CN105859725A - 5,10-dihydroindolo[3,2-b]indole derivative synthesis method - Google Patents

5,10-dihydroindolo[3,2-b]indole derivative synthesis method Download PDF

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CN105859725A
CN105859725A CN201610313040.0A CN201610313040A CN105859725A CN 105859725 A CN105859725 A CN 105859725A CN 201610313040 A CN201610313040 A CN 201610313040A CN 105859725 A CN105859725 A CN 105859725A
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indoline
indole
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CN105859725B (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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    • 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
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Abstract

The invention discloses a 5,10-dihydroindolo[3,2-b]indole derivative synthesis method. The method includes: (1) in a triethylamine solution of 2-iodoaniline derivatives (IV) and 2-acetenyl aniline derivatives (V), adding copper iodide and bis(triphenylphosphine)palladium chloride under nitrogen protection, and heating and refluxing under nitrogen protection to generate 2,2'-(acetenyl-1,2-2-yl) diphenylamine derivatives (III); (2) reacting the compounds (III), pyridines and paratoluensulfonyl chloride to generate compounds (II) at the room temperature; (3) reacting the compounds (II) and copper acetate in dimethylformamide to obtain 5,10-dihydroindolo[3,2-b]indole derivatives (I). The 5,10-dihydroindolo[3,2-b]indole derivative synthesis method has advantages of simplicity in operation, easiness in acquisition of reaction raw materials, mild reaction conditions, realization of substituent type diversity, wide substrate application range and the like.

Description

The synthetic method of 5,10-indoline also [3,2-b] indole derivatives
Technical field
The present invention relates to the synthetic method of 5,10-indoline also [3,2-b] indole derivatives.
Background technology
5,10-indoline also [3,2-b] indole derivatives is the fused ring compound that a class is important, there is many activity In natural product and material molecule, the research in terms of its photoelectric absorption activity the most gradually receives publicity[1].As dinaphtho pyrroles [3, 2-b] pyrroles[2](A) because of its Stability Analysis of Structures, it is easy to store the 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 also [3,2-b] indole[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 In transistor polymer, tool is widely used.Therefore for the natural product containing this class formation or material molecule, can by from This kind of 5,10-indoline also [3,2-b] indole derivatives prepares.
The synthetic method of 5,10-indoline also [3,2-b] indole derivatives of document report mainly has following at present Four classes:
(1) with neighbour, o-dinitrobenzene idol acyl is substrate, by preparing with stannum dichloride reduction in the presence of acetic acid[4]；
(2) with indolone and hydrazine derivative as substrate, prepared by Fei Sheer indole synthesis[5]；
(3) with 6,12-dichloro also [b, f] [1,5] two azocine is substrate, by with the zinc powder of excess at acid bar Reduction preparation under part[2]；
(4) with N-methyl-2,3-bis-bromo indole and 2-bromobenzeneboronic acid are substrate, are generated by the selectivity coupling of palladium chtalyst Dibromide, is then carried out twice carbon nitrogen coupling with primary amine prepared by palladium mediated[6]。
Due to 5,10-indoline also [3,2-b] indole derivatives (I) have uniqueness photoelectric absorption active and potential Pharmacologically active, it is therefore desirable to the preparation various derivant of substituent group type carries out activity research, but current method is difficult to Prepare substituent group type diversity and be prone to the 5 of modified with functional group, 10-indoline also [3,2-b] indole derivatives, also Have no that document report derives with N, N'-(2,2'-(acetylene-1,2-diyl) double (2,1-phenylene)) two (4-methyl benzenesulfonamides) Thing (II) is raw material, and the series connection oxidation reaction mediated by Schweinfurt green prepares 5, and 10-indoline also [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.Korean Chem.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.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of simple to operate, reaction raw materials is easy to get, and reacts bar Part is gentle and can realize the synthesis side of 5,10-indoline also [3,2-b] indole derivatives of substituent group type diversity Method.
(1) in the 2-iodoaniline derivatives (IV) triethylamine solution with 2-acetylenylbenzene amine derivative (V), nitrogen is protected Lower addition Hydro-Giene (Water Science)., two (triphenylphosphine) palladium chloride, be then heated to reflux under nitrogen protective condition, generates 2,2'-(second Alkynes-1,2-diyl) diphenylamine derivatives (III)；
(2) compound (III) is dissolved in dry dichloromethane, adds pyridine and paratoluensulfonyl chloride, at room temperature bar Sulfonamide reaction is occurred to generate N, N'-(2,2'-(acetylene-1,2-diyl) double (2,1-phenylene)) two (4-methylbenzene under part Sulfonamide) derivant (II)；
(3) compound (II) and Schweinfurt green react in dimethylformamide and obtain 5,10-indoline also [3,2-b] Yin Diindyl analog derivative (I)；
Reaction equation is:
R1=H, Me, MeO, F, Cl, Br, diMe；R2=H, Me, OMe, Cl, Br, diMe
R1=H, Me, MeO, F, Cl, Br or diMe；R2=H, Me, MeO, Cl, Br or diMe.
Preferably, Schweinfurt green and N, N'-(2,2'-(acetylene-1,2-diyl) double (2,1-phenylene)) two (4-methylbenzene sulphurs Amide) mol ratio of derivant (II) is 2.2:1.
The present invention has simple to operate, and reaction raw materials is easy to get, and reaction condition is gentle and to realize substituent group type various Property, the advantage such as wide application range of substrates.
Detailed description of the invention
Reaction raw materials 2-iodoaniline derivatives (IV) used in following each embodiment, 2-acetylenylbenzene amine derivative (V), Paratoluensulfonyl chlorides etc. all can conveniently have been bought or prepare.
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiments below is to enable those skilled in the art to be more fully understood that the present invention, but the present invention's is interior Hold and be not limited to illustrated embodiment.
Embodiment 1
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N, N'-(2,2'-(acetylene-1,2-diyl) double (2,1-phenylene)) two (4-methyl benzenesulfonamide) (II-a) Preparation:
Neighbour's Iodoaniline (IV-a) (220.2mg, 1mmol) is dissolved in adjacent acetylenylaniline (V-a) (118.3mg, 1mmol) In triethylamine (50mL), under nitrogen protection, add Hydro-Giene (Water Science). (1.9mg, 0.01mmol), two (triphenylphosphine) palladium chloride (7.0mg, 0.01mmol), is heated to reflux stirring 8h.TLC detection reaction is cooled to room temperature after terminating, and subtracts with a small amount of silica gel (6g) Pressure sucking filtration removes solid residue, and organic facies is dried through anhydrous sodium sulfate and after concentrating under reduced pressure, obtains crude material 2,2'-(acetylene-1, 2-diyl) 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 lower generation sulfonamide reaction to reacting knot Bundle.Adding 3mol/L hydrochloric acid (50mL), extract with dichloromethane in separatory funnel, organic facies is dried through anhydrous sodium sulfate and subtracts Pressure concentrate after, obtain crude material, crude product through column chromatography separating purification, obtain N, N'-(2,2'-(acetylene-1,2-diyls) double (2, 1-phenylene)) two (4-methyl benzenesulfonamide) (II-a): white solid, 424.1mg, yield: 82%, fusing point: 192-194 DEG C ；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) 5,10-bis-p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-a) (differs with the title of power Cause) preparation:
By N, N'-(2,2'-(acetylene-1,2-diyl) double (2,1-phenylene)) two (4-methyl benzenesulfonamide) (II-a) (206.6mg, 0.4mmol) is dissolved in dimethylformamide (4.0mL), adds Schweinfurt green (175.7mg, 0.88mmol), adds Heat to 120 DEG C stirring reaction.TLC detection reaction is cooled to room temperature after terminating, and adds water (40mL), uses acetic acid in separatory funnel Ethyl ester extract, organic facies through anhydrous sodium sulfate be dried and concentrating under reduced pressure after, obtain crude material, crude product through column chromatography separating purification, Obtain 5,10-bis-p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-a): white solid, 168.8mg, receives Rate: 82%, fusing point: 275-277 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(the fluoro-2-of 4-((2-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (II-b) preparation:
With (IV-a) of 2-iodo-4-fluoroaniline (IV-b) alternate embodiment 1, the preparation of (III-a) in the other the same as in Example 1 Method, prepares crude product 2-((2-aminophenyl) acetenyl)-4-fluoroaniline (III-b).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(the fluoro-2-of 4-((2-(4-methylphenyl-sulfonamido) Phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (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 3-fluoro-5,10-bis-p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-b):
With reference to the preparation method of (I-a) in embodiment 1, prepare 3-fluoro-5,10-bis-p-toluenesulfonyl-5,10-dihydro Yin Diindyl also [3,2-b] indole (I-b): gray solid, 170.4mg, yield: 80%, fusing point: 268-270 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(the chloro-2-of 4-((2-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (II-c) preparation:
With (IV-a) of 2-iodo-4-chloroaniline (IV-c) alternate embodiment 1, the preparation of (III-a) in the other the same as in Example 1 Method, prepares crude product 2-((2-aminophenyl) acetenyl)-4-chloroaniline (III-c).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(the chloro-2-of 4-((2-(4-methylphenyl-sulfonamido) Phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (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 3-chloro-5,10-bis-p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-c):
With reference to the preparation method of (I-a) in embodiment 1, prepare 3-chloro-5,10-bis-p-toluenesulfonyl-5,10-dihydro Yin Diindyl also [3,2-b] indole (I-c): white solid, 180.2mg, yield: 82%, fusing point: 254-256 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(the bromo-2-of 4-((2-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (II-d) preparation:
With (IV-a) of 2-iodo-4-bromaniline (IV-d) alternate embodiment 1, the preparation of (III-a) in the other the same as in Example 1 Method, prepares crude product 2-((2-aminophenyl) acetenyl)-4-bromaniline (III-d).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(the bromo-2-of 4-((2-(4-methylphenyl-sulfonamido) Phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (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 3-bromo-5,10-bis-p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-d):
With reference to the preparation method of (I-a) in embodiment 1, prepare 3-bromo-5,10-bis-p-toluenesulfonyl-5,10-dihydro Yin Diindyl also [3,2-b] indole (I-d): gray solid, 199.4mg, yield: 84%, fusing point: 234-236 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) 4-methyl-N-(4-methyl-2-((2-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl) benzene sulfonyl The preparation of amine (II-e):
By (IV-a) of 2-iodo-4-monomethylaniline. (IV-e) alternate embodiment 1, the system of (III-a) in the other the same as in Example 1 Preparation Method, prepares crude product 2-((2-aminophenyl) acetenyl)-4-monomethylaniline. (III-e).
With reference to the preparation method of (II-a) in embodiment 1, prepare 4-methyl-N-(4-methyl-2-((2-(4-aminomethyl phenyl 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 3-methyl-5,10-two p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-e):
With reference to the preparation method of (I-a) in embodiment 1, prepare 3-methyl-5,10-bis-p-toluenesulfonyl-5,10-dihydro Indole also [3,2-b] indole (I-e): yellow solid, 190.2mg, yield: 90%, fusing point: 230-232 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(4-methoxyl group-2-((2-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl)-4-methylbenzene sulphur The preparation of amide (II-f):
With (IV-a) of 2-iodo-4-aminoanisole (IV-f) alternate embodiment 1, in the other the same as in Example 1 (III-a) Preparation method, prepares crude product 2-((2-aminophenyl) acetenyl)-4-aminoanisole (III-f).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(4-methoxyl group-2-((2-(4-aminomethyl phenyl sulphonyl ammonia Base) phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (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 3-methoxyl group-5,10-two p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-f) Standby:
With reference to the preparation method of (I-a) in embodiment 1, prepare 3-methoxyl group-5,10-bis-p-toluenesulfonyl-5,10-bis- Hydrogen indole also [3,2-b] indole (I-f): brown solid, 198.2mg, yield: 91%, fusing point: 205-207 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(2-((3,5-dimethyl-2-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl)-4-methylbenzene The preparation of sulfonamide (II-g):
With 2-iodo-4, (IV-a) of 6-dimethylaniline (IV-g) alternate embodiment 1, in the other the same as in Example 1 (III-a) Preparation method, prepare crude product 2-((2-aminophenyl) acetenyl)-4,6-dimethylaniline (III-g).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(2-((3,5-dimethyl-2-(4-aminomethyl phenyl sulphonyl Amino) phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (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.
(2) 1,3-dimethyl-5,10-bis-p-toluenesulfonyl-5, the system of 10-indoline also [3,2-b] indole (I-g) Standby:
With reference to the preparation method of (I-a) in embodiment 1, preparation 1,3-dimethyl-5,10-bis-p-toluenesulfonyl-5,10- Indoline also [3,2-b] indole (I-g): yellow solid, 206.2mg, yield: 95%, fusing point: 215-217 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N, N'-(2,2'-(acetylene-1,2-diyls) double (4-chloro-2,1-phenylene)) two (4-methyl benzenesulfonamides) (II-h) preparation:
With (IV-a) of 2-iodo-4-chloroaniline (IV-h) alternate embodiment 1, substitute with 4-chloro-2-acetylenylaniline (V-h) (V-a) of embodiment 1, the preparation method of (III-a) in the other the same as in Example 1, prepare crude product 2,2'-(acetylene-1,2-diyl) Double (4-chloroaniline) (III-h).
With reference to the preparation method of (II-a) in embodiment 1, (double (4-is chloro-for 2,2'-(acetylene-1,2-diyls) for preparation N, N'- 2,1-phenylenes)) two (4-methyl benzenesulfonamide) (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.
(2) 3,8-bis-chloro-5,10-bis-p-toluenesulfonyl-5, the system of 10-indoline also [3,2-b] indole (I-h) Standby:
With reference to the preparation method of (I-a) in embodiment 1, preparation 3,8-bis-chloro-5,10-bis-p-toluenesulfonyl-5,10-bis- Hydrogen indole also [3,2-b] indole (I-h): white solid, 158.8mg, yield: 68%, fusing point: 283-285 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(the bromo-2-of 4-((the chloro-2-of 5-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl)-4-methylbenzene The preparation of sulfonamide (II-i):
With (IV-a) of 2-iodo-4-chloroaniline (IV-i) alternate embodiment 1, substitute with 4-bromo-2-acetylenylaniline (V-i) (V-a) of embodiment 1, the preparation method of (III-a) in the other the same as in Example 1, prepare crude product 2-((2-amino-5-bromophenyl) Acetenyl)-4-chloroaniline (III-i).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(the bromo-2-of 4-((the chloro-2-of 5-(4-aminomethyl phenyl sulphonyl Amino) phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (II-i): faint yellow solid, 390.5mg, yield: 62%, molten Point: 188-190 DEG C；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 bromo-8-of 3-chloro-5,10-bis-p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-i) Standby:
With reference to the preparation method of (I-a) in embodiment 1, prepare the bromo-8-of 3-chloro-5,10-bis-p-toluenesulfonyl-5,10- Indoline also [3,2-b] indole (I-i): white solid, 173.4mg, yield: 69%, fusing point: > 300 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N, N'-(2,2'-(acetylene-1,2-diyls) double (4-methyl-2,1-phenylene)) two (4-methyl benzenesulfonamides (II-j) preparation:
With (IV-a) of 2-iodo-4-monomethylaniline. (IV-j) alternate embodiment 1, with 4-methyl-2-acetylenylaniline (V-j) (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'-(acetylene-1,2-bis- Base) double (4-monomethylaniline .) (III-j).
With reference to the preparation method of (II-a) in embodiment 1, prepare N, N'-(2,2'-(acetylene-1,2-diyl) double (4-first Base-2,1-phenylene)) two (4-methyl benzenesulfonamide) (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) .13CNMR(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.
(2) 3,8-dimethyl-5,10-bis-p-toluenesulfonyl-5, the system of 10-indoline also [3,2-b] indole (I-j) Standby:
With reference to the preparation method of (I-a) in embodiment 1, preparation 3,8-dimethyl-5,10-bis-p-toluenesulfonyl-5,10- Indoline also [3,2-b] indole (I-j): white solid, 152.1mg, yield: 70%, fusing point: 284-286 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(the chloro-2-of 4-((5-methyl-2-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl)-4-methyl The preparation of benzsulfamide (II-k):
With (IV-a) of 2-iodo-4-monomethylaniline. (IV-k) alternate embodiment 1, replace with 4-chloro-2-acetylenylaniline (V-k) For (V-a) of embodiment 1, the preparation method of (III-a) in the other the same as in Example 1, prepare crude product 2-((2-amino-5-chlorobenzene Base) acetenyl)-4-monomethylaniline. (III-k).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(the chloro-2-of 4-((5-methyl-2-(4-aminomethyl phenyl sulphur Acylamino-) phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (II-k): faint yellow solid, 429.7mg, yield: 76%, molten Point: 208-210 DEG C；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) 3-chloro-8-methyl-5,10-two p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-k) Preparation:
The preparation method of (I-a) in reference embodiment 1, preparation 3-chloro-8-methyl-5,10-bis-p-toluenesulfonyl-5, 10-indoline also [3,2-b] indole (I-k): white solid, 169.2mg, yield: 75%, fusing point: > 300 DEG C；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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(4-methoxyl group-2-((5-methyl-2-(4-methylphenyl-sulfonamido) phenyl) acetenyl) phenyl)-4- The preparation of methyl benzenesulfonamide (II-l):
With (IV-a) of 2-iodo-4-monomethylaniline. (IV-l) alternate embodiment 1, with 4-methoxyl group-2-acetylenylaniline (V- L) (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-first Phenyl) acetenyl)-4-monomethylaniline. (III-l).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(4-methoxyl group-2-((5-methyl-2-(4-methylbenzene Ylsulfonylamino) phenyl) acetenyl) phenyl)-4-methyl benzenesulfonamide (II-l): faint yellow solid, 476.7mg, yield: 85%, fusing point: 165-167 DEG C；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) 3-methoxyl group-8-methyl-5,10-two p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I- L) preparation:
The preparation method of (I-a) in reference embodiment 1, preparation 3-methoxyl group-8-methyl-5,10-bis-p-toluenesulfonyl- 5,10-indoline also [3,2-b] indole (I-l): white solid, 183.3mg, yield: 82%, fusing point: 273-275 DEG C；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).13CNMR(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
A kind of 5, the synthetic method of 10-indoline also [3,2-b] indole derivatives (I), comprise the steps:
(1) N-(2-((3,5-dimethyl-2-(4-methylphenyl-sulfonamido) phenyl) acetenyl)-4-aminomethyl phenyl)- The preparation of 4-methyl benzenesulfonamide (II-m):
With (IV-a) of 2-iodo-4-monomethylaniline. (IV-m) alternate embodiment 1, with 4,6-dimethyl-2-acetylenylaniline (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 phenyl) acetenyl)-4,6-dimethylaniline (III-m).
With reference to the preparation method of (II-a) in embodiment 1, prepare N-(2-((3,5-dimethyl-2-(4-aminomethyl phenyl sulphonyl Amino) phenyl) acetenyl)-4-aminomethyl phenyl)-4-methyl benzenesulfonamide (II-m): faint yellow solid, 413.4mg, yield: 74%, fusing point: 148-150 DEG C；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-trimethyl-5,10-two p-toluenesulfonyl-5,10-indoline also [3,2-b] indole (I-m) Preparation:
The preparation method of (I-a) in reference embodiment 1, preparation 1,3,8-trimethyl-5,10-bis-p-toluenesulfonyl-5, 10-indoline also [3,2-b] indole (I-m): faint yellow solid, 150.4mg, yield: 68%, fusing point: 235-237 DEG C；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 also [3,2-b] indole derivatives (I), is characterized in that comprising the steps:
    (1) in the 2-iodoaniline derivatives (IV) triethylamine solution with 2-acetylenylbenzene amine derivative (V), add under nitrogen protection Enter Hydro-Giene (Water Science)., two (triphenylphosphine) palladium chloride, be then heated to reflux under nitrogen protective condition, generation 2,2'-(acetylene- 1,2-diyl) diphenylamine derivatives (III)；
    (2) compound (III) is dissolved in dry dichloromethane, adds pyridine and paratoluensulfonyl chloride, at ambient temperature Sulfonamide reaction is occurred to generate N, N'-(2,2'-(acetylene-1,2-diyl) double (2,1-phenylene)) two (4-Methyl benzenesulfonyls Amine) derivant (II)；
    (3) compound (II) and Schweinfurt green react in dimethylformamide and obtain 5,10-indoline also [3,2-b] indoles Derivant (I)；
    Reaction equation is:
    R1=H, Me, MeO, F, Cl, Br, diMe；R2=H, Me, OMe, Cl, Br, diMe
    R1=H, Me, MeO, F, Cl, Br or diMe；R2=H, Me, MeO, Cl, Br or diMe.
  2. Method the most according to claim 1, is characterized in that described Schweinfurt green and N, N'-(2,2'-(acetylene-1,2-diyls) Double (2,1-phenylenes)) mol ratio of two (4-methyl benzenesulfonamide) derivant (II) is 2.2:1.
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CN106478628A (en) * 2016-10-11 2017-03-08 南阳师范学院 A kind of pyrido [2 ', 1 '：2,3] piperidines [1,6 a] pyrroles's salt and its synthetic method
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CN110862396A (en) * 2019-11-29 2020-03-06 浙江工业大学 Synthesis method of pyrrolo [3,4-c ] carbazole-1, 3(2H,6H) -diketone compound
CN113121542A (en) * 2021-04-13 2021-07-16 常州大学 5, 10-indolino [3,2-b ] indole derivative and synthesis method and application thereof

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