Synthesis of dehydrocineole, a new monoterpene from the acarid mite, caloglyphus rodriguezi (arachnida: acari)
✍ Scribed by F.O. Ayorinde; J.W. Wheeler; R.M. Duffield
- Book ID
- 104242258
- Publisher
- Elsevier Science
- Year
- 1984
- Tongue
- French
- Weight
- 207 KB
- Volume
- 25
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
Dehydrocineole, a new monoterpene ether, 6_methylsalicylaldehyde, undecane and tridecane are reported from the opisthonotal gland secretion of the mite, Caloglyphus rodriguezi. A synthesis of dehydrocineole is described. The opisthonotal gland1 secretions of acarid shown to contain a variety of low molecular weight geranial, neral, 6_methylsalicylaldehyde, perillen hydrocarbons ranging from CIo to C15. 2s3 We report gland secretions of Caloglyphgus rodriguezi. mites representing six genera have been organic compounds including: neryl formate, and several saturated and unsaturated here the chemistry of the opisthonotal Gas chromatographic-mass spectroscopic analysis4 of methylene chloride extracts of whole bodies of Caloglyphus rodriguezi showed four major peaks in a ratio of 2:6:9:4. Peak 1 eluting from the column exhibited a mass spectrum with a molecular ion at m/z 152(5), with additional fragment ions at 137(2), 124(17), 109(100), 94(15), 79(61), 77(22), and 43(731. Peak 2 and peak 3 gave molecular ions at m/z 156 and 184 respectively. Their fragmentation patterns and retention times matched those of undecane and tridecane. Peak 4 showed a molecular ion at m/z 136(90) with additional fragment ions at 135(100), 118(15), 107(17), IO5(41, 90(30), 89(20), 79(30), 77(50), 63(15), 55(5), 53(20) and 51(30). Peak 4 thus appeared to be 6-methylsalicylaldehyde.3'6 It was isolated from the mixture by preparative gas chromatography and gave a proton NMR7 spectrum consistent with the structure of 6-methylsalicylaldehyde. It was synthesized from 2-nitro-6-methylbenzoic acid' in four steps giving material identical to the natural product. The compound corresponding to peak 1 was also isolated by preparative gas Reduction of the unknown with hydrogen (Pt) gave 1,8-cineole (11, identified by chromatography.