1-Butanol → Dibutyl carbonate

HRID 1506725Notes

Reaction equation

HRID 1506725 reaction equation
[C:1]([O-:4])([O-:3])=[O:2].[K+].[K+].[CH2:7](O)[CH2:8][CH2:9][CH3:10].Cl[C:13](Cl)(Cl)[C:14]([C:16](Cl)(Cl)Cl)=O.[CH:22](Cl)(Cl)Cl>>[C:1](=[O:4])([O:3][CH2:13][CH2:14][CH2:16][CH3:22])[O:2][CH2:7][CH2:8][CH2:9][CH3:10]

Participants

5

Reactant 4

HCID 2631-ButanolHCID 6212ChloroformHCID 8303HexachloroacetoneHCID 11430Potassium Carbonate

Product 1

HCID 68333Dibutyl carbonate

Conditions

Temperature
10 °C

Procedure

In a three-neck glass-made reactor having internal volume of 10 L in which a dropping funnel and a distillation line having a cooling portion cooled to 10° C. were installed were charged 50 g of K2CO3 (reagent manufactured by Tokyo Chemical Industry Co., Ltd., P1748) and 3408 g (46.0 mol) of 1-butanol (reagent manufactured by Tokyo Chemical Industry Co., Ltd., B0704). After warming at 30° C. by an oil bath, the whole amount of 4154 g (15.7 mol) of hexachloroacetone (reagent manufactured by Tokyo Chemical Industry Co., Ltd., H0335) was added dropwise thereto from the dropping funnel under stirring, while adjusting a dropping rate such that the temperature in the reactor did not exceed 50° C., whereby the whole reagent was added dropwise. After the dropwise addition ended, the temperature of the oil bath was slowly increased up to 100° C. over 2 hours under sufficient stirring. Chloroform generated by the reaction during temperature increase was recovered as liquid from the distillation line installed in the reactor. From the point in time when the temperature of the oil bath reached 100° C., the internal pressure of the system was slowly reduced by using a vacuum pump through a pressure-regulating valve installed in the distillation line, and the pressure was continuously reduced until the pressure finally became 20 mmHg. The surplus 1-butanol and dibutyl carbonate in the reactor produced by the reaction were extracted from the distillation line, and distillation was continuously performed until no liquid existed in the reactor finally, thereby recovering the whole reaction mixture (7486 g, recovery rate of 99%).

Workup

  1. customIn a three-neck glass-made reactor having internal
  2. temperatureAfter warming at 30° C. by an oil bath
  3. customdid not exceed 50° C.
  4. additionwhereby the whole reagent was added dropwise
  5. additionAfter the dropwise addition
  6. temperaturethe temperature of the oil bath was slowly increased up to 100° C. over 2 hours under sufficient stirring
  7. temperatureincrease
  8. distillationwas recovered as liquid from the distillation line
  9. customreached 100° C.

Sources & evidence

ORD record
ord-82be2d079fe8453eb49e452627c9b1f8
Source dataset
uspto-grants-2015_12
Patent number
US09221740B2

Reaction notes

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