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

HRID 553080Notes

Reaction equation

HRID 553080 reaction equation
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]

Participants

11

Reactant 6

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

Product 1

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

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8082PiperidineSolventHCID 21889329Toluene hexaneSolvent

Conditions

Temperature
90 °C

Procedure

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.

Workup

  1. extractionextracted into EtOAc

Sources & evidence

ORD record
ord-c2eaa9f910804f65bf7d16e9a1f6f8e7
Source dataset
uspto-grants-2011_05
Patent number
US07951827B2

Reaction notes

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