CN103965093A - 2-perfluoroalkyl indole compound as well as preparation and application thereof - Google Patents
2-perfluoroalkyl indole compound as well as preparation and application thereof Download PDFInfo
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- CN103965093A CN103965093A CN201410135804.2A CN201410135804A CN103965093A CN 103965093 A CN103965093 A CN 103965093A CN 201410135804 A CN201410135804 A CN 201410135804A CN 103965093 A CN103965093 A CN 103965093A
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- 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
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- 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
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- 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
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Abstract
The invention belongs to the technical field of indole compound synthesis, and discloses a 2-perfluoroalkyl indole compound as well as a preparation method through a reaction of indole/indole derivative and perfluoroalkyl iodide and application thereof. According to the method, the indole/indole derivative reacts with perfluoroalkyl iodide to synthesize the 2-perfluoroalkyl indole compound. According to the preparation method disclosed by the invention, the indole/indole derivative reacts with perfluoroalkyl iodide under the action of an accelerant to directly synthesize the 2-perfluoroalkyl indole compound, the reaction condition is mild, the selection range of an indole substrate is wide, any one of indole and indole derivative can be selected, rigorous requirements such as a water-free and oxygen-free reaction environment and the like are avoided, the operation is simple and easy, and the yield of the prepared 2-perfluoroalkyl indole compound product can be up to 80%; and the method is applicable to synthesis of organic fluorinated compounds, and particularly applicable to synthesis of the 2-perfluoroalkyl indole compound in the fields of biological medical chemistry and the like.
Description
Technical field
The invention belongs to Benzazole compounds synthesis technical field, particularly 2-perfluoroalkyl Benzazole compounds and the preparation method and application that react with perfluoroalkyl iodide with indole derivatives thereof.
Background technology
Perfluoroalkylation reaction is the important organic fluorine chemistry reaction of a class.Along with all-fluoroalkyl compound is in biomedicine, apply more and more widely in the fields such as agronomy and Materials science, and explore effective means perfluoro alkyl group is incorporated in organic compound molecule, be all the focus direction of organic chemistry research all the time.Although in the application in some fields, for example Materials science, the character of all-fluoroalkyl compound is better than trifluoromethyl derivative, and than trifluoromethylation reaction, perfluoroalkylation reaction is but relatively less, especially on aromatic nucleus and aromatic heterocycle.Indoles is the important heteroaromatic compound of a class, and its skeleton is extensively present in natural product and bioactive molecules, is the important organic intermediate of a class.For example β-indolylacetic acid, is the important natural phant growth hormone of a class, in the process such as cell fission and differentiation, fruit development, has brought into play effect.If can optionally fluoro-containing group be introduced in Indole Molecular, not only can improve significantly its biological activity, but also can strengthen its stability and fat-soluble, thereby contribute to absorption, transmission and the diffusion in vivo of indoles drug molecule, simultaneously, the introducing of perfluoro alkyl group, can also increase its application in biomaterial science and pesticide science field, thereby has important potential utility value.But the perfluoroalkylation reaction of indoles is considerably less.
Only have at present two class reactions to build this skeleton structure: between (1), be bonded into polystep reaction and build indole ring, these class methods need polystep reaction, have increased the consumption of pharmaceutical chemicals, not environmental protection, efficient; (2) directly synthetic, these class methods or condition harshness, or need a large amount of oxygenants, and also substrate scope is narrow, has limited it and has applied widely.Therefore, study the perfluoroalkylation that a kind of efficient direct and gentle novel method realizes indoles necessary.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method who reacts synthetic 2-perfluoroalkyl Benzazole compounds with indoles and derivative thereof with perfluoroalkyl iodide.
The 2-perfluoroalkyl Benzazole compounds that provides aforesaid method to prepare is provided another object of the present invention.
Still a further object of the present invention is to provide the application of above-mentioned preparation method in synthetic fluorochemicals.
Object of the present invention realizes by following proposal:
A preparation method for 2-perfluoroalkyl Benzazole compounds, the method utilizes indoles/indole derivatives to react with perfluoroalkyl iodide, the synthetic 2-perfluoroalkyl Benzazole compounds that obtains.
Above-mentioned preparation method realizes by following steps:
Indoles/indole derivatives and perfluoroalkyl iodide be reacting by heating under promotor and dipyridyl effect, obtains 2-perfluoroalkyl Benzazole compounds.
Described promotor is at least one in Red copper oxide and cuprous salt, is preferably Red copper oxide.
The mol ratio of perfluoroalkyl iodide used and indoles/indole derivatives is 1.2:1～2:1;
The mol ratio of promotor used and indoles/indole derivatives is 0.25:1～1:1;
The mol ratio of dipyridyl used and indoles/indole derivatives is 0.1:1～0.4:1.
Described reacting by heating refers at 40～80 DEG C, reacts 24～48h, is preferably at 80 DEG C and reacts 24h.
Preferably, above-mentioned reaction is carried out in organic solvent system, is preferably in DMF solvent system and carries out.
Preferably, the mol ratio of DMF used and indoles/indole derivatives is 26:1～104:1.
In preparation method of the present invention, described indoles/indole derivatives has structure described in structure formula I:
Wherein, R
1for hydrogen, alkyl, hydroxyalkyl or ester alkyl, described alkyl, hydroxyalkyl, ester alkyl are the saturated unit price hydrocarbon chain of straight or branched having separately containing 1 to 6 carbon atom; R
2, R
3the hydrogen or alkyl of respectively doing for oneself, described alkyl is the saturated unit price hydrocarbon chain of straight or branched containing 1 to 6 carbon atom.
In preparation method of the present invention, described indoles/indole derivatives Application Range is wide, can select any one of indole derivatives, can realize the replacement of 2.
In preparation method of the present invention, described perfluoroalkyl iodide structural formula can be expressed as C
nf
2n+1i, the positive integer that n is 2≤n≤6.Perfluoroalkyl iodide used is preferably perfluor butyl iodide.
Shown in the preparation method's of the present invention following formula II of reaction equation:
Wherein, R
ffor C
nf
2n+1, the positive integer that n is 2≤n≤6.
In order to obtain the 2-perfluoroalkyl Benzazole compounds product of purifying, after reaction, can carry out extraction and fractionation purification to reaction solution.
In above-mentioned purifying, can select ethyl acetate to extract.
In above-mentioned purifying, can select column chromatography to carry out separating-purifying.
The 2-perfluoroalkyl Benzazole compounds that above-mentioned preparation method prepares has structure shown in structure formula III:
Wherein, R
1for hydrogen, alkyl, hydroxyalkyl or ester alkyl, described alkyl, hydroxyalkyl, ester alkyl are the saturated unit price hydrocarbon chain of straight or branched having separately containing 1 to 6 carbon atom; R
2, R
3the hydrogen or alkyl of respectively doing for oneself, described alkyl is the saturated unit price hydrocarbon chain of straight or branched containing 1 to 6 carbon atom; R
ffor C
nf
2n+1, the positive integer that n is 2≤n≤6.
The present invention, by fluoro-containing group is introduced in indoles/indole derivatives, can improve its biological activity, and strengthen its stability and fat-soluble, thereby expands the application of indoles/indole derivatives in biomaterial science and pesticide science field.
Preparation method's reaction conditions gentleness of the present invention, indoles substrate range of choice is wide, can select indoles and derivative thereof any one, without harsh reaction environment requirements such as anhydrous and oxygen-frees, operation is simple, the 2-perfluoroalkyl Benzazole compounds product yield preparing can reach 80%, and the method is applicable to synthetic organic fluoride-containing compound, is specially adapted to the synthetic 2-perfluoroalkyl Benzazole compounds in field such as biological medicine chemistry.
Mechanism of the present invention is:
The present invention utilizes indoles/indole derivatives to react with perfluoroalkyl iodide under the effect of promotor; the directly synthetic 2-perfluoroalkyl Benzazole compounds, this reaction conditions gentleness, indoles wide application range of substrates of obtaining; the harsh securing system that does not need anhydrous and oxygen-free, whole operating process is simple.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) reactant of the inventive method is applied widely, and yield is higher, and mild condition is simple, can fairly large productive target product;
(2) the inventive method is without any need for anhydrous and oxygen-free securing system, just lower to conversion unit requirement, can reduce the cost of equipment in practical application;
(3) the inventive method provides a kind of novel method of preparing 2-perfluoroalkyl Benzazole compounds, can be applicable in synthetic fluorochemicals.
Brief description of the drawings
Fig. 1 is the product prepared of the embodiment of the present invention 1
1h NMR collection of illustrative plates.
Fig. 2 is the product prepared of the embodiment of the present invention 1
13c NMR collection of illustrative plates.
Fig. 3 is the product prepared of the embodiment of the present invention 1
19f NMR collection of illustrative plates.
Fig. 4 is the product prepared of the embodiment of the present invention 10
1h NMR collection of illustrative plates.
Fig. 5 is the product prepared of the embodiment of the present invention 10
13c NMR collection of illustrative plates.
Fig. 6 is the product prepared of the embodiment of the present invention 10
19f NMR collection of illustrative plates.
Fig. 7 is the product prepared of the embodiment of the present invention 11
1h NMR collection of illustrative plates.
Fig. 8 is the product prepared of the embodiment of the present invention 11
13c NMR collection of illustrative plates.
Fig. 9 is the product prepared of the embodiment of the present invention 11
19f NMR collection of illustrative plates.
Figure 10 is the product prepared of the embodiment of the present invention 12
1h NMR collection of illustrative plates.
Figure 11 is the product prepared of the embodiment of the present invention 12
13c NMR collection of illustrative plates.
Figure 12 is the product prepared of the embodiment of the present invention 12
19f NMR collection of illustrative plates.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
In reaction flask, add 32.8mg(0.25mmol) reactant 1a(3-skatole), 18.0mg(0.125mmol) and Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 61 μ L(0.35mmol) reactant 2a(perfluor butyl iodide), capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, after separation, obtains corresponding product 3a(3-methyl-2-perfluoro butyl indoles), the yield of product 3a is 80%, reaction formula is as follows:
Embodiment 2
In reaction flask, add 32.8mg(0.25mmol) reactant 1a, 18.0mg(0.125mmol) Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 61 μ L(0.35mmol) reactant 2a, capping, stirring reaction 24 hours at 60 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, obtain corresponding product 3a after separation, the yield of product 3a is 53%.
Embodiment 3
In reaction flask, add 32.8mg(0.25mmol) reactant 1a, 18.0mg(0.125mmol) Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 61 μ L(0.35mmol) reactant 2a, capping, stirring reaction 24 hours at 40 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, obtain corresponding product 3a after separation, the yield of product 3a is 19%.
Embodiment 4
In reaction flask, add 32.8mg(0.25mmol) reactant 1a, 18.0mg(0.125mmol) Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 52 μ L(0.3mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, obtain corresponding product 3a after separation, the yield of product 3a is 69%.
Embodiment 5
In reaction flask, add 32.8mg(0.25mmol) reactant 1a, 18.0mg(0.125mmol) Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 86 μ L(0.5mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, obtain corresponding product 3a after separation, the yield of product 3a is 76%.
Embodiment 6
In reaction flask, add 32.8mg(0.25mmol) reactant 1a, 9.0mg(0.0625mmol) Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 61 μ L(0.35mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, obtain corresponding product 3a after separation, the yield of product 3a is 68%.
Embodiment 7
In reaction flask, add 32.8mg(0.25mmol) reactant 1a, 36.0mg(0.25mmol) Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 61 μ L(0.35mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, obtain corresponding product 3a after separation, the yield of product 3a is 74%.
Embodiment 8
In reaction flask, add 32.8mg(0.25mmol) reactant 1a, 18.0mg(0.125mmol) Cu
2o and 3.9mg(0.025mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 61 μ L(0.35mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, obtain corresponding product 3a after separation, the yield of product 3a is 72%.
Embodiment 9
In reaction flask, add 32.8mg(0.25mmol) reactant 1a, 18.0mg(0.125mmol) Cu
2o and 15.6mg(0.1mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 61 μ L(0.35mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, obtain corresponding product 3a after separation, the yield of product 3a is 75%.
Embodiment 10
In reaction flask, add 40.3mg(0.25mmol) reactant 1b(indoles-3-ethanol), 18.0mg(0.125mmol) and Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 86 μ L(0.5mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, after separation, obtains corresponding product 3b(3-(2-hydroxyethyl)-2-perfluoro butyl indoles), the yield of product 3b is 60%, reaction formula is as follows:
Embodiment 11
In reaction flask, add 47.3mg(0.25mmol) reactant 1c(indole-3-acetic acid methyl esters), 18.0mg(0.125mmol) and Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 86 μ L(0.5mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, after separation, obtains corresponding product 3c(3-(2-perfluoro butyl) indolylacetic acid methyl esters), the yield of product 3c is 55%, reaction formula is as follows:
Embodiment 12
In reaction flask, add 36.3mg(0.25mmol) reactant 1d, 18.0mg(0.125mmol) Cu
2o and 7.8mg(0.05mmol) 2,2-dipyridyl, then add 1.0mL DMF solvent and 86 μ L(0.5mmol) reactant 2a, capping, stirring reaction 24 hours at 80 DEG C; After completion of the reaction, crude product is extracted by ethyl acetate, after separation, obtains corresponding product 3d(1,3-dimethyl-2-perfluoro butyl indoles), the yield of product 3d is 70%, reaction formula is as follows:
Embodiment 13
The product that embodiment 1,10,11 and 12 is prepared carries out Structural Identification, the results are shown in Figure 1～12.
The appraising datum of product 3a:
As shown in Figure 1, product 3a
1h NMR data are:
1h NMR (400MHz, CDCl
3): δ 8.07 (br s, 1H), 7.63 (d, J=8.0Hz, 1H), 7.33-7.28 (m, 2H), 7.20-7.16 (m, 1H), 2.42 (t, J=2.0Hz, 3H).
As shown in Figure 2, product 3a
13c NMR data are:
13c NMR (100MHz, CDCl
3): δ 136.15,128.53,125.10,120.54,120.24,119.62 (t, J=28.5Hz), 116.91 (t, J=3.3Hz), 111.67,8.62 (t, J=1.4Hz).
As shown in Figure 3, product 3a
19f NMR data are:
19f NMR (376MHz, CDCl
3): δ-81.47to-81.54 (m, 3F) ,-109.28to-109.35 (m, 2F) ,-123.45to-123.56 (m, 2F) ,-126.41to-126.54 (m, 2F).
The infrared data of product 3a is: IR (thin film, cm
-1): 3330,3110,2963,1589,1465,1384,1266,1108,961,855,761.
The high resolution mass spectrum data of product 3a are: HRMS (ESI): m/z (M+H
+) calcd.forC
13h
9f
9n
+, 350.0591, found, 350.0579.
The appraising datum of product 3b:
As shown in Figure 4, product 3b
1h NMR data are:
1h NMR (400MHz, CDCl
3): δ 9.08 (br s, 1H), 7.77 (d, J=8.0Hz, 1H), 7.41-7.34 (m, 2H), 7.25-7.21 (m, 1H), 3.96 (t, J=6.8Hz, 2H), 3.24 (t, J=7.2Hz, 2H), 2.30 (br s, 1H).
As shown in Figure 5, product 3b
13c NMR data are:
13c NMR (100MHz, CDCl
3): δ 136.46,127.95,125.09,120.72,120.37,120.45 (t, J=28.5Hz), 116.96 (t, J=2.7Hz), 111.95,63.38,27.79.
As shown in Figure 6, product 3b
19f NMR data are:
19f NMR (376MHz, CDCl
3): δ-81.47to-81.53 (m, 3F) ,-108.12to-108.09 (m, 2F) ,-123.19to-123.33 (m, 2F) ,-126.30to-126.42 (m, 2F).
The infrared data of product 3b is: IR (thin film, cm
-1): 3320,3181,3068,2962,1586,1454,1384,1238,1130,868,737.
The high resolution mass spectrum data of product 3b are: HRMS (ESI): m/z (M+H
+) calcd.forC
13h
9f
9n
+, 380.0697, found, 380.0685.
The appraising datum of product 3c:
As shown in Figure 7, product 3c
1h NMR data are:
1h NMR (400MHz, CDCl
3): δ 8.89 (br s, 1H), 7.71 (d, J=8.0Hz, 1H), 7.36-7.29 (m, 2H), 7.27-7.23 (m, 1H), 4.01 (s, 2H), 3.75 (s, 3H).
As shown in Figure 8, product 3c
13c NMR data are:
13c NMR (100MHz, CDCl
3): δ 171.67,136.24,127.69,125.19,121.05,120.79 (t, J=28.5Hz), 120.18,112.84 (t, J=2.9Hz), 112.00,52.24,29.92.
As shown in Figure 9, product 3c
19f NMR data are:
19f NMR (376MHz, CDCl
3): δ-81.46to-81.53 (m, 3F) ,-108.78to-108.85 (m, 2F) ,-123.30to-123.43 (m, 2F) ,-126.30to-126.43 (m, 2F).
The infrared data of product 3c is: IR (thin film, cm
-1): 3308,2959,1744,1651,1558,1459,1383,1237,1133,964,880,739.
The high resolution mass spectrum data of product 3c are: HRMS (ESI): m/z (M+H
+) calcd.forC
13h
9f
9n
+, 408.0646, found, 408.0662.
The appraising datum of product 3d:
As shown in figure 10, product 3d
1h NMR data are:
1h NMR (400MHz, CDCl
3): δ 7.67 (d, J=8.0Hz, 1H), 7.40-7.35 (m, 2H), 7.22-7.18 (m, 1H), 3.81 (s, 3H), 2.46 (t, J=2.8Hz, 3H).
As shown in figure 11, product 3d
13c NMR data are:
13c NMR (100MHz, CDCl
3): δ 138.68,127.56,124.90,120.95 (t, J=27.2Hz), 120.24,120.13,117.90 (t, J=3.8Hz), 109.88,31.71,9.22 (t, J=3.3Hz).
As shown in figure 12, product 3d
19f NMR data are:
19f NMR (376MHz, CDCl
3): δ-81.42to-81.48 (m, 3F) ,-104.65to-104.73 (m, 2F) ,-122.79to-122.92 (m, 2F) ,-126.40to-126.54 (m, 2F).
The infrared data of product 3d is: IR (thin film, cm
-1): 3120,3012,2960,2919,1596,1462,1361,1166,1067,961,905,855.
The high resolution mass spectrum data of product 3d are: HRMS (ESI): m/z (M+H
+) calcd.forC
13h
9f
9n
+, 364.0748, found, 364.0751.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a preparation method for 2-perfluoroalkyl Benzazole compounds, is characterized in that the method utilizes indoles/indole derivatives to react with perfluoroalkyl iodide, the synthetic 2-perfluoroalkyl Benzazole compounds that obtains.
2. the preparation method of 2-perfluoroalkyl Benzazole compounds according to claim 1, is characterized in that: described indoles/indole derivatives has structure described in structure formula I:
Wherein, R
1for hydrogen, alkyl, hydroxyalkyl or ester alkyl, described alkyl, hydroxyalkyl, ester alkyl are the saturated unit price hydrocarbon chain of straight or branched having separately containing 1 to 6 carbon atom; R
2, R
3the hydrogen or alkyl of respectively doing for oneself, described alkyl is the saturated unit price hydrocarbon chain of straight or branched containing 1 to 6 carbon atom.
3. the preparation method of 2-perfluoroalkyl Benzazole compounds according to claim 1, is characterized in that: the structural formula of described perfluoroalkyl iodide is C
nf
2n+1i, the positive integer that n is 2≤n≤6.
4. the preparation method of 2-perfluoroalkyl Benzazole compounds according to claim 1, it is characterized in that this preparation method realizes by following steps: indoles/indole derivatives and perfluoroalkyl iodide be reacting by heating under promotor and dipyridyl effect, obtain 2-perfluoroalkyl Benzazole compounds.
5. the preparation method of 2-perfluoroalkyl Benzazole compounds according to claim 4, is characterized in that: described promotor is at least one in Red copper oxide and cuprous salt.
6. the preparation method of 2-perfluoroalkyl Benzazole compounds according to claim 4, is characterized in that: the mol ratio of perfluoroalkyl iodide used and indoles/indole derivatives is 1.2:1～2:1; The mol ratio of promotor used and indoles/indole derivatives is 0.25:1～1:1; The mol ratio of dipyridyl used and indoles/indole derivatives is 0.1:1～0.4:1.
7. the preparation method of 2-perfluoroalkyl Benzazole compounds according to claim 4, is characterized in that: described reacting by heating refers at 40～80 DEG C, reaction 24～48h.
8. a 2-perfluoroalkyl Benzazole compounds, is characterized in that obtaining according to the preparation method of the 2-perfluoroalkyl Benzazole compounds described in claim 1～7 any one.
9. 2-perfluoroalkyl Benzazole compounds according to claim 8, is characterized in that having structure shown in structure formula III:
Wherein, R
1for hydrogen, alkyl, hydroxyalkyl or ester alkyl, described alkyl, hydroxyalkyl, ester alkyl are the saturated unit price hydrocarbon chain of straight or branched having separately containing 1 to 6 carbon atom; R
2, R
3the hydrogen or alkyl of respectively doing for oneself, described alkyl is the saturated unit price hydrocarbon chain of straight or branched containing 1 to 6 carbon atom; R
ffor C
nf
2n+1, the positive integer that n is 2≤n≤6.
10. the application in synthetic organic fluoride-containing compound according to the preparation method of the 2-perfluoroalkyl Benzazole compounds described in claim 1～7 any one.
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| CN104357032A (en) * | 2014-10-13 | 2015-02-18 | 中国石油化工股份有限公司 | High-temperature resistant secondary cross-linked gel profile control agent and preparation method thereof |
| CN104892485A (en) * | 2015-06-17 | 2015-09-09 | 上海大学 | 2-perfluoroalkyl indole derivative and synthesis method thereof |
| CN110003081A (en) * | 2019-04-23 | 2019-07-12 | 许昌学院 | A kind of synthetic method for the indoline and tetrahydroisoquinoline that Polyfluoroalkyl replaces |
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