Diisopropylamine → HCID 14372112, compound

HRID 1382995Notes

Reaction equation

HRID 1382995 reaction equation
C([NH:4]C(C)C)(C)C.C([Li])CCC.CCCCCC.[CH3:19][C:20]1[N:25]=[CH:24][C:23]2[CH:26]=[CH:27][O:28][C:22]=2[CH:21]=1.O.O.O.C([O-])(=O)C.[Na+].N[O:38][S:39]([OH:42])(=O)=O>O1CCCC1.C(OCC)C>[S:39]([C:27]1[O:28][C:22]2[CH:21]=[C:20]([CH3:19])[N:25]=[CH:24][C:23]=2[CH:26]=1)(=[O:42])(=[O:38])[NH2:4]

Participants

9

Reactant 6

HCID 7912DiisopropylamineHCID 8058HexaneHCID 76284hydroxylamine-O-sulfonic acidHCID 14005231HCID 14005231, compoundHCID 23665404Sodium Acetate TrihydrateHCID 178418339Butyllithium

Product 1

HCID 14372112HCID 14372112, compoundYield 49%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of distilled diisopropylamine (7.6 ml, 59 mmol) in distilled tetrahydrofuran (60 ml), under a nitrogen atmosphere and cooled to -70° C., was added 1.6M butyl lithium in hexane (34.4 ml, 55 mmol). After stirring for 0.5 hour a solution of 6-methylfuro[3,2-c]pyridine (6.66 g, 50 mmol) in tetrahydrofuran (50 ml) was added dropwise. After stirring 1.5 hours, sulfur dioxide gas was bubbled over the reaction surface to give a tan precipitate. The reaction mixture was allowed to warm to room temperature and then diluted with diethyl ether and the precipitate collected by filtration. This lithium sulfinate salt (17.6 g) was air dried and then dissolved in water (90 ml). Sodium acetate trihydrate (29 g, 0.21 mol) and hydroxylamine-o-sulfonic acid (11.5 g, 0.10 mol) were added and the solution was stirred at room temperature for 20-25 hours as the product precipitated. This product was filtered and dissolved in ethyl acetate/methanol, dried over anhydrous sodium sulfate, and filtered through a charcoal pad. The evaporated residue was triturated with diethyl ether to give nearly pure product (5.19 g, 49% yield). Recrystallization from hot ethyl acetate containing a little methanol to effect initial dissolution afforded pure product, mp 233°-234.5° C.

Workup

  1. additionwas added dropwise
  2. customsulfur dioxide gas was bubbled over the reaction surface
  3. customto give a tan precipitate
  4. filtrationthe precipitate collected by filtration
  5. customdried
  6. dissolutiondissolved in water (90 ml)
  7. stirringthe solution was stirred at room temperature for 20-25 hours as the product
  8. customprecipitated
  9. filtrationThis product was filtered
  10. dissolutiondissolved in ethyl acetate/methanol
  11. dry with materialdried over anhydrous sodium sulfate
  12. filtrationfiltered through a charcoal pad
  13. customThe evaporated residue was triturated with diethyl ether

Sources & evidence

ORD record
ord-8dbf4ef4717e4fc483c82ed757c99170
Source dataset
uspto-grants-1989_02
Patent number
US04808595

Reaction notes

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