3-Chloro-1,1-diethoxypropane → HCID 71294611, compound

HRID 2274716Notes

Reaction equation

HRID 2274716 reaction equation
[CH2:1]([CH:18]([CH:38]([OH:57])[CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46]/[CH:47]=[CH:48]\[CH2:49]/[CH:50]=[CH:51]\[CH2:52][CH2:53][CH2:54][CH2:55][CH3:56])[CH:19]([OH:37])[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26]/[CH:27]=[CH:28]\[CH2:29]/[CH:30]=[CH:31]\[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7]/[CH:8]=[CH:9]\[CH2:10]/[CH:11]=[CH:12]\[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17].C(O[CH:61](OCC)[CH2:62][CH2:63]Cl)C.CC1C=CC(S([O-])(=O)=O)=CC=1.C1C=[CH:83][NH+:82]=[CH:81]C=1.C([O-])(O)=O.[Na+]>C1(C)C=CC=CC=1>[CH2:20]([CH:19]1[CH:18]([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7]/[CH:8]=[CH:9]\[CH2:10]/[CH:11]=[CH:12]\[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH:38]([CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46]/[CH:47]=[CH:48]\[CH2:49]/[CH:50]=[CH:51]\[CH2:52][CH2:53][CH2:54][CH2:55][CH3:56])[O:57][CH:61]([CH2:62][CH2:63][N:82]([CH3:83])[CH3:81])[O:37]1)[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26]/[CH:27]=[CH:28]\[CH2:29]/[CH:30]=[CH:31]\[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36]

Participants

6

Reactant 4

HCID 962173-Chloro-1,1-diethoxypropaneHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 516892Sodium BicarbonateHCID 86678089HCID 86678089, compound

Product 1

HCID 71294611HCID 71294611, compoundYield 58.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of the diol (6Z,9Z,29Z,32Z)-19-((8Z,11Z)-heptadeca-8,11-dien-1-yl)octatriaconta-6,9,29,32-tetraene-18,20-diol (11) (832 mg, 1.05 mmol) and 3-chloropropionaldehyde diethylacetal (351 μL, 2.10 mmol) in toluene (10 mL) was treated with PPTS (100 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 (15 mL, 5.6M in EtOH), treated with tetrabutylammonium iodide (25 mg), transferred to a sealed reaction vessel and heated (80° C., 20 h). Once complete the yellow solution was concentrated and the residue was subjected to chromatography (100% EtOAc) to yield 2-(4,5-di((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 (12) (203 mg, 22% over 2 steps) as a pale yellow oil. Rf 0.41 (8% CH3OH—CHCl3); 1H NMR (400 MHz, CDCl3) 5.43-5.29 (m, 12H), 4.88-4.83 (m, 0.5H), 4.64-4.58 (m, 0.5H), 3.89-3.82 (m, 0.5H), 3.56-3.50 (m, 1H), 3.35-3.27 (m, 0.5H), 2.78 (app. t, 6H), 2.65-2.50 (m, 2H), 2.46-2.31 (m, 6H), 2.11-2.03 (m, 12H), 1.92-1.78 (m, 2H), 1.65-1.11 (m, 57H), 0.90 (t, 9H). FW 876.51, C60H109NO2.

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 (15 mL, 5.6M in EtOH)
  8. additiontreated with tetrabutylammonium iodide (25 mg)
  9. customtransferred to a sealed reaction vessel
  10. temperatureheated (80° C., 20 h)
  11. concentrationwas concentrated

Sources & evidence

ORD record
ord-ecf6ec2f22664d03bff6ad51b7942a8d
Source dataset
uspto-grants-2015_09
Patent number
US09126966B2

Reaction notes

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