Diisopropylamine → HCID 15550613, compound

HRID 1250097Notes

Reaction equation

HRID 1250097 reaction equation
[C:1]([O:5][C:6](=[O:18])[CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15][OH:16])[C:10]=1[CH3:17])([CH3:4])([CH3:3])[CH3:2].C([N-]C(C)C)(C)C.[Li+].C(NC(C)C)(C)C.C([Li])CCC.[C:39]1([N:45]([C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)[C:46](Cl)=[O:47])[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1>O1CCCC1>[C:1]([O:5][C:6](=[O:18])[CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15][O:16][C:46](=[O:47])[N:45]([C:49]2[CH:50]=[CH:51][CH:52]=[CH:53][CH:54]=2)[C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[C:10]=1[CH3:17])([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 65741N,N-Diphenylcarbamic chlorideHCID 2724682Lithium diisopropylamideHCID 11817603HCID 11817603, compoundHCID 178418339Butyllithium

Product 1

HCID 15550613HCID 15550613, compoundYield 73.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-50 °C

Procedure

A solution of (3-hydroxymethyl-2-methylphenoxy)acetic acid te/t-butyl ester (80.1 g, 318 mmol) dissolved in tetrahydrofuran (400 mL) was cooled to −50° C. and treated with lithium diisopropylamide (325 mmol) freshly prepared from diisopropylamine (49 mL) and 2.5M n-butyllithium (130 mL) in tetrahydrofuran (100 mL). After about 10 minutes at −50° C., a solution of diphenylcarbamyl chloride (80.8 g, 350 mmol) dissolved in tetrahydrofuran (100 mL) was added. The entire reaction mixture was stirred for an additional 30 minutes and then allowed to warm to room temperature over a period of 3 hours. The solution was evaporated in vacuo, poured into dilute hydrochloric acid, and extracted with diethyl ether. The organic layer was dried over brine, evaporated, and purified by silica gel chromatography, eluting with acetone/hexane (1:5→1:3), to give {3-[(diphenylcarbamoyloxy)-methyl]-2-methylphenoxy}acetic acid tert-butyl ester as a white solid (104.1 g, 73%).

Workup

  1. additionwas added
  2. customThe entire reaction mixture
  3. temperatureto warm to room temperature over a period of 3 hours
  4. customThe solution was evaporated in vacuo
  5. additionpoured into dilute hydrochloric acid
  6. extractionextracted with diethyl ether
  7. dry with materialThe organic layer was dried over brine
  8. customevaporated
  9. custompurified by silica gel chromatography
  10. washeluting with acetone/hexane (1:5→1:3)

Sources & evidence

ORD record
ord-8183a46002584dc48c541ddd456c63e9
Source dataset
uspto-grants-2002_01
Patent number
US06335459B1

Reaction notes

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