CN110372523B - Dichloroacetic acid-containing dihydroxyl quaternary ammonium salt herbicide, and preparation method and application thereof - Google Patents
Dichloroacetic acid-containing dihydroxyl quaternary ammonium salt herbicide, and preparation method and application thereof Download PDFInfo
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- CN110372523B CN110372523B CN201910743628.3A CN201910743628A CN110372523B CN 110372523 B CN110372523 B CN 110372523B CN 201910743628 A CN201910743628 A CN 201910743628A CN 110372523 B CN110372523 B CN 110372523B
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- ammonium salt
- quaternary ammonium
- dichloroacetic acid
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- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229960005215 dichloroacetic acid Drugs 0.000 title claims abstract description 59
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 38
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 37
- 239000004009 herbicide Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 241000196324 Embryophyta Species 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- GHKMRHRXQRFQCY-UHFFFAOYSA-N 2,2-dihydroxyethylazanium;bromide Chemical compound [Br-].[NH3+]CC(O)O GHKMRHRXQRFQCY-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 10
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000003863 ammonium salts Chemical group 0.000 claims description 4
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 3
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 3
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 11
- 239000003814 drug Substances 0.000 description 11
- 239000002689 soil Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- -1 quaternary ammonium salt compounds Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 244000299507 Gossypium hirsutum Species 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 244000105624 Arachis hypogaea Species 0.000 description 6
- 244000068988 Glycine max Species 0.000 description 6
- 235000010469 Glycine max Nutrition 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 235000020232 peanut Nutrition 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000017060 Arachis glabrata Nutrition 0.000 description 5
- 235000010777 Arachis hypogaea Nutrition 0.000 description 5
- 235000018262 Arachis monticola Nutrition 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 240000006162 Chenopodium quinoa Species 0.000 description 4
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- 201000010099 disease Diseases 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 235000001855 Portulaca oleracea Nutrition 0.000 description 3
- 244000234609 Portulaca oleracea Species 0.000 description 3
- 240000002307 Solanum ptychanthum Species 0.000 description 3
- 241001506766 Xanthium Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 240000006995 Abutilon theophrasti Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- TYZDRHAKWOGSHU-UHFFFAOYSA-N azanium;2,2-dichloroacetate Chemical group [NH4+].[O-]C(=O)C(Cl)Cl TYZDRHAKWOGSHU-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000219144 Abutilon Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000015493 Chenopodium quinoa Nutrition 0.000 description 1
- 241000207892 Convolvulus Species 0.000 description 1
- 241000207894 Convolvulus arvensis Species 0.000 description 1
- 108010060806 Photosystem II Protein Complex Proteins 0.000 description 1
- FKUYMLZIRPABFK-UHFFFAOYSA-N Plastoquinone 9 Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCC1=CC(=O)C(C)=C(C)C1=O FKUYMLZIRPABFK-UHFFFAOYSA-N 0.000 description 1
- 244000061457 Solanum nigrum Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940120124 dichloroacetate Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- MPUVIEGJZFVRLA-UHFFFAOYSA-M ethyl-dihydroxy-methylazanium;bromide Chemical compound [Br-].CC[N+](C)(O)O MPUVIEGJZFVRLA-UHFFFAOYSA-M 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- FKUYMLZIRPABFK-IQSNHBBHSA-N plastoquinone-9 Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC1=CC(=O)C(C)=C(C)C1=O FKUYMLZIRPABFK-IQSNHBBHSA-N 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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Images
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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- 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
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/12—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/16—Halogenated acetic acids
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a dichloroacetic acid dihydroxyl quaternary ammonium salt herbicide, a preparation method and application thereof. The structural general formula of the dichloroacetic acid dihydroxyl quaternary ammonium salt herbicide is shown as follows:
Description
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a herbicide containing dichloroacetic acid dihydroxy quaternary ammonium salt, a preparation method of the herbicide containing dichloroacetic acid dihydroxy quaternary ammonium salt, and application of the herbicide containing dichloroacetic acid dihydroxy quaternary ammonium salt in the aspect of preventing and removing broadleaf weeds.
Background
Dichloroacetic acid is an alpha-chlorinated fatty acid, and is a Photosystem II (PS II) inhibitor for photosynthesis, which inhibits or blocks the electron transfer between plastoquinone QA and QB. The main target of action is the 32kDa D1 polypeptide protein in PS II. After the dichloroacetic acid enters the soil, the dichloroacetic acid is easy to degrade and disappear by dechlorination bacteria, has no accumulation, and is low in toxicity and safe. Therefore, the dichloroacetic acid can be used as a lead compound or an active intermediate for developing a new herbicide. Under the ultraviolet UV radiation, however, dichloroacetic acid is easy to photolyze and dechlorinate to lose the herbicidal activity, and the application of the dichloroacetic acid in the aspect of agricultural production is limited.
At present, no document report of dichloroacetic acid dihydroxyl quaternary ammonium salt compounds and herbicidal activity thereof is found.
Disclosure of Invention
The invention aims to overcome the defects and provide the dichloroacetic acid dihydroxyl quaternary ammonium salt herbicide which greatly improves the weeding activity, has good stability and strong photolysis resistance.
The invention also aims to provide a preparation method of the herbicide containing the dichloroacetic acid dihydroxyl quaternary ammonium salt.
The invention also aims to provide the application of the herbicide containing dichloroacetic acid dihydroxy quaternary ammonium salt in the aspect of controlling and removing broadleaf weeds.
The invention relates to a dichloroacetic acid dihydroxyl quaternary ammonium salt herbicide, which has the following structural general formula:
wherein R is selected from C6-C18 saturated straight-chain alkyl, preferably dodecyl, tetradecyl and hexadecyl.
The invention relates to a preparation method of a dichloroacetic acid-containing dihydroxyl quaternary ammonium salt herbicide, which comprises the following steps:
(1) bromoalkane and N-Methyldiethanolamine (MEDA) with different saturated carbon chain lengths are mixed according to the molar ratio of 1.1-1.2: 1.0, uniformly mixing, controlling the temperature at 110-120 ℃, reacting for 2 hours, recrystallizing and purifying the obtained crude product by using a mixed solution of ethyl acetate and ethanol, and drying in vacuum to obtain alkyl-substituted dihydroxy quaternary ammonium bromide:
(2) adding the alkyl-substituted dihydroxy quaternary ammonium salt bromide obtained in the step (1) into a round-neck flask provided with a magnetic stirrer, dissolving the bromide with a sufficient amount of anhydrous methanol, slowly dropwise adding methanol solution containing potassium hydroxide in an equimolar amount under stirring to perform anion replacement, and reacting at room temperature for 2 hours:
(3) and (4) checking the reaction liquid by using a silver nitrate solution to judge whether the bromide ion is completely exchanged, ending the reaction when no light yellow precipitate exists, and removing white potassium bromide by vacuum filtration. Under the condition of ice-water bath, slowly dropwise adding dichloroacetic acid into the filtrate, adjusting the pH value of the reaction solution to be 5-6 in the process, removing the ice-water bath after the dropwise adding is finished, reacting for 12 hours at room temperature, evaporating and removing methanol by rotary evaporation, repeatedly washing with anhydrous ether for three times, removing unreacted raw materials completely, and performing vacuum drying to obtain the dichloroacetic acid dihydroxyl quaternary ammonium salt herbicide:
in the above preparation method of the dichloroacetic acid-containing bishydroxy quaternary ammonium salt herbicide, the bromoalkane in the step (1) is 1-bromododecane, 1-bromotetradecane or 1-bromohexadecane respectively.
In the preparation method of the herbicide containing dichloroacetic acid dihydroxy quaternary ammonium salt, the alkyl-substituted dihydroxy quaternary ammonium salt bromide in the step (1) is N-methyl-N-dodecyl-N, N-dihydroxyethyl ammonium bromide, N-methyl-N-tetradecyl-N, N-dihydroxyethyl ammonium bromide, N-methyl-N-hexadecyl-N, N-dihydroxyethyl ammonium bromide respectively.
The preparation method of the herbicide containing dichloroacetic acid dihydroxyl quaternary ammonium salt is characterized in that the filtrate in the step (3) mainly contains the hydroxide dihydroxyl quaternary ammonium salt.
In the preparation method of the herbicide containing the dihydroxyl quaternary ammonium salt of dichloroacetic acid, the step (3) ensures that the hydroxylated dihydroxyl quaternary ammonium salt in the filtrate completely reacts, the molar ratio of the dichloroacetic acid to the hydroxylated dihydroxyl quaternary ammonium salt is more than 1, and the amount of the dichloroacetic acid is more than 10 percent of that of the hydroxylated dihydroxyl quaternary ammonium salt.
The invention relates to an application of a dichloroacetic acid-containing dihydroxyl quaternary ammonium salt herbicide in the field of controlling broadleaf weeds.
Compared with the prior art, the invention has the following obvious beneficial effects: the invention adopts two-step synthesis, has simple preparation method, high yield, easy separation and purification and is suitable for large-scale preparation. The dichloroacetic acid dihydroxyl quaternary ammonium salt belongs to ionic compounds, has high stability, is beneficial to the photolysis resistance of the compounds, has excellent herbicidal activity and can effectively prevent and kill broadleaf weeds. In addition, lipophilic long-chain alkyl and hydrophilic dihydroxy polar groups are introduced into the cationic structure design of the quaternary ammonium salt, and the dichloroacetic acid dihydroxy quaternary ammonium salt has high surface activity, so that the surface tension of the liquid medicine is reduced, and the surface wettability and the liquid medicine retention of the weed leaves are improved. Meanwhile, the dichloroacetic acid dihydroxyl quaternary ammonium salt has excellent solubility property and is very soluble in water, alcohol (such as methanol and ethanol), acetone, dimethylformamide and dimethyl sulfoxide; after the herbicide is applied, the compound can easily absorb moisture in the air, is not easy to crystallize and separate out on the leaf surfaces of weeds, and is beneficial to absorption and conduction of liquid medicine. The dichloroacetic acid dihydroxyl quaternary ammonium salt has positive charges, is easily adsorbed by soil particles in an electrostatic manner, and reduces the risk of polluting underground water. The compound has important significance in promoting the practical application of the compound in agricultural production, protecting the agricultural ecological safety and the like.
Drawings
FIG. 1 shows the response of compound (I) to solanum nigrum after treatment at a concentration of 10 g/L.
FIG. 2 shows the reaction symptoms of compound (I) with dichloroacetic acid and dihydroxyquaternary ammonium salt after treatment at a concentration of 10g/L on Chenopodium quinoa.
Detailed Description
Example 1
Preparation of herbicide containing dodecyl methyl dihydroxy ethyl ammonium dichloroacetate (number A) comprising the following steps:
(1) 1-bromododecane and N-Methyldiethanolamine (MEDA) were mixed in a molar ratio of 1.1: 1.0, uniformly mixing, adding the mixture into a three-neck round-bottom flask, controlling the temperature at 110 ℃ for reaction for 2 hours, recrystallizing and purifying the obtained crude product by using a mixed solution of ethyl acetate and ethanol, and drying in vacuum to obtain white N-methyl-N-dodecyl-N, N-dihydroxyethyl ammonium bromide;
(2) 3.68g (10mmol) of N-methyl-N-dodecyl-N, N-dihydroxyethyl ammonium bromide was weighed into a round-necked flask equipped with a magnetic stirrer, dissolved in 20mL of anhydrous methanol, and slowly added dropwise with a methanol solution containing potassium hydroxide in an equal molar amount under stirring for anion exchange reaction at room temperature.
(3) After 2h, checking the reaction liquid by using a silver nitrate solution to judge whether bromide ions are completely exchanged or not, when light yellow precipitates do not exist, finishing the reaction, performing vacuum filtration to remove potassium bromide, slowly dropwise adding 1.42g of dichloroacetic acid into the filtrate under the condition of an ice water bath, adjusting the pH value of the reaction liquid to be 6 in the period, removing the ice water bath after dropwise adding is finished, reacting for 12h at room temperature, performing rotary evaporation to remove methanol, repeatedly washing with anhydrous ether for three times, removing unreacted raw materials, and performing vacuum drying for 24h at the temperature of 50 ℃ to obtain a white solid A;
example 2
Preparation of a herbicide containing tetradecylmethyl dichloroacetate (numbered B) which comprises the following steps:
(1) 1-bromotetradecane and N-Methyldiethanolamine (MEDA) are mixed according to a mol ratio of 1.15: 1.0, uniformly mixing, adding the mixture into a three-neck round-bottom flask, controlling the temperature at 114 ℃ for reaction for 2 hours, recrystallizing and purifying the obtained crude product by using a mixed solution of ethyl acetate and ethanol, and drying in vacuum to obtain white N-methyl-N-tetradecyl-N, N-dihydroxyethyl ammonium bromide;
(2) 3.96g (10mmol) of N-methyl-N-tetradecyl-N, N-dihydroxyethyl ammonium bromide was weighed into a round-bottomed flask equipped with a magnetic stirrer, dissolved in 20mL of anhydrous methanol, and slowly added dropwise with a methanol solution containing an equimolar amount of potassium hydroxide under stirring for anion exchange, and reacted at room temperature:
(3) after 2h, checking the reaction liquid by using a silver nitrate solution to judge whether bromide ions are completely exchanged or not, when light yellow precipitates do not exist, finishing the reaction, performing vacuum filtration to remove potassium bromide, slowly dropwise adding 1.42g of dichloroacetic acid into the filtrate under the condition of an ice water bath, adjusting the pH value of the reaction liquid to be 5 in the period, removing the ice water bath after dropwise adding is finished, reacting for 12h at room temperature, performing rotary evaporation to remove methanol, repeatedly washing with anhydrous ether for three times, removing unreacted raw materials, and performing vacuum drying for 24h at the temperature of 50 ℃ to obtain a white solid B;
example 3
Preparation of herbicide containing cetylmethyldiethanolamine dichloroacetate (code C), comprising the following steps:
(1) 1-bromohexadecane and N-Methyldiethanolamine (MEDA) are mixed according to a molar ratio of 1.2: 1.0, uniformly mixing, adding the mixture into a three-neck round-bottom flask, controlling the temperature at 120 ℃ for reaction for 2 hours, recrystallizing and purifying the obtained crude product by using a mixed solution of ethyl acetate and ethanol, and drying in vacuum to prepare white N-methyl-N-hexadecyl-N, N-dihydroxyethyl ammonium bromide;
(2) weighing 4.24g (10mmol) of N-methyl-N-hexadecyl-N, N-dihydroxyethyl ammonium bromide, adding the N-methyl-N-hexadecyl-N, N-dihydroxyethyl ammonium bromide into a round-mouth flask provided with a magnetic stirrer, dissolving the N-methyl-N, N-dihydroxyethyl ammonium bromide in 20mL of anhydrous methanol, slowly dropwise adding methanol solution containing potassium hydroxide with equal molar quantity under stirring for anion replacement, and reacting at room temperature
(3) After 2h, checking the reaction liquid by using a silver nitrate solution to judge whether bromide ions are completely exchanged or not, when light yellow precipitates do not exist, finishing the reaction, performing vacuum filtration to remove potassium bromide, slowly dropwise adding 1.42g of dichloroacetic acid into the filtrate under the condition of an ice water bath, controlling the pH value of the reaction liquid to be 6 during the period, removing the ice water bath after the dropwise adding is finished, reacting for 12h at room temperature, performing rotary evaporation to remove methanol, repeatedly washing with anhydrous ether for three times, removing unreacted raw materials, and performing vacuum drying at the temperature of 50 ℃ for 24h to obtain a white solid C;
test example 1: indoor herbicidal activity test:
the dichloroacetic acid dihydroxyl quaternary ammonium salt is subjected to a weeding activity test by adopting an indoor pot culture method.
Preparing a medicament: a certain mass of the technical grade of the dihydroxyquaternary ammonium dichloroacetate provided by the invention is weighed by an analytical balance (0.0001g), dissolved by absolute ethyl alcohol and diluted to the required concentration by deionized water of 0.1 percent of tween-80 emulsifier. A total of 5 concentration gradients (1.25g/L, 2.5g/L, 5g/L, 7.5g/L, 10g/L) were set, and a blank (CK) of 0.1% Tween-80 in deionized water with equal amounts of ethanol was used.
The application method comprises the following steps: in a plastic pot with a diameter of 5cm, compound soil (seedling substrate: loam, 1:1, v/v) is quantitatively loaded to 3/4. Soil is moistened by adopting a pot bottom infiltrating irrigation mode. Broad-leaved weed seeds (the germination rates are all more than 85%) such as purslane, black nightshade, quinoa, piemarker, cocklebur, Convolvulus arvensis and the like with full and uniform seeds are respectively and uniformly sown in a pot, and the pot is covered with soil for 1cm and then is moved to a greenhouse for cultivation, wherein the temperature is 22-30 ℃, the illumination period (day and night 16/8) and the relative air humidity is 60 +/-5%. Thinning and fixing the seedlings (15 gramineous weeds per pot and 2-5 broad-leaved weeds per pot) after the seedlings emerge, spraying stem and leaf of the prepared liquid medicine (a hand-press sprayer with the liquid spraying amount of 50 mL/m) when the weeds grow to 4-6 leaf stages2). Each treatment was repeated 3 times, while dichloroacetic acid was also used as a control. After the liquid medicine is naturally dried, the pot is moved into a greenhouse for culture. Symptoms of response and growth of each treated weed were observed 2, 4, 7, 11, 14, 21d after treatment. And after 21d, respectively weighing the fresh weight of the overground parts of the treated weeds, wherein the fresh weight control effect calculation formula is as follows:
and analyzing the significance of the difference by a Duncan adsorption range method.
And (3) test results: after the herbicide is applied for 2-3 days, most of the leaves of the weeds begin to have phytotoxicity spots, then the leaves begin to wither, the stems and leaves lose water and become soft and then droop down, and the weeds die after being dried up for 4-7 days. After 21d, some weeds with less damage grew again, and dead weeds could not regenerate. The 21d weed control after the application is shown in Table 1. The dichloroacetic acid dihydroxyl quaternary ammonium salt compound (I) shows excellent stem and leaf treatment activity on broad-leaved weeds such as purslane, black nightshade, quinoa, abutilon, cocklebur, field bindweed and the like under the treatment of effective concentration of 10 g/L; especially, the prevention effect on black nightshade, cocklebur and piemarker is better than that of the master dichloroacetic acid medicine, and the prevention effect on purslane and quinoa is basically equivalent to that of the master dichloroacetic acid medicine.
TABLE 1 treatment Activity of Dichloroacetic acid bishydroxy quaternary ammonium salt Compound on Stem and leaf of broad leaf weeds
Remarking: the data in the table are all multiple mean values.
Test example 2: and (3) crop safety test:
the test was conducted at the cotton institute test farm (Anyang county, 36.13 ° N, 114.85 ° E, Henan province) of the Chinese academy of agricultural sciences. The method comprises the steps of manually dibbling quantitative 4 dry field crops including cotton, soybean, corn and peanut seeds, wherein the sowing date of the cotton is 5 months and 1 day in 2019, and the remaining is 6 months and 12 days in 2019.
The application method comprises the following steps: soil treatment: spraying the liquid medicine on the soil surface on the day after sowing; stem and leaf treatment: and after the cotton and the corn grow to 3-5 leaves and the soybeans and the peanuts grow to 2-3 compound leaves, uniformly spraying the leaf surfaces of the liquid medicine. Soil treatment and stem leaf treatment are carried out by a Singapore knapsack manual sprayer, and the spraying amount is 750L/hm2. The concentration of the liquid medicine is set to be 20 g/L. And 0.1% Tween-80 deionized water as blank control. Each treatment was repeated 3 times with a cell area of 10m2。
Soil treatment: and observing the emergence of various crops and the growth of seedlings. Stem and leaf treatment: the growth and damage symptoms of various crops are observed, and the safety is evaluated.
And (3) test results:
1) the soil treatment has no influence on the growth and development of 4 dry field crops, and can realize normal seedling emergence with the seedling emergence rate of more than or equal to 80 percent and no seedling shortage and ridge breaking phenomena. And the seedling growth vigor is not different from that of the blank control.
2) The stem and leaf treatment has different degrees of influence on the growth and development of 4 dry field crops, the damage of the soybean is the most serious, the damage of the peanut is the second time, and the results are shown in a table 2. According to field observation, after the application for 5 days, the dichloroacetic acid dihydroxyl quaternary ammonium salt compound (I) and the dichloroacetic acid treatment have similar phytotoxicity symptoms on cotton, corn and peanut: brown contact spots appear on the local parts of cotton leaves, and stalks turn brown; part of the maize leaves appear withered and yellow spots, the heart leaves are deformed and curled, and the plants are short; the peanut leaves appear brown phytotoxicity spots, and part of the leaf tips are dry. The treatment of the dichloroacetic acid dihydroxyl quaternary ammonium salt compound (I) causes severe withered yellow spots on soybean leaves, and partial leaf tips are dry; the dichloroacetic acid treatment resulted in severe white phytotoxic spotting of the soybean leaves, with some leaf tips becoming dry. After 15 days, the normal growth can be recovered, and the new leaves have no phytotoxicity.
TABLE 2 safety of treatment of leaves and leaves of dichloroacetic acid bishydroxy quaternary ammonium salt compound on 4 dry field crops
| Numbering | Concentration of | Cotton | Soybean | Corn (corn) | |
| A | |||||
| 20 | Of moderate degree | Severe severity of disease | Of moderate degree | | |
| B | |||||
| 20 | Of moderate degree | Severe severity of disease | Of moderate degree | | |
| C | |||||
| 20 | Of moderate degree | Severe severity of disease | Of moderate degree | Heavy | |
| Dichloroacetic acid | |||||
| 20 | Light and slight | Severe severity of disease | Light and slight | Heavy weight |
Remarking: 0 means safe, no damage; slight phytotoxicity: the degree of phytotoxicity is 1-10%; moderate phytotoxicity: the degree of phytotoxicity is 11-30%; serious phytotoxicity: the degree of phytotoxicity is 31 to 50 percent; serious phytotoxicity > 50%.
It is therefore recommended to use the bishydroxyquaternary ammonium dichloroacetate herbicide of the present invention in the field by directional spraying.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the present invention without departing from the technical spirit of the present invention.
Claims (7)
1. A dichloroacetic acid dihydroxyl quaternary ammonium salt herbicide has a structural general formula as follows:
wherein,
r is dodecyl, tetradecyl or hexadecyl.
2. A preparation method of a dichloroacetic acid-containing dihydroxyl quaternary ammonium salt herbicide comprises the following steps:
(1) bromoalkane and N-Methyldiethanolamine (MEDA) with different saturated carbon chain lengths are mixed according to the molar ratio of 1.1-1.2: 1.0, uniformly mixing, controlling the temperature at 110-120 ℃, reacting for 2 hours, recrystallizing and purifying the obtained crude product by using a mixed solution of ethyl acetate and ethanol, and drying in vacuum to obtain alkyl-substituted dihydroxy quaternary ammonium bromide:
R＝CnH2n+1,n＝12,14,16
(2) adding the alkyl-substituted dihydroxy quaternary ammonium salt bromide obtained in the step (1) into a round-neck flask provided with a magnetic stirrer, dissolving the bromide with a sufficient amount of anhydrous methanol, slowly dropwise adding methanol solution containing potassium hydroxide in an equimolar amount under stirring to perform anion replacement, and reacting at room temperature for 2 hours:
(3) and (3) checking the reaction liquid by using a silver nitrate solution to judge whether bromide ions are completely exchanged, finishing the reaction when no light yellow precipitate exists, removing white potassium bromide by decompression and suction filtration, slowly dropwise adding dichloroacetic acid into the filtrate under the condition of an ice water bath, adjusting the pH value of the reaction liquid to be 5-6 in the process, removing the ice water bath after the dropwise adding is finished, reacting for 12 hours at room temperature, steaming and removing methanol by rotary evaporation, repeatedly washing with anhydrous ether for three times, removing the raw materials which are not completely reacted, and drying in vacuum to obtain the dichloroacetic acid dihydroxy quaternary ammonium salt herbicide:
3. the process for preparing a bis-hydroxy quaternary ammonium salt herbicide containing dichloroacetic acid as claimed in claim 2, wherein: the bromoalkane in the step (1) is 1-bromododecane, 1-bromotetradecane or 1-bromohexadecane respectively.
4. The process for preparing a bis-hydroxy quaternary ammonium salt herbicide containing dichloroacetic acid as claimed in claim 2, wherein: the alkyl-substituted bishydroxy quaternary ammonium salt bromide in the step (1) is N-methyl-N-dodecyl-N, N-dihydroxyethyl ammonium bromide, N-methyl-N-tetradecyl-N, N-dihydroxyethyl ammonium bromide or N-methyl-N-hexadecyl-N, N-dihydroxyethyl ammonium bromide respectively.
5. The process for preparing a bis-hydroxy quaternary ammonium salt herbicide containing dichloroacetic acid as claimed in claim 2, wherein: the main component of the filtrate in the step (3) is hydroxide dihydroxyl quaternary ammonium salt.
6. The process for preparing a bis-hydroxy quaternary ammonium salt herbicide containing dichloroacetic acid as claimed in claim 2, wherein: and (3) in order to ensure that the hydroxide dihydroxyquaternary ammonium salt in the filtrate completely reacts, the molar ratio of the dichloroacetic acid to the hydroxide dihydroxyquaternary ammonium salt is more than 1, wherein the amount of substances of the dichloroacetic acid is 10 percent more than that of the hydroxide dihydroxyquaternary ammonium salt.
7. The use of the herbicide containing dichloroacetic acid bishydroxy quaternary ammonium salt according to claim 1 for controlling broad-leaved weeds.
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