Hydrochloric Acid → HCID 86713108, compound

HRID 1399430Notes

Reaction equation

HRID 1399430 reaction equation
[C:1]([NH:8][CH2:9][C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])([O:3]C(C)(C)C)=O.Cl.C(N(CC)CC)C.[Cl:28][C:29]1[CH:37]=[C:36]([N+:38]([O-:40])=[O:39])[C:35]([N+:41]([O-:43])=[O:42])=[CH:34][C:30]=1C(O)=O.C1CCC(N=C=NC2CCCCC2)CC1>O1CCOCC1.CN(C1C=CN=CC=1)C.O>[Cl:28][C:29]1[CH:37]=[C:36]([N+:38]([O-:40])=[O:39])[C:35]([N+:41]([O-:43])=[O:42])=[CH:34][C:30]=1[C:1]([NH:8][CH2:9][C:10]([O:12][CH2:13][C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)=[O:11])=[O:3]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 10868DicyclohexylcarbodiimideHCID 357720Benzyl N-(tert-butoxycarbonyl)glycinateHCID 192612782-Chloro-4,5-dinitrobenzoic acid

Product 1

HCID 86713108HCID 86713108, compoundYield 78.4%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent3×

Procedure

A mixture of benzyl N-Bocglycinate (3 g, 11.3 mmol) and HCl in dioxane (20 mL) was stirred at rt for 2 h. Solvents were evaporated under reduced pressure and was diluted with dioxane (20 mL) and triethylamine (2.24 mL, 16.24 mmol). Then 2-chloro-4,5-dinitrobenzoic acid (2 g, 8.1 mmol) was added and cooled to 5° C. A solution of DCC (5.8 g, 28.1 mmol) in dioxane (20 mL) was added followed by catalytic amount of DMAP. The reaction mixture was stirred at rt for 5 h. Few drops of water was added to the reaction mixture and again stirred for 15 min. Reaction mixture was cooled to 0° C. and filtered. The solid was washed with ether (50 mL) and EtOAc (50 mL). The filtrate was poured into water and the organic layer was separated. The aqueous layer was extracted with EtOAc (3×100 mL) and the combined organic layer was washed with brine and dried over anhyd Na2SO4. The solution was filtered and evaporated the solvent. The residue was chromatographed over silica gel column using chloroform:acetone (90:10) as eluents to give the product as a pale yellow color solid (2.5 g, 75%), mp 122-124° C. 1H NMR (400 MHz, CDCl3): δ 8.30 (1H, s), 7.96 (1H, s), 7.39 (5H, s), 6.94 (1H, br s), 5.25 (2H, s), 4.32 (2H, d, J=4.8 Hz); LC-MS (negative ion mode): m/z 392 (M−H)−.

Workup

  1. customSolvents were evaporated under reduced pressure
  2. temperaturecooled to 5° C
  3. stirringThe reaction mixture was stirred at rt for 5 h
  4. stirringagain stirred for 15 min
  5. customReaction mixture
  6. temperaturewas cooled to 0° C.
  7. filtrationfiltered
  8. washThe solid was washed with ether (50 mL) and EtOAc (50 mL)
  9. additionThe filtrate was poured into water
  10. customthe organic layer was separated
  11. extractionThe aqueous layer was extracted with EtOAc (3×100 mL)
  12. washthe combined organic layer was washed with brine
  13. dry with materialdried over anhyd Na2SO4
  14. filtrationThe solution was filtered
  15. customevaporated the solvent
  16. customThe residue was chromatographed over silica gel column

Sources & evidence

ORD record
ord-7f2b35c97c1c4ad4a23237c298353058
Source dataset
uspto-grants-2014_12
Patent number
US08906344B2

Reaction notes

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