Glycine → ethyl-N-(6-amino-2,3-dichlorobenzyl)glycine

HRID 481141

Reaction equation

HRID 481141 reaction equation
Cl.[CH2:2]([N:4]([CH2:9][C:10]1[C:15]([N+:16]([O-])=O)=[CH:14][CH:13]=[C:12]([Cl:19])[C:11]=1[Cl:20])[CH2:5][C:6]([OH:8])=[O:7])[CH3:3].O.O.[Sn](Cl)(Cl)(Cl)Cl.NCC(O)=O.[Sn]>Cl>[CH2:2]([N:4]([CH2:9][C:10]1[C:15]([NH2:16])=[CH:14][CH:13]=[C:12]([Cl:19])[C:11]=1[Cl:20])[CH2:5][C:6]([OH:8])=[O:7])[CH3:3]

Participants

6

Reactant 4

HCID 750GlycineHCID 5352426Tin atomHCID 66640009ethyl N-(2,3-dichloro-6-nitrobenzyl)glycine hydrochloride2×HCID 85782573Tin tetrachloride dihydrate

Product 1

HCID 67080112ethyl-N-(6-amino-2,3-dichlorobenzyl)glycineYield 58%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent2×

Conditions

Temperature
45 °C

Procedure

A suspension of 30 g of ethyl N-(2,3-dichloro-6-nitrobenzyl)glycine hydrochloride (compound VI) in 120 mL of concentrated hydrochloric acid was prepared. Separately, a mixture of tin chloride dihydrate (88.6 g) in 60 mL of hydrochloric acid is prepared. The glycine solution is slowly added to the tin solution and the resulting reaction mixture heated for 2 hours at 40-50° C. The solids are filtered, and the filter cake dissolved in water and methylene chloride. The pH of this solution is adjusted to 12.5 with 50% NaOH. The organic phase is separated and the aqueous phase extracted with methylene chloride. The combined organic phases are washed with water, and dried azeotropically. The solution is concentrated, isopropanol and heptane are added, and the solution cooled to −20 to −30° C. The precipated solids are collected by filtration. The crude product is recrystallized from heptane to give compound I in 58 to 67% yield.

Workup

  1. customwas prepared
  2. customis prepared
  3. customthe resulting reaction mixture
  4. filtrationThe solids are filtered
  5. dissolutionthe filter cake dissolved in water
  6. customThe organic phase is separated
  7. extractionthe aqueous phase extracted with methylene chloride
  8. washThe combined organic phases are washed with water
  9. customdried azeotropically
  10. concentrationThe solution is concentrated
  11. additionisopropanol and heptane are added
  12. temperaturethe solution cooled to −20 to −30° C
  13. filtrationThe precipated solids are collected by filtration
  14. customThe crude product is recrystallized from heptane

Sources & evidence

ORD record
ord-9e15040b8ef64a5d8d0b08f00e16ad53
Source dataset
uspto-grants-2003_11
Patent number
US06653500B2

Linked notes

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