Water → 1-(1,3-Dioxaindan-5-yl)cyclopropane-1-carboxylic acid

HRID 2043209Notes

Reaction equation

HRID 2043209 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([CH2:10][C:11]#N)=[CH:9][C:4]=2[O:3][CH2:2]1.Br[CH2:14][CH2:15]Cl.[OH-:17].[Na+].[OH2:19]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3([C:11]([OH:19])=[O:17])[CH2:15][CH2:14]3)=[CH:9][C:4]=2[O:3][CH2:2]1

Participants

6

Reactant 4

HCID 962WaterHCID 78491-Bromo-2-ChloroethaneHCID 14798Sodium HydroxideHCID 781783,4-(Methylenedioxy)phenylacetonitrile

Product 1

HCID 143496081-(1,3-Dioxaindan-5-yl)cyclopropane-1-carboxylic acidYield 80.1%

Reagents, catalysts & solvents 1

HCID 66133Benzyl triethylammonium chlorideCatalyst

Conditions

Temperature
70 °C

Procedure

A mixture of benzo[1,3]dioxole-5-acetonitrile (5.10 g 31.7 mmol), 1-bromo-2-chloro-ethane (9.000 mL 108.6 mmol), and benzyltriethylammonium chloride (BTEAC, 0.181 g 0.795 mmol) was heated to 70° C. and then 50% (wt./wt.) aqueous sodium hydroxide (26 mL) was slowly added. The reaction was stirred at 70° C. for 24 hours and then heated to reflux (130° C. bath temperature) for 72 hours. The dark brown/black reaction mixture was diluted with water (400 mL) and extracted twice with equal volumes ethyl acetate and dichloromethane. The basic aqueous solution was acidified with concentrated hydrochloric acid to pH less than one and the precipitate was filtered and washed with 1 M hydrochloric acid. The solid material was dissolved in dichloromethane (400 mL) and extracted twice with equal volumes of 1 M hydrochloric acid and once with a saturated aqueous solution of sodium chloride. The organic solution was dried over sodium sulfate and evaporated to dryness to give a white to slightly off-white solid (5.23 g, 25.4 mmol, 80.1%). ESI-MS m/z calc. 206.1. found 207.1 (M+1)+. Retention time of 2.37 minutes. 1H NMR (400 MHz, DMSO-d6) δ 1.07-1.11 (m, 2H), 1.38-1.42 (m, 2H), 5.98 (s, 2H), 6.79 (m, 2H), 6.88 (m, 1H), 12.26 (s, 1H).

Workup

  1. temperatureheated
  2. temperatureto reflux (130° C. bath temperature) for 72 hours
  3. extractionextracted twice with equal volumes ethyl acetate and dichloromethane
  4. filtrationthe precipitate was filtered
  5. washwashed with 1 M hydrochloric acid
  6. dissolutionThe solid material was dissolved in dichloromethane (400 mL)
  7. extractionextracted twice with equal volumes of 1 M hydrochloric acid and once with a saturated aqueous solution of sodium chloride
  8. dry with materialThe organic solution was dried over sodium sulfate
  9. customevaporated to dryness

Sources & evidence

ORD record
ord-d9ee7908aac84bd38e291b7333042d53
Source dataset
uspto-grants-2013_11
Patent number
US08586615B2

Reaction notes

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