Synthesis and Quantitative Structure–Activity Relationship (QSAR) Study of Novel Isoxazoline and Oxime Derivatives of Podophyllotoxin as Insecticidal Agents

Abstract

An ultrahigh-performance liquid chromatography (UHPLC) tandem mass spectrometric (MS/MS) method was developed for the simultaneous quantification of 2-acetyl-4-tetrahydroxybutylimidazole (THI), 2- and 4-methylimidazoles (2-MI and 4-MI), and 5-hydroxymethylfurfural (HMF) in beverage samples. A C30 reversed-phase column was used in this method, providing sufficient retention and total resolution for all targeted analytes, with an MS/MS instrument operated in selected reaction monitoring (SRM) mode for sensitive and selective detection using isotope-labeled 4-methyl-d(3)-imidazole (4-MI-d(3)) as the internal standard (IS). This method demonstrates lower limit of quantification (LLOQ) at 1 ng/mL and coefficient of determination (r(2)) >0.999 for each analyte with a calibration range established from 1 to 500 ng/mL. This method also demonstrates excellent quantification accuracy (84.6-105% at 5 ng/mL, n = 7), precision (RSD < 7% at 5 ng/mL, n = 7), and recovery (88.8-99.5% at 10, 100, and 200 ng/mL, n = 3). Seventeen carbonated beverage samples were tested (n = 2) in this study including 13 dark-colored beverage samples with different flavors and varieties and 4 light-colored beverage samples. Three target analytes were quantified in these samples with concentrations in the range from 284 to 644 ng/mL for 4-MI and from 706 to 4940 ng/mL for HMF. THI was detected in only one sample at 6.35 ng/mL.

Semisynthesis and insecticidal activity of arylmethylamine derivatives of the neolignan honokiol against Mythimna separata Walker

“…For example, the corrected mortality rate of 5b against M. separata after 10 days was only 3.3%, after 20 days it had increased to 34.5%, and after 36 days to 55.2%. Meanwhile, the symptoms of M. separata treated by the tested compounds were also observed in the same way as in our previous works for podophyllotoxin derivatives [9][10][11]. The pupation of the larvae and the adult emergence of M. separata were inhibited by these compounds, therefore, the stage from the larvae to adulthood of M. separata was prolonged as compared with the control group.…”

“…The insecticidal activity of compounds 1-3 and 5a-m against the prethird-instar larvae of M. separata was assessed by the leaf-dipping method as described previously [10]. For each compound, 30 larvae Brought to you by | Freie Universität Berlin Authenticated Download Date | 7/1/15 3:14 PM (ten larvae per group) were used.…”

“…Moreover, arylmethylamine moieties are found in some molecules showing various types of biological properties such as herbicidal, insecticidal, fungicidal, and antitumor activities [8]. In continuation of our program on the development of novel natural-product-based pesticidal agents [9][10][11], herein we semisynthesized a series of novel arylmethylamine derivatives of 1 (5a-m; Scheme 1) by introduction of the arylmethylamine fragment to its skeleton. The oriental armyworm (Mythimna separata Walker) is an important and typical insect pest of crops, and sometimes its outbreaks can spread widely and result in complete crop loss.…”

Synthesis of Novel Oxime Sulfonate Derivatives of 2′(2′,6′)-(Di)chloropicropodophyllotoxins as Insecticidal Agents

“…16 Additionally, Hu et al found that once a 36 chlorine atom was introduced at the C-2' position of podophyllotoxin derivatives, the 37 corresponding compounds showed no significant cytotoxicity. 17 More recently, we have 38 prepared a series of oxime sulfonate derivatives of picropodophyllotoxin 18 (2, Figure 1) and 39 4α/β-acyloxy-2′(2′,6′)-(di)halogenopodophyllotoxin derivatives 19,20 (3, Figure 1) as 40 insecticidal agents, and found some derivatives exhibited more potent insecticidal activity 41 than toosendanin, a commercial botanical insecticide isolated from Melia azedarach. Where T is the mortality rate in the tested compounds group, and C is the mortality rate in the 210 blank control group (T and C were expressed as percentages).…”

Design, Synthesis and Biological Evaluation of Novel Rapamycin Benzothiazole Hybrids as mTOR Targeted Anti-cancer Agents

“…[16][17][18][19] Interestingly, a similar strategy had already been successfully applied in the synthesis of rapamycin derivativezotarolimus, 20) an anti-proliferative drug, which modified by replacement of hydroxyl with tetrazole at C-43 postion. Intrigued by the above observation, using a similar design as zotarolimus, we plan to replace the tetrazole moiety of zotarolimus with benzothiazole group by means of structure-based bioisosterism, 21,22) both of them with the same heterocyclic backbone.…”