CN102718694B - 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 cyano group substituted indole compound and preparation method thereof, is mainly 3-cyano group substituted indole compound and preparation method thereof.
Background technology
Organic cyanide is the very important compound of a class in 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, as aldehyde, ketone, carboxylic acid, amine and acid amides etc., the formation by carbon-carbon bond is one of mode the most basic in organic synthesis to introducing cyano group in organic compound molecule.Indoles is present in natural compounds widely, is a kind of very important heterogeneous ring compound.As the escitalopram that contains cyano group, lexapro is a kind of medicine of effectively depression; Containing the not imperial femara of two cyano group, be a kind of effectively for the medicine of breast carcinoma of early stage assisting therapy; The Kang Shi get that contains cyano group, Casodex is for the active drug of breast carcinoma of early stage assisting therapy.The method activating by c h bond realizes the formation of carbon-cyanogen key on indoles, thereby introduce cyano group, is a kind of very effective and novel method.
The synthetic cyano compound method of reporting in document mainly contains following several:
(1) by sandmeyer reaction (Sandmeyer reaction).This reaction is the method for the effective synthesizing aryl nitrile compound of a class, but due to its more reactions steps, reaction complexity and productive rate are on the low side, has limited its application in synthetic.
(2) by aryl halide compound and cyano group reagent, build aryl nitrile compound.Such reaction is simple, and single stepping just can obtain target product, and a succinct approach is provided for aryl nitrile compound is synthetic.
(3) method directly being activated by guiding c h bond builds aryl nitrile compound.This class reaction conditions is simple, and Atom economy is good, to us, provides a good direction.
The synthetic method of the preparation 3-cyano group substituted indole compound of reporting in existing document has:
(1) from reagent such as indoles and trifluoracetic acids, react obtain through 5 steps, concrete reaction is as follows:
(2) from 3-formaldehyde indoles, react with primary ammonium phosphate with potassium cyanide and obtain 3 cyaniding products:
(3) under palladium catalysis, indoles and cuprous cyanide react and obtain:
(4) from 2 3-position substituted indoles, take DMF as cyano sources, under palladium catalysis, obtain, concrete reaction is as follows:
In sum, the method for preparing 3-cyanoindole has a lot, but these reactions have a lot of defects; to substrate require high; reactions steps is complicated or need to introduce blocking group at 2, and in reaction, is difficult to obtain the product of 3 single cyano group, is often mixture.
Summary of the invention
One of object of the present invention is to provide a kind of 3-cyano group substituted indole compound
Two of object of the present 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 3-cyano group 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 of preparing above-mentioned 3-cyano group substituted indole compound, it is characterized in that the method has following steps: by 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 dinethylformamide, and add the palladium of catalyst levels, 100
oc～130
ounder C, stirring reaction to reaction raw materials disappears; Remove solvent, add 3 N ammonia solns, be extracted with ethyl acetate product, organic phase is removed after drying solvent and is obtained crude product; This crude product, through separation and purification, obtains corresponding 3 cyano group substituted indole compounds; 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-cyano group substituted indole compound of the present invention is the important organic reaction intermediate of a class, by dissimilar organic chemical reactions, and as 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 the important class pharmaceutical intermediate ICS 205-930 of polystep reaction, is the important thrombotonin of a class:
Refer to as Publication about 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. by 3-cyanoindole, can synthesize ocean bisindole alkaloid Nortopsentin (Subba Reddy, the B. V. 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 natural product; Yang, C.; Jiang, B.
bioorg. Med. Chem.
2001,
9, 1773):
The inventive method raw material is easy to get, and to adopt first novel tert-butyl isonitrile be cyano group source, has avoided the use of the metal cyanides that toxicity is large.In reaction, use conventional reaction solvent, operate very simply, condition is moderate, reaction environmental protection, and productive rate reaches as high as 74%, has good application prospect in industrial production.
Embodiment
Embodiment mono-: 1-phenyl-1
hthe preparation of-indoles-3-cyano group
1-phenyl-1
h-indoles-3-cyano group adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 9.7 grams of 1-phenyl-1
h-indoles, 560 milligrams of palladium, 43 grams of additives, 12.5 grams of tert-butyl isonitriles, 150 milliliters of DMFs, are heated to 130 ℃.By thin-layer chromatography method, follow the tracks of reaction, to reaction raw materials 1-phenyl-1
h-indoles disappears; 2. after reaction finishes, the ammonia soln to adding 3 N in system, is extracted with ethyl acetate product, removes solvent after dry with Rotary Evaporators, obtains crude product; 3. column chromatography (sherwood oil: ethyl acetate=6: 1) purifying, obtains 8.1 grams of 1-phenyl-1 for crude product
h-indoles-3-cyano group, productive rate is 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 bis-: 1-(the fluoro-phenyl of 4-)-1
hthe preparation of-indoles-3-cyano group
1-(the fluoro-phenyl of 4-)-1
h-indoles-3-cyano group adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 10.5 grams of fluoro-phenyl of 1-(4-)-1
h-indoles, 560 milligrams of palladium, 43 grams of additives, 12.5 grams of tert-butyl isonitriles, 150 milliliters of DMFs, are heated to 130 ℃.By thin-layer chromatography method, follow the tracks of reaction, to reaction raw materials 1-(the fluoro-phenyl of 4-)-1
h-indoles disappears; 2. after reaction finishes, the ammonia soln to adding 3 N in system, is extracted with ethyl acetate product, removes solvent after dry with Rotary Evaporators, obtains crude product; 3. column chromatography (sherwood oil: ethyl acetate=6: 1) purifying, obtains 7.4 grams of 1-(the fluoro-phenyl of 4-)-1 for crude product
h-indoles-3-cyano group, productive rate is 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 tri-: 1-(4-methoxyl group-phenyl)-1
hthe preparation of-indoles-3-cyano group
1-(4-methoxyl group-phenyl)-1
h-indoles-3-cyano group adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 11.1 grams of 1-(4-methoxyl group-phenyl)-1
h-indoles, 560 milligrams of palladium, 43 grams of additives, 12.5 grams of tert-butyl isonitriles, 150 milliliters of DMFs, are heated to 130 ℃.By thin-layer chromatography method, follow the tracks of reaction, to reaction raw materials 1-(4-methoxyl group-phenyl)-1
h-indoles disappears; 2. after reaction finishes, the ammonia soln to adding 3 N in system, is extracted with ethyl acetate product, removes solvent after dry with Rotary Evaporators, obtains crude product; 3. column chromatography (sherwood oil: ethyl acetate=6: 1) purifying, obtains 4.6 grams of 1-(4-methoxyl group-phenyl)-1 for crude product
h-indoles-3-cyano group, productive rate is 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 tetra-: the preparation of 4-methoxyl group-(1-phenyl)-1H-indoles-3-cyano group
4-methoxyl group-(1-phenyl)-1
h-indoles-3-cyano group adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 11.1 grams of 4-methoxyl groups-(1-phenyl)-1
h-indoles, 560 milligrams of palladium, 43 grams of additives, 12.5 grams of tert-butyl isonitriles, 150 milliliters of DMFs, are heated to 130 ℃.By thin-layer chromatography method, follow the tracks of reaction, to reaction raw materials 4-methoxyl group-(1-phenyl)-1
h-indoles disappears; 2. after reaction finishes, the ammonia soln to adding 3 N in system, is extracted with ethyl acetate product, removes solvent after dry with Rotary Evaporators, obtains crude product; 3. column chromatography (sherwood oil: ethyl acetate=6: 1) purifying, obtains 6.2 grams of 4-methoxyl groups-(1-phenyl)-1 for crude product
h-indoles-3-cyano group, productive rate is 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-cyano group
1-benzyl-1
h-indoles-3-cyano group adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 10.3 grams of 1-benzyl-1
h-indoles, 560 milligrams of palladium, 43 grams of additives, 12.5 grams of tert-butyl isonitriles, 150 milliliters of DMFs, are heated to 130 ℃.By thin-layer chromatography method, follow the tracks of reaction, to reaction raw materials 1-benzyl-1
h-indoles disappears; 2. after reaction finishes, the ammonia soln to adding 3 N in system, is extracted with ethyl acetate product, removes solvent after dry with Rotary Evaporators, obtains crude product; 3. column chromatography (sherwood oil: ethyl acetate=6: 1) purifying, obtains 7.1 grams of 1-benzyl-1 for crude product
h-indoles-3-cyano group, productive rate is 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-cyano group
1-butyl-1
h-indoles-3-cyano group adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 8.6 grams of 1-butyl-1
h-indoles, 560 milligrams of palladium, 43 grams of additives, 12.5 grams of tert-butyl isonitriles, 150 milliliters of DMFs, are heated to 130 ℃.By thin-layer chromatography method, follow the tracks of reaction, to reaction raw materials 1-butyl-1
h-indoles disappears; 2. after reaction finishes, the ammonia soln to adding 3 N in system, is extracted with ethyl acetate product, removes solvent after dry with Rotary Evaporators, obtains crude product; 3. column chromatography (sherwood oil: ethyl acetate=6: 1) purifying, obtains 4.3 grams of 1-butyl-1 for crude product
h-indoles-3-cyano group 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-cyano group
1-allyl group-1
h-indoles-3-cyano group adopts following step: 1. in 250 milliliters of round-bottomed flasks, add 7.8 grams of 1-allyl group-1
h-indoles, 560 milligrams of palladium, 43 grams of additives, 12.5 grams of tert-butyl isonitriles, 150 milliliters of DMFs, are heated to 130 ℃.By thin-layer chromatography method, follow the tracks of reaction, to reaction raw materials 1-allyl group-1
h-indoles disappears; 2. after reaction finishes, the ammonia soln to adding 3 N in system, is extracted with ethyl acetate product, removes solvent after dry with Rotary Evaporators, obtains crude product; 3. column chromatography (sherwood oil: ethyl acetate=6: 1) purifying, obtains 3.8 grams of 1-allyl group-1 for crude product
h-indoles-3-cyano group 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 (1)
1. a preparation method for 3-cyano group substituted indole compound, the structural formula of this compound is:
Wherein: R
1for: methoxyl group; R
2for: Ph, Bn, Allyl or n-Butyl; It is characterized in that the method has following steps: by indoles, mantoquita and tert-butyl isonitrile by 1:(2.0～3.0): the mol ratio of (2.0～3.0) is dissolved in DMF, and adds the palladium of catalyst levels, 100
oc～130
ounder C, stirring reaction to reaction raw materials disappears; Remove solvent, add 3 N ammonia solns, be extracted with ethyl acetate product, organic phase is removed after drying solvent and is obtained crude product; This crude product, through separation and purification, obtains corresponding 3 cyano group substituted indole compounds; The structural formula of described indoles is:
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