3-Chlorobenzoic Acid → (Adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonic acid tert-butylammonium salt

HRID 84978Notes

Reaction equation

HRID 84978 reaction equation
[C:1]([NH3+:5])([CH3:4])([CH3:3])[CH3:2].[C:6]12([CH2:16][O:17][C:18]([C:20]([F:25])([F:24])[S:21]([O-:23])=[O:22])=[O:19])[CH2:15][CH:10]3[CH2:11][CH:12]([CH2:14][CH:8]([CH2:9]3)[CH2:7]1)[CH2:13]2.ClC1C=C(C=CC=1)C(O)=[O:31]>C(Cl)(Cl)Cl>[C:1]([NH3+:5])([CH3:4])([CH3:3])[CH3:2].[C:6]12([CH2:16][O:17][C:18]([C:20]([F:25])([F:24])[S:21]([O-:31])(=[O:23])=[O:22])=[O:19])[CH2:15][CH:10]3[CH2:9][CH:8]([CH2:14][CH:12]([CH2:11]3)[CH2:13]1)[CH2:7]2

Participants

4

Reactant 2

HCID 4473-Chlorobenzoic AcidHCID 131731912(Adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfinic acid tert-butylammonium salt

Product 1

HCID 131731911(Adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonic acid tert-butylammonium salt

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

Within a 1-L three-neck flask, 153 g (purity 86%, 345 mmol, 1.0 eq) of the (adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfinic acid tert-butylammonium salt obtained in Example 5-a was dissolved in 600 g of chloroform. To the resulting solution, 89 g (362 mmol, 1.05 eq) of 70% m-chlorobenzoic acid was slowly added at 0° C. This reaction solution was stirred for 1 hour at room temperature. After that, it was confirmed by 19F NMR of the reaction solution that: the (adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonic acid tert-butylammonium salt was totally consumed; and there was no bromodifluoroacetic acid adamantane-1-ylmethyl ester detected as a by-product. The thus-obtained organic layer was washed with 200 g of 10% aqueous sodium sulfite solution, washed with 500 g of saturated sodium hydrogencarbonate solution and washed twice with 500 g of water. After distillation of chloroform from the washed organic layer, the solid residue was dissolved in a mixed solvent of chloroform, ethyl acetate and diisopropyl ether and then recrystallized. With this, 122 g of target (adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonic acid tert-butylammonium salt was obtained. The purity of the target compound was 99%; and the yield of the target compound was 89%. No fluorine ion (F−) was detected from any liquid waste of this step. Further, 380 ppb of sodium ion (Na+) was detected from the (adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonic acid tert-butylammonium salt obtained in this step.

Workup

  1. customthe (adamantane-1-ylmethyl)oxycarbonyldifluoromethanesulfonic acid tert-butylammonium salt was totally consumed
  2. washThe thus-obtained organic layer was washed with 200 g of 10% aqueous sodium sulfite solution
  3. washwashed with 500 g of saturated sodium hydrogencarbonate solution
  4. washwashed twice with 500 g of water
  5. distillationAfter distillation of chloroform from the washed organic layer
  6. dissolutionthe solid residue was dissolved in a mixed solvent of chloroform, ethyl acetate and diisopropyl ether
  7. customrecrystallized

Sources & evidence

ORD record
ord-632d62da57bc43239b3fa5b4c455ba74
Source dataset
uspto-grants-2014_09
Patent number
US08846966B2

Reaction notes

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