Potassium Hydroxide → [[(2,2-Dimethyl-3-butyn-1-yl)oxy]methyl]benzene

HRID 2405138Notes

Reaction equation

HRID 2405138 reaction equation
[OH-].[K+].[CH2:3]([O:10][CH2:11][C:12]([CH3:20])([CH3:19])[C:13]#[C:14][Si](C)(C)C)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1>CO.O>[CH2:3]([O:10][CH2:11][C:12]([CH3:20])([CH3:19])[C:13]#[CH:14])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

5

Reactant 2

HCID 14797Potassium Hydroxide3×HCID 57488515HCID 57488515, compound

Product 1

HCID 57488516[[(2,2-Dimethyl-3-butyn-1-yl)oxy]methyl]benzene

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 962WaterSolvent3×

Conditions

Temperature
5 °C

Procedure

A 30 L jacketed reactor was charged with methanol (6 vol) which was then cooled to 5° C. Potassium hydroxide (85%, 1.3 equiv) was added to the reactor. A 15-20° C. exotherm was observed as the potassium hydroxide dissolved. The jacket temperature was set to 25° C. A solution of 4-benzyloxy-3,3-dimethyl-1-trimethylsilylbut-1-yne (1.0 equiv) in methanol (2 vol) was added and the resulting mixture was stirred until reaction completion, as monitored by HPLC. Typical reaction time at 25° C. is 3-4 h. The reaction mixture is diluted with water (8 vol) and then stirred for 0.5 h. Hexanes (6 vol) was added and the resulting mixture was stirred for 0.5 h. The phases were allowed to settle and then the aqueous phase (pH 10-11) was drained off and discarded. The organic phase was washed with a solution of KOH (85%, 0.4 equiv) in water (8 vol) followed by water (8 vol). The organic phase was then concentrated down using a rotary evaporator, yielding the title material as a yellow-orange oil. Typical purity of this material is in the 80% range with primarily a single impurity present. 1H NMR (400 MHz, C6D6) δ 7.28 (d, 2H, J=7.4 Hz), 7.18 (t, 2H, J=7.2 Hz), 7.10 (d, 1H, J=7.2 Hz), 4.35 (s, 2H), 3.24 (s, 2H), 1.91 (s, 1H), 1.25 (s, 6H).

Workup

  1. customA 15-20° C. exotherm
  2. dissolutiondissolved
  3. customwas set to 25° C
  4. stirringstirred for 0.5 h
  5. stirringthe resulting mixture was stirred for 0.5 h
  6. concentrationThe organic phase was then concentrated down
  7. customa rotary evaporator

Sources & evidence

ORD record
ord-bb553d46796945878db05101e697f7f1
Source dataset
uspto-grants-2014_08
Patent number
US08802868B2

Reaction notes

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