4-Aminobenzyl alcohol → (4-((4-((3-Azidopropyl)(methyl)amino)-2-methoxyphenyl)diazenyl)phenyl)methanol

HRID 526272Notes

Reaction equation

HRID 526272 reaction equation
NC1C=CC(CO)=CC=1.N([O-])=O.[Na+].[N:14]([CH2:17][CH2:18][CH2:19][N:20]([CH3:29])[C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([O:27][CH3:28])[CH:22]=1)=[N+:15]=[N-:16].CC([O-])=O.[Na+].[OH:35][CH2:36][C:37]1[CH:42]=[CH:41][C:40]([N:43]=[N:44]C2C=CC(O)=CC=2)=[CH:39][CH:38]=1>CCO.O.Cl.CCO>[N:14]([CH2:17][CH2:18][CH2:19][N:20]([CH3:29])[C:21]1[CH:26]=[CH:25][C:24]([N:44]=[N:43][C:40]2[CH:41]=[CH:42][C:37]([CH2:36][OH:35])=[CH:38][CH:39]=2)=[C:23]([O:27][CH3:28])[CH:22]=1)=[N+:15]=[N-:16]

Participants

9

Reactant 5

HCID 693314-Aminobenzyl alcoholHCID 517045Sodium AcetateHCID 23668193Sodium NitriteHCID 61974743HCID 61974743, compoundHCID 1362366624-{2-[4-(Hydroxymethyl)phenyl]hydrazinylidene}cyclohexa-2,5-dien-1-one

Product 1

HCID 86675389(4-((4-((3-Azidopropyl)(methyl)amino)-2-methoxyphenyl)diazenyl)phenyl)methanol

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolventHCID 19096565Water ethanolSolvent

Conditions

Temperature
0 °C

Procedure

4-aminobenzylalcohol (0.275 g, 2.24 mmol) and NaNO2 (0.16 g, 2.35 mmol) were dissolved in EtOH/water (4.5+3.0 mL=7.5 mL), to which 2 N HCl solution (4.5 mL) was added at 0° C. and reaction mixture stirred at 0° C. for 1 hour. Compound 17 (0.45 g, 2.04 mmol) in EtOH was added followed by addition of NaOAc (0.15 g) at 0° C. and mixture stirred for 6 hours at room temperature. The remaining procedure was followed as described for compound 1 to obtain compound 19. Yield: 0.58 g (81%). 1H NMR (500 MHz, CDCl3): δ 1.87 (tt, 2H, J=6.5, 13.0 Hz, Hc), 2.31 (bs, 1H, OH), 3.03 (s, 3H, NCH3, Ha), 3.36 (tt, 2H, J=3.0 & 6.5 Hz, Hd), 3.49 (tt, 2H, J=3.0 & 7.5 Hz, Hb), 4.00 (s, 3H, OMe), 4.67 (s, 2H, Hj), 6.20-6.25 (m, 1H, Hg), 6.30-6.33 (m, 1H, He), 7.35-7.42 (m, 2H, Hi), 7.70-7.80 (m, 3H, Hh, Hf); 13C NMR (125 MHz, CDCl3): δ 26.46 (Cc), 38.62 (Ca), 48.82 (Cd), 49.45 (Cb), 55.20 (OCH3), 64.77 (Cj), 94.94 (Cg), 104.65 (Ce), 118.18 (Cf), 122.33 (Ci), 127.29 (Ch), 133.54 (Cl), 141.85 (Cn), 152.85 (Cm), 152.91 (Ck), 159.19 (Co). EI-MS: [M+H]+ C18H23N6O2 calcd 355.18, obsd 355.16.

Workup

  1. additionwas added at 0° C.
  2. customreaction mixture
  3. stirringmixture stirred for 6 hours at room temperature

Sources & evidence

ORD record
ord-a5535bdc231f4f419cf762221097f8e2
Source dataset
uspto-grants-2016_05
Patent number
US09345781B2

Reaction notes

Loading…