Hydrochloric Acid → HCID 135993593, compound

HRID 2382503Notes

Reaction equation

HRID 2382503 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:8]=1)[NH2:7].Cl.N([O-])=O.[Na+].S(=O)(=O)(O)[NH2:18].[OH-].[Na+].[CH2:24]([C:27]1[CH:32]=[C:31]([O:33][CH3:34])[C:30]([OH:35])=[C:29](CO)[CH:28]=1)[CH:25]=[CH2:26]>O.C(O)C>[CH2:24]([C:27]1[CH:32]=[C:31]([O:33][CH3:34])[C:30]([OH:35])=[C:29]([N:18]=[N:7][C:6]2[CH:8]=[C:2]([Cl:1])[CH:3]=[CH:4][C:5]=2[N+:9]([O-:11])=[O:10])[CH:28]=1)[CH:25]=[CH2:26]

Participants

9

Reactant 6

HCID 313Hydrochloric Acid2×HCID 5987Sulfamic AcidHCID 14798Sodium Hydroxide3×HCID 742185-Chloro-2-nitroanilineHCID 10867203Benzenemethanol, 2-hydroxy-3-methoxy-5-(2-propenyl)-2×HCID 23668193Sodium Nitrite

Product 1

HCID 135993593HCID 135993593, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent5×

Conditions

Temperature
-10 °C

Procedure

In a 1000 ml 3-neck round bottom flask equipped with a magnetic stirrer was added 5-chloro-2-nitroaniline (Acros Organics, 29.9 g, 173 mmol), concentrated aqueous HCl (36.5-38.0%, 75 ml), 150 ml deionized water, and 150 ml absolute ethanol. The suspension was cooled to −10° C. and a solution of sodium nitrite (Sigma-Aldrich, 12.7 g, 184 mmol) in 50 ml water was added dropwise over 30 minutes at −10° C. The reaction mixture was stirred for 1 hour and 324 mg sulfamic acid (Aldrich) was added. After 10 minutes of stirring the solids were filtered out and the cold solution was set aside. A NaOH solution was prepared by dissolving NaOH (Aldrich, 37.7 g, 944 mmol) in 120 ml deionized water. Approximately one fourth of the sodium hydroxide solution was added dropwise to a solution of 4-allyl-2-(hydroxymethyl)-6-methoxyphenol from Example 1 in 100 ml water and 300 ml absolute ethanol. The diazonium mixture and remaining NaOH solution were concurrently added dropwise over 1 hr to the 4-allyl-2-(hydroxymethyl)-6-methoxyphenol solution at −10° C. The resulting dark mixture was stirred at 0° C. for 1 hour and ambient temperature for 2 hours. The contents were poured into 3 liters deionized water and the pH was adjusted to 5 using 1 N HCl. The solid was filtered and dried at 50° C. for 64 hours using P2O5 drying agent to afford 28 g (46%) that was used in the next step without further purification.

Workup

  1. customIn a 1000 ml 3-neck round bottom flask equipped with a magnetic stirrer
  2. stirringAfter 10 minutes of stirring the solids
  3. filtrationwere filtered out
  4. stirringThe resulting dark mixture was stirred at 0° C. for 1 hour and ambient temperature for 2 hours
  5. additionThe contents were poured into 3 liters
  6. filtrationThe solid was filtered
  7. customdried at 50° C. for 64 hours
  8. customto afford 28 g (46%) that
  9. customwas used in the next step without further purification

Sources & evidence

ORD record
ord-449b7f74437240bba217bf17653fe0b4
Source dataset
uspto-grants-2012_09
Patent number
US08262947B2

Reaction notes

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