Background and overview[1][2]
Biphenyltriazolol is also called biphenyltriazolol, a heterocyclic fungicide. Chemical name: 1-biphenyloxy-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butanol-(2). The chemical structural formula is as follows. The original drug is a colorless crystal with a melting point of 123~124°C. It is easily soluble in isopropyl alcohol, toluene, methylene chloride and cyclohexanone. It is insoluble in water and aliphatic hydrocarbons and is relatively stable in acidic and alkaline media. It will not decompose when stored for one year at pH 3 to 10. A broad-spectrum fungicide that mainly inhibits the biosynthesis of ergosterol in bacterial cells. Thereby interfering with the cell membrane structure, deforming bacterial cells, enlarging the tops of hyphae, deforming branches, and inhibiting growth. It can penetrate through the leaves of plants and enter the systemic function of plant body fluid transmission. It is used to prevent and treat rust, powdery mildew, leaf spot, scab, etc. on a variety of plants. It has protective and therapeutic effects. Low toxicity to humans and animals, acute oral LD50>5 000 mg/kg in rats, acute dermal LD50>5 000 mg/kg, slight irritation to eye mucosa, no irritation to skin, moderate toxicity to fish and aquatic organisms. Very low toxicity to bees.
At present, there are many agricultural fungicides, and biphenyltriazole is one of them. It belongs to the fungicide in the field of plant protection and has dual functions of prevention and treatment. It is a necessary component to inhibit the formation of fungal membrane ergosterol, so that the victim There is an accumulation of sterol intermediates in the fungus, while ergosterol gradually decreases and is depleted, thereby interfering with the synthesis of cell membranes, causing cell deformation, enlarged hyphae, deformed branches, and inhibited growth. In addition, it can be quickly absorbed by the growing parts of the plant and transferred mainly to the top. It not only has bactericidal activity, but also promotes crop growth, making the roots developed, leaves dark green, strong plants, and effective tillers increased, thus improving crop growth. It can effectively prevent and control peanut rust, apple leaf spot, pear scab, etc. It is currently one of the most commonly used products in the prevention and control of bacterial diseases.
Preparations[2]
Weigh 220 parts of biphenyltricyclazole original powder, 90 parts of wetting agent alkyl sulfate, 100 parts of dispersing agent fatty alcohol polyoxyethylene ether, 90 parts of disintegrating agent ammonium sulfate, and adsorbent diatomite 100 parts, 50 parts of stabilizer disodium hydrogen phosphate, and 350 parts of filler light calcium carbonate. After mixing them evenly, grind them through a jet mill to obtain the mother powder. Mix the mother powder with 10 parts of the binder polyvinyl alcohol, and then Granulate, dry and sieve to obtain approximately 910 parts of 24.18% diphenyltricyclazole water-dispersible granules.
Detection[3]
Wang Xuemei and others used three second-order correction algorithms, including alternating trilinear decomposition (ATLD), alternating fitting residual (AFR), and self-weighted alternating trilinear decomposition (SWATLD), to analyze the three-dimensional fluorescence spectrum data, respectively. Direct and rapid quantitative determination of biphenyltriazolol content in bananas. When the number of components of the analyzed system is 2, the average recoveries obtained by ATLD, AFR and SWATLD are (98.2±2.6)%, (97.6±2.1)% and (91.5±3.5)% respectively. In addition, the accuracy of the three algorithms was evaluated using the elliptical confidence interval test (EJCR) and quality factors such as sensitivity (SEN), selectivity (SEL) and limit of detection (LOD). The experimental results show that all three algorithms can be successfully used to directly analyze the content of biphenyltriadiol in bananas.
Standard preparation[4]
Preparation of biphenyltriazole alcohol diastereomer A by methanol recrystallization method:
In a reaction kettle equipped with a mechanical stirrer, thermometer, and reflux condensation device, add 320g of biphenyltriazole alcohol raw material (A content 82%, B content 17%, other impurities 1%) and 1900ml anhydrous methanol , heat and reflux to dissolve, filter while hot to remove insoluble matter; the filtrate is reheated to reflux, stir evenly, slowly cool to 10°C, fully crystallize, filter, wash, filter and press to dryness to obtain 210g of the primary crystalline product of isomer A (A content 96%, B content 4%); then add the crystallized product to 1250ml anhydrous methanol, continue to recrystallize once, filter, wash, and vacuum dry at 60°C to constant weight to obtain 156g biphenyltriazole alcohol non-p-p Enantiomer A (A content is 99.4%, B content is 0.42%, the purity of isomer A after deducting water and metal ions is 99.3%, calculated based on the original technical material, the recovery rate of pure isomer A is 59.0%) , white solid, melting point 136.5~137.1℃; 1H NMR(DMSO-d6)δ:8.74(s,1H),8.07(s,1H),7.59(dd,4H),7.42(t,2H),7.32(t ,1H), 7.09(d,2H),6.41(d,1H),5.55(d,-OH),3.58(d,1H),0.94(s,9H).
Preparation of biphenyltriazole alcohol diastereomer B by recrystallization method from ethyl acetate-n-hexane mixed solvent:
Combine the mother liquors of the above two methanol recrystallizations, spin off part of the methanol under reduced pressure, stop rotary evaporation until the total weight of the solution is about 650g, and obtain the biphenyltriazole alcohol solution (containing 490g methanol and 160g biphenyltriazole alcohol , A content 66%, B content 32%, other impurities 2%) heated to 60°C, then slowly cooled to 20°C, fully crystallized, filtered, and the mother liquor was obtained, and 75g of the crystallized product was recovered at one time, and the biphenyltriazole alcohol mother liquor was obtained Concentrate and recrystallize twice using the same solute-to-solvent ratio as in the first concentration to obtain 60g of secondary recovered crystallized product from the mother liquor and 4.2g of tertiary recovered crystallized product. The final mother liquor can be recycled, and the secondary and tertiary recovered crystals can be combined. Recover 64.2g of crystalline product (A content 54%, B content 45%), add 200ml ethyl acetate, heat and reflux to dissolve, then add 250ml n-hexane, stir evenly, slowly cool down to 10°C, fully crystallize, filter, and wash. , 26.4g of the primary crystalline product of isomer B (A content 8.3.��, B content 91.5%); then recrystallize the crystallized product once with a mixed solvent of ethyl acetate-n-hexane in the same way, and vacuum dry at 60°C to constant weight to obtain 19.5g of the diastereoisomer of biphenyltriazole alcohol. Isomer B (B content is 99.0%, A content is 0.3%, other impurities are 0.7%, the purity of B isomer after deducting water and metal ions is 98.5%, calculated based on the original original drug, the recovery rate of pure isomer B is 35.3 %), the mother liquor obtained by recrystallizing twice from ethyl acetate-n-hexane mixed solvent can be recycled. Isomer B is a white solid with a melting point of 144.9~145.5℃; 1HNMR(DMSO-d6)δ:8.79(s,1H), 8.02(s,1H),7.59(dd,4H),7.42(t,2H), 7.32(t,1H),7.13(d,2H),6.35(d,1H),3.85(d,1H),0.91(s,9H).
Main reference materials
[1] Agricultural Dictionary
[2] [Chinese invention] CN200710195292.9 Diphenyltriazole water-dispersible granules and preparation method thereof
[3] Wang Xuemei, Wu Hailong, Nie Jinfang, Yu Ruqin. Rapid detection of diphenyltriazolol content in bananas by three-dimensional fluorescence second-order calibration method [J]. Analytical Chemistry, 2009, 37(06): 811-816.
[4] CN201710156634.X A method for preparing the standard sample of diastereoisomers of biphenyltriazole alcohol with the right to review and authorize
