Dimethylformamide → HCID 86209319, compound

HRID 1815051Notes

Reaction equation

HRID 1815051 reaction equation
[O:1]=[S:2]1(=[O:11])[CH2:7][CH2:6][CH:5]([C:8](O)=[O:9])[CH2:4][CH2:3]1.CN(C=O)C.C(Cl)(=O)C(Cl)=O.[CH2:23]([O:25][C:26]#[CH:27])[CH3:24]>C(Cl)Cl.C1COCC1.C(N(CC)CC)C>[CH2:26]([O:25][C:23]1[C:5]2([CH2:6][CH2:7][S:2](=[O:11])(=[O:1])[CH2:3][CH2:4]2)[C:8](=[O:9])[CH:24]=1)[CH3:27]

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 61239Ether, ethyl ethynylHCID 65578Oxalyl chlorideHCID 1491755Tetrahydro-2H-thiopyran-4-carboxylic acid 1,1-dioxide

Product 1

HCID 86209319HCID 86209319, compoundYield 67%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

A solution of 1,1-dioxo-hexahydro-1λ6-thiopyran-4-carboxylic acid (10.2 g, 57.3 mmol) [prepared according to the procedure of Org. Prep. Proc. Int. 1977, 94] and DMF (0.3 ml) in DCM (120 ml) at rt, was treated dropwise with oxalyl chloride and the resulting slurry stirred for 3d. The crude reaction was then concentrated in vacuo to give an oil which was re-dissolved in THF (100 ml), treated with ethoxyacetylene (10 ml, 50% w/w) and triethylamine (10 ml) and the resulting slurry stirred for 10d at rt. Filtration and concentration of the filtrate in vacuo gave a crude oil which was purified by chromatography (SiO2, 30% EtOAc:hexanes) to give the title compound as a yellow oil (8.9 g, 38.6 mmol, 67%). δH (CDCl3, 300K) 4.88 (1H, s), 4.27 (2H, q, J 7.1 Hz), 3.44-3.37 (2H, m), 3.13-3.05 (2H, m), 2.47-2.40 (2H, m), 2.35-2.29 (2H, m), 1.48 (3H, t, J 7.1 Hz); m/z (ES+, 70V) 230.9 (MH+).

Workup

  1. customThe crude reaction
  2. concentrationwas then concentrated in vacuo
  3. customto give an oil which
  4. filtrationFiltration and concentration of the filtrate in vacuo
  5. customgave a crude oil which
  6. customwas purified by chromatography (SiO2, 30% EtOAc:hexanes)

Sources & evidence

ORD record
ord-6bad974257d448669f4ff32d4b9dfd94
Source dataset
uspto-grants-2005_04
Patent number
US06878718B2

Reaction notes

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