CN107488148A - A kind of hydrocinnamamide insecticides and preparation method thereof - Google Patents
A kind of hydrocinnamamide insecticides and preparation method thereof Download PDFInfo
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- CN107488148A CN107488148A CN201710495522.7A CN201710495522A CN107488148A CN 107488148 A CN107488148 A CN 107488148A CN 201710495522 A CN201710495522 A CN 201710495522A CN 107488148 A CN107488148 A CN 107488148A
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- hydrocinnamamide
- insecticides
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- 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
Abstract
The present invention relates to organic synthesis and applications technical field, more particularly to a kind of hydrocinnamamide insecticides and preparation method thereof, the hydrocinnamamide insecticides are with phenylalanine and substituted phenylacetic acid etc. for raw material, reacted by addition, cyclization, reduction and amidatioon etc., obtained hydrocinnamamide insecticides general structure is as follows：Synthesis condition of the present invention is gentle, easy to operate and safe, and each step reaction yield is high, and post processing mode is simple；The phenalgin Propionamides insecticide of the present invention effectively prevents and treats the pest and disease damage of aquaculture, and while improving the quality and survival rate of breed variety such as fish, culturing pool ecological environment will not be damaged, safe.
Description
Technical field
The present invention relates to organic synthesis and applications technical field, and in particular to a kind of hydrocinnamamide insecticides and its preparation
Method.
Background technology
Along with developing rapidly for China's culture fishery, the species and frequency of disease development of aquatic products disease also increase sharply, and support
Growing family needs by the disease occurred in medical treatment aquaculture process, and the water disinfectant and fish body desinsection widely applied
Agent strong toxicity, drug effect are fast, while also can produce toxic side effect to non-target organism such as fish, endanger fish body health.Chinese patent
CN 103254170B disclose a kind of insecticide containing pyrazole ring, to apple tree apple leaf miner (lepidopterous insects) and rice rice
Water weevil (coleopteron) has prevention effect, although the invention is not limited thereto, due to lacking and aquaculture phase
The clinical and experimental study of pass, the safe influence to aquiculture animal, breeding environment and ecology hangs in doubt, while the hair
Contain trifluoromethyl group in bright insecticide, be easily absorbed by plants, influence the growth of water plant.Chinese patent CN
104542401B discloses a kind of ecological cultivation method of grass carp, and it is peppery that Chinese tallow tree, masson pine, margosa, drought are launched into culturing pool
With the fresh and tender branches and leaves of knotweed, and coordinate Chinese medicine health-care pharmaceutical chemistry carry out the prevention and control of plant diseases, pest control, have chosen plurality of Chinese kind, not only increase and match somebody with somebody
Process processed it is cumbersome, and add cost.So those skilled in the art is still used for aquaculture disease pest in effort research
The noval chemical compound of evil preventing and treating, while to reach more preferable insecticidal effect, improve the peace to non-target organism and cultivation pool environment
Quan Xing.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of hydrocinnamamide insecticides and preparation method thereof, select
The raw material that is easy to get prepares noval chemical compound, and safe operation process is easy, and the compound of preparation effectively prevents aquatic products pest and disease damage, flat to ecology
Weighing apparatus does not influence, and is adapted to industrialized production.
To realize object above, the present invention is achieved by the following technical programs：
A kind of hydrocinnamamide insecticides, it is characterised in that its structure is represented by formula (I)：
R in formula (I)1Selected from hydrogen, methyl or chlorine, R2Selected from hydrogen, methyl, methoxyl group, nitro, hydroxyl, fluorine or chlorine.
Further, R1It is methyl, R2It is nitro.
Further, preparation method comprises the following steps：
(1) addition reaction：4- nitro-acetophenones and DMF dimethylacetal are dissolved in toluene, 90-95 DEG C
12h is reacted, mixed solvent is added after being concentrated under reduced pressure, 0-5 DEG C of standing 2-2.5h, is filtered, dry cake produces a；
(2) annulation：A ethanol solution is slowly added into the ethanol solution of hydrazine hydrate at room temperature, is heated up after 30min
To 80-90 DEG C of reaction 4-6h, a large amount of water are added after being concentrated under reduced pressure, are filtered, washing filter cake is drying to obtain b to neutrality；
(3) reduction reaction：B is dissolved in the reaction dissolvent of dichloromethane and methanol composition, hydrogen is passed through after adding 10%Pd/C
Gas, 8-12h is reacted at room temperature, filtering, filter cake is recrystallized using ethyl acetate and petroleum ether, is drying to obtain c；
(4) amidation process：Phenylalanine is dissolved in dichloromethane, 0-5 DEG C is slowly added to chloride reagent, after 1-1.5h
The dichloromethane solution containing c and organic base is slowly added to, room temperature reaction 12-15h is transferred to after 0.5h, 0-5 DEG C stands 0.5h, mistake
Filter, dry cake produce d, substituted phenylacetic acid are dissolved in into dichloromethane, 0-5 DEG C is slowly added to chloride reagent, slowly adds after 1h
Enter the dichloromethane solution containing d and organic base, be transferred to room temperature reaction 8-10h, stand 0.5h, filtering, dry cake produces e.
Further, it by dichloromethane and petroleum ether according to volume ratio is 1 that the mixed solvent, which is,:20 are mixed to prepare.
Further, the chloride reagent is selected from oxalyl chloride, thionyl chloride, POCl3, phosphorus pentachloride or triphosgene,
Preferably oxalyl chloride.
Further, the organic base is selected from N, N- diisopropyl ethyl amines, tetramethylethylenediamine, pyridine, N, N- diformazans
Base aniline or N, N- diethylaniline, preferably N, N- diisopropyl ethyl amines.
Due to using above-mentioned technical scheme, of the invention is beneficial as follows：
The hydrocinnamamide insecticides of the present invention are raw material from compounds that is easy to get such as phenylalanine and substituted phenylacetic acids, and are closed
It is easy to operate and safe into mild condition；Suitable reaction dissolvent is chosen according to the raw material dissolubility different with product, located after simplifying
Reason mode, the intermediate product and target product of high-purity are obtained, avoid being confined to the mode of operation in laboratory using column chromatography etc.,
It is easy to industrial operation, and its structure is novel, has no report.
The hydrocinnamamide insecticides of the present invention effectively prevent and treat the pest and disease damage of aquaculture, improve the breed varieties such as fish
Quality and survival rate, while culturing pool ecological environment is safe from harm, it is safe.
Brief description of the drawings
Fig. 1 is the reacting flow chart of the present invention.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
Embodiment 1：
N- (4- (1H- pyrazoles -5- bases) phenyl) -2- (2- (3- methyl -4- nitrobenzophenones) acetamido) -3- hydrocinnamamides
(1) addition reaction：By 4- nitro-acetophenones 16.50g (0.10mol) and N,N-dimethylformamide dimethylacetal
17.86g (0.15mol) is dissolved in 10ml toluene, 90-95 DEG C of reaction 12h, mixed solvent, 0 DEG C of standing is added after being concentrated under reduced pressure
2.5h, filtering, dry cake produce 3- (N, TMSDMA N dimethylamine base) -1- (4- nitrobenzophenones) -2- propylene -1- ketone (a) 21.30g, obtained
Rate is 96.8%；
(2) annulation：Slowly add into 80% hydrazine hydrate 7.5ml (0.15mol) ethanol solution 30ml at room temperature
Enter 3- (N, TMSDMA N dimethylamine base) -1- (4- nitrobenzophenones) -2- propylene -1- ketone (a) 11.00g (0.05mol) ethanol solution
90 DEG C of reaction 5h are warming up to after 30ml, 30min, a large amount of water are added after being concentrated under reduced pressure, are filtered, washing filter cake to neutrality, drying is
Obtain 5- (4- nitrobenzophenones) -1H- pyrazoles (b) 8.69g, yield 92.0%；
(3) reduction reaction：5- (4- nitrobenzophenones) -1H- pyrazoles (b) 7.56g (0.04mol) are dissolved in 20ml dichloromethane
With the reaction dissolvent of 20ml methanol composition, hydrogen is passed through after adding 10%Pd/C, 8h is reacted at room temperature, filtering, uses ethyl acetate
Filter cake is recrystallized with petroleum ether, is drying to obtain 5- (4- aminophenyls) -1H- pyrazoles (c) 5.86g, yield 92.1%；
(4) amidation process：Phenylalanine 4.95g (0.03mol) is dissolved in 30ml dichloromethane, 0 DEG C is slowly added to grass
Acyl chlorides, it is slowly added to contain 5- (4- aminophenyls) -1H- pyrazoles (c) 4.29g (0.027mol) and N, N- diisopropyl ethyl after 1
Amine 0.5ml dichloromethane solution, is transferred to room temperature reaction 12h after 0.5h, 0 DEG C of standing 0.5h, filtering, and dry cake produces N-
(4- (1H- pyrazoles -5- bases) phenyl) -2- amino -3- hydrocinnamamides (d), by 3- methyl -4- nitrophenyl-acetic acids 5.85g
(0.03mol) is dissolved in 30ml dichloromethane, and 0 DEG C is slowly added to oxalyl chloride, and (the 4- (1H- pyrazoles -5- bases) containing N- is slowly added to after 1h
Phenyl) -2- amino -3- hydrocinnamamides (d) and N, N- diisopropyl ethyl amine 0.5ml dichloromethane solution 30ml, be transferred to
8h is reacted at room temperature, stands 0.5h, filtering, dry cake produces N- (4- (1H- pyrazoles -5- bases) phenyl) -2- (2- (3- methyl -4-
Nitrobenzophenone) acetamido) -3- hydrocinnamamides (e) 10.44g, yield 80.1%；1H NMR (300MHz, DMSO-d6)δ：
9.70 (s, 1H)；8.32 (s, 1H)；7.96 (s, 1H)；7.87 (m, 2H)；7.80 (m, 2H)；7.58 (m, 2H)；7.52 (m, 2H)；
7.19 (m, 1H)；7.14 (m, 4H)；6.53 (m, 1H)；5.08 (s, 1H)；3.54 (m, 2H)；3.37 (s, 2H)；3.29 (m, 1H)；
2.56 (s, 3H)；ESI-MS m/z (%)：483.1([M+1]+)。
Embodiment 2：
N- (4- (1H- pyrazoles -5- bases) phenyl) -2- (2- (3- methyl -4- chlorphenyls) acetamido) -3- hydrocinnamamides
Operating procedure replaces 3- methyl -4- nitrobenzene in step (4) with embodiment 1 using 3- methyl -4- chlorobenzene acetic acids
Acetic acid, obtain target product；1H NMR (300MHz, DMSO-d6)δ：9.70 (s, 1H)；8.32 (s, 1H)；7.96 (s, 1H)；7.87
(m, 2H)；7.80 (m, 2H)；7.58 (m, 2H)；7.52 (m, 2H)；7.19 (m, 1H)；7.14 (m, 4H)；6.53 (m, 1H)；5.08
(s, 1H)；3.54 (m, 2H)；3.37 (s, 2H)；3.29 (m, 1H)；2.25 (s, 3H)；ESI-MS m/z (%)：472.1([M+1
]+)。
Embodiment 3：
N- (4- (1H- pyrazoles -5- bases) phenyl) -2- (2- (4- fluorophenyls) acetamido) -3- hydrocinnamamides
Operating procedure replaces 3- methyl -4- nitrophenyl-acetic acids using 4- fluorophenylacetic acids in step (4), obtained with embodiment 1
Target product；1HNMR (300MHz, DMSO-d6) δ：9.70 (s, 1H)；8.32 (s, 1H)；7.96 (s, 1H)；7.87 (m, 2H)；
7.80 (m, 2H)；7.58 (m, 2H)；7.52 (m, 2H)；7.19 (m, 1H)；7.14 (m, 4H)；6.53 (m, 1H)；5.08 (s, 1H)；
3.54 (m, 2H)；3.37 (s, 2H)；3.29 (m, 1H)；ESI-MS m/z (%)：442.7([M+1]+)。
Embodiment 4：
N- (4- (1H- pyrazoles -5- bases) phenyl) -2- (2- (3- methyl -4- aminomethyl phenyls) acetamido) -3- hydrocinnamamides
Operating procedure replaces 3- methyl -4- nitros in step (4) with embodiment 1 using 3- methyl -4- methylphenyl acetic acids
Phenylacetic acid, obtain target product；1H NMR (300MHz, DMSO-d6)δ：9.70 (s, 1H)；8.32 (s, 1H)；7.96 (s, 1H)；
7.87 (m, 2H)；7.80 (m, 2H)；7.58 (m, 2H)；7.52 (m, 2H)；7.19 (m, 1H)；7.14 (m, 4H)；6.53 (m, 1H)；
5.08 (s, 1H)；3.54 (m, 2H)；3.37 (s, 2H)；3.29 (m, 1H)；2.28 (s, 3H)；2.23 (s, 3H)；ESI-MS m/z
(%)：452.2([M+1]+)。
Embodiment 5：
N- (4- (1H- pyrazoles -5- bases) phenyl) -2- (2- (3- methyl -4- hydroxy phenyls) acetamido) -3- hydrocinnamamides
Operating procedure replaces 3- methyl -4- nitros in step (4) with embodiment 1 using 3- methyl -4- hydroxyl phenylacetic acids
Phenylacetic acid, obtain target product；1H NMR (300MHz, DMSO-d6)δ：9.70 (s, 1H)；9.68 (s, 1H)；8.32 (s, 1H)；
7.96 (s, 1H)；7.87 (m, 2H)；7.80 (m, 2H)；7.58 (m, 2H)；7.52 (m, 2H)；7.19 (m, 1H)；7.14 (m, 4H)；
6.53 (m, 1H)；5.08 (s, 1H)；3.54 (m, 2H)；3.37 (s, 2H)；3.29 (m, 1H)；2.15 (s, 3H)；ESI-MS m/z
(%)：454.2([M+1]+)。
Three pieces of adjacent culturing pools, respectively blank group, control group and experimental group are chosen, blank group is without using any aquatic products
Insecticide, control group use metrifonate, and insecticidal n-(4- (1H- pyrazoles -5- bases) phenyl) that experimental group is prepared using the present invention -
2- (2- (3- methyl -4- nitrobenzophenones) acetamido) -3- hydrocinnamamides, crucian and both often feeding fish of grass carp are chosen to examine
Examine object, the insecticide impressions of control group and experimental group culturing pool, launch dosage and release time all same, three months
Afterwards, the growing state of three groups of fish is as shown in table 1：
The blank group of table 1, control group and the growing state of experimental group fish
As it can be seen from table 1 the fish survival rate of blank group is less than control group and experimental group, the fish survival rate of experimental group
A little higher than control group, the fish Average weight increasing a day of experimental group are above control group, and insecticide produced by the present invention not only effectively kills
Cause of disease, the fish incidence of disease is low, and does not influence the growth of fish, and fish Average weight increasing a day is suitable with blank group.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply and deposited between these entities or operation
In any this actual relation or order.Moreover, term " comprising ", "comprising" or its any other variant are intended to
Nonexcludability includes, so that process, method, article or equipment including a series of elements not only will including those
Element, but also the other element including being not expressly set out, or it is this process, method, article or equipment also to include
Intrinsic key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that
Other identical element also be present in process, method, article or equipment including the key element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (6)
1. a kind of hydrocinnamamide insecticides, it is characterised in that its structure is represented by formula (I)：
R in formula (I)1Selected from hydrogen, methyl or chlorine, R2Selected from hydrogen, methyl, methoxyl group, nitro, hydroxyl, fluorine or chlorine.
2. hydrocinnamamide insecticides as claimed in claim 1, it is characterised in that R1It is methyl, R2It is nitro.
3. hydrocinnamamide insecticides as claimed in claim 1, it is characterised in that preparation method comprises the following steps：
(1) addition reaction：4- nitro-acetophenones and DMF dimethylacetal are dissolved in toluene, 90-95 DEG C of reaction
12h, mixed solvent is added after being concentrated under reduced pressure, 0-5 DEG C of standing 2-2.5h, is filtered, dry cake produces a；
(2) annulation：A ethanol solution is slowly added into the ethanol solution of hydrazine hydrate at room temperature, is warming up to after 30min
80-90 DEG C of reaction 4-6h, adds a large amount of water, filters after being concentrated under reduced pressure, washing filter cake is drying to obtain b to neutrality；
(3) reduction reaction：B is dissolved in the reaction dissolvent of dichloromethane and methanol composition, hydrogen, room are passed through after adding 10%Pd/C
Temperature reaction 8-12h, filtering, is recrystallized to filter cake using ethyl acetate and petroleum ether, is drying to obtain c；
(4) amidation process：Phenylalanine is dissolved in dichloromethane, 0-5 DEG C is slowly added to chloride reagent, after 1-1.5h slowly
The dichloromethane solution containing c and organic base is added, room temperature reaction 12-15h is transferred to after 0.5h, 0-5 DEG C of standing 0.5h, is filtered,
Dry cake produces d, substituted phenylacetic acid is dissolved in into dichloromethane, 0-5 DEG C is slowly added to chloride reagent, is slowly added to contain after 1h
D and organic base dichloromethane solution, room temperature reaction 8-10h is transferred to, stands 0.5h, filtering, dry cake produces e.
4. hydrocinnamamide insecticides as claimed in claim 3, it is characterised in that the mixed solvent be by dichloromethane and
Petroleum ether is 1 according to volume ratio:20 are mixed to prepare.
5. hydrocinnamamide insecticides as claimed in claim 3, it is characterised in that the chloride reagent be selected from oxalyl chloride,
Thionyl chloride, POCl3, phosphorus pentachloride or triphosgene, preferably oxalyl chloride.
6. hydrocinnamamide insecticides as claimed in claim 3, it is characterised in that the organic base is selected from N, N- diisopropyls
Ethylamine, tetramethylethylenediamine, pyridine, DMA or N, N- diethylaniline, preferably N, N- diisopropyl second
Base amine.
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Cited By (3)
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| WO2020127685A1 (en) * | 2018-12-19 | 2020-06-25 | Leo Pharma A/S | Amino-acid anilides as small molecule modulators of il-17 |
| WO2021250194A1 (en) * | 2020-06-12 | 2021-12-16 | Leo Pharma A/S | Small molecule modulators of il-17 |
| RU2815505C2 (en) * | 2018-12-19 | 2024-03-18 | Лео Фарма А/С | Anilides of amino acids as low-molecular modulators il-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020127685A1 (en) * | 2018-12-19 | 2020-06-25 | Leo Pharma A/S | Amino-acid anilides as small molecule modulators of il-17 |
| US11377425B1 (en) | 2018-12-19 | 2022-07-05 | Leo Pharma A/S | Small molecule modulators of IL-17 |
| RU2815505C2 (en) * | 2018-12-19 | 2024-03-18 | Лео Фарма А/С | Anilides of amino acids as low-molecular modulators il-17 |
| WO2021250194A1 (en) * | 2020-06-12 | 2021-12-16 | Leo Pharma A/S | Small molecule modulators of il-17 |
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Application publication date: 20171219 |