Acrylonitrile → 3,4-dihydro-2H-1-benzopyran-2-carboxylic acid

HRID 1603679

反応式

HRID 1603679 の反応式
NC1CCC=CO1.C(#N)C=C.N12CCN(CC1)CC2.C(C1C=CC2C=CC=CC=2O1)#N.[O:32]1[C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][C:36]=2[CH:35]=[CH:34][CH:33]1[C:42]([OH:44])=[O:43].[OH-].[Na+]>C(O)C.[Pd]>[O:32]1[C:37]2[C:36](=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH2:35][CH2:34][CH:33]1[C:42]([OH:44])=[O:43]

参加物

9

反応物 6

HCID 7855AcrylonitrileHCID 9237DabcoHCID 14798Sodium HydroxideHCID 15552178CyanobenzopyranHCID 21879658Benzopyran carboxylic acid2 回HCID 67079662Dihydroaminopyran

生成物 1

HCID 27236653,4-dihydro-2H-1-benzopyran-2-carboxylic acid

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 702Ethanol溶媒

実験手順

An alternative route to the dihydroaminopyran, O, again starting with Aldehyde M, is described in Thorberg et al., supra. Aldehyde M is reacted with acrylonitrile and 1,4-diazabicyclo[2.2.2]octane (DABCO) at reflux. The cyanobenzopyran is converted to the corresponding benzopyran carboxylic acid with aqueous sodium hydroxide. The benzopyran carboxylic acid (Q) is esterified using a mineral acid in ethanol and reduced by hydrogenation over 5% Pd/C to provide a chroman carboxylic acid. The chroman carboxylic acid is reacted with diphenylphosphorazidate and trimethylamine in benzene at reflux followed by addition of benzyl alcohol and an additional 24 hours at reflux. This provides a benzyloxycarbonyl (SOC) protected amine (R). Hydrogenation of the BOC protected amine provided racemic aminochroman (Q) (Step v). The racemic amine (Q) was resolved using the technique described in WO 93/07135 (Step vi). The resolved (R)-amine (P) is converted to a compound having formula VII following the procedures described in WO 95/11891 (Step vii).

後処理

  1. temperatureat reflux

出典と根拠

ORDレコード
ord-98c72d6630444c11935e0552629283fc
出典データセット
uspto-grants-1999_11
特許番号
US05990114

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