Diisopropylethylamine → HCID 86689289, compound

HRID 537311Notes

Reaction equation

HRID 537311 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].CCN([CH:18]([CH3:20])[CH3:19])C(C)C.[CH2:21]([O:23][C:24]1[CH:25]=[C:26]([CH:32]=[CH:33][CH:34]=1)[O:27][CH2:28][C:29](Cl)=[O:30])[CH3:22].[C:35]([O-:38])(O)=O.[Na+]>C(Cl)Cl>[CH2:21]([O:23][C:24]1[CH:25]=[C:26]([CH:20]=[CH:18][CH:19]=1)[O:27][CH2:28][C:35]([O:8][C:5]1[CH:6]=[CH:7][C:2]([NH:1][C:29](=[O:30])[CH2:28][O:27][C:26]2[CH:32]=[CH:33][CH:34]=[C:24]([O:23][CH2:21][CH3:22])[CH:25]=2)=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1)=[O:38])[CH3:22]

Participants

6

Reactant 4

HCID 81531DiisopropylethylamineHCID 516892Sodium BicarbonateHCID 37588824-Amino-3-NitrophenolHCID 86689279HCID 86689279, compound

Product 1

HCID 86689289HCID 86689289, compoundYield 58%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A 1 L 3-neck flask fitted with a stir-bar, addition funnel, and an Ar inlet was charged with 4-amino-3-nitrophenol (10.1 g, 65.6 mmol) and CH2Cl2 (250 mL). To the resultant suspension cooled in an ice bath, was added iPr2NEt (33.8 g, 45.6 mL, 262 mmol) forming a deep red solution. Acid chloride 47a (32.4 g, 151 mmol) in CH2Cl2 (250 mL) was then added over 30 min. The mixture stirred overnight at rt. Saturated NaHCO3 (300 mL) was added, and the organic phase was washed with saturated NaHCO3 (300 mL) and brine (200 mL). The solution was filtered through phase separation paper and concentrated in vacuo to 36 g of a yellow-brown solid. The solid was triturated with EtOAc:hexanes 1:1 (150 mL), filtered, pressed with rubber dam, and rinsed with EtOAc:hexanes 1:1 (2×25 mL). The material dried to give 19.4 g of 62b as a yellow solid (58%). 1H NMR (300 MHz, CDCl3): δ 11.58 (s, 1H), 8.99 (d, 1H), 8.08 (d, 1H), 7.49 (dd, 1H), 7.33-7.18 (m, 2H), 6.71-6.48 (m, 6H), 4.89 (s, 2H), 4.66 (s, 2H), 4.06 (qt, 2H), 4.03 (qt, 2H), 1.43 (t, 3H), 1.42 (t, 3H) ppm. HPLC analysis (10:10:80 H2O:A1:MeOH) showed a purity of 93% with a retention time of 11.0 min.

Workup

  1. customA 1 L 3-neck flask fitted with a stir-bar, addition funnel
  2. customforming a deep red solution
  3. washthe organic phase was washed with saturated NaHCO3 (300 mL) and brine (200 mL)
  4. filtrationThe solution was filtered through phase separation paper
  5. concentrationconcentrated in vacuo to 36 g of a yellow-brown solid
  6. customThe solid was triturated with EtOAc:hexanes 1:1 (150 mL)
  7. filtrationfiltered
  8. washrinsed with EtOAc:hexanes 1:1 (2×25 mL)
  9. customThe material dried

Sources & evidence

ORD record
ord-9db1789d4fd04075a84144babea20c81
Source dataset
uspto-grants-2014_10
Patent number
US08859780B2

Reaction notes

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