CN109574906A - A kind of preparation method of 3,3 '-two Indoleacetic esters - Google Patents
A kind of preparation method of 3,3 '-two Indoleacetic esters Download PDFInfo
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- CN109574906A CN109574906A CN201710911056.6A CN201710911056A CN109574906A CN 109574906 A CN109574906 A CN 109574906A CN 201710911056 A CN201710911056 A CN 201710911056A CN 109574906 A CN109574906 A CN 109574906A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/22—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with an aralkyl radical attached to the ring nitrogen atom
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Abstract
3,3 '-two Indoleacetic ester type compounds and its derivative are found to have extensive anti-immunity, anti-inflammatory and inhibit oedema isoreactivity.While 3,3 '-two Indoleacetic ester compounds also belong to organic a kind of important intermediate raw material prepared in scope, the compound can be used for synthesizing a variety of bioactive molecules with 3,3'-Diindolylmethane structure, have very high organic synthesis application value.The present invention provides the 3 of a kind of extremely succinct visible light catalytic, the preparation method of 3 '-two Indoleacetic ester type compounds, specifically: using glycine derivative and indole derivatives as raw material, with organic photosensitizer (eosin Y, rose-red or rhodamine 6G) for photochemical catalyst, 10-30h is reacted under room temperature and radiation of visible light, isolates and purifies to obtain product.Compared with prior art, the preparation method have many advantages, such as step is succinct, yield is high, raw material and catalyst are cheap and easy to get, without metal, reaction condition is mild, operation is simple, more suitable for enlarged experiment and 3,3 '-two Indoleacetic ester type compound of large scale preparation.
Description
Technical field
The invention belongs to organic preparation technical fields, more particularly to a kind of 3,3 '-two Indoleacetic ester compounds
Preparation method.
Background technique
3,3 '-two Indoleacetic ester type compounds and its derivative such as Soritin B (bis- (1H-indol-3-yl)-
acetic acid methyl ester)、Soritin C(bis-2,2-(1-methyl-indol-3-yl)acetic acid
Methyl ester), Soritin D (bis-2,2- (1-methyl-indol-3-yl) acetic acid) etc. is found to have
Extensive anti-immunity, anti-inflammatory and inhibition oedema isoreactivity (U.S.Pat.No.20010056112,6444697,6323233).
3,3 '-two Indoleacetic ester compounds also belong to organic a kind of important intermediate raw material prepared in scope simultaneously, such change
Closing object can be used for synthesizing a variety of drug molecules containing 3,3 '-di-indole methyl hydride structures, alkaloids natural products and biology
Reactive intermediate, such as its synthesis that can be used for antimicrobial compound vibrindole A.
Currently, to 3, the preparation method of 3 '-two Indoleacetic ester compounds includes:
Hogan and Sainsbury reports indoles and glyoxalic acid is condensed to yield 3,3 '-two indoles in acid condition first
Guanidine-acetic acid, then the method for being prepared into acyl chlorides and ester.Shown in preparation method such as formula (I).
The shortcomings that such method, is that synthesis step is longer, needs three steps, and preparation process needs to use low temperature, and yield
It is lower.
Jacobs et al. is reported using 3,3'-Diindolylmethane as substrate, first with highly basic act on, then with chloro-formate
Reaction, the method for preparing 3,3 '-two Indoleacetic esters.Shown in preparation method such as formula (II).
The method needs to use n-BuLi, tert-butyl lithium, LiN (i-Pr)2Etc. stronger organic base and chloro-formate, fourth
The cost of material such as base lithium are costly and unstable, and chloro-formate has severe toxicity and strong and stimulating；The reaction is needed compared with low temperature
It is carried out under degree and anhydrous condition, experimental implementation is complicated, and reaction condition is excessively harsh, for environmental pollution and instrument and equipment requirement
It is high.Therefore, which is not suitable for extensive raw material preparation.
Ishikura et al. uses Bartoli indole synthesis, with o-bromonitrobenzene, vinyl Grignard Reagent and glyoxalic acid
For raw material, 3,3 '-two Indoleacetic of one-step synthesis bromo, then debrominate, then esterification obtains 3 under the conditions of sulfuric acid/ethyl alcohol,
3 '-two Indoleacetic esters.Shown in preparation method such as formula (III).
The shortcomings that the method, is that excessively cumbersome step, low yield, reaction preparation process need to use low temperature and without water bar
Part, and the sulfuric acid of tri-butyl tin hydride and strong corrosive with larger toxicity has been used, for environmental pollution and instrument and equipment
It is required that it is high, be not suitable for extensive raw material preparation.
Recently, Huo et al. reports one kind using glycine derivative and indoles as raw material, three (4- bromophenyl) amine chlordene antimony
Hydrochlorate (TBPA+.) it is catalyst preparationThe method of 3,3 '-two Indoleacetic esters.Shown in preparation method such as formula (IV).
The method raw material is cheap and easily-available, yield is high, but needs to use (the 4- bromobenzene of catalyst three of price costly
Base) amine hexa chloro-antimonate (TBPA+.), and catalyst amount is up to 20mol%, therefore synthesis cost is higher, is not suitable for extensive
Raw material preparation.
In conclusion although the method for having several 3,3 '-two Indoleacetic esters of synthesis is seen in report, but at present
Method remain it is clearly disadvantageous, such as complex steps, low yield, severe reaction conditions, using being more toxic reagent, urge
Agent is expensive and dosage is larger etc., and these problems seriously restrict further applying for the above method.
Visible light is a kind of cleaning, abundant, the cheap energy, since two thousand eight, using photochemical catalyst absorb energy come
Excitation chemical reaction gradually causes the extensive attention of scientist.We have developed a kind of derivative using glycine under visible light catalytic
The dehydrogenation coupling reaction of object and indole derivatives is come the method that synthesizes 3,3 '-two Indoleacetic ester compounds, this method operation
Simply, reaction condition mild (under room temperature and radiation of visible light), environmental-friendly, yield 91-98%, and we use inexpensively
Organic photosensitizer eosin Y, rose-red or rhodamine 6G as photochemical catalyst, catalyst amount can be down within 1mol%, because
This reaction cost substantially reduces.
Summary of the invention
That the purpose of the present invention is to provide a kind of raw materials and catalyst is cheap and easily-available, easy to operate, reaction condition is mild and
The preparation method of 3,3 '-two environmental-friendly Indoleacetic ester compounds.
The present invention provides a kind of preparation method of 3,3 '-two Indoleacetic ester type compounds, preparation process such as formulas (V)
It is shown.
Wherein R1Substituent group can be methyl, methoxyl group etc.；R2Substituent group can be methyl, ethyl, benzyl, allyl etc.；
R3Substituent group can be alkyl such as methyl etc., be also possible to electron-withdrawing group such as cyano etc.；R4Substituent group can be methyl, benzyl
Deng.
The preparation process, which is mainly comprised the steps that, sequentially adds glycine derivative, indole derivatives, light into flask
Quick dose, acid and appropriate solvent are stirred at room temperature 10-30 hours under visible light illumination, and saturated sodium bicarbonate solution is then added and quenches
It goes out reaction, ethyl acetate extraction, anhydrous sodium sulfate is dry, and evaporating solvent under reduced pressure, column chromatographs to obtain 3,3 '-two Indoleacetic esters
Compound.
Preferably, in the step, photosensitizer is that eosin Y, rose-red or rhodamine 6G are one of.
Preferably, in the step, it is seen that radiant is 26W energy-saving lamp, sunlight or 5W blue LED lamp wherein one
Kind.
Preferably, in the step, solvent is undried acetonitrile, ethyl alcohol or 1, and 2- dichloroethanes is one of.
Preferably, in the step, acid is that trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid or citric acid are one of.
Preferably, in the step, in the reaction glycine derivative, indole derivatives, photosensitizer and acid mole
Than for 1:2.1:0.01:1.5.
Preferably, in the step, temperature is room temperature, air atmosphere in reaction process.
Compared with prior art, the invention has the following advantages that
1. reaction raw materials are cheap and easy to get, photochemical catalyst is cheap, dosage is few (within 1mol%).
2. reaction step is few (an only step), high income (91-98%).
3. not using metallic catalyst, oxidant, highly basic and the reagent with penetrating odor and toxicity, react in room
It is carried out under mild radiation of visible light, it is environmental-friendly, it is easily operated.
Detailed description of the invention
Fig. 1 is 3,3 '-two Indoleacetic ethyl esters1H NMR spectra
Fig. 2 is 3,3 '-two Indoleacetic ethyl esters13C NMR spectra
Specific embodiment
Following example can make professional and technical personnel know more about the present invention, but not limit this hair in any way
It is bright.The raw materials used present invention is known compound, it is available on the market or can be used means known in the art and be prepared.
The preparation of-two Indoleacetic ethyl ester of embodiment 1:3,3 '
In 25mL flask, 193mg (1mmol) (4- aminomethyl phenyl) ethyl aminoacetate is dissolved in 5.0mL ethyl alcohol, then successively
246 mg (2.1mmol) indoles, 6.9mg (1mol%) eosin Y, 0.11mL (1.5eq) trifluoroacetic acid is added, in 26W energy-saving lamp
It is stirred at room temperature under irradiation 12 hours.Then saturated sodium bicarbonate solution quenching reaction, ethyl acetate extraction, anhydrous sodium sulfate is added
Dry, evaporating solvent under reduced pressure, column chromatography (petrol ether/ethyl acetate=4:1) obtains 312mg product, yield 98%.Pale red is solid
Body.1H NMR(400MHz,CDCl3): δ 8.00 (s, 2H), 7.65 (d, J=8.0Hz, 2H), 7.28 (d, J=8.2Hz, 2H),
7.19 (m, 2H), 7.10 (m, 2H), 6.96 (d, J=2.4Hz, 2H), 5.51 (s, 1H), 4.23 (q, J=7.1Hz, 2H),
1.27 (t, J=7.1Hz, 3H)13C NMR(100MHz,CDCl3):δ173.9,136.2, 126.5,123.5,121.9,
119.4,119.1,113.2,111.3,61.2,40.5,14.1.
The preparation of-two Indoleacetic benzyl ester of embodiment 2:3,3 '
In 25mL flask, 271mg (1mmol) (4- methoxyphenyl) amion acetic acid benzyl ester is dissolved in 5.0mL 1, bis- chloroethene of 2-
Then alkane sequentially adds 246mg (2.1mmol) indoles, 10.2mg (1mol%) rose-red, 0.087mL (1.5eq) phosphoric acid,
It is stirred at room temperature under 5W blue led light irradiation 10 hours.Then saturated sodium bicarbonate solution quenching reaction, ethyl acetate extraction is added
It takes, anhydrous sodium sulfate is dry, evaporating solvent under reduced pressure, and column chromatography (petrol ether/ethyl acetate=4:1) obtains 346mg product, yield
91%.Faint yellow solid.1H NMR(400 MHz,acetone-d6): δ 7.95 (s, 2H), 7.50 (d, J=7.6Hz, 2H),
7.29-6.97(m,13H),5.51(s,1H),5.11(s,2H).13C NMR(100MHz,acetone-d6):δ172.7,
136.9,136.5,128.2,128.0,127.8,126.9,123.6,121.3,119.1,118.7,113.1, 111.3,
66.0,40.7.
The preparation of-two Indoleacetic allyl ester of embodiment 3:3,3 '
In 25mL flask, 221mg (1mmol) (4- methoxyphenyl) amion acetic acid allyl ester is dissolved in 5.0mL acetonitrile, then
246mg (2.1mmol) indoles, 4.8mg (1mol%) rhodamine 6G, 315mg (1.5eq) citric acid are sequentially added, in sunlight
It is stirred at room temperature under irradiation 12 hours.Then saturated sodium bicarbonate solution quenching reaction, ethyl acetate extraction, anhydrous sodium sulfate is added
Dry, evaporating solvent under reduced pressure, column chromatography (petrol ether/ethyl acetate=4:1) obtains 307mg product, yield 93%.Red is solid
Body.1H NMR(400MHz,CDCl3): δ 7.86 (s, 2H), 7.51 (d, J=8.0Hz, 2H), 7.17-7.03 (m, 4H), 6.81
(s,2H),5.81(m,1H),5.44(s,1H),5.17-5.04 (m,2H),4.55(m,2H).13C NMR(100MHz,CDCl3)
δ172.7,136.9,132.7,126.8,123.7,121.3,119.0,118.8, 117.1,113.1,111.4,64.8,
40.7.
The preparation of embodiment 4:3,3 '-two (5- cyanoindole base) methyl acetate
In 25mL flask, 195mg (1mmol) (4- methoxyphenyl) methyl aminoacetate is dissolved in 5.0mL acetonitrile, then according to
Secondary addition 298mg (2.1mmol) 5- cyanoindole, 4.8mg (1mol%) rhodamine 6G, 315mg (1.5eq) citric acid, in 5W
It is stirred at room temperature under blue led light irradiation 12 hours.Then saturated sodium bicarbonate solution quenching reaction is added, ethyl acetate extracts,
Anhydrous sodium sulfate is dry, evaporating solvent under reduced pressure, and column chromatography (petrol ether/ethyl acetate=4:1) obtains 322mg product, yield
91%.Faint yellow solid.1H NMR(400 MHz,acetone-d6): δ 8.06 (s, 2H), 7.61 (m, 4H), 7.40 (d, J=
8.6Hz,2H),5.72(s,1H),3.76(s,3H).13C NMR(100 MHz,acetone-d6):δ172.5,138.2,
130.1,126.5,126.3,124.8,124.2,124.1,120.2,113.5,112.8,101.9,51.8,40.1.
The preparation of embodiment 5:3,3 '-two (5- methyl indol base) methyl acetate
In 25mL flask, 195mg (1mmol) (4- methoxyphenyl) methyl aminoacetate is dissolved in 5.0mL acetonitrile, then according to
Secondary addition 275mg (2.1mmol) 5- methyl indol, 4.8mg (1mol%) rhodamine 6G, 315mg (1.5eq) citric acid, in 5W
It is stirred at room temperature under blue led light irradiation 12 hours.Then saturated sodium bicarbonate solution quenching reaction is added, ethyl acetate extracts,
Anhydrous sodium sulfate is dry, evaporating solvent under reduced pressure, and column chromatography (petrol ether/ethyl acetate=4:1) obtains 312mg product, yield
94%.Lavender solid.1H NMR(400 MHz,acetone-d6):δ10.08(brs,1H),7.41(s,2H),7.28(d,J
=8.3Hz, 2H), 7.20 (s, 2H), 6.93 (d, J=8.3Hz, 2H), 5.47 (s, 1H), 3.71 (s, 3H), 2.39 (s, 6H)
.13C NMR(100MHz,acetone-d6):δ173.5,135.2,135.1,127.5,127.2, 127.1,123.8,123.5,
123.1,118.6,112.7,112.5,111.2,111.1,51.3,40.5,20.9.
The preparation of embodiment 6:3,3 '-two (N- methyl indol base) ethyl acetate
In 25mL flask, 209mg (1mmol) (4- methoxyphenyl) ethyl aminoacetate is dissolved in 5.0mL acetonitrile, then according to
Secondary addition 275mg (2.1mmol) N- methyl indol, 4.8mg (1mol%) rhodamine 6G, 315mg (1.5eq) citric acid, in 5W
It is stirred at room temperature under blue led light irradiation 12 hours.Then saturated sodium bicarbonate solution quenching reaction is added, ethyl acetate extracts,
Anhydrous sodium sulfate is dry, evaporating solvent under reduced pressure, and column chromatography (petrol ether/ethyl acetate=4:1) obtains 318mg product, yield
92%.Light green solid.1H NMR(400 MHz,Acetone-d6):δ10.07(brs,1H),7.30(m,4H),6.98(d,J
=5.4Hz, 2H), 6.86 (d, J=5.5Hz, 2H), 5.51 (s, 1H), 4.23 (q, J=7.1Hz, 2H), 2.26 (s, 6H),
1.27 (t, J=7.1Hz, 3H)13C NMR(100MHz,CDCl3)δ173.8,135.4,132.5, 128.5,120.2,
118.6,118.5,110.3,108.3,61.1,40.2,14.6,11.4.
The preparation of embodiment 7:3,3 '-two (N- benzylindole base) methyl acetate
In 25mL flask, 195mg (1mmol) (4- methoxyphenyl) methyl aminoacetate is dissolved in 5.0mL acetonitrile, then according to
Secondary addition 435mg (2.1mmol) N- benzylindole, 4.8mg (1mol%) rhodamine 6G, 315mg (1.5eq) citric acid, in 5W
It is stirred at room temperature under blue led light irradiation 12 hours.Then saturated sodium bicarbonate solution quenching reaction is added, ethyl acetate extracts,
Anhydrous sodium sulfate is dry, evaporating solvent under reduced pressure, and column chromatography (petrol ether/ethyl acetate=4:1) obtains 460mg product, yield
95%.Faint yellow solid.1H NMR(400 MHz,acetone-d6):δ10.55(brs,1H),7.38(m,14H),7.06(m,
2H),6.87(m,2H),5.65(s,1H),3.51(s,3H).13C NMR(100MHz,acetone-d6):δ173.7,136.6,
136.3,136.2,133.1,128.4,128.3,127.6,121.3,120.4,119.1,111.2, 111.1,109.8,
51.1,41.7。
Claims (6)
1. the preparation method of 3,3 '-two Indoleacetic ester compounds of one kind, it is characterised in that specific steps are as follows: into flask according to
Secondary addition glycine derivative, indole derivatives, photosensitizer, acid and appropriate solvent, are stirred at room temperature 10-30 under visible light illumination
Hour, saturated sodium bicarbonate solution quenching reaction is then added, ethyl acetate extraction, anhydrous sodium sulfate is dry, removes under reduced pressure molten
Agent, column chromatograph to obtain 3,3 '-two Indoleacetic ester compounds, preparation process such as following formula:
Wherein R1Substituent group can be methyl, methoxyl group etc.；R2Substituent group can be methyl, ethyl, benzyl, allyl etc.；R3It takes
Dai Ji can be alkyl such as methyl etc., be also possible to electron-withdrawing group such as cyano etc.；R4Substituent group can be methyl, benzyl etc..
2. the preparation method of according to claim 13,3 '-two Indoleacetic ester compounds, it is characterised in that: described
Photosensitizer be that eosin Y, rose-red or rhodamine 6G are one of.
3. the preparation method of according to claim 13,3 '-two Indoleacetic ester compounds, it is characterised in that: visible
Radiant is that 26W energy-saving lamp, sunlight or 5W blue LED lamp are one of.
4. the preparation method of according to claim 13,3 '-two Indoleacetic ester compounds, it is characterised in that: solvent
It is one of for undried acetonitrile, ethyl alcohol or 1,2- dichloroethanes.
5. the preparation method of according to claim 13,3 '-two Indoleacetic ester compounds, it is characterised in that: acid is
Trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid or citric acid are one of.
6. the preparation method of according to claim 13,3 '-two Indoleacetic ester compounds, it is characterised in that: anti-
The molar ratio for answering middle glycine derivative, indole derivatives, photosensitizer and acid is 1:2.1:0.01:1.5.
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| CN113045556A (en) * | 2019-12-26 | 2021-06-29 | 天津师范大学 | Alkaloid streptandole derivative, preparation thereof and application thereof in preventing and treating plant virus and bacterial diseases |
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