Water → Adipic Acid Hydrate

HRID 1461994Notes

Reaction equation

HRID 1461994 reaction equation
CC1(C)S(=O)(=[O:7])C2CC(=O)N2C1C([O-])=O.[Na+].[C:17]([O:28]CC1C=CC=CC=1)(=[O:27])[CH2:18][CH2:19][CH2:20][CH2:21][C:22]([O:24]CCl)=[O:23].O>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C.CC(C)=O.[Pd]>[OH2:7].[C:17]([OH:28])(=[O:27])[CH2:18][CH2:19][CH2:20][CH2:21][C:22]([OH:24])=[O:23]

Participants

8

Reactant 3

HCID 962WaterHCID 10731820Hexanedioic acid, chloromethyl phenylmethyl esterHCID 23691718Sodium penicillanate 1,1-dioxide

Product 1

HCID 57480892Adipic Acid HydrateYield 208.6%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 74236Tetrabutylammonium BromideCatalystHCID 180AcetoneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To 400 ml acetone is added 48.5 g (0.19 mole) sodium 1,1-dioxopenicillanate, 48.0 g (0.17 mole) benzyl chloromethyl adipate and 19.3 g (0.06 mole) tetrabutylammonium bromide. The mixture is heated at reflux under nitrogen overnight, filtered, washed with acetone and the filtrate evaporated. The residue is taken up in 500 ml ethyl acetate, washed alternately with brine and water, 250 ml portions, brine again and dried (MgSO4). Evaporation of solvent in vacuo afforded 89.6 g light yellow oil. The oil is taken up in 250 ml ethyl acetate, 20.0 g 10% Pd/C added and the mixture is hydrogenated at 3.52 kg/cm2 for one hour. After adding 15 g of fresh catalyst the hydrogenation is continued for 2.5 hours. The catalyst is removed by filtration, the cake washed with acetone (1500 ml) and the combined filtrate and washings evaporated in vacuo to obtain a viscous oil. The oil is taken up in 150 ml acetone and water added slowly to start crystallization, then continued until 800 ml water is added. After stirring 30 minutes, the crystalline product is recovered by filtration, washing with water and air dried to obtain 58.2 g of the title carboxylic acid. Recrystallization from ethyl acetate affords the crystalline monohydrate, m.p. 100°-102° C.

Workup

  1. temperatureThe mixture is heated
  2. temperatureat reflux under nitrogen overnight
  3. filtrationfiltered
  4. washwashed with acetone
  5. customthe filtrate evaporated
  6. washwashed alternately with brine and water, 250 ml portions, brine again
  7. dry with materialdried (MgSO4)
  8. customEvaporation of solvent in vacuo
  9. customafforded 89.6 g light yellow oil
  10. waitis continued for 2.5 hours
  11. customThe catalyst is removed by filtration
  12. washthe cake washed with acetone (1500 ml)
  13. customthe combined filtrate and washings evaporated in vacuo
  14. customto obtain a viscous oil
  15. customcrystallization
  16. additionis added
  17. filtrationthe crystalline product is recovered by filtration
  18. washwashing with water and air
  19. customdried

Sources & evidence

ORD record
ord-d7cc883b136d419dbe58058120849587
Source dataset
uspto-grants-1984_07
Patent number
US04457924

Reaction notes

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