzofuranones - Google Patents
A kind of preparation method of 3- benzofuranones Download PDFInfo
- Publication number
- CN108752299A CN108752299A CN201810788299.XA CN201810788299A CN108752299A CN 108752299 A CN108752299 A CN 108752299A CN 201810788299 A CN201810788299 A CN 201810788299A CN 108752299 A CN108752299 A CN 108752299A
- Authority
- CN
- China
- Prior art keywords
- benzofuranones
- preparation
- nmr
- added
- cdcl
- 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.)
- Granted
Links
- MGKPCLNUSDGXGT-UHFFFAOYSA-N 1-benzofuran-3-one Chemical class C1=CC=C2C(=O)COC2=C1 MGKPCLNUSDGXGT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 claims abstract description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 4
- 150000002989 phenols Chemical class 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 5
- -1 tert-butyl-phenyl Chemical group 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- IPWFJLQDVFKJDU-UHFFFAOYSA-N pentanamide Chemical compound CCCCC(N)=O IPWFJLQDVFKJDU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001311 chemical methods and process Methods 0.000 claims 1
- 239000012453 solvate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- XNERWVPQCYSMLC-UHFFFAOYSA-N phenylpropiolic acid Chemical compound OC(=O)C#CC1=CC=CC=C1 XNERWVPQCYSMLC-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 238000010898 silica gel chromatography Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- 239000011734 sodium Substances 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IRMBDCYYTAHADK-UHFFFAOYSA-N ClOC1=C(C=CC=C1)C(C(=O)C1=C(C=CC=C1)OCl)=O Chemical compound ClOC1=C(C=CC=C1)C(C(=O)C1=C(C=CC=C1)OCl)=O IRMBDCYYTAHADK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- OTAFHZMPRISVEM-UHFFFAOYSA-N chromone Chemical compound C1=CC=C2C(=O)C=COC2=C1 OTAFHZMPRISVEM-UHFFFAOYSA-N 0.000 description 2
- QCPORYSHAZPBCG-UHFFFAOYSA-N n-phenoxyacetamide Chemical class CC(=O)NOC1=CC=CC=C1 QCPORYSHAZPBCG-UHFFFAOYSA-N 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 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
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- PSWDQTMAUUQILQ-UHFFFAOYSA-N 2-[(6-methoxy-4-methylquinazolin-2-yl)amino]-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound N1=C(C)C2=CC(OC)=CC=C2N=C1NC1=NC(=O)C(C)=C(C)N1 PSWDQTMAUUQILQ-UHFFFAOYSA-N 0.000 description 1
- QMPOHKDJNKTEHF-UHFFFAOYSA-N 2-phenyl-2,3-dihydro-1-benzofuran Chemical class O1C2=CC=CC=C2CC1C1=CC=CC=C1 QMPOHKDJNKTEHF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000486679 Antitype Species 0.000 description 1
- 0 CC(*)=CC=C(C)Br Chemical compound CC(*)=CC=C(C)Br 0.000 description 1
- PXJCOBVKRKKWQL-UHFFFAOYSA-N CC(NOc(cc1)ccc1F)=O Chemical compound CC(NOc(cc1)ccc1F)=O PXJCOBVKRKKWQL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125796 compound 3d Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 244000000059 gram-positive pathogen Species 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 241000712461 unidentified influenza virus Species 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans 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 carbon atoms of the hetero ring
- C07D307/83—Oxygen atoms
Abstract
The invention discloses a kind of preparation methods for the 3- benzofuranones for belonging to technical field of organic synthesis.The method is：Phenol derivatives (0.2mmol, 30mg), phenylpropiolic acid (0.2mmol, 29mg), 5% rhodium catalyst, cobalt acetate hydrate, pivalic acid sodium hydrate, methanol 1.0mL are added in 15mL heavy wall pressure pipes, it is open to stir 12 hours at room temperature, after completion of the reaction, with the isolated pure target product of silica gel column chromatography.The preparation method of 3- benzofuranones provided by the present invention has the characteristics that scientific and reasonable, mild condition, easy to operate, the reaction time is short.Its reaction equation is as follows：
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of preparation side of 3- benzofuranones
Method.
Background technology
3- benzofuran ketone compounds have good physiological activity, this heterocyclic compounds and its derivative can conducts
Antioxidant (J.Agric.Food Chem.2006,54,3551.), anti-Type B influenza virus (Eur.J.Med.Chem.2013,
62,534.), the potent antibiotics (Chem.Eur.J.2012,18,16123.) and antibacterials of gram positive pathogens
(Bioorg.Med.Chem.Lett.2012,22,6292.), in view of 3- benzofuran ketone compounds extensive bioactivity and answer
With value, a kind of synthesize 3- benzofuranones new method with developing practicability and effectiveness is of great significance.
The preparation method of 3- benzofuranones has：
1) using Chloro-O-Phenyl diketone and phenyl boric acid as raw material
Seminar of Xu Ming China has developed a kind of using Chloro-O-Phenyl diketone and phenyl boric acid as raw material, [Rh (COE)2Cl]2、Pd
(OAc)2Make catalyst, K3PO4Make alkali, toluene makees solvent, prepare 3- benzofuranone derivatives (Org.Lett.2017,19,
2726)。
2) using 3- hydroxyls chromone and alkynes as raw material
Sanjib Gogoi seminars are using 3- hydroxyls chromone and alkynes as raw material, [RuCl2(p-cymene)2] make catalyst,
PPh3 makees ligand, tert-pentyl alcohol makees solvent, preparation 3- benzofuranone derivatives (Angew.Chem.Int.Ed.2018,57,
456)。
3) using beta naphthal and acetophenone as raw material
Wu Anxin seminars are using beta naphthal and acetophenone as raw material, and iodine makees catalyst, DMSO makees solvent, 100 degrees Celsius
Under the conditions of reacted, prepare 3- benzofuranone derivatives (Org.Lett.2014,16,1732).
3- benzofuranones are synthesized using the above method, are had certain disadvantages and insufficient：1) nitrogen is needed
Protection；2) cumbersome；3) reaction time is long.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of preparations of 3- benzofuranones
Method.
1. a kind of preparation method of 3- benzofuranones, the 3- benzofuranones have Formulas I
Shown in structure：
In Formulas I, wherein R1Selected from hydrogen, 5- methyl, 6- methyl, 7- methyl, 5- fluorine, 5- chlorine, 5- trifluoromethyls；R2Selected from second
Amide groups, n-valeramide base；R3Selected from phenyl, to tert-butyl-phenyl, p-methoxyphenyl；；It is characterized in that, into reactor
It is 1 that molar ratio, which is added,：5% rhodium catalyst, cobalt acetate hydrate, the hydration of pivalic acid sodium is added in 1 phenol derivatives and propiolic acid
Object is added the solvent of one of methanol, 1,2- dichloroethanes, tertriary amylo alcohol, hexafluoroisopropanol, is stirred to react at room temperature, reactional equation
Formula is as follows：
Beneficial effects of the present invention are：The synthetic method science of 3- benzofuranones provided by the invention is closed
Reason provides a kind of new way of a variety of substituent group 3- benzofuranones of synthesis；But also it is easy to get, grasps with raw material
Make the features such as simple, reaction condition is mild, the reaction time is short.
Description of the drawings
Fig. 1 is the NMR spectra of compound 3a prepared by embodiment 1；
Fig. 2 is the NMR spectra of compound 3d prepared by embodiment 4；
Fig. 3 is the NMR spectra of compound 3e prepared by embodiment 5.
Specific implementation mode
The present invention is described in more detail with specific embodiment below in conjunction with the accompanying drawings：
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
The preparation of 3- benzofuranones 3a
By N- phenoxy-acetamides (0.2mmol, 30mg), phenylpropiolic acid (0.2mmol, 29mg), 5% rhodium catalyst, vinegar
Sour cobalt hydrate, pivalic acid sodium hydrate, methanol 1.0mL are added in 15mL heavy wall pressure pipes, and open stirring 12 at room temperature is small
When.After completion of the reaction, N- (3- oxos-are obtained through column chromatography for separation (200-300 mesh silica gel) (petrol ether/ethyl acetate=4/1)
2- phenyl -2,3- Dihydrobenzofuranes -2- bases) acetamide 3a (0.184mmol, 49mg), detach yield 92%.
Spectrum elucidation data 3a:
1H NMR(500MHz,CDCl3):δ7.69-7.68(m,2H),7.63-7.59(m,2H),7.37-7.36(m,2H),
7.16 (d, J=8.15Hz, 1H), 7.07 (t, J=7.35Hz, 1H), 6.56 (s, 1H), 1.95 (s, 1H)13C NMR
(125MHz,CDCl3):δ194.7,170.0,169.4,137.8,134.4,129.7,128.9,125.6,125.1,122.3,
119.8,112.2,91.5,22.3.HRMS(ESI-TOF,[M+Na]+):calcd for C16H13NO3Na,290.0793,
found 290.0796.
Embodiment 2
The 1a in example 1 is replaced with 1b, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3b:
1H NMR(500MHz,CDCl3):δ7.70(brs,2H),7.44-7.38(m,5H),7.08-7.07(m,2H),
6.96(brs,1H),6.50(s,1H),2.32(s,3H),2.00(s,3H).13C NMR(125MHz,CDCl3):δ194.9,
169.8,167.8,138.9,134.6,132.0,129.6,128.9,125.6,124.6,119.6,111.9,91.7,22.4,
20.6.HRMS(ESI-TOF,[M+Na]+):calcd for C17H15NO3Na,304.0950,found 304.0951.
Embodiment 3
The 1a in example 1 is replaced with 1c, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3c:
1H NMR(500MHz,CDCl3):δ 7.71-7.69 (m, 2H), 7.52 (d, J=7.8Hz, 1H), 7.38-7.37 (m,
3H), 6.98 (s, 1H), 6.90 (d, J=7.8Hz, 1H), 6.51 (s, 1H), 2.43 (s, 3H), 1.99 (s, 3H)13C NMR
(125MHz,CDCl3):δ194.1,169.9,169.8,149.8,134.8,129.6,128.9,125.5,124.8,123.8,
117.4,112.4,91.8,22.5,22.4.HRMS(ESI-TOF,[M+Na]+):calcd for C17H15NO3Na,
304.0950,found 304.0952.
Embodiment 4
The 1a in example 1 is replaced with 1d, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3d:
1H NMR(500MHz,CDCl3):δ 7.71-7.70 (m, 2H), 7.47 (d, J=7.5Hz, 1H), 7.43 (d, J=
7.3Hz, 1H), 7.39-7.38 (m, 3H), 6.98 (t, J=7.4Hz, 1H), 6.46 (s, 1H), 2.43 (s, 3H), 2.03 (s,
3H).13C NMR(125MHz,CDCl3):δ195.1,169.7,168.1,138.4,134.7,129.7,128.9,125.5,
122.3,122.2,122.1,119.2,91.4,22.5,24.4.HRMS(ESI-TOF,[M+H]+):calcd for
C17H16NO3Na,282.1130,found 282.1133.
Embodiment 5
The 1a in example 1 is replaced with 1e, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3e:
1H NMR(500MHz,CDCl3):δ7.70-7.68(m,2H),7.44-7.39(m,1H),7.41-7.39(m,3H),
7.34 (td, J=8.8,2.8Hz, 1H), 7.29 (dd, J=6.6,2.7Hz, 1H), 7.14 (dd, J=8.9,3.6Hz, 1H),
6.52(s,1H),2.02(s,3H).13C NMR(125MHz,CDCl3):δ194.2,169.9,165.4,157.9(1JC-F=
242.8Hz),134.0,129.9,129.1,125.6,125.1(2JC-F=25.8Hz), 120.4 (3JC-F=7.2Hz), 113.4
(3JC-F=7.0Hz), 110.4 (2JC-F=24.0Hz), 92.5,22.3.HRMS (ESI-TOF, [M+Na]+):calcd for
C16H12NO3FNa,308.0699,found308.0697.
Embodiment 6
The 1a in example 1 is replaced with 1f, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3f:
1H NMR(500MHz,CDCl3):δ7.66(brs,2H),7.57-7.55(m,2H),7.39(brs,3H),7.13
(d, J=8.3,1H), 6.64 (s, 1H), 1.96 (s, 3H)13C NMR(125MHz,CDCl3):δ193.5,169.9,167.6,
137.4,133.6,129.9,129.1,127.7,125.5,124.6,121.0,113.6,92.3,22.3.HRMS(ESI-TOF,
[M+Na]+):calcd for C16H12NO3ClNa,324.0403,found 324.0407.
Embodiment 7
The 2a in example 1 is replaced with 2b, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3g:
1H NMR(500MHz,CDCl3):δ 7.63-7.59 (m, 4H), 7.40 (d, J=8.3Hz, 2H), 7.16 (d, J=
8.3Hz, 1H), 7.06 (t, J=7.4Hz, 1H), 6.60 (s, 1H), 1.94 (s, 3H), 1.28 (s, 9H)13C NMR(125MHz,
CDCl3):δ194.9,169.8,169.5,152.9,137.7,131.4,125.9,125.3,125.1,122.2,119.9,
112.3,91.5,34.6,31.1,26.9,22.3.HRMS(ESI-TOF,[M+Na]+):calcd for C20H21NO3Na,
346.1419,found 346.1419.
Embodiment 8
The 1a in example 1 is replaced with 1h, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3h:
1H NMR(500MHz,CDCl3):δ 7.91 (s, 1H), 7.85 (d, J=8.6Hz, 2H), 7.68-7.67 (m, 3H),
7.40-7.39(m,3H),7.25(s,1H),6.58(s,1H),2.01(s,3H).13C NMR(125MHz,CDCl3):δ193.2,
170.8,170.0,134.4,133.5,130.0,129.1,125.5,125.0(q,2JC-F=33.6Hz), 123.6 (q,1JC-F=
271.9Hz),122.9,120.2,112,9,92.6,22.2.HRMS(ESI-TOF,[M+Na]+):calcd for
C17H12F3NO3Na,358.0667,found 358.0665.
Embodiment 9
The 1a in example 1 is replaced with 1i, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3i:
1H NMR(500MHz,CDCl3):δ7.70-7.69(m,2H),7.63-7.59(m,2H),7.38-7.37(m,3H),
7.17 (d, J=8.2Hz, 1H), 7.07 (t, J=7.4Hz, 1H), 6.53 (s, 1H), 2.27-2.15 (m, 2H), 1.60-1.53
(m, 2H), 1.37-1.30 (m, 2H), 0.89 (t, J=7.3Hz, 3H)13C NMR(125MHz,CDCl3):δ194.7,173.0,
169.4,137.7,134.6,129.6,128.9,125.6,125.1,122.3,119.9,112.3,91.6,35.1,26.9,
22.1,13.7.HRMS(ESI-TOF,[M+Na]+):calcd for C19H19NO3Na,332.1263,found 332.1266.
Embodiment 10
The 2a in example 1 is replaced with 2c, for other conditions with example 1, experimental result is shown in Table 1.
Spectrum elucidation data 3j:
1H NMR(500MHz,CDCl3):δ 7.64-7.59 (m, 4H), 7.15 (d, J=8.3Hz, 1H), 7.07 (t, J=
7.4Hz, 1H), 6.89 (d, J=8.7Hz, 2H), 6.50 (s, 1H), 3.78 (s, 3H), 1.99 (s, 3H)13C NMR(125MHz,
CDCl3):δ194.9,169.9,169.3,160.7,137.7,127.0,126.2,125.1,122.2,119.9,114.3,
112.2,91.4,55.3,22.3.HRMS(ESI-TOF,[M+Na]+):calcd for C17H15NO4Na,320.0899,found
320.0899.
Table 1
Claims (2)
1. a kind of preparation method of 3- benzofuranones, the 3- benzofuranones have shown in Formulas I
Structure：
In Formulas I, wherein R1Selected from hydrogen, 5- methyl, 6- methyl, 7- methyl, 5- fluorine, 5- chlorine, 5- trifluoromethyls；R2Selected from acetamide
Base, n-valeramide base；R3Selected from phenyl, to tert-butyl-phenyl, p-methoxyphenyl；It is characterized in that, being added into reactor
Molar ratio is 1：5% rhodium catalyst, cobalt acetate hydrate, pivalic acid sodium hydrate is added in 1 phenol derivatives and propiolic acid,
The solvent of one of methanol, 1,2- dichloroethanes, tertriary amylo alcohol, hexafluoroisopropanol is added, is stirred to react at room temperature, chemical process is shown in
Reaction equation II：
2. preparation method described in accordance with the claim 1, it is characterised in that：5% rhodium catalyst, cobalt acetate hydrate, pivalic acid
Sodium hydrate reacts at room temperature 12h in methanol solvate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810788299.XA CN108752299B (en) | 2018-07-18 | 2018-07-18 | A kind of preparation method of 3- benzofuranones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810788299.XA CN108752299B (en) | 2018-07-18 | 2018-07-18 | A kind of preparation method of 3- benzofuranones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108752299A true CN108752299A (en) | 2018-11-06 |
| CN108752299B CN108752299B (en) | 2019-09-27 |
Family
ID=63970492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810788299.XA Active CN108752299B (en) | 2018-07-18 | 2018-07-18 | A kind of preparation method of 3- benzofuranones |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108752299B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851599A (en) * | 2019-03-19 | 2019-06-07 | 青岛科技大学 | A kind of preparation method of 2- aminobenzofuran compounds |
| CN111100101A (en) * | 2019-12-23 | 2020-05-05 | 浙江万里学院 | Catalytic synthesis method of 3-benzofuranone compounds |
| CN112410807A (en) * | 2020-11-18 | 2021-02-26 | 青岛科技大学 | Preparation method of tetra-substituted sulfonated vinyl ether under electrocatalysis |
| CN114044771A (en) * | 2021-10-18 | 2022-02-15 | 成都大学 | Compound with 5-hydroxyfuran-2 (5H) -ketone skeleton and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047177A (en) * | 2017-12-19 | 2018-05-18 | 江苏欣诺科催化剂有限公司 | The method of one-step synthesis benzofurans β-dehydrogenation alpha-non-natural amino acid |
-
2018
- 2018-07-18 CN CN201810788299.XA patent/CN108752299B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047177A (en) * | 2017-12-19 | 2018-05-18 | 江苏欣诺科催化剂有限公司 | The method of one-step synthesis benzofurans β-dehydrogenation alpha-non-natural amino acid |
Non-Patent Citations (3)
| Title |
|---|
| WEN-KUI YUAN等: "Construction of Benzofuran-3(2H)-one Scaffolds with a Quaternary Center via Rh/Co Relay Catalyzed C-H Functionalization/Annulation of N-Aryloxyacetamides and Propiolic Acids", 《ORG. LETT.》 * |
| YANG LI等: "Rhodium(III)-Catalyzed Redox-Neutral C-H Activation/Annulation of N-Aryloxyacetamides with Alkynyloxiranes: Synthesis of Highly Functionalized 2,3-Dihydrobenzofurans", 《J. ORG. CHEM.》 * |
| ZHI ZHOU等: "Cascade Synthesis of 3-Alkylidene Dihydrobenzofuran Derivatives via Rhodium(III)-Catalyzed Redox-Neutral C-H Functionalization/Cyclization", 《ORG. LETT.》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851599A (en) * | 2019-03-19 | 2019-06-07 | 青岛科技大学 | A kind of preparation method of 2- aminobenzofuran compounds |
| CN109851599B (en) * | 2019-03-19 | 2022-03-08 | 青岛科技大学 | Preparation method of 2-aminobenzofuran compound |
| CN111100101A (en) * | 2019-12-23 | 2020-05-05 | 浙江万里学院 | Catalytic synthesis method of 3-benzofuranone compounds |
| CN111100101B (en) * | 2019-12-23 | 2022-11-11 | 浙江万里学院 | Catalytic synthesis method of 3-benzofuranone compounds |
| CN112410807A (en) * | 2020-11-18 | 2021-02-26 | 青岛科技大学 | Preparation method of tetra-substituted sulfonated vinyl ether under electrocatalysis |
| CN112410807B (en) * | 2020-11-18 | 2022-05-20 | 青岛科技大学 | Preparation method of tetra-substituted sulfonated vinyl ether under electrocatalysis |
| CN114044771A (en) * | 2021-10-18 | 2022-02-15 | 成都大学 | Compound with 5-hydroxyfuran-2 (5H) -ketone skeleton and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108752299B (en) | 2019-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108752299B (en) | A kind of preparation method of 3- benzofuranones | |
| CN111205279B (en) | Polysubstituted benzodihydrofuran heterocyclic compound and preparation method and application thereof | |
| CN109942364B (en) | Olefin synthesis method using water as hydrogen source | |
| CN105175328B (en) | It is a kind of using aromatic amine, aromatic aldehyde, ketone synthesis of quinoline derivatives method | |
| CN108373453B (en) | Triazole derivative and preparation method thereof | |
| CN108440384B (en) | Process for the preparation of trifluoromethylated derivatives of isoindolones | |
| CN109879792B (en) | Polysubstituted isoindole compound and preparation method thereof | |
| Kong et al. | Synthesis of spiro dienones from internal acetylene and cyclic 3-iodo enones in the presence of nickel bromide and zinc powder | |
| CN108727385A (en) | A kind of preparation method of polysubstituted dihydro-pyrimidin diindyl ketone derivatives | |
| CN108191735A (en) | The method for the polysubstituted indoles of ketones with Enamino-esters Cyclization that iodine promotes | |
| CN110734354B (en) | Method for preparing biaryl compound from alcohol compound | |
| CN109678862A (en) | A kind of preparation method of polysubstituted diphenylethyllene indole derivatives | |
| CN105198806A (en) | Method for synthesizing quinoline by aromatic amine and diketone | |
| CN111138299A (en) | Solvent-free green synthesis method of triarylmethane compound | |
| CN107954960B (en) | Synthetic method of 1,3-dihydroisobenzofuran compound | |
| CN113956232B (en) | Quinoline-bisindole compound and preparation method and application thereof | |
| CN114031577B (en) | 2H-benzothiazole C2-aryl acylation method | |
| CN110256349B (en) | Polysubstituted pyrazoles and process for their preparation | |
| CN112209866B (en) | Method for preparing 1-tertiary butyl-3, 3-dimethyl indoline compound | |
| CN108546244B (en) | Synthetic method of 3, 3' -diindolylethane compound | |
| CN114988978B (en) | Novel method for one-step synthesis of 1-propenyl aromatic hydrocarbon by catalyzing 3-aryl propanol with heterogeneous catalyst | |
| CN107445879B (en) | Preparation method of Latricinib intermediate | |
| CN113968819B (en) | Synthesis method of polysubstituted pyrazole compound | |
| CN117304076B (en) | Preparation method of N-sulfonyl amidine compound | |
| CN108658718B (en) | Preparation method of trans-stilbene compound |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201218 Address after: 11 / F, Jingang building, south of Lianyungang Road, Sheyang Economic Development Zone, Sheyang County, Yancheng City, Jiangsu Province 224300 Patentee after: Li Zaigao Address before: 266000 Songling Road, Laoshan District, Qingdao, Shandong Province, No. 99 Patentee before: Qingdao University Of Science And Technology |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221228 Address after: Room 707, Administrative Committee of Tancheng Economic Development Zone, Linyi City, Shandong Province, 276000 Patentee after: Tancheng Economic Development Zone Pharmaceutical Development Co.,Ltd. Address before: 11 / F, Jingang building, south of Lianyungang Road, Sheyang Economic Development Zone, Sheyang County, Yancheng City, Jiangsu Province 224300 Patentee before: Li Zaigao |