CN101805320A - Amide compounds and preparation method and applications thereof - Google Patents

Amide compounds and preparation method and applications thereof Download PDF

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CN101805320A
CN101805320A CN 201010176849 CN201010176849A CN101805320A CN 101805320 A CN101805320 A CN 101805320A CN 201010176849 CN201010176849 CN 201010176849 CN 201010176849 A CN201010176849 A CN 201010176849A CN 101805320 A CN101805320 A CN 101805320A
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methyl
general formula
compound
amides
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CN101805320B (en
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孔繁蕾
吴桂秀
马英高
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JIANGSU AGRICULTURAL HORMONE ENGINEERING TECHNOLOGY RESEARCH CENTRE Co Ltd
JIANGSU INSTITUTE OF ECOMONES CO LTD
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JIANGSU AGRICULTURAL HORMONE ENGINEERING TECHNOLOGY RESEARCH CENTRE Co Ltd
JIANGSU INSTITUTE OF ECOMONES CO LTD
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Abstract

The invention discloses amide compounds and a preparation method and applications thereof. The preparation method comprises the following steps: using 2-methyl-6-ethylaniline to react with the compounds in the general formula II and using the product to react with the compounds in the general formula III to obtain amide compounds; or using 2-methyl-6-ethylaniline to react with compounds in the general formula III and using the product to react with the compounds in the general formula II to obtain amide compounds. Amide compounds are used as bactericides for preventing and curing plant diseases. Amide compounds can be combined with other bactericides to form a sterilizing mixture for preventing and curing plant diseases, and the content of amide compounds is 0.1wt%-99.9wt%.

Description

Amides and its production and use
Technical field
The present invention relates to a kind of organic compound and its production and use, particularly relate to a kind of amides and its production and use.
Background technology
Sterilant commonly used at present all is with 2 mostly, 6-xylidine (being called for short DMA) preparation, and 2-methyl-6-ethylaniline (being called for short MEA) mainly is to be used to prepare weedicide.The price of DMA is 3.5～4 times of MEA price normally.
Summary of the invention
The objective of the invention is to overcome the problems referred to above, the purposes that is used for germ-resistant amides and preparation method thereof and this amides that a kind of activity is high, cost is low is provided.
The technical scheme that realizes one of the object of the invention is as follows: a kind of amides, shown in general formula I:
Figure GDA0000021521200000011
R 1Be low-carbon alkyl, low-carbon (LC) thiazolinyl, low-carbon naphthenic;
R 2For-CH 2OCH 3Perhaps Perhaps
Figure GDA0000021521200000013
Described R 1Be methyl or ethyl.
Described R 1Be methyl and R 2For-CH 2OCH 3Perhaps R 1Be methyl and R 2For
Figure GDA0000021521200000021
Perhaps R 1Be methyl and R 2For
Among the formula I, *C is a chiral carbon atom, comprises R body α R, I ' R and RS body α R, I ' S.
Two the technical scheme that realizes the object of the invention is as follows:
The preparation method of above-mentioned amides: by 2-methyl-6-ethylaniline react with the compound of general formula I I earlier, the resultant of institute reacts with the compound of general formula III again and make, perhaps by 2-methyl-6-ethylaniline react with the compound of general formula III earlier, resultant react with the compound of general formula I I again and make;
Figure GDA0000021521200000023
Among the formula II, R 1Be low-carbon alkyl, low-carbon (LC) thiazolinyl, low-carbon naphthenic; X is halogen or aliphatic sulphonic acid ester or aromatic sulfonic acid ester;
In the formula III, R 2For-CH 2OCH 3Perhaps
Figure GDA0000021521200000024
Perhaps
Figure GDA0000021521200000025
Among the formula II, R 1Be methyl or ethyl; X is Cl, Br, CH 3SO 3-,
Figure GDA0000021521200000026
Perhaps
Figure GDA0000021521200000027
In the aforesaid method, carry out the N-alkylated reaction with the compound of general formula I I under 90 ℃～140 ℃ temperature earlier by excessive 2-methyl-6-ethylaniline, the gained alkylide carries out acylation reaction with the compound of general formula III again and makes under 35 ℃～40 ℃ temperature;
Reaction formula is as follows:
Figure GDA0000021521200000031
In the aforesaid method, carry out acylation reaction with the compound of general formula III under 35 ℃～40 ℃ temperature earlier by excessive 2-methyl-6-ethylaniline, the gained acylate carries out the N-alkylated reaction with the compound of general formula I I again and makes under 90 ℃～140 ℃ temperature;
Reaction formula is as follows:
Figure GDA0000021521200000032
Three the technical scheme that realizes the object of the invention is as follows:
The above-mentioned amides of stating is used for controlling plant diseases as sterilant.
Above-mentioned amides and other sterilant are formed Fungicidai mixtures and are used for controlling plant diseases, and the weight percent of amides is 0.1%～99.9%.
The compound of general formula I in its chemical structure, contains a chiral carbon atom in its molecule *There is the chiral axis between a phenyl ring and the nitrogen-atoms simultaneously in C, and therefore α R is arranged, I ' S (the RS racemic modification is called for short the RS body), α R, I ' R (the R enantiomorph is called for short the R body), α S, I ' S (S body) and α S, four optically active isomers of I ' R (SR body).α R wherein, I ' S (RS body) and α R, I ' R (R body) is the fungicidal activity body, and α S, I ' S and α S, I ' R are non-active body.
The positively effect that the present invention has is: the present invention replaces the synthetic compound that has microbe killing properties of DMA with MEA cheap and easy to get.Guaranteeing to greatly reduce production cost and application cost under the situation of drug effect, also helping and overcome resistance, more meeting the demand in current market.
Embodiment
(embodiment 1)
N-(2 methyl-6-ethylbenzene amido)-N-(methoxy ethyl) alanine methyl ester of preparation R body, i.e. Compound I-1, its structural formula is as follows:
Figure GDA0000021521200000041
The 2-methyl 6-ethylaniline and the methyl sulphonyl L-methyl lactate of 90g, the anhydrous sodium carbonate of 25g and the toluene of 200ml that in the four-hole bottle of 500ml, add 202g.Thereby under agitation be warming up to 110 ℃ of reactions that N-(2 methyl-6-ethylbenzene amido) methyl propionate takes place to generate at leisure, stir insulation reaction 4h.Sampling analysis after methyl sulphonyl L-methyl lactate primitive reaction is complete, is cooled to 100 ℃, layering while hot, thus oil reservoir is distilled recovery toluene.And then oil reservoir carried out rectification under vacuum, and reclaim unreacted 2-methyl 6-ethylaniline and transition fraction earlier, regather 97-98 ℃/0.2mmHg fraction, obtain N-(2 methyl-6-ethylbenzene amido) methyl propionate of the R body of 100g.Chlorine analysis of hplc result: content 〉=98%, R/S=96: 4, specific rotation
Figure GDA0000021521200000042
Yield 90.5%.
Getting the above-mentioned N-that makes of 45g (2 methyl-6-ethylbenzene amido) methyl propionate and 25g anhydrous sodium carbonate and 100ml toluene is added to and is warmed up to 35 ℃～40 ℃ in the reaction flask, under agitation thereby the methoxyacetyl chloride with 23g little by little is added drop-wise to the reaction that Compound I-1 takes place to generate in the reaction flask, and stirring insulation 1h down dropwises.Continue to stir insulation reaction 4h.Add the water of 100ml after reaction finishes, the salt in the stirring and dissolving reactant is separated behind the restir 20min, tell lower layer of water, upper solution adds anhydrous sodium sulfate drying, removes toluene solvant, gets the Compound I-1 of the R body of 55.4g, content is 96%, yield 94.5%.Specific rotation
Figure GDA0000021521200000051
Optical purity R/S=95.9/4.1.
This compound 1The data of H NMR spectrum are as follows:
1H?NMR(300MHz，CDCl 3)δ7.32-7.07(m，3H)，4.49(dq，J＝14.7，7.4Hz，1H)，3.79(s，3H)，3.70-3.37(m，2H)，3.31(s，3H)，3.09-2.71(m，2H)，2.46(s，2H)，2.14(s，2H)，1.24(dt，J＝9.5，7.6Hz，3H)，0.99(dd，J＝7.4，4.4Hz，3H)。
(embodiment 2)
Present embodiment is substantially the same manner as Example 1, and difference is: replace methyl sulphonyl L-methyl lactate with Phenylsulfonic acid L-lactic acid fat, replace methoxyacetyl chloride with phenyllacetyl chloride, reinforced molar weight is constant.Make N-(2-methyl-6-ethylbenzene amido)-N-(phenylacetyl) the methyl propionate white crystalline solid of the R body of 63.6g, i.e. Compound I-2, content is 97%, yield 93.8%.m.p：73～75℃，R/S＝96.5∶3.5。Its structural formula is as follows:
(embodiment 3)
Present embodiment is substantially the same manner as Example 1, and difference is: replace methyl sulphonyl L-methyl lactate with toluene sulfonic acide L-methyl lactate, replace methoxyacetyl chloride with furoyl chloride, reinforced molar weight is constant.Make N-(2-methyl-6-ethylbenzene amido)-N-(furancarbonyl) the R-methyl propionate white crystalline solid of the R body of 58.5g, i.e. Compound I-3, content is 96%, yield 92.9%.m.p：80.5-81℃，R/S＝95∶5。
Its structural formula is as follows:
(embodiment 4)
Be used for N-(2 methyl-6-ethylbenzene amido)-N-(methoxy ethyl) alanine methyl ester that embodiment 1 similar method can make the RS body, i.e. Compound I-4, this compound 1The data of H NMR spectrum are as follows:
1H?NMR(300MHz，CDCl 3)δ7.32-7.04(m，3H)，4.49(dq，J＝14.7，7.4Hz，1H)，3.78(s，3H)，3.66-3.39(m，2H)，3.31(s，2H)，3.05-2.75(m，2H)，2.46(s，2H)，2.13(s，2H)，1.24(dt，J＝9.6，7.6Hz，3H)，0.98(dd，J＝7.4，4.4Hz，3H)。
(application examples) tested the cucumber downy mildew fungicidal activity
1, materials and methods
1.1 test sample and preparation
The compound dissolution that each embodiment is made adds the water (weight percent that is compound is 99.9%) that contains the 0.1wt% tween 80 then in small amount of acetone, be diluted to the series concentration soup for examination.
Take identical method preparation with the former medicine of metaxanin (content is 95%).
1.2 test target and crop
The disease title Latin name The mensuration mode
Cucumber downy mildew ??pseudoperonospora?cubenis Live body is potted plant
Host plant is a cucumber, and kind is a Chang Chun Mi Ci.
1.3 test method
1.3.1 handle
Get the potted plant cucumber seedling of the complete unfolded of rough leaf, adopt the manual sprayer processing of spraying, spray pressure is 1.0kg/cm 2, spouting liquid is about 1000L/ha, and it is moistening fully to be sprayed to the blade two sides, and every processing repeats for 2 times, and it is air-dry in the ventilating and cooling place that the back is handled in spraying, inoculates pathogenic bacteria behind the 24h.
1.3.2 inoculation
Adopt inoculator with 5 * 10 5The cucumber downy mildew sporangia suspension of individual/M L sparges the cucumber slice back side, fully wetting to blade, changing over to immediately after the inoculation preserves moisture in 24 ℃, the transfer room of relative humidity＞90% cultivates 36h, move to the room temperature normal management then, treat behind the 5d that blank fully falls ill, adopt the fungicidal activity of appearance method investigation compound.
2, result and analysis
The result shows that Compound I-1, I-2, I-3 and I-4 all have fungicidal activity preferably to cucumber downy mildew, all can reach 100% under 1000mg/L, all obviously is better than metaxanin.Concrete outcome sees Table 1.
Each compound of table 1 is as the sterilization effect of sterilant to cucumber downy mildew

Claims (10)

1. amides, shown in general formula I:
Figure FDA0000021521190000011
R 1Be low-carbon alkyl, low-carbon (LC) thiazolinyl, low-carbon naphthenic;
R 2For-CH 2OCH 3The person
Figure FDA0000021521190000012
Perhaps
Figure FDA0000021521190000013
2. amides according to claim 1 is characterized in that: R 1Be methyl or ethyl.
3. amides according to claim 1 is characterized in that: R 1Be methyl and R 2For-CH 2OCH 3Perhaps R 1Be methyl and R 2For
Figure FDA0000021521190000014
Perhaps R 1Be methyl and R 2For
Figure FDA0000021521190000015
4. according to the described amides of one of claim 1 to 4, it is characterized in that: among the formula I, *C is a chiral carbon atom, comprises R body α R, I ' R and RS body α R, I ' S.
5. the preparation method of the described amides of claim 1, it is characterized in that: by 2-methyl-6-ethylaniline react with the compound of general formula I I earlier, the resultant of institute reacts with the compound of general formula III again and make, perhaps by 2-methyl-6-ethylaniline react with the compound of general formula III earlier, resultant react with the compound of general formula I I again and make;
Among the formula II, R 1Be low-carbon alkyl, low-carbon (LC) thiazolinyl, low-carbon naphthenic; X is halogen or aliphatic sulphonic acid ester or aromatic sulfonic acid ester;
In the formula III, R 2For-CH 2OCH 3Perhaps
Figure FDA0000021521190000022
Perhaps
Figure FDA0000021521190000023
6. the preparation method of amides according to claim 5 is characterized in that: among the formula II, and R 1Be methyl or ethyl; X is Cl, Br, CH 3SO 3-,
Figure FDA0000021521190000024
Perhaps
7. according to the preparation method of claim 5 or 6 described amidess, it is characterized in that: carry out the N-alkylated reaction with the compound of general formula I I under 90 ℃～140 ℃ temperature earlier by excessive 2-methyl-6-ethylaniline, the gained alkylide carries out acylation reaction with the compound of general formula III again and makes under 35 ℃～40 ℃ temperature;
Reaction formula is as follows:
8. according to the preparation method of claim 5 or 6 described amidess, it is characterized in that: carry out acylation reaction with the compound of general formula III under 35 ℃～40 ℃ temperature earlier by excessive 2-methyl-6-ethylaniline, the gained acylate carries out the N-alkylated reaction with the compound of general formula I I again and makes under 90 ℃～140 ℃ temperature;
Reaction formula is as follows:
Figure FDA0000021521190000031
9. the described amides of claim 1 is used for controlling plant diseases as sterilant.
10. purposes according to claim 9 is characterized in that: amides and other sterilant are formed Fungicidai mixtures and are used for controlling plant diseases, and the weight percent of amides is 0.1%～99.9%.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022055267A1 (en) * 2020-09-09 2022-03-17 주식회사 엘지화학 Method for preparing alkyl-d-alaninate
WO2023277590A1 (en) * 2021-06-29 2023-01-05 주식회사 엘지화학 Method for preparing alkyl-d-alaninate, alkyl-d-alaninate, alkyl-d-alaninate derivative, and pharmaceutical or agricultural product including same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH606029A5 (en) * 1974-04-02 1978-10-13 Ciba Geigy Ag N-Furoyl-N-aryl-alanine esters
US4206228A (en) * 1974-04-09 1980-06-03 Ciba-Geigy Corporation Microbicidal aniline derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH606029A5 (en) * 1974-04-02 1978-10-13 Ciba Geigy Ag N-Furoyl-N-aryl-alanine esters
US4206228A (en) * 1974-04-09 1980-06-03 Ciba-Geigy Corporation Microbicidal aniline derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022055267A1 (en) * 2020-09-09 2022-03-17 주식회사 엘지화학 Method for preparing alkyl-d-alaninate
WO2023277590A1 (en) * 2021-06-29 2023-01-05 주식회사 엘지화학 Method for preparing alkyl-d-alaninate, alkyl-d-alaninate, alkyl-d-alaninate derivative, and pharmaceutical or agricultural product including same

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