Triphenylphosphine → 4-(6-(Bromomethyl)-2-chloropyrido[3,2-D]pyrimidin-4-YL)morpholine

HRID 2091832Notes

Reaction equation

HRID 2091832 reaction equation
[Cl:1][C:2]1[N:3]=[C:4]([N:14]2[CH2:19][CH2:18][O:17][CH2:16][CH2:15]2)[C:5]2[N:11]=[C:10]([CH2:12]O)[CH:9]=[CH:8][C:6]=2[N:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:39]N1C(=O)CCC1=O.C1C(=O)N(Br)C(=O)C1.C1C(=O)N(Br)C(=O)C1>ClCCl>[Br:39][CH2:12][C:10]1[CH:9]=[CH:8][C:6]2[N:7]=[C:2]([Cl:1])[N:3]=[C:4]([N:14]3[CH2:19][CH2:18][O:17][CH2:16][CH2:15]3)[C:5]=2[N:11]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 67184N-bromobutanimideHCID 53488008(2-Chloro-4-morpholinopyrido[3,2-d]pyrimidin-6-yl)methanolHCID 86627431NBS N-bromosuccinimide

Product 1

HCID 584049784-(6-(Bromomethyl)-2-chloropyrido[3,2-D]pyrimidin-4-YL)morpholineYield 87.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

(2-Chloro-4-morpholinopyrido[3,2-d]pyrimidin-6-yl)methanol 6 (2.0 g, 0.0071 mol) and 40 mL dichloromethane were cooled to 0° C. and triphenylphosphine (2.2 g, 0.0085 mol) was added. The solution was recooled to 0° C. and N-Bromosuccinimide NBS (1.5 g, 0.0085 mol) was added in one portion. The heterogeneous mixture became homogeneous yellow upon NBS addition. After 30 mins, the progress was checked by tlc. The reaction mixture again became heterogeneous yellow mixture and was stirred overnight at room temperature. A check by LC/MS showed the reaction was complete. The reaction mixture was concentrated to dryness, taken up in MeOH, and filtered to yield 2.13 gm (87%) of 4-(6-(bromomethyl)-2-chloropyrido[3,2-d]pyrimidin-4-yl)morpholine 7 as a yellow solid. More product 7 precipitated from the mother liquor, filtered, and dried to give a second batch (133 mg) of product 7. Analyzed and confirmed by LC/MS.

Workup

  1. customwas recooled to 0° C.
  2. concentrationThe reaction mixture was concentrated to dryness
  3. filtrationfiltered

Sources & evidence

ORD record
ord-9d090dbe16fb49828ab3bc82f2b364d5
Source dataset
uspto-grants-2013_05
Patent number
US08440651B2

Reaction notes

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