Chloromethyl Methyl Ether → 4-Iodo-2-methoxy-3-methoxymethoxymethyl-6-(trimethylsilanyl)pyridine

HRID 2086336Notes

Reaction equation

HRID 2086336 reaction equation
[CH2:1](Cl)[O:2][CH3:3].[I:5][C:6]1[CH:11]=[C:10]([Si:12]([CH3:15])([CH3:14])[CH3:13])[N:9]=[C:8]([O:16][CH3:17])[C:7]=1[CH2:18][OH:19].C(N(C(C)C)C(C)C)C>C(Cl)Cl>[I:5][C:6]1[CH:11]=[C:10]([Si:12]([CH3:14])([CH3:13])[CH3:15])[N:9]=[C:8]([O:16][CH3:17])[C:7]=1[CH2:18][O:19][CH2:1][O:2][CH3:3]

Participants

5

Reactant 3

HCID 7864Chloromethyl Methyl EtherHCID 81531DiisopropylethylamineHCID 120443583-Pyridinemethanol, 4-iodo-2-methoxy-6-(trimethylsilyl)-

Product 1

HCID 111881914-Iodo-2-methoxy-3-methoxymethoxymethyl-6-(trimethylsilanyl)pyridineYield 88.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

MOMCl (2.0 mL, 26.7 mmol) was added dropwise to a 0° C. solution of 2a (3 g, 8.9 mmol) and iPr2EtN (4.6 mL, 26.7 mmol) in dry CH2Cl2 (35 mL). The resulting mixture was allowed to warm to room temperature and stirred overnight. The reaction was quenched with 5% aq. NaHCO3 solution and the product was extracted with CH2Cl2. The combined organic phases were washed with brine, dried over MgSO4 and concentrated under reduced pressure to give 3.0 g (88% yield) of the crude product 3a as an orange oil. The crude product was sufficiently pure for the subsequent reaction. 1H NMR (300 MHz, CDCl3) δ0.27 (s, 9H), 3.46 (s, 3H), 3.98 (s, 3H), 4.71 (s, 2H), 4.75 (s, 2H), 7.51 (s, 1H); 13C NMR (75 MHz, CDCl3) δ−2.08, 53.79, 55.53, 67.85, 96.39, 113.84, 122.6, 132.98, 161.43, 166.37; IR (film, NaCl, cm−1) 2946, 1528, 1340, 1042, 840; LRMS (70 eV, EI) m/z (rel int %) 381 (M+), 366, 336, 320, 306, 169, 128, 84 (100), 73. HRMS m/z calcd for C12H20NO3SiI (M+) 381.0257, found 381.0241.

Workup

  1. customThe reaction was quenched with 5% aq. NaHCO3 solution
  2. extractionthe product was extracted with CH2Cl2
  3. washThe combined organic phases were washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-9f559da2804b494a883f111d8aa98139
Source dataset
uspto-grants-2004_04
Patent number
US06723853B2

Reaction notes

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