Cesium carbonate → HCID 59352090, compound

HRID 2385307Notes

Reaction equation

HRID 2385307 reaction equation
[NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]2([C:21]3[C:12](=[CH:13][C:14]4[O:19][CH2:18][CH2:17][O:16][C:15]=4[CH:20]=3)[O:11][CH2:10]2)[C:2]1=[O:22].Br[CH2:24][CH:25]1[CH2:27][C:26]1([F:29])[F:28].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[F:28][C:26]1([F:29])[CH2:27][CH:25]1[CH2:24][N:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]2([C:21]3[C:12](=[CH:13][C:14]4[O:19][CH2:18][CH2:17][O:16][C:15]=4[CH:20]=3)[O:11][CH2:10]2)[C:2]1=[O:22]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 27614022-(Bromomethyl)-1,1-difluorocyclopropaneHCID 58224164Spiro[furo[2,3-g]-1,4-benzodioxin-8(7H),3'-[3H]indol]-2'(1'H)-one, 2,3-dihydro

Product 1

HCID 59352090HCID 59352090, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

A mixture of 2,3-dihydrospiro[furo[2,3-g][1,4]benzodioxine-8,3′-indol]-2′(1′H)-one (0.29 g, 1.00 mmol), 2-(bromomethyl)-1,1-difluorocyclopropane (0.21 g, 1.20 mmol), cesium carbonate (0.65 g, 2.00 mmol) and N,N′-dimethylformamide (2.5 mL) was heated at 40° C. for 2 h and filtered while hot. The filtrate was allowed to cool to ambient temperature and water was added, causing a precipitate to be deposited. The solid was collected by filtration, washed with water and dried under vacuum. The residue was recrystallized from ethanol/diethyl ether to afford 1′-[(2,2-difluorocyclopropyl)methyl]-2,3-dihydrospiro[furo[2,3-g][1,4]benzodioxine-8,3′-indol]-2′(1′H)-one (0.28 g, 73%) as a colourless solid: mp 162-164° C.; 1H NMR (300 MHz, DMSO-d6) δ 7.35 (ddd, J=7.8, 7.8, 0.9 Hz, 1H), 7.23 (dd, J=7.9 Hz, 1H), 7.17 (d, J=6.9 Hz, 1H), 7.06 (dd, J=7.4, 7.4 Hz, 1H), 6.51 (d, J=1.9 Hz, 1H), 6.13 (d, J=6.2 Hz, 1H), 4.71 (dd, J=9.3 Hz, 1H), 4.69 (dd, J=9.3 Hz, 1H), 4.17 (dd, J=3.7 Hz, 2H), 4.10 (dd, J=3.4 Hz, 2H), 3.87 (d, J=6.9 Hz, 2H), 2.33-2.14 (m, 1H), 1.74-1.60 (m, 1H), 1.48-1.29 (m, 1H); 13C NMR (75 MHz, DMSO-d6) δ 176.5 (d, 4JC-F=15.9 Hz), 154.5 (d, 6JC-F=1.4 Hz), 144.1 (d, 6JC-F=1.9 Hz), 141.9, 137.7 (d, 5JC-F=3.9 Hz), 131.7 (d, 6JC-F=2.3 Hz), 128.8, 123.5, 122.9 (d, 6JC-F=1.6 Hz), 121.2 (d, 5JC-F=4.1 Hz), 114.3 (q, 1JC-F=283.4 Hz), 110.9 (d, 2JC-F=18.1 Hz), 109.1, 98.7 (d, 5JC-F=3.6 Hz), 79.2 (d, 5JC-F=3.7 Hz), 64.1, 63.5, 57.1 (d, 6JC-F=2.4 Hz), 36.6 (t, 3JC-F=5.9 Hz), 20.1 (t, 2JC-F=17.4 Hz), 14.7 (t, 2JC-F=10.7 Hz); MS (ES+) m/z 386.2 (M+1).

Workup

  1. filtrationfiltered while hot
  2. temperatureto cool to ambient temperature
  3. additionwater was added
  4. filtrationThe solid was collected by filtration
  5. washwashed with water
  6. customdried under vacuum
  7. customThe residue was recrystallized from ethanol/diethyl ether

Sources & evidence

ORD record
ord-424c8376f78d4b139b11cd49a39e7d40
Source dataset
uspto-grants-2012_09
Patent number
US08263606B2

Reaction notes

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