Hydrochloric Acid → HCID 137078800, compound

HRID 1482726Notes

Reaction equation

HRID 1482726 reaction equation
[Br:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][C:11]1[CH:17]=[CH:16][C:14]([NH2:15])=[CH:13][CH:12]=1.Cl.[N:19]([O-])=O.[Na+].[C:23]([OH:32])(=[O:31])[C:24]1[C:25](=[CH:27][CH:28]=[CH:29][CH:30]=1)[OH:26]>O.[OH-].[Na+].CCOC(C)=O>[Br:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][C:11]1[CH:17]=[CH:16][C:14]([N:15]=[N:19][C:29]2[CH:28]=[CH:27][C:25]([OH:26])=[C:24]([CH:30]=2)[C:23]([OH:32])=[O:31])=[CH:13][CH:12]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 338Salicylic Acid2×HCID 23668193Sodium NitriteHCID 122449335HCID 122449335, compound

Product 1

HCID 137078800HCID 137078800, compoundYield 40.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolventHCID 14798Sodium HydroxideSolvent2×

Conditions

Temperature
0 °C

Procedure

4-(8-Bromooctyloxy)aniline (2.30 g, 7.7 mmol) was suspended in a mixture of concentrated hydrochloric acid (mL) and water (75 mL). The resulting solution was cooled to 0° C. in an ice bath. Sodium nitrite (0.83 g, 12.1 mmol) in water (10 mL) was added dropwise to the reaction mixture with rapid stirring over about 20 min. The reaction mixture was stirred for an additional 20 min while salicylic acid (3.68 g, 26.6 mmol) was dissolved in an aqueous NaOH solution (8.0 g NaOH in 100 mL H2O). This basic salicylic acid solution was vigorously stirred at 0° C. and the solution of the diazonium salt added dropwise. The pH was maintained at 12-14 by adding 8M NaOH solution. After the addition was complete, the solution was allowed to warm to room temperature and was stirred for an additional 30 min. The mixture was diluted with EtOAc (100 mL), washed with water (3×20 mL), 5% NaHCO3 (2×20 mL), brine, dried over Na2SO4, and filtered. Volatiles were removed in vacuo and the residue subjected to column chromatography on silica gel 60 (230-400 mesh) using EtOAc and methanol (98:2) as elutant. The product (1.40 g, 3.1 mmol, 40%) was obtained as a red-brown solid, mp 180-182° C. 1H NMR (500 MHz, CDCl3) δ 1.25-1.44 (m, 8H), 1.72-1.85 (m, 4H), 3.38 (t, J=Hz, 2H), 3.93 (t, J=6.5 Hz, 2H), 6.86-6.91 (m, 3H), 7.69 (d, J=Hz, 2H), 7.84 (dd, J=10 Hz, Hz, 1H), 8.42 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 25.8, 25.9, 28.0, 28.5, 29.0, 29.1, 29.2, 31.7, 32.7, 33.9, 35.2, 68.1, 113.3, 118.4, 123.1, 124.0, 126.1, 127.5, 144.9, 146.5, 161.0; HRMS (ESI) calculated for C21H26BrN2O4 (M+H)+449.1070, observed 449.1063.

Workup

  1. temperatureThe pH was maintained at 12-14
  2. additionAfter the addition
  3. temperatureto warm to room temperature
  4. stirringwas stirred for an additional 30 min
  5. washwashed with water (3×20 mL), 5% NaHCO3 (2×20 mL), brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. customVolatiles were removed in vacuo

Sources & evidence

ORD record
ord-214f4efec7a94424a8379f138638ec11
Source dataset
uspto-grants-2016_08
Patent number
US09415110B1

Reaction notes

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