CN109776331A - A kind of preparation method of 3- methoxyl group -4- Iodoaniline - Google Patents
A kind of preparation method of 3- methoxyl group -4- Iodoaniline Download PDFInfo
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- CN109776331A CN109776331A CN201910259003.XA CN201910259003A CN109776331A CN 109776331 A CN109776331 A CN 109776331A CN 201910259003 A CN201910259003 A CN 201910259003A CN 109776331 A CN109776331 A CN 109776331A
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- methoxyl group
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Abstract
The present invention relates to the preparation methods of 3- methoxyl group -4- Iodoaniline.It is raw material that the present invention, which chooses 2- methoxyl group -4- nitroaniline cheap and easy to get, and diazo-reaction occurs in acid condition, using the zinc and hydrochloric acid generation reduction reaction after activation, obtains target product 3- methoxyl group -4- Iodoaniline.Processing route of the invention is simple, and raw material is cheap and easy to get, and operation is easy, when being added without phase transfer catalyst, by mild reaction condition, the products collection efficiency that two-step reaction obtains is relatively high and experimentation in the three wastes that generate it is few.
Description
Technical field
The present invention relates to compound synthesis fields, and in particular to the preparation method of 3- methoxyl group -4- Iodoaniline.
Background technique
It is few that the country is faced with the type of organic intermediate containing iodine, the dissatisfactory problem of yield, while by raw material and technique shadow
It rings, preparation method is not green enough, with acid solution, the generation of exhaust gas.Wherein, 3- methoxyl group -4- Iodoaniline be used as containing iodine it is organic in
Mesosome, synthetic method are rarely reported, and techniqueflow is not complete, and face that yield is low, quantity of three wastes is big, the problems such as at high cost.
Summary of the invention
The purpose of the present invention is deficiencies to solve above-mentioned technical problem, provide a kind of low cost and environmentally protective system
Preparation Method.Processing route of the invention is simple, and raw material is cheap and easy to get, simple process, when being added without phase transfer catalyst,
By mild reaction condition, the yield that two-step reaction obtains it is relatively high and generate the three wastes it is few.And reaction temperature compares
Mildly, the creative preparation method for having filled up the 3- methoxyl group -4- Iodoaniline of organic intermediate containing iodine.
The invention reside in the diazotising occurred in preparation process and reduction reactions.First in acid condition, with cheap easy
2- methoxyl group -4- nitroaniline be raw material, by raw material, it, which is dissolved in dilute hydrochloric acid, is acidified, after acidification with sodium nitrite into
Row diazo-reaction generates diazonium salt, after reacting a period of time, then liquor kalii iodide is added into diazo liquid, generates intermediate product
The iodo- 2- methoxyl group -4- nitrobenzene of 1-, restores it with zinc and hydrochloric acid, obtains target product 3- methoxyl group -4- Iodoaniline.
To achieve the above object, the method for the present invention includes the following steps:
(1) synthesis of the iodo- 2- methoxyl group -4- nitrobenzene of 1-.
2- methoxyl group -4- nitroaniline is added in the hydrochloric acid for being dissolved into 20.0% in there-necked flask, magnetic agitation 20-
Reaction solution is cooled to 0 DEG C hereinafter, slowly dripping in low-temp reaction bath by 30min, the stopping when reaction system is stirred to canescence
Add sodium nitrite solution, diazo-reaction occurs；It is tested with potassium iodide starch test paper, stops that sodium nitrite is added dropwise when blue,
Obtain diazotising liquid；Liquor kalii iodide is slowly dropped in diazotising liquid under low temperature bath, 30min is reacted, up to no nitrogen emits
Out, stop reaction；Obtained reaction solution is quenched by sodium bicarbonate solution, salt is washed, and reaction solution is extracted with ethyl acetate, remove
Water layer obtains the iodo- 2- methoxyl group -4- nitrobenzene of peony intermediate product 1- after obtained organic phase vacuum distillation.
(2) synthesis of 3- methoxyl group -4- Iodoaniline.
The iodo- 2- methoxy -4- nitrobenzene of 1- is added in bottle with two necks, 95% ethyl alcohol is added in magnetic agitation at room temperature；Stirring
After 30min, pretreated metallic zinc, hydrochloric acid are successively added into bottle with two necks, and reduction reaction occurs；After stirring 24-72h, use
Ethyl acetate extraction, salt are washed, and remove water layer, organic phase is evaporated under reduced pressure, dark red solid product 3- methoxyl group -4- iodobenzene is obtained
Amine.
It is supplied in the method for the present invention without heat source, temperature of reaction system is no more than 0 DEG C.
Pretreated metallic zinc described in the method for the present invention step (2) is to activate zinc in dilute hydrochloric acid, is located in advance
Zinc after reason.
Concentration of hydrochloric acid is 20% in the method for the present invention, and sodium nitrite solution concentration is 6%.
Beneficial effect of the present invention also resides in: removal of impurity is high during the experiment, first carries out in diazo-reaction generation
Between the iodo- 2- methoxyl group -4- nitrobenzene of product 1-, finally carry out hydrogenating reduction generate target product 3- methoxyl group -4- Iodoaniline.
The three wastes of generation are few, and used reactant low toxicity or nontoxic common substance are tested safer and reaction temperature and compared
Mildly, while efficiently it solves the problems, such as that China's type of organic intermediate containing iodine is few, is the neck such as medicine, pesticide, plastics, dyestuff
The development in domain provides new possibility.
Detailed description of the invention
Fig. 1 is the synthetic line figure of step S1 in the embodiment of the present invention.
Fig. 2 is the synthetic line figure of step S2 in the embodiment of the present invention.
Fig. 3 is the whole synthetic line figure of the embodiment of the present invention.
Specific embodiment
In order to which objects and advantages of the present invention are more clearly understood, the present invention is carried out with reference to embodiments further
It is described in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit this hair
It is bright.
The embodiment of the invention provides a kind of synthetic methods of 3- methoxyl group -4- Iodoaniline, include the following steps:
The synthesis of the iodo- 2- methoxyl group -4- nitrobenzene of S1,1-.
1.7g(0.01mol) 2- methoxyl group -4- nitroaniline is added in the there-necked flask of 100ml and is dissolved into 8ml's
In 20.0% hydrochloric acid, magnetic agitation is opened, reacts 20-30min, is started after reaction system is stirred to canescence subsequent anti-
It answers, after reaction solution is cooled to 0 DEG C hereinafter, temperature is down to 0 DEG C or less in low-temp reaction bath, is slowly added dropwise configured good 6%
Sodium nitrite solution (be added dropwise during control temperature of reaction system be no more than 0 DEG C, prevent the excessively high production for leading to by-product of temperature
It is raw)；It when sodium nitrite solution completion of dropwise addition, is tested with potassium iodide starch test paper, blue is reaction end, obtains diazotising liquid.
Liquor kalii iodide is slowly dropped in diazotising liquid under low temperature bath, has bubble to emerge during being added dropwise and generates a large amount of nitrogen
Gas reacts 30min after being added dropwise, and up to no nitrogen is emerged, stopping is reacted.Obtained reaction solution is passed through into sodium bicarbonate solution
Be quenched, salt is washed, and reaction solution is extracted with ethyl acetate, and removes water layer, after the vacuum distillation of obtained organic phase produce among peony
The iodo- 2- methoxyl group -4- nitrobenzene 2.14g of object 1-, yield 85.16%.
The synthesis of S2,3- methoxyl group -4- Iodoaniline.
The iodo- 2- methoxy -4- nitrobenzene of the 1- of 1.0g (3.58mmol) is added in the bottle with two necks of 50ml, magnetic force is opened
95% ethyl alcohol of 15ml is added in stirring at room temperature, stirs 30min；Suitable zinc granule is added in dilute hydrochloric acid and is activated；To bottle with two necks
In sequentially add 0.8(12mmol) activation after zinc granule, 10ml20% hydrochloric acid solution, be stirred to react 72h at room temperature；Reaction knot
Shu Hou stops reaction, obtained reaction solution is extracted with ethyl acetate, after salt is washed, and removes water layer, and obtained organic phase decompression is steamed
After evaporating, dark red solid product 3- methoxyl group -4- Iodoaniline 2.18g, yield 81.23% are obtained.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, it can also make several improvements and retouch, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (4)
1. a kind of preparation method of 3- methoxyl group -4- Iodoaniline, it is characterised in that under acid condition, with 2- methoxyl group -4- nitro
Aniline is raw material, synthesizes the iodo- 2- methoxyl group -4- nitrobenzene of 1-；It is characterized in that the diazo-reaction occurred in preparation process and
Reduction reaction；
It is characterized by comprising following steps:
(1) synthesis of the iodo- 2- methoxyl group -4- nitrobenzene of 1-；2- methoxyl group -4- nitroaniline is added in there-necked flask and is dissolved into
In 20.0% hydrochloric acid, magnetic agitation 20-30min starts subsequent reactions after reaction system is stirred to canescence, by reaction solution
0 DEG C is cooled to hereinafter, sodium nitrite solution is slowly added dropwise in low-temp reaction bath, and diazo-reaction occurs；Use potassium iodide and starch
Test paper test stops that sodium nitrite is added dropwise when blue, obtains diazotising liquid；Liquor kalii iodide is slowly dropped under low temperature bath
After in diazotising liquid, reaction 30min is emerged up to no nitrogen, stops reaction；Obtained reaction solution is passed through into sodium bicarbonate solution
Be quenched, salt is washed, and reaction solution is extracted with ethyl acetate, and removes water layer, after the vacuum distillation of obtained organic phase produce among peony
The iodo- 2- methoxyl group -4- nitrobenzene of object 1-；
(2) synthesis of 3- methoxyl group -4- Iodoaniline；The iodo- 2- methoxy -4- nitrobenzene of 1- is added in bottle with two necks, magnetic agitation,
95% ethyl alcohol is added at room temperature；After stirring 30min, pretreated metallic zinc, hydrochloric acid are successively added into bottle with two necks, are occurred also
Original reaction；It after stirring 24-72h, is extracted with ethyl acetate, salt is washed, removes water layer, organic phase is evaporated under reduced pressure, kermesinus is obtained
Solid product 3- methoxyl group -4- Iodoaniline.
2. a kind of preparation method of 3- methoxyl group -4- Iodoaniline according to claim 1, it is characterised in that in the method
No heat source supply, temperature of reaction system are no more than 0 DEG C.
3. a kind of preparation method of 3- methoxyl group -4- Iodoaniline according to claim 1, it is characterised in that the method step
Suddenly pretreated metallic zinc described in (2) is to activate zinc in dilute hydrochloric acid, carries out pretreated zinc.
4. a kind of preparation method of 3- methoxyl group -4- Iodoaniline according to claim 1, it is characterised in that in the method
Concentration of hydrochloric acid is 20%, and sodium nitrite solution concentration is 6%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0180870A2 (en) * | 1984-11-06 | 1986-05-14 | Hoechst Aktiengesellschaft | Preparation process of aqueous, highly concentrated pressed cakes of solid materials |
| CN102838556A (en) * | 2012-09-25 | 2012-12-26 | 郑州大学 | Synthesis method of 2-(2-methoxy-4-nitrophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazole monosodium salt |
| US20140194406A1 (en) * | 2011-07-28 | 2014-07-10 | Nerviano Medical Sciences S.R.L. | Alkynyl substituted pyrimidinyl-pyrroles active as kinases inhibitors |
| CN105418526A (en) * | 2015-11-09 | 2016-03-23 | 杭州伽玛生物科技有限公司 | Compound with mono-sulfophenyl tetrazole structure and application of compound with mono-sulfophenyl tetrazole structure |
| CN107057402A (en) * | 2017-06-15 | 2017-08-18 | 杭州荣彩实业有限公司 | A kind of red RRR of hybrid pigment |
-
2019
- 2019-04-02 CN CN201910259003.XA patent/CN109776331A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0180870A2 (en) * | 1984-11-06 | 1986-05-14 | Hoechst Aktiengesellschaft | Preparation process of aqueous, highly concentrated pressed cakes of solid materials |
| US20140194406A1 (en) * | 2011-07-28 | 2014-07-10 | Nerviano Medical Sciences S.R.L. | Alkynyl substituted pyrimidinyl-pyrroles active as kinases inhibitors |
| CN102838556A (en) * | 2012-09-25 | 2012-12-26 | 郑州大学 | Synthesis method of 2-(2-methoxy-4-nitrophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazole monosodium salt |
| CN105418526A (en) * | 2015-11-09 | 2016-03-23 | 杭州伽玛生物科技有限公司 | Compound with mono-sulfophenyl tetrazole structure and application of compound with mono-sulfophenyl tetrazole structure |
| CN107057402A (en) * | 2017-06-15 | 2017-08-18 | 杭州荣彩实业有限公司 | A kind of red RRR of hybrid pigment |
Non-Patent Citations (1)
| Title |
|---|
| AKIYOSHI NUMADATE等: "Development of 2-Thioxoquinazoline-4-one Derivatives as Dual and Selective Inhibitors of Dynamin-Related Protein 1 (Drp1) and Puromycin-Sensitive Aminopeptidase (PSA)", 《CHEM. PHARM. BULL.》 * |
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Application publication date: 20190521 |