Isoprene → 2-Methyl-1-morpholino-2,5-heptadiene

反応式

Br/[CH:2]=[CH:3]\[CH3:4].[CH2:5]=[CH:6][C:7](=[CH2:9])[CH3:8].[NH:10]1[CH2:15][CH2:14][O:13][CH2:12][CH2:11]1>>[CH3:9][C:7](=[CH:6][CH2:5][CH:2]=[CH:3][CH3:4])[CH2:8][N:10]1[CH2:15][CH2:14][O:13][CH2:12][CH2:11]1

参加物

反応物 3

HCID 6557Isoprene

HCID 8083Morpholine

HCID 643834cis-1-Bromo-1-propene

生成物 1

HCID 538104392-Methyl-1-morpholino-2,5-heptadiene収率 40%

実験手順

In a much slower reaction than Example 19, Z-1-bromopropene, isoprene and morpholine gave 2-methyl-1-morpholino-2,5-heptadiene in 40% yield along with higher boiling unidentified products and polymers. The major point of interest in this Example was to determine whether or not the stereochemistry of the Z-1-bromopropene was retained in the product. The product appeared homogeneous by GLC (gas liquid chromatography) and NMR (nuclear magnetic resonance); however, IR (infrared) showed bands characteristic of both cis and trans olefinic groups. Therefore, the product may be a mixture of isomers. Aside from the stereochemistry with respect to the double bonds, the structure can be assigned conclusively from the NMR spectrum. The addition of the 1-propenyl group, therefore, was completely regio-selective, adding to the terminal carbon of the less-substituted double bond of the isoprene. This contrasts with the mixture of positional isomers obtained when this halide was added to 1-hexene (refer Example 4, supra).