Iodine → HCID 53741613, compound

HRID 1606825Notes

Reaction equation

HRID 1606825 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]([C:25](O)=[O:26])[CH2:10][C:11]1[CH:16]=[CH:15][C:14]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH:13][CH:12]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].ClC(OCC)=O.S(C1C=CC(C)=CC=1)(O)(=O)=O.[CH2:45]([O:52][C:53](=[O:56])[CH2:54][NH2:55])[C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1.ClCl.CC1C=C(C2C=CC(N)=C(C)C=2)C=CC=1N.II>O1CCCC1.CO.C(N(CC)CC)C>[CH2:45]([O:52][C:53](=[O:56])[CH2:54][NH:55][C:25](=[O:26])[C@H:9]([CH2:10][C:11]1[CH:12]=[CH:13][C:14]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH:15][CH:16]=1)[NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])[C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1

Participants

9

Reactant 5

HCID 807IodineHCID 10928Ethyl chloroformateHCID 98763O-benzyl-N-((tert-butoxy)carbonyl)-L-tyrosineHCID 6451311O-benzylglycine toluene-p-sulphonateHCID 131710166Chlorine tolidine

Product 1

HCID 53741613HCID 53741613, compoundYield 93%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent2×HCID 8471TriethylamineSolvent2×

Procedure

N-tert-Butyloxycarbonyl-O-benzyltyrosine (LV) (27.6 g) and dry tetrahydrofuran (100 ml) at 0° C. were treated successively with triethylamine (10.3 ml), ethyl chloroformate (7.1 ml) and, after an hr, glycine benzyl ester tosylate (XXXVI) (25 g) and triethylamine (10.3 ml) in dry tetrahydrofuran (100 ml). After being stirred at room temperature during 16 hr, the reaction mixture was evaporated to dryness. The residue was dissolved in ethyl acetate (400 ml) and the solution was washed with 5% citric acid (2×50 ml), 5% sodium bicarbonate solution (2×50 ml) and water 2×50 ml). The organic layer was dried (Na2SO4) and evaporated. The residue was crystallized from methanol-n-hexane to afford the (LVI); 35.7 g, yield 93%; m.p. 101°-4° C; [α]D22 + 1.2° (c 1.29, methanol); Rf4 0.91; single spot with chlorine/tolidine and iodine reagents. τCDCL3 2.65, d, 10H benzylic aromatic protons; 4.86, s,2H and 4.98,s,2H benzylic methylene protons and 8.64,s,9H butyloxy protons.

Workup

  1. customthe reaction mixture was evaporated to dryness
  2. dissolutionThe residue was dissolved in ethyl acetate (400 ml)
  3. washthe solution was washed with 5% citric acid (2×50 ml), 5% sodium bicarbonate solution (2×50 ml) and water 2×50 ml)
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. customevaporated
  6. customThe residue was crystallized from methanol-n-hexane
  7. customto afford the (LVI)

Sources & evidence

ORD record
ord-62e00ded6a1c4baeb7541e4c4c8906f4
Source dataset
uspto-grants-1976_04
Patent number
US03953416

Reaction notes

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