Method of preparing dichloroacetamides

专利摘要:
There are disclosed dichloroacetamides which are antidotes that are particularly and specifically active against the toxic action exerted on maize cultivations by herbicidal esters of N,N-disubstituted glycines; methods for preparing the antidotes, and compositions comprising them, in particular compositions comprising both the antidotes and the herbicidal esters of N,N-disubstituted glycines.
公开号:SU873874A3
申请号:SU772537900
申请日:1977-10-28
公开日:1981-10-15
发明作者:Гоццо Франко；Аббруццесе Луиджи；Сидди Джорджо
申请人:Монтэдисон С.П.А (Фирма)；
IPC主号:

专利说明:

one
The invention relates to a process for the preparation of dichloroacetamides of the general formula
/
I I, 1
cr.
from
where X is hydrogen or chlorine;
R is hydrogen, C -C-alkyl, allyl, which has herbicidal properties and exhibits an antidote to herbicides - N, N-disubstituted glycol ethers.
The use of N, N-disubstituted glycol ethers — N- (chloroacetyl) -N- (2,6-dialkylphenyl) glycine herbicides for weed crops has a detrimental effect on beneficial plants, in particular maize or wheat. As a counter to the specified herbicide, N-diallyl-dichloroacetamide of the formula
 / eleven
I g
where R and R-, - halogenated,
 haloalkyl, alkyl,
alkenylphenyl D J.
However, when using the known 5 compounds of the formula II, it is not possible to completely eliminate the intoxication of useful plants when they are treated with herbicides. .V
The method for producing dichloroacetamides 10 of formula I is based on the known reactions of reacting amines with unsaturated olefins at a higher temperature of 123.
The aim of the invention is a method 18 for the preparation of new compounds of the indicated formula 1, which have an antidote to the herbicides of N, N-disubstituted glycol ethers, in particular against N- (chloroacetyl) -N20 -2,6- (dialkylphenyl) glycine.
This goal is achieved by the fact that dichloroacetamides of formula 1 are obtained by reacting an amine where R has the indicated values, 25 with 1,1,3-trichloro-2-X-propene, where X has the indicated values, at a temperature from room temperature to boiling point in medium benzene, toluene, or a lower aliphatic alcohol, and the resulting P-M- (3,3-dichloro-2-X-allyl) amine, where R and X have the indicated values, process: t: ay dichloroacetamide in an inert organic solvent, in the presence of an excess amount of hydrogen chloride acceptor. The proposed contraries are compatible in all respects with the herbicidal H, M-disubstituted glycol ethers. Of these, compositions with diatomite can be prepared under the usual conditions for the preparation of powders, and, if necessary, in the presence of surfactants, only these compounds or mixtures of them with N, N-di substituted glycol ethers can be used. It is also possible to prepare suspensions, aqueous dispersions of a spray in the presence of surfactants and / or solvents. The effect of contraindication is already noticeable at doses of 0.1 kg / ha in the presence of toxic doses of a herbicide of the general formula (4 kg / ha). Example 1: Preparation of N-a lyl- (3, 3-dichloroallyl) -dichloroacetamide To 1.2 moles of allylamine, dissolved in 200 ml of benzene, 0.3 moles of 3.3 moles are added dropwise with stirring and boiling point. 1-trichloropropene diluted in 50. ml of the same solvent. The mixture is boiled for another 2 hours, then washed with water. And dried. After removal of the solvent, an N-allyl-N- (, 3-dichloroallyl) amine oil is obtained which is distilled at boiling point 7 and 18 mm Hg. To 0.04 mol of the amine dissolved in 50 ml of dichloroethane, 0.02 mol of dichloroacetyl chloride diluted in 20 ml of the same solvent is added dropwise with stirring. The mixture is stirred for another 2 h at room temperature. After removal of the resulting solid (chlorohydrate amine), the solution is dried and evaporated. The residue in the form of a yellow oil is distilled under a reduced pressure of 0.4 mm Hg. and 105-108 C. Found,%: C 50.54; C 34.31; H 3.19; N 5.15. Calculated,%: Ct 51,20; C 34.69; H 3.27i N 5.06. Example 2. Preparation of N-methyl-N- (H, 3-dichlorallyl) dichloroacetamide. To 2 mol of methylamine (33% aqueous solution), 0.2 mol of 3,3,1-trichloroprene dissolved in 120 ml of methanol is added dropwise at room temperature. The mixture is stirred for 3 hours and the mixture is kept at rest during the night. Upon extraction with dichloromethane or ethyl ether and evaporation after drying, a yellowish N-methyl- (3,3-dichloroallyl amine) is obtained in the form of a yellowish oil, which is distilled at boiling point. 51-52c and a reduced pressure of 15 mm Hg. The reaction of this amine with dichloroacetyl chloride, as described in Example 1, gives M-methyl-M- (3,3-dichlorallyl) dichlorocetamide as a yellow oil. Found,%: 855.77; C, 28.02; H, 2.73; N, 5.440. Calculated,%: Ci 56.51j C 28.72; H 2.81, N 5.587. Example 3. Preparation of N- (3,3-dichlorallyl) dichloroacetamide. 0.2 mol of NaJ is added with stirring to 0.2 mol of hexamethylenetetramine dissolved in 300 ml of ethanol, and then 0.2 mol of 3,3,1-trichloropropene is added dropwise to the mixture. The mixture is then stirred for another 2 hours and kept at rest for 24 hours. After saturation with gaseous NSC, the mixture is kept for 12 hours. The solid is then separated by filtration under vacuum and the filtrate is evaporated. The residue of the amine hydrochloride is washed with dichloromethane and dried {t; pl. 215-217 C). The free N- (3, 3-dichloroallyl) amine, obtained from the hydrochloride by alkalizing the aqueous solution and extracted with ethyl ether, boils at Hg. By the reaction of N- (3,3-dichlorallyl) amine with dichloroacetyl chloride, k-ak as described in Example 1, N- (3,3-dichlorallyl) dichloracetamide is obtained. Found,%: CE 58, OU C 25.75; And 2.15, N 6.11. Calculated,%: ce 59.86 C 25.35; H 2.13 N, 5.91. Examples 4-7. In the process described in Example 1, M-methyl-H- (3,3,2-trichloroallyl) amine is obtained from methylamine and 3,3,2,1-tetrachloroprene (BP. 67 s / 15 mm Hg). .), from which, by reaction with dichloroacetyl chloride, N-methyL-N- (3.3, 2-trichloroallyl) dichloroacetamide is obtained in the form of a yellow oil.
Found,%: C 60.20, Se25.06, H 2.11 J. N 5.04,
Calculated,%: Ct 62,12, Ce25.25j H 2.12; N 4.91.
From ethylamine and 3,3,2,1-tetrachloro prene, in Example 1, N-ethyl-N- (3,3,2-trichloroallyl) amine is obtained (bp 91-92 ° C / 35 mm Hg). ). When this product interacts with dichloroacetyl chloride, N-ethyl-N- (3,3,2-trichloroallyl) dichloroacetamide is obtained in the form of a yellow oil.
Found,%: cr 58.74; 0828.09; H 2.72; N 4.40.
Calculated,%: SS. 59.21; 0228.08; H N 4.47.
In Example I, M-isopropyl-M- (3,3,2-trichloroallyl) amine is obtained from isopropylamine and 3,3,2,1-tetrachloropropene (so kip. 84-85 ° 0/18 mm Hg) .
When the product interacts with dichloroacetyl chloride, H-isopropyl-M- (3,3,2-trichloroallyl) dichloroacetamide is obtained (mp. 51-52 0).
Found%: 06 55.38; About 30.77; H 3.17 N 4.00.
Calculated ,,: OV 56,56; O 30, .66, H 3.21} N 3.21.
From propargylamine and 3,3,1-trichl6rpropene of Example 1, N-propyl-M- (3,3-dichlorallyl) amine was prepared (mp. 88910/15 mm Hg). .
When the last compound reacts with dichloroacetyl chloride, H-propargyl-M- (3,3-dichlorallyl) dichloroacetamide is obtained in the form of a yellow oil.
8738746
The dichloroacetamides of formula I have a stronger antidote effect than the known compounds used for this purpose. five

权利要求:
Claims (2)
[1]
1.Patent of France No. 2133793, cl. And 01 N 9/00, published. 1972.
[2]
2. Weigand-Hilgettat, Methods of experiment in organic chemistry, M., Himi, 1968, p. 372.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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US4021224A|1971-12-09|1977-05-03|Stauffer Chemical Company|Herbicide compositions|

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US4033756A|1971-09-17|1977-07-05|Gulf Research & Development Company|Dichloroacetamide treated rice seeds|

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CH574207A5|1973-01-25|1976-04-15|Ciba Geigy Ag|IT1114195B|1977-12-23|1986-01-27|Montedison Spa|TWO DICHLOROACETAMIDE ANTIDUCTS FOR NON-SELECTIVE HERBICIDES PARTICULARLY ACTIVE TO PROTECT THE MAIZE FROM TOXIC ACTION EXERCISED BY GLYCIN ESTERS N, N HERBICIDES REPLACED|

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AU522026B2|1978-09-19|1982-05-13|Sumitomo Chemical Company, Limited|N-benzylhaloacetamide derivatives used as herbicides|

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US4443628A|1979-12-26|1984-04-17|Ppg Industries, Inc.|Antidotal compounds for use with herbicides|

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DE3004871A1|1980-02-09|1981-08-20|Bayer Ag, 5090 Leverkusen|HALOGENALKYLAMID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AN AGAINST AGENT FOR THE PROTECTION OF CULTURAL PLANTS FROM DAMAGE FROM HERBICIDES|

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CA1168056A|1981-10-20|1984-05-29|Attilio Formigoni|Weed-killer composition containing amides asantidotes for alpha-halo-acetanilides|

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JPH0515699B2|1985-06-21|1993-03-02|Tokuyama Soda Kk|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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IT28867/76A|IT1079199B|1976-10-29|1976-10-29|ANTIDOTES, OF THE CLASS OF DICHLOROACETAMIDES PARTICULARLY ACTIVE IN PROTECTING MAIZE FROM TOXIC ACTION EXERCISED BY GLYCINE ESTERS N, N SUBSTITUTED HERBICIDE AND HERBICIDE ASSOCIATION FOR MAIZE CULTURES|

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