CN107382933A - A kind of method that organic catalysis efficiently synthesizes 3 aryl-coumarin class compounds - Google Patents
A kind of method that organic catalysis efficiently synthesizes 3 aryl-coumarin class compounds Download PDFInfo
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- 0 *c1cc(O)c(C=C)cc1 Chemical compound *c1cc(O)c(C=C)cc1 0.000 description 8
- YOEORKQXLLPVDZ-VIFPVBQESA-N C[C@]1(O)Oc2ccccc2C1 Chemical compound C[C@]1(O)Oc2ccccc2C1 YOEORKQXLLPVDZ-VIFPVBQESA-N 0.000 description 2
- WLGTXBUEIYENCK-UHFFFAOYSA-N CC(C)(C)OC(NC1C=CC(Cl)=CC1C1=Cc2ccccc2[U]C1=O)=O Chemical compound CC(C)(C)OC(NC1C=CC(Cl)=CC1C1=Cc2ccccc2[U]C1=O)=O WLGTXBUEIYENCK-UHFFFAOYSA-N 0.000 description 1
- UIDZLTCAKGHACI-UHFFFAOYSA-N CC(C)(C)OC(Nc1cc(F)ccc1C1=Cc2ccccc2OC1=O)=O Chemical compound CC(C)(C)OC(Nc1cc(F)ccc1C1=Cc2ccccc2OC1=O)=O UIDZLTCAKGHACI-UHFFFAOYSA-N 0.000 description 1
- ONTWHPOGWLOYFI-UHFFFAOYSA-N CN(C(C1)=O)c(cc2)c1cc2Cl Chemical compound CN(C(C1)=O)c(cc2)c1cc2Cl ONTWHPOGWLOYFI-UHFFFAOYSA-N 0.000 description 1
- ILEIUTCVWLYZOM-UHFFFAOYSA-N Cc(cc1)cc(C=O)c1O Chemical compound Cc(cc1)cc(C=O)c1O ILEIUTCVWLYZOM-UHFFFAOYSA-N 0.000 description 1
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N O=C1Oc2ccccc2C1 Chemical compound O=C1Oc2ccccc2C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 1
- VJKIABAZNYEWDR-UHFFFAOYSA-N OC(CCC=C1)=C1C(C(Oc1c2)=O)=Cc1ccc2Cl Chemical compound OC(CCC=C1)=C1C(C(Oc1c2)=O)=Cc1ccc2Cl VJKIABAZNYEWDR-UHFFFAOYSA-N 0.000 description 1
- OFWFYSGUKSLYEU-UHFFFAOYSA-N OC(CCC=C1)=C1C1=Cc2cc(F)ccc2OC1=O Chemical compound OC(CCC=C1)=C1C1=Cc2cc(F)ccc2OC1=O OFWFYSGUKSLYEU-UHFFFAOYSA-N 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N Oc1ccccc1C=O Chemical compound Oc1ccccc1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/34—Oxygen atoms in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a kind of method that organic catalysis efficiently synthesizes 3 aryl-coumarin class compounds, and using DBU and/or TMG as catalyst, formula A compounds and formula B compounds react to obtain formula C compounds：Wherein, X NBoc, NAc or O；R1Selected from hydrogen, alkyl, alkoxy, halogen, nitro；R3Selected from hydrogen, alkyl, alkoxy, halogen, nitro.This method has reaction substrate extensive, and mild condition, experimental implementation is simple, the characteristics of convenient post-treatment.
Description
Technical field
The invention belongs to methodology of organic synthesis field, specifically a kind of organic catalysis efficiently synthesizes 3- aryl-coumarin classes
The method of compound.
Background technology
Cumarin (benzo-α-pyranone) is many compounds of a kind of quantity, from natural extraction and artificial synthesized, tool
There are various pharmacological activity and photochemical properties.Research finds that the property and species of the substituent of phenyl ring and pyranone ring are to tonka-bean
The property of plain compound has a significant impact.Therefore, it is necessary to develop the synthesis side for obtaining variation and the cumarin suitably substituted
Method.
Due to the extensive use of 3- aryl-coumarins, various classical ways such as Perkin reactions, Pechmann condensation reactions,
Knoevenagel condensation reactions, Wittig reactions, cross-coupling reaction have been used to the synthesis of 3- aryl-coumarin derivatives.
Although having developed so more synthetic methods, most methods are directed to the thermal condensation of salicylide and Arylacetic acids.
Its shortcoming includes：Severe reaction conditions, post processing is complicated, the reaction time is long, yield is undesirable.So in a mild condition can
The alternative for being enough effectively formed 3- aryl-coumarins will be highly useful.
The content of the invention
It is an object of the invention to provide a kind of method that organic catalysis efficiently synthesizes 3- aryl-coumarin class compounds.
To reach above-mentioned purpose, the present invention uses following technical scheme：
One kind synthesis compoundMethod, using DBU and/or TMG as catalyst, formula A compounds
React to obtain formula C compounds with formula B compounds：
Wherein, X NBoc, NAc or O；R1Selected from hydrogen, alkyl, alkoxy, halogen, nitro；R3Selected from hydrogen, alkyl, alcoxyl
Base, halogen, nitro.
Its reaction mechanism is：Intermolecular condensation occurs for indole-2-ketone and salicylide, then carries out intramolecular open loop, after
And annulation, obtain product.
DBU is the carbon -7- alkene of 1,8- diazabicylos [5.4.0] 11, and TMG is TMG.
Further, the R1Selected from hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, nitro.
Further, the R3Selected from hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, nitro.
Further, the reaction is with dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, toluene, acetonitrile, Isosorbide-5-Nitrae-dioxy
One or more in six rings are solvent.
Further, the dosage of the solvent is at least 1mL.
Further, the dosage of the catalyst is at least 10mol%.
Further, the time of the reaction is at least 3h.
Further, the temperature of the reaction is at least 20 DEG C.
The invention has the advantages that：
The inventive method is the organic catalysis series connection synthesis of 3- aryl-coumarins, using TMS or DBU as catalyst, passes through two
Condensation-open loop-cyclisation the cascade reaction of hydrogen indoles -2- ketone or benzofuran -2 (3H) between -one and salicylide obtains one
The 3- aryl-coumarin class compounds of series.This method has reaction substrate extensive, and mild condition, experimental implementation is simple, rear place
Manage the characteristics of facilitating.Electron-withdrawing substituent and electron donating group on salicylide are all tolerances, almost do not have shadow to yield
Ring；The electronic property of the substituent of Indolin-2-one, steric hindrance, position also do not influence on yield；By indoline
The blocking group of nitrogen-atoms changes acetyl group into by Boc (tertbutyloxycarbonyl), can also favourable conversions into corresponding product.
Embodiment
With reference to specific embodiment, the present invention is described further.
Thin-layer chromatographic analysis (TLC) use 60F254 silica gel plates, 254 and 365nm ultraviolet lights.Silica gel column chromatography uses particle diameter
0.040-0.063mm silica gel.NMR(400MHz for1H NMR,100MHz for 13C NMR) solvent be chloroform or acetone,
With tetramethylsilane (TMS) for internal standard.The unit of chemical shift is ppm, and the unit of coupling constant is Hz.1In H NMR, δ tables
Show chemical shift, s represents unimodal, and d represents bimodal, and t represents triplet, and q represents quartet, and m represents multiplet.13C NMR
In, δ represents chemical shift.High resolution mass spectrum (HRMS) is ionized using ESI.
Embodiment 1
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolDBU and 2.0mL dichloromethanes
Alkane adds seal pipe, reacts 24h at room temperature.After removing solvent, residue obtains product 4aa through silica gel column chromatography after purification,
Yield is 94%.
1H NMR(500Hz,CDCl3):δ(ppm)7.83-7.81(m,2H),7.63-7.59(m,2H),7.46-7.43(m,
2H),7.39-7.36(m,1H),7.29-7.27(m,1H),7.22-7.19(m,1H),7.05(br s,1H),1.47(s,9H)
。13C NMR(126Hz,CDCl3):δ(ppm)161.2,153.7,143.7,136.5,132.1,130.8,129.8,128.3,
127.7,124.9,124.7,124.5,119.3,116.7,80.4,28.3。HRMS:exact mass calculated for
[M+Na]+(C20H19NO4Na)requires m/z 360.1206,found m/z 360.1194。
Embodiment 2
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmol triethylamines and 2.0mL bis-
Chloromethanes adds seal pipe, reacts 24h at room temperature.After removing solvent, residue obtains product after purification through silica gel column chromatography
4aa, yield 26%；Accessory substance is generated in additionYield is 55%.
Embodiment 3
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylides 2a, 0.02mmol DABCO and 2.0mL bis-
Chloromethanes adds seal pipe, reacts 24h at room temperature.After removing solvent, residue obtains product after purification through silica gel column chromatography
4aa, yield 11%；Accessory substance 3aa, yield 66% are generated in addition.
Embodiment 4
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylides 2a, 0.02mmol NH (i-Pr)2With
2.0mL dichloromethane adds seal pipe, reacts 24h at room temperature.After removing solvent, residue obtains after purification through silica gel column chromatography
To product 4aa, yield 16%；Accessory substance 3aa, yield 36% are generated in addition.
Embodiment 5
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylides 2a, 0.02mmol K2CO3/ TBAB and
2.0mL dichloromethane adds seal pipe, reacts 24h at room temperature.After removing solvent, residue obtains after purification through silica gel column chromatography
To product 4aa, yield 30%；Accessory substance 3aa, yield 31% are generated in addition.
Embodiment 6
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmol nafoxidines and 2.0mL
Dichloromethane adds seal pipe, reacts 24h at room temperature.After removing solvent, residue is produced after purification through silica gel column chromatography
Thing 4aa, yield 77%；Accessory substance 3aa, yield 16% are generated in addition.
Embodiment 7
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL dichloromethanes
Alkane adds seal pipe, reacts 24h at room temperature.After removing solvent, residue obtains product 4aa through silica gel column chromatography after purification,
Yield is 96%.
Embodiment 8
0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroforms are added
Enter seal pipe, react 24h at room temperature.After removing solvent, residue obtains product 4aa, yield through silica gel column chromatography after purification
For 97%.
Embodiment 9
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL acetic acid second
Ester adds seal pipe, reacts 24h at room temperature.After removing solvent, residue obtains product 4aa through silica gel column chromatography after purification,
Yield is 89%.
Embodiment 10
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL tetrahydrochysene furans
Mutter and add seal pipe, react 24h at room temperature.After removing solvent, residue obtains product 4aa through silica gel column chromatography after purification,
Yield is 87%.
Embodiment 11
0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL toluene is added
Enter seal pipe, react 24h at room temperature.After removing solvent, residue obtains product 4aa, yield through silica gel column chromatography after purification
For 76%.
Embodiment 12
0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL acetonitriles are added
Enter seal pipe, react 24h at room temperature.After removing solvent, residue obtains product 4aa, yield through silica gel column chromatography after purification
For 85%.
Embodiment 13
By 0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylides 2a, 0.02mmolTMG and 2.0mL1,4- bis-
The ring of oxygen six adds seal pipe, reacts 24h at room temperature.After removing solvent, residue obtains product after purification through silica gel column chromatography
4aa, yield 96%.
Embodiment 14
0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 1.0mL chloroforms are added
Enter seal pipe, react 4h at room temperature.After removing solvent, residue obtains product 4aa through silica gel column chromatography after purification, and yield is
92%.
Embodiment 15
0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroforms are added
Enter seal pipe, react 4h at room temperature.After removing solvent, residue obtains product 4aa through silica gel column chromatography after purification, and yield is
95%.
Embodiment 16
0.20mmol N-Boc-2- indolone 1a, 0.24mmol salicylide 2a, 0.02mmolTMG and 4.0mL chloroforms are added
Enter seal pipe, react 4h at room temperature.After removing solvent, residue obtains product 4aa through silica gel column chromatography after purification, and yield is
91%.
Embodiment 17
0.20mmol compound 1a, 0.24mmol compound 2b, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
4h is reacted at room temperature.After removing solvent, residue obtains product 4ab, yield 91% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ(ppm)7.82-7.79(m,2H),7.44-7.39(m,3H),7.26-7.23(m,
2H), 7.17 (t, J=7.5Hz, 1H), 7.09 (br s, 1H), 2.53 (s, 3H), 1.45 (s, 9H).13C NMR(126Hz,
CDCl3):δ(ppm)161.4,153.7,152.2,144.3,136.6,133.5,130.8,129.8,128.2,127.4,
126.3,126.0,124.7,124.6,124.4,119.1,80.4,28.4,15.6。HRMS:exact mass calculated
for[M-H]-(C21H20NO4)requires m/z 350.1398,found m/z 350.1404。
Embodiment 18
0.20mmol compound 1a, 0.24mmol compound 2c, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
4h is reacted at room temperature.After removing solvent, residue obtains product 4ac, yield 95% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.81-7.79 (m, 2H), 7.42 (t, J=7.8Hz, 1H), 7.30-
7.25(m,2H),7.19-7.13(m,3H),7.07(br s,1H),4.01(s,3H),1.45(s,9H)。13C NMR(126Hz,
CDCl3):δ(ppm)160.8,153.8,147.2,144.0,143.5,136.7,130.8,129.9,128.2,125.0,
124.8,124.6,120.1,119.7,113.8,80.4,56.4,28.4。HRMS:exact mass calculated for[M
+Na]+(C21H21NO5Na)requires m/z 390.1312,found m/z 390.1303。
Embodiment 19
0.20mmol compound 1a, 0.24mmol compound 2d, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ad, yield 90% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.80 (d, J=8.0Hz, 1H), 7.77 (s, 1H), 7.45 (d, J=
8.0Hz, 2H), 7.41 (t, J=7.8Hz, 1H), 7.26-7.23 (m, 2H), 7.17 (t, J=7.5Hz, 1H), 7.06 (s, 1H),
2.50(s,3H),1.45(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)161.5,153.9,153.8,143.9,
143.6,136.6,130.8,129.7,128.0,126.4,126.3,124.7,124.4,117.0,116.9,80.4,28.4,
22.0。HRMS:exact mass calculated for[M-H]-(C21H20NO4)requires m/z 350.1398,found
m/z 350.1404。
Embodiment 20
0.20mmol compound 1a, 0.24mmol compound 2e, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4ae, yield 73% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.80 (d, J=7.5Hz, 1H), 7.74 (s, 1H), 7.46 (d, J=
8.0Hz, 1H), 7.40 (t, J=7.8Hz, 1H), 7.24 (d, J=7.5Hz, 1H), 7.17 (t, J=7.5Hz, 1H), 7.07 (br
s,1H),6.93-6.91(m,2H),3.91(s,3H),1.45(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)163.2,
161.6,155.7,153.8,144.1,136.6,130.9,129.6,129.3,128.4,124.7,124.4,124.0,
113.4,113.1,100.6,80.4,56.0,28.4。HRMS:exact mass calculated for[M+H-Boc]+
(C16H14NO3)requires m/z 268.0968,found m/z 268.0960。
Embodiment 21
0.20mmol compound 1a, 0.24mmol compound 2f, 0.02mmolDBU and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4af, yield 88% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.77 (s, 2H), 7.58-7.55 (m, 1H), 7.42 (t, J=7.8Hz,
1H), 7.25 (d, J=7.5Hz, 1H), 7.18 (t, J=7.5Hz, 1H), 7.16-7.13 (m, 1H), 7.11-7.07 (m, 1H),
6.94(br s,1H),1.44(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)165.7,163.7,160.8,154.9,
153.7,143.2,136.5,130.8,130.0,129.9,128.1,126.5,124.9,124.7,116.2,113.4,
113.2,104.5,104.3,80.5,28.4。HRMS:exact mass calculated for [M+Na]+
(C20H18NO4FNa)requires m/z 378.1112,found m/z 378.1101。
Embodiment 22
0.20mmol compound 1a, 0.24mmol compound 2g, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4ag, yield 84% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.78-7.76 (m, 2H), 7.50 (d, J=8.5Hz, 1H), 7.44-
7.41 (m, 2H), 7.32 (d, J=8.5Hz, 1H), 7.25 (d, J=7.5Hz, 1H), 7.19 (t, J=7.5Hz, 1H), 6.93
(br s,1H),1.44(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)160.6,154.0,153.7,142.9,138.1,
136.5,130.8,130.1,129.1,128.1,127.7,125.6,124.9,124.8,118.0,117.1,80.6,28.4。
HRMS:exact mass calculated for[M-H]-(C20H17NO4Cl)requires m/z 370.0852,found m/
z 370.0858。
Embodiment 23
0.20mmol compound 1a, 0.24mmol compound 2h, 0.02mmolDBU and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4ah, yield 84% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.77-7.75 (m, 2H), 7.60 (s, 1H), 7.47 (d, J=8.5Hz,
1H),7.44-7.42(m,2H)；7.25 (d, J=7.5Hz, 1H), 7.19 (t, J=7.5Hz, 1H), 6.92 (br s, 1H),
1.44(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)160.4,153.9,153.6,142.9,136.4,130.7,
130.0,129.1,128.4,128.1,127.9,126.0,124.9,124.7,120.0,118.3,80.5.28.3。HRMS:
exact mass calculated for[M+H-Boc]+(C15H11NO2Br)requires m/z 315.9968,found m/z
315.9959。
Embodiment 24
0.20mmol compound 1a, 0.24mmol compound 2i, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4ai, yield 81% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 8.24 (s, 1H), 8.18 (d, J=8.5Hz, 1H), 7.86 (s, 1H),
7.75 (d, J=8.5Hz, 1H), 7.71 (d, J=8.0Hz, 1H), 7.45 (t, J=7.5Hz, 1H), 7.29 (d, J=7.5Hz,
1H), 7.22 (d, J=7.5Hz, 1H), 6.86 (br s, 1H), 1.42 (s, 9H).13C NMR(126Hz,CDCl3):δ(ppm)
159.8,153.8,153.2,149.1,141.3,136.3,131.4,130.7,130.6,129.2,128.0,125.3,
124.2,119.6,112.5,80.8,28.3。HRMS:exact mass calculated for[M+H-Boc]+
(C15H11N2O4)requires m/z 283.0713,found m/z 283.0709。
Embodiment 25
0.20mmol compound 1a, 0.24mmol compound 2j, 0.02mmolDBU and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4aj, yield 92% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.80 (d, J=8.0Hz, 1H), 7.76 (s, 1H), 7.44-7.40 (m,
2H), 7.36-7.32 (m, 2H), 7.26-7.24 (m, 1H), 7.18 (t, J=7.5Hz, 1H), 7.05 (br s, 1H), 2.45 (s,
3H),1.45(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)161.5,153.8,152.0,143.9,136.7,134.9,
133.3,130.9,129.9,128.4,128.1,127.7,124.8,124.5,119.2,116.5,80.5,28.4,21.0。
HRMS:exact mass calculated for[M+Na]+(C21H21NO4Na)requires m/z 374.1363,found
m/z 374.1357。
Embodiment 26
0.20mmol compound 1a, 0.24mmol compound 2k, 0.02mmolDBU and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ak, yield 85% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.80 (d, J=8.0Hz, 1H), 7.76 (s, 1H), 7.43 (t, J=
7.8Hz, 1H), 7.36 (d, J=9.0Hz, 1H), 7.26-7.25 (m, 1H), 7.20-7.17 (m, 2H), 7.08 (br s, 1H),
6.99 (d, J=3.0Hz, 1H), 3.87 (s, 3H), 1.45 (s, 9H).13C NMR(126Hz,CDCl3):δ(ppm)161.4,
156.6,153.8,148.3,143.7,136.7,130.9,129.9,128.2,124.8,120.2,119.8,117.9,
110.0,80.5,56.0,28.4。HRMS:exact mass calculated for[M+Na]+(C21H21NO5Na)requires
m/z 390.1312,found m/z 390.1302。
Embodiment 27
0.20mmol compound 1a, 0.24mmol compound 2l, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
4h is reacted at room temperature.After removing solvent, residue obtains product 4al, yield 95% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.77 (d, J=8.0Hz, 1H), 7.75 (s, 1H), 7.45-7.40 (m,
2H),7.33-7.29(m,1H)；7.27-7.25 (m, 2H), 7.19 (t, J=7.5Hz, 1H), 6.97 (br s, 1H), 1.45 (s,
9H)。13C NMR(126Hz,CDCl3):δ(ppm)160.8,160.0,158.0,153.6,149.9,142.6,136.5,
130.7,130.1,129.0,128.0,124.9,124.7,120.1,120.0,119.6,119.4,118.3,113.5,
113.3,80.5.28.3。HRMS:exact mass calculated for[M+Na]+(C20H18FNO4Na)requires m/z
378.1112,found m/z 378.1099。
Embodiment 28
0.20mmol compound 1a, 0.24mmol compound 2m, 0.02mmolDBU and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4am, yield 92% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ(ppm)7.80-7.74(m,2H),7.57-7.38(m,4H),7.29-7.20(m,
2H),6.95(br s,1H),1.46(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)160.6,153.7,152.2,
142.3,136.5,132.0,130.8,130.3,130.2,129.0,128.0,127.5,125.0,124.8,120.4,
118.2,80.6.28.4。HRMS:exact mass calculated for[M+Na]+(C20H18ClNO4Na)requires m/
z 394.0817,found m/z 394.0808。
Embodiment 29
0.20mmol compound 1a, 0.24mmol compound 2n, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4an, yield 96% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.78 (d, J=8.0Hz, 1H), 7.72-7.67 (m, 3H), 7.44 (t, J
=7.8Hz, 1H), 7.32 (d, J=8.5Hz, 1H), 7.25-7.18 (m, 2H), 7.08 (br s, 1H), 1.44 (s, 9H).13C
NMR(126Hz,CDCl3):δ(ppm)160.5,153.6,152.5,142.1,136.5,134.8,130.7,130.4,130.1,
129.0,127.9,124.9,120.9,118.4,117.5,80.5.28.3。HRMS:exact mass calculated for
[M+Na]+(C20H18BrNO4Na)requires m/z 438.0311,found m/z 438.0307。
Embodiment 30
0.20mmol compound 1a, 0.24mmol compound 2o, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4ao, yield 93% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 8.19 (s, 1H), 7.81 (d, J=7.0Hz, 1H), 7.50 (t, J=
8.3Hz, 1H), 7.41 (t, J=7.8Hz, 2H), 7.27 (d, J=7.5Hz, 1H), 7.17 (t, J=7.5Hz, 1H), 7.08 (br
S, 1H), 7.01 (d, J=8.5Hz, 1H), 6.77 (d, J=8.5Hz, 1H), 3.94 (s, 3H), 1.45 (s, 9H).13C NMR
(126Hz,CDCl3):δ(ppm)161.4,156.6,154.8,153.7,139.2,136.6,132.8,131.0,129.7,
128.4,125.6,124.6,110.3,108.9,105.5,80.4,56.2,28.4。HRMS:exact mass calculated
for[M-H]—(C21H20NO5)requires m/z 366.1347,found m/z 366.1352。
Embodiment 31
0.20mmol compound 1a, 0.24mmol compound 2p, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ap, yield 86% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 8.03 (s, 1H), 7.79 (d, J=7.5Hz, 1H), 7.57-7.52 (m,
1H), 7.44 (t, J=7.5Hz, 1H), 7.29-7.19 (m, 3H), 7.07 (t, J=8.5Hz, 1H), 6.92 (br s, 1H),
1.45(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)160.6,159.8,157.8,154.3,153.7,136.6,
136.5,136.4,132.5,130.9,130.2,128.0,124.9,124.7,112.6,110.9,110.8,109.8,
109.7,80.6,28.4。HRMS:exact mass calculated for[M+Na]+(C20H18NO4FNa)requires m/z
378.1112,found m/z 378.1106。
Embodiment 32
0.20mmol compound 1a, 0.24mmol compound 2q, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4aq, yield 92% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 8.18 (s, 1H), 7.82 (d, J=7.5Hz, 1H), 7.52 (t, J=
8.3Hz, 1H), 7.47 (t, J=7.8Hz, 1H)；7.41 (d, J=8.0Hz, 1H), 7.36 (d, J=8.5Hz, 1H), 7.32 (d,
J=8.3Hz, 1H), 7.23 (t, J=7.5Hz, 1H), 6.96 (br s, 1H), 1.47 (s, 9H).13C NMR(126Hz,
CDCl3):δ(ppm)160.5,154.5,153.7,139.9,136.6,132.8,132.1,131.0,130.2,128.6,
125.6,124.9,118.0,115.6,80.6.28.4。HRMS:exact mass calculated for[M+H-Boc]+
(C15H11NO2Cl)requires m/z 272.0473,found m/z 272.0466。
Embodiment 33
0.20mmol compound 1a, 0.24mmol compound 2r, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4ar, yield 87% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 8.13 (s, 1H), 7.80 (d, J=7.5Hz, 1H), 7.57 (d, J=
8.0Hz, 1H), 7.47-7.41 (m, 2H), 7.38 (d, J=7.8Hz, 1H), 7.30 (d, J=8.0Hz, 1H), 7.22 (t, J=
7.5Hz,1H),6.95(br s,1H),1.45(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)160.6,154.3,
153.6,142.4,136.6,132.4,131.0,130.2,129.0,128.9,124.9,122.7,119.4,116.3,80.6,
28.4。HRMS:exact mass calculated for[M+H]+(C20H19NO4Br)requires m/z 416.0492,
found m/z 416.0480。
Embodiment 34
0.20mmol compound 1b, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 4ba, yield 92% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.90 (d, J=8.0Hz, 1H), 7.79 (s, 1H), 7.64 (t, J=
7.8Hz, 1H), 7.59 (d, J=8.0Hz, 1H), 7.46-7.44 (m, 2H), 7.37 (t, J=7.5Hz, 1H), 7.29-7.26
(m,1H),6.41(br s,1H),1.41(s,9H)。13C NMR(126Hz,CDCl3):δ(ppm)159.9,154.3,153.1,
145.8,138.3,132.6,130.7,128.7,128.6,127.4,125.3,125.0,124.5,122.0,118.9,
117.1,81.2,28.3。HRMS:exact mass calculated for[M+H-Boc]+(C15H11NO2Br)requires
m/z 315.9968,found m/z 315.9960。
Embodiment 35
0.20mmol compound 1c, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
4h is reacted at room temperature.After removing solvent, residue obtains product 4ca, yield 97% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.79 (s, 1H), 7.71 (d, J=10.5Hz, 1H), 7.63-7.58 (m,
2H), 7.44 (d, J=8.5Hz, 1H), 7.37 (t, J=7.5Hz, 1H), 7.21 (t, J=7.8Hz, 1H), 7.09 (br s,
1H), 6.86 (t, J=8.0Hz, 1H), 1.46 (s, 9H).13C NMR(126Hz,CDCl3):δ(ppm)164.6,162.6,
161.3,153.8,153.2,144.2,138.6,138.5,132.4,132.2,132.1,128.4,126.7,125.1,
123.0,119.3,116.8,111.3,111.1,110.7,110.5,81.0,28.3。HRMS:exact mass
calculated for[M+H]+(C20H19NO4F)requires m/z 356.1293,found m/z 356.1290。
Embodiment 36
0.20mmol compound 1d, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4da, yield 90% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.09 (d, J=1.6Hz, 2H), 7.99 (s, 1H), 7.73 (dd, J
=1.6,8.0Hz, 1H), 7.68-7.64 (m, 1H), 7.41-7.35 (m, 3H), 7.18 (dd, J=2.0,8.2Hz, 1H), 1.39
(s,9H)。13C NMR(100Hz,(CD3)2CO):δ(ppm)160.5,154.9,153.8,144.2,139.7,135.1,
133.1,132.8,129.5,127.0,126.5,125.4,123.8,122.3,120.6,117.0,80.6,28.4。HRMS:
exact mass calculated for[M-H]-(C20H17NClO4)requires m/z 370.0852,found m/z
370.0862。
Embodiment 37
0.20mmol compound 1e, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ea, yield 95% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.24 (d, J=1.2Hz, 1H), 8.08 (br s, 1H), 8.00 (s,
1H), 7.74 (dd, J=1.4,7.8Hz, 1H), 7.68-7.64 (m, 1H), 7.41-7.37 (m, 2H), 7.35-7.29 (m, 2H),
1.39(s,9H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)160.4,154.9,153.8,144.2,139.9,133.3,
132.8,129.4,127.1,126.9,126.7,125.4,125.1,123.1,120.6,117.0,80.5,28.3。HRMS:
exact mass calculated for[M-H]-(C20H17NBrO4)requires m/z 414.0346,found m/z
414.0357。
Embodiment 38
0.20mmol compound 1f, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4fa, yield 90% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ(ppm)7.92(s,1H),7.72-7.61(m,4H),7.39-7.35(m,
2H),7.22-7.18(m,2H),2.32(s,3H),1.36(s,9H)。13C NMR(100Hz,(CD3)2CO):δ(ppm)160.8,
154.8,154.2,143.6,135.5,134.1,132.5,132.0,130.4,129.3,128.2,125.3,120.6,
116.9,79.8,28.4,20.7。HRMS:exact mass calculated for[M-H]-(C21H20NO4)requires m/
z 350.1398,found m/z 350.1407。
Embodiment 39
0.20mmol compound 1g, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ga, yield 89% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ(ppm)7.95(s,1H),7.72-7.70(m,1H),7.66-7.58(m,
3H),7.40-7.36(m,2H),7.00-6.96(m,2H),3.81(s,3H),1.34(s,9H)。13C NMR(100Hz,(CD3)2CO):δ(ppm)160.6,157.4,154.8,154.5,143.6,132.6,130.8,129.3,128.0,125.4,120.6,
116.9,116.8,115.3,79.6,55.9,28.4。HRMS:exact mass calculated for[M-H]-
(C21H20NO5)requires m/z 366.1347,found m/z 366.1357。
Embodiment 40
0.20mmol compound 1h, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ha, yield 92% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 7.99 (s, 1H), 7.85-7.77 (m, 2H), 7.73 (dd, J=
1.8,7.8Hz,1H),7.68-7.63(m,1H),7.04-7.37(m,2H),7.22-7.16(m,2H),1.36(s,9H)。13C
NMR(100Hz,(CD3)2CO):δ(ppm)160.9,160.4,158.5,154.8,154.3,144.0,134.4,134.3,
132.8,129.5,126.9,125.4,120.5,118.1,117.9,117.0,116.4,116.2,80.0,28.4。HRMS:
exact mass calculated for[M-H]-(C20H17NFO4)requires m/z 354.1147,found m/z
354.1157。
Embodiment 41
0.20mmol compound 1i, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ia, yield 83% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.01 (s, 1H), 7.97 (br s, 1H), 7.91 (d, J=13.6,
1H), 7.74 (dd, J=1.6,8.0Hz, 1H), 7.68-7.64 (m, 1H), 7.43-7.37 (m, 4H), 1.37 (s, 9H).13C
NMR(100Hz,(CD3)2CO):δ(ppm)160.4,154.9,153.9,144.3,137.2,132.8,131.2,130.2,
129.6,129.5,128.7,126.7,125.4,124.9,120.5,117.0,80.3,28.4。HRMS:exact mass
calculated for[M-H]-(C20H17NClO4)requires m/z 370.0852,found m/z 370.0862。
Embodiment 42
0.20mmol compound 1j, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ja, yield 84% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.01 (s, 1H), 7.98 (br s, 1H), 7.87 (d, J=9.6Hz,
1H), 7.74 (dd, J=1.4,7.8Hz, 1H), 7.68-7.64 (m, 1H), 7.57-7.54 (m, 2H), 7.41-7.37 (m, 2H),
1.37(s,9H)。13C NMR(100Hz,(CD3)2CO):δ(ppm)160.4,154.9,153.9,144.3,137.7,134.1,
132.8,132.6,130.4,129.5,126.6,125.4,125.1,120.5,117.0,116.2,80.3,28.4。HRMS:
exact mass calculated for[M-H]-(C20H17NBrO4)requires m/z 414.0346,found m/z
414.0358。
Embodiment 43
0.20mmol compound 1k, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
12h is reacted at room temperature.After removing solvent, residue obtains product 4ka, yield 92% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.55 (br s, 1H), 8.39 (d, J=8.8Hz, 1H), 8.30-
8.26 (m, 2H), 8.14 (s, 1H), 7.76 (dd, J=1.6,8.0Hz, 1H), 7.71-7.66 (m, 1H), 7.42-7.39 (m,
2H),1.42(s,9H)。13C NMR(100Hz,(CD3)2CO):δ(ppm)160.2,155.1,153.4,145.2,144.9,
143.2,133.1,129.7,127.4,127.2,126.1,125.4,121.1,120.5,117.0,81.3,28.3。HRMS:
exact mass calculated for[M-H]-(C20H17N2O6)requires m/z 381.1092,found m/z
381.1104。
Embodiment 44
0.20mmol compound 1l, 0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
4h is reacted at room temperature.After removing solvent, residue obtains product 4la, yield 82% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 8.17 (br s, 1H), 7.84 (s, 1H), 7.75 (d, J=8.5,1H),
7.63-7.59 (m, 2H), 7.47-7.42 (m, 2H), 7.37 (t, J=7.5Hz, 1H), 7.31 (d, J=7.0,1H), 7.28-
7.27(m,1H),2.07(s,3H)。13C NMR(126Hz,CDCl3):δ(ppm)169.1,161.7,153.7,144.4,
135.9,132.3,131.0,130.0,129.4,128.5,127.6,126.5,126.1,125.2,119.4,116.7,24.3。
HRMS:exact mass calculated for[M+H]+(C17H14NO3)requires m/z 280.0968,found m/z
280.0959。
Embodiment 45
0.20mmol compounds 5,0.24mmol salicylide 2a, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6a, yield 97% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.95 (s, 1H), 7.63-7.60 (m, 3H), 7.47 (d, J=8.0Hz,
1H), 7.41-7.36 (m, 2H), 7.32 (d, J=7.5Hz, 1H), 7.08 (d, J=8.0Hz, 1H), 7.04 (t, J=7.5Hz,
1H)。13C NMR(126Hz,CDCl3):δ(ppm)163.4,155.1,153.3,144.0,132.3,131.2,130.8,
128.4,127.6,125.4,123.3,121.6,119.7,119.6,116.8。HRMS:exact mass calculated
for[M+H]+(C15H11NO3)requires m/z 239.0703,found m/z 239.0698。
Embodiment 46
0.20mmol compounds 5,0.24mmol salicylide 2a, 0.02mmolDBU and 2.0mL chloroform are added into seal pipe,
24h is reacted at room temperature.After removing solvent, residue obtains product 6a, yield 93% through silica gel column chromatography after purification.
Embodiment 47
0.20mmol compounds 5,0.24mmol compound 2b, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6b, yield 82% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.48 (s, 1H), 8.00 (s, 1H), 7.55 (d, J=6.0Hz,
1H), 7.48 (d, J=6.4Hz, 1H), 7.38 (dd, J=1.4,6.2Hz, 1H), 7.28-7.25 (m, 2H), 6.98 (dd, J=
0.8,7.2Hz,1H),6.95-6.92(m,1H)。13C NMR(100Hz,(CD3)2CO):δ(ppm)160.9,156.0,152.8,
143.4,133.4,131.9,130.7,126.9,126.1,124.9,123.6,120.4,120.3,117.1,15.3。HRMS:
exact mass calculated for[M-H]-(C16H11O3)requires m/z 251.0714,found m/z
251.0715。
Embodiment 48
0.20mmol compounds 5,0.24mmol compound 2c, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6c, yield 94% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.48 (s, 1H), 8.00 (s, 1H), 7.39 (dd, J=1.5,
7.5Hz, 1H), 7.32-7.25 (m, 4H), 6.98 (dd, J=1.0,8.0Hz, 1H), 6.95-6.92 (m, 1H), 3.98 (s,
3H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)160.6,156.0,147.9,144.0,143.3,131.9,130.7,
127.4,125.2,123.6,121.2,120.4,117.1,114.4,56.6。HRMS:exact mass calculated for
[M-H]-(C16H11O4)requires m/z 267.0663,found m/z 267.0665。
Embodiment 49
0.20mmol compounds 5,0.24mmol compound 2d, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6d, yield 73% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.55 (s, 1H), 8.05 (s, 1H), 7.55 (d, J=8.0Hz,
1H),7.50-7.46(m,1H),7.40-7.34(m,2H),7.29-7.26(m,1H),6.99-6.98(m,1H),6.95-6.92
(m,1H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)159.3,155.9,150.8,148.9,142.5,131.8,
130.9,128.2,125.3,124.6,124.5,123.2,122.6,120.3,118.3,118.2,116.9。HRMS:exact
mass calculated for[M+H]+(C15H10FO3)requires m/z 257.0608,found m/z 257.0604。
Embodiment 50
0.20mmol compounds 5,0.24mmol compound 2e, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6e, yield 74% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.50 (s, 1H), 8.04 (s, 1H), 7.70 (d, J=7.6Hz,
2H),7.40-7.35(m,2H),7.30-7.25(m,1H),7.00-6.92(m,2H)。13C NMR(100Hz,(CD3)2CO):δ
(ppm)159.6,156.0,150.1,142.6,132.3,131.9,131.0,128.1,125.7,123.1,122.1,121.1,
120.4,117.0。HRMS:exact mass calculated for[M+H]+(C15H10ClO3)requires m/z
273.0313,found m/z 273.0309。
Embodiment 51
0.20mmol compounds 5,0.24mmol compound 2f, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6f, yield 75% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.53 (s, 1H), 8.03 (s, 1H), 7.87 (dd, J=1.5,
8.0Hz, 1H), 7.75 (dd, J=1.3,7.8Hz, 1H), 7.40 (dd, J=1.8,7.8Hz, 1H), 7.32 (t, J=8.0Hz,
1H), 7.30-7.26 (m, 1H), 6.99 (dd, J=0.8,7.8Hz, 1H), 6.96-6.93 (m, 1H).13C NMR(126Hz,
(CD3)2CO):δ(ppm)159.7,156.0,151.1,142.6,135.4,131.9,131.0,128.8,128.0,126.2,
123.0,122.1,120.3,117.0,109.7。HRMS:exact mass calculated for[M-H]-(C15H8BrO3)
requires m/z 316.9642,found m/z 316.9639。
Embodiment 52
0.20mmol compounds 5,0.24mmol compound 2g, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6g, yield 84% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.45 (s, 1H), 7.97 (s, 1H), 7.59 (d, J=8.0Hz,
1H), 7.36 (dd, J=2.0,7.5Hz, 1H), 7.27-7.23 (m, 1H), 7.21-7.19 (m, 2H), 6.98-6.96 (m, 1H),
6.94-6.91(m,1H),2.47(s,3H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)161.0,155.9,154.6,
143.5,143.1,131.9,130.6,128.9,126.4,126.0,123.7,120.4,118.1,117.1,117.0,21.7。
HRMS:exact mass calculated for[M+H]+(C16H13O3)requires m/z 253.0859,found m/z
253.0851。
Embodiment 53
0.20mmol compounds 5,0.24mmol compound 2h, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6h, yield 95% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.42 (s, 1H), 7.96 (s, 1H), 7.63 (d, J=8.5Hz,
1H), 7.36 (dd, J=1.8,7.8Hz, 1H), 7.26-7.23 (m, 1H), 6.97-6.90 (m, 4H), 3.94 (s, 3H).13C
NMR(126Hz,(CD3)2CO):δ(ppm)163.7,161.2,156.3,156.0,143.5,131.9,130.5,130.2,
123.8,123.6,120.4,117.2,114.1,113.4,101.1,56.3。HRMS:exact mass calculated for
[M-H]-(C16H11O4)requires m/z 267.0663,found m/z 267.0665。
Embodiment 54
0.20mmol compounds 5,0.24mmol compound 2i, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6i, yield 95% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ(ppm)8.50(s,1H),8.02(s,1H),7.81-7.78(m,1H),
7.36 (dd, J=1.8,7.8Hz, 1H), 7.28-7.17 (m, 3H), 6.97 (dd, J=1.0,8.0Hz, 1H), 6.94-6.91
(m,1H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)166.0,164.0,160.2,155.9,155.7,155.6,
142.5,131.9,131.1,131.0,130.8,126.1,123.3,117.5,117.0,113.1,112.9,104.4,
104.2。HRMS:exact mass calculated for[M-H]-(C15H8FO3)requires m/z 255.0463,found
m/z 255.0464。
Embodiment 55
0.20mmol compounds 5,0.24mmol compound 2j, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6j, yield 86% through silica gel column chromatography after purification.
1H NMR(500Hz,CDCl3):δ (ppm) 7.89 (s, 1H), 7.54 (d, J=8.5Hz, 1H), 7.46 (d, J=
2.0Hz, 1H), 7.38-7.35 (m, 3H), 7.30 (dd, J=1.5,8.0Hz, 1H), 7.06-7.01 (m, 2H).13C NMR
(126Hz,CDCl3):δ(ppm)162.6,154.9,153.4,143.0,138.2,131.3,130.8,129.1,127.4,
126.0,123.0,121.6,119.5,118.2,117.1。HRMS:exact mass calculated for[M+H]+
(C15H10ClO3)requires m/z 273.0313,found m/z 273.0305。
Embodiment 56
0.20mmol compounds 5,0.24mmol compound 2k, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6k, yield 93% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.47 (s, 1H), 8.01 (s, 1H), 7.68 (d, J=8.0Hz,
1H), 7.62 (d, J=2.0Hz, 1H), 7.54 (dd, J=1.8,8.2Hz, 1H), 7.37 (dd, J=2.0,7.6Hz, 1H),
7.29-7.24(m,1H),6.99-6.91(m,2H)。13C NMR(100Hz,(CD3)2CO):δ(ppm)159.9,155.9,
154.9,142.3,131.8,130.9,130.5,128.5,127.6,125.1,123.3,120.4,120.1,119.8,
117.1。HRMS:exact mass calculated for[M+H]+(C15H10BrO3)requires m/z 316.9808,
found m/z 316.9805。
Embodiment 57
0.20mmol compounds 5,0.24mmol compound 2l, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6l, yield 81% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.68 (s, 1H), 8.22-8.17 (m, 3H), 8.01 (d, J=
7.5Hz, 1H), 7.42 (dd, J=1.8,7.8Hz, 1H), 7.31-7.28 (m, 1H), 7.00 (dd, J=0.8,8.3Hz, 1H),
6.97-6.93(m,1H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)159.5,156.0,154.0,149.7,141.2,
131.8,131.3,130.5,130.3,125.8,122.8,120.4,119.8,116.9,112.4。HRMS:exact mass
calculated for[M+H]+(C15H10NO5)requires m/z 284.0553,found m/z 284.0548。
Embodiment 58
0.20mmol compounds 5,0.24mmol compound 2m, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6m, yield 97% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ(ppm)8.46(s,1H),7.96(s,1H),7.51(s,1H),7.44(dd,
J=1.5,8.5Hz, 2H), 7.37 (dd, J=1.8,7.8Hz, 1H), 7.28-7.24 (m, 2H), 6.97 (dd, J=1.0,
8.0Hz,1H),6.95-6.91(m,1H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)160.9,156.0,152.7,
143.0,134.9,132.2,131.9,130.7,128.9,127.2,123.7,120.4,120.3,117.1,116.6,20.7。
HRMS:exact mass calculated for[M-H]-(C16H11O3)requires m/z 251.0714,found m/z
251.0715。
Embodiment 59
0.20mmol compounds 5,0.24mmol compound 2n, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6n, yield 97% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.48 (s, 1H), 7.99 (s, 1H), 7.38 (dd, J=2.0,
7.5Hz, 1H), 7.32 (d, J=9.0Hz, 1H), 7.28-7.25 (m, 2H), 7.21 (dd, J=3.0,9.0Hz, 1H), 6.98
(dd, J=1.0,8.0Hz, 1H), 6.95-6.92 (m, 1H), 3.87 (s, 3H).13C NMR(126Hz,(CD3)2CO):δ(ppm)
161.0,157.1,156.0,148.9,143.0,131.9,130.7,127.6,123.7,121.0,120.3,119.9,
117.9,117.2,111.2,56.2。HRMS:exact mass calculated for [M+H]+(C16H13O4)requires
m/z 269.0808,found m/z 269.0800。
Embodiment 60
0.20mmol compounds 5,0.24mmol compound 2o, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6o, yield 83% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ(ppm)8.52(s,1H),8.02(s,1H),7.55-7.52(m,1H),
7.44-7.42 (m, 2H), 7.38 (dd, J=1.8,7.8Hz, 1H), 7.29-7.26 (m, 1H), 6.98 (dd, J=1.0,
8.0Hz,1H),6.95-6.92(m,1H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)160.6,160.3,158.6,
155.9,150.9,142.0,131.9,130.9,128.4,123.2,121.5,120.4,119.4,119.2,118.8,
118.7,117.0,114.3,114.1。HRMS:exact mass calculated for[M+H]+(C15H10FO3)requires
m/z 257.0608,found m/z 257.0604。
Embodiment 61
0.20mmol compounds 5,0.24mmol compound 2p, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6p, yield 90% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.55 (s, 1H), 8.01 (s, 1H), 7.80 (d, J=2.5Hz,
1H), 7.62 (dd, J=2.5,8.5Hz, 1H), 7.42 (d, J=9.0Hz, 1H), 7.38 (dd, J=1.8,7.8Hz, 1H),
7.29-7.26 (m, 1H), 6.98 (dd, J=1.0,8.0Hz, 1H), 6.95-6.92 (m, 1H).13C NMR(126Hz,(CD3)2CO):δ(ppm)160.0,155.9,153.1,141.7,131.8,131.0,129.7,128.5,128.2,123.2,121.9,
120.3,118.7,117.0。HRMS:exact mass calculated for[M+H]+(C15H10ClO3)requires m/z
273.0313,found m/z 273.0305。
Embodiment 62
0.20mmol compounds 5,0.24mmol compound 2q, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6q, yield 89% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.54 (s, 1H), 8.01 (s, 1H), 7.95 (d, J=2.0Hz,
1H), 7.76 (dd, J=2.0,9.0Hz, 1H), 7.39-7.35 (m, 2H), 7.29-7.26 (m, 1H), 6.98 (dd, J=1.0,
8.0Hz,1H),6.95-6.92(m,1H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)160.0,156.0,153.6,
141.6,134.7,131.8,131.3,131.0,128.5,123.2,122.4,120.3,119.0,117.0。HRMS:exact
mass calculated for[M+H]+(C15H10BrO3)requires m/z 316.9808,found m/z 316.9801。
Embodiment 63
0.20mmol compounds 5,0.24mmol compound 2r, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6r, yield 87% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.47 (s, 1H), 8.17 (s, 1H), 7.54 (t, J=8.3Hz,
1H), 7.38 (dd, J=1.5,7.5Hz, 1H), 7.27-7.24 (m, 1H), 6.99-6.92 (m, 4H), 3.98 (s, 3H).13C
NMR(126Hz,(CD3)2CO):δ(ppm)160.7,157.2,155.9,155.5,137.6,133.1,131.9,130.6,
125.3,123.7,120.4,117.1,110.7,109.2,106.4,56.6。HRMS:exact mass calculated for
[M+H]+(C16H13O4)requires m/z 269.0808,found m/z 269.0802。
Embodiment 64
0.20mmol compounds 5,0.24mmol compound 2s, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6s, yield 97% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ(ppm)8.59(s,1H),8.09(s,1H),7.67-7.62(m,1H),
7.42 (dd, J=1.8,7.8Hz, 1H), 7.30-7.26 (m, 1H), 7.24 (dd, J=0.8,8.3Hz, 1H), 7.19-7.15
(m, 1H), 6.99 (dd, J=1.0,8.5Hz, 1H), 6.96-6.93 (m, 1H).13C NMR(126Hz,(CD3)2CO):δ(ppm)
160.4,159.8,158.4,155.9,155.2,134.9,132.9,132.8,131.9,131.0,127.6,123.1,
120.3,117.0,113.1,111.1,110.9,110.4,110.3。HRMS:exact mass calculated for[M+H
]+(C15H10FO3)requires m/z 257.0608,found m/z 257.0601。
Embodiment 65
0.20mmol compounds 5,0.24mmol compound 2t, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6t, yield 92% through silica gel column chromatography after purification.
1H NMR(400Hz,(CD3)2CO):δ (ppm) 8.56 (s, 1H), 8.22 (s, 1H), 7.62 (t, J=8.1Hz,
1H), 7.48-7.42 (m, 2H), 7.37 (d, J=8.4Hz, 1H), 7.31-7.27 (m, 1H), 7.01-6.93 (m, 2H).13C
NMR(100Hz,(CD3)2CO):δ(ppm)159.8,155.9,155.4,138.3,132.6,132.0,131.1,128.4,
125.8,123.1,120.4,118.8,117.1,116.3。HRMS:exact mass calculated for[M+H]+
(C15H10ClO3)requires m/z 273.0313,found m/z 273.0308。
Embodiment 66
0.20mmol compounds 5,0.24mmol compound 2u, 0.02mmolTMG and 2.0mL chloroform are added into seal pipe,
3h is reacted at room temperature.After removing solvent, residue obtains product 6u, yield 88% through silica gel column chromatography after purification.
1H NMR(500Hz,(CD3)2CO):δ (ppm) 8.61 (s, 1H), 8.19 (s, 1H), 7.65 (dd, J=1.0,
8.0Hz, 1H), 7.55 (t, J=8.0Hz, 1H), 7.45-7.41 (m, 2H), 7.31-7.27 (m, 1H), 7.02-7.00 (m,
1H),6.97-6.94(m,1H)。13C NMR(126Hz,(CD3)2CO):δ(ppm)159.7,155.9,155.2,140.8,
133.0,131.9,131.1,129.3,128.6,122.9,122.5,120.4,120.2,117.0,116.9。HRMS:exact
mass calculated for[M+H]+(C15H10BrO3)requires m/z 316.9808,found m/z 316.9803。
Embodiment 67：Amplification test
5mmol N-Boc-2- indolone 1a, 6mmol salicylide 2a, 0.5mmolTMG and 50mL chloroform are added and sealed
Pipe, reacts 24h at room temperature.After removing solvent, residue obtains product 4aa, yield 81% through silica gel column chromatography after purification.
5mmol compounds 5,6mmol salicylide 2a, 0.5mmolTMG and 50mL chloroform are added into seal pipe, at room temperature
React 4h.After removing solvent, residue obtains product 6a, yield 90% through silica gel column chromatography after purification.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (8)
1. one kind synthesis compoundMethod, using DBU and/or TMG as catalyst, formula A compounds and
Formula B compounds react to obtain formula C compounds：
Wherein, X NBoc, NAc or O；R1Selected from hydrogen, alkyl, alkoxy, halogen, nitro；R3Selected from hydrogen, alkyl, alkoxy, halogen
Element, nitro.
2. according to the method for claim 1, it is characterised in that the R1Selected from hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, nitre
Base.
3. according to the method for claim 1, it is characterised in that the R3Selected from hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, nitre
Base.
4. according to the method described in claims 1 to 3 any one, it is characterised in that it is described reaction with dichloromethane, chloroform,
One or more in ethyl acetate, tetrahydrofuran, toluene, acetonitrile, 1,4- dioxane are solvent.
5. according to the method for claim 4, it is characterised in that the dosage of the solvent is at least 1mL.
6. according to the method described in claims 1 to 3 any one, it is characterised in that the dosage of the catalyst is at least
10mol%.
7. according to the method described in claims 1 to 3 any one, it is characterised in that the time of the reaction is at least 3h.
8. according to the method described in claims 1 to 3 any one, it is characterised in that the temperature of the reaction is at least 20 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039910A (en) * | 2019-12-31 | 2020-04-21 | 云南大学 | Photoinitiated method for synthesizing 3-aryl flavone or coumarin compound and application thereof |
| CN113121485A (en) * | 2021-03-01 | 2021-07-16 | 中山大学 | 3-aryl coumarin derivative and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450134A (en) * | 2012-05-31 | 2013-12-18 | 中国医学科学院药物研究所 | Preparation of coumarin derivative and application of coumarin derivative to control of serious cerebral disease |
| US20150197500A1 (en) * | 2014-01-14 | 2015-07-16 | Euclises Pharmaceuticals, Inc. | No-releasing guanidine-chromene conjugates |
-
2017
- 2017-07-06 CN CN201710545124.1A patent/CN107382933A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450134A (en) * | 2012-05-31 | 2013-12-18 | 中国医学科学院药物研究所 | Preparation of coumarin derivative and application of coumarin derivative to control of serious cerebral disease |
| US20150197500A1 (en) * | 2014-01-14 | 2015-07-16 | Euclises Pharmaceuticals, Inc. | No-releasing guanidine-chromene conjugates |
Non-Patent Citations (1)
| Title |
|---|
| RODERICK WALTER，等: "Synthesis and Cyclization Reactions of3-(2-Hydroxybenzylidene)-2(3H)-coumaranones", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039910A (en) * | 2019-12-31 | 2020-04-21 | 云南大学 | Photoinitiated method for synthesizing 3-aryl flavone or coumarin compound and application thereof |
| CN113121485A (en) * | 2021-03-01 | 2021-07-16 | 中山大学 | 3-aryl coumarin derivative and preparation method and application thereof |
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