1-Butanol → Dibutyl carbonate

HRID 257234ノート

反応式

HRID 257234 の反応式
[CH2:1]([OH:5])[CH2:2][CH2:3][CH3:4].[C:6](=[O:8])=[O:7].[CH2:9](Cl)[CH2:10][CH2:11][CH3:12].C(=O)([O-])N>CC#N.C(OCC)C>[C:6](=[O:8])([O:7][CH2:9][CH2:10][CH2:11][CH3:12])[O:5][CH2:1][CH2:2][CH2:3][CH3:4]

参加物

7

反応物 4

HCID 2631-ButanolHCID 276CarbamateHCID 280Carbon Dioxide5 回HCID 8005Butyl Chloride2 回

生成物 1

HCID 68333Dibutyl carbonate収率 73%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 6342Acetonitrile溶媒2 回

反応条件

温度
85 °C

実験手順

A 160 cc Parr autoclave was charged with 2.22 g (0.03 mol) butanol, 6.9 g (0.035 mol) N-cyclohexyl-N',N',N",N"-tetramethylguanidine and 30 mL CH3CN. The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of CO2 resulted in an exothermic reaction with a rise in temperature to ca. 40° C. Into a Fischer-Porter bottle was added 8.33 g (0.09 mol) butyl chloride in 10 mL CH3CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After 1 h the butyl chloride solution was added all at once under 80 psig CO2 to the pre-formed carbamate anion solution generated in the autoclave. After addition the pressure was raised to 160 psig with carbon dioxide and the reaction mixture was warmed to 85° C. for 16 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, Cl-+HCyTMG filtered off and by G.C. analysis a 73% yield of dibutyl carbonate was calculated. Oil 1H NMR (CDCl3) 4.14(t, J=6.6 Hz, 4H), 1.66 (m, 4H), 1.41 (m, 4H), 0.94 (t, J=7.3 Hz, 6H). 13C{1H} NMR (CDCl3) 155.9, 68.2, 31.2, 19.4, 14.1. IR (film) 1746, 1260; MS (FAB) m/z=175 (MH+).

後処理

  1. customwas attached to a pressure head and at room temperature
  2. customresulted in an exothermic reaction with a rise in temperature to ca. 40° C
  3. additionwas added above the solution
  4. additionAfter addition the pressure
  5. temperatureto cool to room temperature
  6. filtrationfiltered off and by G.C

出典と根拠

ORDレコード
ord-a6c135bcc66647b79dc329f9be6e90db
出典データセット
uspto-grants-1993_11
特許番号
US05260473

反応ノート

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