Chloroacetic Acid → 176753-26-7

HRID 1770316Notes

Reaction equation

HRID 1770316 reaction equation
ClCC(O)=O.[OH:6][CH:7]1[CH2:13][O:12]C(C)(C)[O:10][CH2:9][CH:8]1[N:16]1[CH2:27][CH2:26][NH:25][CH2:24][CH2:23][NH:22][CH2:21][CH2:20][NH:19][CH2:18][CH2:17]1.[OH-].[Na+].Cl>O>[OH:10][CH2:9][CH:8]([N:16]1[CH2:17][CH2:18][NH:19][CH2:20][CH2:21][NH:22][CH2:23][CH2:24][NH:25][CH2:26][CH2:27]1)[CH:7]([OH:6])[CH2:13][OH:12]

Participants

6

Reactant 4

HCID 300Chloroacetic AcidHCID 313Hydrochloric AcidHCID 14798Sodium Hydroxide2×HCID 10852906138147-50-9

Product 1

HCID 10540432176753-26-7Yield 128.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
70 °C

Procedure

72.7 g (767 mmol) of chloroacetic acid is added under ice/water cooling and nitrogen atmosphere to 60.7 g (192 mmol) of the crude product obtained from example 3a in 500 ml of deionized water. Then, the pH is adjusted to 9.5 with about 42 ml of 10 molar sodium hydroxide solution. The reaction solution is heated to 70° C. and the pH is kept at 9.1-9.5 by adding 10 molar sodium hydroxide solution. For 4 hours of additional stirring time, the pH is maintained at 70° C. The reaction mixture is cooled to 30° C. and acidified with 97 ml of conc. HCl to pH=0.8, heated to 60° C. and stirred for one more hour at this temperature. Then, it is evaporated to dryness in a vacuum at this temperature. The residue is mixed twice with 310 ml of MeOH/EtOH each and in each case again evaporated to dryness. The residue is then mixed with 620 ml of methanol and stirred at 50° C. for 30 minutes, cooled in ice/water and suctioned off, NaCl residue is rewashed with ice-cold methanol. The filtrate is evaporated to dryness in a vacuum. The thus obtained crude product is dissolved in 133 ml of deionized water, added on a column (2.0 l of Amberlite® AMB 252c). The column is washed with deionized water until a conductivity of 23 μS is detected in the eluate. Then, the product is eluted with water/NH3. The fractions containing product are combined and evaporated to dryness. 68.2 g (78% of theory) of 10-(1-hydroxymethyl- 2,3-dihydroxypropyl)-1,4,7,10-tetraazacyclododecane is obtained.

Workup

  1. temperaturethe pH is maintained at 70° C
  2. temperatureThe reaction mixture is cooled to 30° C.
  3. temperatureheated to 60° C.
  4. customThen, it is evaporated to dryness in a vacuum at this temperature
  5. additionThe residue is mixed twice with 310 ml of MeOH/EtOH each and in each case
  6. customagain evaporated to dryness
  7. additionThe residue is then mixed with 620 ml of methanol
  8. stirringstirred at 50° C. for 30 minutes
  9. temperaturecooled in ice/water
  10. customThe filtrate is evaporated to dryness in a vacuum
  11. customThe thus obtained crude product
  12. washThe column is washed with deionized water until a conductivity of 23 μS
  13. washThen, the product is eluted with water/NH3
  14. additionThe fractions containing product
  15. customevaporated to dryness

Sources & evidence

ORD record
ord-6dec8decb5b84e10a04c14c10118242e
Source dataset
uspto-grants-1995_01
Patent number
US05386028

Reaction notes

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