CN105461683A - A preparing method of a 2-aminobenzamide compound - Google Patents
A preparing method of a 2-aminobenzamide compound Download PDFInfo
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- CN105461683A CN105461683A CN201510795387.9A CN201510795387A CN105461683A CN 105461683 A CN105461683 A CN 105461683A CN 201510795387 A CN201510795387 A CN 201510795387A CN 105461683 A CN105461683 A CN 105461683A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
A preparing method of a 2-aminobenzamide compound is disclosed. The method includes subjecting a compound shown as a formula II to sulfidation to obtain a compound shown as a formula III, subjecting the compound shown as the formula III and a compound shown as a formula IV to condensation to obtain a compound shown as a formula I. The sulfidation of the compound shown as the formula II and a sulfidation agent is performed under existence of a catalyst and a polar organic solvent. The condensation is performed under existence of an acid neutralizing agent, an organic solvent and diethylenetriamine or triethylenediamine. The method is easily available in raw materials, simple and feasible in process, mild in reaction conditions and easy in industrial production. The purity of the condensation product can be 94-98% by the condensation in particular. The total yield of the two-step reactions can be 85% or above.
Description
Technical field
The invention belongs to technical field of agricultural chemical insecticide, be specifically related to the bromo-1-(3-chloro-2-pyridyl of a kind of Anthranilamide compound 3-) preparation method of-N-[4-thioformamide base-2-methyl-6-(methylamino formyl radical)-phenyl]-1H-pyrazoles-5-methane amide.
Background technology
Chinese patent literature CN103265527A discloses a kind of Anthranilamide compound and its preparation method and application; the chemical name of this Anthranilamide compound is: the bromo-1-(3-chloro-2-pyridyl of 3-)-N-[4-thioformamide base-2-methyl-6-(methylamino formyl radical)-phenyl]-1H-pyrazoles-5-methane amide, its structural formula is as follows:
。
This compound all has good insecticidal activity to the lepidoptera pests such as mythimna separata, snout moth's larva, leafhopper, plant hopper and Diptera, Hemipteran pest.
Preparation method disclosed in the document is obtained by reacting under the existence of the catalyzer such as DMF polar organic solvent and magnesium chloride by vulcanizing agents such as bromine cyanogen insect amide and NaSH.The deficiency of the method is: bromine cyanogen insect amide price is higher and be difficult to obtain.
Summary of the invention
The preparation method the object of the invention is to solve the problem, provide that a kind of raw material is cheap and easy to get, technique simple possible, reaction conditions are gentle, being easy to the Anthranilamide compound of suitability for industrialized production.
The technical scheme realizing the object of the invention is: a kind of preparation method of Anthranilamide compound, it is the compound first being obtained formula III by the compound of formula II through vulcanization reaction, then obtains the compound of formula I through condensation reaction by the compound of formula III and the compound of formula IV.
Described vulcanization reaction is carried out under the existence of catalyzer and polar organic solvent by the compound of formula II and vulcanizing agent.
The vulcanizing agent that described vulcanization reaction adopts is NaSH or H
2s, preferred NaSH; The compound of described formula II and the mol ratio of described vulcanizing agent are 1: 0.5 ~ 1: 3, are preferably 1: 0.8 ~ 1: 1.5.
The catalyzer that described vulcanization reaction adopts is magnesium chloride, zinc chloride or tin chloride, preferred magnesium chloride; The compound of described formula II and the mol ratio of described catalyzer are 1: 0.3 ~ 1: 1, are preferably 1: 0.5 ~ 1: 0.8.
The polar organic solvent that described vulcanization reaction adopts is one in tetrahydrofuran (THF), ethylene glycol monomethyl ether, DMF (DMF), dioxane, acetone, butanone or two kinds of mixed solvents.
Described vulcanization reaction temperature is 0 ~ 100 DEG C, preferably 25 ~ 60 DEG C.
Described vulcanization reaction equation is as follows:
。
Described condensation reaction can be carried out under the existence connecing sour agent and organic solvent, but condensation product content and reaction yield are all undesirable.For this reason, applicant finally finds in above-mentioned condensation reaction, add diethylenetriamine or triethylene diamine can improve condensation product content and reaction yield greatly through testing in large quantities.
The add-on of described diethylenetriamine or triethylene diamine is the 1wt% ~ 5wt% of the compound of formula IV.
Sour agent that what described condensation reaction adopted connect is the one in sodium bicarbonate, saleratus, anhydrous sodium carbonate, Anhydrous potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, 2-picoline, 4-picoline, sodium hydride; Potassium bicarbonate, Anhydrous potassium carbonate or triethylamine; Compound and the described mol ratio connecing sour agent of described formula IV are 1: 1 ~ 1: 1.5.
The organic solvent that described condensation reaction adopts is the one in acetonitrile, benzene, toluene, acetone, butanone, chloroform, methylene dichloride, ethylene dichloride, ethyl acetate; Preferred acetonitrile or acetone.
Described setting-up point is-10 ~ 100 DEG C, preferably 0 ~ 60 DEG C.
The mol ratio of the compound of described formula III and the compound of described formula IV is 1: 0.8 ~ 1: 1.5.
Described condensation reaction equation is as follows:
。
The positively effect that the present invention has: (1) preparation method's raw material of the present invention is cheap and easy to get, technique simple possible, reaction conditions is gentle, is easy to suitability for industrialized production.(2) condensation reaction of the present invention can make condensation product content reach 94% ~ 98%, and two-step reaction total recovery (with 2-amino-5-cyano-N, 3-dimethyl formamide meter) can reach more than 85%.
Embodiment
(embodiment 1)
The present embodiment is the compound 2-amino-5-cyano-N of formula II, 3-dimethyl formamide through the compound 2-amino-5-sulphamide-N of vulcanization reaction preparation formula III, 3-dimethyl formamide.
The compound (0.1mol) of the formula II of 19g and the butanone of 200mL is added in 500mL four-hole bottle, stirring and dissolving, and then add the NaSH(0.1mol that 8g concentration is 70wt%) and the magnesium chloride (0.05mol) of 5g, add first room temperature (15 ~ 25 DEG C, lower same) stir 20min, then be warming up to 55 ± 2 DEG C of reaction 6h.
After reaction terminates, butanone is steamed under first vacuum, then less than the 10 DEG C 100 ~ 150mL that add water are cooled to, and be 3 ~ 5 with the salt acid for adjusting pH of 30wt%, filter after continuing to stir 1h, the washing of filter cake 50mL is once drained afterwards, drying obtains the compound of the formula III of 22.0g, content is 98.0%(HPLC), yield is 96.7%, and fusing point is 200.1 ~ 200.8 DEG C.
(embodiment 2 ~ embodiment 4)
The preparation method of each embodiment is substantially the same manner as Example 1, and difference is in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Formula II compound | 18.9g（0.1mol） | 18.9g（0.1mol） | 37.8g（0.2mol） | 37.8g（0.2mol） |
| NaSH | 8g、70wt% | 8g、70wt% | 18.8g、70wt% | 23.5g、70wt% |
| Magnesium chloride | 5g | 5g | 13.5g | 14.3g |
| Solvent | The butanone of 200mL | The DMF of 200mL | The acetone of 300mL | The tetrahydrofuran (THF) of the DMF+150mL of 150mL |
| Temperature of reaction | 55±2℃ | 55±2℃ | 45±2℃ | 40±2℃ |
| Reaction times | 6h | 7h | 9h | 9h |
| Products weight | 22.0g | 22.5g | 43.5g | 43.0g |
| Content | 98.0% | 95.0% | 97.5% | 96.0% |
| Yield | 96.7% | 95.9% | 95.1% | 92.6% |
| Fusing point | 200.1～200.8℃ | 199.5～201.0℃ | 199.9～201.0℃ | 200.0～201.2℃ |
(embodiment 5)
The present embodiment is the compound 2-amino-5-sulphamide-N of formula III, the compound 3-bromo-1-(3-chloro-2-pyridyl of 3-dimethyl formamide and formula IV)-1H-pyrazoles-5-formyl chloride is through the bromo-1-(3-chloro-2-pyridyl of compound 3-of condensation reaction preparation formula I)-N-[4-thioformamide base-2-methyl-6-(methylamino formyl radical)-phenyl]-1H-pyrazoles-5-methane amide.
The diethylenetriamine of the compound (0.1mol) of the formula III of 22.3g, the acetonitrile of 100mL, the triethylamine (0.12mol) of 12g and 0.5g is added in 500mL four-hole bottle, then at 0 ~ 25 DEG C, drip the acetonitrile solution of the compound (0.1mol) containing 32.1g formula IV of 50mL, add stirring at room temperature 6h.
After reaction terminates, acetonitrile is steamed under first vacuum, then be cooled to less than the 10 DEG C 100 ~ 150mL that add water, and be 1 ~ 2 with the salt acid for adjusting pH of 30wt%, now have yellow solid to separate out, filter after continuing to stir 1h, drain after the washing twice of filter cake 50mL × 2, drying obtains the compound of the formula I of 50.0g, and content is 95.5%(HPLC), yield is 94.1%, and fusing point is 246.8 ~ 247.9 DEG C.
(embodiment 6 ~ embodiment 7)
The preparation method of each embodiment is substantially the same manner as Example 5, and difference is in table 2.
(comparative example 1)
The preparation method of this comparative example is substantially the same manner as Example 5, and difference is in table 2.
Table 2
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | |
| The compound of formula III | 22.3g（0.1mol） | 22.3g（0.1mol） | 44.6g（0.2mol） | 22.3g（0.1mol） |
| The compound of formula IV | 32.1g（0.1mol） | 32.1g（0.1mol） | 64.2g（0.2mol） | 32.1g（0.1mol） |
| Connect sour agent | The triethylamine (0.12mol) of 12g | The saleratus (0.1mol) of 10g | The pyridine (0.22mol) of 17.4g | The triethylamine (0.12mol) of 12g |
| Solvent | 100mL+50mL acetonitrile | 100mL+50mL acetone | 200mL+100mL acetonitrile | 100mL+50mL acetonitrile |
| Diethylenetriamine | 0.5g | Nothing | 1.0g | Without 3--> |
| Triethylene diamine | Nothing | 0.5g | Nothing | Nothing |
| Temperature of reaction | Room temperature | 25～30℃ | 30±5℃ | Room temperature |
| Reaction times | 6h | 9h | 7h | 10h |
| Products weight | 50.0g | 50.0g | 51.0g | 40.0g |
| Content | 95.5% | 96.8% | 94.5% | 80.0% |
| Yield | 94.1% | 95.4% | 95.0% | 63.1% |
| Fusing point | 246.8～247.9℃ | 246.0～247.1℃ | 246.0～247.5℃ | 238.0～245.0℃ |
Compound two step total recovery in formula II: 90 ± 3%.
Claims (9)
1. a preparation method for Anthranilamide compound, is characterized in that: it is the compound first being obtained formula III by the compound of formula II through vulcanization reaction, then obtains the compound of formula I through condensation reaction by the compound of formula III and the compound of formula IV;
Reaction equation is as follows:
；
。
2. the preparation method of Anthranilamide compound according to claim 1, is characterized in that: described vulcanization reaction is carried out under the existence of catalyzer and polar organic solvent by the compound of formula II and vulcanizing agent.
3. the preparation method of Anthranilamide compound according to claim 2, is characterized in that: the vulcanizing agent that described vulcanization reaction adopts is NaSH; The compound of described formula II and the mol ratio of described vulcanizing agent are 1: 0.8 ~ 1: 1.5.
4. the preparation method of Anthranilamide compound according to claim 2, is characterized in that: the catalyzer that described vulcanization reaction adopts is magnesium chloride; The compound of described formula II and the mol ratio of described catalyzer are 1: 0.5 ~ 1: 0.8.
5. the preparation method of Anthranilamide compound according to claim 2, is characterized in that: described vulcanization reaction temperature is 25 ~ 60 DEG C.
6. the preparation method of Anthranilamide compound according to claim 1, is characterized in that: described condensation reaction carries out under the existence connecing sour agent and organic solvent; The mol ratio of the compound of described formula III and the compound of described formula IV is 1: 0.8 ~ 1: 1.5.
7. the preparation method of Anthranilamide compound according to claim 6, is characterized in that: the sour agent that connects that described condensation reaction adopts is saleratus, Anhydrous potassium carbonate or triethylamine; Compound and the described mol ratio connecing sour agent of described formula IV are 1: 1 ~ 1: 1.5.
8. the preparation method of Anthranilamide compound according to claim 6, is characterized in that: described setting-up point is 0 ~ 60 DEG C.
9. according to the preparation method of the Anthranilamide compound one of claim 1 to 8 Suo Shu, it is characterized in that: also adding in described condensation reaction has diethylenetriamine or triethylene diamine; The add-on of described diethylenetriamine or triethylene diamine is the 1wt% ~ 5wt% of the compound of formula IV.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170987A (en) * | 2019-12-30 | 2020-05-19 | 江苏省农用激素工程技术研究中心有限公司 | Novel 3-chloropyrazole bisamide compound and application thereof |
Citations (4)
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|---|---|---|---|---|
| WO2009111553A1 (en) * | 2008-03-05 | 2009-09-11 | E. I. Du Pont De Nemours And Company | Process for preparing 2-amino-5-cyanobenzoic acid derivatives |
| WO2009121288A1 (en) * | 2008-04-01 | 2009-10-08 | 中国中化集团公司 | A preparation method of phenylcarboxamides |
| CN101970397A (en) * | 2007-12-19 | 2011-02-09 | 纳幕尔杜邦公司 | Process for preparing 2-amino-5-cyanobenzoic acid derivatives |
| CN103265527A (en) * | 2013-06-07 | 2013-08-28 | 江苏省农用激素工程技术研究中心有限公司 | Anthranilamide compound as well as preparation method and application thereof |
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Patent Citations (4)
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| CN101970397A (en) * | 2007-12-19 | 2011-02-09 | 纳幕尔杜邦公司 | Process for preparing 2-amino-5-cyanobenzoic acid derivatives |
| WO2009111553A1 (en) * | 2008-03-05 | 2009-09-11 | E. I. Du Pont De Nemours And Company | Process for preparing 2-amino-5-cyanobenzoic acid derivatives |
| WO2009121288A1 (en) * | 2008-04-01 | 2009-10-08 | 中国中化集团公司 | A preparation method of phenylcarboxamides |
| CN103265527A (en) * | 2013-06-07 | 2013-08-28 | 江苏省农用激素工程技术研究中心有限公司 | Anthranilamide compound as well as preparation method and application thereof |
Non-Patent Citations (1)
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| 柴宝山 等: "氰虫酰胺的合成与生物活性", 《农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170987A (en) * | 2019-12-30 | 2020-05-19 | 江苏省农用激素工程技术研究中心有限公司 | Novel 3-chloropyrazole bisamide compound and application thereof |
| CN111170987B (en) * | 2019-12-30 | 2021-04-02 | 江苏省农用激素工程技术研究中心有限公司 | Novel 3-chloropyrazole bisamide compound and application thereof |
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