Hydrazine hydrate (1:1) → HCID 66954115, compound

HRID 390085Notes

Reaction equation

HRID 390085 reaction equation
C(OC[N:10]1[C:18]2[C:17]([NH2:19])=[N:16][CH:15]=[N:14][C:13]=2[C:12]([CH2:20][NH:21][CH2:22][CH:23]2[CH2:28][O:27]C(C)(C)[O:25][CH:24]2[CH2:31][S:32][CH3:33])=[CH:11]1)C1C=CC=CC=1.C(O)(C(F)(F)F)=O.O.O.NN>[Pd]>[NH2:19][C:17]1[C:18]2[NH:10][CH:11]=[C:12]([CH2:20][NH:21][CH2:22][CH:23]([CH:24]([OH:25])[CH2:31][S:32][CH3:33])[CH2:28][OH:27])[C:13]=2[N:14]=[CH:15][N:16]=1

Participants

5

Reactant 3

HCID 24654Hydrazine hydrate (1:1)2×HCID 22392675Trifluoroacetic acid waterHCID 66953639HCID 66953639, compound

Product 1

HCID 66954115HCID 66954115, compoundYield 62.4%

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst2×

Procedure

The product of Example 9.3 (17 mg, 0.036 mmol) was treated with TFA/water (9:1 v/v, 1 mL). After 5 min the mixture was evaporated in vacuo. The residue was redissolved in methanolic ammonia (7M, 4 mL) and Pd-black (17 mg, 0.16 mmol) was added, followed by hydrazine hydrate (250 μL, 5.1 mmol). After 15 min more Pd-black (22 mg, 0.21 mmol) was added and again after further 15 min (55 mg, 0.52 mmol) and also hydrazine hydrate (0.5 mL, 10.2 mmol). Shortly after the mixture was filtered through flux calcined diatomaceous earth and evaporated. The residue was dissolved in MeOH (2 mL) and treated with Amberlyst® A-26(OH) ion exchange resin (˜1 g) for 5 min, the solution was filtered and evaporated in vacuo which gave the product as an oil (7 mg, 62%). 1H NMR (CD3OD) δ 8.16 (s, 1H), 7.48 (s, 1H), 3.97-3.80 (m, 2H), 3.79-3.61 (m, 2H), 3.16-3.05 (m, 1H), 2.85 (dd, J=6.0, 12.1, 1H), 2.79 (dd, J=6.7, 12.0 Hz, 1H), 2.66 (dd, J=4.8, 13.5 Hz, 1H), 2.56 (dd, J=8.0, 13.5 Hz, 1H), 2.11-1.88 (m, 4H). 13C NMR (CD3OD, referenced to the middle methanol peak at 49.0 ppm) δ 150.8, 146.5, 129.1, 114.6, 72.1, 62.1, 45.5, 43.9, 40.1, 16.3. HRMS: (M+H)+ calcd. for C13H22N5O2S: 312.1494. found: 312.1494.

Workup

  1. customAfter 5 min the mixture was evaporated in vacuo
  2. dissolutionThe residue was redissolved in methanolic ammonia (7M, 4 mL)
  3. filtrationShortly after the mixture was filtered through flux
  4. customevaporated
  5. dissolutionThe residue was dissolved in MeOH (2 mL)
  6. additiontreated with Amberlyst® A-26(OH) ion exchange resin (˜1 g) for 5 min
  7. filtrationthe solution was filtered
  8. customevaporated in vacuo which

Sources & evidence

ORD record
ord-9534a52d2ec144b88a8ce3f558b639df
Source dataset
uspto-grants-2013_02
Patent number
US08383636B2

Reaction notes

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