148476-30-6

The invention discloses a spiral armor manman ester and intermediate preparation method, the spiral armor manman ester intermediate is 3 - (2, 4, 6 - trimethyl-phenyl) - 2 - oxo - 1 - oxaspiro [4, 4] nonyl - 3 - ene - 4 - ol, preparation method comprises the following steps: hydroxy cyclopentyl formic acid ethyl ester, 2, 4, 6 - trimethyl phenyl acetic acid in under the action of a dehydrating agent, to carry out the esterification, then generate the cyclization reaction, generating 3 - (2, 4, 6 - trimethyl-phenyl) - 2 - oxo - 1 - oxaspiro [4, 4] nonyl - 3 - ene - 4 - ol. The process short reaction time, the reaction temperature is low, can obviously very high yield.

A series of novel spirocyclic tetronic acid derivatives containing an oxalyl moiety was designed and synthesized via the key intermediate 3-(2,4,6-trimethyl)-2-oxo-1-oxaspiro[4.4]-decyl-3-en-4-ol. The target compounds were identified by 1H NMR and elemental analysis or high-resolution mass spectrum (HRMS). The results of bioassays indicated that most of the target compounds possessed excellent acaricidal activities against carmine spider mite larvae and eggs. Especially, diisopropylamino oxalyl compound 7g and piperidine oxalyl compound 7h were 1.4- and 2.3-fold as high as the activities of commercial Spiromesifen, respectively, against spider mite eggs. Moreover, most of the target compounds exhibited insecticidal activities against Lepidoptera pest. Interestingly, compounds containing alkylamino-substituted oxalyl moiety showed obvious selectivity between spider mite larvae and eggs because the activities against spider mite eggs of 7g and 7h were 25-fold those against spider mite larvae, whereas Spiromesifen had no significant differences in these activities. This meant that the introduction of an oxalyl moiety to spirocyclic tetronic acid might lead to novel biological activity characteristics.

The broad spectrum acaricides spirodiclofen (BAJ2740, trade name: Envidor) and spiromesifen (BSN2060, trade name: Oberon) with an additional excellent activity against whiteflies, both belong to the new chemical class of tetronic acid derivatives discovered at Bayer CropScience during the 1990s. The discovery process starting from herbicidal PPO (protoporphyrinogen oxidase) chemistry, the synthetic routes leading to the products, and some insight into process development of central intermediates is given. Spirodiclofen and spiromesifen have a new mode of action (interference with lipid biosynthesis), show no cross-resistance to any resistant mite or whitefly field population and are therefore valuable tools for resistance management.