CA2022133C - Monoclinic metazachlor and its preparation - Google Patents
Monoclinic metazachlor and its preparation Download PDFInfo
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- CA2022133C CA2022133C CA002022133A CA2022133A CA2022133C CA 2022133 C CA2022133 C CA 2022133C CA 002022133 A CA002022133 A CA 002022133A CA 2022133 A CA2022133 A CA 2022133A CA 2022133 C CA2022133 C CA 2022133C
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- Prior art keywords
- modification
- crystalline modification
- dimethyl
- acetanilide
- monoclinic
- Prior art date
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- Expired - Lifetime
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000005580 Metazachlor Substances 0.000 title description 27
- STEPQTYSZVCJPV-UHFFFAOYSA-N metazachlor Chemical compound CC1=CC=CC(C)=C1N(C(=O)CCl)CN1N=CC=C1 STEPQTYSZVCJPV-UHFFFAOYSA-N 0.000 title description 27
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims abstract description 10
- 229960001413 acetanilide Drugs 0.000 claims abstract description 8
- 239000004009 herbicide Substances 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims description 51
- 230000004048 modification Effects 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000002363 herbicidal effect Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 3
- 239000000654 additive Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 230000008635 plant growth Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- LYXFCGCYJQCSRL-UHFFFAOYSA-N OOSO Chemical compound OOSO LYXFCGCYJQCSRL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- -1 tent-butanol Chemical compound 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Catalysts (AREA)
- Developing Agents For Electrophotography (AREA)
- Ceramic Products (AREA)
Abstract
Monoclinic 2-chloro-(2',6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide of the formula (see formula I) which melts at 76°C.
Processes far its preparation and herbicides.
Processes far its preparation and herbicides.
Description
' __ O.Z. 0050/40985 Monoclinic metazachlor and its preparation The present invention relates to monoclinic 2-chloro-(2',6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide of the formula I
i-v N~ I
which melts at 76°C, and processes for the preparation of this modification, its use as a herbicide, and herbicides which contain this active ingredient.
The important herbicidal active ingredient 2 chloro-(2',6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide I (common names metazachlor) melts, as far as is known, in a range of 78-83°C and crystallizes in a triclinic crystalline forma 'This crystalline form IA is obtained by the methods described in DE-A 2 648 008, DE-A 2 830 764 and EP-A 12216, by crystallization of I from a non-polar or slightly polar solvent, such as cyclohexane or toluene.
I~owever, this known modification IA of metaza-chlor, which is commercially available in the form of concentrated aqueous suspensions, has the disadvantage that it frequently forms agglomerates.
The agents then cannot be sprayed uniformly, if at all:
In efforts aimed'at remedying this deficiency, a monoclinic modification of I, which modification melts at 76°C, was found.
This monoclinic modification IE is obtained if water is added to an aqueous metazachlor solution con-taining sulfur:.c acid, at from 0 to 50°C, in the presence of a water-miscible polar inert organic solv~nt, and the resulting solid is isolated in a conventional manner after crystallization is complete.
In this process, the order in which the active ingredient solution, the organic solvent and the water r.
i-v N~ I
which melts at 76°C, and processes for the preparation of this modification, its use as a herbicide, and herbicides which contain this active ingredient.
The important herbicidal active ingredient 2 chloro-(2',6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide I (common names metazachlor) melts, as far as is known, in a range of 78-83°C and crystallizes in a triclinic crystalline forma 'This crystalline form IA is obtained by the methods described in DE-A 2 648 008, DE-A 2 830 764 and EP-A 12216, by crystallization of I from a non-polar or slightly polar solvent, such as cyclohexane or toluene.
I~owever, this known modification IA of metaza-chlor, which is commercially available in the form of concentrated aqueous suspensions, has the disadvantage that it frequently forms agglomerates.
The agents then cannot be sprayed uniformly, if at all:
In efforts aimed'at remedying this deficiency, a monoclinic modification of I, which modification melts at 76°C, was found.
This monoclinic modification IE is obtained if water is added to an aqueous metazachlor solution con-taining sulfur:.c acid, at from 0 to 50°C, in the presence of a water-miscible polar inert organic solv~nt, and the resulting solid is isolated in a conventional manner after crystallization is complete.
In this process, the order in which the active ingredient solution, the organic solvent and the water r.
- 2 - O.Z. 0050/40985 are mixed with one another is unimportant for the crystallization.
Seeding with crystals of modification IB is not essential but generally proves advantageous.
Particular suitable protic polar inert solvents are alcohols, such as methanol, ethanol, isopropanol, n-propanol, 1-butanol, 2-butanol, isobutanol, tent-butanol, ethylene glycol, propylene glycol, propane-1,3-diol and butanediols, ketones, such as acetone and butan-2-one, ethers, such as tetrahydrofuran and 1,4-dioxane, amides, such as dimethylformamide and N-methylpyrrolidone, and dimethyl sulfoxide and diethylene glycol.
The seed crystals required for the preparation of metazachlor in modification IB in amounts of from 0.01 to 50~ by weight can be obtained for the first time, for example, by recrystallization of metazachlor of modifica-tion IA from the abovementioned polar organic solvents.
In another possible method for the preparation of metazachlor of modification IB, from 0.01 to 50~ by weight of seed crystals of modification IB are added to an aqueous suspension of metazachlor of modification IA
at a pH of from O to 10, with or without the addition of one or more of the abovementianed water-soluble organic solvents, at from O to 45°C, and stirring is carried out at from 0.1 to 20 hours. Modification IA xs transformed into modification IB.
This transformation also takes place in a similar manner when an aqueous suspension of modification IA is milled in the presence of the stated organic solvents with the addition of geed crystals of modification IB.
Characteristic physical data for distinguishing between the two modifications are summarized in the Table below.
Seeding with crystals of modification IB is not essential but generally proves advantageous.
Particular suitable protic polar inert solvents are alcohols, such as methanol, ethanol, isopropanol, n-propanol, 1-butanol, 2-butanol, isobutanol, tent-butanol, ethylene glycol, propylene glycol, propane-1,3-diol and butanediols, ketones, such as acetone and butan-2-one, ethers, such as tetrahydrofuran and 1,4-dioxane, amides, such as dimethylformamide and N-methylpyrrolidone, and dimethyl sulfoxide and diethylene glycol.
The seed crystals required for the preparation of metazachlor in modification IB in amounts of from 0.01 to 50~ by weight can be obtained for the first time, for example, by recrystallization of metazachlor of modifica-tion IA from the abovementioned polar organic solvents.
In another possible method for the preparation of metazachlor of modification IB, from 0.01 to 50~ by weight of seed crystals of modification IB are added to an aqueous suspension of metazachlor of modification IA
at a pH of from O to 10, with or without the addition of one or more of the abovementianed water-soluble organic solvents, at from O to 45°C, and stirring is carried out at from 0.1 to 20 hours. Modification IA xs transformed into modification IB.
This transformation also takes place in a similar manner when an aqueous suspension of modification IA is milled in the presence of the stated organic solvents with the addition of geed crystals of modification IB.
Characteristic physical data for distinguishing between the two modifications are summarized in the Table below.
- 3 - O.Z. 0050/40985 TABLE
Method of measurement Unit IA IB
Differential thermal °C 79 76 analysis IR spectroscopy* cm-1 3160, 1300 1360, 780 X-ray diffraction pattern (diffraction angle 2 e) degrees 8.2; 8.4 9.9; 12.3 Solid-state 13C-NMR
spectroscopy*
(against adamantane) s in ppm 62.5; 137.1 51.4; 139.1 Modification from X-ray structural analysis - triclinic monoclinic Microscopy - amorphous coffin-lid-.
(crystal form) shaped * Selected signals The effect of the invention is as follows:
Formulated product containing metazachlor of the known modification IA changes during storage. The size of the suspended particles increases continuously; in the formulated product, this is evident in the formation of fragments right up to complete solidification of the previously liquid product, so that uniform application of the product is no longer ensured.
Formulated product containing metazachlor of modification IB does not have'this undesirable behavior and can be applied s.atisfactoriiy every after prolonged storage.
During these investigations, a further metastable metazachlor modification IC which melts at 84°C was found.
This modification is obtained by heating metazachlor of modification IA to 84°C and milling the melt formed.
On standing, the metazachlor modification IC, which has a half-life of about 5 days, is transformed into modification IB, which melts at 76°C.
The Examples which follow illustrate the novel s~ .r, ~l v3 ~~'~;.~.~.ar~
-- 4 -- O.Z. OOSO/40985 process:
1. Precipitation of an acidic aqueous metazachlor solu-tion with seeding with modification IB.
a) 1,250 ml of water and 22 ml of methanol are initially taken at 25°C. For seeding, 3.8 g of metazachlor of modification IB are added. 62.5 g of a 40~ strength metazac'~lor solution in 60~
strength sulfuric acid are then added slowly while stirring, stirring is continued for one hour and a further 562.5 g of the metazachlor solution are then added rapidly. After complete precipitation, the precipitate is isolated, washed with water and dried. 247 g of metazachlor of modification IB are obtained.
b) 7.6 g of methanol and 51 g of water are added to a solution of 63 g of metazachlor of modification IA in 90 g of 60~ strength sulfuric acid, while stirring, at 40°C. After the addition of 3 g of metazachlor of modification IB, 133 ml of water are added in the course of two hours and then a further 113 ml of water are added rapidly. Stir-rir_g is continued for two hours and the product is filtered off under suction, washed with 200 ml of water and then dried. 62.3 g of metazachlor of modification IB are obtained.
2. Preparation of metazachlor of modification IB by transformation of the crystalline modification IA in aqueous suspension.
1 g of modification IB is added to a suspension of 10 g of metazachlor of modification IA in 127 g of 15~ strength sulfuric acid and 2 g of methanol, the mixture is stirred for 20 hours at 20°C and the product is filtered off under suction and washed with 500 ml of water. Metazachlor of modification IB is obtained.
3. Preparation of metazachlor of modification IB by crystallization from methanolic aqueous solution - 5 - O.Z. 0050/40985 A mixture of 2,2 1 of methanol and 1,500 g of metazachlor of modification IA is converted into a solution at 50°C. The solution is slowly allowed to reach room temperature, and 5.2 1 of water are slow-s ly added to the partially crystallizing mixture.
Filtration under suction and washing with 1 1 of water give 1,485 g of metazachlor of modification Ig.
Method of measurement Unit IA IB
Differential thermal °C 79 76 analysis IR spectroscopy* cm-1 3160, 1300 1360, 780 X-ray diffraction pattern (diffraction angle 2 e) degrees 8.2; 8.4 9.9; 12.3 Solid-state 13C-NMR
spectroscopy*
(against adamantane) s in ppm 62.5; 137.1 51.4; 139.1 Modification from X-ray structural analysis - triclinic monoclinic Microscopy - amorphous coffin-lid-.
(crystal form) shaped * Selected signals The effect of the invention is as follows:
Formulated product containing metazachlor of the known modification IA changes during storage. The size of the suspended particles increases continuously; in the formulated product, this is evident in the formation of fragments right up to complete solidification of the previously liquid product, so that uniform application of the product is no longer ensured.
Formulated product containing metazachlor of modification IB does not have'this undesirable behavior and can be applied s.atisfactoriiy every after prolonged storage.
During these investigations, a further metastable metazachlor modification IC which melts at 84°C was found.
This modification is obtained by heating metazachlor of modification IA to 84°C and milling the melt formed.
On standing, the metazachlor modification IC, which has a half-life of about 5 days, is transformed into modification IB, which melts at 76°C.
The Examples which follow illustrate the novel s~ .r, ~l v3 ~~'~;.~.~.ar~
-- 4 -- O.Z. OOSO/40985 process:
1. Precipitation of an acidic aqueous metazachlor solu-tion with seeding with modification IB.
a) 1,250 ml of water and 22 ml of methanol are initially taken at 25°C. For seeding, 3.8 g of metazachlor of modification IB are added. 62.5 g of a 40~ strength metazac'~lor solution in 60~
strength sulfuric acid are then added slowly while stirring, stirring is continued for one hour and a further 562.5 g of the metazachlor solution are then added rapidly. After complete precipitation, the precipitate is isolated, washed with water and dried. 247 g of metazachlor of modification IB are obtained.
b) 7.6 g of methanol and 51 g of water are added to a solution of 63 g of metazachlor of modification IA in 90 g of 60~ strength sulfuric acid, while stirring, at 40°C. After the addition of 3 g of metazachlor of modification IB, 133 ml of water are added in the course of two hours and then a further 113 ml of water are added rapidly. Stir-rir_g is continued for two hours and the product is filtered off under suction, washed with 200 ml of water and then dried. 62.3 g of metazachlor of modification IB are obtained.
2. Preparation of metazachlor of modification IB by transformation of the crystalline modification IA in aqueous suspension.
1 g of modification IB is added to a suspension of 10 g of metazachlor of modification IA in 127 g of 15~ strength sulfuric acid and 2 g of methanol, the mixture is stirred for 20 hours at 20°C and the product is filtered off under suction and washed with 500 ml of water. Metazachlor of modification IB is obtained.
3. Preparation of metazachlor of modification IB by crystallization from methanolic aqueous solution - 5 - O.Z. 0050/40985 A mixture of 2,2 1 of methanol and 1,500 g of metazachlor of modification IA is converted into a solution at 50°C. The solution is slowly allowed to reach room temperature, and 5.2 1 of water are slow-s ly added to the partially crystallizing mixture.
Filtration under suction and washing with 1 1 of water give 1,485 g of metazachlor of modification Ig.
Claims (7)
1. A monoclinic crystalline modification of
2-chloro-(2',6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide of the formula I
said modification melting at 76°C.
2. A process for the preparation of a monoclinic crystalline modification of the compound of the formula I as claimed in claim 1, wherein a triclinic crystalline modification 2-chloro-(2', 6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide is recrystal-lined from a polar inert organic solvent and the solid is isolated after crystallization is complete.
said modification melting at 76°C.
2. A process for the preparation of a monoclinic crystalline modification of the compound of the formula I as claimed in claim 1, wherein a triclinic crystalline modification 2-chloro-(2', 6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide is recrystal-lined from a polar inert organic solvent and the solid is isolated after crystallization is complete.
3. A process for the preparation of a monoclinic crystalline modification of the compound of the formula I as claimed in claim 1, wherein a triclinic crystalline modification of 2-chloro-(2', 6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide is crystallized from aqueous solution containing sulfuric acid, at from 0 to 50°C, in the presence of a polar water-miscible inert organic solvent.
4. A process for the preparation of a monoclinic crystalline modification of the compound of the formula I as claimed in claim 1, wherein an aqueous suspension of a triclinic crystalline modification 2-chloro-(2', 6'-dimethyl-N-pyrazol-1-ylmethyl)-acetanilide, which modification melts at 79°C, is milled, at from 0 to 45°C, with a polar water-miscible inert organic solvent in the presence of crystals of a monoclinic crystalline modification of 2-chloro-(2', 6'-dimethyl-N-pyrazol-1-ymelting)-acetanilide, which melts at 76°C.
5. A herbicide containing conventional inert additives and a herbicidally effective amount of the monoclinic crystalline modification claimed in claim 1.
6. A herbicide as claimed in claim 5, which contains from 0.1 to 95o by weight of said monoclinic crystalline modification which melts at 76°C.
7. A method for controlling undesirable plant growth, wherein the seeds, the plants and/or their habitat are or is treated with a herbicidally effective amount of the monoclinic crystalline modification claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3925253A DE3925253A1 (en) | 1989-07-29 | 1989-07-29 | MONOCLINES METAZACHLOR AND METHOD FOR THE PRODUCTION THEREOF |
| DEP3925253.1 | 1989-07-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2022133A1 CA2022133A1 (en) | 1991-01-30 |
| CA2022133C true CA2022133C (en) | 2000-09-19 |
Family
ID=6386183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002022133A Expired - Lifetime CA2022133C (en) | 1989-07-29 | 1990-07-27 | Monoclinic metazachlor and its preparation |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0411408B1 (en) |
| JP (1) | JP2935547B2 (en) |
| KR (1) | KR0177808B1 (en) |
| AT (1) | ATE96785T1 (en) |
| BR (1) | BR9003682A (en) |
| CA (1) | CA2022133C (en) |
| DE (2) | DE3925253A1 (en) |
| DK (1) | DK0411408T3 (en) |
| ES (1) | ES2059918T3 (en) |
| HU (1) | HU205910B (en) |
| ZA (1) | ZA905911B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4436293A1 (en) | 1994-10-11 | 1996-04-18 | Basf Ag | Stable mixture containing water and metazachlor |
| DE10210409A1 (en) * | 2002-03-09 | 2003-09-18 | Feinchemie Schwebda Gmbh | Purely triclinic metazachlor and process for its manufacture |
| DE10337162A1 (en) | 2003-08-11 | 2005-03-17 | Basf Ag | Storage-stable herbicidal mixtures with metazachlor |
| ES2381634T3 (en) | 2004-04-01 | 2012-05-30 | Basf Se | Herbicidal mixtures that act synergistically |
| PL2280602T3 (en) | 2008-04-29 | 2016-01-29 | Basf Se | Herbicide mixture |
| AR075093A1 (en) * | 2008-10-14 | 2011-03-09 | Basf Se | PENDIMETALINE AND METAZACHLOR CRYSTAL COMPLEXES, PROCESS TO PREPARE THEM AND AGRICULTURAL COMPOSITIONS THAT CONTAIN THEM. |
| JP5697655B2 (en) | 2010-02-23 | 2015-04-08 | 日本化薬株式会社 | Stable crystals of 2-ethyl-3,7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) quinolin-4-ylmethyl carbonate, method for producing the same, and agrochemical composition containing the crystals |
| EA023773B1 (en) | 2011-08-25 | 2016-07-29 | Басф Се | Herbicidal compositions comprising chloroacetamides |
| WO2017009054A1 (en) | 2015-07-10 | 2017-01-19 | BASF Agro B.V. | Herbicidal composition comprising cinmethylin and metazachlor |
| EA201890267A1 (en) | 2015-07-10 | 2018-07-31 | Басф Агро Б.В. | HERBICIDE COMPOSITION CONTAINING METAZACHLOR AND QUINOLINCARBONIC ACIDS |
| GB201911300D0 (en) * | 2019-08-07 | 2019-09-18 | Johnson Matthey Plc | Molecular complexes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2648008C3 (en) * | 1976-10-23 | 1980-09-04 | Basf Ag, 6700 Ludwigshafen | Acetanilide |
| DE2830764A1 (en) * | 1978-07-13 | 1980-01-31 | Basf Ag | ACETANILIDE |
| DE2849442A1 (en) * | 1978-11-15 | 1980-05-29 | Basf Ag | METHOD FOR PRODUCING MOST PURE PYRAZOLIC COMPOUNDS |
| DE2930448A1 (en) * | 1979-07-26 | 1981-02-26 | Bayer Ag | COUNTERPROTECTOR FOR THE PROTECTION OF CULTURAL PLANTS FROM HERBICIDE DAMAGE |
-
1989
- 1989-07-29 DE DE3925253A patent/DE3925253A1/en not_active Withdrawn
-
1990
- 1990-07-18 JP JP2188173A patent/JP2935547B2/en not_active Expired - Lifetime
- 1990-07-20 EP EP90113914A patent/EP0411408B1/en not_active Expired - Lifetime
- 1990-07-20 DE DE90113914T patent/DE59003309D1/en not_active Expired - Lifetime
- 1990-07-20 ES ES90113914T patent/ES2059918T3/en not_active Expired - Lifetime
- 1990-07-20 DK DK90113914.7T patent/DK0411408T3/en active
- 1990-07-20 AT AT90113914T patent/ATE96785T1/en not_active IP Right Cessation
- 1990-07-27 HU HU904660A patent/HU205910B/en unknown
- 1990-07-27 CA CA002022133A patent/CA2022133C/en not_active Expired - Lifetime
- 1990-07-27 BR BR909003682A patent/BR9003682A/en not_active IP Right Cessation
- 1990-07-27 KR KR1019900011442A patent/KR0177808B1/en not_active Expired - Lifetime
- 1990-07-27 ZA ZA905911A patent/ZA905911B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0411408B1 (en) | 1993-11-03 |
| BR9003682A (en) | 1991-09-03 |
| JP2935547B2 (en) | 1999-08-16 |
| KR910002804A (en) | 1991-02-26 |
| HUT54661A (en) | 1991-03-28 |
| DE3925253A1 (en) | 1991-01-31 |
| DK0411408T3 (en) | 1993-12-20 |
| EP0411408A1 (en) | 1991-02-06 |
| KR0177808B1 (en) | 1999-03-20 |
| HU904660D0 (en) | 1991-01-28 |
| CA2022133A1 (en) | 1991-01-30 |
| ES2059918T3 (en) | 1994-11-16 |
| JPH0366671A (en) | 1991-03-22 |
| ZA905911B (en) | 1992-03-25 |
| HU205910B (en) | 1992-07-28 |
| DE59003309D1 (en) | 1993-12-09 |
| ATE96785T1 (en) | 1993-11-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |