With the increasing evolution of pesticide resistance, pyrimidinamine derivatives are considered promising agricultural compounds because of their outstanding activity and their mode of action which is different from other fungicides. But diflumetorim, the commercial pyrimidinamine fungicide, is not effective in controlling corn rust (Puccinia sorghi). In this study, a series of pyrimidinamine derivatives were designed and synthesized using pyrimidifen as a template according to the bioisosterism. The new compounds showed excellent fungicidal activity. Among these compounds, (S)-5-chloro-6-(difluoromethyl)-2-methyl-N-(1-((5-(trifluoromethyl)pyridin- 2-yl)oxy)propan-2-yl)pyrimidin-4-amine, T33, had the best control effect on corn rust with EC50 values of 0.60 mg/L, versus commercial fungicide tebuconazole (1.65 mg/L). The synthesis, characterization, and activity data of the compounds are presented in the text, and the structure-activity relationships are discussed.

A series of novel pyridazinone derivatives were designed and synthesized by replacing 4-(tert-butyl)phenyl moiety of pyridaben with 2-phenylthiazole or oxazole fragments via activity substructure connecting approach. The structures of all target compounds were characterized through NMR, MS, and elemental analysis. Bioassay results exhibit that most compounds showed potent bioactivities againstAphis fabae,Tetranychus urticae,Erysiphe graminis, and/orPuccinia polysora. Among the newly synthesized compounds, 2-(tert-butyl)-4-chloro-5-(((2-phenylthiazol-4-yl)methyl)thio)pyridazin-3(2H)-one (12b) displays remarkable insecticidal activity againstA fabae. Its LC(50)value (2.73 mg/L) is better than that of pyridaben (5.46 mg/L), although inferior to that of imidacloprid (0.51 mg/L). In addition to its extraordinary insecticidal activity, compound12balso exerts 96.9% fungicidal activities againstP polysoraat 500 mg/L in vivo, significantly superior to that of pyridaben (50.0%), while slightly lower than that of tebuconazole (100%). This article discusses the synthesis, bioassay results, and structure-activity relationship of this series of novel pyridazinone derivatives.

Purpose: To develop and evaluate new formulas to determine the magnetic resonance imaging (MRI)-based estimated foetal weight (EFW) more than a week before delivery. Methods: The study included 153 women with singleton pregnancies who gave birth to live, normal neonates within 15-21 days of the MRI examination for whom foetal body volume biometry data were available at term. All foetuses were randomly divided into a testing group (102) and a validation group (51). Regression analysis was used to determine the single volume or the combination of volume and MRI-to-delivery interval that determined the EFW. The accuracy of the two new models and the primary existing model developed by Baker et al. were evaluated in validation group. Results: The two new models had similar mean percentage errors (MPEs) (3.9% vs 3.9%) and proportions of pregnancies with an MPE < 10% (92.2% vs 90.2%); the model incorporating volume and MRI-to-delivery had relatively higher proportions of pregnancies with an MPE < 5% (72.5% vs 64.7%) and EFWs in agreement with the birth weights. The error in the Baker model was almost twice that in the new models. Conclusion: The accuracy of foetal weight estimation more than one week before delivery using the model developed by Baker et al. was poor and was significantly improved by the new models. A combination of the foetal body volume and MRI-to-delivery interval will enable the more accurate determination of the EFWs.

Diflumetorim is a member of pyrimidinamine fungicides that possess excellent antifungal activities. Nevertheless, as reported that the activity of diflumetorim to corn rust (Puccinia sorghi) was not ideal (EC50 = 53.26 mg/L). Herein, a series of novel pyrimidinamine derivatives containing phenyl-thiazole/oxazole moiety were designed based on our previous study and the structural characteristics of diflumetorim, synthesized and bioassayed to discover novel fungicides with excellent antifungal activities. Among these compounds, T18 gave the optimal fungicidal activity, which respectively offers control effects with EC50 values of 0.93 mg/L against P. sorghi and 1.24 mg/L against E. graminis, significantly superior to commercial fungicides diflumetorim, tebuconazole, and flusilazole. Cell cytotoxicity results suggested that compound T18 has lower toxicities than diflumetorim. Furthermore, DFT calculation indicated that the phenyl-thiazole/oxazole moiety plays an unarguable role in the improvement of activity, which will contribute to designing and developing more potent compounds in the future.

A series of novel imidazo[4,5-b]pyridine derivatives were synthesized and their structures were characterized by NMR spectroscopy, mass spectrometry and elemental analysis. The results of bioassays showed that some compounds exhibit good fungicidal activity against Puccinia polysora. In particular, compound 7b showed an EC50 value of 4.00 mg/L, which was comparable with that of tebuconazole. Besides, preliminary structure-activity relationship was discussed.

PURPOSE:To determine whether birth weight can be reliably estimated using three-dimensional (3D) magnetic resonance imaging (MRI) foetal body volume at term. METHOD:Foetuses between 37+5 weeks and 41 weeks of gestation were delivered within 7 days after MRI and ultrasound (US) examinations. 3D foetal models were reconstructed from MRI data, and body volume was calculated. The MRI-based weight estimations were calculated using the Baker equation and the modified Baker equation with a higher density coefficient. The US-based weight estimations were determined using the formula by Hadlock. Estimations based on MRI and US were compared with the birth weights. RESULTS:Among 22 foetuses that underwent both US and MRI evaluations within 48 h before labour, the mean random errors for the estimated weight based on US, the Baker equation and the modified Baker equation were 6.5%, 4.8%, and 4.8%, respectively, and these methods correctly estimated the weights of 77.3%, 86.4% and 100% of the foetuses to within 10% of the actual birth weight. The weights of 95.5% of the foetuses were underestimated by the Baker equation. Similar findings were observed among 103 estimations based on both US and MRI within 7 days before delivery. The mean relative error of the MRI-determined estimate of foetal weight using the modified Baker equation was not significantly associated with foetal sex, birth weight, gestational age at MRI examination, the MRI-to-delivery interval or the type of MRI scanner. CONCLUSION:A modified Baker equation with a high-density coefficient can improve the accuracy of foetal weight estimation based on 3D MRI foetal volume at term, and its accuracy was not significantly affected by foetal characteristics or the type of MRI scanner among births occurring within 7 days after examinations.

A series of nitropyridyl-based dichloropropene ethers were prepared and evaluated for their insecticidal activities against main lepidopteran pests such as M. separate, P. xylostella and P. litura. The compounds showed a broad-spectrum of remarkable insecticidal activities. Especially 4a (2,6-dichloro-4-(3,3-dichloroallyloxy)phenyl 3-[5-nitro-2-pyridyloxy]propyl ether) and 11a (2-(4-(3-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)propoxy)phenoxy)-5-nitropyridine) displayed potent activities comparable to that of Pyridalyl, the only commercialized dichloropropene ether insecticide thus far. The structure-activity relationship was also discussed.

Pyrazolecarboxamide fungicides are one of the most important classes of agricultural fungicides, which belong to succinodehydrogenase inhibitors (SDHIS). To discover new pyrazolecarboxamide analogues with broad spectrum and high activity, a class of new compounds of pyrazole carboxamide derivatives containing thiazole or oxazole ring were designed by scaffold hopping and bioisosterism, and 36 pyrazole carboxamide derivatives with antifungal activity were synthesized. Those compounds were evaluated against five phytopathogenic fungi, Gibberella zeae, Phytophythora capsici, Sclerotonia sclerotiorum, Erysiphe graminis and Puccinia sorghi. The results indicated that most of the compounds displayed good fungicidal activities, especially against E. graminis. Theoretical calculations were carried out at the B3LYP/6-31G (d, p) level and the full geometry optimization was carried out using the 6-31G (d, p) basis set, and the frontier orbital energy, atomic net charges, molecular docking were discussed, and the structure-activity relationships were also studied.

A series of novel thiazole acrylonitrile derivatives was designed and synthesized utilizing NC‐510 as a precursor. Their structures were characterized by NMR spectrometry, MS, and elemental analysis. The results of bioassay indicated that some of these title compounds exhibited 100% mortality at 50 mg/L against Aphis fabae. In particular, the compound 11c displayed the best activity: Its LC50 value achieved 1.45 mg/L, and its insecticidal potency is comparable with that of NC‐510.

A series of novel N-allyloxy/propargyloxy aryloxyphenoxy propionamide compounds was designed and prepared. The structures of the synthesized compounds were confirmed by means of 1H NMR, 13C NMR, LC-MS, elemental analysis and IR. The bioassay results indicate that when against Digitaria sanguinalis and Echinochloa crus-galli, (R)-N-(propargyloxy)-2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy}propanamide(1m)(IC50=6.8 and 6.5 g/hm2, respectively) and (R)-N-(allyloxy)-2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy}propanamide(1r)(IC50=7.4 and 6.0 g/hm2, respectively) are much more effective than commercial aryloxyphenoxypropionic ester herbicide clodinafop- propargyl (IC50=46.5 and 14.6 g/hm2, respectively). The results of crop selectivity show that compounds 1m and 1r are safe to soybean, rape and cotton and can be used as herbicides for soybean, rape and cotton crop.

In an attempt to find leading thiazole carboxanilides exhibiting fungicidal activities, we designed and synthesized a new series of 2-sulfursubstituted thiazole carboxanilides via the reaction between 2-sulfur substituted thiazole carboxylic acid chlorides and substituted aniline. The fungicidal activities of the title compounds against Rhizoctonia solani were screened and the results were remarkable. The most potent compound 8i, N-[2,6-dichloro-4-(trifluoromethyl)phenyl]-2-methylthio-4-(trifluoromethyl)thiazole-5-carboxamide, was identified. The fungicidal EC50 of compound 8i against Rhizoctonia solani was 1.28 mg/L, being comparable to that of Thifluzamide. The results indicate that compound 8i can be considered as a lead compound for further research.

In attempt to lead compounds exhibiting both insecticidal and fungicidal activities, a series of O-benzyl oxime-ether derivatives were designed and synthesized by introducing beta-methoxyacrylate pharmacophore into a scaffold. The insecticidal activity against Aphis fabae and the fungicidal activity against Erysiphe graminis were screened. The title compounds exhibited remarkable insecticidal and fungicidal activities. The most potent compound 6d was identified. Its insecticidal LC50 against A. fabae is 6.4 mg/L, which is lower than that of chlorfenapyr (19.4 mg/L) and even close to the level of imidacloprid (4.8 mg/L). Its fungicidal EC90 in preventive and curative treatment against E. graminis are 2.2 and 4.8 mg/L, respectively, which are lower than azoxystrobin (7.0 and 5.9 mg/L). These results indicate that compound 6d can be considered as a lead for further developing new O-benzyl oxime-ether typed candidates with both fungicidal and insecticidal activities.

OBJECTIVE:To analyse anatomical characteristics of the pelvic floor in young nulliparous volunteers based on three-dimensional MRI.METHODS:Thin-slice MRI was performed in 25 young nulliparous volunteers in Southern Medical University, MRI were imported into Mimics 10.01 for 3D reconstruction.Using 3D models we measured follow indicators: the levator ani muscle volume (LVOL) , levator plate angle (LPA), levator hiatus width (LH-W)and length (LH-L), distance between symphysis and levator sling muscle (LSG).RESULTS:(1) 25 cases of pelvic three-dimensional models was successfully constructed, including the pelvis, pelvic organs and the pelvic floor muscles (including the ischial coccyx muscle, levator ani muscle and its various components, perineal muscles), the models could be able to clearly reflect the level of the pelvic floor muscles; (2) 25 cases of levator ani muscle measurement results:LVOL: (34 ± 6) cm(3), LPA: (43 ± 4) °, LH-W: (33 ± 4) mm, LH-L: (54 ± 5) mm, left LSG: (18.8 ± 2.5) mm, right LSG: (18.3 ± 2.5) mm.CONCLUSIONS:It is an effective way to use the computer to reconstruct the 3D model of female pelvic floor muscles using MRI data set. The quantitative analysis of levator ani muscle three-dimensional model can be assessed pelvic floor function, which is of great value in clinical practice.It is helpful to understand the pelvic floor disorders pathogenesis, clinical diagnosis, treatment options and treatment evaluation to provide reference standards.

Aryloxyphenoxypropionic acid(APP) herbicides inhibiting acetyl-CoA carboxylase(ACCase) have been identified as one of the most important herbicides. As part of continuous efforts to search for new herbicides with high efficacy, broad-spectrum activity and safety to crops, the commercialized APP herbicide metamifop was used as lead compounds for further optimization. Sixteen new N-arylmethyl 2-(4-arylxoyphenoxy) propionamide compounds were designed and prepared by multistep synthetic procedures starting from (R)-(+) 2-(4-hydroxyphenoxy) propanoic acid, and their structures were characterized by H-1 NMR, C-13 NMR, LC/MS, IR and elemental analysis. Steric configuration was confirmed by chiral column liquid chromatography. The bioassay results indicated that all compounds exhibited >90% activity against crabgrass (Digitaria sanguinalis L.), barnyard grass(Echinochloa crus-galliL.) and green foxtail(Setaria Viridis L.) at 2250 g/ha. Further herbicidal activity and phytotoxicit to crops results indicated that(R)-(+)-N-[(6-chloropyridin-3-yl)methyl]-2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)-propanamide (2b) was more effective against Digitaria sanguinalis (IC50 = 15. 4 g/ha) and Echinochloa crus-galli (IC50 = 22. 8 g/ha) than metamifop(IC50 = 31. 9 g/ha and 25. 0 g/ha). In particular, compound 2b was safe to rice (Xiang zao xian 24) and more effective against Leptochloa than commercial cyhalofop-butyl. The herbicidal activity is related to steric configuration that the compounds of R configuration have more effective activity.

A carboxylic ester group was introduced to three series of isoindolinedione substituted benzoxazinone derivatives. Some of these analogues exhibited good herbicidal activities, and the injury symptoms against weeds included leaf cupping, crinkling, bronzing, and necrosis, typical of protox inhibitor herbicides. Structurally, they were classified as Chemical Group A (4-carboxylic ester group-6-isoindolinyl-benzoxazinones), B (4-carboxylic ester group-7-isoindolinyl-benzoxazinones), and C (4-carboxylic ester group-6- tetrahydroisoindolinyl-benzoxazinones). All of the tested compounds were structurally confirmed by (1)H NMR, IR, mass spectroscopy, and elemental analysis. Preliminary bioassay data of these three classes of compounds showed that, in general, the order of the herbicidal effectiveness is C > A > B. Several of the lead compounds, for example, C10 (methyl 2-(6-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-2-methyl-3-oxo-2H-benzo[b][1,4] oxazin-4(3H)-yl) propano-ate), C12 (ethyl 2-(6-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-2- methyl-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) propanoate), and C13 (ethyl 2-(6-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-2-methyl-3-oxo-2H-benzo-[b][1,4]oxazin-4(3H)-yl) butanoate), exhibited greater than 80% control at 75 g a.i./ha in both pre- and postemergence treatments against dicotyledonous weeds, such as Abutilon theophrasti Medic, Chenopodium album L., and Amaranthus ascendens L., and monocotyledon weeds, such as Digitaria sanguinalis L., Echinochloa crus-galli L., and Setaria viridis L. On the basis of advanced screening tests and crop selectivity, compounds C10, C12, and C13 are safer to crops than flumioxazin. Compounds C10, C12, and C13 are potent to develop as pre-emergent herbicides used in peanut, soybean, maize, and cotton fields.

BACKGROUND Although more than ten strobilurin analogues have been commercialized since 1996 as fungicides, only one was available as an acaricide as of 2003. To search for novel strobilurin analogues with unique biological activities, a synthetic screening programme was carried out. RESULTS Syntheses of compounds analogous to the commercialized fungicide metominostrobin and the acaricide fluacrypyrim led to the discovery of a lead compound, (E)-2-[2-[[3,5-bis(trifluoromethyl)phenoxy]methyl]phenyl]-2-(methoxyimino)-N-methylacetamide (3b), that showed moderate acaricidal activity against Tetranychus urticae Koch. Compound 3b has a 3,5-(CF(3))(2)-phenoxymethyl group instead of the unsubstituted phenoxy substituent in metominostrobin. Optimization of compound 3b was achieved by introducing an oxime ether bridge along with an alkylthio(alkyl) branch in place of the oxymethylene chain between two aromatic moieties, as well as by replacing the methoxyiminoacetamide group with a methoxyacrylate structure, leading to (E)- methyl 2-[2-[[[(Z)[1-(3,5-bis(trifluoromethyl)phenyl)-2-methylthioethylidene]amino]oxy] methyl]phenyl]-3-methoxyacrylate (6c) and (E)- methyl 2-[2-[[[(Z)[1-(3,5-bis(trifluoromethyl)phenyl)-1-methylthiomethylidene]amino]oxy]methyl]phenyl]-3-methoxyacrylate (9a, HNPC-A3066). CONCLUSION The above two compounds (6c, 9a) were shown to exhibit potent acaricidal and fungicidal activity. Compound 9a (HNPC-A3066) also exhibits larvicidal and ovicidal activities against various acarids. The acaricidal potency is comparable with those of commercial acaricides such as fluacrypyrim, tebufenpyrad and chlorfenapyr.

Strobilurins have become one of the most important classes of agricultural fungicides. To search for novel strobilurin compounds with unique biological activities, novel bis(trifluoromethyl)phenyl-based strobilurin analogues were synthesized by the reaction of 1-bis(trifluoromethyl)phenyl based methanone oxime with corresponding strobilurin pharmacophores in the presence of bases such as potassium hydroxide, potassium carbonate, or sodium hydride. (E)-Methyl 2-(2-((((Z)(1-(3,5-bis(trifluoromethyl) phenyl)-1-methoxymethylidene)amino)oxy)methyl)phenyl)-3-methoxyacrylate and (Z)-methyl-N-(E)-2-((E)-(5,6-dihydro-1,4,2-dioxazin-3-yl)(methoxyimino)methyl)benzyloxy-3,5-bis(trifluoromethyl)benzimidate were more effective against Erysiphe graminis and sphaerotheca fuligine than commercial strobilurin fungicides metominostrobin, azoxystrobin, and trifloxystrobin.

The solid-phase synthesis of 7-fluoro-1,4-2H-benzoxazine 3(4H)-ones on Wang resin via esterification,etherification,reduction,cyclization and cleavage reactions was studied,and the reaction conditions were optimized after analyzing the reaction kinetics according to the IR spectrum.

The solid-phase synthesis of 7-fluoro-1,4-2H-benzoxazine 3 (4H)-ones on Wang resin via esterification, etherification, reduction, cyclization and cleavage reactions was studied, and the reaction conditions were optimized after analyzing the reaction kinetics according to the IR spectrum.