CN102863360A - Synthetic method of novel nitro arylideneamino guanidine derivatives - Google Patents
Synthetic method of novel nitro arylideneamino guanidine derivatives Download PDFInfo
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- CN102863360A CN102863360A CN 201210391540 CN201210391540A CN102863360A CN 102863360 A CN102863360 A CN 102863360A CN 201210391540 CN201210391540 CN 201210391540 CN 201210391540 A CN201210391540 A CN 201210391540A CN 102863360 A CN102863360 A CN 102863360A
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- 0 CSC(NC*)=* Chemical compound CSC(NC*)=* 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N NCc1ccccc1 Chemical compound NCc1ccccc1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N O=C(c(cccc1)c1C(Cl)=O)Cl Chemical compound O=C(c(cccc1)c1C(Cl)=O)Cl FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a new synthetic method of a novel insecticide nitro arylideneamino guanidine compound (I). S-methyl isothiourea is used as an initial raw material and subjected to steps of nitrification, imidization, aminolysis, hydrazinolysis, condensation and the like so that a target compound can be conveniently prepared. The new synthetic method of the novel insecticide nitro arylideneamino guanidine compound (I) has the advantages of being safe, temperate in reaction conditions and few in side reaction, and products are easy to purify.
Description
Technical field
The present invention relates to a kind of synthetic method of novel nitro contracting aminoguanidine compounds.
Background technology
In patent application WO2010060231A1, we disclose the synthetic method of a kind of novel nitro contracting aminoguanidine compounds (I) and as the application of sterilant, this compounds has efficiently, low toxicity, characteristics that security is good.But in its synthesis technique, there is following obvious defective, the one, raw material nitroguanidine explosive, all there are potential safety hazard in transportation and storage, the 2nd, the hydrazinolysis step side reaction of nitroguanidine is many, be difficult to control and hold reaction end, cause yield very low, the 3rd, when alkylation, easily generate the replacement by product on 3 N atoms.This patent discloses the synthetic method of a kind of improved novel nitro contracting aminoguanidine compounds (I).
Disclosure of the Invention
The synthetic method that the purpose of this invention is to provide a kind of novel nitro contracting aminoguanidine compounds.
The mode of the best that invention is implemented
Synthetic method of the present invention may further comprise the steps:
Below in conjunction with concrete example, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted implementation condition in the following example, usually according to normal condition, or according to the condition of making business men and advising.Unless otherwise indicated, otherwise per-cent and umber calculate by mass.
The below sets forth synthetic method provided by the present invention take the positive propionic aldehyde contracting of N-nitro-N '-benzyl-4-aminoguanidine as example.
Example N-nitro-N '-benzyl-4-valeraldehyde contracting aminoguanidine (R among the formula I
1Be phenyl, R
2Be hydrogen, R
3Be normal-butyl) synthetic:
1) 2-methyl isophthalic acid-nitro isothiourea is synthetic
The concentrated nitric acid 60mL of adding 65% and 98% vitriol oil 120mL in the 500mL there-necked flask, cryosel is bathed and is cooled to about-10 ℃, adds several times S-methyl-isourea 20g (0.144mol), after adding, continue to stir 1h under the ice bath, pour reaction solution in the ice (about 1000g), separate out white solid, filter, solid (ethanol: water=1: 2) recrystallization, get white needles solid 8.6g, yield is 44.3%, fusing point 156-157 ℃.
1H?NMR(DMSO-d
6)δppm：9.14(brs，2H)，2.40(s，3H)
2) S-methyl-N-nitro-N '-phthalyl isothiourea is synthetic
In the 500mL there-necked flask, add 20g (0.148mol) 2-methyl isophthalic acid-nitro isothiourea, add the 250mL pyridine, ice bath 10 minutes, then drip phthalyl chloride 45g (0.222mol), time for adding is about 20 minutes, solution gradually becomes chocolate, drip rear continuation and under ice bath, stirred 30 minutes, then reaction solution is poured into (the 100mL concentrated hydrochloric acid adds 400mL water) in the cold dilute hydrochloric acid of 1L, leave standstill, suction filtration, get the chocolate solid, use ethyl alcohol recrystallization, get white needles solid 32.7g, yield 83.4%, fusing point 121-122 ℃.
1H?NMR(CDCl
3)δppm：7.96-8.00(m，2H)，7.85-7.89(m，2H)，2.66(s，3H)
3) N-benzyl-S-methyl-N '-nitro isothiourea (IV-1) is synthetic
In the 500mL there-necked flask, add S-methyl-N-nitro-N '-O-phthalic isothiourea 10g (about 0.038mol), add the 250mL acetonitrile, stir under the ice bath, after 10 minutes, drip benzylamine 4.44g (about 0.042mol), the about 5-6 of time for adding minute, after dropwising, it is muddy that solution becomes gradually, white solid occurs, continuation is stirred after 30 minutes under ice bath, react complete, slough acetonitrile, get white powder solid 6.4g with ethyl alcohol recrystallization, yield 75%, fusing point 80-81 ℃.
1H?NMR(CD
3COCD
3)δppm：10.2(brs，1H)，7.15-7.30(m，5H)，4.60(d，J＝6.1Hz，2H)，2.38(s，3H)
4) N-benzyl-N '-nitro-3-aminoguanidine (V-1) is synthetic
In the 50mL there-necked flask, add N-benzyl-S-methyl-N '-nitro isothiourea 1g (0.0044mol), add 15mL ethanol, be heated to dissolution of solid, begin to drip 85% hydrazine hydrate 0.31g (0.0053mol), tail gas NaOH solution absorption refluxed 20 minutes, and reaction solution is concentrated, leave standstill, solid is separated out, and filters the solid recrystallizing methanol, get bulk crystals 0.47g, yield 51%.
1H?NMR(CD
3COCD
3)δppm：9.90(s，1H)，8.11(brs，1H)，7.21-7.35(m，5H)，4.80(s，2H)，4.37(s，2H)
5) N-nitro-N '-benzyl-4-valeraldehyde contracting aminoguanidine is synthetic
In the 50mL there-necked flask, add N-benzyl-N '-nitro-3-aminoguanidine 1.3g (0.0062mol), add methyl alcohol 40mL, Glacial acetic acid 0.5mL, heated and stirred is approximately to 60 ℃, begin to drip propionic aldehyde 0.4g (0.0068mol), time for adding is about 3 minutes, is warming up to backflow after dripping, if still have a small amount of solid not dissolve, can add a small amount of propionic aldehyde, until solid all dissolves, refluxed stopped heating 20 minutes.Column chromatography, eluent are sherwood oil: ethyl acetate (4: 1) gets bulk crystals 1.27g, yield 83%, fusing point 145-146 ℃.
1H?NMR(CD
3COCD
3)δppm：11.69(s，1H)，7.45(t，J＝5.1Hz，1H)，7.32-7.40(m，5H)，6.55(brs，1H)，4.60(d，J＝5.8Hz，2H)，2.31-2.41(m，2H)，1.12(t，J＝7.5Hz，3H)
Ultimate analysis
Claims (5)
1. can be with the synthetic target compound structural formula of this route
Formula I
Wherein:
R1 is the saturated or unsaturated aliphatic hydrocarbyl moiety of C1～C10, benzyl, substituted benzyl, picolyl, haloperidid methyl, halo thiazole methyl, furfuryl, tetrahydrofuran methyl, oxazole methyl;
R2 is hydrogen, C1～C5 is saturated or unsaturated aliphatic hydrocarbyl moiety, phenyl, substituted-phenyl, pyridyl, substituted pyridinyl;
R3 is hydrogen, C1～C10 is saturated or unsaturated aliphatic hydrocarbyl moiety, furyl, phenyl, substituted-phenyl, benzyl or substituted benzyl.
2. one kind prepares the described compound method of claim 1, may further comprise the steps:
1) compound shown in the nitrated production II of S-methyl-isothiourea;
Formula II
2) reaction of compound and phthalyl chloride shown in the formula IV generates compound shown in the formula III;
Formula III
3) compound shown in compound shown in the formula III and the formula IV production V;
Formula IV formula V
4) compound shown in the reaction of compound and hydrazine hydrate shown in the formula V production VI;
Formula VI
5) compound shown in the compound production I shown in compound shown in the formula VI and the formula VII;
Formula VII
R
1, R
2And R
3Definition identical with claim 1.
3. according to method described in the right 2-3, it is characterized in that: in the step 3, reaction is carried out in acetonitrile, ice bath, and the mol ratio of III and IV is 1: 1～1: 1.15.
4. according to method described in the right 2-4, it is characterized in that: in the step 4, reaction is carried out in ethanol, and temperature is 60～80 ℃.
5. according to method described in the right 2-5, it is characterized in that: in the step 5, reaction is carried out in methyl alcohol or ethanol, and as catalyzer, temperature is 50～80 ℃ without catalyzer or available acetic acid, hydrochloric acid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103444762A (en) * | 2013-09-26 | 2013-12-18 | 江苏省绿盾植保农药实验有限公司 | Composite pesticide capable of preventing rice pests |
| CN103444763A (en) * | 2013-09-26 | 2013-12-18 | 江苏省绿盾植保农药实验有限公司 | Composite pesticide containing E imidacloprid guanidine |
| CN104557620A (en) * | 2014-12-30 | 2015-04-29 | 中国农业大学 | Strobilurin compound containing nitrohydrazinecarboximidamide structure as well as preparation method and application of strobilurin compound |
| CN104557619A (en) * | 2014-12-30 | 2015-04-29 | 中国农业大学 | Methoxyimino phenylacetate compounds containing nitrohydrazinecarboximidamide structures as well as preparation method and application of methoxyimino phenylacetate compounds |
| CN105503661A (en) * | 2016-01-12 | 2016-04-20 | 西安近代化学研究所 | Method for synthesizing 1-amino-3-nitroguanidine |
| CN106538588A (en) * | 2016-12-08 | 2017-03-29 | 深圳诺普信农化股份有限公司 | A kind of Synergistic insecticidal compositions containing double third ring worm esters |
-
2012
- 2012-10-16 CN CN 201210391540 patent/CN102863360A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103444762A (en) * | 2013-09-26 | 2013-12-18 | 江苏省绿盾植保农药实验有限公司 | Composite pesticide capable of preventing rice pests |
| CN103444763A (en) * | 2013-09-26 | 2013-12-18 | 江苏省绿盾植保农药实验有限公司 | Composite pesticide containing E imidacloprid guanidine |
| CN103444763B (en) * | 2013-09-26 | 2016-02-10 | 江苏省绿盾植保农药实验有限公司 | A kind of composite insecticide containing penta pyrrole worm guanidine |
| CN104557620A (en) * | 2014-12-30 | 2015-04-29 | 中国农业大学 | Strobilurin compound containing nitrohydrazinecarboximidamide structure as well as preparation method and application of strobilurin compound |
| CN104557619A (en) * | 2014-12-30 | 2015-04-29 | 中国农业大学 | Methoxyimino phenylacetate compounds containing nitrohydrazinecarboximidamide structures as well as preparation method and application of methoxyimino phenylacetate compounds |
| CN105503661A (en) * | 2016-01-12 | 2016-04-20 | 西安近代化学研究所 | Method for synthesizing 1-amino-3-nitroguanidine |
| CN106538588A (en) * | 2016-12-08 | 2017-03-29 | 深圳诺普信农化股份有限公司 | A kind of Synergistic insecticidal compositions containing double third ring worm esters |
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