1,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochloride → 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitrobenzoate

HRID 1922546Notes

Reaction equation

HRID 1922546 reaction equation
[F:1][C:2]([F:17])([F:16])[CH2:3][CH2:4][CH2:5][O:6][C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][CH:8]=1.Cl.CN(C)CCCN=C=NCC.[N+:30]([C:33]1[CH:34]=[C:35]([CH:57]=[C:58]([N+:60]([O-:62])=[O:61])[CH:59]=1)[C:36]([O:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][O:45][C:46](=[O:56])/[CH:47]=[CH:48]/[C:49]1[CH:54]=[CH:53][C:52](O)=[CH:51][CH:50]=1)=[O:37])([O-:32])=[O:31]>ClCCl.CN(C)C1C=CN=CC=1>[N+:30]([C:33]1[CH:34]=[C:35]([CH:57]=[C:58]([N+:60]([O-:62])=[O:61])[CH:59]=1)[C:36]([O:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][O:45][C:46](=[O:56])/[CH:47]=[CH:48]/[C:49]1[CH:50]=[CH:51][C:52]([O:12][C:11](=[O:13])[C:10]2[CH:14]=[CH:15][C:7]([O:6][CH2:5][CH2:4][CH2:3][C:2]([F:16])([F:17])[F:1])=[CH:8][CH:9]=2)=[CH:53][CH:54]=1)=[O:37])([O-:32])=[O:31]

Participants

6

Reactant 3

HCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 223614014-(4,4,4-Trifluorobutoxy)benzoic acidHCID 598504266-[((2E)-{4-hydroxyphenyl}prop-2-enoyl)oxy]hexyl 3,5-dinitrobenzoate

Product 1

HCID 581935656-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitrobenzoateYield 79%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

8.61 g (0.0347 Mol) of 4-(4,4,4-trifluorobutoxy)benzoic acid are suspended in 100 ml of dichloromethane. 0.42 g (0.0035 Mol) of 4-Dimethylaminopyridine are added at room temperature. 7.98 g (0.04163 Mol) of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC hydrochloride) are added at 0° C. The solution is stirred for 1 h at 0° C. 15.90 g (0.0347 Mol) of 6-[((2E)-{4-hydroxyphenyl}prop-2-enoyl)oxy]hexyl 3,5-dinitrobenzoate dissolved in 50 ml of dichloromethane are added dropwise to the solution at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature the reaction mixture is partitioned between dichloromethane and water. The mixture is acidified with HCl 25%. The organic phase is washed repeatedly with water, dried over sodium sulphate, filtered and concentrated by rotary evaporation. Chromatography of the residue on 600 g silica gel using toluene:ethyl acetate (99:1) as eluant and crystallization from ethyl acetate/hexane (1:2) yielded 18.82 g (79%) of 6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl 3,5-dinitrobenzoate as white crystals.

Workup

  1. additionare added dropwise to the solution at 0° C.
  2. stirringto stir at room temperature overnight
  3. customAfter 22 hours at room temperature the reaction mixture is partitioned between dichloromethane and water
  4. washThe organic phase is washed repeatedly with water
  5. dry with materialdried over sodium sulphate
  6. filtrationfiltered
  7. concentrationconcentrated by rotary evaporation
  8. customcrystallization from ethyl acetate/hexane (1:2)

Sources & evidence

ORD record
ord-4e35ec975db543e9b18eb92c041761b0
Source dataset
uspto-grants-2012_05
Patent number
US08173749B2

Reaction notes

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