CN104177283B - The method preparing bisindole methane derivative in the presence of amine salt - Google Patents
The method preparing bisindole methane derivative in the presence of amine salt Download PDFInfo
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- CN104177283B CN104177283B CN201410326348.XA CN201410326348A CN104177283B CN 104177283 B CN104177283 B CN 104177283B CN 201410326348 A CN201410326348 A CN 201410326348A CN 104177283 B CN104177283 B CN 104177283B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
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- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
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- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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Abstract
The invention discloses a kind of method preparing bisindole methane derivative in the presence of amine salt, with amine salt as catalyst, making indole or indole derivatives and aldehyde reaction obtain bisindole methane derivative, wherein amine salt is anilinechloride, o-chloroaniline hydrochloride, o-aminoanisole hydrochlorate, pyrrole hydrochloride, aniline trifluoro-methanyl sulfonate or aniline trifluoroacetate.The present invention is simple to operate, and reaction condition is gentle, the response time is short, and catalyst is cheap and easy to get, nontoxic, stable to air and water, good substrate applicability, and target substance productivity is high, can be widely used for the preparation of bisindole methane derivative.
Description
Technical field
The method that the present invention relates to prepare bisindole methane derivative in the presence of amine salt.
Background technology
Bis-indolyl alkyl compounds and derivant thereof are that a class is widely present in colored section plant and continent and ocean is former
Biological metabolite, they mostly have certain physiologically active, such as: antitumor, antiviral, antibacterial and antiinflammatory
Deng.Bis-indolyl alkyl compounds is also the key intermediate of the much structure complex biological alkali of synthesis, can be used for building tree
Dendritic macromolecules skeleton.During additionally bis-indolyl alkyl compounds is also commonly used for dyestuff.Along with bis (indolyl) methane and spread out
The continuous expansion in biologic applications field, it enjoys organic chemist and medicine scholar's extensive concern.
The preparation of bis-indolyl alkyl compounds is mainly sour as catalyst with Bronsted acid or Lewis, catalyzing indole
Required product is obtained with aldehydes or ketones.B.P.Bandgar (Tetrahedron Letters44 (2003) in 2003
1959-1961) with I2For preparing bisindole methane derivative under catalyst, room temperature condition, but the method catalysis
Agent consumption is too much.University Of Suzhou in 2005 records and waits (CN1706829A) to use solid acid SO along pretty4 2-/TiO2Make
For catalyst, indole and aldehyde one step are prepared bisindole methane derivative, the method high-efficient simple, but used
Catalyst preparation step is loaded down with trivial details, needs the TiCl extremely sensitive to air4, repeatedly process up to 36 at 100 DEG C
Hour, then carrying out after-treatment again at 600 DEG C of high temperature, preparation condition harshness greatly limit its application.Later,
Claudio C.Silveira is with glycerol and CeCl3(Tetrahedron Letters50 (2009) 6060-6063) conduct
Catalyst synthesis bisindole methane derivative, this catalyst reusable edible, but catalyst is used noble metal, valency
Lattice are expensive, react temperature required higher.InCl in 20103(Carbohydr.Res.2010,345,1708)、FeCl3
The simple Lewis acid catalyst such as (J.Org.Chem.2010,75 (15): 5240-5249) is used to catalysis
Indole and imines prepare bisindole methane derivative the most efficiently, but reaction needed raw material is that activity is higher
The substituted sulfimide of N-, its preparation process is complicated and imines has certain toxicity.Tomasz M.Kubczyk in 2011
Double indole is obtained with nanoporous aluminosilicate (Green Chem., 2011,13,2320-2325) catalyzing indole and aldehyde
Methane Derivatives, this catalyst is to water, thermally-stabilised, but the process preparing catalyst is complicated.Taizhou University in 2012
Li Bailin (CN102766081A) discloses a kind of use ionic liquid [(HSO3-p)2im][CF3SO3] it is catalyst
The method of preparation bisindole methane derivative, the reaction of this method is the gentleest, but double alkyl sulfonic acid type ionic liquid system
Standby complicated, expensive.[Ir (COD) (SnCl in 20133)Cl(m-Cl)]2Coordination compound (Tetrahedron, 2013,
69:2816-2826) it is found to realize being catalyzed N-sulfimide and indole reaction prepares bis (indolyl) methane and spreads out
Biology, but it is expensive, raw material obtains and is difficult to equally.The same year occurs in that TPPMS/CBr4(ACS
Sustainable Chem.Eng.2013,1,549-553) it is that catalyst indole obtains with carbonyl compound and acetal
To bis-indolyl alkyl compounds, this catalyst stabilization is easy to get, and is not required to anhydrous and oxygen-free condition, catalysis capable of circulation 10 times,
But substrate requirements is high, catalyst system and catalyzing is complicated.In addition, xanthic acid, LiClO4、In(OTf)3、Y(OTf)3、
Dy(OTf)3Preparing this compounds etc. being also used for catalysis, all there is certain deficiency in these methods, such as the response time
Long, use is expensive metallic catalyst, substrate active require that height, severe reaction conditions, operating process are pacified not
Congruence.
Summary of the invention
The technical problem to be solved is to overcome existing bisindole methane derivative preparation method to exist
Shortcoming, it is provided that the simple preparation method of a kind of bisindole methane derivative, the catalyst used by the method is cheap and easy to get,
Nontoxic, stable to air and water, reaction condition is gentle, the response time is short, and target substance productivity is high, simple to operate,
Good substrate applicability.
Solve above-mentioned technical problem and be the technical scheme is that by aldehyde with indole or indole derivatives be in molar ratio
1:2～4 is dissolved in organic solvent, adds amine salt, and the addition of amine salt is the 5%～15% of aldehyde mole, room temperature
React 5～30 minutes, obtain bisindole methane derivative.
Above-mentioned amine salt is anilinechloride, o-chloroaniline hydrochloride, o-aminoanisole hydrochlorate, pyrroles's hydrochloric acid
Any one in salt, aniline trifluoro-methanyl sulfonate, aniline trifluoroacetate, preferably anilinechloride or adjacent chlorine
Anilinechloride；Organic solvent be oxolane, dimethyl sulfoxide, ethyl acetate, acetonitrile, dichloromethane, chloroform,
Any one in benzene, toluene.
Above-mentioned aldehyde is further preferredAny in hexahydrobenzaldehyde, isovaleral
One, representative H, C that in formula, A, B, C are the most independent1～C3Alkyl, C1～C3Alkoxyl, CN,
F、Cl、Br、NO2In any one, M represents any one in N, O, S: described indole derives
Thing further preferred 5-bromo indole or N-methylindole.
The present invention, in the presence of amine salt, makes indole or indole derivatives and aldehyde reaction obtain bis (indolyl) methane and derives
Thing, the method is simple to operate, reacts efficient, gentle, and amine salt is cheap and easy to get, nontoxic, stable to air and water,
Good substrate applicability, can be widely used for the preparation of bisindole methane derivative.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in more detail, but invention which is intended to be protected is not limited only to
These embodiments.
Embodiment 1
As a example by preparing following formula: compound 3,3'-(Phenylmethylene)bis[1H-indole, raw materials used and preparation method thereof as follows:
By 0.106g (1.0mmol) benzaldehyde, 0.234g (2.0mmol) indole, 0.0165g (0.1mmol)
O-chloroaniline hydrochloride adds in 1mL acetonitrile, and room temperature reaction 10 minutes, stopped reaction, with ethyl acetate and stone
The mixed liquor that volume ratio is 3:1 of oil ether is flowing phase column chromatography for separation, obtains the double indole phenyl first of bright pink solid
Alkane, its productivity is 99%.Products therefrom Bruker Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer
Characterizing, characterizing data is:1H NMR (400MHz, DMSO) δ: 10.83 (d, J=1.3Hz,
2H), 7.46-7.20 (m, 8H), 7.15 (d, J=7.3Hz, 1H), 7.04 (dd, J=11.1,4.0Hz,
2H), 6.92-6.78 (m, 4H), 5.86 (s, 1H)；13C NMR (101MHz, DMSO) δ:
144.98,136.63,128.32,128.01,126.67,125.76,123.56,120.89,119.14,118.19,
118.10,111.45.
Embodiment 2
In embodiment 1, o-chloroaniline hydrochloride is replaced with equimolar anilinechloride, room temperature reaction 30
Minute, other steps are same as in Example 1, are prepared as pink solid 3,3'-(Phenylmethylene)bis[1H-indole, and its productivity is 98%.
Embodiment 3
In embodiment 1, o-chloroaniline hydrochloride is replaced with equimolar aniline trifluoroacetate, room temperature reaction
30 minutes, other steps were same as in Example 1, were prepared as pink solid 3,3'-(Phenylmethylene)bis[1H-indole, and its productivity is
99%.
Embodiment 4
In embodiment 1, o-chloroaniline hydrochloride is replaced with equimolar o-aminoanisole hydrochlorate, room temperature
Reacting 30 minutes, other steps are same as in Example 1, are prepared as pink solid 3,3'-(Phenylmethylene)bis[1H-indole, and it produces
Rate is 90%.
Embodiment 5
In embodiment 1, o-chloroaniline hydrochloride is replaced with equimolar pyrrole hydrochloride, room temperature reaction 30
Minute, other steps are same as in Example 1, are prepared as pink solid 3,3'-(Phenylmethylene)bis[1H-indole, and its productivity is 80%.
Embodiment 6
In embodiment 1, o-chloroaniline hydrochloride is replaced with equimolar aniline trifluoro-methanyl sulfonate, room temperature
Reacting 30 minutes, other steps are same as in Example 1, are prepared as pink solid 3,3'-(Phenylmethylene)bis[1H-indole, and it produces
Rate is 85%.
Embodiment 7
As a example by preparing double (5-bromo indole) the m-methoxyphenyl methane of following formula: compound, raw materials used and system
Preparation Method is as follows:
In embodiment 1, benzaldehyde used is replaced with equimolar m-methoxybenzaldehyde, indole equimolar
5-bromo indole replace, other steps are same as in Example 1, are prepared as first between dark red solid double 5-bromo indole
Phenyl methane, its productivity is 99%, characterizes data and is:1H NMR (400MHz, DMSO) δ: 11.12
(s, 2H), 7.51 (s, 2H), 7.40 (s, 2H), 7.22 (s, 4H), 6.97 (s, 4H), 5.88 (s,
1H), 3.69 (s, 3H)；13C NMR (101MHz, DMSO) δ: 159.19,145.94,135.27,
129.19,128.40,125.23,123.47,121.21,120.59,117.53,114.46,113.58,110.97,
110.93,54.83.
Embodiment 8
As a example by preparing the double N-methylindole phenylmethane of following formula: compound, raw materials used and preparation method thereof as follows:
In embodiment 1, indole used is replaced with equimolar N-methylindole, other steps and embodiment 1
Identical, it is prepared as the double N-methylindole phenylmethane of pink solid, its productivity is 90%, characterizes data and is:1H
NMR (400MHz, DMSO) δ: 7.36 (d, J=8.3Hz, 4H), 7.28 (dd, J=17.5,7.8Hz,
4H), 7.13 (dt, J=27.4,7.4Hz, 3H), 6.90 (t, J=7.4Hz, 2H), 6.82 (s, 2H),
5.83 (s, 1H), 3.69 (s, 6H)；13C NMR (101MHz, DMSO) δ: 150.04,142.26,
133.45,133.31,133.07,132.05,131.07,126.14,124.33,123.53,122.58,114.80,
37.47。
Embodiment 9
As a example by preparing the double indole o-methoxyphenyl methane of following formula: compound, raw materials used and preparation method thereof as
Under:
In embodiment 1, benzaldehyde used is replaced with equimolar o-methoxybenzaldehyde, other steps and reality
Executing example 1 identical, be prepared as the double indole o-methoxyphenyl methane of faint yellow solid, its productivity is 94%, characterizes number
According to for:1H NMR (400MHz, DMSO) δ: 10.75 (s, 2H), 7.34 (d, J=8.1Hz, 2H),
7.22 (d, J=7.9Hz, 2H), 7.19-7.10 (m, 2H), 7.01 (dt, J=9.0,6.2Hz, 3H),
6.89-6.70 (m, 6H), 6.22 (s, 1H), 3.87-3.74 (m, 3H)；13C NMR (101MHz,
DMSO) δ: 156.26,136.57,132.63,129.11,126.97,126.74,123.55,120.77,120.01,
118.89,118.08,117.80,111.39,110.81,55.53,40.12,39.91,39.70,39.50,39.29,
39.08,38.87,31.44.
Embodiment 10
As a example by preparing the double indole m-methoxyphenyl methane of following formula: compound, raw materials used and preparation method thereof as
Under:
In embodiment 1, benzaldehyde used is replaced with equimolar m-methoxybenzaldehyde, other steps and reality
Executing example 1 identical, be prepared as the double indole m-methoxyphenyl methane of Fructus Citri tangerinae pink solid, its productivity is 96%, characterizes number
According to for:1H NMR (400MHz, CDCl3) δ: 7.81 (s, 2H), 7.33 (d, J=7.9Hz, 2H),
7.27 (d, J=8.1Hz, 2H), 7.15-7.06 (m, 3H), 6.96-6.83 (m, 4H), 6.68 (dd, J
=8.1,2.2Hz, 1H), 6.59 (d, J=1.4Hz, 2H), 5.78 (s, 1H), 3.66 (s, 3H)；13C
NMR (101MHz, CDCl3) δ: 158.55,144.71,135.66,128.08,126.07,122.53,
120.89,120.27,118.88,118.55,118.21,113.73,110.24,109.96,54.08,39.21.
Embodiment 11
As a example by preparing the double indole p-methoxyphenyl methane of following formula: compound, raw materials used and preparation method thereof as
Under:
In embodiment 1, benzaldehyde used is replaced with equimolar P-methoxybenzal-dehyde, other steps and reality
Executing example 1 identical, be prepared as the double indole p-methoxyphenyl methane of pink solid, its productivity is 99%, characterizes data
For:1H NMR (400MHz, DMSO) δ: 7.89 (s, 2H), 7.37 (dd, J=16.7,7.9Hz,
4H), 7.25 (m, 2H), 7.16 (t, J=7.2Hz, 2H), 7.01 (d, J=7.0Hz, 2H),
6.82 (m, 2H), 6.65 (s, 2H), 5.84 (s, 1H), 3.78 (d, J=2.1Hz, 3H)；13C
NMR (101MHz, DMSO) δ: 157.93,136.73,136.23,129.60,127.10,123.49,
121.90,120.11,120.00,119.20,113.58,110.98,55.21,39.36.
Embodiment 12
As a example by preparing the double indole Chloro-O-Phenyl methane of following formula: compound, raw materials used and preparation method thereof as follows:
In embodiment 1, benzaldehyde used is replaced with equimolar o-chlorobenzaldehyde, other steps and embodiment
1 is identical, is prepared as the double indole p-nitrophenyl methylmethane of white solid, and its productivity is 85%, characterizes data and is:1H
NMR (400MHz, DMSO) δ: 10.86 (s, 2H), 7.45 (m, 1H), 7.36 (s, 1H),
7.25 (m, 6H), 7.04 (t, J=7.4Hz, 2H), 6.87 (t, J=7.3Hz, 2H), 6.75 (s,
2H), 6.20 (s, 1H), 3.33 (s, 1H), 2.49 (s, 3H)；13C NMR (101MHz, DMSO)
δ: 141.81,136.59,132.64,130.17,129.19,127.70,126.94,126.46,123.96,120.98,
118.62,118.35,116.46,111.54,36.09.
Embodiment 13
As a example by preparing the double indole p-nitrophenyl methylmethane of following formula: compound, raw materials used and preparation method thereof as follows:
In embodiment 1, benzaldehyde used is replaced with equimolar paranitrobenzaldehyde, room temperature reaction 10 minutes,
Other steps are same as in Example 1, are prepared as the double indole isopentyl methane of white solid, and its productivity is 87%, table
Levying data is:1H NMR (400MHz, DMSO) δ 11.05 (s, 1H), 8.41 (s, 1H), 8.09 (d, J=8.1Hz,
1H), 8.01 (d, J=7.6Hz, 1H), 7.60 (dd, J=13.4,7.9Hz, 2H), 7.39 (d, J=8.1Hz, 1H),
7.14 6.95 (m, 5H), 6.74 (d, J=8.0Hz, 2H), 6.53 (t, J=8.2Hz, 2H), 6.08 (d, J=6.9Hz,
1H)；13C NMR(101MHz,DMSO)δ147.94,147.80,146.60,136.52,133.95,129.66,
128.74,125.73,123.65,121.67,121.56,121.37,119.00,118.74,116.62,116.19,113.04,
111.62,53.39.
Embodiment 14
As a example by preparing the double indole-α-furyl methane of following formula: compound, raw materials used and preparation method thereof as follows:
In embodiment 1, benzaldehyde used is replaced with equimolar furaldehyde, other steps and embodiment
1 is identical, is prepared as the double indole-α-furyl methane of pink solid, and its productivity is 81%, characterizes data and is:1H NMR
(400MHz, CDCl3) δ: 7.92 (s, 2H), 7.50 (d, J=8.0Hz, 2H), 7.40-7.33 (m,
3H), 7.23-7.16 (m, 2H), 7.10-7.04 (m, 2H), 6.87 (d, J=1.9Hz, 2H), 6.32 (dd,
J=3.1,1.9Hz, 1H), 6.08 (d, J=3.2Hz, 1H), 5.96 (s, 1H)；13C NMR (101MHz,
CDCl3) δ: 157.15,141.14,136.37,126.67,123.07,121.98,119.73,119.33,117.18,
111.14,110.16,106.57,33.78.
Embodiment 15
As a example by preparing the double indole cyclohexyl-methane of following formula: compound, raw materials used and preparation method thereof as follows:
In embodiment 1, benzaldehyde used is replaced with equimolar hexahydrobenzaldehyde, other steps and embodiment
1 is identical, is prepared as the double indole cyclohexyl-methane of pink solid, and its productivity is 70%, characterizes data and is:1H NMR
(400MHz, CDCl3) δ: 8.15 (s, 2H), 7.61 (d, J=8.1Hz, 2H), 7.26 (d, J=8.0
Hz, 2H), 7.16 (s, 2H), 7.11 (t, J=7.2Hz, 2H), 7.10 (d, J=7.2Hz, 2H),
4.15 (s, 1H), 2.21-2.23 (m, 1H), 1.79-1.82 (m, 2H), 1.70-1.75 (m, 2H), 1.68-1.69
(m, 2H)；13C NMR (101MHz, CDCl3) δ: 140.82,137.45,124.22,122.08,121.77,
120.45,119.89,111.98,42.7,40.6,32.4,29.8,26.7.
Embodiment 16
As a example by preparing the double indole isopentyl methane of following formula: compound, raw materials used and preparation method thereof as follows:
In embodiment 1, benzaldehyde used is replaced with equimolar isovaleral, room temperature reaction 30 minutes, its
His step is same as in Example 1, is prepared as the double indole isopentyl methane of white solid, and its productivity is 52%, characterizes
Data are:1H NMR (400MHz, CDCl3) δ: 7.63-7.47 (m, 4H), 7.15 (d, J=8.1Hz,
2H), 7.07-7.01 (m, 2H), 6.95 (td, J=7.6,0.9Hz, 2H), 6.75 (d, J=2.0Hz,
2H), 4.49 (t, J=7.7Hz, 1H), 1.98 (dd, J=14.1,6.9Hz, 2H), 1.54 (dt, J=13.3,
6.7Hz, 1H), 0.88 (d, J=6.6Hz, 6H)；13C NMR (101MHz, CDCl3) δ: 136.64,
127.17,121.76,121.52,120.53,119.66,119.06,111.20,45.28,31.71,26.01,
22.94。
Embodiment 17
As a example by preparing the double indole p-methylphenyl methane of following formula: compound, raw materials used and preparation method thereof as follows:
In embodiment 1, benzaldehyde used is replaced with equimolar p-tolyl aldehyde, room temperature reaction 10 points
Clock, other steps are same as in Example 1, are prepared as the double indole p-methylphenyl methane of white solid, and its productivity is
95%, characterizing data is:1H NMR (400MHz, CDCl3) δ: 7.85 (s, 2H), 7.41 (d, J=
8.1Hz, 2H), 7.20-7.33 (m, 6H), 7.10 (d, J=8.0Hz, 2H), 7.06 (t, J=8.1Hz,
2H), 6.70 (d, J=2.5Hz, 2H), 5.85 (s, 1H), 2.38 (s, 3H)；13C NMR (101MHz,
CDCl3) δ: 157.11,135.73,135.23,129.10,126.99,123.19,121.55,119.81,119.20,
118.60,113.43,110.62,54.19,23.36.
Acetonitrile in above example also can be by isopyknic dichloromethane, oxolane, dimethyl sulfoxide, acetic acid second
Ester, chloroform, benzene or toluene are replaced.
Claims (2)
1. in the presence of amine salt, prepare 3 for one kind, the method for 3 '-bisindole methane derivative, it is characterised in that: by aldehyde
It is dissolved in organic solvent for 1:2～4 in molar ratio with indole or indole derivatives, adds amine salt, the addition of amine salt
Amount is the 5%～15% of aldehyde mole, and room temperature reaction 5～30 minutes obtain 3,3 '-bisindole methane derivative；
Above-mentioned amine salt is anilinechloride, o-chloroaniline hydrochloride, o-aminoanisole hydrochlorate, pyrroles's hydrochloric acid
Any one in salt, aniline trifluoro-methanyl sulfonate, aniline trifluoroacetate；Organic solvent be oxolane,
Any one in dimethyl sulfoxide, ethyl acetate, acetonitrile, dichloromethane, chloroform, benzene, toluene；
Above-mentioned aldehyde isAny one in hexahydrobenzaldehyde, isovaleral, formula
Representative H, C that middle A, B, C are the most independent1～C3Alkyl, C1～C3Alkoxyl, CN, F, Cl,
Br、NO2In any one, M represents any one in N, O, S；Described indole derivatives is 5-
Bromo indole or N-methylindole.
Preparation 3 in the presence of amine salt the most according to claim 1, the method for 3 '-bisindole methane derivative,
It is characterized in that: described amine salt is anilinechloride or o-chloroaniline hydrochloride.
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| WO2000053313A2 (en) * | 1999-03-09 | 2000-09-14 | Arqule, Inc. | Lanthanide catalysts for synthesis of compounds and combinatorial libraries |
| CN1837193A (en) * | 2006-04-26 | 2006-09-27 | 浙江大学 | Process for preparing diindolylmethane derivatives |
| CN101935297A (en) * | 2010-07-27 | 2011-01-05 | 浙江大学 | 3,3- diindolyl derivative and preparation method thereof |
| CN102617442A (en) * | 2011-01-27 | 2012-08-01 | 桂林商源植物制品有限公司 | Preparation method and use of 3,3'-methylenebis(1H-Indole) |
| CN103467354A (en) * | 2013-09-16 | 2013-12-25 | 陕西师范大学 | Method for preparing diindolyl methane derivatives |
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