Pyridine → HCID 21517629, compound

HRID 1578900Notes

Reaction equation

HRID 1578900 reaction equation
O[CH:2]([N:10]1[CH:13]([S:14][CH2:15][C:16]#[C:17][CH3:18])[CH:12]([NH:19][C:20]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:11]1=[O:39])[C:3]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4].N1C=CC=CC=1.S(Cl)([Cl:48])=O>O1CCCC1.O1CCOCC1>[Cl:48][CH:2]([N:10]1[CH:13]([S:14][CH2:15][C:16]#[C:17][CH3:18])[CH:12]([NH:19][C:20]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)([C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)[C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:11]1=[O:39])[C:3]([O:5][C:6]([CH3:8])([CH3:7])[CH3:9])=[O:4]

Participants

6

Reactant 3

HCID 1049PyridineHCID 24386Thionyl ChlorideHCID 21517661HCID 21517661, compound

Product 1

HCID 21517629HCID 21517629, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 312751,4-DioxaneSolvent3×

Procedure

1-(1-Hydroxy-1-t-butoxycarbonylmethyl)-3-(triphenylmethylamino)-4-(but-2-ynylthio)azetidin-2-one (0.44g) was dissolved in a 1:1 mixture of dry tetrahydrofuran and dioxan (10ml) and the solution, under nitrogen, was cooled to -10°. Pyridine (0.2g) in dry dioxan (2.5ml) was added, followed by the dropwise addition of thionyl chloride (0.19ml) in dioxan (2.5ml) over 2-3 minutes. After a further 15 minutes the precipitated solid was filtered off and the filtrate evaporated to dryness. Dry toluene was added to the residue and decanted off from any solid. The organic solution was evaporated to dryness and re-evaporation from dry ether gave 1-(1-chloro-1-t-butoxycarbonylmethyl)-3-(triphenylmethylamino)-4-(but-2-ynylthio)azetidin-2-one as an amorphous solid (0.45g). νmax (CHCl3) 1775, 1740 cm-1. This chloride, without further purification was dissolved in ethanol-free chloroform and the solution, under nitrogen, was cooled in an ice-bath. m-chloroperbenzoic acid (0.16g) in chloroform was added dropwise over a few minutes. After a further 30 minutes the organic solution was washed with saturated aqueous sodium bicarbonate, then with brine, and finally dried and evaporated. Re-evaporation of the residue from dry ether gave 1-(1-chloro-1-t-butoxycarbonylmethyl)-3-(triphenylmethylamino)-4-(but-2-ynylthio)azetidin-2-one sulphoxide (as an amorphous solid νmax (CHCl3) 1785, 1740 cm-1. This sulphoxide, without further purification, was treated under nitrogen with triphenylphosphine (0.52g) and 2,6-dimethyl pyridine (0.125g) in dry dioxan (10ml) at 50° for 17 hours. The mixture was filtered and the filtrate evaporated to dryness. Chromatography on silica --H gave 1-(1-t-butoxycarbonyl-1-triphenylphosphoranylidenemethyl)-3-(triphenylmethylamino)-4-(but-2-ynylthio)azetidin-2-one sulphoxide (0.2g) as a white solid. νmax (CHCl3) 1760 (b), 1730 (b) cm-1.

Workup

  1. temperaturethe solution, under nitrogen, was cooled to -10°
  2. filtrationAfter a further 15 minutes the precipitated solid was filtered off
  3. customthe filtrate evaporated to dryness
  4. additionDry toluene was added to the residue
  5. customdecanted off from any solid
  6. customThe organic solution was evaporated to dryness and re-evaporation from dry ether

Sources & evidence

ORD record
ord-01e27fcb70bc4ae28a802baa9c493ede
Source dataset
uspto-grants-1976_02
Patent number
US03939157

Reaction notes

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