Formaldehyde → HCID 24812255, compound

HRID 1804420Notes

Reaction equation

HRID 1804420 reaction equation
[OH:1][C@@H:2]([CH2:14][N:15]1[CH2:20][CH2:19][N:18]([S:21]([C:24]2[CH:29]=[CH:28][C:27]([O:30][CH3:31])=[CH:26][CH:25]=2)(=[O:23])=[O:22])[CH2:17][CH2:16]1)[CH2:3][O:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([N+:11]([O-])=O)[CH:6]=1.[K+].[Br-].C=O.N1CCNCC1>C(OCC)(=O)C.[OH-].[OH-].[Pd+2].C(Cl)(Cl)Cl>[NH2:11][C:7]1[CH:6]=[C:5]([CH:10]=[CH:9][CH:8]=1)[O:4][CH2:3][C@@H:2]([OH:1])[CH2:14][N:15]1[CH2:16][CH2:17][N:18]([S:21]([C:24]2[CH:29]=[CH:28][C:27]([O:30][CH3:31])=[CH:26][CH:25]=2)(=[O:23])=[O:22])[CH2:19][CH2:20]1

Participants

8

Reactant 4

HCID 712FormaldehydeHCID 4837Piperazine3×HCID 253877Potassium BromideHCID 24812254HCID 24812254, compound

Product 1

HCID 24812255HCID 24812255, compound

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalyst2×HCID 6212ChloroformSolventHCID 8857Ethyl AcetateSolvent

Procedure

Pd(OH)2/C at 20% [1.54 g, 2.2 mM Pd(OH)2] is suspended in a solution of (S)-2-hydroxy-3-[4-(4-methoxyphenylsulfonyl)piperazin-1-yl)-1-(3-nitrophenoxy)propane (3.30 g, 7.73 mM) (Example 27) in ethyl acetate (43 ml). The mixture is maintained in agitation in atmosphere of H2 (10 atm) for 30 hours. The catalyst is then removed by filtering the reaction mixture on Celite, and the solvent is distilled under vacuum. A white solid is obtained (97% of yield). Pf 138.5-139.6° Cs. [α]D=−10.7 (c 1.06, CHCl3). FT-IR (KBr): 3456, 3371, 3100, 3063, 2945, 2916, 2853, 1597, 1576, 1497, 1456, 1343, 1328, 1302, 1263, 1195, 1161, 1096, 948, 839, 809, 773, 737, 694, 660 cm −1. 1NMRs (300 MHz CDCl3, δ): 7.71-7.67 (m, 2H, aromatic protons); 7.05-6.98 (m, 3H, aromatic protons); 6.30-6.29 (d, 1H, J=2.2 Hz, aromatic proton); 6.27-6.26 (m, 1H, aromatic proton); 6.23-6.22 (t, J=2.2 Hz, 1H, aromatic proton); 4.05-3.97 (m, 1H, CHOH); 3.89-3.88 (m, 5H, CH2O and OCH3), 3.70-3.10 (bs, 2H, NH2); 3.10-2.85 (bs, 5H, 2 CH2N of piperazine and OH); 2.79-2.69 (m, 2H, CH2N of piperazine); 2.58-2.45 (m, 4H, CH2N of piperazine and CHOHCH2N). 13C NMRs (75 MHz CD3OD, δ): 163.39, 159.95, 148.03, 130.35, 130.16, 127.15, 114.51, 108.55, 104.67, 101.90, 70.09, 66.07, 60.46, 55.87, 52.69, 46.28. MS-ESI m/z (%): 444 [M+Na]+ (100). Anal. Calc. for C20H27N3O5S: C, 56.99; H, 6.46; N, 9.97. Found: C, 56.91; H, 6.41; N, 9.69.

Workup

  1. temperatureThe mixture is maintained in agitation in atmosphere of H2 (10 atm) for 30 hours
  2. customThe catalyst is then removed
  3. filtrationby filtering the reaction mixture on Celite
  4. distillationthe solvent is distilled under vacuum
  5. customA white solid is obtained
  6. custom(97% of yield)
  7. customPf 138.5-139.6° Cs

Sources & evidence

ORD record
ord-283e407667b64e33be057db575bc6a88
Source dataset
uspto-grants-2013_01
Patent number
US08354412B2

Reaction notes

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