Trifluoroacetic acid → HCID 21268834, compound

HRID 1194777Notes

Reaction equation

HRID 1194777 reaction equation
S1C2SCC(C(O)=O)C[C:4]=2[CH:3]=[CH:2]1.[C:13]1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=C[CH:14]=1.C(O[C:35]([NH:37][CH:38]1[CH2:43][S:42][C:41]2[S:44][CH:45]=[CH:46][C:40]=2[CH2:39]1)=O)(C)(C)C.[C:47](O[C:52]([NH:54][CH:55]1[CH2:60][S:59][C:58]2[S:61][C:62]([C:64]([CH3:67])([CH3:66])[CH3:65])=[CH:63][C:57]=2[CH2:56]1)=O)(C)([CH3:49])[CH3:48].F[C:69](F)(F)[C:70](O)=O>C(O)(C)(C)C.C(N(CC)CC)C>[C:64]([C:62]1[S:61][C:58]2[S:59][CH2:60][CH:55]([N:54]([CH2:52][CH2:13][CH3:14])[CH2:2][CH2:3][CH3:4])[CH2:56][C:57]=2[CH:63]=1)([CH3:65])([CH3:66])[CH3:67].[CH2:48]([N:37]([CH2:35][CH2:69][CH3:70])[CH:38]1[CH2:43][S:42][C:41]2[S:44][CH:45]=[CH:46][C:40]=2[CH2:39]1)[CH2:47][CH3:49]

Participants

9

Reactant 5

HCID 6422Trifluoroacetic acidHCID 199401P,P-Diphenylphosphinic azideHCID 21268832HCID 21268832, compoundHCID 21268846HCID 21268846, compoundHCID 70390489HCID 70390489, compound

Product 2

HCID 21268834HCID 21268834, compoundHCID 21268838HCID 21268838, compound

Reagents, catalysts & solvents 2

HCID 6386tert-ButanolSolventHCID 8471TriethylamineSolvent

Procedure

A mixture of 9.15 g of 5,6-dihydro-4H-thieno[2,3-b]- thiopyran-5-carboxylic acid, 10 ml of diphenylphosphoryl azide and 6.5 ml of triethylamine in 200 ml of t-butanol is refluxed for 5 hours. After removal of the solvent in vacuo the residue is dissolved in ether and washed with 1N sodium hydroxide. After drying over magnesium sulfate the solvent is removed in vacuo to yield a mixture of N-t-butoxycarbonyl-5,6-dihydro-4H-thieno[2,3-b]-thiopyran-5-amine and N-t-butoxycarbonyl-2-t-butyl-5,6-dihydro-4H-thieno-[2,3-b]thiopyran-5-amine. The mixture is treated with 25 ml of trifluoroacetic acid and refluxed for 15 minutes. After removal of solvent the residue is treated with 40 ml of N-propyl iodide in 100 ml of toluene in the presence of 27 g of sodium carbonate in 150 ml of water. The resulting mixture is refluxed with stirring for 3 days. The solvent is removed from the organic layer and the residue is chromatographed on silica gel to afford 2-t-butyl-N,N-dipropyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-5-amine (hydrochloride salt, m.p. 227°-233°), and N,N-dipropyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-5-amine (hydrochloride salt, m.p. 163°-167°) of Example 2.

Workup

  1. temperatureis refluxed for 5 hours
  2. customAfter removal of the solvent in vacuo the residue
  3. dissolutionis dissolved in ether
  4. washwashed with 1N sodium hydroxide
  5. dry with materialAfter drying over magnesium sulfate the solvent
  6. customis removed in vacuo
  7. customto yield
  8. temperaturerefluxed for 15 minutes
  9. customAfter removal of solvent the residue
  10. additionis treated with 40 ml of N-propyl iodide in 100 ml of toluene in the presence of 27 g of sodium carbonate in 150 ml of water
  11. temperatureThe resulting mixture is refluxed
  12. customThe solvent is removed from the organic layer
  13. customthe residue is chromatographed on silica gel

Sources & evidence

ORD record
ord-1a44c0f180e04501b54edd10a7ab7d68
Source dataset
uspto-grants-1989_03
Patent number
US04816474

Reaction notes

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