Tetrahydrofuran → N-(2-methylphenyl)-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydronaphthalen-1-amine

HRID 928637Notes

Reaction equation

HRID 928637 reaction equation
Br[C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[CH:10]([NH:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[CH3:19])[CH2:9][CH2:8][CH2:7]2.C1COCC1.[Li]CCCC.[Li]C(C)(C)C.C(O[B:39]1[O:43][C:42]([CH3:45])([CH3:44])[C:41]([CH3:47])([CH3:46])[O:40]1)(C)C>CCCCC>[CH3:46][C:41]1([CH3:47])[C:42]([CH3:45])([CH3:44])[O:43][B:39]([C:2]2[CH:3]=[CH:4][CH:5]=[C:6]3[C:11]=2[CH:10]([NH:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[CH3:19])[CH2:9][CH2:8][CH2:7]3)[O:40]1

Participants

7

Reactant 5

HCID 8028TetrahydrofuranHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 118072604(8-Bromo-1,2,3,4-tetrahydronaphthalen-1-yl)(2-methylphenyl)amineHCID 178418306HCID 178418306, compoundHCID 178418339Butyllithium

Product 1

HCID 123397142N-(2-methylphenyl)-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydronaphthalen-1-amine

Reagents, catalysts & solvents 1

HCID 8003PentaneSolvent

Procedure

To a solution of 30.8 g (97.5 mmol) (8-bromo-1,2,3,4-tetrahydronaphthalen-1-yl)(2-methylphenyl)amine in 500 ml THF 39.0 ml (97.5 mmol) of 2.5M nBuLi in hexanes was added at −80° C. in argon atmosphere. The resulting mixture and stirred for 1 h at this temperature, and then 125 ml (200 mmol) of 1.7M tBuLi in pentane was added. The obtained mixture was stirred for 1 h at the same temperature. Further on, 36.3 g (195 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. After that the cooling bath was removed, and the resulting mixture was stirred for 1 h at room temperature. Then, 10 ml of water was added, and this mixture was evaporated to dryness. The residue was diluted with 500 ml of water, and the title product was extracted with 3×200 ml of ethyl acetate. The combined organic extract was dried over Na2SO4 and evaporated to dryness. Yield 24.8 g (70%) of a yellow oil. Anal. Calc. For C23H30BNO2: C, 76.04; H, 8.32; N, 3.86. Found: C, 76.29; H, 8.60; N, 3.59. 1H NMR (CDCl3): δ 7.68-7.69 (m, 1H, 7-H in tetrahydronaphtalene); 7.24-7.33 (m, 3H, 5,6-H in tetrahydronaphtalene and 5-H in 2-methylphenyl); 7.13 (m, 1H, 3-H in 2-methylphenyl); 7.04 (m, 1H, 6-H in 2-methylphenyl); 6.74-6.77 (m, 1H, 4-H in 2-methylphenyl); 5.38-5.39 (m, 1H, 1-H in tetrahydronaphtalene); 3.78 (m, 1H, NH); 2.85-3.02 (m, 2H, 4-H in tetrahydronaphtalene); 2.21-2.26 (m, 1H, 3- or 3′-H in tetrahydronaphtalene); 2.12 (s, 3H, CH3 in 2-methylphenyl); 1.81-2.00 (m, 3H, 3′- or 3-H and 2-H in tetrahydronaphtalene); 1.20 (s, 6H, CH3 in BPin); 1.13 (s, 6H, CH3 in BPin).

Workup

  1. stirringThe obtained mixture was stirred for 1 h at the same temperature
  2. customAfter that the cooling bath was removed
  3. stirringthe resulting mixture was stirred for 1 h at room temperature
  4. additionThen, 10 ml of water was added
  5. customthis mixture was evaporated to dryness
  6. additionThe residue was diluted with 500 ml of water
  7. extractionthe title product was extracted with 3×200 ml of ethyl acetate
  8. extractionThe combined organic extract
  9. dry with materialwas dried over Na2SO4
  10. customevaporated to dryness

Sources & evidence

ORD record
ord-d2e61ecf5b544fafb39d79b4119efbff
Source dataset
uspto-grants-2016_03
Patent number
US09290519B2

Reaction notes

Loading…