CN108148070A - A kind of synthetic method of furanone and compound of isobioquin group - Google Patents
A kind of synthetic method of furanone and compound of isobioquin group Download PDFInfo
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- CN108148070A CN108148070A CN201810226250.5A CN201810226250A CN108148070A CN 108148070 A CN108148070 A CN 108148070A CN 201810226250 A CN201810226250 A CN 201810226250A CN 108148070 A CN108148070 A CN 108148070A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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Abstract
The invention discloses the synthetic methods of a kind of furanone and compound of isobioquin group, belong to technical field of organic synthesis.The present invention synthesizes furanone and compound of isobioquin group by N alkoxy aryls Carbox amide with 4 hydroxyl, 2 acetylenic acid ester type compound, one pot of cascade reaction, have many advantages, such as that easy to operate, mild condition, wide application range of substrates, regioselectivity are good, be suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to the synthesis of a kind of furanone and compound of isobioquin group
Method.
Background technology
Condensed nitrogen/oxygen helerocyclics is widely present in nature, and often there is good biology and drug to live
Property.For example, the treatment cardiovascular and cerebrovascular disease of many Clinical practices, AIDS and mental disease drug molecule comprising condensed nitrogen/
This structural unit of oxa- ring.Furanone and isoquinolines are the important members in condensed nitrogen/oxygen helerocyclics, unique
Structure and function become effective herbicide, insecticide and fungicide etc., have very high research and application value.To mesh
Before until, the synthesis furanone of the document report and method of compound of isobioquin group is simultaneously few, and these literature methods are still
It is difficult to obtain there are raw material, the deficiencies of reaction step is cumbersome, severe reaction conditions part.Therefore, it studies and develops from simple easy
Raw material set out, the new method of furanone and compound of isobioquin group synthesized via easy operating procedure, not only have
There is important theory significance, and with important application value.
Invention content
The technical problem to be solved by the present invention is to provide the synthetic methods of a kind of furanone and compound of isobioquin group, should
Synthetic method is closed by one pot of cascade reaction of N- alkoxy aryls Carbox amide and 4- hydroxyl -2- acetylenic acids ester type compound
It is good with easy to operate, mild condition, wide application range of substrates, regioselectivity into furanone and compound of isobioquin group
The advantages that, it is suitable for industrialized production.
The present invention adopts the following technical scheme that solve above-mentioned technical problem：
The synthetic method of a kind of furanone and compound of isobioquin group, it is characterised in that specifically building-up process is：By N-
Alkoxy aryl Carbox amide 1 and 4- hydroxyl -2- acetylenic acids ester type compound 2 are dissolved in solvent, then add in catalyst
And additive, obtained furanone and compound of isobioquin group 3 are stirred to react in 80-120 DEG C under air or nitrogen atmosphere, it should
Reaction equation in synthetic method is：
Wherein R1For hydrogen, fluorine, chlorine, bromine, C1-4Linear or branched alkyl group, methoxyl group, phenyl or substituted-phenyl, substituted-phenyl
Substituent group on phenyl ring is fluorine, chlorine, bromine, methyl or methoxy, R2For phenyl or C1-4Linear or branched alkyl group, R3For phenyl or
C1-4Linear or branched alkyl group, R4For C1-4Linear or branched alkyl group, R5For C1-4Linear or branched alkyl group, solvent are Isosorbide-5-Nitrae-dioxy six
Ring, methanol, isopropanol, acetonitrile or glycol dimethyl ether, catalyst close rhodium (III) dimerization for dichloro (pentamethylcyclopentadiene base)
Body ([RhCp*Cl2]2), additive is cesium acetate, potassium fluoride, silver acetate, sodium acetate, potassium acetate, potassium carbonate or sodium carbonate.
Further preferably, the N- alkoxy aryls Carbox amide 1,4- hydroxyl -2- acetylenic acid ester type compounds
2nd, the ratio between amount for the substance that feeds intake of catalyst and additive is 1:1-2:0.025:1-2.
The synthetic method of a kind of furanone and compound of isobioquin group, it is characterised in that specifically building-up process is：By N-
Alkoxy aryl Carbox amide 1 and 4- hydroxyl -2- acetylenic acids ester type compound 4 are dissolved in solvent, then add in catalyst
And additive, obtained furanone and compound of isobioquin group 5 are stirred to react in 80-120 DEG C under air or nitrogen atmosphere, it should
Reaction equation in synthetic method is：
Wherein R1For hydrogen, fluorine, chlorine, bromine, C1-4Linear or branched alkyl group, methoxyl group, phenyl or substituted-phenyl, substituted-phenyl
Substituent group on phenyl ring is fluorine, chlorine, bromine, methyl or methoxy, R4For C1-4Linear or branched alkyl group, R5For C1-4Linear chain or branch chain
Alkyl, n 1,2 or 3, solvent are Isosorbide-5-Nitrae-dioxane, methanol, isopropanol, acetonitrile or glycol dimethyl ether, and catalyst is dichloro
(pentamethylcyclopentadiene base) closes rhodium (III) dimer ([RhCp*Cl2]2), additive is cesium acetate, potassium fluoride, silver acetate, vinegar
Sour sodium, potassium acetate, potassium carbonate or sodium carbonate.
Further preferably, the N- alkoxy aryls Carbox amide 1,4- hydroxyl -2- acetylenic acid ester type compounds
4th, the ratio between amount for the substance that feeds intake of catalyst and additive is 1:1-2:0.025:1-2.
The present invention has the following advantages：(1) building-up process is simple, efficient, passes through N- alkoxy aryl formamides compounds
Object directly obtains furanone and compound of isobioquin group with 4- hydroxyl -2- acetylenic acids one pot of cascade reaction of ester type compound, i.e., logical
It crosses one pot of cascade reaction and constructs out six-membered heterocycle and five yuan of oxa- rings simultaneously, combined coefficient is higher；(2) reaction condition is mild,
It is easy to operate；(3) substrate is applied widely；(4) conversion zone is selectively good.Therefore, the present invention is furanone and isoquinolin
The synthesis of ketone compounds provides a kind of new method rapidly and efficiently.
Specific embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright range.
Embodiment 1
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(DME, 3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), dichloro (pentamethylcyclopentadiene
Base) close rhodium (III) dimer ([RhCp*Cl2]2, 7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), it will be mixed
It closes object and is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, be subsequently cooled to room temperature, filter, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel
Post separation (methylene chloride/methanol=200/1) obtains white solid product 3a (99.7mg, 87%).The characterization number of the compound
According to as follows：1H NMR(400MHz,DMSO-d6)δ:1.64 (s, 6H), 7.59 (t, J=7.6Hz, 1H), 7.85 (t, J=8.0Hz,
1H), 8.23 (d, J=8.4Hz, 1H), 8.27 (d, J=7.6Hz, 1H), 12.73 (br s, 1H)13C NMR(100MHz,
DMSO-d6)δ:24.6,80.8,97.5,122.1,124.6,127.5,127.8,131.7,133.8,163.0,163.2,
167.1.HRMS calcd for C13H11NO3Na:252.0631[M+Na]+,found:252.0645。
Embodiment 2
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), 1,4- dioxane are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with cesium acetate (192.0mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere,
Room temperature is subsequently cooled to, is filtered, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white
Solid product 3a (81.4mg, 71%).
Embodiment 3
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), methanol (3mL), 4- are added in the reaction tube of 15mL
Hydroxy-4-methyl-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and vinegar
Mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature by sour caesium (192.0mg, 1.0mmol),
It filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white solid product 3a
(65.3mg, 57%).
Embodiment 4
In the reaction tube of 15mL add in N- methoxy benzamides (1a, 75.6mg, 0.5mmol), isopropanol (3mL),
4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and
Mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room by cesium acetate (192.0mg, 1.0mmol)
Temperature filters, and mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white solid product 3a
(87.1mg, 76%).
Embodiment 5
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), acetonitrile (3mL), 4- are added in the reaction tube of 15mL
Hydroxy-4-methyl-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and vinegar
Mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature by sour caesium (192.0mg, 1.0mmol),
It filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white solid product 3a
(66.5mg, 58%).
Embodiment 6
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with cesium acetate (192.0mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere,
Room temperature is subsequently cooled to, is filtered, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white
Solid product 3a (90.5mg, 79%).
Embodiment 7
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with silver acetate (166.9mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere,
Room temperature is subsequently cooled to, is filtered, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white
Solid product 3a (90.5mg, 79%).
Embodiment 8
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with sodium acetate (82.0mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, so
Postcooling filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white admittedly to room temperature
Body product 3a (83.7mg, 73%).
Embodiment 9
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with potassium acetate (98.1mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, so
Postcooling filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white admittedly to room temperature
Body product 3a (89.4mg, 78%).
Embodiment 10
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with potassium carbonate (138.2mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere,
Room temperature is subsequently cooled to, is filtered, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white
Solid product 3a (91.7mg, 80%).
Embodiment 11
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with sodium carbonate (106.0mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere,
Room temperature is subsequently cooled to, is filtered, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white
Solid product 3a (87.1mg, 76%).
Embodiment 12
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with potassium fluoride (58.1mg, 1.0mmol), mixture is stirred to react 12h in 80 DEG C in a nitrogen atmosphere, so
Postcooling filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white admittedly to room temperature
Body product 3a (91.7mg, 80%).
Embodiment 13
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with potassium fluoride (58.1mg, 1.0mmol), mixture is stirred to react 12h in 120 DEG C in a nitrogen atmosphere, so
Postcooling filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white admittedly to room temperature
Body product 3a (97.4mg, 85%).
Embodiment 14
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with potassium fluoride (29.1mg, 0.5mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, so
Postcooling filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white admittedly to room temperature
Body product 3a (64.2mg, 56%).
Embodiment 15
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with potassium fluoride (58.1mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in air atmosphere, so
Postcooling filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white admittedly to room temperature
Body product 3a (79.1mg, 69%).
Embodiment 16
N- methoxy benzamides (1a, 75.6mg, 0.5mmol), glycol dimethyl ether are added in the reaction tube of 15mL
(3mL), 4- hydroxy-4-methyls-valerylene acetoacetic ester (2a, 78.1mg, 0.5mmol), [RhCp*Cl2]2(7.7mg,
0.0125mmol) with potassium fluoride (58.1mg, 1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, so
Postcooling filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (methylene chloride/methanol=200/1) and obtains white admittedly to room temperature
Body product 3a (52.7mg, 46%).
Embodiment 17
1b (82.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3b (98.5mg, 81%).The change
The characterize data for closing object is as follows：1H NMR(400MHz,DMSO-d6)δ:1.64(s,6H),2.49(s,3H),7.41-7.43(m,
1H), 8.08 (s, 1H), 8.13 (d, J=8.0Hz, 1H), 12.69 (s, 1H)13C NMR(100MHz,DMSO-d6)δ:21.5,
24.6,80.7,97.2,121.8,122.3,127.8,128.8,131.7,144.3,162.8,163.4,167.2.HRMS
calcd for C14H13NO3Na:266.0788[M+Na]+,found:266.0789。
Embodiment 18
1c (103.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained product as light yellow solid 3c (102.7mg, 72%).
The characterize data of the compound is as follows：1H NMR(400MHz,DMSO-d6)δ:1.32(s,9H),1.62(s,6H),7.63(dd,
J1=8.4Hz, J2=1.6Hz, 1H), 8.14 (d, J=8.4Hz, 1H), 8.28 (d, J=1.6Hz, 1H), 12.66 (br s,
1H).13C NMR(100MHz,DMSO-d6)δ:24.6,30.7,35.0,80.7,97.6,117.9,122.3,125.3,127.6,
131.7,156.8,162.7,163.3,167.3.HRMS calcd for C17H19NO3Na:308.1257[M+Na],found:
308.1262。
Embodiment 19
1d (90.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3d (101.1mg, 78%).It should
The characterize data of compound is as follows：1H NMR(600MHz,DMSO-d6)δ:1.64 (s, 6H), 3.90 (s, 3H), 7.15 (d, J=
8.4Hz, 1H), 7.67 (s, 1H), 8.14 (d, J=8.4Hz, 1H), 12.60 (s, 1H)13C NMR(100MHz,DMSO-d6)δ:
24.6,55.6,80.7,97.1,103.8,116.1,117.9,129.9,133.8,162.5,163.4,163.9,
167.2.HRMS calcd for C14H13NO4Na:282.0737[M+Na]+,found:282.0738。
Embodiment 20
1e (84.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3e (74.2mg, 60%).The change
The characterize data for closing object is as follows：1H NMR(600MHz,DMSO-d6)δ:1.65 (s, 6H), 7.46 (t, J=9.0Hz, 1H), 7.89
(d, J=9.0Hz, 1H), 8.30-8.32 (m, 1H), 12.85 (s, 1H)13C NMR(100MHz,DMSO-d6)δ:24.5,
81.1,97.1(d,4JC-F=3.1Hz), 107.4 (d,2JC-F=23.0Hz), 115.8 (d,2JC-F=23.5Hz), 121.5,
131.5(d,3JC-F=10.9Hz), 134.0 (d,3JC-F=11.2Hz), 162.3,164.5,165.2 (d,1JC-F=
251.1Hz),166.9.19F NMR(565MHz,DMSO-d6)δ:-103.91.HRMS calcd for C13H10FNO3Na:
270.0537[M+Na]+,found:270.0537。
Embodiment 21
1f (113.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3f (120.6mg, 79%).It should
The characterize data of compound is as follows：1H NMR(600MHz,DMSO-d6)δ:1.67 (s, 6H), 7.49 (t, J=7.8Hz, 1H),
7.56 (t, J=7.2Hz, 2H), 7.76 (d, J=7.2Hz, 2H), 7.90 (d, J=8.4Hz, 1H), 8.31 (d, J=8.4Hz,
1H),8.50(s,1H),12.77(s,1H).13C NMR(100MHz,DMSO-d6)δ:24.6,80.9,97.5,119.6,
123.5,126.1,127.1,128.6,128.7,129.2,132.2,138.9,145.2,162.8,163.7,167.2.HRMS
calcd for C19H16NO3:306.1125[M+H]+,found:306.1124。
Embodiment 22
1g (82.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3g (103.4mg, 85%).It should
The characterize data of compound is as follows：1H NMR(400MHz,DMSO-d6)δ:1.63(s,6H),2.44(s,3H),7.64-7.67
(m, 1H), 8.01 (s, 1H), 8.13 (d, J=8.0Hz, 1H), 12.63 (br s, 1H)13C NMR(100MHz,DMSO-d6)δ:
21.0,24.6,80.7,97.5,122.0,124.5,127.4,129.2,134.9,137.1,162.3,162.8,
167.2.HRMS calcd for C14H13NO3Na:266.0788[M+Na]+,found:266.0784。
Embodiment 23
1h (90.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3h (45.4mg, 35%) and 3h'
(35.0mg, 27%).The characterize data of compound 3h is as follows：1H NMR(400MHz,DMSO-d6)δ:1.64(s,6H),3.89
(s,3H),7.49(dd,J1=8.4Hz, J2=2.4Hz, 1H), 7.67 (d, J=2.4Hz, 1H), 8.20 (d, J=8.4Hz,
1H),12.75(s,1H).13C NMR(100MHz,DMSO-d6)δ:24.7,55.4,80.8,97.6,109.0,122.9,
123.8,125.2,126.1,158.5,160.9,162.6,167.3.HRMS calcd for C14H13NO4Na:282.0737[M
+Na]+,found:282.0737.The characterize data of compound 3h' is as follows：1H NMR(400MHz,CDCl3)δ:1.75(s,6H),
3.97 (s, 3H), 7.23 (d, J=7.6Hz, 1H), 7.49 (t, J=7.6Hz, 1H), 8.02 (d, J=7.6Hz, 1H), 13.43
(s,1H).13C NMR(100MHz,CDCl3)δ:25.6,56.4,79.0,100.7,116.0,120.1 123.8,126.1,
128.7,156.5,162.1,165.5,165.8.HRMS calcd for C14H13NO4Na:282.0737[M+Na]+,found:
282.0747。
Embodiment 24
1i (92.8mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3i (25.0mg, 19%) and 3i'
(47.5mg, 36%).The characterize data of compound 3i is as follows：1H NMR(600MHz,DMSO-d6)δ:1.66(s,6H),7.90
(d, J=8.4Hz, 1H), 8.15 (s, 1H), 8.26 (d, J=8.4Hz, 1H), 12.92 (s, 1H)13C NMR(100MHz,
DMSO-d6)δ:24.5,81.1,97.3,124.2,126.1,126.9,130.4,132.0,133.9,161.9,163.4,
166.9.HRMS calcd for C13H10ClNO3Na:286.0241[M+Na]+,found:286.0243.The table of compound 3i'
It is as follows to levy data：1H NMR(400MHz,DMSO-d6)δ:1.64 (s, 6H), 7.58 (t, J=8.0Hz, 1H), 7.90 (d, J=
8.0Hz, 1H), 8.28 (d, J=7.6Hz, 1H), 12.94 (br s, 1H)13C NMR(100MHz,DMSO-d6)δ:24.8,
78.8,97.0,127.2,127.7,128.2,128.7,130.6,136.3,162.1,164.3,165.3.HRMS calcd
for C13H10ClNO3Na:286.0241[M+Na]+,found:286.0245。
Embodiment 25
1j (115.0mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3j (57.0mg, 37%) and 3j'
(27.7mg, 18%).The characterize data of compound 3j is as follows：1H NMR(400MHz,DMSO-d6)δ:1.65(s,6H),8.02
(dd,J1=8.8Hz, J2=2.0Hz, 1H), 8.19 (d, J=8.8Hz, 1H), 8.29 (d, J=2.0Hz, 1H), 12.91 (s,
1H).13C NMR(100MHz,DMSO-d6)δ:24.5,81.1,97.3,120.2,124.3,126.2,129.9,130.6,
136.5,161.8,163.5,166.8.HRMS calcd for C13H10BrNO3Na:329.9736[M+Na]+,found:
329.9743.The characterize data of compound 3j' is as follows：1H NMR(400MHz,DMSO-d6)δ:1.64 (s, 6H), 7.50 (t, J=
7.6Hz,1H),8.11(dd,J1=8.0Hz, J2=1.2Hz, 1H), 8.32 (dd, J1=7.6Hz, J2=1.2Hz, 1H),
12.92(s,1H).13C NMR(100MHz,DMSO-d6)δ:24.8,78.8,97.3,116.5,127.6,128.1,128.5,
132.3,140.2,162.1,164.1,165.3.HRMS calcd for C13H10BrNO3Na:329.9736[M+Na]+,
found:329.9744。
Embodiment 26
1k (82.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3k (36.5mg, 30%).The change
The characterize data for closing object is as follows：1H NMR(600MHz,DMSO-d6)δ:1.59(s,6H),2.77(s,3H),7.33(s,1H),
7.66(s,1H),8.18(s,1H),12.47(s,1H).13C NMR(150MHz,DMSO-d6)δ:23.8,25.1,80.8,
97.7,120.6,123.2,130.9,133.6,133.8,142.3,163.7,164.4,167.8.HRMS calcd for
C14H13NO3Na:266.0788[M+Na]+,found:266.0789。
Embodiment 27
1l (90.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3l (44.1mg, 34%).The change
The characterize data for closing object is as follows：1H NMR(400MHz,DMSO-d6)δ:1.60 (s, 6H), 3.87 (s, 3H), 7.10 (d, J=
8.4Hz, 1H), 7.73 (t, J=7.6Hz, 1H), 7.87 (d, J=7.6Hz, 1H), 12.39 (br s, 1H)13C NMR
(100MHz,DMSO-d6)δ:24.5,55.8,80.1,96.4,109.9,113.2,113.6,134.4,134.9,161.0,
161.1,163.7,167.2.HRMS calcd for C14H13NO4Na:282.0737[M+Na]+,found:282.0738。
Embodiment 28
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 2b (184.2mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature.It filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 3m (100.3mg, 78%).The characterize data of the compound is as follows：1H NMR
(400MHz,CDCl3)δ:0.88 (t, J=7.2Hz, 6H), 2.18-2.31 (m, 4H), 7.64-7.68 (m, 1H), 7.87-7.91
(m, 1H), 8.47 (d, J=8.0Hz, 1H), 8.58 (d, J=8.0Hz, 1H), 13.29 (s, 1H)13C NMR(100MHz,
CDCl3)δ:7.4,29.8,86.9,103.1,123.4,124.2,128.0,128.2,132.2,134.6,159.0,166.2,
168.4.HRMS calcd for C15H15NO3Na:280.0944[M+Na]+,found:280.0948。
Embodiment 29
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 2c (184.2mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature, filter, and mother liquor is mixed silica gel and is spin-dried for, and cross silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 3n (77.2mg, 60%).The characterize data of the compound is as follows：1H NMR
(600MHz,CDCl3)δ:0.93 (t, J=6.6Hz, 3H), 1.19-1.21 (m, 1H), 1.47-1.49 (m, 1H), 1.85 (s,
3H), 2.12-2.22 (m, 2H), 7.65 (t, J=7.2Hz, 1H), 7.88 (t, J=7.2Hz, 1H), 8.47 (d, J=7.8Hz,
1H), 8.55 (d, J=7.8Hz, 1H), 13.28 (s, 1H)13C NMR(100MHz,CDCl3)δ:13.9,16.7,24.3,
39.8,83.7,101.5,123.4,124.2,128.0,128.2,132.4,134.7,160.9,166.2,168.0.HRMS
calcd for C15H15NO3Na:280.0944[M+Na]+,found:280.0944。
Embodiment 30
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 2d (198.3mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature, filter, and mother liquor is mixed silica gel and is spin-dried for, and cross silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 3o (88.2mg, 65%).The characterize data of the compound is as follows：1H NMR
(600MHz,CDCl3)δ:0.83 (d, J=6.6Hz, 3H), 0.99 (d, J=7.2Hz, 3H), 1.70-1.76 (m, 1H), 1.82
(s, 3H), 2.03-2.07 (m, 1H), 2.18-2.21 (m, 1H), 7.65 (t, J=7.8Hz, 1H), 7.88 (t, J=7.8Hz,
1H), 8.46 (d, J=7.8Hz, 1H), 8.57 (d, J=7.8Hz, 1H), 13.26 (s, 1H)13C NMR(100MHz,CDCl3)
δ:23.6,24.2,24.3,25.1,46.0,83.7,101.6,123.5,124.2,128.0,128.1,132.4,134.7,
161.2,166.2,167.9.HRMS calcd for C16H17NO3Na:294.1101[M+Na]+,found:294.1102。
Embodiment 31
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 2e (198.3mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature, filter, and mother liquor is mixed silica gel and is spin-dried for, and cross silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 3p (51.5mg, 38%).The characterize data of the compound is as follows：1H NMR
(400MHz,DMSO-d6)δ:0.96(s,9H),1.64(s,3H),7.58-7.62(m,1H),7.84-7.88(m,1H),8.24
(d, J=7.6Hz, 1H), 8.32 (d, J=8.0Hz, 1H), 12.39 (s, 1H)13C NMR(100MHz,DMSO-d6)δ:18.3,
25.1,37.6,87.7,99.4,122.1,124.4,127.6,127.8,131.3,133.9,161.5,162.9,
167.6.HRMS calcd for C16H17NO3Na:294.1101[M+Na]+,found:294.1101。
Embodiment 32
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 2f (218.2mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature, filter, and mother liquor is mixed silica gel and is spin-dried for, and cross silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 3q (23.3mg, 16%).The characterize data of the compound is as follows：1H NMR
(400MHz,DMSO-d6)δ:2.10(s,3H),7.38-7.46(m,3H),7.49-7.52(m,2H),7.59-7.63(m,1H),
7.85-7.89 (m, 1H), 8.23 (d, J=7.6Hz, 1H), 8.35 (d, J=7.6Hz, 1H), 12.73 (s, 1H)13C NMR
(100MHz,DMSO-d6)δ:22.7,83.0,97.9,122.3,124.7,125.8,127.7,127.8,128.8,129.0,
131.3,133.9,137.8,162.2,162.9,167.4.HRMS calcd for C18H14NO3:292.0968[M+H]+,
found:292.0973。
Embodiment 33
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 2g (142.2mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature, filter, and mother liquor is mixed silica gel and is spin-dried for, and cross silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 3a (95.1mg, 83%).
Embodiment 34
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 2h (184.2mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature, filter, and mother liquor is mixed silica gel and is spin-dried for, and cross silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 3a (94.0mg, 82%).
Embodiment 35
1m (82.6mg, 0.5mmol), DME (3mL), 4- hydroxy-4-methyls-valerylene are added in the reaction tube of 15mL
Acetoacetic ester (2a, 156.2mg, 1.0mmol), [RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg,
1.0mmol), mixture is stirred to react 12h in 100 DEG C in a nitrogen atmosphere, is subsequently cooled to room temperature, filtered, mother liquor mixes silicon
Glue is spin-dried for, and is crossed silica gel post separation (methylene chloride/methanol=200/1) and is obtained white solid product 3a (97.4mg, 85%).
Embodiment 36
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 4a (168.2mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature, filter, and mother liquor is mixed silica gel and is spin-dried for, and cross silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 5a (83.0mg, 65%).The characterize data of the compound is as follows：1H NMR
(400MHz,DMSO-d6)δ:1.90 (s, 6H), 2.24-2.26 (m, 2H), 7.53 (t, J=7.2Hz, 1H), 7.78 (t, J=
7.2Hz,1H),8.16-8.21(m,2H),12.67(br s,1H).13C NMR(100MHz,DMSO-d6)δ:24.5,37.0,
90.4,98.8,121.9,124.6,127.4,127.8,131.4,133.8,160.5,163.0,167.1.HRMS calcd
for C15H13NO3Na:278.0788[M+Na]+,found:278.0788。
Embodiment 37
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 4b (182.2mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature.It filters, mother liquor is mixed silica gel and is spin-dried for, and crosses silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 5b (96.9mg, 72%).The characterize data of the compound is as follows：1H NMR
(600MHz,DMSO-d6)δ:1.18-1.22(m,1H),1.48-1.58(m,4H),1.66-1.67(m,3H),1.97-2.02
(m, 2H), 7.50 (t, J=7.2Hz, 1H), 7.74-7.77 (m, 1H), 8.14 (d, J=7.8Hz, 1H), 8.19 (d, J=
8.4Hz,1H),12.59(s,1H).13C NMR(100MHz,CDCl3)δ:22.0,24.7,34.2,82.9,100.7,123.4,
124.3,127.9,128.1,132.6,134.6,162.0,166.2,168.1.HRMS calcd for C16H15NO3Na:
292.0944[M+Na]+,found:292.0948。
Embodiment 38
In the reaction tube of 15mL add in 1a (75.6mg, 0.5mmol), DME (3mL), 4c (196.2mg, 1.0mmol),
[RhCp*Cl2]2(7.7mg, 0.0125mmol) and potassium fluoride (58.1mg, 1.0mmol), by mixture in a nitrogen atmosphere in
100 DEG C are stirred to react 12h, are subsequently cooled to room temperature, filter, and mother liquor is mixed silica gel and is spin-dried for, and cross silica gel post separation (dichloromethane/first
Alcohol=200/1) obtain white solid product 5c (39.7mg, 28%).The characterize data of the compound is as follows：1H NMR
(600MHz,DMSO-d6)δ:1.61-1.63(m,2H),1.72-1.75(m,6H),1.81-1.84(m,2H),2.17-2.22
(m,2H),7.59-7.61(m,1H),7.85-7.87(m,1H),8.24(dd,J1=7.8Hz, J2=0.6Hz, 1H), 8.29 (d,
J=7.8Hz, 1H), 12.70 (s, 1H)13C NMR(100MHz,DMSO-d6)δ:21.6,26.8,36.5,85.2,96.7,
122.1,124.6,127.4,127.8,131.7,133.8,163.0,164.2,167.4.HRMS calcd for
C17H17NO3Na:306.1101[M+Na]+,found:306.1100。
Basic principle, main features and advantages embodiment above describes the present invention.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the originals of the present invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (4)
1. the synthetic method of a kind of furanone and compound of isobioquin group, it is characterised in that specifically building-up process is：By N- alkane
Oxygroup aryl methanamide compounds 1 and 4- hydroxyl -2- acetylenic acids ester type compound 2 are dissolved in solvent, then add in catalyst and
Additive is stirred to react obtained furanone and compound of isobioquin group 3, the conjunction under air or nitrogen atmosphere in 80-120 DEG C
It is into the reaction equation in method：
Wherein R1For hydrogen, fluorine, chlorine, bromine, C1-4Linear or branched alkyl group, methoxyl group, phenyl or substituted-phenyl, on substituted-phenyl phenyl ring
Substituent group for fluorine, chlorine, bromine, methyl or methoxy, R2For phenyl or C1-4Linear or branched alkyl group, R3For phenyl or C1-4Straight chain
Or branched alkyl, R4For C1-4Linear or branched alkyl group, R5For C1-4Linear or branched alkyl group, solvent is Isosorbide-5-Nitrae-dioxane, first
Alcohol, isopropanol, acetonitrile or glycol dimethyl ether, catalyst close rhodium (III) dimer for dichloro (pentamethylcyclopentadiene base)
([RhCp*Cl2]2), additive is cesium acetate, potassium fluoride, silver acetate, sodium acetate, potassium acetate, potassium carbonate or sodium carbonate.
2. the synthetic method of furanone according to claim 1 and compound of isobioquin group, it is characterised in that：Described
N- alkoxy aryls Carbox amide 1,4- hydroxyl -2- acetylenic acids ester type compound 2, catalyst and additive the substance that feeds intake
The ratio between amount be 1:1-2:0.025:1-2.
3. the synthetic method of a kind of furanone and compound of isobioquin group, it is characterised in that specifically building-up process is：By N- alkane
Oxygroup aryl methanamide compounds 1 and 4- hydroxyl -2- acetylenic acids ester type compound 4 are dissolved in solvent, then add in catalyst and
Additive is stirred to react obtained furanone and compound of isobioquin group 5, the conjunction under air or nitrogen atmosphere in 80-120 DEG C
It is into the reaction equation in method：
Wherein R1For hydrogen, fluorine, chlorine, bromine, C1-4Linear or branched alkyl group, methoxyl group, phenyl or substituted-phenyl, on substituted-phenyl phenyl ring
Substituent group for fluorine, chlorine, bromine, methyl or methoxy, R4For C1-4Linear or branched alkyl group, R5For C1-4Linear or branched alkyl group, n
It is 1,2 or 3, solvent is Isosorbide-5-Nitrae-dioxane, methanol, isopropanol, acetonitrile or glycol dimethyl ether, and catalyst is dichloro (five first
Cyclopentadienyl group) close rhodium (III) dimer ([RhCp*Cl2]2), additive for cesium acetate, potassium fluoride, silver acetate, sodium acetate,
Potassium acetate, potassium carbonate or sodium carbonate.
4. the synthetic method of furanone according to claim 3 and compound of isobioquin group, it is characterised in that：Described
N- alkoxy aryls Carbox amide 1,4- hydroxyl -2- acetylenic acids ester type compound 4, catalyst and additive the substance that feeds intake
The ratio between amount be 1:1-2:0.025:1-2.
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| CN110105274A (en) * | 2019-06-10 | 2019-08-09 | 河南师范大学 | A kind of synthetic method of 3- (2- aminoaryl) quinolines |
| CN111675712A (en) * | 2020-06-23 | 2020-09-18 | 河南师范大学 | Synthesis method of pyrazolone benzodiazepine compound |
| CN112480049A (en) * | 2020-12-27 | 2021-03-12 | 河南师范大学 | Synthetic method of indeno [1,2-c ] furan compound |
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| CN110105274A (en) * | 2019-06-10 | 2019-08-09 | 河南师范大学 | A kind of synthetic method of 3- (2- aminoaryl) quinolines |
| CN110105274B (en) * | 2019-06-10 | 2020-09-01 | 河南师范大学 | Synthetic method of 3- (2-amino aryl) quinoline compound |
| CN111675712A (en) * | 2020-06-23 | 2020-09-18 | 河南师范大学 | Synthesis method of pyrazolone benzodiazepine compound |
| CN112480049A (en) * | 2020-12-27 | 2021-03-12 | 河南师范大学 | Synthetic method of indeno [1,2-c ] furan compound |
| CN112480049B (en) * | 2020-12-27 | 2023-09-08 | 河南师范大学 | Synthesis method of indenone [1,2-c ] furan compound |
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