Hexamethylenetetramine → 6-Methoxy-3-methyl-2-oxo-1a,2,3,7b-tetrahydro-1H-3-aza-cyclopropa[a]naphthalene-5-carbaldehyde

To a flame dried round bottom flask equipped with a nitrogen cap was added 972 mg (4.8 mmol) 6-Methoxy-3-methyl-1,1a,3,7b-tetrahydro-3-aza-cyclopropa[a]naphthalen-2-one, 40 ml of trifluoroacetic acid and 806 mg (5.7 mmol) of hexamethylene tetraamine. The mixture was stirred under reflux for 1.5 hours and then cooled to ambient temperature. The reaction mixture was quenched in 200 ml ice and then treated with solid sodium carbonate until pH 9 was reached. The aqueous phase was extracted with chloroform (3×30 ml). The combined organics were then washed with brine followed by drying over sodium sulfate and evaporation in vacuo. The crude residue was taken up in ethyl acetate whereupon crystals formed. Four crops totaling 373 mg were obtained. The mother liquors were purified by silica gel column chromatography eluting with 1/1 ethyl acetate/hexane to afford another 98 mg (total yield 42%) of a white solid which was used directly in the following step. Mass spectrum APCI m/e 232 (p+1).

1. customTo a flame dried round bottom flask
2. customequipped with a nitrogen
3. customcap
4. temperatureunder reflux for 1.5 hours
5. customThe reaction mixture was quenched in 200 ml ice
6. additiontreated with solid sodium carbonate until pH 9
7. extractionThe aqueous phase was extracted with chloroform (3×30 ml)
8. washThe combined organics were then washed with brine
9. dry with materialby drying over sodium sulfate and evaporation in vacuo
10. customformed
11. customwere obtained
12. customThe mother liquors were purified by silica gel column chromatography
13. washeluting with 1/1 ethyl acetate/hexane
14. customto afford another 98 mg (total yield 42%) of a white solid which

ORDレコード

ord-4b7d2fcd4ee14de09547bebf77cae88b

出典データセット

uspto-grants-2006_10

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US07119207B2