Trichloroacetonitrile → 2-(Trichloromethyl)-4,7-dihydro-2H-1,3-dioxepin-2-amine

HRID 2309111Notes

Reaction equation

HRID 2309111 reaction equation
[CH2:1]([OH:6])/[CH:2]=[CH:3]\[CH2:4][OH:5].[Na].[Cl:8][C:9]([Cl:13])([Cl:12])[C:10]#[N:11]>C(O)(=O)C>[NH2:11][C:10]1([C:9]([Cl:13])([Cl:12])[Cl:8])[O:6][CH2:1][CH:2]=[CH:3][CH2:4][O:5]1

Participants

5

Reactant 3

HCID 11011TrichloroacetonitrileHCID 6437902-Butene-1,4-diol, (2Z)-HCID 5360545Sodium

Product 1

HCID 139839612-(Trichloromethyl)-4,7-dihydro-2H-1,3-dioxepin-2-amine

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To cis-2-butene-1,4-diol (22.28 g, 252.9 mmole) there was added a catalytic amount of sodium followed by a slow addition at ~0° C. of trichloroacetonitrile (110 g, 3 equivalents). Upon completion of the trichloroacetonitrole addition, the solution was stirred at room temperature for 16 hours. The solution was acidified with 1 ml glacial acetic acid and stirred for 15 minutes. The resulting solution was distilled under reduced pressure (0.25 mm Hg) and several fractions were collected at different temperatures. The minor fraction (9.71 g) collected between 98°-110° was characterized as the cyclic title product. IR (KBr): 3430-3350, 3040, 2940-2920, 1607, 1110 and 825 cm-1. 1H NMR was consistent with the indicated structure.

Workup

  1. additionUpon completion of the trichloroacetonitrole addition
  2. stirringstirred for 15 minutes
  3. distillationThe resulting solution was distilled under reduced pressure (0.25 mm Hg) and several fractions
  4. customwere collected at different temperatures
  5. customThe minor fraction (9.71 g) collected between 98°-110°

Sources & evidence

ORD record
ord-e3df2f716ef5473b9b77262a81b37261
Source dataset
uspto-grants-1987_09
Patent number
US04692538

Reaction notes

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