Triethylamine → HCID 67417308, compound

HRID 2035401Notes

Reaction equation

HRID 2035401 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]2[C@@H:13]([O:14][CH2:15][O:16][CH3:17])[C@H:12]([O:18][CH2:19][O:20][CH3:21])[C@H:11]([O:22][CH2:23][O:24][CH3:25])[CH:10]([CH2:26][O:27][CH2:28][O:29][CH3:30])[O:9]2)=[CH:4][C:3]=1[CH2:31]O.C(N(CC)CC)C.CS(Cl)(=O)=O.[Br-:45].[Li+]>C1(C)C=CC=CC=1.C(OCC)(=O)C>[Br:45][CH2:31][C:3]1[CH:4]=[C:5]([C@H:8]2[C@@H:13]([O:14][CH2:15][O:16][CH3:17])[C@H:12]([O:18][CH2:19][O:20][CH3:21])[C@H:11]([O:22][CH2:23][O:24][CH3:25])[CH:10]([CH2:26][O:27][CH2:28][O:29][CH3:30])[O:9]2)[CH:6]=[CH:7][C:2]=1[Cl:1]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 82050Lithium BromideHCID 67418199HCID 67418199, compound

Product 1

HCID 67417308HCID 67417308, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 21584019Toluene ethylacetateSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of the product from step B (470 mg, 0.98 mmol) and triethylamine (0.54 mL, 3.90 mmol) in toluene/ethyl acetate (1:1, 12 mL) at 0° C. was added dropwise methanesulfonyl chloride (0.15 mL, 1.95 mmol). The reaction mixture was stirred at 0° C. for 2 h. The white precipitate formed during the reaction was filtered off and washed with ethyl acetate. The combined filtrate and washing were concentrated. The residual oil was dissolved in acetone (6 mL) and treated with lithium bromide (850 mg, 10.0 mmol) at 0° C. After stirring at room temperature for 1 h, the reaction was quenched with water (25 mL) and extracted with ethyl acetate (4×). The combined extracts were dried over sodium sulfate, filtered, and concentrated to give compound (2S,3R,4S,5R)-2-(3-(bromomethyl)-4-chlorophenyl)-3,4,5-tris(methoxymethoxy)-6-((methoxymethoxy)methyl)tetrahydro-2H-pyran (517 mg, 97%) as a white solid: 1H NMR (CDCl3, 500 MHz) δ 7.46 (d, J=2.0 Hz, 1H), 7.37 (d, J=8.3 Hz, 1H), 7.30 (dd, J=8.3, 2.0 Hz, 1H), 4.91 (d, J=6.4 Hz, 1H), 4.89-4.86 (m, 2H), 4.77 (d, J=6.4 Hz, 1H), 4.66 (s, 2H), 4.60-4.55 (m, 2H), 4.54 (d, J=6.4 Hz, 1H), 4.17 (d, J=9.4 Hz, 1H), 4.13 (d, J=6.5 Hz, 1H), 3.92 (dd, J=11.2, 1.6 Hz, 1H), 3.75 (t, J=8.8 Hz, 1H), 3.71 (dd, J=11.2, 5.2 Hz, 1H), 3.63-3.58 (m, 2H), 3.52 (t, J=9.3 Hz, 1H), 3.450 (s, 3H), 3.446 (s, 3H), 3.34 (s, 3H), 2.79 (s, 3H); ESI MS m/z 543 [M+H]+.

Workup

  1. customThe white precipitate formed during the reaction
  2. filtrationwas filtered off
  3. washwashed with ethyl acetate
  4. washThe combined filtrate and washing
  5. concentrationwere concentrated
  6. dissolutionThe residual oil was dissolved in acetone (6 mL)
  7. stirringAfter stirring at room temperature for 1 h
  8. customthe reaction was quenched with water (25 mL)
  9. extractionextracted with ethyl acetate (4×)
  10. dry with materialThe combined extracts were dried over sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-2106854c17ff427186e3924a739f0876
Source dataset
uspto-grants-2013_11
Patent number
US08575114B2

Reaction notes

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