Piperazine → HCID 23729300, compound

HRID 1804419Notes

Reaction equation

HRID 1804419 reaction equation
C([O:8][C:9]1[CH:36]=[CH:35][C:12]([O:13][CH2:14][C@@H:15]([OH:34])[CH2:16][N:17]2[CH2:22][CH2:21][N:20]([S:23]([C:26]3[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][CH:27]=3)(=[O:25])=[O:24])[CH2:19][CH2:18]2)=[CH:11][CH:10]=1)C1C=CC=CC=1.C(Cl)(Cl)Cl.[K+].[Br-].N1CCNCC1>C(Cl)Cl.[Pd]>[OH:34][C@@H:15]([CH2:16][N:17]1[CH2:22][CH2:21][N:20]([S:23]([C:26]2[CH:27]=[CH:28][C:29]([O:32][CH3:33])=[CH:30][CH:31]=2)(=[O:24])=[O:25])[CH2:19][CH2:18]1)[CH2:14][O:13][C:12]1[CH:35]=[CH:36][C:9]([OH:8])=[CH:10][CH:11]=1

Participants

7

Reactant 4

HCID 4837Piperazine2×HCID 6212ChloroformHCID 253877Potassium BromideHCID 24812348HCID 24812348, compound

Product 1

HCID 23729300HCID 23729300, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6344DichloromethaneSolvent

Procedure

Pd/C at 10% (290 mg) is suspended in a solution of (S)-1-(4-benzyloxyphenoxy)-2-hydroxy-3-[4-(4-methoxyphenylsulfonyl)piperazin-1-yl)propane (Example 26) (583 mg, 1.14 mM) in CH2Cl2 (10 ml) and maintained in agitation in H2 atmosphere (1 atm) for 18 hours. The catalyst is then removed by filtering the reaction mixture on Celite, and the solvent is distilled under vacuum. The oily residue is crystallized (ethyl acetate/petroleum ether). A white solid is obtained (90% of yield). Pf 148.3-149.2° C.s. [α]D=−7.6 (c 1.07, CHCl3). FT-IR (KBr): 3466, 3050, 2969, 2941, 2921, 2896, 2864, 1593, 1576, 1511, 1468, 1458, 1445, 1348, 1328, 1306, 1254, 1234, 1200, 1177, 1165, 1136, 1101, 1051, 1017, 946, 833, 804, 737 cm−1. 1NMRs (500 MHz CD3OD, δ): 7.90-7.80 (bs, 1H, OH); 7.71-7.68 (m, 2H, aromatic protons); 7.13-7.10 (m, 2H, aromatic protons); 6.75-6.73 (m, 2H, aromatic protons); 6.68-6.66 (m, 2H, aromatic protons); 4.00-3.98 (m, 1H, CHOH), 3.88 (s, 3H, OCH3), 3.86-3.83 (dd, 1H, J=9.7 and 4.4 Hz, CH2OAr); 3.80-3.77 (dd, 1H, J=9.7 and 5.9 Hz, CH2OAr); 3.70-3.50 (bs, 1H, OH); 2.98 (m, 4H, 2 CH2N of piperazine); 2.60 (m, 4H, 2 CH2 of piperazine); 2.55-2.52 (dd, 1H, J=13.0 and 4.8 Hz, CHOHCH2N); 2.50-2.46 (dd, 1H, J=13.0 and 7.5 Hz, CHOHCH2N). 13C NMRs (75 MHz CD3OD, δ): 163.72, 152.47, 150.31, 129.97, 126.98, 115.60, 115.55, 114.25, 71.35, 67.31, 60.45, 55.08, 52.81, 46.07. MS-ESI m/z (%): 445 [M+Na]+ (100). MS-MS (445): 445(100), 335 (69), 292 (54), 279 (13), 250 (8), 222 (32). Anal. Calc. for C20H26N2O5S: C, 56.86; H, 6.20; N, 6.63. Found: C, 57.03; H, 6.16; N, 6.66.

Workup

  1. temperaturemaintained in agitation in H2 atmosphere (1 atm) for 18 hours
  2. customThe catalyst is then removed
  3. filtrationby filtering the reaction mixture on Celite
  4. distillationthe solvent is distilled under vacuum
  5. customThe oily residue is crystallized (ethyl acetate/petroleum ether)
  6. customA white solid is obtained
  7. custom(90% of yield)
  8. customPf 148.3-149.2° C

Sources & evidence

ORD record
ord-e772b63fb075440c91b8261a3f041cb6
Source dataset
uspto-grants-2013_01
Patent number
US08354412B2

Reaction notes

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