CN107382816A - It is a kind of without the method that triaryl and four arylmethanes are built under catalysts conditions - Google Patents
It is a kind of without the method that triaryl and four arylmethanes are built under catalysts conditions Download PDFInfo
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- CN107382816A CN107382816A CN201710504410.3A CN201710504410A CN107382816A CN 107382816 A CN107382816 A CN 107382816A CN 201710504410 A CN201710504410 A CN 201710504410A CN 107382816 A CN107382816 A CN 107382816A
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- China
- Prior art keywords
- triaryl
- alkyl
- arylmethanes
- catalysts conditions
- under catalysts
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- HHTSSSRAILAYRY-UHFFFAOYSA-N COc1ccc(C(c2ccc[s]2)c(cc2)ccc2O)cc1 Chemical compound COc1ccc(C(c2ccc[s]2)c(cc2)ccc2O)cc1 HHTSSSRAILAYRY-UHFFFAOYSA-N 0.000 description 1
- WDVMZHRAXNHYGK-UHFFFAOYSA-O OC(C[n]1c(cccc2)c2c(C(C(CC2)=CC=C2[ClH+])c2ccccc2)c1)=O Chemical compound OC(C[n]1c(cccc2)c2c(C(C(CC2)=CC=C2[ClH+])c2ccccc2)c1)=O WDVMZHRAXNHYGK-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- 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
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
Abstract
The invention discloses a kind of without the method that triaryl and four arylmethanes are built under catalysts conditions, methods described can be room temperature without catalyst, temperature, solvent be to be reacted under the conditions of hexafluoroisopropanol, sodium carbonate.It is proposed by the present invention a kind of without the method that triaryl and four arylmethanes are built under catalysts conditions, realize S under no catalysts conditionsN1 reaction, raw material is simple and easy to get, and reaction condition is gentle, practicality simple to operate, and reactivity is high, and raw material conversion is complete, and convenient separation, yield is high, and reaction has green economy, environmentally friendly.
Description
Technical field
The present invention relates to chemosynthesis technical field, more particularly to one kind is without structure structure triaryl under catalysts conditions
With the method for four arylmethanes.
Background technology
The side such as triaryl and four arylmethanes treatment diabetes, cancer, angiocardiopathy, angiocardiopathy, cell infection
Face, which has, widely applies.It also can not be ignored in the important function of analytical chemistry, materials chemistry etc..Therefore, it is efficiently green
Triaryl is synthesized color and four arylmethane class compounds are extremely urgent.However, the report for synthesizing such compound is extremely limited,
Most of by transition metal-catalyzed, cost is high, and pollution is big.
Bibliography
(a)R.Palchaudhuri,V.Nesterenko,P.J.Hergenrother,J.Am.Chem.Soc.2008,
130,10274.
(b)Shagufta,A.K.Srivastava,R.Sharma,R.Mishra,A.K.Balapure,
P.S.R.Murthy,G.Panda,Bioorgan.Med.Chem.2006,14,1497.
(c)B.A.Ellsworth,W.R.Ewing,E.Jurica,U.S.Patent Application 2011/
0082165A1,Apr 7,2011.
(d)R.A.Al-Qawasmeh,Y.Lee,M.Y.Cao,X.P.Gu,A.Vassilakos,J.A.Wright,
A.Young,Bioorg.Med.Chem.Lett.2004,14,347.
The content of the invention
It is an object of the invention to provide a kind of without the side of structure structure triaryl and four arylmethanes under catalysts conditions
Method.Present invention practicality simple to operate, yield is good, and reaction has green economy, environmentally friendly, is easy to industrialize.
It is a kind of without under catalysts conditions structure structure triaryl and four arylmethanes method, methods described is without catalysis
Agent, reaction equation and condition are as follows：
In formula：
Temperature：Room temperature；
Solvent：HFIP；
Time：12 hours；
Described R1 is H, F, Cl, Br, I, cyano group, hydroxyl, amino, carboxyl, alkyl, haloalkyl, alkoxy, alkane sulphur
Base, alkenyl, alkynyl, nitro, sulfydryl, hydroxy alkyl, hydroxy alkoxy base, aminoalkoxy, alkyl-O-C (=O)-, aryl, virtue
Base alkyl, heteroaryl, heteroaryl alkyl, heterocyclic radical, cycloheteroalkylalkyl, cycloalkyl, aryloxy group, heteroaryloxy, haloalkyl oxygen
Base or monosubstituted or identical or different polysubstituted of cycloalkyl-alkyl；
Described R2 is H, F, Cl, Br, I, cyano group, hydroxyl, amino, carboxyl, alkyl, haloalkyl, alkoxy, alkane sulphur
Base, alkenyl, alkynyl, nitro, sulfydryl, hydroxy alkyl, hydroxy alkoxy base, aminoalkoxy, alkyl-O-C (=O)-, aryl, virtue
Base alkyl, heteroaryl, heteroaryl alkyl, heterocyclic radical, cycloheteroalkylalkyl, cycloalkyl, aryloxy group, heteroaryloxy, haloalkyl oxygen
Base or monosubstituted or identical or different polysubstituted of cycloalkyl-alkyl；
Described R3 is H, F, Cl, Br, I, cyano group, hydroxyl, amino, carboxyl, alkyl, haloalkyl, alkoxy, alkane sulphur
Base, alkenyl, alkynyl, nitro, sulfydryl, hydroxy alkyl, hydroxy alkoxy base, aminoalkoxy, alkyl-O-C (=O)-, aryl, virtue
Base alkyl, heteroaryl, heteroaryl alkyl, heterocyclic radical, cycloheteroalkylalkyl, cycloalkyl, aryloxy group, heteroaryloxy, haloalkyl oxygen
Base or a kind of substituent of cycloalkyl-alkyl；
Described Nu is one kind in electron rich aromatic ring, aniline, thiophenol, active methylene group, anthrone；
Comprise the following steps：Take the carbonic acid of 0.2mmol diaryl or triaryl chloride, 0.4mmol Nu and 0.4mmol
Potassium adds 2mL HFIP, is stirred at room temperature and is reacted in tube sealing, determines response situation by TLC, after completion of the reaction
Pass through pillar layer separation.Preferably, the mol ratio of diaryl or the triaryl chloride and Nu is 1:2.
Preferably, the temperature is 25 DEG C.
Preferably, the solvent can also be TFE.
Preferably, the alkali is sodium carbonate.
Preferably, the alkali can also be triethylamine, potassium carbonate, sodium hydroxide.
Preferably, the alkali can not also add.
Preferably, the amount of the alkali is 2 equivalents.
Preferably, the reaction obtains triaryl and four arylmethane chemical combination for diaryl or triaryl chloride with Nu
Thing, reaction temperature be room temperature, reaction dissolvent HFIP, alkali be sodium carbonate when result it is optimal, reach 90%.
It is proposed by the present invention it is a kind of without under catalysts conditions structure structure triaryl and four arylmethanes method, first
Realize S under no catalysts conditionsN1 reaction, raw material is simple and easy to get, and reaction condition is gentle, practicality simple to operate, reactivity
Height, raw material conversion is complete, and convenient separation, yield is high, and reaction has green economy, environmentally friendly.
Embodiment
The present invention is made with reference to specific embodiment further to explain.
Embodiment 1：The optimization of condition
The potassium carbonate of 0.2mmol diaryl or triaryl chloride, 0.4mmol Nu and 0.4mmol is taken to add in tube sealing
Enter 2mL HFIP, be stirred at room temperature and reacted, response situation is determined by TLC, pass through column chromatography point after completion of the reaction
From.
Under identical reaction conditions, solvent for use is different, and reaction yield is also different, and specific yield is as follows：
Note：Yield is separation yield.
Embodiment 2：Without structure structure triaryl and four arylmethanes under catalysts conditions
Yield is separation yield.
Embodiment 3：
Nuclear magnetic resonance spectroscopy is carried out to product made from the present embodiment：
White solid, 90%yield；1H NMR(500MHz,CDCl3)δ7.25-7.22(m,3H),7.20-7.19
(m, 3H), 7.12-7.07 (m, 5H), 6.78 (t, J=5.0Hz, 1H), 6.75 (d, J=5.0Hz, 4H), 6.68 (d, J=
8.1Hz,1H),6.62(s,1H),3.72(s,6H),3.63(s,3H)ppm.13C NMR(125MHz,CDCl3)δ157.6,
147.3,139.1,138.2,131.7,130.7,130.2,128.2,127.4,125.6,123.0,121.3,118.7,
112.6,109.2,58.0,55.2,33.1ppm.ESI HRMS:calcd.for C30H27NO2+Na 456.1939,found
456.1942.
Embodiment 4：
Nuclear magnetic resonance spectroscopy is carried out to product made from the present embodiment：
White solid, 82%yield；1H NMR(500MHz,CDCl3)δ7.29–7.26(m,5H),7.20-7.18
(m,5H),6.83-6.82(m,5H),6.68(s,1H),6.14(s,1H),3.83(s,6H),3.72(s,3H),3.47(s,3H)
ppm.13C NMR(125MHz,CDCl3)δ157.5,153.0,147.1,139.1,133.0,131.7,130.6,130.5,
128.3,127.3,125.8,123.0,112.6,111.5,109.6,104.5,58.0,55.5,55.2,32.9ppm.ESI
HRMS:calcd.for C31H29NO3+H 486.2045,found 486.2044.
Embodiment 5：
Nuclear magnetic resonance spectroscopy is carried out to product made from the present embodiment：
White solid, 82%yield；1H NMR (500MHz, CDCl3) δ 7.24-7.17 (m, 5H), 7.15 (d, J=
8.7Hz, 1H), 7.08 (d, J=8.8Hz, 4H), 7.05 (dd, J=8.7,1.9Hz, 1H), 6.76 (d, J=8.9Hz, 4H),
6.66 (s, 1H), 6.61 (d, J=1.8Hz, 1H), 3.78 (d, J=4.8Hz, 6H), 3.68 (s, 3H) ppm.13C NMR
(125MHz,CDCl3)δ157.6,146.7,138.7,136.9,131.5,131.1,130.5,128.8,127.4,126.0,
124.8,123.1,122.0,121.6,121.5,112.7,110.0,57.8,55.1,32.9ppm.ESI HRMS:
calcd.for C30H26ClNO2+H 468.1730,found 468.1722,470.1713.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (9)
- It is 1. a kind of without the method that triaryl and four arylmethanes are built under catalysts conditions, it is characterised in that methods described without Catalyst, reaction equation and condition are as follows：In formula：Temperature：Room temperature；Solvent：HFIP；Time：12 hours；Described R1 is H, F, Cl, Br, I, cyano group, hydroxyl, amino, carboxyl, alkyl, haloalkyl, alkoxy, alkylthio group, alkene Base, alkynyl, nitro, sulfydryl, hydroxy alkyl, hydroxy alkoxy base, aminoalkoxy, alkyl-O-C (=O)-, aryl, aryl alkane Base, heteroaryl, heteroaryl alkyl, heterocyclic radical, cycloheteroalkylalkyl, cycloalkyl, aryloxy group, heteroaryloxy, haloalkyl epoxide or Monosubstituted or identical or different polysubstituted of cycloalkyl-alkyl；Described R2 is H, F, Cl, Br, I, cyano group, hydroxyl, amino, carboxyl, alkyl, haloalkyl, alkoxy, alkylthio group, alkene Base, alkynyl, nitro, sulfydryl, hydroxy alkyl, hydroxy alkoxy base, aminoalkoxy, alkyl-O-C (=O)-, aryl, aryl alkane Base, heteroaryl, heteroaryl alkyl, heterocyclic radical, cycloheteroalkylalkyl, cycloalkyl, aryloxy group, heteroaryloxy, haloalkyl epoxide or Monosubstituted or identical or different polysubstituted of cycloalkyl-alkyl；Described R3 is H, F, Cl, Br, I, cyano group, hydroxyl, amino, carboxyl, alkyl, haloalkyl, alkoxy, alkylthio group, alkene Base, alkynyl, nitro, sulfydryl, hydroxy alkyl, hydroxy alkoxy base, aminoalkoxy, alkyl-O-C (=O)-, aryl, aryl alkane Base, heteroaryl, heteroaryl alkyl, heterocyclic radical, cycloheteroalkylalkyl, cycloalkyl, aryloxy group, heteroaryloxy, haloalkyl epoxide or A kind of substituent of cycloalkyl-alkyl；Described Nu is one kind in electron rich aromatic ring, aniline, thiophenol, active methylene group, anthrone；Comprise the following steps：Take the potassium carbonate of 0.2mmol diaryl or triaryl chloride, 0.4mmol Nu and 0.4mmol in In tube sealing, 2mL HFIP is added, is stirred at room temperature and is reacted, response situation is determined by TLC, passed through after completion of the reaction Pillar layer separation.
- 2. it is according to claim 1 a kind of without the method that triaryl and four arylmethanes are built under catalysts conditions, its It is characterised by, the mol ratio of diaryl or the triaryl chloride and Nu is 1:2.
- 3. it is according to claim 1 a kind of without the method that triaryl and four arylmethanes are built under catalysts conditions, its It is characterised by, the temperature range is 25 DEG C.
- 4. it is according to claim 1 a kind of without the method that triaryl and four arylmethanes are built under catalysts conditions, its It is characterised by, the solvent can also be TFE.
- It is 5. according to claim 1 a kind of without the side of structure structure triaryl and four arylmethanes under catalysts conditions Method, it is characterised in that the alkali is sodium carbonate.
- It is 6. according to claim 1 a kind of without the side of structure structure triaryl and four arylmethanes under catalysts conditions Method, it is characterised in that the alkali can also be triethylamine, potassium carbonate, sodium hydroxide.
- It is 7. according to claim 1 a kind of without the side of structure structure triaryl and four arylmethanes under catalysts conditions Method, it is characterised in that the alkali can not also add.
- It is 8. according to claim 1 a kind of without the side of structure structure triaryl and four arylmethanes under catalysts conditions Method, it is characterised in that the amount of the alkali is 2 equivalents.
- It is 9. according to claim 1 a kind of without the side of structure structure triaryl and four arylmethanes under catalysts conditions Method, it is characterised in that the reaction obtains triaryl and four arylmethane compounds for diaryl or triaryl chloride with Nu, Reaction temperature be room temperature, reaction dissolvent HFIP, alkali be sodium carbonate when result it is optimal, reach 90%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484439A (en) * | 2019-01-29 | 2020-08-04 | 天津师范大学 | Indole triarylmethane derivative based on salicylaldehyde and synthetic method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484439A (en) * | 2019-01-29 | 2020-08-04 | 天津师范大学 | Indole triarylmethane derivative based on salicylaldehyde and synthetic method thereof |
| CN111484439B (en) * | 2019-01-29 | 2021-08-24 | 天津师范大学 | Indole triarylmethane derivative based on salicylaldehyde and synthetic method thereof |
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Application publication date: 20171124 |