Triphenylphosphine → 6-[2-(Morpholin-4-yl)ethoxy]-1,3-benzothiazol-2-amine

HRID 736476Notes

Reaction equation

HRID 736476 reaction equation
[NH2:1][C:2]1[S:3][C:4]2[CH:10]=[C:9]([OH:11])[CH:8]=[CH:7][C:5]=2[N:6]=1.O[CH2:13][CH2:14][N:15]1[CH2:20][CH2:19][O:18][CH2:17][CH2:16]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[N:15]1([CH2:14][CH2:13][O:11][C:9]2[CH:8]=[CH:7][C:5]3[N:6]=[C:2]([NH2:1])[S:3][C:4]=3[CH:10]=2)[CH2:20][CH2:19][O:18][CH2:17][CH2:16]1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 334622-Amino-6-benzothiazololHCID 611632-MorpholinoethanolHCID 220568ethyl N-ethoxycarbonyliminocarbamate

Product 1

HCID 224786596-[2-(Morpholin-4-yl)ethoxy]-1,3-benzothiazol-2-amineYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of benzothiazole 225 (3.62 g, 21.8 mmol) in THF at room temperature under nitrogen, were successively added 4-(2-hydroxyethyl)morpholine (3.17 mL, 26.1 mmol), triphenylphosphine (7.43 g, 28.3 mmol) followed by a dropwise addition of diethyl azodicarboxylate (4.46 mL, 28.3 mmol). The solution was stirred for 3.5 h and THF was partially removed in vacuo. The mixture was partitioned between ethyl acetate and H2O. The combined organic layers were extracted with 1N HCl. The combined acidic extracts were neutralized using a saturated aqueous solution of NaHCO3 and the precipitate was dissolved with ethyl acetate. These combined organic layers were washed with brine, dried over MgSO4, and concentrated. The filtrate was concentrated to afford the title compound 226 (5.83 g, 96% yield) as a light yellow oil. 1H NMR: (Acetone-d6) δ (ppm): 7.37 (d, J=8.8 Hz, 1H), 7.34 (d, J=2.6 Hz, 1H), 6.94 (dd, J=8.8, 2.6 Hz, 1H), 6.60 (bs, 2H), 4.19 (t, J=6.2 Hz, 2H), 3.70-3.67 (m, 4H), 2.90 (s, 2H), 2.81 (t, J=6.2 Hz, 2H), 2.62-2.58 (m, 4H).

Workup

  1. customat room temperature
  2. customTHF was partially removed in vacuo
  3. customThe mixture was partitioned between ethyl acetate and H2O
  4. extractionThe combined organic layers were extracted with 1N HCl
  5. dissolutionthe precipitate was dissolved with ethyl acetate
  6. washThese combined organic layers were washed with brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated
  9. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-6c12825422df47c1aea2622b506e92fd
Source dataset
uspto-grants-2009_09
Patent number
US07595343B2

Reaction notes

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