Triphenylphosphine → HCID 68408307, compound

HRID 1176163Notes

Reaction equation

HRID 1176163 reaction equation
[CH2:1]([O:13][C:14]1[CH:19]=[CH:18][C:17](I)=[CH:16][CH:15]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:40][Si:41]([C:44]#[CH:45])([CH3:43])[CH3:42].[NH4+].[Cl-]>N1CCCCC1.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:1]([O:13][C:14]1[CH:19]=[CH:18][C:17]([C:45]#[C:44][Si:41]([CH3:43])([CH3:42])[CH3:40])=[CH:16][CH:15]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 25517Ammonium ChlorideHCID 66111TrimethylsilylacetyleneHCID 10883601Benzene, 1-(dodecyloxy)-4-iodo-

Product 1

HCID 68408307HCID 68408307, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8082PiperidineSolvent

Conditions

Temperature
50 °C

Procedure

4-(Dodecyloxy)iodobenzene (4.04 g, 1.04×10−2 mol), triphenylphosphine (0.165 g, 6.29×10−4 mol), CuI (0.108 g, 5.67×10−4 mol) and Pd(PPh3)2Cl2 (0.153 g, 2.18×10−4 mol) were dissolved in 40 ml of dry piperidine under N2. (Trimethylsilyl)acetylene (3.00 ml, 2.12×10−2 mol) was added and the mixture was stirred at 50° C. for 6 h under N2. After cooling, the reaction mixture was poured into aq. NH4Cl and extracted with CH2Cl2 (three times). The combined organic layers were washed with aq. NH4Cl, water, and dried over Na2SO4. The crude product was chromatographed on silica gel with 4:1 hexane:CH2Cl2 as the eluent. Yield=3.633 g (97% based on 4.04 g of 4-(dodecyloxy)iodobenzene). 1H NMR (250 MHz, CDCl3): δ 7.39 (d, 2H, J=8.9 Hz, Ph), 6.80 (d, 2H, J=9.0 Hz, Ph), 3.94 (t, 2H, J=6.6 Hz, —OCH2—), 1.77 (quint, 2H, J=6.6 Hz, —OCH2CH2—), 1.17-1.50 (m, 18H, —CH2—), 0.88 (t, 3H, J=6.6 Hz, —CH3), 0.24 (s, 9H, Si—CH3). CI MS m/z: 358.268 (M+) (calcd 358.269).

Workup

  1. temperatureAfter cooling
  2. extractionextracted with CH2Cl2 (three times)
  3. washThe combined organic layers were washed with aq. NH4Cl, water
  4. dry with materialdried over Na2SO4
  5. customThe crude product was chromatographed on silica gel with 4:1 hexane

Sources & evidence

ORD record
ord-06155a86bd304016abeaf05e10819f05
Source dataset
uspto-grants-2010_11
Patent number
US07842758B2

Reaction notes

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