Hydrochloric Acid → HCID 58098583, compound

HRID 2382504Notes

Reaction equation

HRID 2382504 reaction equation
[CH2:1]([C:4]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([OH:12])=[C:6]([N:13]=[N:14][C:15]2[CH:20]=[C:19]([Cl:21])[CH:18]=[CH:17][C:16]=2[N+:22]([O-])=O)[CH:5]=1)[CH:2]=[CH2:3].[OH-].[Na+].C(S(O)=O)(N)=N.Cl>O.C(O)C>[CH2:1]([C:4]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([OH:12])=[C:6]([N:13]2[N:22]=[C:16]3[CH:17]=[CH:18][C:19]([Cl:21])=[CH:20][C:15]3=[N:14]2)[CH:5]=1)[CH:2]=[CH2:3]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium Hydroxide2×HCID 61274Thiourea dioxideHCID 135993593HCID 135993593, compound

Product 1

HCID 58098583HCID 58098583, compoundYield 20%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent2×

Conditions

Temperature
80 °C

Procedure

In a 1 L round bottom flask equipped with a magnetic stirrer, addition funnel, powder addition funnel, and nitrogen inlet was added 4-allyl-2-((5-chloro-2-nitrophenyl)diazenyl)-6-methoxyphenol (27.9, 80.2 mmol) from Example 2 and 300 ml absolute ethanol. NaOH (19.3 g, 483 mmol) was dissolved in 140 ml deionized water and approximately one-fourth by volume was added dropwise to the reaction mixture. The reaction mixture was heated to 80° C. and formamidinesulfinic acid (Aldrich, 26.0 g, 241 mmol) was added slowly and concurrently with the remaining sodium hydroxide solution over 30 minutes. The reaction mixture was poured into 3 L deionized water and acidified to pH 4 with 1 N HCl. The yellow solid was dried for 20 hours at 42° C. and then purified by dissolving in hot toluene and then filtering out the dark impurities. The filtrate was concentrated down and purified via recrystallizions in ethanol and diethyl ether to give the pure product (5 g, 20%). 1H NMR (CDCl3) delta: 11.03 (s, 1H, phenol OH), 7.94 (s, 1H, Ar—H benzotriazole ring, 4-position), 7.89 (m, 1H, Ar—H benzotriazole ring, 7-position), 7.80 (s, 1H, Ar—H phenol, 5-position), 7.44 (m, 1H, Ar—H benzotriazole ring, 6-position), 6.81 (s, 1H, Ar—H phenol, 3-position), 6.00 (m, 1H, HC═CH2), 5.16 (m, 2H, HC═CH2), 3.97 (s, 3H, CH3O), 3.43 (d, 2H, Ar—CH2).

Workup

  1. customIn a 1 L round bottom flask equipped with a magnetic stirrer, addition funnel, powder addition funnel, and nitrogen inlet
  2. additionapproximately one-fourth by volume was added dropwise to the reaction mixture
  3. additionThe reaction mixture was poured into 3 L
  4. customThe yellow solid was dried for 20 hours at 42° C.
  5. custompurified
  6. dissolutionby dissolving in hot toluene
  7. filtrationfiltering out the dark impurities
  8. concentrationThe filtrate was concentrated down
  9. custompurified via recrystallizions in ethanol

Sources & evidence

ORD record
ord-b47c37e90cf44c17bdc3dda04d8683f2
Source dataset
uspto-grants-2012_09
Patent number
US08262947B2

Reaction notes

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