2- Decenedioic acid

The 3.8-nonadienoate 91, obtained by dimerization-carbonylation, has been converted into several natural products. The synthesis of brevicomin is described in Chapter 3, Section 2.3. Another royal jelly acid [2-decenedioic acid (149)] was prepared by cobalt carbonyl-catalyzed carbonylation of the terminal double bond, followed by isomerization of the double bond to the conjugated position to afford 149[122], Hexadecane-2,15-dione (150) can be prepared by Pd-catalyzed oxidation of the terminal double bond, hydrogenation of the internal double bond, and coupling by Kolbe electrolysis. Aldol condensation mediated by an organoaluminum reagent gave the unsaturated cyclic ketone 151 in 65% yield. Finally, the reduction of 151 afforded muscone (152)[123]. n-Octanol is produced commercially as described beforc[32]. 

Nonadienoate (73) is used for the synthesis of another royal jelly acid, 2-decenedioic acid (146) (130). The terminal double bond was car-bonylated with Co2(CO)8 coordinated by pyridine. Linear ester was obtained in 80% selectivity. Hydrolysis and double-bond migration promoted by strong base produced royal jelly acid (146) as a crystalline compound. 

Carbonylation of butadiene in alcohol catalyzed by Pd(OAc)2/PPli3 affords 3,8-nonadienoate 142 in high yield52, 53. The synthesis of 2-decenedioic acid (144) (royal jelly acid) may be carried out as follows54 Carbonylation of 142 in alcohol... 

Decenedioic acid Very-long-chain acyl-CoA... 

For instance, with aliphatic alcohols the alkyl nona-3,8-dienoates are formed [25, 26], This nonadienoate can be used for the synthesis of another royal jelly acid, the 2-decenedioic acid (Equation 22). Carbonyla-tion of the nonadienoate in alcohol using Co2(CO)g/pyridine as the catalyst yields a linear diester which can be transformed into the royal jelly acid by hydrolysis and concomitant double bond migration [27]. 

The chemistry of royal jelly has been extensively studied. Chemical constituents reported to be present hydroxy fatty acids, including 10-hydroxy-fra j -2-decenoic acid (royal jelly acid 10-HDA), which ranges between 1.64% and 4.24% (usually 2.0-2.5%) in fresh royal jelly and up to 7.0% in the freeze-dried product (usual range 4.5-5.5%), 10-hydro-xydecanoic acid (0.60-1.25%) " 10-acet-oxydecanoic acid, 11-S-hydroxydodecanoic acid, hydroxy-2 -decenoic acid 10-phosphate, and others gluconic acid, sebacic acid and 2-decenedioic acid, /)-hydroxyben-zoic acid, 3-hydroxydecanoic, 8-hydroxyde-canoic, and 3,10-dihydroxydecanoic acids ° sterols including methylenecholesterol (ca. 

Fig. 14.5 Chromatogram of organic acids extracted using diethyl ether and ethyl acetate from the urine of a patient with suberylglycinuria and separated as their methyl derivatives (diazomethane) on 3 per cent SE-30 on Chromosorb W (DMCS, 80-100 mesh) using temperature programming from 80°C to 250°C at 6°C min Peak identifications are 1, 3-hydroxybutyrate 2, adipate 3, 3-methyladipate 4, pimelate (heptanedioate) 5, octenedioate 6, suberate (octanedioate) 7, hexanoylglycine plus 4-hydroxyphenylacetate 8, azeleate (nonanedioate) 9, decenedioate 10, sebacate (decanedioate) 11, hippurate 12, unknown, 13, suberylglycine. (Redrawn with modifications from Truscott et al., 1979)...

Fig. 14.7 Chromatogram of organic acids extracted using ethyl acetate and diethyl ether from the urine of a child with Jamaican vomiting sickness, separated as their methyl derivatives (diazomethane) on 5 per cent OV-1 using temperature programming from 70°C to 300°C at 4°C min with a 4 min initial isothermal delay. Peak identifications are 1, 3-hydroxybutyrate plus 3-hydroxyisovalerate (approx. 4 6) 2, ethylmalonate 3, methylsuccinate 4, octanoate 5, glutarate 6, adipate 7, isovalerylglycine 8, 4-octenedioate plus furandicarboxylate 9, suberate (octanedioate) 10, /i-hexanoyl-glycine 11, decenedioate 12, sebacate (decanedioate) 13, hippurate 14, n-pentadecanoate (internal standard) 15, palmitate 16, stearate. (Redrawn with modifications from Tanaka et al, 1976)...

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