• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The herbicidal preparation contains, as active component, a compound of the formula I. The substituents have the meaning given in the patent claim. The abovementioned compounds are prepared by cyclization of corresponding N-alkenylhalocyanamides in the presence of a catalytic amount of iron(II) ions. <IMAGE>
    公开号:SU942590A3
    申请号:SU762421801
    申请日:1976-11-23
    公开日:1982-07-07
    发明作者:Гордон Тич Юджин
    申请人:Стауффер Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD FOR OBTAINING N-SUBSTITUTED HALOIDPYRROLIDINONES-2
    one
    The invention relates to methods for producing novel pyrrolidinone-2 derivatives having valuable herbicidal properties that can be used in agriculture.
    The reaction of cyclization of N-alkenyl haloalkylamines to pyrrolidinone-2 derivatives is known.
    The purpose of the invention is to obtain new pyrrolidinone-2 derivatives with high herbicidal activity.
    The goal is achieved based on a known reaction method for the preparation of N-substituted halopyrrolidinones-2 of the general formula
    . 4-ct. I
    ZCHg-HC-CHa
    where R is alkyl with 1-6 carbon atoms, alkeiyl with 3b carbon atoms, halogen kil with 1-6 carbon atoms, cycloalkyl with 3-7 carbon atoms. yes, cycloalkylalkyl with k-B carbon atoms, benzyl, chlorobenzyl or group
    .pvRi
    U
    X is hydrogen or chlorine
    and when R group
    QBi 2 then X is methyl, and Y is chlorine or bromine,
    provided that when R is allyl, then Y and Z is bromine or chlorine, and provided that when R is cyclohexyl, then X is not chlorine;
    R. is hydrogen, alkyl with 1-6 carbon atoms, acetyl, chlorine, iodine, trifluoromethyl, nitro30 cyano-, alkoxy-, alkio-, alkylsulfonyl, alkylsulfinyl group, in which the alkyl contains I- and volumes of carbon, trifluoromethyl -io-, trifluoro25 3 methylsulfinyl-, trifluoromethylsulfonyl-, pentafluoro propionamido- or 3 methyl ureido group; Rrt is hydrogen, alkyl with 1-6 carbon atoms, chlorine or trifluoromethyl, which consists in the fact that the N-alkyl halide acylamide of the formula Z is (ixx-d; CH2 CH-CH2 where R, X and Y have the indicated values) rearrangement in the presence of a catalytic amount of divalent iron ions at 50lao c., chloride or iron bromide is used as a catalyst. The process is carried out in a high boiling solvent medium. Dimethyl ether glycol ether, dimethylformamide, dimethyl acetamide, dimethyl sulfate could be used oxide, mesitylene, etc. The compounds obtained by the proposed method can exist in the form of cis and trans isomers. The starting N-alkenyl halo-acylamide of general formula Ii, in particular N-alkenyl-halo-acylanilides, can be obtained by acylation of the corresponding N-alkenylamines, for example N - Alkenyl anilides. Preparation of allyl-N-butylamine 50 g of N-allyl butyramide, obtained by reacting allylamine with butyryl chloride, are dissolved in 100 ml of benzene and sodium bis (2-methoxyethoxy) - alum the hydride in 300 ml of benzene under reflux under nitrogen. The boiling is continued for another hour after the addition is complete, then the mixture is cooled and added dropwise to the solution obtained by mixing 200 ml of a 50% sodium hydroxide solution and 300 g of crushed ice. The aqueous layer was extracted three times with 100 ml of benzene and the combined extracts were dried over magnesium sulfate. The product is then converted to the hydrochloride with an excess of 20% ethereal sodium hydrogen chloride. The hydrochloric acid salt is filtered and dried. The yield is 35 g (this salt is used without further purification). Preparation of N-allyl-N-butyldichloroacetamide. 10.5 g of allyl-M-butylamine hydrochloride are added to 100 ml of methylene chloride, and then 1.5 g of triethylamine are added. The mixture was stirred in a water bath at room temperature while 10, g of dichloroacetyl chloride was added dropwise. Stirring is continued for another 30 minutes after completion of addition. The mixture is washed with water and the solvent is removed in vacuo. Output 13 g, p jP 1, A603 Intermediate compound is used without further purification. Example 1. Preparation of N-allyl-3-chloro-chloromethyl-2-pyrrolidinone. 20.8 g of M, M-diallyl dichloroacetamide is mixed with 25 g of diethylene glycol dimethyl ether (diglyme), 1 g of ferric chloride (feC q -kHqO) is added and the mixture is heated under reflux for 30 minutes. The transformation is controlled by the appearance in the IR spectrum of a new carbonyl band. Another 1 g of ferric chloride is added and the boiling is continued for another 30 minutes. The reaction mixture is diluted with methylene chloride, washed with water, dried and volatile products are distilled off. The dark liquid residue was distilled under vacuum; 8, k g of light yellow oil were obtained with a bp. 124-127 ° C (0.25 mm; pZO 1,1,850). The PMR and C-NMR spectra show that the product is a mixture of cisi trans isomers with a ratio of 2: 1. Example 2. Getting 1-allyl-3-bromo-A-bromomethyl-2-pyrrolidinone. 10.9 g of M, H-diallyldibromoacetamide is dissolved in 15 ml of diglyme, and then 1 g of anhydrous iron bromide is added. The mixture was heated under reflux and the conversion to pyrrolidinone was monitored by gas chromatography. After the conversion is complete, the product is diluted with methylene chloride, washed with water, dried with anhydrous sulfate mA, and treated with silica gel to remove gums. The solvent is removed in vacuo. Obtain 8.1 g of product, nif 1.5350. Example 3- Preparation of N-benzyl-3-chloro-chloromethyl-2-pyrrolidinone. 11.1 g of N-allyl-M-benzyldichloroamide amide is dissolved in 12 ml of diglyme and 1 g of anhydrous ferric chloride is added. The mixture is refluxed under nitrogen until the conversion to pyrrolidinone is complete. The mixture is diluted with methylene chloride, washed with 5% hydrochloric acid solution, separated, dried with anhydrous magnesium sulphate, treated with activated charcoal and easily evaporated under vacuum. The yield is 6 g, nU 1.5387. . Example j. Preparation of N-cyclopropylmethyl-3-chloro-chloromethyl-2-pyrrolidinone. 12.1 g of M-allyl-M-cyclopropylmethyl dichloroacetamide is dissolved in 15 ml of diglyme and 1 g of anhydrous ferric chloride is added. The mixture was refluxed under nitrogen for 25 minutes. After the conversion is complete, the diglyme is removed in vacuo and the mixture is dissolved in benzene, washed with 5% hydrochloric acid solution, separated, dried with anhydrous magnesium sulfate, treated with activated carbon, filtered through silica gel, and the solvent removed in vacuo. Yield - 8.8 g of product,,. Example 5- Preparation of N-butyl-3 chloro-4-chloromethyl-2-pyrrolidine 11 g of H-allyl-M-butyldichloroacetamide is dissolved in 15 ml of diglyme and 1 g of anhydrous ferric chloride is added. The mixture was refluxed under nitrogen for 25 minutes. The transformation is controlled by gas chromatography. The diglyme is removed in vacuo and the mixture is diluted with benzene, washed with hydrochloric acid, dried with anhydrous magnesium sulfate, treated with activated carbon to remove gummy products and filtered through florisil. The solvent is distilled off in vacuo. Obtain 8.1 g of product, p 1 4731., Preparation of N-allyl-meta-trifluoromethylanilium. meta-Trifluoromethyl acetanilide is obtained from aniline by reaction with trifluoroacetic anhydride. 192 g of acetanyl and dissolved in 300 ml of tetrahydrofuran (THF) and added dropwise with stirring to a suspension of sodium hydride in 200 ml of THF under a nitrogen atmosphere at room temperature. When the evolution of hydrogen is complete, 121 g of allyl bromide is added, the mixture is heated under reflux for 1 hour and stirred overnight. The mixture is filtered, the volatile products are distilled off. vacuum, the residue is diluted with methylene chloride, washed with water, dried and the volatile products are distilled off in vacuo. The output of N-allyl-meta-triptoreline 205 g, 1.4532. The product is sufficiently pure for use in the next step without further purification. The product is added to a mixture of 200 ml of concentrated hydrochloric acid and 250 ml of water. The two-phase system is heated to reflux with stirring until a clear solution is obtained (h). The mixture is cooled and treated with sodium hydroxide. The N-allylanilide released is extracted with methylene chloride, dried over magnesium sulfate and distilled off volatile products. 170 g of product are obtained. The product has purity. The be-, substance is dissolved in ether and precipitated in the form of hydrochloride with an ethereal solution of hydrogen chloride. Exit 173.g, so pl. 10 -106 ° C. Preparation of N-allyl-meta-trifluoromethyldichloroaceganilide. 23.8 g of N-allyl-meta-trifluoromethylaniline hydrochloride are suspended in 200 ml of methylene chloride, 21 g of triethylamine are added and the mixture is stirred on a water bath at room temperature, adding dropwise 15 g of dichloroacetyl chloride. After the addition was complete and stirred for 30 minutes, the mixture was washed with sodium hydroxide solution, 1% hydrochloric acid solution and water, dried over magnesium sulfate and the solvent was distilled off in vacuo. The residue is dissolved in ether and treated with 10 g of a 20% ethereal hydrogen chloride solution. The precipitate formed is filtered off and the ether is distilled off in vacuo. . Get 27 g of the product, .klkQ. Example 6. Obtaining N-meta-trifluoromethylphenyl-3 chloro-4-chloromethyl-2-pyrrolidinone. 30 ml of diglyme is added to 2 g of ferric chloride (FeCf,), heated to boiling point under nitrogen atmosphere and 10 g of a mixture of water with diglyme removed. To the resulting reaction mixture, 12.5 g of N-allyl-m-trifluoromethyldichloroacetanyl was added and boiling continued for 15 minutes. The conversion to the desired product was determined by GLC. After the conversion is complete (refluxing for 30 minutes), the mixture is cooled, diluted with methylene chloride, washed with hydrochloric acid, dried with magnesium sulfate, treated with activated carbon and Florisil, filtered and the solvent removed in vacuo. ; Yield - 10 g of maela, p | 0 1.5032. The resulting oil (ni 1.5032) was left overnight and part of it crystallized. This substance is triturated with carbon disulfide and a suspension of crystals is obtained. The crystals are separated by filtration. This crystalline product has a trans configuration of mp. . When cooling the sulfur-permeable filtrate, a new crystalline substance is obtained. After separation and drying, these crystals are identified by NMR and have the cis configuration, e.g. 79 80s Example 7- Preparation of N-meta-chlorophenyl-3-chloro-chloromethyl-2-pyrrolidinone. 2 g FeC. suspended in 30 ml of diglyme and heated to boiling under nitrogen, then 10 mixture of water and diglyme are distilled. 11.1 g of N-allyl-m-chloro-dichloroacetanilide is added and the boiling is continued with 20 times. The reaction is monitored by GLC. After the conversion is complete (20 minutes), the mixture is cooled, the chlorides are broken down with methylene chloride and washed with hydrochloric acid, dried with magnesium sulfate, treated with florisil and activated carbon, filtered under vacuum, the solvent is distilled off. The product is a thick dark oil, crystallizes on standing. The crystals are purified by recrystallization from carbon tetrachloride. The product yield 2.9 g, so pl. 93-9 C. o. Example 8. Preparation of N-phenyl-2, 3-Dichloro - + - chloromethyl-2-pyrrolidinone. 1 g of FeCP2-Hi2 0 is suspended in 25 ml of diglyme and 20 g of N-allyltrichloroacetanilide is added. The mixture is then refluxed under nitrogen. After 15 minutes, the mixture was diluted with benzene and washed with water. The product is crystallized from benzene. A sample is recrystallized from ethanol to give a product with mp. 133-134 ° C. Example 9- Preparation of N-meta-trifluoromethylphenyl-3-bromo-1-bromomethyl-2-pyrrolidinone. 1 g of anhydrous iron bromide (FeBr, 2) is suspended in 15 g of diglyme, 9) 6 g of N-allyl-meth-trifluoromethyldibromoacetanilide are added and the mixture is heated under reflux in a nitrogen atmosphere for 15 minutes. The mixture is cooled, diluted with methylene chloride, extracted with water and hydrochloric acid solution, dried, treated with florisil, filtered and the solvent is distilled off in vacuo. Output - 7.6 g of a dark liquid. Example 10. Preparation of N-meta-nitrophenyl-3-chloro-chloromethyl-2-pyrrolidinone. A mixture of 10.1 g of N-allyl-meta-nito-dichloroacetanilide, 15 ml of diglyme 1 g of anhydrous ferric chloride (FeCCij) was boiled under reflux under nitrogen for 1 hour and then cooled. The mixture is diluted with benzene, washed with hydrochloric acid, the solution is treated with magnesium sulfate and activated carbon, filtered through a layer of florisil and the solvent is distilled off under vacuum. A thick oil is obtained, which solidifies upon standing. Trituration with ether gives 3 g of crystalline solid with a mp. 102-10itc. The following compounds were obtained according to the indicated procedures, given in Table. 1 and 2. 1.1-Allyl-3 chloro-chloromethyl-2-pyrrolidinone. 2.1-Allyl-3, 3-Dichloro-chloromethyl 2-pyrolidinone. 3- 1-Ethyl-3 chloro-chloromethyl-2-pyrrolidinone. 4. 1-Ethyl-3, -Dichloro-chloromethyl-2-pyrrolidinone. 5.1-Cyclohexyl- -chloro - + - chlorome-2-pyrrolidinone. 6.1-Allyl-3 chloro-chloromethyl-2-pyrrolidinone. 7.1-Methyl-3-chloro-chloromethyl-2-pyrrolidinone. 8.1-Propyl-3-chloro - + - chloromethyl-2-pyrrolidinone. 9-1-Allyl-3 bromo-4-bromomethyl-2-pyrrolidinone. 10.M-2,3 Dibromopropyl-3-chloro-4-chloromethyl-2-pyrrolidinone, 11.M-Amyl-3 chloro-chloromethyl-2-pyrrolidinone. 12.M-Butyl-3 chloro-chloromethyl-2-pyrolidinone. 13. M-Isobutyl-3 chloro-chlorometh -2-pyrrolidinone. 1. M-Cyclopropylmethyl-3 chloro-chloromethyl-2-pyrrolidinone. 15-N-Benzyl-3 hpor-4-chloromethyl-pyrrolidinone. 16. M-para-Chlorobenzyl-3-chloro-chloromethyl-2-pyrrolidinone. 17.1-Phenyl-3 chloro-chloromethyl-2-pyrrolidinone. 18.1-Phenyl-3,3-Dichloro-chloromethyl-2-pyrrolidinone. 19- 1- (2,6-Dimethylphenyl) -3-chloro-chloro-methyl-2-pyrolidinone. 20.1-meta-Chlorophenyl-3-chloro-chloromethyl-2-pyrrolidinone. 21.T-para-Chlorophenyl-3-chloro-chloromethyl-2-pyrrolidinone. 22.1-meta-Trifluoromethylphenyl-3-chloro-chloromethyl-2-pyrrole di «it. 23.1-Phenyl-3-chloro-3-methyl-L-chloro methyl-2-pyrrolidinone. 2k. 1- (3, -Dichlorophenyl) -3,3 Dichloro-chloromethyl-2-pyrrolidinone. 25.1-meta-Trifluoromethyl-3,3-Dichloro-chloromethyl-2-pyrrolidinone. 26.N-meta-Trifluoromethylphenyl-3-chloro-3-methyl-3-chloromethyl-2-pyrrolidinone. 27.1-para-Tolyl-3-chloro-hlgrmethyl-2-pyrrog1 Dinon. 28.1-meta-Fluorophenyl-3-chloro-chloromethyl-2-pyrrolidinone. 29.H-meta-Trifluoromethyl-3-brOm-4-bromomethyl-2-feast Rolidi non. 30.M-3, -Dichlorophenyl-3-chloro- | -chloromethyl-2-pyrrolidinone. 31.N-meta-Nitrophenyl-3-hpor- -chloromethyl-2-pyrrolidinone. 32.M-3,5-Dichlorophenyl-3-xpor-4-chlormeth-2-pyrrolidinone. 33.M-meta-Trifylmethylphenyl-3-chloro- - il-chloroethyl) -2-pyrrlidinone 0 3. N-meta-cyanophenyl-3-chloro-chloromethyl-2-pyrrolidinone. 35. N-3,5-Dichlorophenyl-3,3-Dichloro-4-chloromethyl-2-pyrrolidinone. 36. M-meta-Trifluoromethylphenyl-3,3-dichloro - "- (1-chloroethyl) -2-pyrrolidinone. 37. M-meta-cyanophenyl-3,3-Dichloro - "- chloromethyl-2-pyrrolidinone. s8. H-3-Trifluoromethyl - + - chlorophenyl-3-chloro-t-chloromethyl-2-pyrrolidinone. 39. H-3-Trifluoromethyl- -chlorophenyl 3, 3-Dichloro-chloromethyl-2-pyrrolidinone. Tso. N-Meta-Tiforopropylmethyl-3-chloro-chloromethyl-2-pyrrolidinone. 1. M- (meta-methylthiophenyl) -3-chloro-4-chloromethyl-2-pyrrolidinone. . M- (meta-Trifluoromethylsulfiniphenyl) -3-chloro-4-chloromethyl-2-pyrrolidinone. . H- (meth-Methylsulfinylphenyl) -3-chloro-chloromethyl-2-pyrrolidinone. kk. H- (meth-Methylsulfonylphenyl} -3-chloro-chloromethyl-2-pyrrolidinone. KS-M- (meta-Trifluoromethylsulfonylphenyl) -3-chloro-chloromethyl-2-pyrrolidinone. 6. H- (3,5-bis -Trifluoromethylphenyl) -3-chloro-chloromethyl-2-pyrrole dinone, kj, N-meta-methoxyphenyl-3-chloro-chloromethyl-2-pyrrolidinone, W. N-meta-Acetylphenyl-3-chloro-J-chloromethyl -2-pyrro / mdinone. H-meta-Tolyl-3-chloro-chloromethyl-2-pyrrolidinone50. N-meta-Trifluoromethylphenyl-α-chloromethyl-2-pyrrolidino. 51. S-meta-Lromphenyl-3-chloro. -4-chloromethyl-2-pyrrolidinone. 52.H-ortho-Chlorophenyl-N-3-chloro- "- chloromethyl-2-pyrrolidinone. 53.M-meta-Iodophenyl-3-chloro-" - chlorine thyl-2-pyrrolidinone 5. N-para-Methoxyphenyl-3-chloro-1 | -chloromethyl-2-pyrrol dinone 55. ortho-Trifluoromethyl-3-chloro-chloromethyl-2-pyrrolidine non, 56. N- (meta-Perfluoropropionamidophenyl) -3-chloro-chloromethyl-2-pyrrolidinone 57.H- (meta-Methylureidophenyl) -3-x-prop-chloromethyl-2-pyrrolidinone. 58. cis-1 meta-Trifluoromethylphenyl-3 - chloro-chloromethyl-2-pyrrolidinone. 59. trans-1-meta-trifluoromethylphenium-3- "ent -" - chloromethyl-2-py rrolidinone. The compounds shown in Table 1 correspond to the following formula: r-i- "t | - fR Table ZCHj-HiJ - CK2
    Continued table. 2
    The structure is confirmed by IR analysis. Test as pre-emergent herbicides. Using an analytical balance, weigh 20 mg of the compound on a piece of weighted parchment paper. The paper and compound are placed in a 30-ml wide-necked bottle and 3 ml of acetone containing 1 Secret 20 (polyoxyethylene sorbitan monolaurate) is added to dissolve the compound. If the substance is insoluble 8-acetone, then another solvent is used instead, such as water, alcohol or dimethylformamide (DMF). If DMF is used, then only 0.5 ml or less is used to dilute the compound, and then another solvent is used to keep the volume up to 3 ml. 3 ml of the solution is uniformly sprayed onto the surface of the soil contained in the small box, one day after sowing the seeds of weeds in the soil of the box. For spraying the liquid, use dry air under a pressure of 0.352 kg / cm. The application dose is 91072 kg / g and the volume of the sprayed liquid is 1353.25 l / ha. The day before the treatment, the box, which measures 17.78 12.7 7 cm, is filled to a depth of 5.08 cm with sandy loam soil. Seeds of seven different types of weeds are sown in separate rows, using one view of a row across the crate width. The seeds are covered with soil. So that they beat the seeds to a depth of 1.27 cm. They sow so many seeds that, depending on the size of the plants, obtain approximately 2050 seedlings per row. Use bristle seeds (Setaria spp.) - SchT; millet chicken (Echinochloa cr.) - PC; Byzantine oats (Avena sativa) - OB; Amaranthus retrofl. KSch; mustard (Brassica jun) - Gr; sorrel curly (Rumex crispus) SchK; Rosicky blood (Digitaria sanguinaH s) - RK. After processing, the crates are placed in a greenhouse at 21.1-29, C and watered by spraying. Two weeks after treatment, the extent of damage or destruction compared to untreated control plants of the same age is determined. Damage score from 0 to 100% is recorded for each species as a percentage of destruction, where Q% is no damage, 100% is total death. Test as post-harvest herbicides. Seeds of six plant species; Rosykovka krovuyu (RK), chicken millet (PC), Byzantine oats (OM), mustard (Gy), curly sorrel (SchK) and common beans (Phaseolus v.) (FD) are sown in boxes as well as for pre-emergence sorting. Boxes are placed in a greenhouse at 21.1-2E, and watered daily by spraying. After 10-1 days after sowing, when the first leaves of the bean plants are almost completely open and the first three-leaved leaves begin to form, the plants are sprinkled. The sprayed liquid is prepared by weighing 20 mg of the test compound, dissolving it in 5 ml of acetone containing 1% Tween 20 (polyoxyethylene sorbitan monolaurate), and then adding 5 ml of water. Spray the leaves with a solution using a liquid sprayer at an air pressure of 0.352 kg / cm. The concentration of the sprayed liquid is 0.2% and the dose is 9.072 kg / ha. The volume of sprayed liquid is em, 50 kg / ha. The results of these tests are presented in Table. 3, where the percentage of weeds is negligible at an 8 pound / acre dose of gericides.
    T a b l i
    cc 3
     Percentage killing at a dose of 20 pounds per acre before and after the occurrence
    seedlings. The test results of pre-emergence herbicides at a dose of
    20 pounds / acre Test results of post-harvest herbicides at a dose of
    20 pounds / acre
    Continued table. 3 29 Compounds 58 (cis) and 59 (trans) were biologically tested as a herbicide using a pre-emergence surface technique. In tab. The results obtained with a dose of 0.25 lb / acre (0.283 kg / ha), 0.5 lb / acre (0.56 kg / ha) and
    8 (cis)
    0.25
    100
    100
    100
    0.5
    100
    100
    100
    1.0
    9 (trans)
    0.25
    97
    98
    0.5
    1.0
    100
    100
    100 100
    0.25
    Monster) 100 100
    0.5
    1.0 100 100 EXAMPLE. OS — CP oats — clap claims 1. Method for preparing N-substituted halopyrrolidinones-2 of the general formula IX „ZCH2-HC-CU2 where R is alkyl with 1- 6 carbon atoms, alkenyl with 3-6 carbon atoms, haloalkyl with 1 carbon atoms, cycloalkyl with 3-7 carbon atoms, cycloalkylalkyl with 4-8 carbon atoms, benzyl, chloro benzyl or group i X - hydrogen or chlorine, and when R is a group X is methyl and Y is chlorine or bromine, provided that when R is allyl, then Y and Z are bromine or chlorine.
    kO 30 70
    0 99
    ten
    . 27 33
    20 20 5 ((Y
    20
    73 90 95 32 52 73 65 80 90
    60
    50
    67 L O
    80
    80
    00 20 i + O 80 60 90
    0 o
    ABOUT
    ABOUT
    ABOUT
    ABOUT
    Ltd
    ABOUT
    20 10 kQ 60
    10 o
    oh oh
    7
    30 60
    20 50
    23
    10 20
    +3 0. . : 22 1.0 lb / acre (1.13 kg / ha). Indeed, mixtures of about kO% cis and 6Q% trans isomers are given for comparison. From Table .. it is clear that the cis isomer has a greater herbicidal activity. Table C annual morning flower; and provided that when R is o-hexyl, then X is not a chloro-hydrogen, alkyl with 1-6 carbon atoms, acetyl, chlorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkio, alkylsulfonyl, alkylsulfinyl group in which alkyl contains carbon I - atoms, trifluoromethylthio, trifluoromethylsulfinyl-, trifluoromethylsulfonyl-, pentafluoropropibnamido- or Zmetilureidogruppz; Rn is hydrogen, anKVfn with 1-6 carbon atoms, chlorine or trifluoromethyl, characterized by the fact that kenyl haloacyl amide of the general form I is Z-CXY-C; (where R, X and Y have the indicated values are rearranged in the presence of a catalytic amount of ions, ferrous iron at, 2, The method according to claim 1, distinguished by the fact that chloride or methyl bromide is used as the catalyst. 3. The method according to claim 1, characterized by the fact that the process is carried out in the presence of a high-boiling solvent.The priority is as follows: 28.03-75 with R is alkyl with 1-6 atoms of carbon, alkenyl with 3-6 atoms carbon, haloalkyl with 1-6 carbon atoms, cycloalkyl with carbon atoms, cycloalkylalkyl with 4-8 atoms carbon, benzyl; R is hydrogen, alkyl with 1-6 carbon atoms, chloro-trifluoromethyl, nitro, cyano-, alkoxy-, alktio-, alkylsulfonyl-, alkylsulfinyl-, in which alkyl with I- carbon atoms, trifluoromethylthio, trifluoromethylsulfinyl -, trifluoromethyl group; Rn, X, Y all the values. 09.01.76 with R - chlorobenzyl; R acetyl, bromine, iodine, pentafluoropropionamido, Zmethylureido group; R, X, Y - all values.
    权利要求:
    Claims (4)
    [1]
    Claim
    1. The method of obtaining N-substituted halogen-pyrrolidinones-2 of the General formula I where R
    1 x 0
    Y-C- <I L '*
    ZCH 2 -HC-CH 2
    - alkyl with 1-6 carbon atoms, alkenyl with 3-6 carbon atoms, haloalkyl with 1-6 carbon atoms, cycloalkyl with 37 carbon atoms, cycloalkylalkyl with 4-8 carbon atoms, benzyl, chlorine benzyl or a group and once XX - hydrogen or chlorine, methyl, and Y is chlorine or bromine, provided that when R is allyl, then U and Z are bromine or chlorine,
    OUTs - annual morning flower;
    and provided that when R is cyclohexyl, then X is not chlorine;
    R ^ is hydrogen, alkyl with 1-6 carbon atoms, acetyl, chlorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkthio, 40 alkylsulfonyl, alkylsulfinyl, in which alkyl contains 1-4 carbon atoms, trifluoromethylthio , trifluoromethylsulfinyl, trifluoro45 methylsulfonyl, pentafluoropropiOnamido or 3methylureido group;
    R ^ - hydrogen, alkyl with 1-6 carbon atoms, chlorine or tri50 - fluoromethyl, • characterized in that N-alkenylhaloacylammide general formula I I
    Z-CXY-C ^
    N-R.
    23 e4 where R, X and Y have the indicated meanings, are rearranged in the presence of a catalytic amount of ions, ferrous iron at 50–190 ° С.
    [2]
    2. The method of pop. ^ characterized in that iron chloride or bromide are used as a catalyst. Yu
    [3]
    3- Pop Method ^ characterized in that the process is carried out in the presence of a high boiling point 1 solvent. fifteen
    Priority by signs:
    03/28/75 at R - alkyl with 1-6 atoms of 24 carbon atoms, alkenyl with 3 _ 6 carbon atoms, haloalkyl with 1-6 carbon atoms, cycloalkyl with 3–7 carbon atoms, cycloalkylalkyl with
    [4]
    4-8 carbon atoms, benzyl; R 4 hydrogen, alkyl with 1-6 carbon atoms, chloro-trifluoromethyl, nitro-, cyano-, alkoxy-, alkthio-, alkylsulfonyl-, alkylsulfinyl-, in which alkyl with 1-4 carbon atoms, trifluoromethylthio-, trifluoromethylsulfinyl-, trifluoromethyl group; R ^, X, Y are all values.
    09-01-76 at R - chlorobenzyl; R 4 acetyl, bromine, iodine, pentafluoropropionamido, 3 ~ methylureido group; Rη, X, Y are all values.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU942590A3|1982-07-07|Process for producing n-substituted halopyrrolidinones-2
    AU635421B2|1993-03-18|1-h-3-aryl-pyrrolidine-2,4-dione derivatives
    US4110105A|1978-08-29|Aromatic N-substituted halo-substituted-2-pyrrolidinones and their utility as herbicides
    DE69324552T4|2006-05-04|N&#39;-substituted-N, insecticides N&#39;Diacylhydrazin
    EP0005341A2|1979-11-14|Polysubstituted butanoic acids, esters and derivatives thereof useful as herbicides, Compositions containing them and their use
    US4157257A|1979-06-05|Benzenesulfonamide derivatives
    US3168561A|1965-02-02|N-alkoxy 2-alkyl-4-chlorophenoxyacetamides for the control of pests
    AU613309B2|1991-08-01|Use of malonic acid derivative compounds for retarding plant growth
    GB1566523A|1980-04-30|Imidazo-isoindole-diones
    US4210589A|1980-07-01|Method of preparation for aromatic N-substituted halo-substituted 2-pyrrolidinones
    US4069038A|1978-01-17|Acyclic and alicyclic N-substituted halo-2-pyrrolidinones and their utility as herbicides
    US3718455A|1973-02-27|Method of combatting weeds with {60 -naphthoxy acetamides
    US4062977A|1977-12-13|Substituted-N-|-α-|-α-alkoxyacetamides and their use as miticides
    AU638349B2|1993-06-24|Heterocycle-substituted benzene derivative, production thereof, and herbicide containing the same as active ingredient
    US4110103A|1978-08-29|Dihydroimidazoisoindolediones and the use thereof as herbicidal agents
    US3166591A|1965-01-19|Phenoxyacetamides for the control of pests
    US4119636A|1978-10-10|Preparation of acyclic and alicyclic N-substituted halo-2-pyrrolidinones
    US4268681A|1981-05-19|Novel 4,5-dichloro-imidazole derivatives and their use as plant protection agents
    US3166589A|1965-01-19|Phenoxyacetamides for the control of pests
    US4051254A|1977-09-27|Sulfonamido-and amidophenyl n-methylcarbamates and use as insecticides
    US4312663A|1982-01-26|Cyclicacylaminoperfluoroalkanesulfonanilides and derivatives thereof
    US4197311A|1980-04-08|Cyanomethyl trithiocarbonate compounds useful as ovicidal agents
    EP0376072B1|1994-02-16|Fungicidal and herbicidal agents and substituted 2-cyclohexen-1-yl amine derivatives, and their preparation
    US3714230A|1973-01-30|Dinitrophenyl ester pesticides
    US4380464A|1983-04-19|N,N-Diacylaminoperfluoroalkanesulfonanilides and derivatives thereof
    同族专利:
    公开号 | 公开日
    IL49289A|1979-09-30|
    YU40279B|1985-12-31|
    YU80076A|1983-01-21|
    BG29122A3|1980-09-15|
    DE2612731A1|1976-10-07|
    CA1076588A|1980-04-29|
    JPS6011695B2|1985-03-27|
    IT1057396B|1982-03-10|
    BG29135A3|1980-09-15|
    HU179058B|1982-08-28|
    PL102693B1|1979-04-30|
    DK145891C|1983-09-12|
    PH15176A|1982-08-31|
    ES446388A1|1977-10-01|
    AU1241376A|1977-09-29|
    NL7603193A|1976-09-30|
    DD126149A5|1977-06-22|
    MY8000091A|1980-12-31|
    DK145891B|1983-04-05|
    DE2661042C2|1989-11-09|
    DK135776A|1976-09-29|
    FR2305434A1|1976-10-22|
    JPS5289666A|1977-07-27|
    DE2612731C2|1986-06-26|
    AU502662B2|1979-08-02|
    NL187313C|1991-08-16|
    IN143281B|1977-10-29|
    IL49289D0|1976-05-31|
    BR7601774A|1977-10-25|
    PL100036B1|1978-08-31|
    MX3355E|1980-10-13|
    FR2305434B1|1981-08-07|
    BE839977A|1976-09-24|
    NL187313B|1991-03-18|
    NZ180424A|1978-03-06|
    GB1522869A|1978-08-31|
    CH625394A5|1981-09-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS49134835A|1973-05-08|1974-12-25|AU527254B2|1979-02-26|1983-02-24|Stauffer Chemical Company|Synergistic herbicides|
    EP0055215B1|1980-12-19|1985-01-30|Ciba-Geigy Ag|Fluoropyrrolidinones, process for their preparation, herbicides containing them and their use|
    DK162087C|1983-06-16|1992-02-24|Stauffer Chemical Co|PROCEDURE FOR THE PREPARATION OF N-ARYLHALOGEN PYROLIDONES|
    FI74385C|1983-12-05|1988-02-08|Stauffer Chemical Co|SYNERGISTIC HERBICIDBLANDNINGAR AV TIOKARBAMAT OCH PYRROLIDONFOERENING.|
    EP0205391B1|1985-05-22|1988-10-26|Rhone-Poulenc Chimie|Process for the preparation of n-alkenyl-m-trifluoromethyl anilines|
    FR2582300B1|1985-05-22|1987-07-10|Rhone Poulenc Spec Chim|PROCESS FOR THE PREPARATION OF N-2 ALCENE-2 YL M-TRIFLUOROMETHYLANILINES|
    FR2589150B2|1985-10-25|1987-11-20|Rhone Poulenc Spec Chim|PROCESS FOR THE PREPARATION OF N ALCENE-2 YL M.TRIFLUOROMETHYLANILINES|
    FR2625197B1|1987-12-23|1990-04-27|Rhone Poulenc Chimie|PROCESS FOR ACYLATION OF N, N-DIALLYLANILINE|
    FR2634761B1|1988-07-29|1990-11-23|Rhone Poulenc Chimie|PROCESS FOR THE PREPARATION OF N-ALLYL AND N-ALKYLANILINES|
    US5189220A|1988-07-29|1993-02-23|Rhone-Poulenc Chimie|Process for preparing N-alkylanilines and N-allylanilines catalyzed by iodides|
    FR2634762B1|1988-07-29|1990-11-02|Rhone Poulenc Chimie|PROCESS FOR THE PREPARATION OF N-ALLYL AND ALKYL-ANILINES|
    US5210305A|1988-07-29|1993-05-11|Rhone-Poulenc Chimie|Process for preparing n-alkylanilines and n-allylanilines|
    FR2643902B1|1989-03-03|1991-10-11|Rhone Poulenc Chimie|PROCESS FOR THE PREPARATION OF N-ALLYLMETATRIFLUOROMETHYLANILINE|
    JPH02237970A|1989-03-13|1990-09-20|Mitsui Toatsu Chem Inc|4-ethyl-1--2-pyrrolidinone derivative and herbicide containing the derivative as active component|
    FR2663927A1|1989-06-05|1992-01-03|Rhone Poulenc Chimie|PROCESS FOR THE PREPARATION OF N MONOALKYL- OR ALKENYLANILINES.|
    JP2728937B2|1989-06-14|1998-03-18|三井東圧化学株式会社|1--3-halogen-4--2-pyrrolidinone derivatives and herbicides containing these as active ingredients|
    FR2665439B1|1990-08-02|1992-11-06|Rhone Poulenc Chimie|N-ALLYLATION REAGENT AND METHOD FOR SYNTHESIS OF N ACYL, N ALLYLANILINE.|
    EP0470000B1|1990-08-02|1997-11-12|Rhone-Poulenc Chimie|Allylation reagent and method of synthesis using it|
    US5538985A|1994-01-27|1996-07-23|Mitsui Toatsu Chemicals, Inc.|Pyrrolidinone derivatives|
    EP2052612A1|2007-10-24|2009-04-29|Bayer CropScience AG|Herbicide combination|
    DE102008037629A1|2008-08-14|2010-02-18|Bayer Cropscience Ag|Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US56327975A| true| 1975-03-28|1975-03-28|
    US56328075A| true| 1975-03-28|1975-03-28|
    US05/647,963|US4110105A|1975-03-28|1976-01-09|Aromatic N-substituted halo-substituted-2-pyrrolidinones and their utility as herbicides|
    US05/647,962|US4069038A|1975-03-28|1976-01-09|Acyclic and alicyclic N-substituted halo-2-pyrrolidinones and their utility as herbicides|
    [返回顶部]