CN105348288B - A kind of synthetic method of 5,10 indoline [3,2 b] Benzazole compounds - Google Patents
A kind of synthetic method of 5,10 indoline [3,2 b] Benzazole compounds Download PDFInfo
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- CN105348288B CN105348288B CN201510911887.4A CN201510911887A CN105348288B CN 105348288 B CN105348288 B CN 105348288B CN 201510911887 A CN201510911887 A CN 201510911887A CN 105348288 B CN105348288 B CN 105348288B
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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Abstract
A kind of synthetic method of 5,10 indoline [3,2 b] Benzazole compounds is prepared present invention relates particularly to one kind, belongs to organic compound technique applied technical field.5,10 indoline [3,2 b] Benzazole compounds are the extremely important chemical intermediates of a class, especially a kind of skeleton of very potential electroluminescent organic material, with very high application value.The present invention overcomes the defect of prior art, and a kind of simple new method for efficiently preparing 5,10 indoline [3,2 b] Benzazole compounds is innovatively proposed first, by using metal palladium catalyst, the conversion of reaction can be efficiently realized.
Description
Technical field
Present invention relates particularly to the synthetic method that one kind prepares one kind 5,10- indoline [3,2-b] Benzazole compounds,
Belong to organic compound technique applied technical field.
Background technology
5,10- indoline [3,2-b] Benzazole compounds are the extremely important chemical intermediates of a class, especially a kind of non-
The skeleton of normal potential electroluminescent organic material, with very high application value.It is shown below：
。
The content of the invention
The present invention overcomes the defect of prior art, and a kind of simple efficiently preparation 5,10- dihydros Yin is innovatively proposed first
The new method of diindyl [3,2-b] Benzazole compounds, by using metal palladium catalyst, can efficiently realize the conversion of reaction.
Formula（I）
Such as above formula（I）Shown, the present invention utilizes the iodo- aniline of 2-（Substrate 1）With substituted indoles（Substrate 2）It is used as starting
Raw material, in the presence of metal palladium catalyst, is reacted in reaction dissolvent, synthesizes 5,10- indoline [3,2-b] indoles
Class compound.
In the present invention, R1, R3It is hydrogen, halogen, hetero atom, alkyl；R2 It is alkyl；PG is Ts, Ns (4- nitrobenzene sulphonyls
Base), Ms, Boc.
Preferably, R1, R3It is F, Cl, alkane, R2It is methyl.PG is Ts, Ns.
In the present invention, R1, R2,R3Above-mentioned group is included but are not limited to, for example, R1, R3It can also be polysubstituted
Base, all kinds of side chains.
In the present invention, the usage ratio of the indoles of the iodo- amino benzenes derivates of initiation material 2- and substitution is 1:1-
1.5.Preferably, both usage ratios are 1:1.1.
In the present invention, the palladium catalyst is Pd (OAc)2、PdCl2、Pd(TFA)2、PdCl2Or PdCl (dppf)2
(PPh3)。
Preferably, the palladium catalyst is Pd (TFA)2。
The consumption of the catalyst is the 1-10 mol% of raw material 1.
Preferably, the consumption of the catalyst is 10 mol%.
In the present invention, the co-catalyst is Ag2O、AgOAc, AgOTf。
Preferably, the co-catalyst is Ag2O。
The co-catalyst consumption is the 1-30 mol% of substrate 1.
Preferably, the co-catalyst consumption is 20 mol%.
In the present invention, the additive is TBAC（Tetrabutylammonium chloride）、TBAB（TBAB）Or TBAI（Four fourths
Base ammonium iodide）.
Preferably, the additive is TBAB（TBAB）.
Preferably, the additive amount altogether is 20 mol%.
In the present invention, the alkali is Cu (OAc)2, K2CO3、Cs2CO3Or DMAP（4,4- dimethylamino naphthyridines）.
Preferably, the alkali is Cu (OAc)2。
Preferably, the consumption of the alkali is 2.0 equivalents.The alkali can also be NaOH more than including but is not limited to,
KOH, Na2CO3, DBU (bicyclic amidine).
In the present invention, the reaction dissolvent is toluene, chlorobenzene, DMA or acetonitrile.Preferably, it is to be carried out instead in chlorobenzene
Should.
More than the reaction dissolvent includes but is not limited to, dimethylbenzene, Isosorbide-5-Nitrae-dioxane, DMF, DMSO can also be.
In the present invention, the synthetic reaction is in 80-150oCarried out at a temperature of C.Preferably, it is 150oEnter at a temperature of C
Row reaction.
In the present invention, the synthesising reacting time is 10-24 hours.It is preferred that, it is reaction 24 hours.
Specifically, synthetic reaction of the present invention is that in reaction bulb A, the iodo- aniline of 2- (substrate 1, X mmol) is dissolved in into Z
In mL reaction dissolvents, at room temperature, substituted indoles is sequentially added（Substrate 2, Y mmol), catalyst Pd (TFA)2 (W
Mmol%), part dppf (V mmol%), additive TBAB (U mol%), alkali Cu (OAc)2(s mol%).Reaction exists
80-150 o10-24 hour is reacted under C.Reaction process is detected with TLC.After completion of the reaction, directly add silica gel, be spin-dried for post layer
Analysis, isolated target product 3.
The advantage of synthetic reaction of the present invention includes：Each raw material is very simple used in synthetic method of the present invention, is work
Industry commodity, simple and easy to get, wide material sources, and performance is highly stable, it is not necessary to special preservation condition.It is each used in the present invention
It is also all conventional commercial reagents to plant metallic catalyst and additive, highly stable, and with cost is low, yield is high, work
The few characteristic of skill letter, pollution, is applicable to large-scale production completely.
5,10- indoline [3,2-b] Benzazole compounds that the present invention is synthesized are a kind of very potential Organic Electricities
The skeleton of electroluminescent material, the reaction scheme of innovative design of the present invention for synthesize this kind of compound provide one it is generally applicable
Preparation method.The traditional method for synthesizing 5,10- indoline [3,2-b] Benzazole compounds is usually to need multistep to synthesize,
And hardly possible operation, yield are very low, and industrial applications are caused with very big limitation.
Patent of the present invention, the derivative using the indoles of commercialization and adjacent Iodoaniline is reaction raw materials, in metal palladium catalyst
Under effect, reaction obtains polysubstituted 5,10- indoline [3,2-b] Benzazole compounds.Operation is fairly simple, reaction
Mild condition, yield is higher, is adapted to large-scale industrial production.
Embodiment
With reference to specific examples below, the present invention is described in further detail, and of the invention protects content not limit to
In following examples.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and excellent
Point is all included in the present invention, and using appended claims as protection domain.Implement the present invention process, condition,
Reagent, experimental method etc., are the universal knowledege and common knowledge of this area, this hair in addition to the following content specially referred to
It is bright that content is not particularly limited.Data given by following examples include concrete operations and reaction condition and product.Product is pure
Degree is identified by nuclear-magnetism.
Embodiment 1
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(75%)。1H NMR (400 MHz, CDCl3): δ 8.74 (d, J = 2.4 Hz, 1H), 8.36 (d, J = 2.4
Hz, 1H), 7.94 (d, J = 2.8 Hz, 1H), 7.74 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 2.8
Hz, 1H), 7.42-7.25 (m, 6H), 3.82 (s, 3H), 2.34 (s, 3H). 13C-NMR (100 MHz,
CDCl3): δ 139.4,136.5, 135.8, 134.8, 130.0,128.2,124.9, 124.0, 122.2, 121.7,
120.2, 119.9, 119.8, 114.5, 113.2, 109.6, 37.8, 21.3. MS (EI) m/z 374 (M+);
HRMS calculated values are C22H18N2O2S 374.1089, actual value is 374.1090.
Embodiment 2
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(OAc)2 (0.01 mmol, 2.8 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(15%).Analyze data be the same as Example 1.
Embodiment 3
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1 mg),
2a (0.11 mmol, 41 mg), PdCl2(dppf)(0.01 mmol, 7.8 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(26%).Analyze data be the same as Example 1.
Embodiment 4
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 7.8 mg), AgOAc (0.02 mmol,
3.2 mg), TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg) is weighed into successively
Nitrogen is changed in reaction tube, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24
Hour.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(31%).Analyze data be the same as Example 1.
Embodiment 5
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1 mg),
2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 7.8 mg), Ag2O (0.02 mmol, 4.6 mg),
Tetrabutylammonium iodide (0.02 mmol, 7.4 mg), copper acetate (2.0 equivalents, 32 mg), is weighed into reaction tube, takes out successively
Sky changes nitrogen, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reacts 24 hours.TLC
After detection reaction terminates, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa (45%).
Analyze data be the same as Example 1.
Embodiment 6
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 7.8 mg), Ag2O (0.02 mmol, 4.6
Mg), tetrabutylammonium iodide (0.02 mmol, 7.4 mg), potassium carbonate (2.0 equivalents, 28 mg) is weighed into reaction tube successively,
Nitrogen is changed in evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reacts 24 hours.
After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(33%).Analyze data be the same as Example 1.
Embodiment 7
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 7.8 mg), Ag2O (0.02 mmol, 3.2
Mg), tetrabutylammonium iodide (0.02 mmol, 7.4 mg), cesium carbonate (2.0 equivalents, 65mg) is weighed into reaction tube successively,
Nitrogen is changed in evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reacts 24 hours.
After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(36%).Analyze data be the same as Example 1.
Embodiment 8
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 7.8 mg), Ag2O (0.02 mmol, 4.6
Mg), tetrabutylammonium iodide (0.02 mmol, 7.4 mg), pyridine (2.0 equivalents, 14 mg) is weighed into reaction tube successively, takes out
Sky changes nitrogen, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reacts 24 hours.TLC
After detection reaction terminates, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa (36%).
Analyze data be the same as Example 1.
Embodiment 9
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 100oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(56%).Analyze data be the same as Example 1.
Embodiment 10
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds toluene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(22%).Analyze data be the same as Example 1.
Embodiment 11
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds DMF (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reacts 24 hours.
After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(32%).Analyze data be the same as Example 1.
Embodiment 12
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds DMA (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reacts 24 hours.
After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(41%).Analyze data be the same as Example 1.
Embodiment 13
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 12 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(35%).Analyze data be the same as Example 1.
Embodiment 14
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 36 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(74%).Analyze data be the same as Example 1.
Embodiment 15
5- methyl isophthalic acids 0- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2a (0.15 mmol, 56 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 36 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3aa
(74%).Analyze data be the same as Example 1.
Embodiment 16
3,10- dimethyl -5- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1b (0.1 mmol, 14.5
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ba
(81%)。1H NMR (400 MHz, CDCl3): δ 8.74 (d, J = 2.4 Hz, 1H), 8.34 (d, J = 2.4
Hz, 1H), 7.94 (d, J = 2.8 Hz, 1H), 7.74 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 2.8
Hz, 1H), 7.42-7.25 (m, 5H), 3.81 (s, 3H), 2.34 (s, 3H), 2.31 (s, 3H). 13C-NMR
(100 MHz, CDCl3): δ 139.3,136.4, 135.8, 134.6, 130.0,128.2,124.9, 124.1,
122.3, 121.7,120.2, 119.9, 119.8, 114.5, 113.2, 109.6, 37.8, 21.6, 21.3. MS
(EI) m/z 388 (M+);HRMS calculated values are C23H20N2O2S 388.1245, actual value is 233.1247.
Embodiment 17
Chloro- 10- methyl -5- p-toluenesulfonyls -5,10- indoline [3,2-b] indoles of 3-：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1c (0.1 mmol, 16.5
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ca
(83%)。1H NMR (400 MHz, CDCl3): δ 8.76 (d, J = 2.4 Hz, 1H), 7.96 (d, J = 2.8
Hz, 1H), 7.74 (d, J = 8.4 Hz, 2H), 7.69 (d, J = 2.8 Hz, 1H), 7.46-7.18 (m,
6H), 3.81 (s, 3H), 2.34 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ 139.4, 135.8,
134.8, 134.6, 130.0,128.2,125.6, 124.9, 124.0, 122.4, 122.2, 121.7, 121.6,
119.9, 119.8, 114.5, 113.2, 112.5, 37.9, 21.4. MS (EI) m/z 408 (M+);HRMS is counted
Calculation value is C22H17ClN2O2S 408.0699, actual value is 408.0697.
Embodiment 18
Fluoro- 10- dimethyl -5- p-toluenesulfonyls -5,10- indoline [3,2-b] indoles of 3-：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1d (0.1 mmol, 14.9
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3da
(81%)。1H NMR (400 MHz, CDCl3): δ 8.74 (d, J = 2.4 Hz, 1H), 7.94 (d, J = 2.8
Hz, 1H), 7.84 (s, 1H), 7.75 (d, J = 8.4 Hz, 2H), 7.70 (d, J = 2.8 Hz, 1H),
7.40-7.18 (m, 5H), 3.83 (s, 3H), 2.33 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ
157.6(d, J = 142 Hz), 139.4, 135.8, 134.8, 134.6, 130.0,128.4,125.7, 124.9,
124.0, 122.4, 122.4, 121.7, 121.5, 119.9, 119.8, 114.5, 113.2, 112.5, 37.8,
21.5. MS (EI) m/z 392 (M+);HRMS calculated values are C22H17FN2O2S 392.0995, actual value is
392.0996。
Embodiment 19
Bromo- 10- dimethyl -5- p-toluenesulfonyls -5,10- indoline [3,2-b] indoles of 3-：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1e (0.1 mmol, 20.9
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ea
(53%)。1H NMR (400 MHz, CDCl3): δ 8.74 (d, J = 2.4 Hz, 1H), 7.95 (d, J = 2.8
Hz, 1H), 7.73 (d, J = 8.4 Hz, 2H), 7.67 (d, J = 2.8 Hz, 1H), 7.40-7.25 (m,
6H), 3.82 (s, 3H), 2.34 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ 139.5, 135.7,
135.5, 134.8, 130.1,128.3,124.9, 124.7, 124.0, 122.4, 122.2, 121.0, 119.9,
119.8, 114.5, 113.2, 110.2, 37.9, 21.4. MS (EI) m/z 452 (M+);HRMS calculated values are
C22H17BrN2O2S 452.0194, actual value is 452.0196.
Embodiment 20
10- methyl -4- cyano group -5- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1f (0.1 mmol, 15.6
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3fa
(66%)。1H NMR (400 MHz, CDCl3): δ 8.74 (d, J = 2.4 Hz, 1H), 7.94 (d, J = 2.8
Hz, 1H), 7.87 (d, J = 2.4 Hz, 1H), 7.74 (d, J = 8.4 Hz, 2H), 7.60 (d, J = 2.8
Hz, 1H), 7.42-7.25 (m, 5H), 3.82 (s, 3H), 2.34 (s, 3H). 13C-NMR (100 MHz,
CDCl3): δ 139.4, 137.2, 135.8, 134.8, 131.4, 130.0,128.3,125.9, 124.0, 122.2,
119.9, 119.8, 117.1, 114.5, 113.9, 113.2, 104.5, 37.9, 21.4. MS (EI) m/z 399
(M+);HRMS calculated values are C23H17N3O2S 399.1041, actual value is 399.1042.
Embodiment 21
The 3- tert-butyl groups -10- methyl -5- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1g (0.1 mmol, 18.7
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ga
(85%)。1H NMR (400 MHz, CDCl3): δ 8.72 (d, J = 2.4 Hz, 1H), 8.59 (d, J = 2.4
Hz, 1H), 7.84 (d, J = 2.8 Hz, 1H), 7.78 (d, J = 8.4 Hz, 2H), 7.73 (d, J = 2.8
Hz, 1H), 7.42 (d, J = 8.4 Hz, 2H), 7.33-7.20 (m, 3H), 3.81 (s, 3H), 2.34 (s,
3H), 1.35 (s, 9H). 13C-NMR (100 MHz, CDCl3): δ 153.1, 139.5, 136.3, 135.8,
134.5, 130.1, 128.3,124.8, 124.2, 122.5, 121.8, 120.2, 119.9, 119.8, 114.5,
113.2, 109.6, 37.8, 34.5, 31.3, 21.3. MS (EI) m/z 430 (M+);HRMS calculated values are
C26H26N2O2S 430.1715, actual value is 430.1718.
Embodiment 22
Chloro- 4,10- dimethyl -5- p-toluenesulfonyls -5,10- indoline [3,2-b] indoles of 3-：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1h (0.1 mmol, 17.9
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ha
(74%)。1H NMR (400 MHz, CDCl3): δ 8.74 (d, J = 2.4 Hz, 1H), 7.94 (d, J = 2.8
Hz, 1H), 7.74 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), 7.33-7.25 (m,
3H), 3.81 (s, 3H), 2.34 (s, 3H), 2.31 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ
139.4, 135.8, 134.8, 134.6, 130.1, 130.0,128.2,127.7, 124.9, 124.0, 122.4,
122.2, 119.8, 119.1, 114.5, 113.2, 109.5, 37.9, 21.4, 13.6. MS (EI) m/z 422
(M+);HRMS calculated values are C23H19ClN2O2S 422.0856, actual value is 422.0857.
Embodiment 23
1- methoxyl groups -10- methyl -5- p-toluenesulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1i (0.1 mmol, 16.1
mg), 2a (0.11 mmol, 41 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ia
(78%)。1H NMR (400 MHz, CDCl3): δ 8.73 (d, J = 2.4 Hz, 1H), 7.94 (d, J = 2.8
Hz, 1H), 7.93 (d, J = 2.8 Hz, 1H), 7.73 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.0
Hz, 2H), 7.33-7.25 (m, 3H), 6.72 (d, J = 2.4 Hz, 1H), 3.84 (s, 3H), 3.81 (s,
3H), 2.33 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ 146.5, 139.3, 135.8, 134.6,
130.0, 129.5, 128.2, 124.9, 122.2, 121.2, 121.1, 119.9, 119.8, 114.5, 113.2,
104.5, 55.8, 38.1, 21.3. MS (EI) m/z 404 (M+);HRMS calculated values are C23H20N2O3S
404.1195, actual value is 404.1192.
Embodiment 24
5- methyl isophthalic acids 0- is to nitro sulfonyl -5,10- indoline [3,2-b] indoles：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2b (0.11 mmol, 44 mg) Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ab
(72%)。1H NMR (400 MHz, CDCl3): δ 8.74 (d, J = 2.8 Hz, 1H), 8.39 (d, J = 8.4
Hz, 2H), 8.36 (d, J = 2.4 Hz, 1H), 8.12 (d, J = 8.4 Hz, 2H), 7.94 (d, J = 2.8
Hz, 1H), 7.59 (d, J = 2.8 Hz, 1H), 7.42-7.25 (m, 4H), 3.82 (s, 3H). 13C-NMR
(100 MHz, CDCl3): δ 152.8,143.9, 136.5, 135.8, 129.2, 124.9, 124.0, 122.2,
121.7, 120.2, 119.9, 119.8, 114.5, 113.2, 109.6, 37.8. MS (EI) m/z 405 (M+);
HRMS calculated values are C21H15N3O4S 405.0783, actual value is 405.0780.
Embodiment 25
Fluoro- 5- methyl isophthalic acids 0- p-toluenesulfonyls -5,10- indoline [3,2-b] indoles of 3-：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2c (0.11 mmol, 43 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ac
(70%)。1H NMR (400 MHz, CDCl3): δ1H NMR (400 MHz, CDCl3): δ 8.36 (d, J = 2.4
Hz, 1H), 8.22 (d, J = 6.4 Hz, 1H), 7.91 (d, J = 2.8 Hz, 1H), 7.75 (d, J = 8.4
Hz, 2H), 7.59 (d, J = 2.8 Hz, 1H), 7.42-7.40 (m, 4H), 7.05 (t, J = 2.4Hz,
1H), 3.83 (s, 3H), 2.33 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ 157.5(d, J = 142
Hz), 139.5, 135.9, 134.6, 134.5, 130.1,128.4,125.5, 124.9, 124.1, 122.4,
122.3, 121.7, 121.5, 119.9, 119.8, 114.6, 113.3, 112.5, 37.8, 21.6. MS (EI)
m/z 392 (M+);HRMS calculated values are C22H17FN2O2S 392.0995, actual value is 392.0996.
Embodiment 26
Chloro- 5- methyl isophthalic acids 0- p-toluenesulfonyls -5,10- indoline [3,2-b] indoles of 3-：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2d (0.11 mmol, 44 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ad
(79%)。1H NMR (400 MHz, CDCl3): δ 8.36 (d, J = 2.4 Hz, 1H), 7.88 (d, J = 2.8
Hz, 1H), 7.74 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 2.8 Hz, 1H), 7.42-7.40 (m,
4H), 7.09 (d, J = 2.8 Hz, 1H), 3.81 (s, 3H), 2.34 (s, 3H). 13C-NMR (100 MHz,
CDCl3): δ 139.4, 136.5,134.8, 133.9, 130.0, 128.2,125.6, 124.9, 124.0, 122.5,
122.2, 121.7, 121.6, 119.9, 119.8, 114.5, 113.2, 112.5, 37.9, 21.4. MS (EI)
m/z 408 (M+);HRMS calculated values are C22H17ClN2O2S 408.0699, actual value is 408.0697.
Embodiment 27
Fluoro- 4,5- dimethyl -10- p-toluenesulfonyls -5,10- indoline [3,2-b] indoles of 3-：
In 25 mL test tube reactor, with nitrogen exchange of air 3 times.By substrate 1a (0.1 mmol, 13.1
mg), 2e (0.11 mmol, 45 mg), Pd(TFA)2 (0.01 mmol, 3.0 mg), Ag2O (0.02 mmol, 4.6
), mg TBAB (0.02 mmol, 6.4 mg), copper acetate (2.0 equivalents, 32 mg), are weighed into reaction successively
Nitrogen is changed in pipe, evacuation, and adds chlorobenzene (2 mL) under nitrogen atmosphere.Reaction system is heated to 150oC, reaction 24 is small
When.After TLC detection reactions terminate, system is cooled to room temperature.Directly add silica gel, be spin-dried for column chromatography, obtain white solid 3ae
(58%)。1H NMR (400 MHz, CDCl3): δ 8.36 (d, J = 2.4 Hz, 1H), 7.74 (d, J = 8.4
Hz, 2H), 7.73 (d, J = 2.8 Hz, 1H), 7.59 (d, J = 2.8 Hz, 1H), 7.42-7.40 (m,
4H), 6.94 (t, J = 3.2 Hz, 1H), 3.82 (s, 3H), 2.34 (s, 3H), 2.33 (s, 3H). 13C-
NMR (100 MHz, CDCl3): δ 158.4, 139.4, 136.5, 134.8, 130.0,128.2,126.9, 124.0,
122.2, 121.7,120.2, 119.9, 118.2, 113.7, 109.8, 109.6, 37.8, 21.3. MS (EI) m/
z 406 (M+);HRMS calculated values are C23H19FN2O2S 406.1151, actual value is 406.1152.
Claims (8)
1. one kind 5, the synthetic method of 10- indoline [3,2-b] Benzazole compounds, it is characterised in that with the iodo- phenyl amines of 2-
Derivative is reaction raw materials with the indoles replaced, in the presence of metal palladium catalyst, and reaction obtains 5,10- in reaction dissolvent
Indoline [3,2-b] Benzazole compounds；Course of reaction such as formula（I）It is shown；
；
Wherein, R1, R3It is hydrogen, halogen, alkane group；R2 It is alkane group；PG is Ts, Ns, Ms, Boc.
2. the synthetic method of 5,10- indoline [3,2-b] Benzazole compounds as claimed in claim 1, it is characterised in that
The palladium catalyst is Pd (OAc)2、PdCl2 、Pd(TFA)2、PdCl2Or PdCl (dppf)2(PPh3)；Wherein, the catalyst
Pd(OAc)2、PdCl2 、Pd(TFA)2、PdCl2Or PdCl (dppf)2(PPh3) consumption be 1-10mol%.
3. the synthetic method of 5,10- indoline [3,2-b] Benzazole compounds as claimed in claim 1, it is characterised in that
The co-catalyst is Ag2O、AgOAc, AgOTf；Wherein, the co-catalyst Ag2O, AgOAc, or AgOTf consumption is 1-
30mol%。
4. the synthetic method of 5,10- indoline [3,2-b] Benzazole compounds as claimed in claim 1, it is characterised in that
The additive is TBAC, TBAB or TBAI.
5. the synthetic method of 5,10- indoline [3,2-b] Benzazole compounds as claimed in claim 1, it is characterised in that
The alkali is Cu (OAc)2, K2CO3、Cs2CO3Or DMAP.
6. the synthetic method of 5,10- indoline [3,2-b] Benzazole compounds as claimed in claim 1, it is characterised in that
The reaction dissolvent is toluene, chlorobenzene, DMA or acetonitrile.
7. the synthetic method of 5,10- indoline [3,2-b] Benzazole compounds as claimed in claim 1, it is characterised in that
The synthetic reaction is in 80-150oC is carried out.
8. the synthetic method of 5,10- indoline [3,2-b] Benzazole compounds as claimed in claim 1, it is characterised in that
The reaction time is 10-24h.
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