Water → 3-Nitro-4-[2-(trimethylsilyl)ethynyl]benzonitrile

HRID 553080ノート

反応式

HRID 553080 の反応式
Cl.Cl.C(NC(C1C=CC(C2C=C(C3C=CC(C(=N)NC(C)C)=CC=3)[O:17][N:16]=2)=CC=1)=N)(C)C.[CH3:32][Si:33]([CH3:45])([CH3:44])[C:34]#[C:35][C:36]1[CH:43]=[CH:42][CH:41]=[CH:40][C:37]=1C#N.BrC1C=CC([C:51]#[N:52])=CC=1Cl.C[Si](C#C)(C)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[OH2:81]>N1CCCCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I.C1(C)C=CC=CC=1.CCCCCC>[N+:16]([C:37]1[CH:40]=[C:41]([CH:42]=[CH:43][C:36]=1[C:35]#[C:34][Si:33]([CH3:32])([CH3:44])[CH3:45])[C:51]#[N:52])([O-:17])=[O:81]

参加物

11

反応物 6

HCID 962WaterHCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 136597272-[(Trimethylsilyl)ethynyl]benzonitrileHCID 166593954-Bromo-3-chlorobenzonitrileHCID 178457512HCID 178457512、化合物

生成物 1

HCID 166592593-Nitro-4-[2-(trimethylsilyl)ethynyl]benzonitrile

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒HCID 8082Piperidine溶媒HCID 21889329Toluene hexane溶媒

反応条件

温度
90 °C

実験手順

3-nitro-4-[2-(trimethylsilyl)ethynyl]benzonitrile (61 b) was prepared from aryl bromide 60b as an off-white solid (1.61 g, 66%): mp 81-82° C. (toluene/hexane); 1H NMR δ 8.69 (d, J=1.6 Hz, 1H), 8.20 (dd, J=8.0 and 1.6 Hz, 1H), 7.94 (d, J=8.2 Hz, 1H), 0.27 (s, 9H); HPLC (Method B) tR 8.39 min (100 area % at 254 nm). Anal. (C12H12N2O2Si) C, H, N. 3-chloro-4[(2-(trimethylsilyl)ethynyl]benzonitrile (61c). A mixture of aryl bromide 60c, (3.96 g, 18.2 mmol), (trimethylsilyl)acetylene (1.80 g, 18.23 mmol), PPh3 (0.24 g, 0.91 mol), Pd (PPh3)4 (0.11 g, 0.09 mmol), and CuI (0.17 g, 0.91 mmol) in piperidine was stirred at 90° C. for 1 h. The reaction mixture was poured into water and extracted into EtOAc. Column chromatography [hexanes/EtOAc (40:1)] gave a white solid (3.24 g, 37%); mp 82-83° C.; 1H NMR δ 8.27 (d, J=1.9 Hz, 1H), 8.02 (d, J=8.4 Hz, 1H), 7.78 (dd, J=8.3 and 1.9 Hz, 1H), 0.27 (s, 9H); HPLC (Method B) tR 9.41 min (100 area % at 265 nm). Anal. (C12H12ClNSi) C, H, N, Cl. 4-chloro-3-[2-(trimethylsilyl)ethynyl]benzonitrile (61e) was prepared from aryl iodide 60f to give a white solid (3.11 g, 88%): mp 72-73° C. (hexanes); 1H NMR δ 8.12 (d, J=1.6 Hz, 1H), 7.90 (dd, J=8.2 and 1.6 Hz, 1H), 7.80 (d, J=8.2 Hz, 1H), 0.27 (s, 9H); HPLC (Method B) tR 9.35 min (100 area % at 254 nm). Anal. (C12H12ClNSi) C, H, N, Cl. 4-methoxy-3-[(trimethylsilyl)ethynyl]benzonitrile (61f) was prepared from aryl bromide 60g to give a white solid (8.67 g, 80%): mp 63-64° C. (hexanes; 1H NMR δ 7.87 (d, J=2.2 Hz, 1H), 7.86 (dd, J=9.7 and 2.2 Hz, 1H), 7.24 (d, J=9.7 Hz, 1H), 3.91 (s, 3H), 0.27 (s, 9H); HPLC (Method B) tR 8.31 min (98.12 area % at 254 nm). Anal. (C13H15NOSi) C, H, N. 3-Chloro-4-(3-hydroxy-3-methylbut-1-ynyl)benzonitrile (62b). 2-Methyl-3-butyn-2-ol (2.5 equiv) was added to a mixture of an aryl bromide 60c, K2CO3 (2.5 equiv), CuI (4 mol %), PPh3 (8 mol %), and 10% Pd/C (2 mol %) in DME and water. See Bleicher, L. S. et al., J. Org. Chem., 63, 1109-1118 (1998). The biphasic mixture was stirred at reflux under Ar overnight, and was then filtered (Celite) and partitioned between water and EtOAc. Column chromatography gave a white solid (4.25 g, 77%): mp 63-65° C. (hexane); 1H NMR δ 8.18 (d, J=1.5 Hz, 1H), 7.83 (dd, J=8.1 and 1.6 Hz, 1H), 7.69 (d, J=8.1 Hz, 1H), 5.68 (s, 1H), 1.50 (s, 6H); HPLC (Method B) tR 5.00 min (100 area % at 265 nm). Anal. (C12H10ClNO) C, H, N, Cl.

後処理

  1. extractionextracted into EtOAc

出典と根拠

ORDレコード
ord-c2eaa9f910804f65bf7d16e9a1f6f8e7
出典データセット
uspto-grants-2011_05
特許番号
US07951827B2

反応ノート

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