Diethyl Malonate → HCID 22262962、化合物

HRID 489822

反応式

HRID 489822 の反応式
C[C@H]1C[O:29][C@@:5]2([O:9][C@H:8]3C[C@H]4[C@@H]5CC=C6C[C@@H](O)CC[C@]6(C)[C@H]5CC[C@]4(C)[C@H:7]3[C@@H]2C)[CH2:4]C1.C(OCC)(=O)C[C:33](OCC)=[O:34].[CH2:42]([C:44]1([CH2:48][OH:49])[CH2:47][O:46][CH2:45]1)[CH3:43].C([Sn](=O)CCCC)CCC>>[CH2:42]([C:44]12[CH2:47][O:46][C:45]([CH2:4][C:5]([O:9][CH2:8][CH3:7])=[O:29])([O:49][CH2:48]1)[O:34][CH2:33]2)[CH3:43]

参加物

5

反応物 4

HCID 7761Diethyl MalonateHCID 61221Dibutyltin oxideHCID 76444Oxt-101HCID 99474Diosgenin

生成物 1

HCID 22262962HCID 22262962、化合物

反応条件

温度
140 °C

実験手順

Into a 4 l three necked flask equipped with a stirrer, a distilling column, a nitrogen in- and outlet, a heating jacket, a thermocouple, and a vacuum pump were charged 1920 g of diethyl malonate (12 moles), 464 g of 3-ethyl-3-hydroxymethyl oxetane (4 moles), and 2,5 g of dibutyl tin oxide. The reaction mixture was heated to 140° C. upon which temperature the ethanol distillation began. The reaction temperature was gradually increased to 200° C. during 6 hours. During this time 171 g of ethanol were collected as distillate. The temperature was lowered to 100° C. and the pressure was lowered to 29 mbar by application of vacuum. The excess diethylmalonate was distilled off. The pressure was further lowered to 0.03 mbar and the temperature was gradually increased to 156° C. Three fractions of distillate were collected. The third fraction (100–104° C./0.03 mbar) consisted of 379 g, which according to GC analysis contained 75% of 4-ethyl-1-(ethoxycarbonylmethyl)-2,6,7-trioxabicyclo[2.2.2]octane having the following structure

後処理

  1. distillationthe ethanol distillation
  2. temperatureThe reaction temperature was gradually increased to 200° C. during 6 hours
  3. distillationDuring this time 171 g of ethanol were collected as distillate
  4. customwas lowered to 100° C.
  5. distillationThe excess diethylmalonate was distilled off
  6. temperaturethe temperature was gradually increased to 156° C
  7. distillationThree fractions of distillate were collected
  8. customThe third fraction (100–104° C./0.03 mbar)

出典と根拠

ORDレコード
ord-3acc812c26734cadabbdc462384f148e
出典データセット
uspto-grants-2005_12
特許番号
US06979719B1

関連ノート

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