3,5-Di-tert-butyl-4-hydroxybenzoic acid → HCID 9996322, compound

HRID 466046Notes

Reaction equation

HRID 466046 reaction equation
C(Cl)(=O)C(Cl)=O.[CH3:7][C:8]([C:11]1[CH:12]=[C:13]([CH:17]=[C:18]([C:21]([CH3:24])([CH3:23])[CH3:22])[C:19]=1[OH:20])[C:14](O)=[O:15])([CH3:10])[CH3:9].[NH2:25][NH:26][C:27]([NH2:29])=[S:28]>C(Cl)Cl.CN(C)C=O.O1CCCC1>[CH3:7][C:8]([C:11]1[CH:12]=[C:13]([CH:17]=[C:18]([C:21]([CH3:24])([CH3:23])[CH3:22])[C:19]=1[OH:20])[C:14]([NH:25][NH:26][C:27](=[S:28])[NH2:29])=[O:15])([CH3:10])[CH3:9]

Participants

7

Reactant 3

HCID 150073,5-Di-tert-butyl-4-hydroxybenzoic acidHCID 65578Oxalyl chlorideHCID 2723789Thiosemicarbazide

Product 1

HCID 9996322HCID 9996322, compoundYield 92.2%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Oxalyl chloride (11.5 g, 0.091 mole) is added dropwise to a stirred 0° C. solution of 3,5-bis(1,1-dimethyethyl)-4-hydroxybenzoic acid (15.0 g, 0.059 mole) in methylene chloride (120 ml) and N,N-dimethylformamide (0.5 ml). After one hour, the solvent is removed in vacuo. The residue is dissolved in tetrahydrofuran (70 ml) and added dropwise to a stirred 0° C. suspension of thiosemicarbazide (10.9 g, 0.120 mole) in tetrahydrofuran (300 ml). After the addition is complete the mixture is allowed to warm to room temperature and stir 18 hours. The mixture is concentrated in vacuo and the residue filtered through a plug of flash silica gel using a 1:1 ethyl acetate/heptane mixture as eluent. Concentration and trituration with 1:1 isopropyl ether/hexane yielded 17.6 g (19.4 g theor., 91%) of 2-[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzoyl]hydrazinecarbothioamide, mp 210°-211° C.

Workup

  1. customthe solvent is removed in vacuo
  2. dissolutionThe residue is dissolved in tetrahydrofuran (70 ml)
  3. additionadded dropwise to a stirred 0° C.
  4. additionAfter the addition
  5. concentrationThe mixture is concentrated in vacuo
  6. filtrationthe residue filtered through a plug of flash silica gel using a 1:1 ethyl acetate/heptane mixture as eluent
  7. concentrationConcentration and trituration with 1:1 isopropyl ether/hexane

Sources & evidence

ORD record
ord-cf4047ca37cf4616a2cf62ae576fb88e
Source dataset
uspto-grants-1992_10
Patent number
US05155122

Reaction notes

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