HCID 86674678, compound → HCID 86674680, compound

HRID 1523009Notes

Reaction equation

HRID 1523009 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15]/[C:16](/[C:22](/[CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][O:36][CH:37]1[CH2:42][CH2:41][CH2:40][CH2:39][O:38]1)=[CH:23]/[C:24]([O:26][CH3:27])=[O:25])=[CH:17]\[C:18]([O:20][CH3:21])=[O:19]>CO>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16](=[C:22]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][O:36][CH:37]1[CH2:42][CH2:41][CH2:40][CH2:39][O:38]1)[CH2:23][C:24]([O:26][CH3:27])=[O:25])[CH2:17][C:18]([O:20][CH3:21])=[O:19]

Participants

3

Reactant 1

HCID 86674678HCID 86674678, compound

Product 1

HCID 86674680HCID 86674680, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A flame-dried round-bottomed flask was charged with Mg° (15 equiv, 18.75 mmol, 456 mg) and equipped with a condenser. (2E,4E)-dimethyl 3,4-bis(8-((tetrahydro-2H-pyran-2-yl)oxy)octyl)hexa-2,4-dienedioate (1 equiv, 744 mg, 1.25 mmol) was added in MeOH (16 mL) and the reaction was stirred at rt. After ˜30 min, the reaction began refluxing and was left to reflux for ˜45 min upon which time the reaction was permitted to cool to it, quenched with sat. aq. NH4Cl (5 mL), diluted with Et2O (15 mL), and H2O (20 mL). The liquid was decanted into a separatory funnel and the remaining solid was washed several times with Et2O. The layers were separated and the aqueous layer extracted with Et2O (3×20 mL). The combined organic layers were washed with brine (30 mL), dried with Na2SO4 and concentrated in vacuo to afford Dimethyl 3,4-bis(8-((tetrahydro-2H-pyran-2-yl)oxy)octyl)hex-3-enedioate (565 mg crude mass, ˜90% pure by 1HNMR, 0.95 mmol, 76%) as an inseparable 2:1 mixture of isomers which was used in the next reaction without further purification. TLC Rf=0.41 (20% EtOAc/Hex); 1HNMR (500 MHz): δ 4.61-4.56 (2H), 3.91-3.85 (2H), 3.77-3.70 (2H), 3.67 (s, 4H), 3.66 (s, 2H), 3.54-3.47 (2H), 3.42-3.35 (2H), 3.12 (s, 2.7H), 3.11 (s, 1.3H), 2.16-2.07 (4H), 1.90-1.80 (2H), 1.76-1.69 (2H), 1.63-1.49 (12H), 1.40-1.24 (20H); 13CNMR (125 MHz): δ 172.4, 172.2, 130.7, 130.6, 98.9, 67.7, 62.4, 51.8, 37.6, 37.2, 33.3, 32.9, 30.8, 29.8, 29.71, 29.68, 29.49, 29.47, 28.3, 28.1, 26.2, 25.5, 19.7; FTIR: 2926, 2854, 1737, 1434, 1295, 1200, 1156, 1136, 1119, 1078, 1022, 988, 869, 814 cm−1; HRMS-ESI: calc. for C34H60NaO8(M+Na)+: 619.4186. found: 619.4174.

Workup

  1. additionA flame-dried round-bottomed flask was charged with Mg° (15 equiv, 18.75 mmol, 456 mg)
  2. customequipped with a condenser
  3. temperaturethe reaction began refluxing
  4. waitwas left
  5. temperatureto reflux for ˜45 min upon which time the reaction
  6. temperatureto cool to it
  7. customquenched with sat. aq. NH4Cl (5 mL)
  8. additiondiluted with Et2O (15 mL), and H2O (20 mL)
  9. customThe liquid was decanted into a separatory funnel
  10. washthe remaining solid was washed several times with Et2O
  11. customThe layers were separated
  12. extractionthe aqueous layer extracted with Et2O (3×20 mL)
  13. washThe combined organic layers were washed with brine (30 mL)
  14. dry with materialdried with Na2SO4
  15. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3fd05a1b8dcd40bfb5ad38e3986cdadd
Source dataset
uspto-grants-2015_07
Patent number
US09079835B2

Reaction notes

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