3-Butyn-1-OL → HCID 86584412, compound

HRID 1581931Notes

Reaction equation

HRID 1581931 reaction equation
[Cl:1][C:2]1[N:7]=[C:6](Cl)[CH:5]=[CH:4][N:3]=1.[CH2:9]([OH:13])[CH2:10][C:11]#[CH:12]>C(N(CC)CC)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[Cl:1][C:2]1[N:7]=[C:6]([C:12]#[C:11][CH2:10][CH2:9][OH:13])[CH:5]=[CH:4][N:3]=1

Participants

6

Reactant 2

HCID 135663-Butyn-1-OLHCID 775312,4-Dichloropyrimidine

Product 1

HCID 86584412HCID 86584412, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

2,4-Dicloropyrimidine (4.47 g, 0.03 M) was dissolved in triethylamine (250 ml) under argon. (Ph3P)2PdCl2 (420 mg, 0.006 M, CuI (28 mg, 0.00015 M) and 3-butyn-1-ol (2.36 ml, 0.03 M) were added and the mixture was stirred at ambient temperature for 18 hrs. After evaporation to dryness, water (250 ml), was added and extracted with dichloromethane. The combined organic phases were dried and evaporated to dryness. The residual oil was chromatographed, eluting with iso-hexane/ethyl acetate 1:1 to yield 4-(2 chloro-4-pyrimidyl)-3-butyn-1-ol as an oil (3.3 g) NMR (CDCl3) d 8.5, (d 1H); 7.3, (d 1H); 3.9, (t 2H); 2.8, (m 2H); 1.6, (s 1H). Mass Spec found MH+ 183. This material was hydrogenated as described above, but in the presence of 1 equivalent of triethylamine, to give the required saturated alcohol which was oxidised using the previously described Swern oxidation to give the required 4-(4-pyrimidyl)-butan-1-al. NMR CDCl3 d 9.8, (s 1H); 9.1; (s 1H); 8.5, (d 1H); 7.1, (d 1H); 2.8, (t 2H); 2.5, (t 2H); 2.1, (m 2H). Mass spec found MH− 149.

Workup

  1. customAfter evaporation to dryness, water (250 ml)
  2. additionwas added
  3. extractionextracted with dichloromethane
  4. customThe combined organic phases were dried
  5. customevaporated to dryness
  6. customThe residual oil was chromatographed
  7. washeluting with iso-hexane/ethyl acetate 1:1

Sources & evidence

ORD record
ord-03a938b03c9c47319cf5c754973ea1f3
Source dataset
uspto-grants-2004_05
Patent number
US06734183B2

Reaction notes

Loading…