Triphenylphosphine → 7-Cyclopropyl-2,4-dichloro-6,7-dihydro-[1,4]dioxino[2,3-d]pyrimidine

HRID 528469Notes

Reaction equation

HRID 528469 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]([Cl:8])[C:5](O)=[C:4]([O:10][C:11]2([CH2:14][OH:15])[CH2:13][CH2:12]2)[N:3]=1.[C:16]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[CH:13]1([CH:11]2[O:10][C:4]3[N:3]=[C:2]([Cl:1])[N:7]=[C:6]([Cl:8])[C:5]=3[O:15][CH2:14]2)[CH2:12][CH2:16]1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 867117522,4-Dichloro-6-(1-hydroxymethyl-cyclopropoxy)-pyrimidin-5-ol

Product 1

HCID 867117537-Cyclopropyl-2,4-dichloro-6,7-dihydro-[1,4]dioxino[2,3-d]pyrimidineYield 72%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2,4-dichloro-6-(1-hydroxymethyl-cyclopropoxy)-pyrimidin-5-ol (135 mg, 0.54 mmol) and triphenylphosphine (180 mg, 0.65 mmol) in THF (8 mL) was added DIAD (128 μL, 0.65 mmol) and the mixture stirred at RT for 30 minutes, then concentrated in vacuo. The resulting residue was purified by column chromatography (SiO2, gradient 0-25% ethyl acetate in cyclohexane) affording 7-Cyclopropyl-2,4-dichloro-6,7-dihydro-[1,4]dioxino[2,3-d]pyrimidine as a white solid (90 mg, 72%). 1H NMR (400 MHz, CDCl3): δ 4.30 (2H, s), 1.36-1.29 (2H, m), 1.01-0.95 (2H, m).

Workup

  1. concentrationconcentrated in vacuo
  2. customThe resulting residue was purified by column chromatography (SiO2, gradient 0-25% ethyl acetate in cyclohexane)

Sources & evidence

ORD record
ord-8600446a29054a17b8be197c6ff3e37a
Source dataset
uspto-grants-2016_05
Patent number
US09346817B2

Reaction notes

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