131929-60-7

Spinosyn A

1H-as-Indaceno[3,2-d]oxacyclododecin-7,15-dione,2-[(6-deoxy-2,3,4-tri-O-methyl-α-L-mannopyranosyl)oxy]-13-[[(2R,5S,6R)-5-(dimethylamino)tetrahydro-6-methyl-2H-pyran-2-yl]oxy]-9-ethyl-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-tetradecahydro-14-methyl-,(2R,3aS,5aR,5bS,9S,13S,14R,16aS,16bR)-;(2R,3aS,5aR,5bS,9S,13S,14R,16aS,16bR)-2-[(6-Deoxy-2,3,4-tri-O-methyl-α-L-mannopyranosyl)oxy]-13-[[(2R,5S,6R)-5-(dimethylamino)tetrahydro-6-methyl-2H-pyran-2-yl]oxy]-9-ethyl-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-tetradecahydro-14-methyl-1H-as-indaceno[3,2-d]oxacyclododecin-7,15-dione;A 83543A;Lepicidin A;Spinosyn A;(-)-Spinosyn A;Spinosad A

131929-60-7

C41H65NO10

InChIKey=SRJQTHAZUNRMPR-UYQKXTDMSA-N

731.96

731.96

1312995-182-4

DTXSID8037598

Light grey to white crystals

2932209090

Heterocyclic Compound

111.22000

4.80

1.16±0.1 g/cm3(Predicted)

84ºC to 99.5ºC

801.5±65.0 °C(Predicted)

438.5±34.3 °C

1.540

Spinosyn A: 290 mg l -1 (pH 5); Spinosyn D: 29 mg l -1 (pH 5)

Spinosyn A: 3.2 x 10 -8 Pa Spinosyn D: 2.1 x 10 -8 Pa

Slightly stale water /Spinosad/

Forosamine at the 17-position of spinosyns A and D was hydrolyzed under mild acidic conditions to give the corresponding 17-pseudoaglycones. The tri-O-methylrhamnose at the 9-position of the 17-pseudoaglycone of spinosyn A was hydrolyzed under more vigorous acidic conditions to give the aglycone of spinosyn A. However, these conditions led to decomposition of the 17-pseudoaglycone of spinosyn D, presumably due to more facile protonation of the 5,6-double bond to produce a tertiary carbonium ion which undergoes further rearrangements. Spinosyns J and L (3'-O-demethyl spinosyn A and D, respectively) obtained from fermentation of biosynthetically-blocked mutant strains of Saccharopolyspora spinosa, were oxidized to give the corresponding 3'-keto-derivatives and the resultant keto-sugars were then beta-eliminated under basic conditions to give the 9-pseudoaglycones of spinosyns A and D respectively. Forosamine at the 17-position of the 9-pseudoaglycone of spinosyn D was then readily hydrolyzed to yield the aglycone of spinosyn D.