5,5-Diethyl-1,3-dioxane-2-thione → 3,3-Diethyl-1,5,7,16-tetraoxadispiro[5.2.5.2]hexadec-11-ene

HRID 990154Notes

Reaction equation

HRID 990154 reaction equation
C([Sn]1(CCCC)[O:10][CH2:9][C:8]2([CH2:15][CH2:14][CH:13]=[CH:12][CH2:11]2)[CH2:7][O:6]1)CCC.[CH2:20]([C:22]1([CH2:29][CH3:30])[CH2:27][O:26][C:25](=S)[O:24][CH2:23]1)[CH3:21]>>[CH2:20]([C:22]1([CH2:29][CH3:30])[CH2:27][O:26][C:25]2([O:6][CH2:7][C:8]3([CH2:15][CH2:14][CH:13]=[CH:12][CH2:11]3)[CH2:9][O:10]2)[O:24][CH2:23]1)[CH3:21]

Participants

3

Reactant 2

HCID 187669565,5-Diethyl-1,3-dioxane-2-thioneHCID 187669573,3-Dibutyl-2,4-dioxa-3-stannaspiro[5.5]undec-8-ene

Product 1

HCID 226347393,3-Diethyl-1,5,7,16-tetraoxadispiro[5.2.5.2]hexadec-11-eneYield 94%

Procedure

To the above solution of 3,3-dibutyl-2,4-dioxa-3-stannaspiro[5.5]undec-8-ene 2 was added 5,5-diethyl-1,3-dioxane-2-thione 1 (10.39 g, 59.6 mmol) in several small portions at room temperature over a period of 20 min. The resulting mixture was allowed to stir at room temperature for 24 hours. The reaction was monitored by TLC (silica gel, 25% ether/hexanes). The reaction mixture was then concentrated under reduced pressure and the residue taken up with ethyl ether (white suspension formed upon standing). The ether solution was filtered and concentrated under reduced pressure to give light yellowish oil. The crude material was purified by column chromatography (silica gel, 10-15% ethyl ether/hexanes). The desired 3,3-diethyl-1,5,7,16-tetraoxadispiro[5.2.5.2]hexadec-11-ene (DECH 3) was obtained as colorless oil in 94% yield. 1H-NMR (CDCl3, 300 MHz) δ5.68-5.58 (m, 2H), 3.74-3.68 (4s, 8H), 2.08-1.94 (m, 4H), 1.63-1.56 t, 2H, J=6.6 Hz), 1.46-1.37 (q, 4H, J=7.5 Hz), 0.84-0.76 (t, 6H, J=7.5 Hz); —C-NMR (CDCl3, 75 MHz) δ126.03, 124.16, 114.68, 70.03, 69.32, 34.27, 30.50, 26.44, 23.14, 21.30, 13.92, 7.01; IR (neat) (cm−1) 3020, 2960, 2880, 1640, 1450, 1360, 1250, 1220, 1200, 1185, 1160, 1105, 1020, 995, 920, 730, 655; Anal. Calcd for C16H26O4: C, 68.06%; H, 9.28%; Found: C, 68.20%; H, 9.59%.

Workup

  1. concentrationThe reaction mixture was then concentrated under reduced pressure
  2. filtrationThe ether solution was filtered
  3. concentrationconcentrated under reduced pressure
  4. customto give light yellowish oil
  5. customThe crude material was purified by column chromatography (silica gel, 10-15% ethyl ether/hexanes)

Sources & evidence

ORD record
ord-a3d57e522a544230992e490f78c941fd
Source dataset
uspto-grants-2002_10
Patent number
US06458865B2

Reaction notes

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