3-Chloro-1,1-diethoxypropane → HCID 71294568, compound

HRID 2274712Notes

Reaction equation

HRID 2274712 reaction equation
[CH3:1][CH2:2][CH2:3][CH2:4][CH2:5]/[CH:6]=[CH:7]\[CH2:8]/[CH:9]=[CH:10]\[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH:18]([OH:40])[CH2:19][CH:20]([OH:39])[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28]/[CH:29]=[CH:30]\[CH2:31]/[CH:32]=[CH:33]\[CH2:34][CH2:35][CH2:36][CH2:37][CH3:38].C(O[CH:44](OCC)[CH2:45][CH2:46]Cl)C.CC1C=CC(S([O-])(=O)=O)=CC=1.C1C=[CH:66][NH+:65]=[CH:64]C=1.C([O-])(O)=O.[Na+]>C1(C)C=CC=CC=1>[CH2:17]([CH:18]1[CH2:19][CH:20]([CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28]/[CH:29]=[CH:30]\[CH2:31]/[CH:32]=[CH:33]\[CH2:34][CH2:35][CH2:36][CH2:37][CH3:38])[O:39][CH:44]([CH2:45][CH2:46][N:65]([CH3:66])[CH3:64])[O:40]1)[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]/[CH:10]=[CH:9]\[CH2:8]/[CH:7]=[CH:6]\[CH2:5][CH2:4][CH2:3][CH2:2][CH3:1]

Participants

6

Reactant 4

HCID 962173-Chloro-1,1-diethoxypropaneHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 516892Sodium BicarbonateHCID 86678087HCID 86678087, compound

Product 1

HCID 71294568HCID 71294568, compoundYield 457.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of the diol (6Z,9Z,29Z,32Z)-octatriaconta-6,9,29,32-tetraene-18,20-diol (7) (940 mg, 1.68 mmol) and 3-chloropropionaldehyde diethylacetal (563 μL, 3.36 mmol) in toluene (15 mL) was treated with PPTS (50 mg) and heated (80° C., 2 h). After cooling (rt) the reaction mixture was poured into sat. aq. NaHCO3, extracted with EtOAc, washed with brine, dried (Na2SO4), filtered and concentrated. The crude product was dissolved in a solution of (CH3)2NH (25 mL, 5.6M in EtOH), transferred to a sealed reaction vessel and heated (80° C., 16 h). Once complete the yellow solution was concentrated and the residue was subjected to chromatography (100% EtOAc) to yield 2-(4-((8Z,11Z)-heptadeca-8,11-dien-1-yl)-6-((9Z,12Z)-octadeca-9,12-dien-1-yl)-1,3-dioxan-2-yl)-N,N-dimethylethanamine (8) (585 mg, 54% over 2 steps) as a pale yellow oil. Rf 0.5 (10% CH3OH—CH2Cl2); 1H NMR (400 MHz, CDCl3) 5.46-5.29 (m, 8H), 4.85 (t, 0.5H), 4.59 (t, 0.5H), 4.08-3.98 (m, 0.5H), 3.80-3.70 (m, 0.5H), 3.60-3.50 (m, 1H), 2.78 (app. t, 4H), 2.50-2.37 (m, 2H), 2.32-2.21 (m, 6H), 2.13-2.02 (m, 8H), 1.88-1.72 (m, 2H), 1.63-1.22 (m, 40H), 0.91 (t, 6H). FW 643.47, C43H79NO2.

Workup

  1. temperatureAfter cooling (rt) the reaction mixture
  2. extractionextracted with EtOAc
  3. washwashed with brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. dissolutionThe crude product was dissolved in a solution of (CH3)2NH (25 mL, 5.6M in EtOH)
  8. customtransferred to a sealed reaction vessel
  9. temperatureheated (80° C., 16 h)
  10. concentrationwas concentrated

Sources & evidence

ORD record
ord-fd4a340b06494d71a7926d39facf1d22
Source dataset
uspto-grants-2015_09
Patent number
US09126966B2

Reaction notes

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