CN108947866A - N-(2- methyl -3- Phenylbenzoyl)-N '-tertiary butyl hydrazine and its synthetic method - Google Patents
N-(2- methyl -3- Phenylbenzoyl)-N '-tertiary butyl hydrazine and its synthetic method Download PDFInfo
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- CN108947866A CN108947866A CN201810922680.0A CN201810922680A CN108947866A CN 108947866 A CN108947866 A CN 108947866A CN 201810922680 A CN201810922680 A CN 201810922680A CN 108947866 A CN108947866 A CN 108947866A
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- methyl
- aqueous solution
- tertiary butyl
- butyl hydrazine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/04—Preparation of hydrazides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
- C07C243/38—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/305—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with sulfur or sulfur-containing compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses N-(2- methyl -3- Phenylbenzoyls)-N '-tertiary butyl hydrazine and its synthetic method, the compound is white solid, and melting range:, being slightly soluble in water by 156-159 DEG C, is soluble in ethyl alcohol, methylene chloride, the organic solvents such as ethyl acetate.The compound has many advantages, such as that mobility is small, desinsection effective time is long, high-efficient, small toxicity, environmental-friendly, synthesis technology is simple, yield is high compared with existing tebufenozide intermediate N tert-butyl hydrazine derivative.
Description
Technical field
The present invention relates to N-(2- methyl -3- Phenylbenzoyls)-N '-tertiary butyl hydrazine and its synthetic method.
Background technique
2- methyl biphenyl class compound causes two phenyl ring to have certain dihedral angle, does not exist since 2- there are methyl
The features such as in approximately the same plane, this kind of benzene derivate has toxicity low, water-soluble small, environmentally friendly, such as 2-methyl-3-biphenylmethanol (2-
Methyl-3-phenyl benzil alcohol) therefore it is usually used in as intermediates such as pesticides, hydrazide kind compound has extremely strong bioactivity,
If N- tert-butyl-N '-(4- ethylbenzoyl) hydrazine, N- tert-butyl-N '-(2 methyl -3- methoxybenzoyl) hydrazine are synthesis respectively
The intermediate of pesticide tebufenozide and methoxyfenozide, but this kind of hydrazine, due to water-soluble preferable, the pesticide of synthesis is more liquid,
The disadvantages of residual effect time is short.In the present invention, inventor designs synthesis and obtains N-(2- methyl -3- Phenylbenzoyl) the tertiary fourth of-N ' -
The advantages that base hydrazine, with poorly water-soluble, mobility is small, and the residual effect time is long.
Summary of the invention
The object of the present invention is to provide N-(2- methyl -3- Phenylbenzoyls)-N '-tertiary butyl hydrazine and its synthetic method.
The present invention realizes that process is as follows:
Structure formula (I) compound represented,
。
The preparation method of structure formula (I) compound represented, comprising the following steps:
(1) 2- methyl -3- Phenylbenzoic acid is made in 2- methyl-3-phenyl benzil alcohol Jones reagent oxidation, and with ethyl alcohol weight
Crystallization；
(2) synthesized 2- methyl -3- Phenylbenzoic acid is dissolved in toluene, thionyl chloride is added dropwise, acyl chlorides is made, wait react
Afterwards, extra thionyl chloride is extracted；
(3) Tertiary butyl hydrazine hydrochloride is added in sodium hydrate aqueous solution according to molar ratio 1:1, is then dripped at 3~4 DEG C
Add 2- methyl -3- Phenylbenzoyl chloride and sodium hydrate aqueous solution, drips rear insulation reaction and obtain chemical combination shown in structure formula (I)
Object.
In above-mentioned steps (2), 50~90 DEG C are warming up to, thionyl chloride is added dropwise.
In above-mentioned steps (3), insulation reaction after 2- methyl -3- Phenylbenzoyl chloride and sodium hydrate aqueous solution is dripped,
Then heating dissolves all solids, and 1~3 M salt acid elution is added into organic layer, static, and white solid is precipitated, filters,
It is recrystallized to give this product.
Compound N-(2- methyl -3- Phenylbenzoyl)-N '-tertiary butyl hydrazine or N '-(2- methyl -3- phenyl benzoyl
Base)-N- tertiary butyl hydrazine, molecular formula are as follows: C18H22N2O, white solid, melting range: 156-159 DEG C, being slightly soluble in water, be soluble in ethyl alcohol,
Methylene chloride, the organic solvents such as ethyl acetate.The compound is compared with existing tebufenozide intermediate N tert-butyl hydrazine derivative
Have many advantages, such as that mobility is small, desinsection effective time is long, high-efficient, small toxicity, environmental-friendly, synthesis technology is simple, yield is high.
Specific embodiment
1 compound 2(2- methyl -3- Phenylbenzoic acid of embodiment) preparation
By 40 g CrO3It pours into the volumetric flask for filling 120 mL water, adds the dense H of 34.5 mL2SO4, shake up, then dilute with water
It releases to 150 mL, matches to obtain Jones reagent；30g 2- methyl-3-phenyl benzil alcohol, 32mL are separately added into three-necked flask
90 mL Jones reagents are added dropwise in water, 200 mL acetone, ice-water bath, and control reaction temperature is 25 DEG C, react 6 h, use thin layer
Chromatogram tracking reaction, methylene chloride disappear to substrate point as solvent and aldehyde point disappear, stop reaction, reaction needs 6 h.
Decompression removal acetone, has a large amount of precipitatings to generate, filters, and filter cake is washed with water to white, dry 30 g yield 99% of crude product, will
Crude product is dissolved in ethyl alcohol (amount of ethyl alcohol be product quality 2 times), is heated 60 DEG C, is all dissolved, filtering, by filtrate electronic
It is cooled to -10 DEG C under stirring, then filters crystal, dry 28g, micro melting point measures its melting range: 151-153 DEG C.
2 compound 3(2- methyl -3- Phenylbenzoyl chloride of embodiment) synthesis
5 g compounds 2 are added in three-necked flask, 1-2 drop DMF is instilled, adds 10 mL toluene, load onto tail gas absorption
Device is warming up to 80 DEG C, then 10 mL SOCl are added dropwise2, after dripping, continue 1 h of isothermal reaction, be cooled to room temperature, then remove
Extra SOCl2 , product Compound 3 is obtained, does not purify and is directly used in lower step synthesis.
3 compound 4(N- tert-butyl-N ' of embodiment-(2- methyl -3- phenyl benzoyl) hydrazine) synthesis
3.9g Tertiary butyl hydrazine hydrochloride and 40 mL methylene chloride are weighed, is added in four-hole boiling flask, under nitrogen protection, 0 DEG C
0.3 M sodium hydrate aqueous solution, 100 mL is added dropwise, after being added dropwise, then compound 3 and 0.3 M sodium hydroxide are added dropwise simultaneously
100 mL of aqueous solution keeps the dropwise addition of the two to synchronously complete, and at 4-5 DEG C, thin-layer chromatography tracking is anti-for entire reaction temperature control
Answer, solvent: methylene chloride: ethyl acetate (2:1) after 1.5 h, is warming up to 30 DEG C, keeps all solids in reaction system molten
Solution, then static layering, separates oil reservoir, and oil reservoir is stood after being washed twice with 15 mL 2M hydrochloric acid, existing a large amount of white solid analysis
Out, it filters, is dried to obtain 5.5g product, melting range: 186-189 DEG C.
Claims (5)
1. structure formula (I) compound represented,
。
2. the preparation method of compound shown in claim 1, it is characterised in that the following steps are included:
(1) 2- methyl -3- Phenylbenzoic acid is made in 2- methyl-3-phenyl benzil alcohol Jones reagent oxidation, and with ethyl alcohol weight
Crystallization；
(2) synthesized 2- methyl -3- Phenylbenzoic acid is dissolved in toluene, thionyl chloride is added dropwise, acyl chlorides is made, wait react
Afterwards, extra thionyl chloride is extracted；
(3) Tertiary butyl hydrazine hydrochloride is added in sodium hydrate aqueous solution according to molar ratio 1:1, is then dripped at 3~4 DEG C
Add 2- methyl -3- Phenylbenzoyl chloride and sodium hydrate aqueous solution, drips rear insulation reaction and obtain chemical combination shown in structure formula (I)
Object.
3. preparation method according to claim 2, it is characterised in that: in step (2), be warming up to 50~90 DEG C, chlorine is added dropwise
Change sulfoxide.
4. preparation method according to claim 2, it is characterised in that: in step (3), drip 2- methyl -3- phenyl benzene
Insulation reaction after formyl chloride and sodium hydrate aqueous solution, then heating dissolves all solids, and 1~3 is added into organic layer
M salt acid elution, it is static, white solid is precipitated, filters, is recrystallized to give this product.
5. application of the compound shown in structure formula (I) as pesticide intermediate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810922680.0A CN108947866A (en) | 2018-08-11 | 2018-08-11 | N-(2- methyl -3- Phenylbenzoyl)-N '-tertiary butyl hydrazine and its synthetic method |
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| CN201810922680.0A CN108947866A (en) | 2018-08-11 | 2018-08-11 | N-(2- methyl -3- Phenylbenzoyl)-N '-tertiary butyl hydrazine and its synthetic method |
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| CN201810922680.0A Pending CN108947866A (en) | 2018-08-11 | 2018-08-11 | N-(2- methyl -3- Phenylbenzoyl)-N '-tertiary butyl hydrazine and its synthetic method |
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Citations (7)
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|---|---|---|---|---|
| CN1248576A (en) * | 1998-08-27 | 2000-03-29 | 罗姆和哈斯公司 | Process for preparing substituted hydrazide by using carboxylic acid |
| CN101591308A (en) * | 2009-06-26 | 2009-12-02 | 南开大学 | A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use |
| CN102040541A (en) * | 2009-10-20 | 2011-05-04 | 赵静 | Method for synthesizing N-(3-methoxy-2-methyl benzene formoxyl)-N-tertiary butyl hydrazine |
| CN102633746A (en) * | 2012-04-05 | 2012-08-15 | 南开大学 | Di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole and preparation method and application of di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole |
| CN102863355A (en) * | 2012-09-24 | 2013-01-09 | 浙江禾田化工有限公司 | Purifying method of N-(3-methoxy-2-methyl benzoyl)-N'-tert-butylhydrazine |
| CN104803879A (en) * | 2015-03-27 | 2015-07-29 | 江苏长青农化南通有限公司 | Preparation technology of methoxyfenozide |
| CN106632099A (en) * | 2016-12-17 | 2017-05-10 | 长江大学 | Azophenylene-1-bishydrazide carboxylate compound and bactericidal composition comprising compound |
-
2018
- 2018-08-11 CN CN201810922680.0A patent/CN108947866A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248576A (en) * | 1998-08-27 | 2000-03-29 | 罗姆和哈斯公司 | Process for preparing substituted hydrazide by using carboxylic acid |
| CN101591308A (en) * | 2009-06-26 | 2009-12-02 | 南开大学 | A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use |
| CN102040541A (en) * | 2009-10-20 | 2011-05-04 | 赵静 | Method for synthesizing N-(3-methoxy-2-methyl benzene formoxyl)-N-tertiary butyl hydrazine |
| CN102633746A (en) * | 2012-04-05 | 2012-08-15 | 南开大学 | Di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole and preparation method and application of di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole |
| CN102863355A (en) * | 2012-09-24 | 2013-01-09 | 浙江禾田化工有限公司 | Purifying method of N-(3-methoxy-2-methyl benzoyl)-N'-tert-butylhydrazine |
| CN104803879A (en) * | 2015-03-27 | 2015-07-29 | 江苏长青农化南通有限公司 | Preparation technology of methoxyfenozide |
| CN106632099A (en) * | 2016-12-17 | 2017-05-10 | 长江大学 | Azophenylene-1-bishydrazide carboxylate compound and bactericidal composition comprising compound |
Non-Patent Citations (2)
| Title |
|---|
| SATOSHI UENO等: "[4+2] Cycloaddition of o-Xylylenes with Imines Using Palladium Catalyst", 《J. AM. CHEM》 * |
| 邵敬华等: "甲氧虫酰肼的合成", 《现代农药》 * |
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Application publication date: 20181207 |