Benzene → HCID 86747541, compound

HRID 260398Notes

Reaction equation

HRID 260398 reaction equation
C(N)CC.[C:5]1([O:11][C:12]([N:14]2[CH:27]([C:28]#[CH:29])[C:26]3[CH2:25][CH2:24][CH2:23][CH:22]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[C:21]=3[C:20]3[CH:19]=[CH:18][C:17]([O:38][CH2:39][C:40]4[CH:45]=[CH:44][CH:43]=[CH:42][C:41]=4[N+:46]([O-:48])=[O:47])=[CH:16][C:15]2=3)=[O:13])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[CH:49]1C=C[CH:52]=[CH:51][CH:50]=1>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>[C:5]1([O:11][C:12]([N:14]2[CH:27]([C:28]#[C:29]/[CH:49]=[CH:50]\[C:51]#[C:52][Si:31]([CH3:34])([CH3:33])[CH3:32])[C:26]3[CH2:25][CH2:24][CH2:23][CH:22]([O:30][Si:31]([C:34]([CH3:36])([CH3:37])[CH3:35])([CH3:33])[CH3:32])[C:21]=3[C:20]3[CH:19]=[CH:18][C:17]([O:38][CH2:39][C:40]4[CH:45]=[CH:44][CH:43]=[CH:42][C:41]=4[N+:46]([O-:48])=[O:47])=[CH:16][C:15]2=3)=[O:13])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

6

Reactant 3

HCID 241Benzene2×HCID 7852PropylamineHCID 22401268HCID 22401268, compound

Product 1

HCID 86747541HCID 86747541, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
25 °C

Procedure

A mixture of Pd(PPh3)4 (1.12 g, 0.97 mmol), 1-chloro-4-(trimethylsilyl)-but-1-3n-3-yne (4.60 g, 28.98 mmol), and n-propylamine (2.38 mL, 28.98 mmol) in degassed benzene (100 mL) was stirred at 25° C. for 15 minutes. The resultant solution was added to a mixture of Compound 143b (79:21, mixture of diastereomers, 11.80 g, 19.32 mmol) and CuI (0.74 g, 3.86 mmol) in degassed benzene (300 mL) via a syringe followed by stirring at 25° C. for five hours. The reaction was quenched with saturated aqueous NH4Cl, extracted with ethyl ether (500 mL), washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuo. Purification of the crude product by flash column chromatography (silica gel, 20 percent ethyl ether in petroleum ether) gave Compound 232 (12.3 g, 87 percent): amorphous solid; Rf =0.51 (silica, 25 percent ethyl ether in petroleum ether); IR (CHCl3) νmax 2957, 2932, 1716, 1613, 1506, 1495, 1384, 1344, 1306, 1253, 1200, 1093, 1025, 858, 844 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 8.19 (d, J=8.1 Hz, 1 H, aromatic), 7.97 (d, J=7.7 Hz, 1 H, aromatic), 7.80-7.17 (m, 9 H, H1, H4and aromatic), 6.93-6.84 (m, 1 H, H2), 5.96 (br s, 0.79 H, H6), 5.93 (br s, 0.21 H, H6), 5.88-5.77 (m, 2 H, olefinic), 5.58 (s, 2 H, benzylic), 5.03 (br s, 0.79 H, H10), 4.73 (br s, 0.21 H, H10), 2.67-2.50 (m, 1 H, H7), 2.39-2.26 (m, 1 H, H7), 2.16-1.91 (m, 3 H, H8 and H9), 1.84-1.70 (m, 1 H, H8 or H9), 1.02 (s, 1.89 H, SiC(CH3)3), 0.90 (s, 7.11 H, SiC(CH3)3), 0.27 (s, 9 H, Si(CH3)3), 0.18 (s, 3 H, SiCH3), 0.16 (s, 3 H, SiCH3); MS (FAB+) m/e (rel intensity) 865 (M+Cs, 72), 732 (42), 675 (82), 639 (28), 585 (100), 450 (34), 330 (39), 279 (52), 198 (42); HRMS for C42H48N2O6Si2Cs (M+Cs), calcd 865.2105, found 865.2111.

Workup

  1. stirringby stirring at 25° C. for five hours
  2. customThe reaction was quenched with saturated aqueous NH4Cl
  3. extractionextracted with ethyl ether (500 mL)
  4. washwashed with brine
  5. dry with materialdried over anhydrous Na2SO4
  6. concentrationconcentrated in vacuo
  7. customPurification of the crude product by flash column chromatography (silica gel, 20 percent ethyl ether in petroleum ether)

Sources & evidence

ORD record
ord-44c7dcd92ede442f864184cbfed37568
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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