Triethylamine → HCID 86738020, compound

HRID 371351Notes

Reaction equation

HRID 371351 reaction equation
[CH3:1][C:2]1([CH3:14])[CH2:7][O:6][P:5]([NH:9][C:10]([CH3:13])([CH3:12])[CH3:11])(=[O:8])[O:4][CH2:3]1.C([Li])CCC.[S:20](Cl)Cl.[CH3:23]/[C:24](/[S:31][CH3:32])=[N:25]\[O:26][C:27]([NH:29][CH3:30])=[O:28].C(N(CC)CC)C>O1CCCC1.CCCCCC.C(O)(C)C>[CH3:11][C:10]([N:9]([P:5]1(=[O:8])[O:4][CH2:3][C:2]([CH3:14])([CH3:1])[CH2:7][O:6]1)[S:20][CH2:30][NH:29][C:27]([O:26][N:25]=[C:24]([S:31][CH3:32])[CH3:23])=[O:28])([CH3:13])[CH3:12]

Participants

9

Reactant 5

HCID 8471TriethylamineHCID 25353Sulfur dichlorideHCID 5353758(E)-MethomylHCID 108228551,3,2-Dioxaphosphorinan-2-amine, N-(1,1-dimethylethyl)-5,5-dimethyl-, 2-oxideHCID 178418339Butyllithium

Product 1

HCID 86738020HCID 86738020, compound

Reagents, catalysts & solvents 3

HCID 3776IsopropanolSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent2×

Procedure

To a slurry of N-(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinan-2-yl)-1,1-dimethylethanamine (15.7 g., 70.8 mmoles) in tetrahydrofuran (50 ml.) at -5° is added over a ten minute period a solution of n-butyl lithium in hexane (46 ml. of 1.6M; 74 mmoles) with rapid stirring under dry nitrogen. This is stirred for 60 minutes at -5° and then transferred under dry nitrogen to an addition funnel and added over a 30 minute period to a solution of freshly distilled sulfur dichloride in tetrahydrofuran (25 ml.) at -5° with stirring. Stirring is continued for two hours at -5° and then filtered under dry nitrogen. The filter cake is washed with tetrahydrofuran (50 ml.) and the filtrates combined and concentrated in vacuo at ≤35°. The residue is redissolved in tetrahydrofuran (75 ml.), cooled to -5°, solid cuprous chloride (0.3 g.) added at once followed immediately by the addition of a solution of methomyl (11.5 g.; 70.8 mmoles) and triethylamine (9.8 ml., 70.8 mmoles) with stirring under dry nitrogen. About four minutes are required. Stirring is continued for two hours at -5°. The reaction mixture is then concentrated in vacuo at ≤45° and the residue taken up in methylene chloride (500 ml.) and washed with ice-water (2×300 ml.). The organic phase is vacuum filtered through celite and dried (anhydrous sodium sulfate). It is then concentrated in vacuo at ≤45° giving 28 g. of viscous oil. Preliminary absorption chromatography on silica gel using 2:1 ethyl acetate:Skellysolve B gives 15 g. of yellow oil. Chromatography of this material on silica gel using 1:4 isopropanol:Skellysolve B gives 4.4 g. (15% yld) as a white crystalline solid; MP 133.5°-134.5° (recrystallized from ethylacetate).

Workup

  1. stirringThis is stirred for 60 minutes at -5°
  2. customtransferred under dry nitrogen to an addition funnel
  3. stirringwith stirring
  4. stirringStirring
  5. filtrationfiltered under dry nitrogen
  6. washThe filter cake is washed with tetrahydrofuran (50 ml.)
  7. concentrationconcentrated in vacuo at ≤35°
  8. dissolutionThe residue is redissolved in tetrahydrofuran (75 ml.)
  9. temperaturecooled to -5°
  10. additionsolid cuprous chloride (0.3 g.) added
  11. stirringwith stirring under dry nitrogen
  12. waitAbout four minutes are required
  13. stirringStirring
  14. waitis continued for two hours at -5°
  15. concentrationThe reaction mixture is then concentrated in vacuo at ≤45°
  16. washwashed with ice-water (2×300 ml.)
  17. filtrationfiltered through celite
  18. dry with materialdried (anhydrous sodium sulfate)
  19. concentrationIt is then concentrated in vacuo at ≤45°
  20. customgiving 28 g
  21. customPreliminary absorption chromatography on silica gel using 2:1 ethyl acetate
  22. customSkellysolve B gives 15 g
  23. customMP 133.5°-134.5° (recrystallized from ethylacetate)

Sources & evidence

ORD record
ord-c4ab924394db4697b7ec200db1bb1b26
Source dataset
uspto-grants-1985_07
Patent number
US04531006

Reaction notes

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