CN105859725B - The synthetic method of 5,10 indoline simultaneously [3,2 b] indole derivatives - Google Patents

The synthetic method of 5,10 indoline simultaneously [3,2 b] indole derivatives Download PDF

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CN105859725B
CN105859725B CN201610313040.0A CN201610313040A CN105859725B CN 105859725 B CN105859725 B CN 105859725B CN 201610313040 A CN201610313040 A CN 201610313040A CN 105859725 B CN105859725 B CN 105859725B
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derivatives
indoline
preparation
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nmr
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CN105859725A (en
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杜云飞
于均超
赵康
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Tianjin University
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D487/04—Ortho-condensed systems

Abstract

The invention discloses the synthetic method of 5,10 indoline simultaneously [3,2 b] indole derivatives, step is：(1) in the triethylamine solution of 2 iodoaniline derivatives (IV) and 2 acetylenylbenzene amine derivatives (V); nitrogen protection is lower to add cuprous iodide, two (triphenylphosphine) palladium chlorides; then it is heated to reflux under nitrogen protective condition; generation 2; the diyl of 2'(acetylene 1,2) diphenylamine derivatives (III)；(2) compound (III), pyridine and paratoluensulfonyl chloride, at ambient temperature reaction are generated into compound (II)；(3) compound (II) is reacted with copper acetate in dimethylformamide obtains 5,10 indoline simultaneously [3,2 b] indole derivatives (I)；The present invention has simple to operate, and reaction raw materials are easy to get, and reaction condition is gentle and can realize substituent type diversity, the advantages that wide application range of substrates.

Description

The synthetic method of 5,10- indoline simultaneously [3,2-b] indole derivatives
Technical field
The present invention relates to the synthetic method of 5,10- indoline simultaneously [3,2-b] indole derivatives.
Background technology
Simultaneously [3,2-b] indole derivatives are a kind of important fused ring compounds to 5,10- indoline, many activity be present In natural products and material molecule, the research of its photoelectric absorption activity aspect also gradually attracts attention[1].As dinaphtho pyrroles [3, 2-b] pyrroles[2](A) because its Stability Analysis of Structures, the easily stored characteristic being not easily decomposed, it is often used as Organic Light Emitting Diode and has The test material of field effect transistors.5,10- indoline simultaneously [3,2-b] indoles[3](B) analog is simplified as its structure, It is the acene condensed ring molecule with pyrrolo- [3,2-b] pyrroles's parent nucleus, is constructing high-spin organic polymer and organic effect There is extensive use in transistor polymer.Therefore for natural products or material molecule containing this class formation, can by from Simultaneously [3,2-b] indole derivatives are prepared this kind of 5,10- indoline.
The synthetic method of the 5,10- indoline of document report simultaneously [3,2-b] indole derivatives mainly has following at present Four classes：
(1) it is substrate with neighbour, o-dinitrobenzene idol acyl, reduces preparation in the presence of acetic acid by using stannous chloride[4]；
(2) using indolone and hydrazine derivative as substrate, prepared by Fei Sheer indole synthesis[5]；
(3) with 6,12- dichloros, simultaneously [b, f] [1,5] two azocine is substrate, by using the zinc powder of excess in acid bar Reduce and prepare under part[2]；
(4) with the bromo indole of N- methyl -2,3- bis- and 2- bromobenzeneboronic acids for substrate, generation is coupled by the selectivity of palladium chtalyst Dibromide, then carry out the preparation of carbon nitrogen coupling twice with primary amine by palladium mediated[6]。
Due to 5,10- indoline, simultaneously [3,2-b] indole derivatives (I) have unique photoelectric absorption active and potential Pharmacological activity, it is therefore desirable to prepare the various derivative of substitution base type to carry out activity research, but current method is difficult Prepare substituent type diversity and be easy to 5, the 10- indoline of modified with functional group simultaneously [3,2-b] indole derivatives, Have no that document report is derivative with N, N'- (2,2'- (acetylene -1,2- diyls) are double (2,1- phenylene)) two (4- methyl benzenesulfonamides) Thing (II) is raw material, and the series connection oxidation reaction mediated by copper acetate prepares 5,10- indoline, and simultaneously [3,2-b] indoles derive Thing (I).
Referring specifically to documents below：
[1]Murray,M.M.；Kaszynski,P.；Kaisaki,D.A.；Chang,W.；Dougherty, D.A.J.Am.Chem.Soc.,1994,116,8152.
[2]Qiu,L.；Yu,C.；Zhao,N.；Chen,W.；Guo,Y.；Wan,X.；Yang,R.；Liu, Y.Chem.Commun.,2012,48,12225.
[3]Jin,Y.；Kim,K.；Song,S.；Kim,J.；Kim,J.；Park,S.H.；Lee,K.；Suh, H.Bull.KoreanChem.Soc.,2006,27,1043.
[4]Heller,G.Ber.Dtsch.Chem.Ges.,1917,50,1202.
[5](a)Grinyov,A.N.；Ryabova,S.Y.；Khim.Geterotsikl.Soedin.,1982,199；(b) Grinyov,A.N.；Ryabova,S.Y.Khim.Geterotsikl.Soedin.,1982,201.
[6]Hung,T.Q.；Hancker,S.；Villinger,A.；Lochbrunner,S.；Dang,T.T.； Friedrich,A.；Breitsprecherb,F.；Langer,P.Org.Biomol.Chem.,2015,13,583.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of simple to operate, reaction raw materials are easy to get, and react bar Part is gentle and can realize the synthesis side of the 5,10- indoline of substituent type diversity simultaneously [3,2-b] indole derivatives Method.
(1) in the triethylamine solution of 2- iodoaniline derivatives (IV) and 2- acetylenylbenzenes amine derivative (V), nitrogen protection Lower addition cuprous iodide, two (triphenylphosphine) palladium chlorides, are then heated to reflux under nitrogen protective condition, generate 2,2'- (second Alkynes -1,2- diyls) diphenylamine derivatives (III)；
(2) compound (III) is dissolved in dry dichloromethane, pyridine and paratoluensulfonyl chloride is added, in room temperature bar Sulfonamide reaction generation N, N'- (2,2'- (acetylene -1,2- diyls) are double (2,1- phenylene)) two (4- methylbenzenes occur under part Sulfonamide) derivative (II)；
(3) compound (II) is reacted with copper acetate in dimethylformamide obtains 5,10- indoline simultaneously [3,2-b] Yin Diindyl analog derivative (I)；
Reaction equation is：
R1=H, Me, MeO, F, Cl, Br or diMe；R2=H, Me, MeO, Cl, Br or diMe.
Preferably, copper acetate and N, N'- (2,2'- (acetylene -1,2- diyls) are double (2,1- phenylene)) two (4- methylbenzene sulphurs Acid amides) derivative (II) mol ratio be 2.2:1.
The present invention has simple to operate, and reaction raw materials are easy to get, and reaction condition is gentle and can realize and substitutes base type various Property, the advantages that wide application range of substrates.
Embodiment
Reaction raw materials 2- iodoaniline derivatives (IV) used in following each embodiments, 2- acetylenylbenzenes amine derivative (V), Paratoluensulfonyl chloride etc. conveniently can be bought or be prepared.
With reference to specific embodiment, the present invention is further illustrated.
Embodiments below is in order that those skilled in the art better understood when the present invention, but the present invention's is interior Appearance is not limited to illustrated embodiment.
Embodiment 1
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N, N'- (2,2'- (acetylene -1,2- diyls) are double (2,1- phenylene)) two (4- methyl benzenesulfonamides) (II-a) Preparation：
Adjacent Iodoaniline (IV-a) (220.2mg, 1mmol) and adjacent acetylenylaniline (V-a) (118.3mg, 1mmol) are dissolved in In triethylamine (50mL), nitrogen protection is lower to add cuprous iodide (1.9mg, 0.01mmol), two (triphenylphosphine) palladium chlorides (7.0mg, 0.01mmol), it is heated to reflux stirring 8h.TLC detection reactions are cooled to room temperature after terminating, and are subtracted with a small amount of silica gel (6g) Pressure, which filters, removes solid residue, and organic phase obtains crude material 2 through anhydrous sodium sulfate drying and after being concentrated under reduced pressure, 2'- (acetylene -1, 2- diyls) diphenylamines (III-a).
By crude product 2,2'- (acetylene -1,2- diyl) diphenylamines (III-a) is dissolved in dry methylene chloride (20mL), adds pyrrole Pyridine (1.3mL) and paratoluensulfonyl chloride (437.9mg, 2.1mmol), be stirred at room temperature it is lower generation sulfonamide reaction to react knot Beam.3mol/L hydrochloric acid (50mL) is added, is extracted in separatory funnel with dichloromethane, organic phase is through anhydrous sodium sulfate drying and subtracts After pressure concentration, obtain crude material, crude product obtains N through column chromatography separating purification, N'- (2,2'- (acetylene -1,2- diyls) it is double (2, 1- phenylenes)) two (4- methyl benzenesulfonamides) (II-a)：White solid, 424.1mg, yield：82%, fusing point：192-194℃ ；1H NMR(600MHz,CDCl3) δ 7.66 (d, J=7.4Hz, 4H), 7.58 (d, J=8.2Hz, 2H), 7.38-7.29 (m, 4H), 7.21 (d, J=7.7Hz, 4H), 7.12 (t, J=7.5Hz, 2H), 6.97 (s, 2H), 2.37 (s, 6H)13C NMR(150MHz, CDCl3)δ144.4,137.6,136.0,132.4,130.4,129.8,127.2,124.9,121.0,114.0,90.2,21.6.
(2) preparation of the p-toluenesulfonyl -5,10- indoline of 5,10- bis- simultaneously [3,2-b] indoles (I-a)：
By N, N'- (2,2'- (acetylene -1,2- diyls) are double (2,1- phenylene)) two (4- methyl benzenesulfonamides) (II-a) (206.6mg, 0.4mmol) is dissolved in dimethylformamide (4.0mL), is added copper acetate (175.7mg, 0.88mmol), is added Heat is to 120 DEG C of stirring reactions.TLC detection reactions are cooled to room temperature after terminating, and add water (40mL), acetic acid is used in separatory funnel Ethyl ester extracts, and organic phase obtains crude material through anhydrous sodium sulfate drying and after being concentrated under reduced pressure, crude product through column chromatography separating purification, Obtain the p-toluenesulfonyl -5,10- indoline of 5,10- bis- simultaneously [3,2-b] indoles (I-a)：White solid, 168.8mg, receive Rate：82%, fusing point：275-277℃；1H NMR(600MHz,CDCl3) δ 8.52 (d, J=7.0Hz, 2H), 8.35 (d, J= 7.3Hz, 2H), 7.50 (d, J=7.7Hz, 4H), 7.43 (s, 4H), 7.00 (d, J=7.8Hz, 4H), 2.25 (s, 6H)13C NMR(150MHz,CDCl3)δ145.0,140.5,133.9,129.7,128.1,126.6,125.7,124.9,121.2, 120.4,115.7,21.6.
Embodiment 2
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (the fluoro- 2- of 4- ((2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-b) preparation：
With (IV-a) of iodo- 4- fluoroanilines (IV-b) alternate embodiments 1 of 2-, the preparation of (III-a) in the other the same as in Example 1 Method, prepare crude product 2- ((2- aminophenyls) acetenyl) -4- fluoroanilines (III-b).
With reference to the preparation method of (II-a) in embodiment 1, N- (the fluoro- 2- of 4- ((2- (4- methylphenyl-sulfonamidos) are prepared Phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-b)：Faint yellow solid, 390.8mg, yield：73%, fusing point:189- 191℃；1H NMR(600MHz,CDCl3) δ 7.65 (d, J=8.2Hz, 2H), 7.59 (d, J=8.1Hz, 2H), 7.54 (d, J= 8.3Hz, 1H), 7.51 (dd, J=9.0,5.0Hz, 1H), 7.35 (t, J=8.1Hz, 1H), 7.29 (d, J=7.6Hz, 1H), 7.20 (d, J=8.1Hz, 2H), 7.17 (d, J=8.0Hz, 2H), 7.12 (t, J=7.5Hz, 1H), 7.07 (d, J=8.6Hz, 1H), 7.07-7.03 (m, 1H), 7.00 (s, 1H), 6.96 (dd, J=8.3,2.6Hz, 1H), 2.37 (s, 3H), 2.36 (s, 3H).13C NMR(150MHz,CDCl3)δ159.6(d,JC-F=246.5Hz), 144.4,144.3,137.7,136.2,135.9, 133.7(d,JC-F=2.7Hz), 132.5,130.6,129.8,129.8,127.3,127.2,125.0,124.6 (d, JC-F= 8.7Hz),121.5,118.7(d,JC-F=24.2Hz), 117.6 (d, JC-F=22.7Hz), 117.0 (d, JC-F=9.8Hz), 114.0,90.8,89.2,21.6,21.6.
(2) preparation of the fluoro- p-toluenesulfonyl -5,10- indoline of 5,10- bis- of 3- simultaneously [3,2-b] indoles (I-b)：
With reference to the preparation method of (I-a) in embodiment 1, fluoro- p-toluenesulfonyl -5, the 10- dihydro Yin of 5,10- bis- of 3- are prepared Diindyl simultaneously [3,2-b] indoles (I-b)：Gray solid, 170.4mg, yield：80%, fusing point：268-270℃；1H NMR(600MHz, CDCl3) δ 8.51 (d, J=7.7Hz, 1H), 8.34 (d, J=8.2Hz, 1H), 8.29 (dd, J=9.2,4.5Hz, 1H), 8.21 (d, J=9.7Hz, 1H), 7.55-7.38 (m, 6H), 7.15 (t, J=7.9Hz, 1H), 7.02 (t, J=8.7Hz, 4H), 2.27 (s,6H).13C NMR(150MHz,CDCl3)δ160.4(d,JC-F=241.1Hz), 145.1 (d, JC-F=7.1Hz), 140.5, 136.7,133.8,133.6,129.8,129.7,129.6,127.5(d,JC-F=3.7Hz), 126.6,126.5,126.2, 125.0,121.4,121.3,120.2,116.9(d,JC-F=9.3Hz), 115.7,113.4 (d, JC-F=25.3Hz), 107.3 (d,JC-F=27.3Hz), 21.6. (has two signal overlaps together)
Embodiment 3
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (the chloro- 2- of 4- ((2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-c) preparation：
With (IV-a) of iodo- 4- chloroanilines (IV-c) alternate embodiments 1 of 2-, the preparation of (III-a) in the other the same as in Example 1 Method, prepare crude product 2- ((2- aminophenyls) acetenyl) -4- chloroanilines (III-c).
With reference to the preparation method of (II-a) in embodiment 1, N- (the chloro- 2- of 4- ((2- (4- methylphenyl-sulfonamidos) are prepared Phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-c)：Faint yellow solid, 419.3mg, yield：76%, fusing point：164- 166℃；1H NMR(600MHz,CDCl3) δ 7.65 (d, J=7.7Hz, 4H), 7.57 (d, J=7.9Hz, 1H), 7.53 (d, J= 9.1Hz, 1H), 7.38 (t, J=7.8Hz, 1H), 7.31 (d, J=6.8Hz, 2H), 7.23 (d, J=8.4Hz, 5H), 7.15 (t, J=7.6Hz, 1H), 6.93 (s, 1H), 6.85 (s, 1H), 2.39 (s, 6H)13C NMR(150MHz,CDCl3)δ144.5, 144.3,137.7,136.2,135.9,132.6,131.9,130.6,130.3,130.3,129.9,129.8,127.4, 127.2,127.2,125.1,122.7,121.9,116.0,114.2,91.2,88.7,26.9,21.6.
(2) preparation of the chloro- p-toluenesulfonyl -5,10- indoline of 5,10- bis- of 3- simultaneously [3,2-b] indoles (I-c)：
With reference to the preparation method of (I-a) in embodiment 1, chloro- p-toluenesulfonyl -5, the 10- dihydro Yin of 5,10- bis- of 3- are prepared Diindyl simultaneously [3,2-b] indoles (I-c)：White solid, 180.2mg, yield：82%, fusing point：254-256℃；1H NMR(600MHz, CDCl3) δ 8.51 (d, J=6.7Hz, 2H), 8.33 (d, J=8.2Hz, 1H), 8.27 (d, J=9.0Hz, 1H), 7.46 (dt, J =11.1,8.3Hz, 6H), 7.39 (d, J=8.9Hz, 1H), 7.03 (t, J=6.6Hz, 4H), 2.28 (s, 6H)13C NMR (150MHz,CDCl3)δ145.3,145.2,140.6,138.7,133.8,133.7,130.9,129.8,129.8,129.3, 126.9,126.6,126.6,126.2,125.8,125.0,121.4,121.3,120.8,120.0,116.7,115.7,21.6. (having two signal overlaps together)
Embodiment 4
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (the bromo- 2- of 4- ((2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-d) preparation：
With (IV-a) of iodo- 4- bromanilines (IV-d) alternate embodiments 1 of 2-, the preparation of (III-a) in the other the same as in Example 1 Method, prepare crude product 2- ((2- aminophenyls) acetenyl) -4- bromanilines (III-d).
With reference to the preparation method of (II-a) in embodiment 1, N- (the bromo- 2- of 4- ((2- (4- methylphenyl-sulfonamidos) are prepared Phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-d)：Gray solid, 452.7mg, yield：76%, fusing point：168- 170℃；1H NMR(600MHz,CDCl3) δ 7.63 (t, J=7.8Hz, 3H), 7.53 (d, J=8.2Hz, 1H), 7.41 (s, 2H), 7.34 (s, 2H), 7.30 (d, J=7.5Hz, 1H), 7.20 (d, J=7.8Hz, 4H), 7.14-7.08 (m, 2H), 2.37 (s, 6H).13C NMR(150MHz,CDCl3)δ144.5,144.3,137.7,136.7,136.2,135.9,134.8,133.2, 132.6,130.7,129.9,129.8,127.2,127.2,125.1,122.7,121.9,117.6,116.2,114.21, (91.4,88.5,21.6. having two signal overlaps together)
(2) preparation of the bromo- p-toluenesulfonyl -5,10- indoline of 5,10- bis- of 3- simultaneously [3,2-b] indoles (I-d)：
With reference to the preparation method of (I-a) in embodiment 1, bromo- p-toluenesulfonyl -5, the 10- dihydro Yin of 5,10- bis- of 3- are prepared Diindyl simultaneously [3,2-b] indoles (I-d)：Gray solid, 199.4mg, yield：84%, fusing point：234-236℃；1H NMR(600MHz, CDCl3) δ 8.66 (s, 1H), 8.51 (d, J=7.6Hz, 1H), 8.33 (d, J=8.2Hz, 1H), 8.22 (d, J=8.9Hz, 1H), 7.53 (d, J=8.9Hz, 1H), 7.50-7.40 (m, 6H), 7.02 (d, J=3.8Hz, 4H), 2.27 (s, 6H)13C NMR (150MHz,CDCl3)δ145.3,145.2,140.6,139.1,133.7,133.7,129.8,129.8,129.1,128.5, 126.8,126.6,126.6,126.3,125.1,123.8,121.8,121.4,120.0,118.6,117.0,115.7,21.6. (having two signal overlaps together)
Embodiment 5
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) 4- methyl-N- (4- methyl -2- ((2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) benzene sulfonyl The preparation of amine (II-e)：
With (IV-a) of iodo- 4- methylanilines (IV-e) alternate embodiments 1 of 2-, the system of (III-a) in the other the same as in Example 1 Preparation Method, prepare crude product 2- ((2- aminophenyls) acetenyl) -4- methylanilines (III-e).
With reference to the preparation method of (II-a) in embodiment 1,4- methyl-N- (4- methyl -2- ((2- (4- aminomethyl phenyls are prepared Sulfonamido) phenyl) acetenyl) phenyl) benzsulfamide (II-e)：Faint yellow solid, 430.2mg, yield：81%, fusing point： 178-180℃；1H NMR(600MHz,CDCl3) δ 7.66 (d, J=7.9Hz, 2H), 7.62 (d, J=7.9Hz, 2H), 7.57 (d, J=8.4Hz, 1H), 7.45 (d, J=8.4Hz, 1H), 7.33 (t, J=7.7Hz, 1H), 7.29 (d, J=7.6Hz, 1H), 7.21–7.13(m,5H),7.13–7.08(m,2H),7.04(s,1H),6.89(s,1H),2.37(s,3H),2.36(s,3H), 2.30(s,3H).13C NMR(150MHz,CDCl3)δ144.3,144.2,137.6,136.1,135.1,135.0,132.60, 132.3,131.3,130.3,129.8,129.8,129.7,127.3,127.2,124.8,121.8,120.9,114.4, 114.0,90.6,89.6,21.6,20.7. (there are two signal overlaps together)
(2) preparation of the p-toluenesulfonyl -5,10- indoline of 3- methyl -5,10- two simultaneously [3,2-b] indoles (I-e)：
With reference to the preparation method of (I-a) in embodiment 1, p-toluenesulfonyl -5, the 10- dihydro of 3- methyl -5,10- bis- is prepared Indoles simultaneously [3,2-b] indoles (I-e)：Yellow solid, 190.2mg, yield：90%, fusing point：230-232℃；1H NMR (600MHz,CDCl3) δ 8.40 (d, J=6.5Hz, 1H), 8.27-8.22 (m, 1H), 8.22-8.18 (m, 1H), 8.13 (t, J= 7.3Hz, 1H), 7.48-7.35 (m, 5H), 7.31 (dd, J=3.8,2.2Hz, 1H), 7.18-7.12 (m, 1H), 6.91-6.83 (m, 4H), 2.41 (s, 3H), 2.11 (d, J=4.1Hz, 6H)13C NMR(150MHz,CDCl3)δ144.9,144.8,140.5, 138.8,134.8,133.9,133.9,129.7,129.7,128.3,128.2,127.1,126.6,125.6,124.9, (121.1,121.1,120.6,120.5,115.7,115.4,21.7,21.6. having two signal overlaps together)
Embodiment 6
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (4- methoxyl groups -2- ((2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) -4- methylbenzene sulphurs The preparation of acid amides (II-f)：
With (IV-a) of iodo- 4- aminoanisoles (IV-f) alternate embodiments 1 of 2-, in the other the same as in Example 1 (III-a) Preparation method, prepare crude product 2- ((2- aminophenyls) acetenyl) -4- aminoanisoles (III-f).
With reference to the preparation method of (II-a) in embodiment 1, N- (4- methoxyl groups -2- ((2- (4- aminomethyl phenyl sulphonyl ammonia is prepared Base) phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-f)：Gray solid, 470.1mg, yield：86%, fusing point： 138-140℃；1H NMR(600MHz,CDCl3) δ 7.66 (d, J=7.8Hz, 2H), 7.56 (d, J=7.7Hz, 3H), 7.44 (d, J=8.7Hz, 1H), 7.33 (t, J=7.6Hz, 1H), 7.26 (d, J=5.0Hz, 1H), 7.20 (d, J=7.4Hz, 2H), 7.15 (d, J=7.4Hz, 2H), 7.10 (t, J=7.5Hz, 1H), 7.06 (s, 1H), 6.91 (d, J=8.8Hz, 1H), 6.81 (s, 1H),6.72(s,1H),3.81(s,3H),2.37(s,3H),2.35(s,3H).13C NMR(150MHz,CDCl3)δ157.2, 144.3,144.1,137.7,136.2,136.1,132.3,130.4,130.4,129.8,129.6,127.3,127.2, 125.3,124.8,121.0,120.9,116.7,116.5,114.0,90.6,89.4,55.7 21.6. (has two signal overlaps Together)
(2) system of the p-toluenesulfonyl -5,10- indoline of 3- methoxyl groups -5,10- two simultaneously [3,2-b] indoles (I-f) It is standby：
With reference to the preparation method of (I-a) in embodiment 1, the p-toluenesulfonyl -5,10- bis- of 3- methoxyl groups -5,10- bis- is prepared Hydrogen indoles simultaneously [3,2-b] indoles (I-f)：Brown solid, 198.2mg, yield：91%, fusing point：205-207℃；1H NMR (600MHz,CDCl3) δ 8.49 (d, J=7.3Hz, 1H), 8.32 (d, J=7.5Hz, 1H), 8.23 (d, J=9.1Hz, 1H), 8.01 (s, 1H), 7.47 (d, J=7.9Hz, 2H), 7.45-7.37 (m, 4H), 7.03 (d, J=9.1Hz, 1H), 6.99 (dd, J =12.0,8.5Hz, 4H), 3.93 (s, 3H), 2.25 (s, 6H)13C NMR(150MHz,CDCl3)δ157.4,144.9, 144.8,140.5,135.0,133.8,133.7,129.7,129.6,129.0,128.3,126.6,126.6,125.7, 125.0,121.5,121.1,120.6,116.8,115.8,114.4,103.8,55.7,21. 6. (have two signal overlaps one Rise)
Embodiment 7
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (2- ((3,5- dimethyl -2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) -4- methylbenzenes The preparation of sulfonamide (II-g)：
With (IV-a) of iodo- 4,6- dimethylanilines (IV-g) alternate embodiments 1 of 2-, in the other the same as in Example 1 (III-a) Preparation method, prepare crude product 2- ((2- aminophenyls) acetenyl) -4,6- dimethylanilines (III-g).
With reference to the preparation method of (II-a) in embodiment 1, N- (2- ((3,5- dimethyl -2- (4- aminomethyl phenyl sulphonyl is prepared Amino) phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-g)：White solid, 446.7mg, yield：82%, fusing point： 162-164℃；1H NMR(600MHz,CDCl3) δ 7.71 (d, J=7.8Hz, 2H), 7.59 (d, J=7.7Hz, 2H), 7.50 (d, J=8.2Hz, 1H), 7.41 (s, 1H), 7.28 (d, J=7.8Hz, 1H), 7.22-7.18 (m, 3H), 7.08-7.04 (m, 5H), 6.37(s,1H),2.35(s,3H),2.32(s,3H),2.31(s,3H),2.21(s,3H).13C NMR(150MHz,CDCl3)δ 143.9,143.8,138.1,137.7,137.5,137.4,136.6,133.2,132.5,132.2,131.0,129.7, 129.6,129.5,127.3,127.3,124.5,122.0,120.7,114.9,92.8,88.0,21.6,21.5,20.8, 18.9.
The system of p-toluenesulfonyl -5, the 10- indoline of (2) 1,3- dimethyl -5,10- bis- simultaneously [3,2-b] indoles (I-g) It is standby：
With reference to the preparation method of (I-a) in embodiment 1, the p-toluenesulfonyl -5,10- of 1,3- dimethyl -5,10- bis- is prepared Indoline simultaneously [3,2-b] indoles (I-g)：Yellow solid, 206.2mg, yield：95%, fusing point：215-217℃；1H NMR (600MHz,CDCl3) δ 8.19 (d, J=5.4Hz, 1H), 8.14 (d, J=7.5Hz, 1H), 7.92 (s, 1H), 7.34 (d, J= 7.7Hz, 2H), 7.28 (d, J=4.0Hz, 2H), 6.97 (s, 1H), 6.90 (d, J=7.7Hz, 2H), 6.82 (d, J=7.7Hz, 2H), 6.66 (d, J=7.7Hz, 2H), 2.69 (s, 3H), 2.35 (s, 3H), 2.13 (s, 3H), 2.09 (s, 3H)13C NMR (150MHz,CDCl3)δ144.9,144.4,141.2,139.8,136.2,134.3,131.6,131.3,131.2,130.9, 130.4,129.8,128.8,126.8,126.6,125.4,124.7,122.1,121.5,119.0,115.2,21.6,21.6, (21.5,21.5. having two signal overlaps together)
Embodiment 8
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N, N'- (2,2'- (acetylene -1,2- diyls) are double (chloro- 2, the 1- phenylenes of 4-)) two (4- methyl benzenesulfonamides) (II-h) preparation：
With (IV-a) of iodo- 4- chloroanilines (IV-h) alternate embodiments 1 of 2-, substituted with the chloro- 2- acetylenylanilines (V-h) of 4- (V-a) of embodiment 1, the preparation method of (III-a), prepares crude product 2,2'- (acetylene -1,2- diyl) in the other the same as in Example 1 Double (4- chloroanilines) (III-h).
With reference to the preparation method of (II-a) in embodiment 1, N is prepared, (double (4- is chloro- for 2,2'- (acetylene -1,2- diyls) by N'- 2,1- phenylenes)) two (4- methyl benzenesulfonamides) (II-h)：Faint yellow solid, 374.7mg, yield：64%, fusing point：188- 190℃；1H NMR(600MHz,CDCl3) δ 7.61 (d, J=7.7Hz, 4H), 7.45 (d, J=8.7Hz, 2H), 7.28 (d, J= 8.8Hz,2H),7.23(s,2H),7.22–7.15(m,6H),2.38(s,6H).13C NMR(150MHz,CDCl3)δ144.5, 136.7,136.0,132.1,130.6,130.5,129.9,127.2,123.5,116.1,89.6,21.6.
The system of chloro- p-toluenesulfonyl -5, the 10- indoline of 5,10- bis- of (2) 3,8- bis- simultaneously [3,2-b] indoles (I-h) It is standby：
With reference to the preparation method of (I-a) in embodiment 1, the chloro- p-toluenesulfonyls -5,10- bis- of 5,10- bis- of 3,8- bis- are prepared Hydrogen indoles simultaneously [3,2-b] indoles (I-h)：White solid, 158.8mg, yield：68%, fusing point：283-285℃；1H NMR (600MHz,CDCl3) δ 8.50 (s, 2H), 8.26 (d, J=9.0Hz, 2H), 7.47 (d, J=7.9Hz, 4H), 7.42 (d, J= 9.1Hz, 2H), 7.05 (d, J=7.9Hz, 4H), 2.29 (s, 6H)13C NMR(150MHz,CDCl3)δ145.5,138.8, 133.5,131.0,129.9,128.1,126.6,126.3,121.1,120.9,116.7,21.6.
Embodiment 9
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (the bromo- 2- of 4- ((the chloro- 2- of 5- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) -4- methylbenzenes The preparation of sulfonamide (II-i)：
With (IV-a) of iodo- 4- chloroanilines (IV-i) alternate embodiments 1 of 2-, substituted with the bromo- 2- acetylenylanilines (V-i) of 4- (V-a) of embodiment 1, the preparation method of (III-a), prepares crude product 2- ((2- amino -5- bromophenyls) in the other the same as in Example 1 Acetenyl) -4- chloroanilines (III-i).
With reference to the preparation method of (II-a) in embodiment 1, N- (the bromo- 2- of 4- ((the chloro- 2- of 5- (4- aminomethyl phenyl sulphonyl is prepared Amino) phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-i)：Faint yellow solid, 390.5mg, yield：62%, melt Point：188-190℃；1H NMR(600MHz,CDCl3) δ 7.63 (t, J=7.5Hz, 4H), 7.49 (d, J=8.8Hz, 1H), 7.44 (dd, J=13.8,5.3Hz, 2H), 7.35 (s, 1H), 7.31 (dd, J=8.8,2.1Hz, 1H), 7.23 (d, J=7.9Hz, 4H), 7.21 (d, J=2.1Hz, 1H), 6.99 (d, J=14.6Hz, 2H), 2.40 (s, 6H)13C NMR(150MHz,CDCl3)δ 144.6,144.6,136.8,136.3,136.0,135.9,134.9,133.6,132.0,130.8,130.6,129.9, 129.9,127.3,127.2,123.3,123.2,117.8,115.9,115.8,89.8,89. 5,21.6. (has two signal weights Stack)
(2) system of the chloro- p-toluenesulfonyl -5,10- indoline of 5,10- bis- of the bromo- 8- of 3- simultaneously [3,2-b] indoles (I-i) It is standby：
With reference to the preparation method of (I-a) in embodiment 1, the chloro- p-toluenesulfonyls -5,10- of 5,10- bis- of the bromo- 8- of 3- are prepared Indoline simultaneously [3,2-b] indoles (I-i)：White solid, 173.4mg, yield：69%, fusing point：>300℃；1H NMR (600MHz,CDCl3) δ 8.65 (s, 1H), 8.49 (s, 1H), 8.25 (d, J=8.7Hz, 1H), 8.20 (d, J=8.9Hz, 1H), 7.56 (d, J=9.0Hz, 1H), 7.47 (d, J=8.0Hz, 4H), 7.42 (d, J=9.0Hz, 1H), 7.05 (d, J=7.7Hz, 4H),2.29(s,6H).13C NMR(150MHz,CDCl3)δ145.5,145.5,139.2,138.8,133.5,133.5, 131.0,129.9,129.9,129.1,127.9,127.8,126.6,126.3,123.9,121.5,121.0,120.9, (118.8,117.0,116.7,21.6. having two signal overlaps together)
Embodiment 10
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N, N'- (2,2'- (acetylene -1,2- diyls) are double (4- methyl -2,1- phenylene)) two (4- methyl benzenesulfonamides (II-j) preparation：
With (IV-a) of iodo- 4- methylanilines (IV-j) alternate embodiments 1 of 2-, with 4- methyl -2- acetylenylanilines (V-j) (V-a) of alternate embodiment 1, the preparation method of (III-a), prepares crude product 2,2'- (acetylene -1,2- bis- in the other the same as in Example 1 Base) double (4- methylanilines) (III-j).
With reference to the preparation method of (II-a) in embodiment 1, N, N'- (2,2'- (acetylene -1,2- diyl) double (4- first are prepared Base -2,1- phenylenes)) two (4- methyl benzenesulfonamides) (II-j)：Brown solid, 461.2mg, yield：85%, fusing point：213- 215℃；1H NMR(600MHz,CDCl3) δ 7.62 (d, J=7.8Hz, 4H), 7.46 (d, J=8.3Hz, 2H), 7.18 (d, J= 7.8Hz, 4H), 7.15 (d, J=8.4Hz, 2H), 7.08 (s, 2H), 6.83 (s, 2H), 2.37 (s, 6H), 2.30 (s, 6H)13C NMR(150MHz,CDCl3)δ144.2,136.2,135.0,134.9,132.5,131.2,129.7,127.2,121.7, 114.3,90.0,21.6,20.7.
The system of p-toluenesulfonyl -5, the 10- indoline of (2) 3,8- dimethyl -5,10- bis- simultaneously [3,2-b] indoles (I-j) It is standby：
With reference to the preparation method of (I-a) in embodiment 1, the p-toluenesulfonyl -5,10- of 3,8- dimethyl -5,10- bis- is prepared Indoline simultaneously [3,2-b] indoles (I-j)：White solid, 152.1mg, yield：70%, fusing point：284-286℃；1H NMR (600MHz,CDCl3) δ 8.27 (s, 2H), 8.19 (d, J=8.4Hz, 2H), 7.46 (d, J=7.5Hz, 4H), 7.23 (d, J= 8.2Hz, 2H), 6.99 (d, J=7.4Hz, 4H), 2.51 (s, 6H), 2.26 (s, 6H)13C NMR(150MHz,CDCl3)δ 144.7,138.7,134.7,133.9,129.6,128.3,126.9,126.6,121.0,120.7,115.4,21.7,21.6.
Embodiment 11
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (the chloro- 2- of 4- ((5- methyl -2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) -4- methyl The preparation of benzsulfamide (II-k)：
With (IV-a) of iodo- 4- methylanilines (IV-k) alternate embodiments 1 of 2-, replaced with the chloro- 2- acetylenylanilines (V-k) of 4- For (V-a) of embodiment 1, the preparation method of (III-a), prepares crude product 2- ((2- amino -5- chlorobenzenes in the other the same as in Example 1 Base) acetenyl) -4- methylanilines (III-k).
With reference to the preparation method of (II-a) in embodiment 1, N- (the chloro- 2- of 4- ((5- methyl -2- (4- aminomethyl phenyl sulphurs are prepared Acylamino-) phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-k)：Faint yellow solid, 429.7mg, yield：76%, melt Point：208-210℃；1H NMR(600MHz,CDCl3) δ 7.64 (d, J=7.7Hz, 2H), 7.60 (d, J=7.6Hz, 2H), 7.51 (d, J=8.8Hz, 1H), 7.43 (d, J=8.3Hz, 1H), 7.28 (d, J=8.8Hz, 1H), 7.20 (dd, J=19.1, 10.0Hz,6H),7.10(s,1H),7.01(s,1H),6.77(s,1H),2.39(s,3H),2.38(s,3H),2.32(s,3H) .13C NMR(150MHz,CDCl3)δ144.5,144.2,136.3,136.3,135.9,135.3,135.1,132.8,131.8, 131.6,130.3,130.2,129.9,129.8,127.2,127.2,122.6,122.3,115.7,114.4,91.6,88.0, 21.6,21.6,20.7.
(2) the 3- chloro- p-toluenesulfonyl -5,10- indoline of 8- methyl -5,10- two simultaneously [3,2-b] indoles (I-k) Prepare：
With reference to the preparation method of (I-a) in embodiment 1, chloro- p-toluenesulfonyl -5 of 8- methyl -5,10- bis- of 3- are prepared, 10- indoline simultaneously [3,2-b] indoles (I-k)：White solid, 169.2mg, yield：75%, fusing point：>300℃；1H NMR (600MHz,CDCl3) δ 8.48 (s, 1H), 8.28 (s, 1H), 8.24 (d, J=8.9Hz, 1H), 8.20 (d, J=8.5Hz, 1H), 7.46 (d, J=7.8Hz, 4H), 7.37 (d, J=8.9Hz, 1H), 7.28 (s, 1H), 7.02 (d, J=7.8Hz, 4H), 2.52 (s,3H),2.28(s,3H),2.27(s,3H).13C NMR(150MHz,CDCl3)δ145.2,145.0,138.9,138.7, 134.9,133.7,133.6,130.9,129.8,129.7,129.3,127.6,127.1,126.6,126.6,125.7, (121.6,121.2,120.7,120.3,116.7,115.4,21.7,21.6. having two signal overlaps together)
Embodiment 12
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (4- methoxyl groups -2- ((5- methyl -2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) phenyl) -4- The preparation of methyl benzenesulfonamide (II-l)：
With (IV-a) of iodo- 4- methylanilines (IV-l) alternate embodiments 1 of 2-, with 4- methoxyl group -2- acetylenylanilines (V- L) (V-a) of alternate embodiment 1, the preparation method of (III-a), prepares crude product 2- ((2- amino -5- first in the other the same as in Example 1 Phenyl) acetenyl) -4- methylanilines (III-l).
With reference to the preparation method of (II-a) in embodiment 1, N- (4- methoxyl groups -2- ((5- methyl -2- (4- methylbenzenes are prepared Ylsulfonylamino) phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamides (II-l)：Faint yellow solid, 476.7mg, yield： 85%, fusing point：165-167℃；1H NMR(600MHz,CDCl3) δ 7.62 (d, J=7.7Hz, 2H), 7.56 (d, J=7.7Hz, 2H), 7.46 (dd, J=12.1,9.6Hz, 2H), 7.19 (d, J=7.8Hz, 2H), 7.16 (d, J=6.5Hz, 3H), 7.04 (s, 1H), 6.91 (d, J=8.9Hz, 1H), 6.81 (s, 1H), 6.77 (s, 1H), 6.63 (s, 1H), 3.81 (s, 3H), 2.37 (s, 6H),2.31(s,3H).13C NMR(150MHz,CDCl3)δ157.1,144.2,144.1,136.3,136.2,135.1, 134.9,132.6,131.2,130.4,129.7,129.6,127.2,127.2,125.2,121.9,117.2,116.6, (116.4,114.5,89.9,89.8,55.6,21.6,20.7. having two signal overlaps together)
(2) p-toluenesulfonyl -5,10- indoline of 3- methoxyl groups -8- methyl -5,10- two simultaneously [3,2-b] indoles (I- L) preparation：
The preparation method of (I-a) in reference embodiment 1, the p-toluenesulfonyl of preparation 3- methoxyl group -8- methyl -5,10- bis- - 5,10- indoline simultaneously [3,2-b] indoles (I-l)：White solid, 183.3mg, yield：82%, fusing point：273-275℃；1H NMR(600MHz,CDCl3) δ 8.26 (s, 1H), 8.19 (t, J=8.6Hz, 2H), 7.99 (s, 1H), 7.49-7.36 (m, 4H), (7.24 d, J=8.5Hz, 1H), 6.99 (dd, J=17.7,10.3Hz, 5H), 3.92 (s, 3H), 2.51 (s, 3H), 2.26 (s, 6H).13C NMR(150MHz,CDCl3)δ157.3,144.8,144.7,138.8,135.0,134.8,133.8,133.7, 129.6,129.5,129.0,128.5,127.1,126.6,126.6,121.6,121.0,120.8,116.8,115.4, (114.3,103.6,55.7,21.7,21.6. having two signal overlaps together)
Embodiment 13
The synthetic method of 5,10- of one kind indoline simultaneously [3,2-b] indole derivatives (I), comprises the following steps：
(1) N- (2- ((3,5- dimethyl -2- (4- methylphenyl-sulfonamidos) phenyl) acetenyl) -4- aminomethyl phenyls) - The preparation of 4- methyl benzenesulfonamides (II-m)：
With (IV-a) of iodo- 4- methylanilines (IV-m) alternate embodiments 1 of 2-, with 4,6- dimethyl -2- acetylenylanilines (V-m) (V-a) of alternate embodiment 1, the preparation method of (III-a) in the other the same as in Example 1, prepare crude product 2- ((2- amino- 5- aminomethyl phenyls) acetenyl) -4,6- dimethylanilines (III-m).
With reference to the preparation method of (II-a) in embodiment 1, N- (2- ((3,5- dimethyl -2- (4- aminomethyl phenyl sulphonyl is prepared Amino) phenyl) acetenyl) -4- aminomethyl phenyls) -4- methyl benzenesulfonamides (II-m)：Faint yellow solid, 413.4mg, yield： 74%, fusing point：148-150℃；1H NMR(600MHz,CDCl3) δ 7.66 (d, J=7.9Hz, 2H), 7.57 (d, J=7.9Hz, 2H), 7.39 (d, J=8.3Hz, 1H), 7.32 (s, 1H), 7.14 (d, J=7.8Hz, 2H), 7.08-7.02 (m, 4H), 6.98 (d, J=8.2Hz, 2H), 6.64 (s, 1H), 2.32 (s, 3H), 2.29 (s, 6H), 2.25 (s, 3H), 2.21 (s, 3H)13C NMR (150MHz,CDCl3)δ143.7,143.6,138.1,137.5,137.4,136.7,135.1,134.5,133.1,132.5, 132.5,130.9,130.5,129.6,129.5,127.3,127.2,122.0,121.6,115.4,92.1,88.3,21.5, 21.5,20.8,20.7,19.0.
(2) 1,3,8- trimethyls -5,10- two p-toluenesulfonyl -5,10- indoline simultaneously [3,2-b] indoles (I-m) Prepare：
With reference to the preparation method of (I-a) in embodiment 1, p-toluenesulfonyl -5 of 1,3,8- trimethyls -5,10- bis- are prepared, 10- indoline simultaneously [3,2-b] indoles (I-m)：Faint yellow solid, 150.4mg, yield：68%, fusing point：235-237℃；1H NMR(600MHz,CDCl3) δ 8.10 (d, J=8.5Hz, 1H), 8.06 (s, 1H), 7.98 (s, 1H), 7.43 (d, J=7.8Hz, 2H), 7.19 (d, J=8.5Hz, 1H), 7.06 (s, 1H), 7.02 (d, J=7.9Hz, 2H), 6.93 (d, J=7.7Hz, 2H), 6.79 (d, J=7.8Hz, 2H), 2.78 (s, 3H), 2.50 (s, 3H), 2.45 (s, 3H), 2.26 (s, 3H), 2.23 (s, 3H)13C NMR(150MHz,CDCl3)δ144.8,144.4,141.2,138.1,136.1,134.4,134.3,131.7,131.2, 131.2,130.7,130.4,129.7,128.7,126.9,126.8,126.6,124.8,122.3,121.4,118.9, 114.9,21.6,21.5. (there are two signal overlaps together).

Claims (2)

  1. The synthetic method of 1.5,10- indoline simultaneously [3,2-b] indole derivatives (I), it is characterized in that comprising the following steps：
    (1) in the triethylamine solution of 2- iodoaniline derivatives (IV) and 2- acetylenylbenzenes amine derivative (V), nitrogen protection is lower to be added Enter cuprous iodide, two (triphenylphosphine) palladium chlorides, be then heated to reflux under nitrogen protective condition, 2,2'- of generation (acetylene- 1,2- diyls) diphenylamine derivatives (III)；
    (2) 2,2'- (acetylene -1,2- diyl) diphenylamine derivatives (III) is dissolved in dry dichloromethane, add pyridine and Paratoluensulfonyl chloride, at ambient temperature occur sulfonamide reaction generation N, N'- (2,2'- (acetylene -1,2- diyls) it is double (2, 1- phenylenes)) two (4- methyl benzenesulfonamides) derivatives (II)；
    (3) (4- methyl benzenesulfonamides) derivative (II) of N, N'- (2,2'- (acetylene -1,2- diyls) are double (2,1- phenylene)) two Reacted with copper acetate in dimethylformamide and obtain 5,10- indoline simultaneously [3,2-b] indole derivatives (I)；
    Reaction equation is：
    R1=H, Me, MeO, F, Cl or Br；R2=H, Me, MeO, Cl or Br.
  2. 2. according to the method for claim 1, it is characterized in that the copper acetate and N, N'- (2,2'- (acetylene -1,2- diyls) Double (2,1- phenylenes)) two (4- methyl benzenesulfonamides) derivatives (II) mol ratio be 2.2:1.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103098253A (en) * 2010-09-13 2013-05-08 新日铁住金化学株式会社 Organic electroluminescent element
US20140306197A1 (en) * 2013-04-10 2014-10-16 Pusan National University Industry-University Cooperation Foundation Compound and organic light-emitting device comprising the same
CN105348288A (en) * 2015-12-11 2016-02-24 山东理工大学 Synthetic method of 5,10-indoline[3,2-b] indole compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103098253A (en) * 2010-09-13 2013-05-08 新日铁住金化学株式会社 Organic electroluminescent element
US20140306197A1 (en) * 2013-04-10 2014-10-16 Pusan National University Industry-University Cooperation Foundation Compound and organic light-emitting device comprising the same
CN105348288A (en) * 2015-12-11 2016-02-24 山东理工大学 Synthetic method of 5,10-indoline[3,2-b] indole compound

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
N-Methyl Transfer Induced Copper-Mediated Oxidative Diamination of Alkynes;Hon Eong Ho，等;《Organic Letters》;20160506;第18卷(第10期);2487-2490页 *
Synthesis of Benzofuro- and Indolo[3,2-b]indoles via Palladium-Catalyzed Double N-Arylation and Their Physical Properties;Minh Anh Truong，等;《Journal of Organic Chemistry》;20151027;第80卷(第22期);11566-11572页 *

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