Diglyme → HCID 22822244, compound

HRID 1902547Notes

Reaction equation

HRID 1902547 reaction equation
[Cl-].[Li+].[BH4-].[Na+].COCCOCCOC.C[O:15][C:16]([C:18]1[N:19]=[CH:20][C:21]2[C:26]([CH:27]=1)=[C:25]([N:28]=[C:29]1[N:33]3[CH2:34][C:35]4[CH:36]=[CH:37][CH:38]=[CH:39][C:40]=4[CH2:41][C@H:32]3[CH2:31][S:30]1)[CH:24]=[CH:23][CH:22]=2)=O>O>[OH:15][CH2:16][C:18]1[N:19]=[CH:20][C:21]2[C:26]([CH:27]=1)=[C:25]([N:28]=[C:29]1[N:33]3[CH2:34][C:35]4[CH:36]=[CH:37][CH:38]=[CH:39][C:40]=4[CH2:41][C@H:32]3[CH2:31][S:30]1)[CH:24]=[CH:23][CH:22]=2

Participants

6

Reactant 4

HCID 8150DiglymeHCID 433294Lithium ChlorideHCID 4311764Sodium borohydrideHCID 22822255HCID 22822255, compound

Product 1

HCID 22822244HCID 22822244, compoundYield 45.9%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

Lithium chloride (1.01 g), sodium borohydride (0.91 g) and diglyme (diethylene glycol dimethyl ether) (100 cc) are mixed at 0° C. The mixture is stirred for 30 minutes at 0° C. and (S)-3-[(3-methoxycarbonylisoquinol-5-yl)imino]-1,5,10,10a-tetrahydrothiazolo[3,4-b]-isoquinoline (4.7 g) is added. Stirring is continued for 1 hour at 0° C. and then for 2 hours at 20° C. Water (1 liter) is added and the mixture is extracted with methylene chloride (3×150 cc). The organic extracts are combined, washed with water, dried over magnesium sulphate and filtered and the filtrate is concentrated to dryness under reduced pressure (40 mm Hg; 5.3 kPa) at 40° C. The residue is dissolved in methylene chloride (20 cc) and the solution is poured onto a column of diameter 3 cm, containing silica gel (120 g) in methylene chloride. Elution is carried out with an ethyl acetate/cyclohexane mixture (70/30 by volume), 300 cc fractions being collected. Fractions 7 to 11 are combined and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C. The residue is recrystallised from butyl acetate (100 cc). After filtration, washing with diisopropyl ether and drying, (S)-3-[(3-hydroxymethylisoquinol-5-yl)-imino]-1,5,10,10a-tetrahydrothiazolo[3,4-b]isoquinoline (2 g) is obtained, as a white solid, m.p.=210° C.

Workup

  1. stirringStirring
  2. waitis continued for 1 hour at 0° C.
  3. waitfor 2 hours at 20° C
  4. extractionthe mixture is extracted with methylene chloride (3×150 cc)
  5. washwashed with water
  6. dry with materialdried over magnesium sulphate
  7. filtrationfiltered
  8. concentrationthe filtrate is concentrated to dryness under reduced pressure (40 mm Hg; 5.3 kPa) at 40° C
  9. dissolutionThe residue is dissolved in methylene chloride (20 cc)
  10. additionthe solution is poured onto a column of diameter 3 cm
  11. additioncontaining silica gel (120 g) in methylene chloride
  12. washElution
  13. custombeing collected
  14. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C
  15. customThe residue is recrystallised from butyl acetate (100 cc)
  16. filtrationAfter filtration
  17. washwashing with diisopropyl ether
  18. customdrying

Sources & evidence

ORD record
ord-987efd0b43f44c94851ce677ac900f38
Source dataset
uspto-grants-1982_12
Patent number
US04363909

Reaction notes

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