Dimethylformamide → HCID 86209319, compound

HRID 1991040Notes

Reaction equation

HRID 1991040 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 3 d. 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 10 d 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, 47.1 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. stirringthe resulting slurry stirred for 10 d at rt
  5. filtrationFiltration and concentration of the filtrate in vacuo
  6. customgave a crude oil which
  7. customwas purified by chromatography (SiO2, 30% EtOAc:hexanes)

Sources & evidence

ORD record
ord-90f8f12190b541fcb219ee581721c352
Source dataset
uspto-grants-2010_01
Patent number
US07645770B2

Reaction notes

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