tert-Butanol → HCID 10494362, compound

HRID 849302Notes

Reaction equation

HRID 849302 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([C:16]([OH:18])=[O:17])[CH:11]=2)=[CH:6][CH:5]=1)([O-:3])=[O:2].C(Cl)(=O)C(Cl)=O.[C:25](O)([CH3:28])([CH3:27])[CH3:26].[Li]CCCC>C(Cl)Cl.CN(C=O)C.C1COCC1>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([C:16]([O:18][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:17])[CH:11]=2)=[CH:8][CH:9]=1)([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 6386tert-ButanolHCID 65578Oxalyl chlorideHCID 30139383-Biphenylcarboxylic acid, 4'-nitro-HCID 178418339Butyllithium

Product 1

HCID 10494362HCID 10494362, compoundYield 57%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 15 (1.215 g, 5 mmol) in 30 mL of methylene chloride was added oxalyl chloride (0.65 mL, 7.45 mmol) and one drop of DMF. The mixture was stirred until no further bubbling was observed. The clear solution was exaporated to dryness to give the crude acid chloride. To another flask containing 7.0 mL of tert-butanol was added n-BuLi (1.8 M in hexane, 2.8 mL, 5.04 mmol) under a water bath. The turbid solution was stirred for 5 min at room temperature and then the above acid chloride in 20 mL of THF was added through a dropping funnel. The mixture was stirred overnight before the solvents were evaporated. The residue was dissolved into methylene chloride and washed with 0.5 N NaOH. The organic layer was dried over MgSO4 and evaporated. The residue was recrystallized from methanol to give pale yellow crystals (851 mg, 57%). m.p. 110.5-111.0° C. 1H NMR (CDCl3) δ 8.32 (d, 7.8 Hz, 2H), 8.24 (s, 1H), 8.06 (d, 7.7 Hz, 1H), 7.77 (m, 3H), 7.56 (t, 7.7 Hz, 1H), 1.63 (s, 9H). 13C NMR (CDCl3) δ 165.1, 147.1, 146.5, 138.7, 132.8, 131.0, 129.6, 129.0, 128.2, 127.8, 124.0, 81.4, 28.0, LRMS (EI) for C17H17O4N 299 (M+, 20), 243 (70), 266 (30), 152 (25; HRMS (EI) calcd 299.1157, obsd 299.1192. Anal. (C17H17NO4) C, H, N.

Workup

  1. customno further bubbling
  2. customto give the crude acid chloride
  3. stirringThe turbid solution was stirred for 5 min at room temperature
  4. stirringThe mixture was stirred overnight before the solvents
  5. customwere evaporated
  6. dissolutionThe residue was dissolved into methylene chloride
  7. washwashed with 0.5 N NaOH
  8. dry with materialThe organic layer was dried over MgSO4
  9. customevaporated
  10. customThe residue was recrystallized from methanol

Sources & evidence

ORD record
ord-1ad270b257bd4ec9ba581e03c1c6ad73
Source dataset
uspto-grants-2000_01
Patent number
US06011175

Reaction notes

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