CN109438280A - A kind of preparation method of chloro amine - Google Patents
A kind of preparation method of chloro amine Download PDFInfo
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- CN109438280A CN109438280A CN201811502482.5A CN201811502482A CN109438280A CN 109438280 A CN109438280 A CN 109438280A CN 201811502482 A CN201811502482 A CN 201811502482A CN 109438280 A CN109438280 A CN 109438280A
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- chloro amine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention belongs to technical field of organic synthesis, and in particular to a kind of preparation method of chloro amine.The preparation method of chloro amine of the present invention, comprising the following steps: by hydroxylamine salt, water, acetone, be stirring evenly and then adding into sodium hydroxide solution, 1~2h is reacted at room temperature, it is added 1,3- dichloropropylene and phase transfer catalyst later, heating water bath and controlled at 60~90 DEG C of 5~10h of reaction, stratification later, oily phase is separated and collects, with extractant extraction oil phase 2~3 times, extract liquor is dry with anhydrous sodium sulfate, later removed under reduced pressure solvent to get.The preparation method of chloro amine of the invention, acetoxime first is made using hydroxylamine salt and acetone as raw material, then 1 is added, 3- dichloropropylene and phase transfer catalyst carry out reacting obtained chloro amine, chloro amine purity made from preparation method of the present invention is up to 99% or more, and yield is suitble to industrialized production up to 88% or more.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of preparation method of chloro amine.
Background technique
Chloro amine, that is, O-3- chloro-2-propene base azanol is a kind of insignificant pesticide and medicine intermediate, especially extensive
For synthesizing cyclohexene type herbicides, such as clethodim, tepraloxydim, cycloxydim, methoxyphenone, butroxydim, clefoxidim,
Such herbicide is ACCase inhibitor, is selective herbicide after a seed bud, for most of annual and perennial standing grain
Undergraduate course weeds have special efficacy.
The common method of existing synthesis chloro amine is to be passed through into the toluene solution of acetonitrile and dehydrated alcohol largely
Hydrogen chloride gas forms acetyl-hydroxamic acid ethyl ester, then using tetrabutylammonium bromide as phase transfer catalysis (PTC) in sodium hydroxide solution
Agent carries out resetting the obtained product of condensation with trans- 1,3- dichloropropylene.Due to using a large amount of hydrogen chloride gas in reaction process,
Pollution and corrosion condition are more serious, are unfavorable for industrialized production.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of chloro amine, ammonium chloride yield height and nothing that this method obtains
Pollution.
To achieve the above object, the technical scheme is that
A kind of preparation method of chloro amine, comprising the following steps:
By hydroxylamine salt, water, acetone, it is stirring evenly and then adding into sodium hydroxide solution, 1~2h is reacted at room temperature, is added later
1,3- dichloropropylene and phase transfer catalyst, heating water bath and controlled at 60~90 DEG C of 5~10h of reaction are stood point later
Layer, separates and collects oily phase, and with extractant extraction oil phase 2~3 times, extract liquor is dry with anhydrous sodium sulfate, later removed under reduced pressure
Solvent to get.
Further, the hydroxylamine salt and the molar ratio of the acetone are 0.5:1~1.1.
Further, the hydroxylamine salt and the molar ratio of 1, the 3- dichloropropylene are 0.5:1~1.5.
Further, the extractant is ethyl acetate.
Further, the hydroxylamine salt is hydroxyl sulfate or hydroxylamine hydrochloride.
Further, the hydroxylamine salt is hydroxyl sulfate.
Further, the phase transfer catalyst is tetrabutylammonium bromide, trioctylmethylammonium chloride, cetyl trimethyl bromine
Change ammonium, any one in triethyl benzyl ammonia chloride.
Further, the mass fraction of the sodium hydroxide solution is 10~30%.
Further, 1~2h of the reaction at room temperature obtains acetoxime.
Further, heating water bath and control reaction temperature be 70~80 DEG C.
First acetoxime, the system of acetoxime is made using hydroxylamine salt and acetone as raw material in the preparation method of chloro amine of the invention
It is not necessary that a large amount of hydrogen chloride gas is added during standby, pollution and corrosion condition are smaller；Then add 1,3- dichloropropylene and
Phase transfer catalyst carries out reacting obtained chloro amine, and since acetoxime is present in water phase, and 1,3- dichloropropylene is present in and has
In machine phase, the two phase objectionable intermingling, the chance of two kinds of molecular collisions is seldom, does not react, when there are phase transfer catalyst,
Water phase can be brought into organic phase or organic phase is brought into water phase by phase transfer catalyst makes acetoxime and 1,3- bis-
Chloropropene reacts and then chloro amine is made, and improves reaction rate and yield.The preparation method of chloro amine of the present invention, it is obtained
Chloro amine purity is up to 99% or more, and yield is suitble to industrialized production up to 88% or more.
Specific embodiment
Embodiment 1
The preparation method of the present embodiment chloro amine, comprising the following steps:
Hydroxyl sulfate, water, acetone are added in three-necked flask, is stirring evenly and then adding into the hydroxide that mass fraction is 10%
Sodium solution reacts 2h at room temperature, obtains acetoxime, and 1,3- dichloropropylene and phase transfer catalyst tetrabutyl phosphonium bromide are added later
Ammonium, heating water bath and controlled at 70 DEG C of reaction 8h, stratification, separates and collects oily phase, be extracted with ethyl acetate later
Oily phase 2 times, extract liquor is dry with anhydrous sodium sulfate, later removed under reduced pressure solvent to get；Mole of the hydroxyl sulfate and acetone
Than for 0.5:1；The hydroxyl sulfate and the molar ratio of 1,3- dichloropropylene are 0.5:1.
The yield of chloro amine made from the present embodiment is 90%, purity 99%.
Embodiment 2
The preparation method of the present embodiment chloro amine, comprising the following steps:
Hydroxyl sulfate, water, acetone are added in three-necked flask, is stirring evenly and then adding into the hydroxide that mass fraction is 20%
Sodium solution reacts 1h at room temperature, obtains acetoxime, and 1,3- dichloropropylene and phase transfer catalyst cetyl front three are added later
Base ammonium bromide, heating water bath and controlled at 90 DEG C of reaction 5h, stratification, separates and collects oily phase later, with acetic acid second
Ester extraction oil phase 3 times, extract liquor is dry with anhydrous sodium sulfate, later removed under reduced pressure solvent to get；The hydroxyl sulfate and acetone
Molar ratio be 0.5:1.1；The hydroxyl sulfate and the molar ratio of 1,3- dichloropropylene are 0.5:1.2.
The yield of chloro amine made from the present embodiment is 88%, purity 99.2%.
Embodiment 3
The preparation method of the present embodiment chloro amine, comprising the following steps:
Hydroxyl sulfate, water, acetone are added in three-necked flask, is stirring evenly and then adding into the hydroxide that mass fraction is 30%
Sodium solution reacts 1h at room temperature, obtains acetoxime, and 1,3- dichloropropylene and phase transfer catalyst trioctylphosphine chlorination are added later
Ammonium, heating water bath and controlled at 80 DEG C of reaction 7h, stratification, separates and collects oily phase, be extracted with ethyl acetate later
Oily phase 3 times, extract liquor is dry with anhydrous sodium sulfate, later removed under reduced pressure solvent to get；Mole of the hydroxyl sulfate and acetone
Than for 0.5:1.1；The hydroxyl sulfate and the molar ratio of 1,3- dichloropropylene are 0.5:1.5.
The yield of chloro amine made from the present embodiment is 89%, purity 99.3%.
Embodiment 4
The preparation method of the present embodiment chloro amine, comprising the following steps:
Hydroxyl sulfate, water, acetone are added in three-necked flask, is stirring evenly and then adding into the hydroxide that mass fraction is 30%
Sodium solution reacts 1h at room temperature, obtains acetoxime, and 1,3- dichloropropylene and phase transfer catalyst trioctylphosphine chlorination are added later
Ammonium, heating water bath and controlled at 60 DEG C of reaction 10h, stratification, separates and collects oily phase, be extracted with ethyl acetate later
Oily phase 3 times, extract liquor is dry with anhydrous sodium sulfate, later removed under reduced pressure solvent to get；Mole of the hydroxyl sulfate and acetone
Than for 0.5:1.1；The hydroxyl sulfate and the molar ratio of 1,3- dichloropropylene are 0.5:1.3.
The yield of chloro amine made from the present embodiment is 89%, purity 99%.
First acetoxime, the system of acetoxime is made using hydroxylamine salt and acetone as raw material in the preparation method of chloro amine of the invention
It is not necessary that a large amount of hydrogen chloride gas is added during standby, pollution and corrosion condition are smaller；Then add 1,3- dichloropropylene and
Phase transfer catalyst carries out reacting obtained chloro amine, and since acetoxime is present in water phase, and 1,3- dichloropropylene is present in and has
In machine phase, the two phase objectionable intermingling, the chance of two kinds of molecular collisions is seldom, does not react, when there are phase transfer catalyst,
Water phase can be brought into organic phase or organic phase is brought into water phase by phase transfer catalyst makes acetoxime and 1,3- bis-
Chloropropene reacts and then chloro amine is made.The preparation method of chloro amine of the present invention, chloro amine purity obtained up to 99% with
On, and yield is suitble to industrialized production up to 88% or more.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas
Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention
Within.
Claims (9)
1. a kind of preparation method of chloro amine, which comprises the following steps:
By hydroxylamine salt, water, acetone, it is stirring evenly and then adding into sodium hydroxide solution, 1~2h is reacted at room temperature, 1,3- is added later
Dichloropropylene and phase transfer catalyst, heating water bath and controlled at 60~90 DEG C of 5~10h of reaction, stratification later, point
Out and oily phase is collected, with extractant extraction oil phase 2~3 times, extract liquor is dry with anhydrous sodium sulfate, later removed under reduced pressure solvent,
To obtain the final product.
2. the preparation method of chloro amine according to claim 1, which is characterized in that the hydroxylamine salt is rubbed with the acetone
You are than being 0.5:1~1.1.
3. the preparation method of chloro amine according to claim 1, which is characterized in that the hydroxylamine salt and 1, the 3- dichloro
The molar ratio of propylene is 0.5:1~1.5.
4. the preparation method of chloro amine according to claim 1, which is characterized in that the extractant is ethyl acetate.
5. the preparation method of chloro amine according to claim 1, which is characterized in that the hydroxylamine salt is hydroxyl sulfate or salt
Sour azanol.
6. the preparation method of chloro amine according to claim 1, which is characterized in that the phase transfer catalyst is the tetrabutyl
Ammonium bromide, trioctylmethylammonium chloride, cetyl trimethylammonium bromide, any one in triethyl benzyl ammonia chloride.
7. the preparation method of chloro amine according to claim 1, which is characterized in that the quality of the sodium hydroxide solution point
Number is 10~30%.
8. the preparation method of chloro amine according to claim 1, which is characterized in that 1~2h of the reaction at room temperature is obtained
Acetoxime.
9. the preparation method of chloro amine according to claim 1, which is characterized in that heating water bath simultaneously controls reaction temperature and is
70~80 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498728A (en) * | 2019-09-06 | 2019-11-26 | 湖南莱万特化工有限公司 | Trans- 1,3- dichloropropylene and cis- 1,3- dichloropropylene compound and its process flow |
| CN112358416A (en) * | 2020-11-03 | 2021-02-12 | 北京科技大学 | Preparation method of trans-3-chloro-2-propenyl hydroxylamine |
| CN112500311A (en) * | 2020-12-02 | 2021-03-16 | 河南普美济华医药科技有限公司 | Preparation process of O-3-chloro-2-propenyl hydroxylamine free alkali |
| CN114105810A (en) * | 2021-12-07 | 2022-03-01 | 山东科加工业技术研究院有限公司 | Preparation method of chloramine |
-
2018
- 2018-12-10 CN CN201811502482.5A patent/CN109438280A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498728A (en) * | 2019-09-06 | 2019-11-26 | 湖南莱万特化工有限公司 | Trans- 1,3- dichloropropylene and cis- 1,3- dichloropropylene compound and its process flow |
| CN112358416A (en) * | 2020-11-03 | 2021-02-12 | 北京科技大学 | Preparation method of trans-3-chloro-2-propenyl hydroxylamine |
| CN112500311A (en) * | 2020-12-02 | 2021-03-16 | 河南普美济华医药科技有限公司 | Preparation process of O-3-chloro-2-propenyl hydroxylamine free alkali |
| CN112500311B (en) * | 2020-12-02 | 2023-03-24 | 河南普美济华医药科技有限公司 | Preparation process of O-3-chloro-2-propenyl hydroxylamine free alkali |
| CN114105810A (en) * | 2021-12-07 | 2022-03-01 | 山东科加工业技术研究院有限公司 | Preparation method of chloramine |
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Application publication date: 20190308 |