CN103570585B - Paradiethylamino methylene amine propyl benzoate compound and preparation method thereof - Google Patents
Paradiethylamino methylene amine propyl benzoate compound and preparation method thereof Download PDFInfo
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- CN103570585B CN103570585B CN201310536422.6A CN201310536422A CN103570585B CN 103570585 B CN103570585 B CN 103570585B CN 201310536422 A CN201310536422 A CN 201310536422A CN 103570585 B CN103570585 B CN 103570585B
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Abstract
The invention discloses a paradiethylamino methylene amine propyl benzoate compound and a preparation method thereof. The structural formula of the paradiethylamino methylene amine propyl benzoate compound is described in the specification. The preparation method comprises the following steps: enabling para-formamido propyl benzoate to react with phosphorus oxychloride (POC13) in an organic solvent under an alkaline condition, so as to obtain a paraisonitrile propyl benzoate solution, wherein the reaction temperature is controlled at 50-90 DEG C and the reaction time is controlled at 0.25-4 hours; then adding diethylamine and Cu2O, and controlling the temperature at 70-130 DEG C to react for 2-24 hours to obtain reaction liquid; taking an oil layer after standing and layering the obtained reaction liquid; extracting the obtained water layer by ethyl acetate, taking an oil layer, and merging the oil layers obtained twice, and removing the ethyl acetate in a spin steaming manner; and carrying out column chromatography, and removing a solvent, so as to obtain the lignocaine methylene amine propyl benzoate compound with effects in the insecticidal and fungicidal aspects. The preparation method disclosed by the invention is simple in reaction process, and mild in reaction condition; the yield can be up to about 80%.
Description
Technical field
The present invention relates to a kind of to diethylin methylene propyl aminobenzoate compound and preparation method thereof.
Background technology
Amidine is the carboxylic acid analogue that nitrogen replaces, and amidine compound is that some have the fragment of the material of physiologically active, is important synthetic intermediate in organic synthesis.Amidine is very important compound, is widely used in microbiotic, diuretic(s), antiphlogistic drug, wormer and broad spectrum acaricides.Also may be used for the preparation of nitrogen heterocyclic, more and more receive now the concern of people.Chlordimeform, N-(4-chlorine o-tolyl)-N, N-dimethyl carbonamidine, a kind of high-efficiency broad spectrum organonitrogen agricultural insecticidal medicine and Acaricide, there are drug-fast insects all effective to organophosphorus, organochlorine and carbamate insecticides, belong to moderate toxicity, but the carinogenicity of its meta-bolites 4-chlorine o-toluidine is higher than parent compound 10 times.So find low toxicity highly effective pesticide, especially the agricultural chemicals of low toxicity meta-bolites is very important.
Summary of the invention
An object of the present invention is the toxicity in order to reduce formamidine compound metabolism product, there is provided a kind of new amidine compound namely to diethylin methylene propyl aminobenzoate, its meta-bolites is para-amino benzoic acid, para-amino benzoic acid can help to synthesize folic acid, plays an important role when human body utilizes protein.
Two of object of the present invention is to provide above-mentioned a kind of preparation method to diethylin methylene propyl aminobenzoate.
Technical scheme of the present invention
A kind of to diethylin methylene propyl aminobenzoate compound, its structural formula is as follows:
。
Above-mentioned a kind of preparation method to diethylin methylene propyl aminobenzoate compound, will to formamido group propyl benzoate and POCl
3in the basic conditions, control temperature is 50-90 DEG C, and time 0.25-4h carries out being obtained by reacting isonitrile yl benzoic acid propyl ester solution, then adds diethylamine and Cu
2o, control temperature is 70-130 DEG C and carries out reaction 2-24h, after the reaction solution stratification obtained, get oil reservoir, gained aqueous layer with ethyl acetate extracts, get oil reservoir, merge the oil reservoir of twice gained, anhydrous magnesium sulfate drying, revolve and steam removing ethyl acetate, then with sherwood oil and ethyl acetate mixtures for developping agent, calculate by volume, i.e. sherwood oil: ethyl acetate is carry out column chromatography under the condition of the ratio of 5:1, revolve and steam except desolventizing, the oily liquids obtained is namely to diethylin methylene propyl aminobenzoate compound, the equation of its synthetic reaction process is as follows:
。
Above-mentioned a kind of preparation method to diethylin methylene propyl aminobenzoate, specifically comprises the steps:
(1), in organic solvent, will to formamido group propyl benzoate and POCl
3in the basic conditions, control temperature of reaction is 50-90 DEG C, and the time, 0.25-4h reacted, and obtains isonitrile yl benzoic acid propyl ester solution;
Described organic solvent is benzene,toluene,xylene or chlorobenzene;
Described alkali is triethylamine or Diisopropylamine;
Reaction process used to formamido group propyl benzoate, POCl
3, alkali and organic solvent amount, by formamido group propyl benzoate: POCl
3: alkali: organic solvent is that the ratio of 1mol:1.1-2.0mol:3.0-10.0mol:4-5L calculates;
(2), in step (1) gained in isonitrile yl benzoic acid propyl ester solution, add diethylamine and Cu
2o, control temperature is 70-130 DEG C and carries out reaction 2-24h, after the reaction solution stratification obtained, get oil reservoir, gained aqueous layer with ethyl acetate extracts, get oil reservoir, merge the oil reservoir of twice gained, anhydrous magnesium sulfate drying, revolves and steams removing ethyl acetate, then with sherwood oil and ethyl acetate mixtures for developping agent, calculate by volume, i.e. sherwood oil: ethyl acetate is carry out column chromatography under the condition of the ratio of 5:1, revolve and steam except desolventizing, the oily liquids obtained is diethylin methylene propyl aminobenzoate;
Diethylamine, Cu that above-mentioned reaction is used
2the amount of O, presses isonitrile yl benzoic acid propyl ester: diethylamine: Cu
2the mol ratio of O calculates, namely to formamido group propyl benzoate: diethylamine: Cu
2o is 1:1.5-3.0:0.1-0.3.
Above-mentioned one, to diethylin methylene propyl aminobenzoate compound, due to diethylin methylene propyl aminobenzoate and chlordimeform similar, therefore may be used for a kind of potential desinsection and the agricultural chemicals killing mite.
Beneficial effect of the present invention
One of the present invention, to diethylin methylene propyl aminobenzoate compound, due to diethylin methylene propyl aminobenzoate and chlordimeform similar, therefore may be used for a kind of potential desinsection and the agricultural chemicals killing mite.Further compared with chlordimeform, because its meta-bolites is para-amino benzoic acid, para-amino benzoic acid can help to synthesize folic acid, and play an important role when human body utilizes protein, therefore its meta-bolites toxicity is little, harmless.
Further; a kind of preparation method to diethylin methylene propyl aminobenzoate compound of the present invention; because raw material used is easy to get; therefore have the feature that production cost is lower, this preparation method's step is few, simple to operate further; reaction conditions is gentle; by product is few, and yield reaches 71.2-81.4%, is convenient to large-scale production.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but do not limit the present invention.
embodiment 1
To a preparation method for diethylin methylene propyl aminobenzoate, specifically comprise the steps:
(1), in 25mL round-bottomed flask, add 0.5g (0.0024mol) 4-formamido group propyl benzoate, add 10mL organic solvent, then add 1.71g alkali, stir, instillation 0.41g POCl
3, control temperature is 90 DEG C, and time 0.25h reacts, and obtains isonitrile yl benzoic acid propyl ester solution;
Described organic solvent is toluene;
Described alkali is Diisopropylamine;
Reaction process used to formamido group propyl benzoate, POCl
3, alkali and organic solvent amount, by formamido group propyl benzoate: POCl
3: alkali: organic solvent is that the ratio of 1mol:1.1mol:7mol:4.17L calculates;
(2), in step (1) gained in isonitrile yl benzoic acid propyl ester solution, add 0.26g diethylamine and 0.035gCu
2o, control temperature is 100 DEG C and carries out reaction 14h, after the reaction solution stratification obtained, get oil reservoir, gained aqueous layer with ethyl acetate extracts, get oil reservoir, merge the oil reservoir of twice gained, anhydrous magnesium sulfate drying, revolve and steam removing ethyl acetate, then with sherwood oil and ethyl acetate mixtures for developping agent, calculate by volume, i.e. sherwood oil: ethyl acetate is carry out column chromatography under the condition of the ratio of 5:1, revolve and steam except desolventizing, the 0.49g oily liquids obtained is diethylin methylene propyl aminobenzoate, and productive rate is 77.8%;
Diethylamine, Cu that above-mentioned reaction is used
2the amount of O, presses isonitrile yl benzoic acid propyl ester: diethylamine: Cu
2the mol ratio of O calculates, namely to diethylin methylene propyl aminobenzoate: diethylamine: Cu
2o is 1:1.5:0.1.
Namely the oily liquids of above-mentioned gained detects through Bruker company 300 type nuclear magnetic resonance analyser diethylin methylene propyl aminobenzoate, and its nuclear magnetic resonance data is as follows:
1HNMR：δ 1.02（t，3H），1.23（t，6H），1.77（m，2H），3.,42（m，4H），4.24（t，2H），6.96（d，2H），7.58（s，1H），7.94（d，2H）。
Above-mentioned data results shows that the oily liquids product of gained is that structural formula is as follows:
To diethylin methylene propyl aminobenzoate compound.
embodiment 2
(1), in 25mL round-bottomed flask, add 0.5g4-formamido group propyl benzoate, add 10mL organic solvent, then add 0.74g alkali, stir, instillation 0.56g POCl
3, control temperature is 50 DEG C, and the time, 4h reacted, and obtains isonitrile yl benzoic acid propyl ester solution;
Described organic solvent is benzene;
Described alkali is triethylamine;
Reaction process used to formamido group propyl benzoate, POCl
3, alkali and organic solvent amount, by formamido group propyl benzoate: POCl
3: alkali: organic solvent is that the ratio of 1mol:1.5mol:3mol:4.17L calculates;
(2), in step (1) gained in isonitrile yl benzoic acid propyl ester solution, add 0.35g diethylamine and 0.08gCu
2o, control temperature is 70 DEG C and carries out reaction 24h, after the reaction solution stratification obtained, get oil reservoir, gained aqueous layer with ethyl acetate extracts, get oil reservoir, merge the oil reservoir of twice gained, anhydrous magnesium sulfate drying, revolve and steam removing ethyl acetate, then with sherwood oil and ethyl acetate mixtures for developping agent, calculate by volume, i.e. sherwood oil: ethyl acetate is carry out column chromatography under the condition of the ratio of 5:1, revolve and steam except desolventizing, the 1.79g oily liquids obtained is diethylin methylene propyl aminobenzoate, and productive rate is 71.2%;
Diethylamine, Cu that above-mentioned reaction is used
2the amount of O, presses isonitrile yl benzoic acid propyl ester: diethylamine: Cu
2the mol ratio of O calculates, namely to diethylin methylene propyl aminobenzoate: diethylamine: Cu
2o is 1:2:0.23.
embodiment 3
(1), in 25mL round-bottomed flask, add 0.5g4-formamido group propyl benzoate, add 10mL organic solvent, then add 2.4g alkali, stir, instillation 0.74g POCl
3, control temperature is 70 DEG C, and time 2h reacts, and obtains isonitrile yl benzoic acid propyl ester solution;
Described organic solvent is dimethylbenzene;
Described alkali is triethylamine;
Reaction process used to formamido group propyl benzoate, POCl
3, alkali and organic solvent amount, by formamido group propyl benzoate: POCl
3: alkali: organic solvent is that the ratio of 1mol:2mol:10mol:4.17L calculates;
(2), in step (1) gained in isonitrile yl benzoic acid propyl ester solution, add 0.53g diethylamine and 0.1gCu
2o, control temperature is 130 DEG C and carries out reaction 2h, after the reaction solution stratification obtained, get oil reservoir, gained aqueous layer with ethyl acetate extracts, get oil reservoir, merge the oil reservoir of twice gained, anhydrous magnesium sulfate drying, revolve and steam removing ethyl acetate, then with sherwood oil and ethyl acetate mixtures for developping agent, calculate by volume, i.e. sherwood oil: ethyl acetate is carry out column chromatography under the condition of the ratio of 5:1, revolve and steam except desolventizing, the 0.51g oily liquids obtained is diethylin methylene propyl aminobenzoate, and productive rate is 81.4%;
Diethylamine, Cu that above-mentioned reaction is used
2the amount of O, presses isonitrile yl benzoic acid propyl ester: diethylamine: Cu
2the mol ratio of O calculates, namely to diethylin methylene propyl aminobenzoate: diethylamine: Cu
2o is 1:3:0.3.
Above said content be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (1)
1., to a preparation method for diethylin methylene propyl aminobenzoate, the described structural formula to diethylin methylene propyl aminobenzoate compound is as follows:
, its preparation process of its feature specifically comprises the steps:
(1), in organic solvent, will to formamido group propyl benzoate and POCl
3in the basic conditions, control temperature of reaction is 0-90 DEG C, and the time, 0.25-4h reacted, and obtains isonitrile yl benzoic acid propyl ester solution;
Described organic solvent is benzene,toluene,xylene or chlorobenzene;
Described alkali is triethylamine or Diisopropylamine;
Reaction process used to formamido group propyl benzoate, POCl
3, alkali and organic solvent amount, by formamido group propyl benzoate: POCl
3: alkali: organic solvent is that the ratio of 1mol:1.1-2.0mol:3.0-10.0mol:4-5L calculates;
(2), in step (1) gained in isonitrile yl benzoic acid propyl ester solution, add diethylamine and Cu
2o, control temperature is 70-130 DEG C and carries out reaction 2-24h, after the reaction solution stratification obtained, get oil reservoir, gained aqueous layer with ethyl acetate extracts, get oil reservoir, merge the oil reservoir of twice gained, anhydrous magnesium sulfate drying, revolves and steams removing ethyl acetate, then with sherwood oil and ethyl acetate mixtures for developping agent, calculate by volume, i.e. sherwood oil: ethyl acetate is carry out column chromatography under the condition of the ratio of 5:1, revolve and steam except desolventizing, the oily liquids obtained is diethylin methylene propyl aminobenzoate;
Diethylamine, Cu that above-mentioned reaction is used
2the amount of O, presses isonitrile yl benzoic acid propyl ester: diethylamine: Cu
2the mol ratio of O calculates, namely to formamido group propyl benzoate: diethylamine: Cu
2o is 1:1.5-3.0:0.1-0.3.
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