Hydrochloric Acid → HCID 25000770, compound

HRID 226254Notes

Reaction equation

HRID 226254 reaction equation
C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[C:20]([Cl:24])(Cl)(Cl)Cl.O[CH2:26][CH:27]1[CH2:32][CH2:31][CH2:30][N:29]([CH2:33][CH2:34][NH:35][C:36]2[C:49]3[C:48](=[O:50])[C:47]4[C:42](=[CH:43][CH:44]=[CH:45][CH:46]=4)[C:41](=[O:51])[C:40]=3[C:39]([NH:52][CH2:53][CH2:54][N:55]3[CH2:60][CH2:59][CH2:58][CH:57](CO)[CH2:56]3)=[CH:38][CH:37]=2)[CH2:28]1.[ClH:63].P(C1C=CC=CC=1)(C1C=CC=CC=1)(C1C=CC=CC=1)=O>C(Cl)Cl.CCOC(C)=O.CCO>[Cl:63][CH2:26][CH:27]1[CH2:32][CH2:31][CH2:30][N:29]([CH2:33][CH2:34][NH:35][C:36]2[C:49]3[C:48](=[O:50])[C:47]4[C:42](=[CH:43][CH:44]=[CH:45][CH:46]=4)[C:41](=[O:51])[C:40]=3[C:39]([NH:52][CH2:53][CH2:54][N:55]3[CH2:60][CH2:59][CH2:58][CH:57]([CH2:20][Cl:24])[CH2:56]3)=[CH:38][CH:37]=2)[CH2:28]1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 5943Carbon TetrachlorideHCID 11776Triphenylphosphine2×HCID 13097Triphenylphosphine OxideHCID 68830679HCID 68830679, compound

Product 1

HCID 25000770HCID 25000770, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21584252Ethanol ethylacetateSolvent

Procedure

Ph3P (377.7 mg, 1.44 mmol) and CCl4 (425 μL, 432 mmol) were stirred for 15 min. before it was added dropwise to a stirred solution of HAQ38 (125 mg, 0.24 mmol) in dry CH2Cl2 (5 mL) under N2 at reflux temperature. The reaction mixture was kept at reflux temperature for 4 h before it was cooled down to RT. Ethereal HCl was added to the solution and after 1 h of stirring, the precipitated solid was filtered off. To remove excess of Ph3P and Ph3PO, the precipitated solid was dissolved in warm CH3OH (10 mL). While stirring the dark blue solution at reflux, a mixture of EtOAc and EtOH (1:1) was added until precipitation of solid was observed. The solution was set aside for 1 h before the precipitated product was isolated by filtration; the excess Ph3P and Ph3PO remained in the EtOAc/EtOH solution. The title compound was afforded as a dark blue solid (98.3 mg, 65%). M.p. dec.>300° C.; δH (250 MHz; CDCl3); 1.1 (m, 2H, 2×CH2CHCH2Cl), 1.75 (m, 6H, CH2CH2CH and 2×CH2CH2CH2), 2.05 (m, 4H, ring-H), 2.18 (3×d, 2H, J=3 Hz and 10 Hz, 2×NCH2CH2), 2.73 (t, 4H, J=9 Hz, 2×HNCH2CH2N), 2.8 (m, 2H, ring-H), 2.96 (2×d, 2H, 2×NCH2CH), 3.5 (m, 8H, 2×CHCH2Cl and 2×HNCH2CH2N), 7.25 (s, 2H, C(2)H and C(3)H), 7.7 (m, 2H, C(6)H and C(7)H), 8.3 (m, 2H, C(5)H, C(8)H) and 10.75 (t, 2H, C(1)NH and C(4)NH); dC(62.9 MHz; CDCl3); 24.42, 28.34, 38.47, 40.56, 48.14, 54.22, 57.52, 57.60, 110.30, 123.52, 126.12, 132.01, 134.56, 145.82 and 182.65; FAB MS, m/z(M+H)+ 557; IR υmax/cm−1; 3400 (NH), 3090, 2960-2825 (CH2, CH3), 1650, 1600, 1585, 1525, 1275, 1025 and 740; Anal. calcd for C30H38Cl2N4O2.2HCl.2H2O: C, 54.06; H, 6.65; N, 8.41. Found: C, 54.07; H, 6.27; N, 8.14.

Workup

  1. temperatureat reflux temperature
  2. temperatureat reflux temperature for 4 h before it
  3. filtrationthe precipitated solid was filtered off
  4. customTo remove excess of Ph3P and Ph3PO
  5. dissolutionthe precipitated solid was dissolved in warm CH3OH (10 mL)
  6. stirringWhile stirring the dark blue solution
  7. temperatureat reflux
  8. additiona mixture of EtOAc and EtOH (1:1)
  9. additionwas added until precipitation of solid
  10. customwas isolated by filtration

Sources & evidence

ORD record
ord-21caef166d6e4430a11c731e18f05491
Source dataset
uspto-grants-2009_07
Patent number
US07557215B2

Reaction notes

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