Boron tribromide → HCID 136121098, compound

HRID 508656Notes

Reaction equation

HRID 508656 reaction equation
C([C:3]1[C:8]([NH:9][CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:7][N:6]=[C:5]([C:16]2[CH:21]=[CH:20][C:19]([O:22]CC3C=CC=CC=3)=[C:18]([C:30]34[CH2:39][CH:34]5[CH2:35][CH:36]([CH2:38][CH:32]([CH2:33]5)[CH2:31]3)[CH2:37]4)[CH:17]=2)[N:4]=1)C.B(Br)(Br)Br>C(Cl)Cl>[C:30]12([C:18]3[CH:17]=[C:16]([C:5]4[N:6]=[CH:7][C:8]([NH:9][CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:3][N:4]=4)[CH:21]=[CH:20][C:19]=3[OH:22])[CH2:37][CH:36]3[CH2:38][CH:32]([CH2:33][CH:34]([CH2:35]3)[CH2:39]1)[CH2:31]2

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 89586761HCID 89586761, compound

Product 1

HCID 136121098HCID 136121098, compoundYield 102.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of ethyl 2-[3-(1-adamantyl)-4-benzyloxyphenyl]-5-(carbethoxymethylamino)pyrimidine (51 mg, 0.10 mmol), 1.0 M BBr3 (0.56 mmol) in CH2Cl2 (0.6 mL) and CH2Cl2 (1.4 mL) was stirred at −78° C. under argon for 2 h, quenched with H2O (10 mL) and extracted with EtOAc (100 mL). The extract was washed (water and brine) and dried. After solvent removal at reduced pressure, the residue was chromatographed (1:4 EtOAc/hexane) to give 41.6 mg (99%) of 2-[3-(1-adamantyl)-4-hydroxyphenyl]-5-(carbethoxymethylamino)pyrimidine as a pale-tan solid, mp 190° C. (dec). IR 3432, 2904, 1708, 1211 cm−1; 1H NMR (CDCl3) δ 1.32 (t, J=7.2 Hz, 3H, OCH2CH3), 1.79 (bs, 6H, AdCH2), 2.09 (bs, 3H, AdCH), 2.21 (m, 6H, AdCH2), 4.30 (q, J=7.2 Hz, 2H, OCH2CH3), 4.60 (m, 1H, NH), 4.72 (s, 2H, NHCH2CO), 5.85 (s, 1H, OH), 6.71 (d, J=8.4 Hz, 1H, 5′-ArH), 8.03 (dd, J=8.4 Hz, 2.1 Hz, 1H, 6′-ArH), 8.27 (d, J=2.1 Hz, 1H, 2′-ArH), 8.45 ppm (s, 2H, 4-ArH, 6-ArH). HRMS calcd C24H29N3O3 [M+H]+ 408.2287. found 408.2291.

Workup

  1. customquenched with H2O (10 mL)
  2. extractionextracted with EtOAc (100 mL)
  3. washThe extract was washed (water and brine)
  4. customdried
  5. customAfter solvent removal at reduced pressure
  6. customthe residue was chromatographed (1:4 EtOAc/hexane)

Sources & evidence

ORD record
ord-5bf76639073545e7b63892abdb23237a
Source dataset
uspto-grants-2015_08
Patent number
US09096544B2

Reaction notes

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