Ethyl butyrate → 5-[(2'-Cyanobiphenyl-4-yl)methyl]-4,6-dioxononane

HRID 274252

反応式

HRID 274252 の反応式
[O:1]=[C:2]([CH2:6][C:7](=[O:11])[CH2:8][CH2:9][CH3:10])[CH2:3][CH2:4][CH3:5].C(C(C)=O)CC.C(OCC)(=O)CCC.[NH2-].[Li+].[H-].[Na+].Br[CH2:31][C:32]1[CH:37]=[CH:36][C:35]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][C:39]=2[C:44]#[N:45])=[CH:34][CH:33]=1>CN(C=O)C>[C:44]([C:39]1[CH:40]=[CH:41][CH:42]=[CH:43][C:38]=1[C:35]1[CH:34]=[CH:33][C:32]([CH2:31][CH:6]([C:7](=[O:11])[CH2:8][CH2:9][CH3:10])[C:2](=[O:1])[CH2:3][CH2:4][CH3:5])=[CH:37][CH:36]=1)#[N:45]

参加物

8

反応物 6

HCID 7762Ethyl butyrateHCID 78952-PentanoneHCID 24532Lithium amideHCID 24758Sodium hydrideHCID 264544,6-NonanedioneHCID 15019124'-(Bromomethyl)-2-cyanobiphenyl

生成物 1

HCID 200928635-[(2'-Cyanobiphenyl-4-yl)methyl]-4,6-dioxononane収率 104.6%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒2 回

実験手順

15.6 g of 4,6-dioxononane, prepared from methyl propyl ketone and ethyl butyrate in the presence of lithium amide (according to CA 42 : 4129 f), are dissolved in 160 ml of anhydrous DMF. 4 g of 60% NaH are added in portions. When the exothermic effect has subsided, the mixture is cooled to room temperature and a solution of 27.2 g of 4'-bromomethyl-2-cyanobiphenyl, prepared in Example 4, in 90 ml of DMF is introduced dropwise. The mixture is stirred for 30 min at room temperature and then heated at 60° C. for 2 h. It is concentrated under vacuum and the concentrate is taken up in a water/dichloromethane mixture and acidified with a dilute solution of HCl. After decantation, the aqueous phase is extracted twice with dichloromethane. The organic phases are washed with water, dried and then concentrated to give 36.3 g of an oil, which is purified by chromatography twice in succession (eluent: chloroform, then cyclohexane 90%/ethyl acetate 10% respectively) to give a solid identified by NMR as being the enol tautomer melting at 105° C., and an oil corresponding to the diketone tautomeric form.

後処理

  1. additionis introduced dropwise
  2. temperatureheated at 60° C. for 2 h
  3. concentrationIt is concentrated under vacuum
  4. extractionAfter decantation, the aqueous phase is extracted twice with dichloromethane
  5. washThe organic phases are washed with water
  6. customdried
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-93a37d520490420fbbdb674b463811c7
出典データセット
uspto-grants-1995_02
特許番号
US05389632

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