CN1583730A - Synthesis of 5-iodo-1,4-twice substituted-1,2,3-trioxazole compound - Google Patents

Synthesis of 5-iodo-1,4-twice substituted-1,2,3-trioxazole compound Download PDF

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CN1583730A
CN1583730A CN 200410024929 CN200410024929A CN1583730A CN 1583730 A CN1583730 A CN 1583730A CN 200410024929 CN200410024929 CN 200410024929 CN 200410024929 A CN200410024929 A CN 200410024929A CN 1583730 A CN1583730 A CN 1583730A
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iodo
replaces
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triazole
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CN100335467C (en
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吴永明
邓娟
李亚
陈庆云
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

A process for synthesizing 5-iodo-1,4-bisubstituent-1,2,3-trinitroazole by one-step method with local selectivity features the reaction between organic triazo compound, terminated alkynyl hydrocarbon, coprus iodide, ICl and amine.

Description

The one kettle way regioselectivity is synthesized 5-iodo-1, and 4-two replaces-1,2, the 3-3-triazole compounds
Technical field
The present invention relates to a kind of 5-iodo-1,4-two replaces-1,2, the synthetic method of 3-3-triazole compounds, and this method can the one kettle way regioselectivity be synthesized.
Background technology
1,2, the 3-triazole is the very important compound of a class, industrial it be widely used in the sanitas of brightening agent, metal and alloy of pigment, fiber and the stablizer of organism and polymkeric substance, it is used to weedicide on agricultural, sterilant is in that pharmaceutically it is used in the medicine of multiple difference in functionality.Because this compounds is not present in occurring in nature, it all is that method by chemosynthesis prepares.The most frequently used preparation 1,2, the method for 3-triazole be by 1 of organic azide and alkynes, and the 3-dipolar addition reacts to be realized.But in this method, for asymmetric acetylene hydrocarbon compound, often generate two kinds of different positional isomerss after reacting, this has just caused very big influence to the cost for preparing this compounds, and has increased the three wastes.In recent years, the someone utilizes 1 of catalytic organic azide of monovalence copper and alkynes, and the 3-dipolar addition has reacted carrying out successfully 1, and it is synthetic that 4-two replaces-1,2,3 triazole regioselectivities.The present invention is exactly on this basis, and by add the 3rd component iodine monochloride in system, the method with regioselectivity of success has been introduced the iodine atom in the 5-position, thereby with the synthetic 5-iodo-1 of the method one kettle way of regioselectivity, 4-two replaces-1,2, the 3-3-triazole compounds.
Summary of the invention
The present invention is a kind of 5-iodo-1, and 4-two replaces-1,2, the synthetic method of 3-3-triazole compounds, and this method can the one kettle way regioselectivity be synthesized.
Reaction equation of the present invention is as follows:
Figure A20041002492900031
In the formula: R 1Can be: C 1-C 9Alkyl ,-CH 2(CF 2) nF;-CH 2CH 2(CF 2) nF; Aryl; R 2Can be: C 1-C 9Alkyl, aryl, ester group and amide group; R 3Can be: C 1-C 9Alkyl, aryl, R=C 1-8Alkyl, n=2-8.
In the method for the present invention, in organic solvent, be R with molecular formula 1N 3Organic azide, molecular formula is
Figure A20041002492900041
Terminal alkyne, cuprous iodide, iodine monochloride and molecular formula are NR 3 3Tertiary amine, under 10-100 ℃ of temperature the reaction 1-30 hour.Described organic azide, terminal alkyne, cuprous iodide, iodine monochloride, the mol ratio of tertiary amine is followed successively by 1: 0.8-1.5: 0.8-1.5: 0.8-2.5: 1-20.More tertiary amine is to not influence of reaction.The mol ratio of recommending is 1: 1-1.2: 1-1.2: 1-1.5: 1-5.Optimal temperature is between 20-40 ℃. Organic solvent can be a tetrahydrofuran (THF), acetonitrile, N, dinethylformamide, benzene etc.Reaction of the present invention also can detect with TLC, treats that raw material disappears, stopped reaction, get final product behind the purifying product.
Method of the present invention is preferably under anhydrous and oxygen-free and the nitrogen protection carries out, and can improve reaction yield.
The typical reaction result of some of this reaction is listed in the table below:
Table 1: the synthetic 5-iodo-1 of one kettle way regioselectivity, 4-two replaces-1,2, the 3-3-triazole compounds
Entry Azide(1) Alkyne(2) Product3 Yield a(％)
1 CF 3CH 2N 3
Figure A20041002492900043
48
2 CF 3CH 2N 3
Figure A20041002492900044
61
3 CF 3CH 2N 3 82
4 CF 3CH 2N 3
Figure A20041002492900051
73
5 HCF 2CF 2CH 2N 3
Figure A20041002492900052
77
6 HCF 2CF 2CH 2N 3 63
7 HCF 2CF 2CH 2N 3 76
8 HCF 2CF 2CH 2N 3
Figure A20041002492900055
74
9 C 6F 13(CH 2) 2N 3
Figure A20041002492900056
48
10 CF 3(CF 2) 5CH 2N 3 78
11 CF 3(CF 2) 5CH 2N 3 81
12 PhCH 2N 3
Figure A20041002492900061
72
13 PhCH 2N 3
Figure A20041002492900062
72
14 n-C 8H 17N 3
Figure A20041002492900063
34
The tool present embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Typical operational procedure:
1. at anhydrous and oxygen-free, under the nitrogen protection, in reaction tubes, add R 1CH 2N 3(0.5mmol), terminal alkynes 2 (0.5mmol), CuI (0.5mmol), Bu 3N (0.6mmol), THF (5ml), ICl (0.5mmol) reacts 20h under the room temperature, and aftertreatment gets product 3.
2. at anhydrous and oxygen-free, under the nitrogen protection, in reaction tubes, add R 1CH 2N 3(0.5mmol), terminal alkynes 2 (0.5mmol), CuI (0.5mmol), Et 3N (0.6mmol), THF (5ml), ICl (0.5mmol), 80 ℃ are reacted 20h down, and aftertreatment gets product 3.
3. at anhydrous and oxygen-free, under the nitrogen protection, in reaction tubes, add R 1CH 2CH 2N 3(0.5mmol), terminal alkynes 2 (0.5mmol), CuI (0.5mmol), Bu 3N (0.6mmol), THF (5ml), ICl (0.5mmol) reacts 20h under the room temperature, and aftertreatment gets product 3.
4. at anhydrous and oxygen-free, under the nitrogen protection, in reaction tubes, add R 1CH 2N 3(0.5mmol), terminal alkynes 2 (0.5mmol), CuI (0.5mmol), Bu 3N (0.6mmol), acetonitrile (5ml), ICl (0.5mmol) reacts 20h under the room temperature, and aftertreatment gets product 3.
5-Iodo-4-phenyl-1-(2，2，2-trifluoro-ethyl)-1H-[1，2，3]triazole(3aa)
5-iodo-4-phenyl-1-(2,2, the 2-trifluoroethyl)-1H-1,2,3 triazoles
White solid; Mp:164-165 ℃; 1H NMR δ 5.10 (q, J=8Hz, 2H), 7.44-7.54 (m, 3H), 7.93-7.97 (m, 2H); 19F NMR δ-69.71 (t, J=8Hz, 3F); IR 1100,1189,1400,1447cm -1MS m/z 353 (M +, 7), 325 (42), 242 (41), 198 (51), 89 (100); Ultimate analysis, C 10H 7F 3IN 3: calculated value C, 34.02; H, 2.00; N, 11.90; F, 16.14. measured value: C, 34.03; H, 2.22; N, 11.91; F, 16.48.
4-Butyl-5-iodo-1-(2，2，2-trifluoro-ethyl)-1H-[1，2，3]triazole(3ab)
5-iodo-4-butyl-1-(2,2, the 2-trifluoroethyl)-1H-1,2,3 triazoles
White solid; 1H NMR δ 0.96 (t, J=7Hz, 3H), 1.65-1.77 (m, 2H), 1.34-1.47 (m, 2H), 2.70 (t, J=8Hz, 2H), 5.99 (q, J=8Hz, 2H); 19F NMR δ-69.99 (t, J=8Hz, 3F); IR 1120,1169,1397,1525,2322,2967,3018cm -1MSm/z 333 (M +, 1), 262 (97), 206 (50), 178 (19), 136 (100); Ultimate analysis, C 8H 11F 3IN 3: calculated value C, 28.85; H, 3.33; N, 12.62; F, 17.11. measured value: C, 28.87; H, 3.35; N, 12.57; F, 17.20.
Allyl?5-Iodo-1-(2，2，2-trifluoro-ethyl)-1H-[1，2，3]triazole-4-carboxylic?ester(3ac)
5-iodo-1-(2,2, the 2-trifluoroethyl)-1H-1,2, the 3 triazoles-rare propyl ester of 4-formic acid
White solid; 1H NMR δ 4.92 (d, J=5Hz, 2H), 5.15 (q, J=8Hz, 2H), 5.34 (d, J=11Hz, 1H), 5.48 (d, J=17Hz, 1H), 6.00-6.14 (m, 1H); 19F NMR δ-69.61 (t, J=8Hz, 3F); IR 1114,1178,1266,1519,1720,2976,3020cm -1MS m/z 360 (M +-1,4), 276 (7), 233 (15), 153 (49), 41 (100); Ultimate analysis, C 8H 7F 3IN 3O 2: calculated value C, 26.61; H, 1.95; N, 11.64; F, 15.79. measured value: C, 26.51; H, 2.18; N, 11.52; F, 15.29.
Allyl?5-Iodo-1-(2，2，2-trifluoro-ethyl)-1H-[1，2，3]triazole-4-carboxylic?amide(3ad)
5-iodo-1-(2,2, the 2-trifluoroethyl)-1H-1,2, the 3 triazoles-rare propylamine of 4-formic acid
White solid; 1H NMR δ 4.09 (t, J=8Hz, 2H), 5.54 (q, J=8Hz, 2H), 5.21 (d, J=11Hz, 1H), 5.30 (d, J=17Hz, 1H), 5.85-5.99 (m, 1H), 7.25-7.39 (br, 1H); 19F NMR δ-69.71 (t, J=8Hz, 3F); IR 1117,1178,1265,1557,1652,2961,3399cm -1MS m/z 360 (M +, 8), 276 (11), 233 (40), 205 (34), 150 (67), 56 (100); Ultimate analysis, C 8H 8F 3IN 4O: calculated value C, 26.69; H, 2.24; N, 15.56; F, 15.83. measured value: C, 26.67; H, 2.39; N, 15.50; F, 15.67.
5-Iodo-4-phenyl-1-(2，2，3，3-tetrafluoro-propyl)-1H-[1，2，3]triazole(3ba)
5-iodo-4-phenyl-1-(2,2,3,3-tetrafluoro propyl group)-1H-1,2,3 triazoles
White solid; Mp:152-153 ℃; 1H NMR δ 5.07 (t, J=13Hz, 2H), 6.04 (tt, J 1=3Hz, J 2=53Hz, 1H), 7.42-7.55 (m, 3H), 7.92-7.99 (m, 2H); 19F NMR δ-136.87 (d, J=52Hz, 2F) ,-118.68 (t, J=12Hz, 2F); IR 1093,1236,1538cm -1MS m/z 385 (M +, 3), 366 (1), 357 (32), 230 (51), 89 (100); Ultimate analysis, C 11H 8F 4IN 3: calculated value C, 34.31; H, 2.09; N, 10.91; F, 19.73. measured value: C, 34.16; H, 2.17; N, 10.97; F, 19.88.
4-Butyl-5-iodo-1-(2，2，3，3-tetrafluoro-propyl)-1H-[1，2，3]triazole(3bb)
5-iodo-4-butyl-1-(2,2,3,3-tetrafluoro propyl group)-1H-1,2,3 triazoles
White solid; 1H NMR δ 0.96 (t, J=7Hz, 3H), 1.32-1.46 (m, 2H), 1.62-1.76 (m, 2H), 2.70 (t, J=8Hz, 2H), 4.94 (t, J=13Hz, 2H), 5.98 (tt, J 1=3Hz, J 2=53 Hz, 1H); 19F NMR δ-137.14 (d, J=53Hz, 2F) ,-119.10 (t, J=13Hz, 2F); IR 1107,1235,1437,2966cm -1MS m/z 346 (M +-19,2), 294 (100), 238 (42), 210 (39), 168 (98); Ultimate analysis, C 9H 12F 4IN 3: calculated value C, 29.61; H, 3.31; N, 11.51; F, 20.82. measured value: C, 29.23; H, 3.28; N, 11.32; F.20.87.
Allyl?5-Iodo-1-(2，2，3，3-tetrafluoro-propyl)-1H-[1，2，3]triazole-4-carboxylic?ester(3bc)
5-iodo-1-(2,2,3,3-tetrafluoro propyl group)-1H-1,2, the 3 triazoles-rare propyl ester of 4-formic acid
White solid; Mp:75-76 ℃; 1H NMR δ 4.89-4.92 (m, 2H), 5.07 (t, J=14Hz, 2H), 5.31-5.51 (m, 2H), 5.81-6.18 (m, 2H); 19F NMR δ-136.19 (d, J=52Hz, 2F) ,-117.96 (t, J=14Hz, 2F); IR 1108,1226,1518,1718,3012cm -1MS m/z 393 (M +); Ultimate analysis, C 9H 8F 4IN 3O 2: calculated value C, 27.50; H, 2.05; N, 10.69; F, 19.33. measured value: C, 27.44; H, 2.28; N, 10.62; F, 19.40.
Allyl 5-Iodo-1-(2,2,3,3-tetrafluoro-propyl)-1H-[1,2,3] triazole-4-carboxylic amide (3bd) 5-iodo-1-(2,2,3,3-tetrafluoro propyl group)-1H-1,2, the 3 triazoles-rare propylamine of 4-formic acid
White solid; Mp:114-115 ℃; 1H NMR δ 4.07-4.13 (m, 2H), 5.05 (t, J=14Hz, 2H), 5.19-5.33 (m, 2H), 5.80-6.18 (m, 2H); 19F NMR δ-136.12 (d, J=53Hz, 2F) ,-117.95 (t, J=14Hz, 2F); IR 1117,1258,1557,1646,2959,3382cm -1MS m/z 392 (M +, 11), 265 (47), 237 (31), 182 (100), 51 (38); Ultimate analysis, C 9H 9F 4IN 4O: calculated value C, 27.57; H, 2.31; N, 14.29; F, 19.38. measured value: C, 27.71; H, 2.37; N, 14.14; F, 19.14.
5-Iodo-4-phenyl-1-(, 3,3,4,4,5,5,6,6,7,7,, 8,8,8-tridecafluoro-oxtyl)-1H-[1,2,3] triazole (3ca) 5-iodo-4-phenyl-1-(3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl groups)-1H-1,2,3 triazoles
White solid; Mp:164-165 ℃; 1H NMR δ 4.3 (t, 2H), 5.20 (t, J=14Hz, 2H), 7.40-7.60 (m, 3H), 7.92-8.03 (m, 2H); 19F NMR δ-126.36 (2F) ,-123.27--122.92 (4F) ,-121.91 (2F) ,-115.14 (2F) ,-80.96 (3F); IR 1139,1209,3024cm -1MS m/z 603 (M +, 1), 575 (20), 448 (29), 242 (35), 89 (100); Ultimate analysis, C 15H 7F 13IN 3: calculated value C, 29.87; H, 1.17; N, 6.97; F, 40.95. measured value: C, 29.91; H, 1.46; N, 7.14; F, 41.03.
Allyl 5-Iodo-1-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-heptyl)-1H-[1,2,3] triazole-4-carboxylic ester (3cc) 5-iodo-1-(2,2,3,3,4,4,5,5,6,6,7,7,7-ten trifluoro heptyl)-1H-1,2, the 3 triazoles-rare propyl ester of 4-formic acid
White solid; Mp:133-134 ℃; 1H NMR δ 4.94-4.97 (m, 2H), 5.21 (t, J=14Hz, 2H), 5.36-5.50 (m, 2H), 5.05-6.17 (m, 1H); 19F NMR δ-126.10 (2F) ,-122.83 (4F) ,-121.79 (2F) ,-114.77 (2F) ,-81.00 (3F); IR 1140,1229,1522,1730cm -1MS m/z 611 (M +); Ultimate analysis, C 13H 7F 13IN 3O 2: calculated value C, 25.55; H, 1.15; N, 6.88; F, 40.42. measured value: C, 25.57; H, 1.09; N, 6.92; F, 40.60.
Allyl 5-Iodo-1-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-heptyl)-1H-[1,2,3] triazole-4-carboxyli amide (3cd) 5-iodo-1-(2,2,3,3,4,4,5,5,6,6,7,7,7-ten trifluoro heptyl)-1H-1,2, the 3 triazoles-rare propylamine of 4-formic acid
White solid; Mp:114-115 ℃; 1H NMR δ 4.10 (t, J=6Hz, 2H), 5.15 (t, J=14Hz, 2H), 5.30 (d, J=17Hz, 1H), 5.21 (d, J=9Hz, 1H), 7.25-7.39 (br, 1H); 19F NMR δ-123.12 (2F) ,-122.83 (4F) ,-121.91 (2F) ,-115.13 (2F) ,-80.96 (3F); IR 1151,1200,1556,1655,3421cm -1MS m/z 610 (M +, 13), 591 (3), 526 (10), 483 (25), 455 (35), 400 (81), 80 (56), 56 (100); Ultimate analysis, C 13H 8F 13IN 4O: calculated value C, 25.59; H, 1.32; N, 9.18; F, 40.48. measured value: C, 25.64; H, 1.36; N, 9.10; F, 40.60.
1-Benzyl-5-iodo-4-phenyl-1H-[1，2，3]triazole(3da)
5-iodo-4-phenyl-1-benzyl-1H-1,2,3 triazoles
White solid; Mp:128-129 ℃; 1H NMR δ 5.72 (s, 2H), 7.32-7.53 (m, 8H), 7.94-8.00 (m, 2H); IR 1155,1230,1446,3031cm -1MS m/z 361 (M +, 2), 234 (6), 206 (39), 91 (100); Ultimate analysis, C 15H 12IN 3: calculated value C, 49.88; H, 3.35; N, 11.63. measured value: C, 49.79; H, 3.42; N, 11.65.
1-Benzyl-5-iodo-1H-[1，2，3]triazole-4-carboxylic?acid?allyl?ester(3dc)
5-iodo-1-benzyl-1H-1,2, the 3 triazoles-rare propyl ester of 4-formic acid
White solid; 1H NMR δ 4.87-4.89 (m, 2H), 5.29-5.33 (m, 1H), 5.41-5.48 (m, 2H), 5.68 (s, 2H), 5.99-6.10 (m, 1H), 7.25-7.31 (m, 2H), 7.32-7.37 (m, 3H); MS m/x 369 (M +, 1), 242 (13), 91 (100); Ultimate analysis, C 13H 12IN 3O 2: calculated value C, 42.30; H, 3.28; N, 11.38. measured value: C, 42.23; H, 3.27; N, 11.30.
5-Iodo-1-octyl-4-phenyl-1H-[1，2，3]triazole(3ea)
5-iodo-1-octyl group-4-phenyl-1H-1,2,3 triazoles
White solid; Mp:76-77 ℃; 1H NMR δ 0.90 (m, 3H), 1.23-1.45 (m, 10H), 1.95-2.00 (m, 2H), 4.45 (t, J=7Hz, 2H), 7.41-7.51 (m, 3H), 7.93-7.97 (m, 2H); IR 1153,1227,1447,2919cm -1MS m/z 383 (M +, 6), 243 (100), 228 (41), 116 (88), 91 (54); Ultimate analysis, C 16H 22IN 3: calculated value C, 50.14; H, 5.49; N, 10.96. measured value: C, 50.25; H, 5.69; N, 10.85.

Claims (5)

1, a kind of 5-iodo-1,4-two replaces-1,2, the synthetic method of 3-3-triazole compounds, it is characterized in that in organic solvent and 10-100 ℃ of temperature under, molecular formula is R 1N 3Organic azide, molecular formula is
Figure A2004100249290002C1
Terminal alkyne, cuprous iodide, iodine monochloride and molecular formula are NR 3 3Tertiary amine reaction-hour, described organic azide, terminal alkyne, cuprous iodide, iodine monochloride, the mol ratio of tertiary amine is followed successively by 1: 0.8-1.5: 0.8-1.5: 0.8-2.5: 1-20, wherein, R 1Be C 1-C 9Alkyl ,-CH 2(CF 2) nF ,-CH 2CH 2(CF 2) nF or aryl; R 2Be C 1-C 9Alkyl, aryl, ester group and amide group; R 3Be C 1-C 9Alkyl, perhaps aryl, R=C 1-8Alkyl, n=2-8.
2, a kind of 5-iodo-1 as claimed in claim 1,4-two replaces-1,2, and the synthetic method of 3-3-triazole compounds is characterized in that temperature of reaction is 20-40 ℃.
3, a kind of 5-iodo-1 as claimed in claim 1,4-two replaces-1,2, and the synthetic method of 3-3-triazole compounds is characterized in that described organic solvent is a tetrahydrofuran (THF), acetonitrile, N, dinethylformamide or benzene.
4, a kind of 5-iodo-1 as claimed in claim 1,4-two replaces-1,2, and the synthetic method of 3-3-triazole compounds is characterized in that carrying out under anhydrous and oxygen-free and nitrogen protection.
5, a kind of 5-iodo-1 as claimed in claim 1,4-two replaces-1,2, the synthetic method of 3-3-triazole compounds is characterized in that described organic azide, terminal alkyne, cuprous iodide, iodine monochloride, it is 1 that the mol ratio of tertiary amine is followed successively by: 1-1.2: 1-1.2: 1-1.5: 1-5.
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