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Synthesis method of stable isotope labeled pyrethroid

A stable isotope, pyrethroid technology, applied in organic chemistry methods, chemical instruments and methods, preparation of carbon-based compounds, etc., can solve the problem that raw materials are difficult to obtain, the natural abundance of m-phenoxybenzaldehyde requires a large amount, and it is easy to cause Abundance dilution and other issues to achieve the effect of reducing the generation of side reactions

Active Publication Date: 2019-09-20
PLANTS & ANIMALS & FOOD TESTING QUARANTINE TECH CENT SHANGHAI ENTRY EXIT INSPECTION & QUARANTINE BUREAU +1
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  • Description
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AI Technical Summary

Problems solved by technology

The synthesis of natural abundance m-phenoxybenzaldehyde mostly adopts the sommlet method, alkali hydrolysis oxidation method, and acid oxidation method (nitric acid and sodium nitrite are oxidation reagents) with m-methoxybenzyl chloride as raw material. The stability of these methods Isotope-labeled m-methoxybenzyl chloride, the raw materials are difficult to obtain, the reaction route is long, and the use of strong acid and strong base is easy to cause abundance dilution, and high vacuum distillation or sodium bisulfite is often used to obtain natural abundance m-phenoxybenzaldehyde Precipitation purification requires expensive and sophisticated equipment or produces a large amount of waste acid, waste alkali, and waste water, and the natural abundance of m-phenoxybenzaldehyde in the crude substrate is also very large, which is obviously not suitable for small quantities, high prices, and abundant Synthesis of isotope-labeled m-phenoxybenzaldehyde with high degree of easy dilution

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  • Synthesis method of stable isotope labeled pyrethroid
  • Synthesis method of stable isotope labeled pyrethroid
  • Synthesis method of stable isotope labeled pyrethroid

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preparation example Construction

[0028] A synthetic method for stable isotope-labeled pyrethroids provided by the invention comprises the following steps:

[0029] S1) Potassium phenate labeled with stable isotope is used as a labeling precursor, which reacts with m-bromobenzaldehyde under microwave conditions to generate an intermediate stable isotope-labeled m-phenoxybenzaldehyde; the stable isotope-labeled potassium phenate is a stable isotope 13 C label, stable isotope D label or stable isotope 13 C and D are double-labeled; the substituted chrysanthemum acid chloride is dichloro chrysanthemum acid chloride, dibromochrysanthemum acid chloride, trifluoromethyl chrysanthemum acid chloride, 2,2,3,3-tetramethylcyclopropanecarbonyl chloride or isopropyl p-chloro Phenylacetyl. In the step S1, the molar ratio of stable isotope-labeled potassium phenate to m-bromobenzaldehyde is 1:1-1:10, the reaction temperature is -50-200° C., and the reaction time is 0.1-2 hours. Exceeding the range will cause a huge waste o...

Embodiment 1

[0040] A stable isotope labeled cypermethrin-D 5 The preparation method, this method comprises the following steps:

[0041] 1. m-phenoxybenzaldehyde-D 5 Synthesis

[0042] Add potassium phenate-D to the 80mL reaction bottle 5 2.7g, activated cuprous chloride 1g, add m-bromobenzaldehyde 4g, DMSO (dimethyl sulfoxide) 10ml, helium protection, closed system, set microwave power 50 watts, pressure 50psi, reaction temperature 140 ℃, The reaction time is 5min. Column chromatography separation after reaction finishes, obtains 3.71g m-phenoxybenzaldehyde-D 5 , Yield 92.5%, GC detection, purity 99.5%, mass spectrometry detection, isotope abundance 99.5atom%D.

[0043] 2. Cypermethrin-D 5 Synthesis

[0044] In a 35mL reaction bottle, sequentially add 4g of sodium cyanide, 3g of heavy water, and m-phenoxybenzaldehyde-D 5 1.75g, add chrysanthemum acid chloride 4g, close the system, set the microwave power to 40 watts, the pressure to 40psi, the reaction temperature to 40°C, and t...

Embodiment 2

[0046] A stable isotope labeled permethrin- 13 C 6 The preparation method, this method comprises the following steps:

[0047] 1. m-phenoxybenzaldehyde- 13 C 6 Synthesis

[0048] Add potassium phenate- 13 C 6 5.5g, activated cuprous bromide 1.5g, add m-bromobenzaldehyde 8.1g, dioxane 15ml, argon protection, closed system, set microwave power 100 watts, pressure 80psi, reaction temperature 150 ℃, reaction time 4min. Column chromatography separation after reaction finishes, obtains 7.56g m-phenoxybenzaldehyde- 13 C 6 , yield 94.3%, GC detection, purity 99.6%, mass spectrometry detection, isotope abundance 99.8atom% 13 c.

[0049] 2. Permethrin- 13 C 6 Synthesis

[0050] In a 35mL reaction flask, sequentially add 1g of sodium borohydride, 3g of deuterated methanol, and m-phenoxybenzaldehyde- 13 C 6 0.88g, stir for 5min, add chrysanthemum acid chloride 2g, close the system, set the microwave power to 70 watts, the pressure to 45psi, the reaction temperature to 60°C...

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Abstract

The invention discloses a synthesis method of stable isotope labeled pyrethroid. The method includes: taking stable isotope labeled potassium phenate as the labeled precursor for reaction with m-bromobenzaldehyde in inert gas protection under a microwave condition to generate a key intermediate stable isotope labeled m-phenoxybenzaldehyde, then carrying out reaction with substituted chrysanthemoyl chloride under a liquid phase alkaline microwave condition to generate stable isotope labeled pyrethroid. The synthesis method of stable isotope labeled pyrethroid provided by the invention is simple, safe and reliable, after simple separation and purification, the chemical purity of the product can reach 99% or above, and the isotope abundance is 99% or above, the product can be applied to biological metabolism, food safety, inspection and quarantine, environmental monitoring and other fields, and compared with foreign products, the product obtained by the method provided by the invention has the advantages of good quality and low cost.

Description

technical field [0001] The invention relates to a method for synthesizing a stable isotope label, in particular to a method for synthesizing a stable isotope-labeled pyrethroid. Background technique [0002] Pyrethroid pesticides have high efficacy, low toxicity, fast decomposition, less residue, and wide application. They are widely used in crops. However, after application, a considerable part will enter the soil, the atmosphere and remain in crops. Enter the human body along the food chain. Due to the long residual period of certain pyrethroid insecticides, they are not only highly toxic to agricultural beneficial organisms such as bees, silkworms, and butterflies, but also highly toxic to aquatic organisms such as fish, shrimp, crabs, and shellfish. Some pyrethroid pesticides are environmental hormone substances, which also have a great impact on the normal physiological activities of mammals, so long-term exposure even at low doses can cause chronic diseases, and some ...

Claims

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Application Information

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IPC IPC(8): C07C253/00C07C255/39C07C67/14C07C69/747
CPCC07C45/64C07C253/00C07C67/14C07B2200/05C07C2601/02C07C47/575C07C255/39C07C69/747
Inventor 邓晓军徐仲杰白少飞赵超敏王浩然孙雯古淑青潘洁
Owner PLANTS & ANIMALS & FOOD TESTING QUARANTINE TECH CENT SHANGHAI ENTRY EXIT INSPECTION & QUARANTINE BUREAU
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