Toluene → alpha-Cyano-3-phenoxybenzyl (1R,trans)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate

HRID 127016Notes

Reaction equation

HRID 127016 reaction equation
[CH3:1][C:2]1([CH3:15])[C@H:4]([CH:5]=[N:6][O:7][CH2:8][CH:9]2[CH2:11][CH2:10]2)[C@H:3]1[C:12]([OH:14])=[O:13].[C:16]([CH:18](Br)[C:19]1[CH:24]=[CH:23][CH:22]=[C:21]([O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:20]=1)#[N:17].C(=O)([O-])[O-].[K+].[K+].C1(C)C=CC=CC=1>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.O>[CH3:1][C:2]1([CH3:15])[C@H:4]([CH:5]=[N:6][O:7][CH2:8][CH:9]2[CH2:10][CH2:11]2)[C@H:3]1[C:12]([O:14][CH:18]([C:16]#[N:17])[C:19]1[CH:24]=[CH:23][CH:22]=[C:21]([O:25][C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[CH:20]=1)=[O:13]

Participants

8

Reactant 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 12713810alpha-Cyano-3-phenoxybenzyl bromideHCID 53706710(1R,trans)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylic acid

Product 1

HCID 86737089alpha-Cyano-3-phenoxybenzyl (1R,trans)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylateYield 80.8%

Reagents, catalysts & solvents 3

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 962WaterSolvent

Procedure

A mixture of 1.8 g of (1R,trans)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylic acid, 2.30 g of α-cyano-3-phenoxybenzyl bromide, 0.05 g of tetrabutylammonium hydrogen sulfate, 0.05 g of benzyltriethylammonium chloride, 0.58 g of potassium carbonate, 10 ml of toluene and 6 ml of water was heated at 60°-70° for 4 hours, let stand overnight at room temperature and reheated at 60°-70° for an additional eight hours. The resulting reaction mixture separated into layers. The toluene layer was separated, washed with water, then with saturated sodium bicarbonate and saturated sodium chloride, dried over magnesium sulfate and stripped to give an oil. This oil was chromatographed on silica gel with a mixture of ether-pentane (1:4 ratio) as the eluant to give 2.7 g of desired product as a yellow oil, [α]D25 -16.2, (CHCl3 ; c=0.02 g/cc).

Workup

  1. temperaturewas heated at 60°-70° for 4 hours
  2. waitreheated at 60°-70° for an additional eight hours
  3. customThe resulting reaction mixture
  4. customseparated into layers
  5. customThe toluene layer was separated
  6. washwashed with water
  7. dry with materialwith saturated sodium bicarbonate and saturated sodium chloride, dried over magnesium sulfate
  8. customto give an oil
  9. customThis oil was chromatographed on silica gel with a mixture of ether-pentane (1:4 ratio) as the eluant

Sources & evidence

ORD record
ord-0b64c4aa82874efa87ae78aef68c0a86
Source dataset
uspto-grants-1981_03
Patent number
US04254277

Reaction notes

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