Lithium Hydroxide → HCID 86665166, compound

HRID 1094490Notes

Reaction equation

HRID 1094490 reaction equation
[NH2:1][C:2]([NH2:4])=[S:3].C[O:6][C:7]([C:9]1[C:18]2[C:13](=[CH:14][C:15]([CH2:19][C:20](=O)[CH2:21][C:22](OCC)=[O:23])=[CH:16][CH:17]=2)[CH:12]=[CH:11][CH:10]=1)=[O:8].[Li+].[OH-]>C(O)(C)(C)C.[OH-].[Na+].CCOC(C)=O>[O:23]=[C:22]1[NH:4][C:2](=[S:3])[NH:1][C:20]([CH2:19][C:15]2[CH:14]=[C:13]3[C:18](=[CH:17][CH:16]=2)[C:9]([C:7]([OH:8])=[O:6])=[CH:10][CH:11]=[CH:12]3)=[CH:21]1

Participants

7

Reactant 3

HCID 3939Lithium HydroxideHCID 2723790ThioureaHCID 66640348HCID 66640348, compound

Product 1

HCID 86665166HCID 86665166, compound

Reagents, catalysts & solvents 3

HCID 6386tert-ButanolSolventHCID 8857Ethyl AcetateSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
100 °C

Procedure

3.46 g (45.4 mMol) thiourea are added to a solution of 29.7 mMol 6-(3-ethoxycarbonyl-2-oxo-propyl)-naphthalene-1-carboxylic acid methyl ester in 25 ml tert-butanol. Then 13.3 g (119 mMol) potassium tert-butyrate are added (exothermic). After 50 min, the mixture is heated for 4.5 h in an oil bath of 100° C. Cooling to rt gives an almost solid mixture, which is redissolved by addition of 59 ml of a 1 M aq. solution of LiOH and stirring during 40 min. This solution is diluted with 500 ml of a 0.33 M solution of NaOH and EtOAc. The organic phase is separated off, washed with 300 ml of a 0.33 M solution of NaOH and discarded. The aq. phases are acidified by addition of 2 N HCl (pH=3), the precipitated product filtered off, washed with 0.001 N HCl and dried in vacuo at 80° C. The crude material is stirred in a boiling mixture of 0.6 l CH3CN, 60 ml EtOAc, 120 ml MeOH and 120 ml THF. Filtration of the hot suspension then leads to the title compound: m.p.: 334-337° C.

Workup

  1. temperatureCooling to rt
  2. customgives an almost solid mixture, which
  3. customThe organic phase is separated off
  4. washwashed with 300 ml of a 0.33 M solution of NaOH
  5. additionThe aq. phases are acidified by addition of 2 N HCl (pH=3)
  6. filtrationthe precipitated product filtered off
  7. washwashed with 0.001 N HCl
  8. customdried in vacuo at 80° C
  9. stirringThe crude material is stirred in a boiling mixture of 0.6 l CH3CN, 60 ml EtOAc, 120 ml MeOH and 120 ml THF
  10. filtrationFiltration of the hot suspension

Sources & evidence

ORD record
ord-a3c3401e92ad4f3986142deadab65d9f
Source dataset
uspto-grants-2012_03
Patent number
US08133886B2

Reaction notes

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