Hydrochloric Acid → Boc-Thr(Bzl)-Ser(Bzl)-Ser(Bzl)-Glu(OBzl)-OH

HRID 26331Notes

Reaction equation

HRID 26331 reaction equation
[NH:1](C(OC(C)(C)C)=O)[C@H:2]([C:12]([NH:14][C@H:15]([C:25]([NH:27][C@H:28]([C:41]([OH:43])=[O:42])[CH2:29][CH2:30][C:31](=[O:40])[O:32][CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)=[O:26])[CH2:16][O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:13])[CH2:3][O:4][CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.Cl.[NH:52]([C:74]([O:76][C:77]([CH3:80])([CH3:79])[CH3:78])=[O:75])[C@H:53]([C:64]([O:66]N1C(=O)CCC1=O)=O)[C@@H:54]([CH3:63])[O:55][CH2:56][C:57]1[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=1.CCN(CC)CC>C1COCC1.CN(C=O)C.CS(C)=O>[NH:52]([C:74]([O:76][C:77]([CH3:78])([CH3:79])[CH3:80])=[O:75])[C@H:53]([C:64]([NH:1][C@H:2]([C:12]([NH:14][C@H:15]([C:25]([NH:27][C@H:28]([C:41]([OH:43])=[O:42])[CH2:29][CH2:30][C:31](=[O:40])[O:32][CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)=[O:26])[CH2:16][O:17][CH2:18][C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)=[O:13])[CH2:3][O:4][CH2:5][C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1)=[O:66])[C@@H:54]([CH3:63])[O:55][CH2:56][C:57]1[CH:58]=[CH:59][CH:60]=[CH:61][CH:62]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8471Triethylamine2×HCID 12879029Boc-Thr(Bzl)-OSuHCID 131711277Boc-Ser(Bzl)-Ser(Bzl)-Glu(OBzl)-OH

Product 1

HCID 131711276Boc-Thr(Bzl)-Ser(Bzl)-Ser(Bzl)-Glu(OBzl)-OH

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

Boc-Ser(Bzl)-Ser(Bzl)-Glu(OBzl)-OH (71.6 g, 104 mmol) was treated with 2.7 liters of freshly prepared 3.9 N HCl in THF for 45 minutes. The mixture was evaporated to dryness and the residue evaporated twice more with THF to give a solid mass (59.3 g; mp 161°-165°). It was collected and washed with ether and stirred in 500 ml of DMF with Boc-Thr(Bzl)-OSu (38.2 g, 94 mmol) in the presence of Et3N (25 ml) at 0° for 1 hour and then at 25° for 15 hours. More Et3N (14.5 ml) was added in serveral portions during this time to maintain the reaction slightly basic. Some insoluble matter formed was filtered off and the filtrate evaporated to an oil which was dissolved in EtOAc (1.5 liters), washed with 5% HOAc, H2O (2 times), dried (Na2SO4), and evaporated to a solid mass. The product was recrystallized from EtOAc and petroleum ether to yield, 64.8 g (78.1%); mp 115°-118°; [α]D25 =+11.64° (c 1, DMSO).

Workup

  1. customThe mixture was evaporated to dryness
  2. customthe residue evaporated twice more with THF
  3. customto give a solid mass (59.3 g; mp 161°-165°)
  4. customIt was collected
  5. washwashed with ether
  6. temperatureto maintain
  7. customthe reaction slightly basic
  8. customSome insoluble matter formed
  9. filtrationwas filtered off
  10. customthe filtrate evaporated to an oil which
  11. dissolutionwas dissolved in EtOAc (1.5 liters)
  12. washwashed with 5% HOAc, H2O (2 times)
  13. dry with materialdried (Na2SO4)
  14. customevaporated to a solid mass
  15. customThe product was recrystallized from EtOAc and petroleum ether
  16. customto yield

Sources & evidence

ORD record
ord-5b86cc1232fb4c7090a131188ab81147
Source dataset
uspto-grants-1979_04
Patent number
US04148788

Reaction notes

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