CN101558758B - L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof - Google Patents
L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof Download PDFInfo
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- CN101558758B CN101558758B CN200910057324A CN200910057324A CN101558758B CN 101558758 B CN101558758 B CN 101558758B CN 200910057324 A CN200910057324 A CN 200910057324A CN 200910057324 A CN200910057324 A CN 200910057324A CN 101558758 B CN101558758 B CN 101558758B
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Abstract
The invention discloses an L-alpha-amino acid ester contained Z-configuration anabasine pesticide and a preparation method thereof. The structure is shown by a general formula (I). The prior anabasinepesticide only has a function of disinsection and has no function of promoting the growth of crops. The preparation method comprises the following steps: preparing a hydrochlorate of an L-alpha-aminoacid methyl ester or ethyl ester; adding the prepared hydrochlorate of the L-alpha-amino acid methyl ester or the ethyl ester, nitenpyram, 37 percent formaldehyde and triethylamine into a round-bottom three-necked flask; and placing the round-bottom three-necked flask containing the solution in a microwave reactor, controlling the reaction temperature not more than 75 DEG C, and carrying out microwave reaction for 30 minutes to prepare the L-alpha-amino acid ester contained Z-configuration anabasine pesticide shown by the general formula (I). The L-alpha-amino acid ester contained Z-configuration anabasine pesticide has the advantages of high efficient insecticidal activity, good insecticidal effect, low toxicity, safety of human beings and livestock, crop growth promotion, simple using method, simple preparation method, and short reaction time.
Description
Technical field
The invention belongs to agricultural chemical insecticide, specifically a kind of Z formula configuration anabasine sterilant and preparation that contains the L-α-An Jisuanzhi.
Background technology
Anabasine insecticide be after organic phosphates, amino formate, pyrethroid insecticides the 4th generation sterilant.The anabasine material is as nAChR (nAChRs) agonist; Neural system (nAChRs) to insect optionally works; It has not only shown high-affinity to (nAChRs), but also has shown unionized property and medium physics-chem characteristic such as water-soluble.Because it has the unique insecticidal mechanism and the performance of high-efficiency low-toxicity, become the higher effective and lower toxic pesticide new variety that modern agriculture needs rapidly.Because anabasine compound has the existence of C=N or the two keys of C=C, so anabasine compound has Z formula and two kinds of configurations of E formula.Japan Wu Tian company use chloro-pyridine compounds and E.C. 3.1.1.7 regulator have synthesized and have contained chloro pyridine nitroethylene base class compound Ti304, are good sterilants in the E formula configuration anabasine, and sucking property insect is had special efficacy; Du pont company has made the Ti304 compound that the Z of higher insecticidal activity formula configuration is arranged through introducing heterocycle.But these not the anabasine pesticide of isomorphism type only have insecticidal action, do not have the function that promotes crop growth.Amino acid is the neccessary composition that constitutes life; Aminoacid component in the agricultural chemicals also has the vital role that promotes crop growth except having insecticidal effect.But up to now, production and the use that the anabasine insecticide agricultural chemicals that contains the L-α-An Jisuanzhi is arranged all do not seen in countries in the world.Patent documentation both domestic and external and public publication are not seen the report of the anabasine insecticide that contains the L-α-An Jisuanzhi yet.
The present invention is that raw material has synthesized the serial Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi with the L-a-amino acid in the world first, and has measured the efficient insecticide activity of this sterilant, has realized the new breakthrough of domestic and international anabasine insecticide agricultural chemicals.
Summary of the invention
The present invention seeks to for a kind of Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi that had not only had the efficient insecticide activity but also can promote crop growth is provided;
Another object of the present invention provides the Z formula configuration anabasine method for producing insecticide of the above-mentioned L-of containing α-An Jisuanzhi.
The object of the invention is realized through following technical scheme.
Contain the Z formula configuration anabasine sterilant of L-α-An Jisuanzhi, general formula (I) is:
Wherein: R is hydrogen, methyl (CH
3), sec.-propyl (CH (CH
3)
2), benzyl (CH
2C
6H
5), isobutyl-(CH
2CH (CH
3)
2), methylthio ethyl (CH
2CH
2SCH
3), rubigan (p-Cl-C
6H
5) in a kind of.
R ' is methyl (CH
3), ethyl (C
2H
5), n-propyl (n-C
3H
7), normal-butyl (n-C
4H
9) in a kind of.
The Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi of general formula (I) expression, the preparation method is following:
The hydrochloride of preparation L-a-amino acid methyl esters or ethyl ester, general formula (II):
A. the L-a-amino acid is dissolved in 1mol/L thionyl chloride-methanol solution, controlled temperature prepares L-a-amino acid methyl ester hydrochloride below-5 ℃;
B. the L-a-amino acid is dissolved in ethanolic soln, controlled temperature below 0 ℃, dripping thionyl chloride, preparation L-a-amino acid carbethoxy hydrochloride;
(2) preparation contains the Z formula configuration anabasine sterilant of L-α-An Jisuanzhi, and general formula (I) as above.
A. the L-a-amino acid methyl esters of above-mentioned (1) preparation or hydrochloride (II), Ti304,37% formaldehyde, the triethylamine of ethyl ester are put in the three-necked round bottom flask;
The three-necked round bottom flask that b. above-mentioned solution will be housed is put into microwave reactor, and controlled temperature is below 75 ℃, and microwave reaction 30 minutes makes the Z formula configuration anabasine sterilant that general formula (I) contains the L-α-An Jisuanzhi.
The Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi with general formula (I) is a raw material, processes emulsion, aqueous suspension and water emulsion pesticide.
The reaction formula of above-mentioned preparation process is:
Main points of the present invention are:
With the L-a-amino acid is raw material; Both had the efficient insecticide activity with the best high-efficiency low-toxicity anabasine insecticide Ti304 of insecticidal effect in the world today is synthetic, had the Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi that promotes the crop growth function again.
The inventive method makes the hydrochloride (II) of L-α-An Jisuanzhi earlier, makes the Z formula configuration anabasine sterilant (I) that contains the L-α-An Jisuanzhi again.
When synthetic (II), the hydrochloride of different L-α-An Jisuanzhi can adopt diverse ways:
In the preparation of L-a-amino acid ethyl ester, the L-a-amino acid is dissolved in ethanol temperature control dripping thionyl chloride again.When preparation L-a-amino acid methyl ester hydrochloride, adopt 1mol/L thionyl chloride-methanol solution, this synthesising method reacting condition is gentle, and the reaction times is short, and easy to operate, product does not need further purification, and yield and purity are all higher.
Adopt novel microwave process for synthesizing to improve productive rate and also greatly shortened the reaction times.For example adopt heating reflux method to need 6 hours usually, the present invention adopts microwave process for synthesizing only to need 30 minutes.
The Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi with general formula (I) expression has good insecticidal activity, and the effective active composition of useful as pesticides is made the various pesticide formulation.Example emulsion, aqueous suspension and aqueous emulsion etc.
Advantage of the present invention is:
1, has efficient insecticide activity, good disinsection effect.
2, toxicity is low, the person poultry safety.
3, promote crop growth.
4, method of use is easy.
5, the preparation method is simple.
6, the reaction times is short.
The present invention is that raw material has synthesized the serial Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi with the L-a-amino acid in the world first, has tangible novelty and creativeness; The present invention has measured the efficient insecticide activity of this sterilant, has significant practicality in modern times in the agriculture prodn.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
A kind of Z formula configuration anabasine sterilant with the active L-of the containing α-An Jisuanzhi of efficient insecticide, represent with general formula (I):
Wherein: R is hydrogen, methyl (CH
3), sec.-propyl (CH (CH
3)
2), benzyl (CH
2C
6H
5), isobutyl-(CH
2CH (CH
3)
2), methylthio ethyl (CH
2CH
2SCH
3), rubigan (p-Cl-C
6H
5) in a kind of; R ' is methyl (CH
3) and ethyl (C
2H
5), n-propyl (n-C
3H
7), normal-butyl (n-C
4H
9) in a kind of.
The instance of the Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi of the present invention's preparation is:
(Ia), (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine ETHYLE ACETATE;
(Ib), (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-sec.-propyl)-ETHYLE ACETATE;
(Ic), (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-benzyl)-ETHYLE ACETATE;
(Id), (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-methyl)-methyl acetate;
(Ie), (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-benzyl)-methyl acetate;
(If) (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-sec.-propyl)-methyl acetate;
(Ig), (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-isobutyl-)-methyl acetate.
Embodiment 1:
Preparation (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine ETHYLE ACETATE (Ia):
The glycocoll of 20mL absolute ethyl alcohol and 3.76g is placed the three-necked round bottom flask of 100mL, bathe cooling and drip the new sulfur oxychloride 6mL that steams with cryosel, temperature control added below-5 ℃ in about 30 minutes.Naturally rise to the room temperature post-heating and be back to solid and all dissolve, the cold slightly white foam shape solid that promptly obtains after continuing to reflux 15 minutes.Excessive sulfur oxychloride is removed in decompression, and suction filtration is washed with ether in the cooling back, gets white needle-like crystals (IIa) with absolute ethyl alcohol-ether recrystallization.
With 5.30g Ti304,3.33g glycine ethyl ester hydrochloride, 3.3mL triethylamine and 3.8mL concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together; The three-necked flask that mixed reaction solution is housed is placed microwave reactor; Temperature adjustment is 65 ℃ in 5 minutes; And decompression steams solvent after being incubated 30 minutes, adds the 20mL water dissolution and also extracts at twice with 40mL ETHYLE ACETATE.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ETHYLE ACETATE: sherwood oil=column chromatography got yellowish colour purity article in 2: 1, and productive rate is 82.8%.
Ultimate analysis: measured value C%51.32 H%6.08 N%17.60
Calculated value C%51.35 H%6.10 N%17.58
IR (KBr compressing tablet cm
-1): 2,951 2,872 1744 (C=O), 1546 (NO
2) 1303 (VasC-O-C) 1251 (VaC-O-C), 1H NMR (CDCl3/400MHz): 8.238-8.243 (d, J=2.0Hz, 1H, pyridine hydrogen), 7.636-7.662 (m, 1H; Pyridine hydrogen), 7.242-7.263 (d, J=8.4Hz, 1H, pyridine hydrogen), 4.429-4.466 (d, J=14.8Hz; 1H), and 4.111-4.165 (q, J=7.2Hz, 2H, COOCH2), 4.067-4.106 (d, J=15.6Hz; 1H), and 3.648-3.746 (m, 4H), 3.368 (s, 2H, NCH
2CO) 3.140-3.228 (m, 1H), 2.984 (s, 3H, NCH
3), 2.808-2.891 (m, 1H), 1.204-1.240 (t, J=7.2Hz, 3H, COOCH
2CH
3), 1.083-1.119 (t, J=7.2Hz, 3H, NCH
2CH
3).
Embodiment 2:
Preparation (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-sec.-propyl)-ETHYLE ACETATE (Ib):
The L-alpha-aminoisocaproic acid of 20mL absolute ethyl alcohol and 5.85g is placed the three-necked round bottom flask of 100mL, bathe cooling and drip the new sulfur oxychloride 6mL that steams with cryosel, temperature control added below-5 ℃ in about 30 minutes.Naturally rise to the room temperature post-heating and be back to solid and all dissolve, the cold slightly white foam shape solid that promptly obtains after continuing to reflux 15 minutes.Excessive sulfur oxychloride is removed in decompression, and suction filtration is washed with ether in the cooling back, gets white needle-like crystals (IIb) with absolute ethyl alcohol-ether recrystallization.
With 5.30g Ti304,4.67g L-alpha-aminoisocaproic acid carbethoxy hydrochloride, 3.3mL triethylamine and 3.8mL concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together; The three-necked flask that mixed reaction solution is housed is placed microwave reactor; Temperature adjustment is 70 ℃ in 5 minutes; And decompression steams solvent after being incubated 25 minutes, adds the 20mL water dissolution and also extracts at twice with 40mL ETHYLE ACETATE.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains orange-yellow oily thing.With ETHYLE ACETATE: sherwood oil=column chromatography got yellow pure article in 3: 1, and productive rate is 84.5%.
Ultimate analysis: measured value C%55.56 H%7.11 N%15.43
Calculated value C%55.54 H%7.10 N%15.44
IR (KBr compressing tablet cm
-1): 2,954 2,869 1732 (C=O), 1552 (NO
2) 1301 (VasC-O-C) 1251 (VaC-O-C), 1H NMR (CDCl3/400MHz): 8.301-8.324 (d, J=9.2Hz, 1H, pyridine hydrogen); (7.672-7.763 m, 1H, pyridine hydrogen), 7.316-7.336 (d, J=8.0Hz; 1H, pyridine hydrogen), 4.511-4.549 (d, J=15.2Hz, 1H); 4.144-4.196 (q, J=7.2Hz, 2H, COOCH
2), 4.113-4.151 (d, J=15.2Hz, 1H), 3.659-3.879 (m, 4H), 3.520-3.556 (t, J=7.2Hz, 1H, NCHCO), 3.223-3.326 (m, 1H), 2.927 (s, 3H, NCH
3), 2.860-2.975 (m, 1H), 1.571-1.749 (m, 1H, CH
2CH), 1.604-1.654 (m, 2H, CH
2CH), 1.267-1.303 (t, J=7.2Hz, 3H, COOCH
2CH
3), 1.150-1.203 (q, J=7.2Hz, 3H, NCH
2CH
3), 0.966-0.981 (d, J=6.0Hz, 3H, CHCH
3), 0.934-0.949 (d, J=6.0Hz, 3H, CHCH
3).
Embodiment 3:
Preparation (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-benzyl)-ETHYLE ACETATE (Ic);
L-α-phenylalanine(Phe) of 20mL absolute ethyl alcohol and 8.25g is placed the three-necked round bottom flask of 100mL, bathe cooling and drip the new sulfur oxychloride 6mL that steams with cryosel, temperature control added below-5 ℃ in about 30 minutes.Naturally rise to the room temperature post-heating and be back to solid and all dissolve, the cold slightly white foam shape solid that promptly obtains after continuing to reflux 15 minutes.Excessive sulfur oxychloride is removed in decompression, and suction filtration is washed with ether in the cooling back, gets white needle-like crystals (IIc) with absolute ethyl alcohol-ether recrystallization.
With 5.30g Ti304,5.47g L-α-phenylalanine ethyl ester hydrochloride, 3.3mL triethylamine and 3.8mL concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together; The three-necked flask that mixed reaction solution is housed is placed microwave reactor; Temperature adjustment is 75 ℃ in 4 minutes; And decompression steams solvent after being incubated 30 minutes, adds the 20mL water dissolution and also extracts at twice with 40mL ETHYLE ACETATE.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains orange-yellow oily thing.With ETHYLE ACETATE: sherwood oil=column chromatography got yellow pure article in 4: 1, and productive rate is 84.5%.
Ultimate analysis: measured value C%59.07 H%6.20 N%14.35
Calculated value C%59.05 H%6.21 N%14.33
IR (KBr compressing tablet cm
-1): 2,937 2,865 1727 (C=O), 1552 (NO
2) 1300 (VasC-O-C) 1250 (VaC-O-C);
1H NMR (CDCl3/400MHz): 8.290-8.300 (d, J=4.0Hz, 1H, pyridine hydrogen), 7.655-7.714 (m, 1H; Pyridine hydrogen), 7.247-7.343 (m, 5H, Ph) 7.202-7.217 (d, J=6.0Hz, 1H; Pyridine hydrogen), and 4.497-4.535 (d, J=15.2Hz, 1H), 4.154-4.191 (d; J=14.8Hz, 1H), 4.084-4.138 (m, 2H, COOCH
2), 3.735-3.920 (m, 4H), 3.213-3.290 (m, 1H), 3.026-3.162 (m, 2H, PhCH
2), 2.871-2.933 (m, 1H), 2.777-2.755 (d, J=8.8Hz 3H, NCH
3), 1.250-1.286 (t, J=7.2Hz, 1H, CH
2CH), 1.135-1.174 (m, 6H).
Embodiment 4: and preparation (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-methyl)-methyl acetate (Id).
In 250mL three-necked bottle (being with dry alkali lye absorption unit), add 150mL methyl alcohol; Cryosel is bathed and is cooled to below-10 ℃; Drip the new sulfur oxychloride that steams of 21.60mL under the magnetic agitation; The control rate of addition makes temperature of reaction be no more than 0 ℃, reacts to be warming up to room temperature naturally after one hour, gets sulfur oxychloride-methanol solution of 150mL 1mol/L.
On the 100mL three-necked flask, reflux condensing tube is installed and (is met CaCl
2And alkali lye absorption unit) tap funnel and TM.50mL methyl alcohol is added in the reaction flask, bathes with cryosel and be cooled to below-10 ℃, stir and slowly drip the new sulfur oxychloride that steams of 3.6mL down, control rate of addition in the dropping process, with the temperature that keeps reaction solution below 0 ℃.Dropwise one hour above-mentioned solution of continued stirring and be transferred in the 100mL single port flask that fills 4.45g L-α-Bing Ansuan, reflux one hour, removal of solvent under reduced pressure gets white solid.Above-mentioned solid matter is dissolved in sulfur oxychloride-methanol solution of 50mL 1mol/L, reflux one hour, decompression steams solvent and gets white solid (IId).
With 5.30g Ti304,3.33g L-α-Bing Ansuan methyl ester hydrochloride, 3.3mL triethylamine and 3.8mL concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together; The three-necked flask that mixed reaction solution is housed is placed microwave reactor; Temperature adjustment is 65 ℃ in 6 minutes; And decompression steams solvent after being incubated 25 minutes, adds the 20mL water dissolution and also extracts at twice with 40mL ETHYLE ACETATE.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains orange-yellow oily thing.With ETHYLE ACETATE: sherwood oil=column chromatography got yellow pure article in 2: 1, and productive rate is 86.2%.
Ultimate analysis: measured value C%51.32 H%6.08 N%17.60
Calculated value C%51.31 H%6.10 N%17.63
IR (KBr compressing tablet cm
-1): 2,937 2,874 1734 (C=O), 1550 (NO
2) 1303 (VasC-O-C) 1251 (VaC-O-C),
1H NMR (CDCl3/400MHz): 8.306 (s, 1H, pyridine hydrogen), 7.676-7.742 (t, 1H; J=26.4Hz pyridine hydrogen), 7.278-7.332 (t, J=21.6Hz, 1H, pyridine hydrogen); 4.504-4.560 (m, 1H), 4.111-4.190 (t, J=31.6Hz, 1H); 3.778-3.814 (m, 4H), 3.732 (s, 3H, COOCH
3), 3.575-3.611 (q, J=14.4Hz, 1H, NCHCO), 3.251-3.269 (m, 1H), 2.970 (s, 3H, NCH
3), 2.888-2.923 (m, 1H), 1.397-1.414 (d, 3H, J=6.8Hz, CHCH
3), 1.132-1.150 (q, J=7.2Hz, 3H, NCH
2CH
3).
Embodiment 5:
Preparation (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-benzyl)-methyl acetate (Ie);
In 250mL three-necked bottle (being with dry alkali lye absorption unit), add 150mL methyl alcohol; Cryosel is bathed and is cooled to below-10 ℃; Drip the new sulfur oxychloride that steams of 21.60mL under the magnetic agitation; The control rate of addition makes temperature of reaction be no more than 0 ℃, reacts to be warming up to room temperature naturally after one hour, gets sulfur oxychloride-methanol solution of 150mL 1mol/L.
On the 100mL three-necked flask, reflux condensing tube is installed and (is met CaCl
2And alkali lye absorption unit) tap funnel and TM.50mL methyl alcohol is added in the reaction flask, bathes with cryosel and be cooled to below-10 ℃, stir and slowly drip the new sulfur oxychloride that steams of 3.6mL down, control rate of addition in the dropping process, with the temperature that keeps reaction solution below 0 ℃.Dropwise one hour above-mentioned solution of continued stirring and be transferred in the 100mL single port flask that fills 8.95g L-α-phenylalanine(Phe), reflux one hour, removal of solvent under reduced pressure gets white solid.Above-mentioned solid matter is dissolved in sulfur oxychloride-methanol solution of 50mL 1mol/L, reflux one hour, decompression steams solvent and gets white solid (IIe).
With 5.30g Ti304,5.15g L-α-phenylalanine methyl ester hydrochloride, 3.3mL triethylamine and 3.8mL concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together; The three-necked flask that mixed reaction solution is housed is placed microwave reactor; Temperature adjustment is 75 ℃ in 5 minutes; And decompression steams solvent after being incubated 30 minutes, adds the 20mL water dissolution and also extracts at twice with 40mL ETHYLE ACETATE.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains orange-yellow oily thing.With ETHYLE ACETATE: sherwood oil=column chromatography got yellow pure article in 3: 1, and productive rate is 82.4%.
Ultimate analysis: measured value C%58.29 H%5.95 N%14.78
Calculated value C%58.31 H%5.93 N%14.75
IR (KBr compressing tablet cm
-1): 2,949 2,872 1732 (C=O), 1552 (NO
2) 1301 (VasC-O-C) 1252 (VaC-O-C);
1H NMR (CDCl3/400MHz): 8.261-8.266 (d, J=2.0Hz, 1H, pyridine hydrogen), 7.656-7.662 (m, 1H, pyridine hydrogen); 7.271-7.319 (m, 5H, Ph) 7.226-7.243 (d, J=6.8Hz, 1H, pyridine hydrogen), 4.472-4.510 (d; J=15.2Hz, 1H), 4.136-4.174 (d, J=15.2Hz, 1H), 4.088-4.126 (m; 1H), and 3.767-3.871 (m, 4H), 3.725 (s, 3H, COOCH
3), 3.619-3.627 (m, 1H), 3.027-3.053 (m, 2H, PhCH2), 2.877 (S, 3H, NCH3), 1.205-1.245 (t, J=16Hz, 1H, CH2CH), 1.133-1.168 (t, J=14,3H, NCH
2CH
3);
Embodiment 6: and preparation (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-sec.-propyl)-methyl acetate (If).
In 250mL three-necked bottle (being with dry alkali lye absorption unit), add 150mL methyl alcohol; Cryosel is bathed and is cooled to below-10 ℃; Drip the new sulfur oxychloride that steams of 21.60mL under the magnetic agitation; The control rate of addition makes temperature of reaction be no more than 0 ℃, reacts to be warming up to room temperature naturally after one hour, gets sulfur oxychloride-methanol solution of 150mL 1mol/L.
On the 100mL three-necked flask, reflux condensing tube is installed and (is met CaCl
2And alkali lye absorption unit) tap funnel and TM.50mL methyl alcohol is added in the reaction flask, bathes with cryosel and be cooled to below-10 ℃, stir and slowly drip the new sulfur oxychloride that steams of 3.6mL down, control rate of addition in the dropping process, with the temperature that keeps reaction solution below 0 ℃.Dropwise one hour above-mentioned solution of continued stirring and be transferred in the 100mL single port flask that fills 5.85g L-alpha-aminoisocaproic acid, reflux one hour, removal of solvent under reduced pressure gets white solid.Above-mentioned solid matter is dissolved in sulfur oxychloride-methanol solution of 50mL 1mol/L, reflux one hour, decompression steams solvent and gets white solid (IIf).
With 5.30g Ti304,3.67g L-alpha-aminoisocaproic acid methyl ester hydrochloride, 3.3mL triethylamine and 3.8mL concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together; The three-necked flask that mixed reaction solution is housed is placed microwave reactor; Temperature adjustment is 65 ℃ in 8 minutes; And decompression steams solvent after being incubated 20 minutes, adds the 20mL water dissolution and also extracts at twice with 40mL ETHYLE ACETATE.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains glassy yellow oily matter.With ETHYLE ACETATE: sherwood oil=column chromatography got yellow pure article in 3: 1, and productive rate is 85.7%.
Ultimate analysis: measured value C%53.58 H%6.63 N%16.44
Calculated value C%53.60 H%6.62 N%16.45
IR (KBr compressing tablet cm
-1): 2,954 2,869 1732 (C=O), 1552 (NO
2) 1301 (VasC-O-C) 1251 (VaC-O-C),
1H NMR (DMSO/400MHz): 8.304-8.323 (d, J=7.6Hz, 1H, pyridine hydrogen), 7.740-7.810 (m, 1H; Pyridine hydrogen), 7.464-7.509 (d, J=18.0Hz, 1H, pyridine hydrogen), 4.504-4.515 (d; J=4.4Hz, 1H), 4.191-4.229 (d, J=15.2Hz, 1H); 3.782-3.929 (m, 4H), 3.624 (s, 3H, COOCH
3), 3.514-3.545 (t, J=12.4Hz, 1H, NCHCO), 3.135-3.184 (m, 1H), 2.980 (s; 3H, NCH3), 2.889-2.915 (m, 1H), 1.476-1.644 (m, 1H, CH2CH); 1.603-1.624 (m, 2H, CH2CH), 1.105-1.123 (q, J=7.2Hz, 3H, NCH2CH
3), 0.929-0.943 (d, J=5.6Hz, 3H, CHCH
3), 0.877-0.891 (d, J=5.6Hz, 3H, CHCH
3).
(C＝0.01g/mL?CH
3COCH
3)。
Embodiment 7: and preparation (2H, 6H)-4-[[(6-chloro-3-picolyl) ethylamino-]-2,6-dihydro-3-methyl-5-nitro]-1-pyrimidine-(1 '-isobutyl-)-methyl acetate (Ig).
In 250mL three-necked bottle (being with dry alkali lye absorption unit), add 150mL methyl alcohol; Cryosel is bathed and is cooled to below-10 ℃; Drip the new sulfur oxychloride that steams of 21.60mL under the magnetic agitation; The control rate of addition makes temperature of reaction be no more than 0 ℃, reacts to be warming up to room temperature naturally after one hour, gets sulfur oxychloride-methanol solution of 150mL 1mol/L.
On the 100mL three-necked flask, reflux condensing tube is installed and (is met CaCl
2And alkali lye absorption unit) tap funnel and TM.50mL methyl alcohol is added in the reaction flask, bathes with cryosel and be cooled to below-10 ℃, stir and slowly drip the new sulfur oxychloride that steams of 3.6mL down, control rate of addition in the dropping process, with the temperature that keeps reaction solution below 0 ℃.Dropwise one hour above-mentioned solution of continued stirring and be transferred in the 100mL single port flask that fills 7.25g L-α-Xie Ansuan, reflux one hour, removal of solvent under reduced pressure gets white solid.Above-mentioned solid matter is dissolved in sulfur oxychloride-methanol solution of 50mL 1mol/L, reflux one hour, decompression steams solvent and gets white solid (IIg).
With 5.30g Ti304,4.34g L-α-valine methyl ester hydrochloride, 3.3mL triethylamine and 3.8mL concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together; The three-necked flask that mixed reaction solution is housed is placed microwave reactor; Temperature adjustment is 70 ℃ in 5 minutes; And decompression steams solvent after being incubated 30 minutes, adds the 20mL water dissolution and also extracts at twice with 40mL ETHYLE ACETATE.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains glassy yellow oily matter.With ETHYLE ACETATE: sherwood oil=column chromatography got yellow pure article in 2: 1, and productive rate is 83.2%.
Ultimate analysis: measured value C%54.60 H%6.87 N%15.92
Calculated value C%54.63 H%6.88 N%15.90
IR (KBr compressing tablet cm
-1): 2,964 2,875 1731 (C=O), 1553 (NO
2) 1300 (VasC-O-C) 1249 (VaC-O-C),
1H NMR (CDCl3/400MHz): 8.283-8.317 (d * d, J=13.6Hz, 1H, pyridine hydrogen), 7.736-7.788 (m, 1H; Pyridine hydrogen), 7.310-7.330 (d, J=8.0Hz, 1H, pyridine hydrogen); 4.488-4.496 (d, J=3.2Hz, 1H), 4.130-4.239 (d * d, 1H); 3.723-3.810 (m, 4H), 3.701 (s, 3H, COOCH
3), 3.632-3.638 (d, J=2.4Hz, 1H, NCHCO), 3.036-3.065 (m, 1H), 2.957 (s, 3H, NCH
3), 2.928-2.949 (m, 1H), 1.217-1.252 (m, 1H, CHCH), 1.039-1.079 (q, J=16Hz, 3H, NCH
2CH
3), 0.961-0.947 (d, J=5.6Hz, 3H, CHCH
3), 0.904-0.920 (d, J=5.6Hz, 3H, CHCH
3).
Embodiment 8:
The insecticidal activity assay of target compound: adopt national southern test center Standard operation procedure SOP to measure.
(1) test target:
Nilaparvata lugen (brown planthopper) (Nilaparvata legen), mythimna separata (Mythima separata), aphis craccivora (Aphismedicagini); Above worm kind is that indoor for many generations to raise throughout the year or gather from the field indoor feeding many for the worm kind.
(2) plant and instrument:
Electronic analytical balance, petridish, liquid-transfering gun, Potter spray tower, writing brush.
(3) chemicals treatment:
Take by weighing the former medicine of certain mass with analytical balance (0.0001g), add the solvent (DMF) that contains 0.1% tween-80, be mixed with 1～5% preparation.Take by weighing the preparation of certain mass, adding distil water is mixed with the soup of measuring desired concn with the dilution of acetone topical application.
Estimate SOP (sterilant volume) according to pesticide bioactivity, general sieve concentration is selected 500mg/L.
(4) TP:
A. paddy rice brown paddy plant hopper screening---the quantitative spray method of petridish seedling worm:
The paddy rice seedling is fixed in the petridish with white quartz sand; Use CO
2Anaesthetize 3 mid-term in age nymph, place under the POTTER spray tower spraying.The spraying back covers with the transparent plastics cup, is put in the observation ward behind the mark.Check result behind the 72h.
B. mythimna separata screening---soak the seedling feeding method:
Leaf of Semen Maydis is fully soaked into the back dry in the shade naturally in soup, put into petridish, connect 3 mid-term in age larva, add a cover mark and be placed in the observation ward.Check result behind the 72h.
C. aphis craccivora screening---pickling process
If the broad bean blade is cut off two ends, and the back side is placed on the fritter cotton up, places in the plastic culture dish, adds less water, connects aphis craccivora and becomes aphid to produce aphid.Remove into aphid behind the 24h, continue behind the cultivation 2d blade behind the abundant 5s of infiltration, to be placed on the cotton natural airing again in soup.Check result behind the 24h.
Table 1 has been enumerated Z formula configuration anabasine sterilant Ia～Ig of containing the L-α-An Jisuanzhi and has been 500,100 and handles the mortality ratio of Nilaparvata lugen (brown planthopper), mythimna separata, aphis craccivora during 20ppm in concentration.Test data in the table shows: the Z formula configuration anabasine sterilant Ia～Ih that contains the L-α-An Jisuanzhi all has insecticidal activity, and wherein to kill the Nilaparvata lugen (brown planthopper) activity the highest for Ia, when concentration 100ppm, can reach 100%.It is the highest that Ie, Ig kill the mythimna separata activity, when concentration 100ppm, can reach 80-100%.Even especially Ie also has 50% the activity of killing to mythimna separata when the lower concentration of 20ppm, significantly insecticidal effect is arranged.The Z formula configuration anabasine sterilant Ia, Id, Ie, And if the Ig that contain the L-α-An Jisuanzhi all have the higher activity of killing to aphis craccivora when concentration 500ppm.
Table 1: contain the killing rate (%) of the Z formula configuration anabasine sterilant Ia～Ig of L-α-An Jisuanzhi to Nilaparvata lugen (brown planthopper), mythimna separata, aphis craccivora
The embodiment of the invention described above is not limited to the present invention.For a person skilled in the art, the preparation method of product of the present invention can change.All within spirit of the present invention and principle, that is done is equal to replacement, improves etc., all should be included within protection scope of the present invention.
Claims (2)
1. Z formula configuration anabasine sterilant that contains the L-α-An Jisuanzhi is characterized in that the chemical structure of this sterilant is shown in general formula (I):
Wherein: R is hydrogen, methyl, sec.-propyl, benzyl, isobutyl-; R ' is a kind of in methyl and ethyl, n-propyl, the normal-butyl.
2. the said Z formula configuration anabasine method for producing insecticide that contains the L-α-An Jisuanzhi of claim 1 is characterized in that, comprises the steps:
(1) preparation has the L-a-amino acid methyl esters of logical formula II structure or the hydrochloride of ethyl ester, and wherein, R is hydrogen, methyl, sec.-propyl, benzyl, isobutyl-; R ' is a kind of in methyl and the ethyl:
A. the L-a-amino acid is dissolved in 1mol/L thionyl chloride-methanol solution, controlled temperature prepares L-a-amino acid methyl ester hydrochloride below-5 ℃;
B. the L-a-amino acid is dissolved in absolute ethyl alcohol, controlled temperature below 0 ℃, dripping thionyl chloride, preparation amino acid carbethoxy hydrochloride;
(2) preparation contains the Z formula configuration anabasine sterilant of L-α-An Jisuanzhi, and general formula (I) as above;
A. the hydrochloride of the L-a-amino acid methyl esters of Ti304,37% formaldehyde solution, triethylamine and above-mentioned (1) preparation or ethyl ester being dissolved in puts in the three-necked round bottom flask in the ethanol;
Ti304,37% formaldehyde solution, triethylamine are 5.30g: 3.8ml: 3.3ml: 30ml with the amount of ethanol ratio;
The hydrochloride of L-a-amino acid methyl esters or ethyl ester is glycine ethyl ester hydrochloride, L-alpha-aminoisocaproic acid carbethoxy hydrochloride, L-α-phenylalanine ethyl ester hydrochloride, L-α-Bing Ansuan methyl ester hydrochloride, L-α-phenylalanine methyl ester hydrochloride, L-alpha-aminoisocaproic acid methyl ester hydrochloride or L-α-valine methyl ester hydrochloride;
The amount ratio of the hydrochloride of Ti304 and L-a-amino acid methyl esters or ethyl ester is one of following ratio:
1. Ti304 and glycine ethyl ester hydrochloride amount ratio are 5.30g: 3.33g;
2. Ti304 and L-alpha-aminoisocaproic acid carbethoxy hydrochloride amount ratio are 5.30g: 4.67g;
3. Ti304 and L-α-phenylalanine ethyl ester hydrochloride amount ratio is 5.30g: 5.47g;
4. Ti304 and L-α-Bing Ansuan methyl ester hydrochloride amount ratio are 5.30g: 3.33g;
5. Ti304 and L-α-phenylalanine methyl ester hydrochloride amount ratio is 5.30g: 5.15g;
6. Ti304 and L-alpha-aminoisocaproic acid methyl ester hydrochloride amount ratio are 5.30g: 3.67g;
7. Ti304 and L-α-valine methyl ester hydrochloride amount ratio is 5.30g: 4.34g;
The three-necked round bottom flask that b. above-mentioned solution will be housed is put into microwave reactor, and controlled temperature makes the Z formula configuration anabasine sterilant that general formula (I) contains the L-α-An Jisuanzhi microwave reaction below 75 ℃ 30 minutes.
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