CN102718694A - 3-cyan substituted indole compound and synthetic method thereof - Google Patents
3-cyan substituted indole compound and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to a 3-cyan substituted indole compound and a synthetic method thereof. The constitutional formula of the compound is that R1 is a methoxy group, and R2 is phenyl (Ph), benzyl (Bn), allyl or n-butyl. According to the synthetic method of the 3-cyan substituted indole compound, raw materials are easy to obtain, novel tertiary butyl isonitrile is firstly used as a source of cyan, and high toxic metal cyanide is avoided to be used. During the reaction, conventional reaction solvents are used, the operation is simple, the operation condition is moderate, the reaction is environment-friendly, the top yield can reach 74%, and the 3-cyan substituted indole compound has a good application prospect in industrial production.
Description
Technical field
The present invention relates to a kind of cyanic acid substituted indole compound and preparation method thereof, mainly is 3-cyanic acid substituted indole compound and preparation method thereof.
Background technology
Organic cyanide is one type of very important compound in the organic synthesis.Cyano compound is not only important pharmaceutical intermediate; And be the important structure of colouring substance; And they are easy to be converted into other useful functional compounds; Like aldehyde, ketone, carboxylic acid, amine and acid amides etc., in organic compound molecule, introducing cyanic acid through the formation of carbon-carbon bond is one of mode the most basic in the organic synthesis.Indoles is present in the natural compounds widely, is a kind of very important heterogeneous ring compound.As containing the escitalopram of cyanic acid, lexapro is a kind of medicine of effectively depression; The not imperial femara that contains two cyanic acid is a kind of medicine that is used for the breast carcinoma of early stage assisting therapy effectively; The Kang Shide that contains cyanic acid, Casodex are used for the active drug of breast carcinoma of early stage assisting therapy.Realizing the formation of carbon on the indoles-cyanogen key through c h bond activatory method, is a kind of very effective and novel method thereby introduce cyanic acid.
The synthetic cyano compound method of reporting in the document mainly contains following several kinds:
(1) through sandmeyer reaction (Sandmeyer reaction).This reaction is the method for one type of effective synthesizing aryl nitrile compound, but because its more reactions step, reaction complicacy and productive rate are on the low side, have limited its application in synthetic.
(2) make up the aryl nitrile compound through aryl halide compound and cyanic acid reagent.Such reaction is simple, and single stepping just can obtain title product, and a succinct approach is provided for the aryl nitrile compound is synthetic.
(3) directly make up the aryl nitrile compound by guiding c h bond activatory method.This type reaction conditions is simple, and Atom economy is good, to us a good direction is provided.
The compound method of the preparation 3-cyanic acid substituted indole compound of reporting in the existing literature has:
(1) obtain through the reaction of 5 steps from reagent such as indoles and trifluoracetic acids, concrete reaction as follows:
(2) obtain 3 cyaniding products from 3-formaldehyde indoles and Potssium Cyanide and primary ammonium phosphate reaction:
(3) under the palladium catalysis, indoles and cuprous cyanide react and obtain:
(4) from 2 3-position substituted indoles, be cyano sources with DMF, obtain concrete the reaction as follows under the palladium catalysis:
In sum, the method for preparing the 3-cyanoindole has a lot, but these reactions have a lot of defectives; Requirement to substrate is high; Reactions step is complicated or need introduce blocking group at 2, and in reaction, is difficult to obtain the product of single 3 cyanic acidization, often is mixture.
Summary of the invention
One of the object of the invention is to provide a kind of 3-cyanic acid substituted indole compound
Two of the object of the invention is to provide a kind of preparation method of this compound.
For achieving the above object, the reaction mechanism that the inventive method adopts is:
R is: methoxyl group
R
1For: Ph, Bn, Allyl or n-Butyl.
According to above-mentioned reaction mechanism, the present invention has adopted following technical scheme:
A kind of 3-cyanic acid substituted indole compound is characterized in that the structural formula of this compound is:
Wherein: R
1For: methoxyl group; R
2For: Ph, Bn, Allyl or n-Butyl.
A kind of method for preparing above-mentioned 3-cyanic acid substituted indole compound; It is characterized in that this method has following steps: with indoles, mantoquita and tert-butyl isonitrile by 1: (2.0~3.0): the mol ratio of (2.0~3.0) is dissolved in N; In the dinethylformamide; And the palladium of adding catalyst levels, 100
oC~130
oStirring reaction to reaction raw materials disappears under the C; Remove solvent, add 3 N ammonia solns, use the ethyl acetate extraction product, organic phase is removed solvent and is got crude product after drying; This crude product promptly obtains corresponding 3 cyanic acid substituted indole compounds through separation and purification; The structural formula of described indoles is:
Wherein: R
1For: methoxyl group; R
2For: Ph, Bn, Allyl or n-Butyl; Described mantoquita is: trifluoracetic acid copper.
3-cyanic acid substituted indole compound of the present invention is one type of important organic reaction midbody, through dissimilar organic chemical reactionses, and like hydrolysis reaction, reduction reaction, oxidizing reaction can synthesize a series of indole derivatives quickly and easily.Relevant reaction is exemplified below:
1. under alkaline action condition, can synthesize 3-carboxamide indoles (Beevers, R. E.; Buckley, G. M.
Bioorg. Med. Chem. Lett.
2006, 16,2535); In phosphoric acid buffer, utilize quinoline-degrading bacterium can obtain into acid product (Wang, M. X.
Tetrahedron Lett.
1995, 36,9561):
2. utilizing 3-cyanoindole compound can pass through one type of important pharmaceutical intermediate ICS 205-930 of polystep reaction, is one type of important thrombotonin:
See also following document:
(1)?Swain,?C.?J.;?Baker,?R.;?Kneen,?C.;?Herbert,?R.;?Moseley,?J.;?Saunders,?J.;?Seward,?E.?M.;?Stevenson,?G.?I.;?Beer,?M.;?Stanton,?J.;?Watling,?K.;?Balls,?R.?G.?
J.?Med.?Chem.?
1992,?35,?1019.
(2)?Richardson,?B.?P.;?Engel,?G.;?Donatach,?P.;?Stadler,?P.?A.?
Nature,?
1985,?316,?126.
3. can synthesize ocean bisindole alkaloid Nortopsentin (Subba Reddy, B. V. through the 3-cyanoindole with remarkable anti-tumor activity; Begum, Z.; Reddy, Y. J.; Yadav, J. S.
Tetrahedron Lett.
2010,
51, 3334), this Alkaloid is present in (Xiong, W. in the natural product; Yang, C.; Jiang, B.
Bioorg. Med. Chem.
2001,
9, 1773):
The inventive method raw material is easy to get, and the novel tert-butyl isonitrile of employing is the cyanic acid source first, has avoided the use of the big metal cyanides of toxicity.Use conventional reaction solvent in the reaction, operate very simply, condition is moderate, reacts environmental protection, and productive rate reaches as high as 74%, in industrial production, has good application prospects.
Embodiment
Embodiment one: 1-phenyl-1
HThe preparation of-indoles-3-cyanic acid
1-phenyl-1
H-indoles-3-cyanic acid adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 9.7 gram 1-phenyl-1
H-indoles, 560 milligrams of palladium, 43 gram additives, 12.5 gram tert-butyl isonitriles, 150 milliliters of N, dinethylformamide is heated to 130 ℃.Follow the tracks of reaction with the thin-layer chromatography method, to reaction raw materials 1-phenyl-1
H-indoles disappears; 2. after reacting end, in system, add the ammonia soln of 3 N, use the ethyl acetate extraction product, solvent is removed with Rotary Evaporators in dry back, gets crude product; 3. (sherwood oil: purifying ETHYLE ACETATE=6: 1) obtains 8.1 gram 1-phenyl-1 to crude product with column chromatography
H-indoles-3-cyanic acid, productive rate are 74%.Fusing point: 120-121 ℃.
IR?(KBr,?cm -1 ):?2223,?1599,?1539,?1501,?1458,?1224,?736,?694.
1 H?NMR?(CDCl 3 ,?500?MHz):? δ?=?7.85-7.82?(m,?1H),?7.81?(s,?1H),?7.59-7.56?(m,?2H),?7.53-7.47?(m,?4H),?7.37-7.33?(m,?2H).
13 C?NMR?(CDCl 3 ,?125?MHz): δ?=?137.9,?135.7,?134.8,?130.1,?128.5,?128.1,?125.0,?124.7,?122.9,?120.1,?115.7,?111.6,?88.2.
LC/MS?m/z?(relative?intensity):?219?[M+1
+].
Embodiment two: 1-(4-fluoro-phenyl)-1
HThe preparation of-indoles-3-cyanic acid
1-(4-fluoro-phenyl)-1
H-indoles-3-cyanic acid adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 10.5 gram 1-(4-fluoro-phenyl)-1
H-indoles, 560 milligrams of palladium, 43 gram additives, 12.5 gram tert-butyl isonitriles, 150 milliliters of N, dinethylformamide is heated to 130 ℃.Follow the tracks of reaction with the thin-layer chromatography method, to reaction raw materials 1-(4-fluoro-phenyl)-1
H-indoles disappears; 2. after reacting end, in system, add the ammonia soln of 3 N, use the ethyl acetate extraction product, solvent is removed with Rotary Evaporators in dry back, gets crude product; 3. (sherwood oil: purifying ETHYLE ACETATE=6: 1) obtains 7.4 gram 1-(4-fluoro-phenyl)-1 to crude product with column chromatography
H-indoles-3-cyanic acid, productive rate are 63%.Fusing point: 164-167 ℃.
IR?(KBr,?cm -1 ):?2227,?1539,?1515,?1460,?1215,?837,?740.
1 H?NMR?(CDCl 3 ,?500?MHz):? δ=?7.84-7.82?(m,?1H),?7.76?(s,?1H),?7.48-7.42?(m,?3H),?7.37-7.34?(dd,?
1 J?=?6.0?Hz,?
2 J?=?3.0?Hz,?2H),?7.29-7.26?(t,?
J?=?8.0?Hz,?2H).
19 F-NMR?(470?MHz,?CDCl 3 ): δ=?-112.0?(m).
13 C?NMR?(CDCl 3 ,?125?MHz): δ=?162.2?(d,?
1 J C-F ?=?248.75?Hz),?135.9,?134.8,?133.9?(d,?
4 J C-F ?=?2.5?Hz),?127.9,?127.0?(d,?
3 J C-F ?=?2.5?Hz),?124.8,?123.0,?120.2,?117.1?(d,?
2 J C-F ?=?23.75?Hz),?115.5,?111.4,?88.4.
LC/MS?m/z?(relative?intensity):?237?[M+1
+].
Anal.?Calcd.?For?C 15 H 9 FN 2 :?C,?76.26;?H,?3.84;?N,?11.86.?Found:?C,?76.39;?H,?4.001;?N,?11.98.
Embodiment three: 1-(4-methoxyl group-phenyl)-1
HThe preparation of-indoles-3-cyanic acid
1-(4-methoxyl group-phenyl)-1
H-indoles-3-cyanic acid adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 11.1 gram 1-(4-methoxyl group-phenyl)-1
H-indoles, 560 milligrams of palladium, 43 gram additives, 12.5 gram tert-butyl isonitriles, 150 milliliters of N, dinethylformamide is heated to 130 ℃.Follow the tracks of reaction with the thin-layer chromatography method, to reaction raw materials 1-(4-methoxyl group-phenyl)-1
H-indoles disappears; 2. after reacting end, in system, add the ammonia soln of 3 N, use the ethyl acetate extraction product, solvent is removed with Rotary Evaporators in dry back, gets crude product; 3. (sherwood oil: purifying ETHYLE ACETATE=6: 1) obtains 4.6 gram 1-(4-methoxyl group-phenyl)-1 to crude product with column chromatography
H-indoles-3-cyanic acid, productive rate are 36%.Fusing point: 126-129 ℃.
IR?(KBr,cm –1 ):?2219,?1535,?1513,?1458,?1245,?1219,?1028,?836,?754.
1 H-NMR?(500?MHz,?CDCl 3 ):? δ=?7.83-7.80?(m,?1H),?7.74?(s,?1H),?7.44-7.41?(m,?1H),?7.39-7.36?(AA’?of?AA’BB’,?
J?=?9.0?Hz,?2H),?7.34-7.32?(m,?2H),?7.08-7.06?(BB’?of?AA’BB’,?
J?=?8.5?Hz,?2H),?3.90?(s,?3H).
13 C-NMR?(CDCl 3 ,?125?MHz): δ=?159.6,?136.2,?135.1,?130.7,?127.9,?126.5,?124.5,?122.7,?120.0,?115.8,?115.2,?111.6,?87.5,?55.8.
LC/MS?m/z?(relative?intensity):?249?[M+1
+].
Embodiment four: the preparation of 4-methoxyl group-(1-phenyl)-1H-indoles-3-cyanic acid
4-methoxyl group-(1-phenyl)-1
H-indoles-3-cyanic acid adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 11.1 gram 4-methoxyl group-(1-phenyl)-1
H-indoles, 560 milligrams of palladium, 43 gram additives, 12.5 gram tert-butyl isonitriles, 150 milliliters of N, dinethylformamide is heated to 130 ℃.Follow the tracks of reaction with the thin-layer chromatography method, to reaction raw materials 4-methoxyl group-(1-phenyl)-1
H-indoles disappears; 2. after reacting end, in system, add the ammonia soln of 3 N, use the ethyl acetate extraction product, solvent is removed with Rotary Evaporators in dry back, gets crude product; 3. (sherwood oil: purifying ETHYLE ACETATE=6: 1) obtains 6.2 gram 4-methoxyl group-(1-phenyl)-1 to crude product with column chromatography
H-indoles-3-cyanic acid, productive rate are 36%.Fusing point: 105-106 ℃.
IR?(KBr,?cm –1 ):?2225,?1624,?1598,?1534,?1504,?1487,?1246,?1238,?1207,?1056,?823,?755,?700.
1 H-NMR?(500?MHz,?CDCl 3 ):? δ=?7.75?(s,?1H),?7.58-7.55?(t,?
J?=?8.0?Hz,?2H),?7.49-7.46?(m,?3H),?7.41-7.39?(d,?
J?=?9.0?Hz,?1H),?7.22?(d,
?J?=?2.5?Hz,?1H),?6.98-6.95?(dd,?
1 J?=?9.0?Hz,?
2 J?=?2.5?Hz,?1H),?3.91?(s,?3H).
13 C-NMR?(CDCl 3 ,?125?MHz): δ=?156.4,?138.0,?134.4,?130.5,?130.0,?128.9,?128.3,?124.7,?115.8,?115.3,?112.6,?100.9,?87.7,?55.9.
MS?(EI)?m/z?(relative?intensity):?248?(100)?[M+].
HR-MS?(ESI)?m/z?calcd?for?C
16H
12N
2O?[M
+]
Embodiment five: the preparation of 1-benzyl-1H-indoles-3-cyanic acid
1-benzyl-1
H-indoles-3-cyanic acid adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 10.3 gram 1-benzyls-1
H-indoles, 560 milligrams of palladium, 43 gram additives, 12.5 gram tert-butyl isonitriles, 150 milliliters of N, dinethylformamide is heated to 130 ℃.Follow the tracks of reaction with the thin-layer chromatography method, to reaction raw materials 1-benzyl-1
H-indoles disappears; 2. after reacting end, in system, add the ammonia soln of 3 N, use the ethyl acetate extraction product, solvent is removed with Rotary Evaporators in dry back, gets crude product; 3. (sherwood oil: purifying ETHYLE ACETATE=6: 1) obtains 7.1 gram 1-benzyls-1 to crude product with column chromatography
H-indoles-3-cyanic acid, productive rate are 61%.Fusing point: 69-72 ℃.
IR?(KBr,?cm -1 ):?2212,?1531,?1468,?1393,?1179,?745,?735,?696.
1 H?NMR?(CDCl 3 ,?500?MHz): δ=?7.79-7.77?(m,?1H),?7.60?(s,?1H),?7.37-7.30?(m,?6H),?7.16-7.14?(d,?
J?=?7.5?Hz,?2H),?5.34?(s,?2H).
13 C?NMR?(CDCl 3 ,?125?MHz): δ=?135.7,?135.3,?135.1,?129.2,?128.5,?128.1,?127.2,?124.1,?122.4,?120.1,?115.9,?111.0,?86.3,?51.0.
LC/MS?m/z?(relative?intensity):?233?[M+1
+].
Embodiment six: the preparation of 1-butyl-1H-indoles-3-cyanic acid
1-butyl-1
H-indoles-3-cyanic acid adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 8.6 gram 1-butyl-1
H-indoles, 560 milligrams of palladium, 43 gram additives, 12.5 gram tert-butyl isonitriles, 150 milliliters of N, dinethylformamide is heated to 130 ℃.Follow the tracks of reaction with the thin-layer chromatography method, to reaction raw materials 1-butyl-1
H-indoles disappears; 2. after reacting end, in system, add the ammonia soln of 3 N, use the ethyl acetate extraction product, solvent is removed with Rotary Evaporators in dry back, gets crude product; 3. (sherwood oil: purifying ETHYLE ACETATE=6: 1) obtains 4.3 gram 1-butyl-1 to crude product with column chromatography
H-indoles-3-cyanic acid is brown liquid, and productive rate is 43%.
IR?(KBr,?cm –1 ):?2217,?1531,?1467,?1395,?1363,?1187,?744.
1 H-NMR?(500?MHz,?CDCl 3 ):? δ?=?7.77-7.75?(d,?
J?=?7.5?Hz,?1H),?7.59?(s,?1H),?7.42-7.40?(d,
?J?=?8.5?Hz,?1H),?7.35-7.32?(t,?
J?=?7.5?Hz,?1H),?7.30-7.27?(t,?
J?=?8.0?Hz,?1H),?4.18-4.14?(t,?
J?=?7.5?Hz,?2H),?1.88-1.81?(m,?2H),?1.39-1.31?(m?,2H),?0.97-0.94?(t,?
J?=?7.5?Hz,?3H).
13 C-NMR?(CDCl 3 ,?125?MHz): δ=?135.4,?134.8,?128.1,?123.8,?122.1,?120.1,?116.2,?110.7,?85.6,?47.1,?32.0,?20.1,?13.7.
MS?(EI)?m/z?(relative?intensity):?198?(45)?[M
+],?155?(100).
HR-MS?(ESI)?m/z?calcd?for?C
13H
14N
2?[M
+]?198.1157,?found?198.1154.
Embodiment seven: the preparation of 1-allyl group-1H-indoles-3-cyanic acid
1-allyl group-1
H-indoles-3-cyanic acid adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 7.8 gram 1-allyl groups-1
H-indoles, 560 milligrams of palladium, 43 gram additives, 12.5 gram tert-butyl isonitriles, 150 milliliters of N, dinethylformamide is heated to 130 ℃.Follow the tracks of reaction with the thin-layer chromatography method, to reaction raw materials 1-allyl group-1
H-indoles disappears; 2. after reacting end, in system, add the ammonia soln of 3 N, use the ethyl acetate extraction product, solvent is removed with Rotary Evaporators in dry back, gets crude product; 3. (sherwood oil: purifying ETHYLE ACETATE=6: 1) obtains 3.8 gram 1-allyl groups-1 to crude product with column chromatography
H-indoles-3-cyanic acid is brown liquid, and productive rate is 42%.
IR?(KBr,?cm –1 ):?2218,?1645,?1615,?1531,?1466,?1391,?1182,?933,?742.
1 H-NMR?(500?MHz,?CDCl 3 ): δ=?7.77?(d,?
J?=?8.0?Hz,?1H),?7.61?(s,?1H),?7.39?(d,?
J?=?8.0?Hz,?1H),?7.35-7.28?(m,?2H),?6.03-5.94?(m,?1H),?5.32-5.30?(d,?
J?=?10.5?Hz,?1H),?5.17-5.13?(d,
?J?=?17.5?Hz,?1H),?4.77?(d,?
J?=?5.5?Hz,?2H).
13 C-NMR?(CDCl 3 ,?125?MHz): δ=?135.5,?134.8,?131.8,?128.0,?124.0,?122.3,?120.1,?119.1,?116.0,?110.9,?86.1,?49.6.
LC/MS?m/z?(relative?intensity):?183?[M+1
+]。
Claims (2)
2. method for preparing 3-cyanic acid substituted indole compound according to claim 1; It is characterized in that this method has following steps: with indoles, mantoquita and tert-butyl isonitrile by 1: (2.0~3.0): the mol ratio of (2.0~3.0) is dissolved in N; In the dinethylformamide; And the palladium of adding catalyst levels, 100
oC~130
oStirring reaction to reaction raw materials disappears under the C; Remove solvent, add 3 N ammonia solns, use the ethyl acetate extraction product, organic phase is removed solvent and is got crude product after drying; This crude product promptly obtains corresponding 3 cyanic acid substituted indole compounds through separation and purification; The structural formula of described indoles is:
Wherein: R
1For: methoxyl group; R
2For: Ph, Bn, Allyl or n-Butyl; Described mantoquita is: trifluoracetic acid copper.
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Cited By (2)
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CN103467386A (en) * | 2013-09-10 | 2013-12-25 | 上海大学 | Aryl pyrimidine ortho-position monocyano compounds and synthesis method thereof |
CN110240554A (en) * | 2019-06-27 | 2019-09-17 | 上海大学 | α-thioether aryl acetonitrile compound and its synthetic method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1665809A (en) * | 2001-06-21 | 2005-09-07 | 艾文蒂斯药品有限公司 | Azaindoles |
CN101219986A (en) * | 2007-01-09 | 2008-07-16 | 上海睿智化学研究有限公司 | 3-cyanogen radical indole compounds and its synthetic method |
CN101541748A (en) * | 2006-01-13 | 2009-09-23 | Ptc医疗公司 | Methods for treating hepatitis C |
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CN1665809A (en) * | 2001-06-21 | 2005-09-07 | 艾文蒂斯药品有限公司 | Azaindoles |
CN101541748A (en) * | 2006-01-13 | 2009-09-23 | Ptc医疗公司 | Methods for treating hepatitis C |
CN101219986A (en) * | 2007-01-09 | 2008-07-16 | 上海睿智化学研究有限公司 | 3-cyanogen radical indole compounds and its synthetic method |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103467386A (en) * | 2013-09-10 | 2013-12-25 | 上海大学 | Aryl pyrimidine ortho-position monocyano compounds and synthesis method thereof |
CN103467386B (en) * | 2013-09-10 | 2015-05-27 | 上海大学 | Aryl pyrimidine ortho-position monocyano compounds and synthesis method thereof |
CN110240554A (en) * | 2019-06-27 | 2019-09-17 | 上海大学 | α-thioether aryl acetonitrile compound and its synthetic method |
CN110240554B (en) * | 2019-06-27 | 2021-02-23 | 上海大学 | Alpha-thioether aryl acetonitrile compound and synthetic method thereof |
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