Hydrochloric Acid → HCID 86707303, compound

HRID 873502Notes

Reaction equation

HRID 873502 reaction equation
BrC(CCCCCC)CCC[C:6]1[C:18]2[NH:17][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]=2[CH:9]=[CH:8][CH:7]=1.[CH2:25]([Li])[CH2:26][CH2:27][CH3:28].[B:30]([O:35]C)(OC)[O:31]C.Cl>O.C1COCC1>[CH2:28]([N:17]1[C:18]2[CH:6]=[CH:7][CH:8]=[C:9]([B:30]([OH:35])[OH:31])[C:10]=2[C:11]2[C:16]1=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:27][CH2:26][CH2:25][CH2:10][CH2:18][CH2:6][CH2:7][CH2:8][CH3:9]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 86707304HCID 86707304, compoundHCID 178418339Butyllithium

Product 1

HCID 86707303HCID 86707303, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-30 °C

Procedure

By using the standard procedure, to a dry 100 mL two-neck round-bottom flask containing 4-bromodecylcarbazole 16 (3.86 g, 10 mmol) and dry THF (50 mL) was dropwise added 1.6 M of n-butyl lithium (10 mL, 15 mmol) under N2 at −78° C. while maintaining a good stirring. After stirring for 1 h, trimethyl borate (2.0 mL, 18 mmol) was added in one portion, and then the mixture was stirred for 1 h at −78° C. Water and HCl (3M) were in turn added when the mixture was naturally warmed to −30° C. Then the reaction mixture was poured into water wad extracted with ethyl acetate (3×50 mL). The combined organic phase was dried with anhydrous Na2SO4, filtered and evaporated to dryness under 35° C. The crude product was then loaded on silica gel column and eluted with dichloromethane and petroleum ether/ethyl acetate affording a pale-white solid (3.6 g, 68%). 1H NMR (400 MHz, DMSO-d6, δ) 8.59 (s, 1H), 8.10 (d, J=7.6 Hz, 1H), 7.93-7.88 (m, 3H), 7.59-7.52 (m, 2H), 7.45-7.41 (m, 1H), 7.22-7.18 (m, 1H), 4.39-4.37 (m, 2H), 1.76-1.74 (m, 2H), 1.25-1.16 (m, 14H), 0.84 (t, J=7.4 Hz, 3H). 13C NMR (100 MHz, DMSO-d6, δ) 141.6, 140.1, 131.8, 125.5, 122.3, 121.5, 119.9, 118.9, 109.3, 108.3, 42.2, 31.3, 28.9, 28.8, 28.7, 28.6, 28.5, 26.5, 22.1, 13.9. MS (FAB): m/z (M+).

Workup

  1. customat −78° C.
  2. temperaturewhile maintaining a good stirring
  3. stirringthe mixture was stirred for 1 h at −78° C
  4. additionadded when the mixture
  5. extractionwad extracted with ethyl acetate (3×50 mL)
  6. dry with materialThe combined organic phase was dried with anhydrous Na2SO4
  7. filtrationfiltered
  8. customevaporated to dryness under 35° C
  9. washeluted with dichloromethane and petroleum ether/ethyl acetate affording a pale-white solid (3.6 g, 68%)

Sources & evidence

ORD record
ord-327f243460684a3abe33c0f179189eef
Source dataset
uspto-grants-2015_03
Patent number
US08975419B2

Reaction notes

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