CN105732333A - Preparation method of 1,2-dimethoxy-4-iodobenzene-3,5,6-trichlorobenzene - Google Patents
Preparation method of 1,2-dimethoxy-4-iodobenzene-3,5,6-trichlorobenzene Download PDFInfo
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- CN105732333A CN105732333A CN201610070818.XA CN201610070818A CN105732333A CN 105732333 A CN105732333 A CN 105732333A CN 201610070818 A CN201610070818 A CN 201610070818A CN 105732333 A CN105732333 A CN 105732333A
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- dimethoxy
- iodobenzene
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- chlorine
- chain fatty
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- PUCISUQLWLKKJH-UHFFFAOYSA-N COc(c(OC)c1)ccc1I Chemical compound COc(c(OC)c1)ccc1I PUCISUQLWLKKJH-UHFFFAOYSA-N 0.000 description 1
- HYGLYMBXAVQKMY-UHFFFAOYSA-N Cc(c(Cl)c(C)c(I)c1Cl)c1OC Chemical compound Cc(c(Cl)c(C)c(I)c1Cl)c1OC HYGLYMBXAVQKMY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 1,2-dimethoxy-4-iodobenzene-3,5,6-trichlorobenzene.The preparation method comprises the steps that chlorination is performed by taking 4-iodo-1,2-dimethoxybenzene as a raw material, taking low-carbon-chain fatty acid as solvent and taking hydrogen peroxide and hydrochloric acid or chlorine as a chlorine source, an excessive amount of free chlorine is destroyed by a hydrosulphite solution after reacting is completed, suction filtration, washing under thermal stirring, suction filtration and drying are performed, and then the product with the purity higher than 97% is obtained.TLC shows that the product is a single spot, and HPLC shows that the content is higher than 97%.According to the preparation method of 1,2-dimethoxy-4-iodobenzene-3,5,6-trichlorobenzene, column chromatography is avoided, operation is simple, and the yield and the purity are high.
Description
Technical field
The present invention relates to the preparation method of a kind of compound intermediate, especially one 1,2-dimethoxy
The preparation method of-4-iodobenzene-3,5,6-trichloro-benzene.
Background technology
1,2-dimethoxy-4 '-iodobenzene-3,5,6-trichloro-benzenes are a kind of important intermediate, current document report
Road is less, Chem.Res.Toxicol., Vol.12, No.8,1999 use chloroforms as solvent,
Hydrochloric acid and hydrogen peroxide, as chlorine source, use the disagreeableness chloroform of environment as solvent, react for heterogeneous body
System, it is high unfriendly to environment that employing column chromatography carries out isolated and purified cost, and yield low (36%).
Summary of the invention
The technical problem to be solved is to provide and a kind of can overcome above-mentioned prior art shortcoming
1,2-dimethoxy-4 '-iodobenzene-3,5,6-trichloro-benzene preparation method.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: a kind of 1,2-dimethoxy
Base-4-iodobenzene-3, the preparation method of 5,6-trichloro-benzenes, with 4-iodo-1,2-dimethoxy benzene be raw material,
With low carbon chain fatty acid as solvent, carry out chlorine as chloro for chlorine source using hydrogen peroxide and hydrochloric acid or chlorine
In generation, after having reacted, destroy the free chlorine of excess with bisulfite solution, through sucking filtration, thermal agitation
Washing, sucking filtration and be dried to obtain purity product more than 97%.
Specifically, by weight the 4-iodo-1 for 1:8～1:10,2-dimethoxy benzene and low carbon chain fat
Fat acid adds reaction vessel, drips hydrogen peroxide/hydrochloric acid or be passed through chlorine and enter at a temperature of 15～35 DEG C
Row chloro, HPLC monitoring reaction is complete, adds bisulfite solution and destroys the free chlorine of excess, filters
Obtain crude product, crude product adds weight ratio be the low carbon chain fatty acid of 1:1～1:5 and water post-heating extremely
50-60 DEG C is stirred 1-5 hour, is cooled to room temperature, and sucking filtration, water wash and is dried to obtain product.
Described low carbon chain fatty acid is one or several combinations in formic acid, acetic acid, propanoic acid.
Preferably, the weight ratio of described low carbon chain fatty acid and water is 1:5, and 50-60 DEG C is stirred 2 hours.
The invention has the beneficial effects as follows: yield is high (80%), it is to avoid column chromatography, the high (HPLC of product assay
Content is high, and more than 97%).
Accompanying drawing explanation
HPLC liquid phase figure (acetonitrile: water=90:10, the flow velocity 1ml/min of Fig. 1 product.Detection wavelength
230nm, chromatographic column: C18,4.6X250mm).
Detailed description of the invention
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings:
The present invention 1,2-dimethoxy-4 '-iodobenzene-3,5,6-trichloro-benzenes, its structure below figure institute
Show:
The synthesis equation of the present invention:
The 1 of the present invention, 2-dimethoxy-4 '-iodobenzene-3, the preparation method of 5,6-trichloro-benzenes, with 4-iodine
-1,2-dimethoxy benzene is raw material, with low carbon chain fatty acid as solvent, with hydrogen peroxide and hydrochloric acid or chlorine
Gas is that chlorine source carries out chloro as chloro, after having reacted, destroys the trip of excess with bisulfite solution
From chlorine, through sucking filtration, thermal agitation washing, sucking filtration be dried to obtain purity product more than 97%.
Specifically, by weight the 4-iodo-1 for 1:8～1:10,2-dimethoxy benzene and low carbon chain
Fatty acid adds reaction vessel, drips hydrogen peroxide/hydrochloric acid or be passed through chlorine at a temperature of 15～35 DEG C
Carrying out chloro, HPLC monitoring reaction is complete, adds sodium sulfite solution and destroys the free chlorine of excess,
It is filtrated to get crude product, adds after crude product adds the low carbon chain fatty acid and water that weight ratio is 1:1～1:5
Heat stirs 1-5 hour to 50-60 DEG C, is cooled to room temperature, and sucking filtration, water wash and is dried to obtain product.
TLC is single speckle.HPLC content is more than 97%.
Described low carbon chain fatty acid is one or several combinations in formic acid, acetic acid, propanoic acid.
Preferably, the weight ratio of described low carbon chain fatty acid and water is 1:5, and 50-60 DEG C is stirred 2 hours.
A kind of 1,2-dimethoxy-4 '-iodobenzene-3,5,6-trichloro-benzene preparation methoies are as follows:.
Embodiment 1
The 4-iodo-1,2-diformazan of 2.64g is added in the reaction bulb with the 100ml of device for absorbing tail gas
Epoxide benzene and the acetic acid of 26ml, be then sequentially added into 30ml concentrated hydrochloric acid, control reacting liquid temperature 15-20
Degree, is slowly added dropwise the 10ml hydrogen peroxide with the dilution of 5ml glacial acetic acid, drips complete, keeps 15-25 degree
Stirring and within 12 hours, be sampled HPLC monitoring, raw material is less than 1%, adds the saturated sulfurous acid of about 30ml
Filtering after hydrogen sodium solution, filter cake is transferred in 100ml reaction bulb, adds the acetic acid of 10ml and 30ml
Water, is warming up to 50-55 degree and stirs 1 hour, be down to room temperature sucking filtration, use little water drip washing, and TLC tests
For single speckle.Obtain 3.01g white solid, yield 82%., HPLC content is more than 97.8%.
Embodiment 2
The 4-iodo-1,2-diformazan of 1.32g is added in the reaction bulb with the 100ml of device for absorbing tail gas
Epoxide benzene and the formic acid of 6ml and 6ml propanoic acid, be then sequentially added into 15ml concentrated hydrochloric acid, control reactant liquor
Temperature 25-30 degree, is slowly added dropwise the 5ml hydrogen peroxide with the dilution of 2.5ml formic acid, drips complete, keeps
The stirring of 25-30 degree is sampled HPLC monitoring for 12 hours, and raw material is less than 1%, adds about 15ml saturated
Sodium sulfite solution after filter, filter cake is transferred in 100ml reaction bulb, add 5ml formic acid and
The water of 20ml, is warming up to 50-60 degree and stirs 5 hours, be down to room temperature sucking filtration, use little water drip washing,
TLC test is single speckle.Obtain 1.46g white solid, yield 80%.HPLC content is more than 98.1%.
Embodiment 3
The 4-iodo-1,2-diformazan of 5.28g is added in the reaction bulb with the 250ml of device for absorbing tail gas
Epoxide benzene and the acetic acid of 52ml, be then sequentially added into 60ml concentrated hydrochloric acid, control reacting liquid temperature 25-35
Degree, is slowly added dropwise the 20ml hydrogen peroxide with the dilution of 10ml propanoic acid, drips complete, keeps 25-35 degree to stir
Mixing 12 hours and be sampled HPLC monitoring, raw material is less than 1%, adds the saturated bisulfite of about 60ml
Filtering after sodium solution, filter cake is transferred in 250ml reaction bulb, adds the propanoic acid of 20ml and 100ml
Water, is warming up to 50-55 degree and stirs 3 hours, be down to room temperature sucking filtration, use little water drip washing, and TLC tests
For single speckle.Obtain 5.75g white solid, yield 80.5%.HPLC content is more than 97.9%.
Embodiment 4
The 4-iodo-1,2-diformazan of 2.11g is added in the reaction bulb with the 100ml of device for absorbing tail gas
Epoxide benzene and the acetic acid of 20ml, be slowly introducing chlorine, to HPLC monitoring raw material less than 1%, adds about
Filtering after the sodium sulfite solution that 24ml is saturated, filter cake is transferred in 100ml reaction bulb, adds 8ml
Acetic acid and the water of 20ml, be warming up to 50-55 degree and stir 1 hour, be down to room temperature sucking filtration, with a little
Water wash, TLC test is single speckle.Obtain 2.36g white solid, yield 80.5%., HPLC
Content is more than 97.8%.
In sum, present disclosure is not limited in the above embodiments, having in same area
The scholar of knowledge can propose other embodiment within technological guidance's thought of the present invention easily, but this
Within kind embodiment is included in the scope of the present invention.
Claims (4)
1. one kind 1,2-dimethoxy-4 '-iodobenzene-3, the preparation method of 5,6-trichloro-benzenes, its feature exists
In, with 4-iodo-1,2-dimethoxy benzene is raw material, with low carbon chain fatty acid as solvent, with hydrogen peroxide and
Hydrochloric acid or chlorine are that chlorine source carries out chloro as chloro, after having reacted, break with bisulfite solution
The free chlorine of bad excess, through sucking filtration, thermal agitation washing, sucking filtration be dried to obtain purity more than 97%
Product.
The preparation of 1,2-dimethoxy-4 ' the most according to claim 1-iodobenzene-3,5,6-trichloro-benzene
Method, it is characterised in that by weight the 4-iodo-1 for 1:8～1:10,2-dimethoxy benzene and low-carbon (LC)
Chain fatty acid adds reaction vessel, drips hydrogen peroxide/hydrochloric acid or be passed through chlorine at a temperature of 15～35 DEG C
Gas carries out chloro, and HPLC monitoring reaction is complete, adds bisulfite solution and destroys the free chlorine of excess,
It is filtrated to get crude product, crude product adds low carbon chain fatty acid and water post-heating that weight ratio is 1:1～1:5
Stirring 1-5 hour to 50-60 DEG C, be cooled to room temperature, sucking filtration, water wash and are dried to obtain product.
1,2-dimethoxy-4 ' the most according to claim 1 and 2-iodobenzene-3,5,6-trichloro-benzene
Preparation method, it is characterised in that described low carbon chain fatty acid is the one in formic acid, acetic acid, propanoic acid
Or several combinations.
The system of 1,2-dimethoxy-4 ' the most according to claim 2-iodobenzene-3,5,6-trichloro-benzene
Preparation Method, it is characterised in that the weight ratio of described low carbon chain fatty acid and water is 1:5,50-60 DEG C
Stir 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610070818.XA CN105732333B (en) | 2016-02-02 | 2016-02-02 | A kind of preparation method of the trichloro-benzene of 1,2 dimethoxy, 4 iodobenzene 3,5,6 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610070818.XA CN105732333B (en) | 2016-02-02 | 2016-02-02 | A kind of preparation method of the trichloro-benzene of 1,2 dimethoxy, 4 iodobenzene 3,5,6 |
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| CN105732333A true CN105732333A (en) | 2016-07-06 |
| CN105732333B CN105732333B (en) | 2018-01-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113286783A (en) * | 2019-01-30 | 2021-08-20 | 住友化学株式会社 | Method for producing chlorobenzene compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161802A (en) * | 2006-10-12 | 2008-04-16 | 李建成 | Method for manufacturing polyglycerol compound (medium-carbon) fatty acid ester |
| CN102796018A (en) * | 2012-09-07 | 2012-11-28 | 濮阳天健生物科技有限公司 | Method for preparing D-valine by asymmetric transformation process |
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2016
- 2016-02-02 CN CN201610070818.XA patent/CN105732333B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161802A (en) * | 2006-10-12 | 2008-04-16 | 李建成 | Method for manufacturing polyglycerol compound (medium-carbon) fatty acid ester |
| CN102796018A (en) * | 2012-09-07 | 2012-11-28 | 濮阳天健生物科技有限公司 | Method for preparing D-valine by asymmetric transformation process |
Non-Patent Citations (2)
| Title |
|---|
| S.N.JOSHI,ET AL: "Synthesis of Sterically Hindered Polychlorinated Biphenyl Derivatives", 《SYNTHESIS》 * |
| STEPHEN C. WALLER ET AL: "2,2′,3,3′,6,6′-Hexachlorobiphenyl Hydroxylation by Active Site Mutants of Cytochrome P450 2B1 and 2B11", 《CHEM. RES. TOXICOL.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113286783A (en) * | 2019-01-30 | 2021-08-20 | 住友化学株式会社 | Method for producing chlorobenzene compound |
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