Allyl Alcohol → 2-Chloro-4-allyloxy-5[(6-methyl-3-pyridinyl)methyl]pyrimidine

HRID 223293Notes

Reaction equation

HRID 223293 reaction equation
[Cl:1][C:2]1[N:7]=[C:6](Cl)[C:5]([CH2:9][C:10]2[CH:11]=[N:12][C:13]([CH3:16])=[CH:14][CH:15]=2)=[CH:4][N:3]=1.[Na].[CH2:18]([OH:21])[CH:19]=[CH2:20]>O1CCCC1>[Cl:1][C:2]1[N:7]=[C:6]([O:21][CH2:18][CH:19]=[CH2:20])[C:5]([CH2:9][C:10]2[CH:11]=[N:12][C:13]([CH3:16])=[CH:14][CH:15]=2)=[CH:4][N:3]=1

Participants

5

Reactant 3

HCID 7858Allyl Alcohol2×HCID 5360545SodiumHCID 133743332,4-Dichloro-5-[(6-methyl-3-pyridinyl)methyl]pyrimidine

Product 1

HCID 201959762-Chloro-4-allyloxy-5[(6-methyl-3-pyridinyl)methyl]pyrimidineYield 88%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 118.0 g (0.465 mol) of 2,4-dichloro-5-[(6-methyl-3-pyridinyl)methyl]pyrimidine from Example 1 in 200 ml of allyl alcohol and 300 ml of tetrahydrofuran at 0°-5° was added dropwise over 2 hours a solution of the sodium salt of allyl alcohol [generated from 22.4 g (0.465) of sodium hydride (50% oil dispersion) and 200 ml of allyl alcohol]. The mixture was stirred 30 minutes at 5°, warmed to room temperature and concentrated. The resulting oil was dissolved in 1 L of methylene chloride, washed with water, dried over sodium sulfate, filtered, and concentrated to give 112.0 g (0.0409 mol, 88%) of 2-chloro-4-allyloxy-5[(6-methyl-3-pyridinyl)methyl]pyrimidine as crystals: IR(Nujol) 2850, 2650, 1655, 1580, 1560 cm-1 ; 1H NMR(D6 -DMSO/CDCl3) δ2.45 (s, 3H), 3.85 (s, 2H), 4.90 (dd, 2H), 5.25 (dd, 1H), 5.34 (dd, 1H), 6.00 (m, 1H), 7.10 (d, 1H), 7.48 (dd, 1H), 8.30 (s, 1H), 8.35 (d, 1H).

Workup

  1. concentrationconcentrated
  2. dissolutionThe resulting oil was dissolved in 1 L of methylene chloride
  3. washwashed with water
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-f0af7a780ff24ed294c7d95307bf5560
Source dataset
uspto-grants-1982_10
Patent number
US04352933

Reaction notes

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