WO2024067094A1 - 烯草酮组合物及含有该组合物的乳油和母药 - Google Patents

烯草酮组合物及含有该组合物的乳油和母药 Download PDF

Info

Publication number
WO2024067094A1
WO2024067094A1 PCT/CN2023/118525 CN2023118525W WO2024067094A1 WO 2024067094 A1 WO2024067094 A1 WO 2024067094A1 CN 2023118525 W CN2023118525 W CN 2023118525W WO 2024067094 A1 WO2024067094 A1 WO 2024067094A1
Authority
WO
WIPO (PCT)
Prior art keywords
clethodim
thioglycolate
thioglycolic acid
composition
weight
Prior art date
Application number
PCT/CN2023/118525
Other languages
English (en)
French (fr)
Inventor
郭庆春
焦其帅
李成伟
李玉华
Original Assignee
兰升生物科技集团股份有限公司
河北兰润植保科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 兰升生物科技集团股份有限公司, 河北兰润植保科技有限公司 filed Critical 兰升生物科技集团股份有限公司
Publication of WO2024067094A1 publication Critical patent/WO2024067094A1/zh

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides

Definitions

  • the present invention relates to a clethodim composition, which contains clethodim or an agriculturally acceptable salt thereof and thioglycolic acid or thioglycolic acid ester.
  • the present invention further relates to a clethodim emulsifiable concentrate and a parent drug containing the composition.
  • Clethodim is an important cyclohexanedione oxime herbicide with the following structure:
  • Clethodim has the advantages of broad spectrum, high efficiency and low toxicity, but due to the presence of hydroxyl, double bond, oxime and other functional groups in its molecular structure, it is unstable and easily degraded. Moisture, oxygen, ultraviolet light and temperature in the daily environment can cause the degradation of Clethodim. Therefore, effective measures are urgently needed to reduce its degradation during long-distance transportation and long-term storage.
  • clethodim The commonly used preparation of clethodim is emulsifiable concentrate.
  • the present invention aims to provide a stable clethodim composition, which contains clethodim or an agriculturally acceptable salt thereof and thioglycolic acid or thioglycolic acid ester.
  • the present invention provides:
  • a clethodim composition comprising clethodim or an agriculturally acceptable salt thereof and thioglycolic acid or a thioglycolic acid ester.
  • composition according to (1) above wherein the thioglycolate is C 1-20 alkyl thioglycolate, more preferably C 1-10 alkyl thioglycolate.
  • composition according to (1) or (2) above, wherein the thioglycolate is one or more selected from isooctyl thioglycolate, ethyl thioglycolate, 1,4-butylene bis(thioglycolate), and ethylene glycol bis(thioglycolate).
  • Clethodim emulsifiable concentrate comprising the composition according to any one of (1) to (4) above; preferably, the content of the composition of the present invention is 10-70% by weight, preferably 10-40% by weight, and specifically can be, for example, about 10-15% by weight, 25-30% by weight, 35-40% by weight, or 50-60% by weight, relative to the total weight of the emulsifiable concentrate.
  • a parent drug of clethodim which contains the composition according to any one of the above (1) to (4); preferably, the weight ratio of the composition to the solvent in the parent drug is (5-90):(95-10), preferably (20-50):(80-50), more preferably (30-60):(70-40), and specifically can be, for example, 37:63 or 50:50.
  • thioglycolate is C 1-20 alkyl thioglycolate, more preferably C 1-10 alkyl thioglycolate.
  • thioglycolate is one or more selected from isooctyl thioglycolate, ethyl thioglycolate, 1,4-butylene bis(thioglycolate), and ethylene glycol bis(thioglycolate).
  • % means percentage by weight, and “about” means within the range of ⁇ 10%, preferably ⁇ 5%.
  • the degradation rate is an important indicator for measuring the stability of clethodim or its agriculturally acceptable salt.
  • the initial content of clethodim or its agriculturally acceptable salt is recorded as w1, the content during the measurement is recorded as w2, and the degradation rate is calculated as (w1-w2)/w1 ⁇ 100%.
  • the content can be measured by a known method such as high performance liquid chromatography.
  • the stability of clethodim or its agriculturally acceptable salt is improved by adding thioglycolic acid or thioglycolic acid ester to clethodim as a stabilizer.
  • the thioglycolate used in the present invention is preferably a C 1-20 thioglycolate, more preferably a C 1-10 thioglycolate.
  • the alkanol may be a monohydric alcohol, a dihydric alcohol or a polyhydric alcohol.
  • thioglycolate examples include isooctyl thioglycolate, ethyl thioglycolate, 1,4-butylene bis(thioglycolate), ethylene glycol bis(thioglycolate), and the like. These may be used alone or in combination of two or more.
  • any one of isooctyl thioglycolate, ethyl thioglycolate, 1,4-butylene bis(thioglycolate), and ethylene glycol bis(thioglycolate) is used as the stabilizer.
  • the weight of the thioglycolic acid or thioglycolic acid ester is 0.001-20%, preferably 0.001-10%, and more preferably 0.005-5%, relative to the weight of clethodim or its agriculturally acceptable salt. Specifically, it can be, for example, about 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 2%, 3%, 4%, 5%, etc., but is not limited to these specific values.
  • composition of the present invention can be prepared into a preparation suitable for clethodim by a known method with suitable adjuvants or auxiliaries allowed for use in pesticides.
  • suitable adjuvants or auxiliaries allowed for use in pesticides.
  • the preparations of clethodim are known, including but not limited to emulsifiable concentrates.
  • the present invention first discovered that thioglycolic acid or thioglycolic acid ester has a stabilizing effect on clethodim or its agriculturally acceptable salt, reducing or delaying its degradation. Therefore, the present application also relates to the use of thioglycolic acid or thioglycolic acid ester as a stabilizer for clethodim or its agriculturally acceptable salt. In this use, the specific examples and dosage of thioglycolic acid or thioglycolic acid ester are as described above.
  • the present application also relates to a clethodim emulsifiable concentrate containing the composition of the present invention as described above, which can be prepared by a known method for preparing emulsifiable concentrates by combining the composition of the present invention with the adjuvants and adjuvants for preparing emulsifiable concentrates allowed on pesticides.
  • the amount of the composition of the present invention is preferably 10-70% by weight, more preferably 10-60% by weight, and further preferably 10-40% by weight. In some specific embodiments, the amount of the composition of the present invention is about 10-15% by weight, 25-30% by weight, 35-40% by weight, or 50-60% by weight.
  • the present application also relates to a parent drug of clethodim containing the composition of the present invention as described above.
  • the composition of the present invention is prepared by mixing the composition of the present invention with a solvent, wherein the weight ratio of the composition of the present invention to the solvent is (5-50):(95-50), preferably (20-50):(80-50), and more preferably (30-60):(70-40). In some specific embodiments, the weight ratio of the composition of the present invention to the solvent is about 37:63 or 50:50.
  • Specific examples of the solvent include, but are not limited to, solvent oil, and the like, such as 150# solvent oil, 200# solvent oil, and the like.
  • Isooctyl thioglycolate (JS for short) was added to the original drug of clethodim (produced by Hebei Lansheng Biotechnology Co., Ltd.), the weight ratio of clethodim: isooctyl thioglycolate was 100:1, and the mixture was placed in a 35°C thermostat, and the clethodim content was detected by high performance liquid chromatography at the time shown in Table 1.
  • Day 0 refers to the day of drug addition
  • *2 refers to the content measured on the day after adding isooctyl thioglycolate.
  • Isooctyl thioglycolate was added to clethodim technical (produced by Hebei Lansheng Biotechnology Co., Ltd.) in the amounts shown in Table 3, and the mixture was placed in a constant temperature box at 40° C.
  • the clethodim content was detected by high performance liquid chromatography at the times shown in the table, and the detection method was the same as in Example 1.
  • table 3 *1 Content measured on the day after adding isooctyl thioglycolate.
  • clethodim technical produced by Hebei Lansheng Biotechnology Co., Ltd.
  • Ethyl mercaptoacetate (JSY for short) was added to the product, and the product was placed in a constant temperature box at 40°C.
  • the content of clethodim was detected by high performance liquid chromatography on day 0 and on days 7, 14 and 21, respectively, using the same detection method as in Example 1.
  • table 5 *1 Content measured on the day after adding ethyl thioglycolate.
  • thioglycolate or thioglycolic acid is an effective stabilizer for clethodim, which can reduce the degradation rate of clethodim, thereby solving the stability problem of clethodim during storage or transportation and improving the quality.
  • Table 7 *1 Content measured on the day after adding propylene carbonate or 2-mercaptobenzothiazole and propylene carbonate.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

本申请涉及烯草酮组合物，其含有烯草酮或其农业上可接受的盐和巯基乙酸或巯基乙酸酯。本申请还涉及巯基乙酸或巯基乙酸酯作为烯草酮或其农业上可接受的盐的稳定剂的用途。本申请进一步涉及含有本发明组合物的烯草酮乳油和母药。

Description

烯草酮组合物及含有该组合物的乳油和母药 技术领域
本发明涉及烯草酮组合物，该组合物含有烯草酮或其农业上可接受的盐和巯基乙酸或巯基乙酸酯。本发明进一步涉及含有该组合物的烯草酮乳油和母药。
背景技术
烯草酮是一种重要的环己二酮肟类除草剂，具有如下所示的结构：
烯草酮具有广谱、高效、低毒的优点，但由于其分子结构中含有羟基、双键、肟等官能团，具有不稳定、易降解的特性，日常环境中的水份、氧气、紫外线和温度等因素都会造成烯草酮的降解。因此，亟需有效措施来减少其在长途运输和长期存储等中的降解问题。
目前，有通过将烯草酮原药溶于溶剂中制成母药形式以提高运输或存储稳定性的尝试。
烯草酮的常用制剂为乳油。
发明内容
本发明旨在提供一种稳定的烯草酮组合物，该组合物含有烯草酮或其农业上可接受的盐和巯基乙酸或巯基乙酸酯。
具体地，本发明提供：
(1)烯草酮组合物，其含有烯草酮或其农业上可接受的盐和巯基乙酸或巯基乙酸酯。
(2)根据上述(1)所述的组合物，其中所述巯基乙酸酯是巯基乙酸C1-20烷醇酯，更优选为巯基乙酸C1-10烷醇酯。
(3)根据上述(1)或(2)所述的组合物，其中所述巯基乙酸酯是选自巯基乙酸异辛酯、巯基乙酸乙酯、双(巯基乙酸)-1,4-丁二酯、双(巯基乙酸)乙二醇酯中的一种或两种以上。
(4)根据上述(1)至(3)中任意一项所述的组合物，其中相对于烯草酮或其农业上可接受的盐的重量，所述巯基乙酸或巯基乙酸酯的重量为0.001-20％，优选为0.001-10％，更优选为0.005-5％，具体可以为例如约0.005％、0.01％、0.05％、0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1.0％、1.1％、1.2％、1.3％、1.4％、1.5％、2％、3％、4％、5％等。
(5)烯草酮乳油，其含有根据上述(1)-(4)中任意一项所述的组合物；优选地，相对于乳油的总重量，本发明组合物的含量为10-70重量％，优选为10-40重量％，具体可以为例如约10～15重量％、25～30重量％、35～40重量％、或50～60重量％等。
(6)烯草酮母药，其含有根据上述(1)-(4)中任意一项所述的组合物；优选地，母药中所述组合物与溶剂的重量比为(5-90):(95-10)，优选为(20-50):(80-50)，更优选为(30-60):(70-40)，具体可以为例如37：63或50：50。
(7)巯基乙酸或巯基乙酸酯作为烯草酮或其农业上可接受的盐的稳定剂 的用途。
(8)根据上述(7)所述的用途，其中所述巯基乙酸酯是巯基乙酸C1-20烷醇酯，更优选为巯基乙酸C1-10烷醇酯。
(9)根据上述(8)所述的用途，其中所述巯基乙酸酯是选自巯基乙酸异辛酯、巯基乙酸乙酯、双(巯基乙酸)-1,4-丁二酯、双(巯基乙酸)乙二醇酯中的一种或两种以上。
(10)根据上述(7)-(9)中任意一项所述的用途，其中相对于烯草酮或其农业上可接受的盐的重量，所述巯基乙酸或巯基乙酸酯用量为0.001-20％，优选为0.001-10％，更优选为0.005-5％，具体可以为例如约0.005％、0.01％、0.05％、0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1.0％、1.1％、1.2％、1.3％、1.4％、或1.5％。
具体实施方式
本申请中，如无特别说明，“％”均表示重量百分含量，“约”表示在±10％、优选±5％的范围。
降解率是用来衡量烯草酮或其农业上可接受的盐稳定性的重要指标。将烯草酮或其农业上可接受的盐的起始含量记为w1，测定时的含量记为w2，降解率的计算方式为(w1-w2)/w1×100％。含量可以通过高效液相色谱法等公知的方法测定。
本发明中，通过往烯草酮中添加巯基乙酸或巯基乙酸酯作为稳定剂来提高烯草酮或其农业上可接受的盐的稳定性。
本发明所用巯基乙酸酯优选为巯基乙酸C1-20烷醇酯，更优选为巯基乙酸C1 -10烷醇酯。所述烷醇可以为一元醇、二元醇或多元醇。
作为巯基乙酸酯的具体例子，可以列举巯基乙酸异辛酯、巯基乙酸乙酯、双(巯基乙酸)-1,4-丁二酯、双(巯基乙酸)乙二醇酯等，它们可以单独使用，也可以组合两种以上使用。
在一些具体实施方式中，使用巯基乙酸异辛酯、巯基乙酸乙酯、双(巯基乙酸)-1,4-丁二酯、双(巯基乙酸)乙二醇酯中的任意一种作为稳定剂。
本发明的组合物中，相对于烯草酮或其农业上可接受的盐的重量，所述巯基乙酸或巯基乙酸酯的重量为0.001-20％，优选为0.001-10％，更优选为0.005-5％。具体可以为例如约0.005％、0.01％、0.05％、0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1.0％、1.1％、1.2％、1.3％、1.4％、1.5％、2％、3％、4％、5％等，但不限于这些具体值。
本发明的组合物可以与农药中允许使用的合适辅料或助剂通过公知的方法制成适合烯草酮使用的制剂，烯草酮的制剂是已知的，包括但不限于乳油等。
本发明首次发现巯基乙酸或巯基乙酸酯对烯草酮或其农业上可接受的盐具有稳定作用，降低或延缓其降解。因此，本申请还涉及巯基乙酸或巯基乙酸酯作为烯草酮或其农业上可接受的盐的稳定剂的用途。在该用途中，巯基乙酸或巯基乙酸酯的具体例子和用量等如上述所述。
本申请还涉及含有如上所述的本发明组合物的烯草酮乳油，该乳油可以通过将本发明的组合物与农药上允许的乳油制备用辅料和助剂通过公知的乳油制备方法制备。相对于乳油的总重量，本发明组合物的用量优选为10-70重量％，更优选为10-60重量％，进一步优选为10-40重量％。在一些具体实施方式中，本发明组合物的用量约为10～15重量％、25～30重量％、35～40重量％或50～60重量％。
本申请还涉及含有如上所述的本发明组合物的烯草酮母药。该母药可以通 过将本发明的组合物与溶剂混合来制备，本发明组合物与溶剂的重量比为(5-50):(95-50)，优选为(20-50):(80-50)，更优选为(30-60):(70-40)。在一些具体实施方式中，本发明组合物与溶剂的重量比约为37：63或50：50。所述溶剂的具体例子包括但不限于溶剂油等，可以列举例如150#溶剂油、200#溶剂油等。
实施例
以下通过具体实施例对本发明进行更详细的说明，但本发明不限于这些实施例。在不脱离本发明主旨范围内的任何修改或变更均落入本发明的范围。
实施例1 35℃下1％巯基乙酸异辛酯对烯草酮降解的抑制
往烯草酮原药(河北兰升生物科技有限公司生产)中加入巯基乙酸异辛酯(简称为JS)，烯草酮:巯基乙酸异辛酯的重量比为100：1，于35℃恒温箱中放置，分别于表1所示的时间通过高效液相色谱法检测烯草酮含量。检测方法如下：试样用无水的按1：1体积比混合的丙酮+石油醚溶解，以乙腈：水＝80：20(混合后用甲酸调PH约为4.0-4.5)为流动相，C18柱分离，紫外检测器检测，检测波长为254nm，外标法定量。
以不加巯基乙酸异辛酯的同批次烯草酮原药作为空白对照。
结果如表1所示，和空白对照相比，加入1％巯基乙酸异辛酯能够有效抑制烯草酮的降解。
表1


*1：0天是指加药当天；*2：是指加入巯基乙酸异辛酯后当天测定的含量。
实施例2 25℃下0.1％巯基乙酸异辛酯对烯草酮降解的抑制
往烯草酮原药(河北兰升生物科技有限公司生产)中加入巯基乙酸异辛酯，烯草酮:巯基乙酸异辛酯的重量比为100：0.1，于25℃恒温箱中放置，分别于表2所示的时间通过高效液相色谱法检测烯草酮含量，检测方法同实施例1。
以不加巯基乙酸异辛酯的同批次烯草酮原药作为空白对照。
结果如表2所示，和空白对照相比，加入0.1％巯基乙酸异辛酯能够有效抑制烯草酮的降解。
表2

*1：0天是指加药当天；*2：是指加入巯基乙酸异辛酯后当天测定的含量。
实施例3其它添加量的巯基乙酸异辛酯对烯草酮降解的抑制
分别按照表3所示的添加量往烯草酮原药(河北兰升生物科技有限公司生产)中加入巯基乙酸异辛酯，于40℃恒温箱中放置，分别于表中所示的时间通过高效液相色谱法检测烯草酮含量，检测方法同实施例1。
以不加巯基乙酸异辛酯的同批次烯草酮原药作为空白对照。
结果如表3所示，和空白对照相比，其他添加量的巯基乙酸异辛酯也能有效抑制烯草酮的降解。
表3

*1：加入巯基乙酸异辛酯后当天测定的含量。
实施例4双(巯基乙酸)-1,4-丁二酯对烯草酮降解的抑制
分别按照表4所示的添加量往烯草酮原药(河北兰升生物科技有限公司生产)中加入双(巯基乙酸)-1,4-丁二酯(简称为JSD)，于40℃恒温箱中放置，分别于0天和第8天通过高效液相色谱法检测烯草酮含量，检测方法同实施例1。
以不加双(巯基乙酸)-1,4-丁二酯的同批次烯草酮原药作为空白对照。
结果如表4所示，和空白对照相比，各添加量的双(巯基乙酸)-1,4-丁二酯均能有效抑制烯草酮的降解。
表4

*1：加入双(巯基乙酸)-1,4-丁二酯后当天测定的含量。
实施例5巯基乙酸乙酯对烯草酮降解的抑制
分别按照表5所示的添加量往烯草酮原药(河北兰升生物科技有限公司生 产)中加入巯基乙酸乙酯(简称为JSY)，于40℃恒温箱中放置，分别于0天和第7、14和21天通过高效液相色谱法检测烯草酮含量，检测方法同实施例1。
以不加巯基乙酸乙酯的同批次烯草酮原药作为空白对照。
结果如表5所示，和空白对照相比，各添加量的巯基乙酸乙酯能有效抑制烯草酮的降解。
表5

*1：加入巯基乙酸乙酯后当天测定的含量。
实施例6双(巯基乙酸)乙二醇酯对烯草酮降解的抑制
往烯草酮原药(河北兰升生物科技有限公司生产)中加入双(巯基乙酸)乙二醇酯(简称为JSS)，烯草酮:双(巯基乙酸)乙二醇酯的重量比为100：0.3。于40℃恒温箱中放置，分别于0天和第7、14、21和28天通过高效液相色谱法检测烯草酮含量，检测方法同实施例1。
以不加双(巯基乙酸)乙二醇酯的同批次烯草酮原药作为空白对照。
结果如表6所示，和空白对照相比，双(巯基乙酸)乙二醇酯能有效抑制烯草酮的降解。
表6

*1：加入双(巯基乙酸)乙二醇酯后当天测定的含量。
由上可知，巯基乙酸酯或巯基乙酸是有效的烯草酮稳定剂，能够降低烯草酮的降解率，从而解决烯草酮在存储或运输中的稳定性问题，提高质量。
比较例1 2-巯基苯并噻唑对烯草酮降解的抑制
往烯草酮原药(河北兰升生物科技有限公司生产)中加入2-巯基苯并噻唑(0.1％，相对于烯草酮重量)的碳酸丙烯酯(2％，相对于烯草酮重量)溶液，或单加入碳酸丙烯酯2％(作为溶剂对照)，于30℃恒温箱中放置，分别于表7所示的时间通过高效液相色谱法检测烯草酮含量，检测方法同实施例1。结果如表7所示。
表7

*1：加入碳酸丙烯酯或2-巯基苯并噻唑和碳酸丙烯酯后当天测定的含量。
由表7的结果可知，2-巯基苯并噻唑跟溶剂对照相比，降解率反而更高，因此可以认为其对烯草酮的降解不具有抑制作用。

Claims (10)

  1. 烯草酮组合物，其含有烯草酮或其农业上可接受的盐和巯基乙酸或巯基乙酸酯。
  2. 权利要求1所述的组合物，其中所述巯基乙酸酯是巯基乙酸C1-20烷醇酯，更优选为巯基乙酸C1-10烷醇酯。
  3. 权利要求1或2所述的组合物，其中所述巯基乙酸酯是选自巯基乙酸异辛酯、巯基乙酸乙酯、双(巯基乙酸)-1,4-丁二酯、双(巯基乙酸)乙二醇酯中的一种或两种以上。
  4. 权利要求1至3中任意一项所述的组合物，其中相对于烯草酮或其农业上可接受的盐的重量，所述巯基乙酸或巯基乙酸酯的重量为0.001-20％，优选为0.001-10％，更优选为0.005-5％。
  5. 烯草酮乳油，其含有权利要求1至4中任意一项所述的组合物；
    优选地，相对于乳油的总重量，本发明组合物的含量为10-70重量％，优选为10-40重量％。
  6. 烯草酮母药，其含有权利要求1至4中任意一项所述的组合物；
    优选地，母药中所述组合物与溶剂的重量比为(5-90):(95-10)，优选为(20-50):(80-50)，更优选为(30-60):(70-40)。
  7. 巯基乙酸或巯基乙酸酯作为烯草酮或其农业上可接受的盐的稳定剂的用途。
  8. 权利要求7所述的用途，其中所述巯基乙酸酯是巯基乙酸C1-20烷醇酯， 更优选为巯基乙酸C1-10烷醇酯。
  9. 权利要求8所述的用途，其中所述巯基乙酸酯是选自巯基乙酸异辛酯、巯基乙酸乙酯、双(巯基乙酸)-1,4-丁二酯、双(巯基乙酸)乙二醇酯中的一种或两种以上。
  10. 权利要求7-9中任意一项所述的用途，其中相对于烯草酮或其农业上可接受的盐的重量，所述巯基乙酸或巯基乙酸酯用量为0.001-20％，优选为0.001-10％，更优选为0.005-5％。
PCT/CN2023/118525 2022-09-30 2023-09-13 烯草酮组合物及含有该组合物的乳油和母药 WO2024067094A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211215598.7A CN117837590A (zh) 2022-09-30 2022-09-30 烯草酮组合物及含有该组合物的乳油和母药
CN202211215598.7 2022-09-30

Publications (1)

Publication Number Publication Date
WO2024067094A1 true WO2024067094A1 (zh) 2024-04-04

Family

ID=90476082

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/118525 WO2024067094A1 (zh) 2022-09-30 2023-09-13 烯草酮组合物及含有该组合物的乳油和母药

Country Status (2)

Country Link
CN (1) CN117837590A (zh)
WO (1) WO2024067094A1 (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030149097A1 (en) * 2000-06-09 2003-08-07 Wolfgang Beilfuss Storage-stable compositions of glycerol monoalkyl ethers
CN107581188A (zh) * 2017-10-13 2018-01-16 南京扬子鸿利源化学品有限责任公司 一种烯草酮乳油及其制备方法
CN108184827A (zh) * 2018-01-29 2018-06-22 中国农业大学 一种环己烯酮类除草剂乳油制剂及其制备方法
CN111675639A (zh) * 2020-06-29 2020-09-18 江苏七洲绿色化工股份有限公司 一种除水剂在提高烯草酮体系稳定性中的应用以及烯草酮体系
CN114766478A (zh) * 2022-05-16 2022-07-22 中农立华生物科技股份有限公司 一种用于烯草酮制剂的复配乳化剂及其制备方法
CN115669659A (zh) * 2021-07-21 2023-02-03 沈阳中化农药化工研发有限公司 一种烯草酮乳油及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030149097A1 (en) * 2000-06-09 2003-08-07 Wolfgang Beilfuss Storage-stable compositions of glycerol monoalkyl ethers
CN107581188A (zh) * 2017-10-13 2018-01-16 南京扬子鸿利源化学品有限责任公司 一种烯草酮乳油及其制备方法
CN108184827A (zh) * 2018-01-29 2018-06-22 中国农业大学 一种环己烯酮类除草剂乳油制剂及其制备方法
CN111675639A (zh) * 2020-06-29 2020-09-18 江苏七洲绿色化工股份有限公司 一种除水剂在提高烯草酮体系稳定性中的应用以及烯草酮体系
CN115669659A (zh) * 2021-07-21 2023-02-03 沈阳中化农药化工研发有限公司 一种烯草酮乳油及其制备方法和应用
CN114766478A (zh) * 2022-05-16 2022-07-22 中农立华生物科技股份有限公司 一种用于烯草酮制剂的复配乳化剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG HAO; ZHANG CHENGWEN; LIU YILING: "Study on the Degradation Factors of Clethodim", NONGYAO KEXUE YU GUANLI - PESTICIDE SCIENCE AND MANAGEMENT, NONGYE BU, NONGYAO JIANDINGSUO, BEIJING, CN, no. 4, 15 November 1997 (1997-11-15), CN , pages 21 - 22, XP009553725, ISSN: 1002-5480 *

Also Published As

Publication number Publication date
CN117837590A (zh) 2024-04-09

Similar Documents

Publication Publication Date Title
US11844783B2 (en) Formulations of bendamustine
JP2018109005A (ja) ベンダムスチン製剤
JP2003526612A (ja) タキソイド抗新生物薬を含有する安定化した注射可能な医薬組成物
JP5325779B2 (ja) 医薬組成物
WO2024067094A1 (zh) 烯草酮组合物及含有该组合物的乳油和母药
EP2916818A1 (en) Enema composition for treatment of ulcerative colitis having long term stability
JP5340493B2 (ja) ニコランジル含有医薬組成物
WO2015055974A1 (en) Proton pump inhibitor paste compositions
EP3178927A1 (en) Protein-stabilizing agent and protein-stabilizing method
JP2017057202A (ja) ボルテゾミブ含有凍結乾燥医薬組成物およびその製造方法
SK540290A3 (en) Parenterally applicable pharmaceutical composition containing bis-indole alkaloid and preparation method thereof
TW201707707A (zh) 包含吲哚化合物之製劑及其製備方法
KR102427941B1 (ko) 이부프로펜 및 아르기닌을 함유하는 안정성이 개선된 주사용 제제
GB2564515A (en) Pharmaceutical composition and a method for manufacturing the same
WO2023176875A1 (ja) 還元型補酵素Ｑ１０のＦｏｒｍＩＩ型結晶を含有する固体組成物の保存方法及び前記固体組成物を含有する梱包体
JP2007016005A (ja) オキシグルタチオン含有水溶液
GB2524351A (en) Proton Pump Inhibitor Paste Compositions
JP2019505561A (ja) ペメトレキセド製剤
JPS5919934B2 (ja) レチノ−ル脂肪酸エステルの安定化法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23870331

Country of ref document: EP

Kind code of ref document: A1