Triphenylphosphine → 1,3-Dichloro-5,6,8a,9-tetrahydro-8H-7,10-dioxa-2,4,4b-triaza-phenanthrene

HRID 334139Notes

Reaction equation

HRID 334139 reaction equation
CC(OC(/N=N/C(OC(C)C)=O)=O)C.[Cl:15][C:16]1[N:21]=[C:20]([Cl:22])[C:19](O)=[C:18]([N:24]2[CH2:29][CH2:28][O:27][CH2:26][CH:25]2[CH2:30][OH:31])[N:17]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCOCC1>[Cl:22][C:20]1[C:19]2[O:31][CH2:30][CH:25]3[N:24]([CH2:29][CH2:28][O:27][CH2:26]3)[C:18]=2[N:17]=[C:16]([Cl:15])[N:21]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 866673574-(2,6-dichloro-5-hydroxy-4-pyrimidinyl)-3-Morpholinemethanol

Product 1

HCID 866673581,3-Dichloro-5,6,8a,9-tetrahydro-8H-7,10-dioxa-2,4,4b-triaza-phenanthreneYield 38.2%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A mixture of [4-(2,6-dichloro-5-methoxy-pyrimidin-4-yl)-morpholin-3-yl]-methanol (614 mg, 2.09 mmol) and lithium chloride (246 mg, 5.80 mmol) in anhydrous DMF (5 mL) was heated at 160° C. for 10 mins in a microwave reactor, then concentrated in vacuo to give 2,4-dichloro-6-(3-hydroxymethyl-morpholin-4-yl)-pyrimidin-5-ol. DIAD (452 μL, 2.3 mmol) was added to a solution of 2,4-dichloro-6-(3-hydroxymethyl-morpholin-4-yl)-pyrimidin-5-ol (2 mmol) and triphenyl phosphine (603 mg, 2.3 mmol) in 1,4-dioxane (5 mL) and the mixture stirred at RT for 1 h, then concentrated in vacuo. The resulting residue was purified by column chromatography (SiO2, 0 to 50% ethyl acetate in cyclohexane) affording 1,3-Dichloro-5,6,8a,9-tetrahydro-8H-7,10-dioxa-2,4,4b-triaza-phenanthrene (200 mg, 37%). LCMS (method A): RT=2.91 min, [M+H]−=262/264.

Workup

  1. concentrationconcentrated in vacuo
  2. customThe resulting residue was purified by column chromatography (SiO2, 0 to 50% ethyl acetate in cyclohexane)

Sources & evidence

ORD record
ord-e3beb31d0e19414093267c259cc6fa1c
Source dataset
uspto-grants-2014_11
Patent number
US08883799B2

Reaction notes

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