Potassium Hydroxide → HCID 58418749, compound

HRID 557502Notes

Reaction equation

HRID 557502 reaction equation
[OH-].[K+].[Br:3][C:4]1[CH:16]=[C:15]([C:17]([CH3:20])([CH3:19])[CH3:18])[CH:14]=[CH:13][C:5]=1[CH2:6][CH:7]([CH2:11][CH3:12])[C:8](O)=[O:9].S(Cl)([Cl:23])=O>O>[Br:3][C:4]1[CH:16]=[C:15]([C:17]([CH3:20])([CH3:19])[CH3:18])[CH:14]=[CH:13][C:5]=1[CH2:6][CH:7]([CH2:11][CH3:12])[C:8]([Cl:23])=[O:9]

Participants

5

Reactant 3

HCID 14797Potassium HydroxideHCID 24386Thionyl ChlorideHCID 66991064HCID 66991064, compound

Product 1

HCID 58418749HCID 58418749, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a mixture of sodium ethoxide obtained from 13.7 g (0.60 mol) of sodium metal and 375 ml of dry ethanol and 193 g (0.50 mol) of diethyl (2-bromo-4-tert-butylbenzyl)malonate 65.5 g (0.60 mol) of ethyl bromide was added dropwise by vigorous stirring. This mixture was refluxed for 4 hours, then cooled, and a solution of 100 g of KOH in 270 ml of water was added. The obtained mixture was refluxed for 5 hours, then ethanol was distilled off. A mixture of the obtained solution and 1.5 liters of cold water was acidified by 1 M HCl to pH 1. The precipitate was decanted and then dissolved in 500 ml of ether. This solution was evaporated to dryness, and the residue was decarboxilated for ca. 2 hours at 180° C. To the obtained 2-(2-bromo-4-tert-butylbenzyl)butanoic acid 128 ml (209 g, 1.76 mol) of thionyl chloride was added. The resulting mixture was stirred for 12 hours at room temperature. An excess of thionyl chloride was distilled off. Fractional rectification of the residue gave 116 g (70%) of yellowish liquid, b.p. 137° C.-142° C./1 mm Hg. Anal. calc. for C15H20BrClO: C, 54.32; H, 6.08. Found: C, 54.43; H, 6.20. 1H NMR (CDCl3): δ 7.54 (d, J=1.9 Hz, 1H, 3-H in C6H3), 7.25 (dd, J=8.0 Hz, J=1.9 Hz, 1H, 5-H in C6H3), 7.16 (d, J=8.0 Hz, 1H, 6-H in C6H3), 3.24-3.06 (m, 2H, CH2CHCH2Me), 2.93 (dd, J=13.6 Hz, J=6.1 Hz, 1H, CHCH2Me), 1.89-1.69 (m, 2H, CH2Me), 1.28 (s, 9H, tBu), 1.02 (t, J=7.5 Hz, CH2Me). 13C{1H} NMR (CDCl3): δ 176.4, 152.1, 133.9, 130.9, 130.1, 124.7, 124.4, 58.3, 37.1, 34.5, 31.1, 24.9, 11.0.

Workup

  1. additionwas added dropwise by vigorous stirring
  2. temperatureThis mixture was refluxed for 4 hours
  3. temperaturecooled
  4. temperatureThe obtained mixture was refluxed for 5 hours
  5. distillationethanol was distilled off
  6. additionA mixture of the obtained solution and 1.5 liters of cold water
  7. customThe precipitate was decanted
  8. dissolutiondissolved in 500 ml of ether
  9. customThis solution was evaporated to dryness
  10. distillationAn excess of thionyl chloride was distilled off

Sources & evidence

ORD record
ord-83c6b954db34459fa392e479649a0b37
Source dataset
uspto-grants-2011_11
Patent number
US08058461B2

Reaction notes

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