CN105669357B - A kind of green preparation process of 1,4- diiodo-benzenes - Google Patents
A kind of green preparation process of 1,4- diiodo-benzenes Download PDFInfo
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- CN105669357B CN105669357B CN201610129881.6A CN201610129881A CN105669357B CN 105669357 B CN105669357 B CN 105669357B CN 201610129881 A CN201610129881 A CN 201610129881A CN 105669357 B CN105669357 B CN 105669357B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
Abstract
The present invention relates to a kind of green preparation process of Isosorbide-5-Nitrae diiodo-benzene, this method includes：Iodine and aniline are subjected to electrophilic substitution reaction in the solution of weak alkaline medium, separation it is dry paraiodoaniline crude product；Diazo-reaction is occurred into for paraiodoaniline crude product and sodium nitrite solution and concentrated acid, is made diazol, extra sodium nitrite in removing system；Chloroform and liquor kalii iodide are added in into reaction system, after being kept for 5~10 DEG C react 3~6 hours, is slowly increased to room temperature, the reaction was continued 2~6 hours, isolates and purifies to obtain Isosorbide-5-Nitrae diiodo-benzene from reaction product.The invention has the advantages that and advantageous effect：Product purity is high, significantly reduces production cost；It realizes the comprehensive utilization of potassium iodide waste liquid resource, reduces production cost；Simplify opertions engineering, improve the yield of product.
Description
Technical field
The present invention relates to a kind of green preparation process of 1,4- diiodo-benzenes.
Background technology
Isosorbide-5-Nitrae-diiodo-benzene is a kind of important organic intermediate, and a variety of substitution functional groups of synthesis are reacted with different activities group
Compound, in fields extensive applications such as medicine, pesticide and materials, synthesis is with applying great researching value.
There are many synthetic methods of Isosorbide-5-Nitrae-diiodo-benzene, and the diazotising iodide process of wherein arylamine is relatively conventional method.This
Class method is broadly divided into following several.
Para-phenylene diamine dihydrochloride diazotising, then reacted with potassium iodide into line replacement, the amino of diphenylamines is replaced by iodine, obtains
1,4- diiodo-benzenes.Since raw material p-phenylenediamine is by diazotising, diazotising yield are relatively low twice；In addition, 4- chlorosulfonylations in product
The content of benzene and benzene iodide is very high, it is difficult to detach.
In order to simplify reaction step, chemist uses paraiodoaniline diazotising, then is reacted with potassium iodide into line replacement,
Obtain product 1,4- diiodo-benzenes.Due to paraiodoaniline source rareness, not easy to maintain and higher price, it is difficult to scale in the industry
Using.
At present, the usual aniline of producing of Isosorbide-5-Nitrae-diiodo-benzene carries out phenyl ring parental materials iodine in alkalescent sodium bicarbonate medium
Change, passing through sodium nitrite and acetic acid as diazo reagent, cuprous iodide and hydroiodic acid are as displacer reagent.Due to acetic acid
Solidification point is 16.6 DEG C, and when low temperature diazotising, which easily solidifies, causes to react insufficient.In addition, the price phase of cuprous iodide and hydroiodic acid
To higher, and the dosage of hydroiodic acid is big so that reaction cost is higher.
Invention content
The purpose of the present invention is deficiencies to solve above-mentioned technical problem, provide a kind of low cost and environmentally protective 1,
The preparation method of 4- diiodo-benzenes, this method raw material are easy to get, and yield is high, is adapted to industrial-scale production.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of green of 1,4- diiodo-benzenes prepares work
Skill, this method include：
(1) iodine and aniline are subjected to electrophilic substitution reaction in the solution of weak alkaline medium, separation is dry to iodine
Aniline crude product；Liquid is the liquor kalii iodide of reaction generation, is directly used in subsequent iodization reaction；
(2) diazo-reaction is occurred into for paraiodoaniline crude product and sodium nitrite solution and concentrated acid, diazol is made, removed
Extra sodium nitrite in system；
(3) chloroform and liquor kalii iodide are added in into reaction system, after being kept for -5~-10 DEG C react 3~6 hours, slowly
It is warmed to room temperature, the reaction was continued 2~6 hours, isolates and purifies to obtain Isosorbide-5-Nitrae-diiodo-benzene from reaction product.
By said program, the weak alkaline medium is the aqueous solution of saleratus.
By said program, the concentration of aqueous solution of saleratus is 5%~20% (w/w).
By said program, the molar ratio of aniline and iodine described in step 1) is 1：1.0~1.1, reaction temperature 5
~10 DEG C, 3~8 hours reaction time.
By said program, the feed postition of the iodine is is added portionwise after pulverizing.
By said program, the concentrated acid described in step 2) is concentrated hydrochloric acid or the concentrated sulfuric acid.
By said program, the molar ratio of concentrated acid and paraiodoaniline described in step 2) is 5~20：1.
By said program, the molar ratio of sodium nitrite and paraiodoaniline described in step 2) is 1.05~1.2：1, it is described
The reaction temperature of diazo-reaction is -10~-5 DEG C, 3~6 hours reaction time.
By said program, for the feed postition of sodium nitrite to be slowly added dropwise, time for adding is 15~120 minutes.
By said program, the liquor kalii iodide is the liquor kalii iodide recycled.
Compared to existing material and technology, the invention has the advantages that and advantageous effect：
(1) iodine raw material availability is close to 100%, product purity height under optimal conditions, significantly reduces production cost；
(2) sodium bicarbonate, coproduction liquor kalii iodide are substituted using saleratus in the course of iodization of aniline.Reaction generation
Liquor kalii iodide is directly used in subsequent reactions step generation product Isosorbide-5-Nitrae-diiodo-benzene, is significantly reduced reaction without any processing
The generation of waste liquid in pilot process realizes the comprehensive utilization of potassium iodide waste liquid resource, reduces production cost；
(3) intermediate of each step generation is not required to the conjunction that purification just can be directly used for next step among reaction of the invention
Into simplifying opertions engineering, improve the yield of product.
Description of the drawings
Fig. 1 is the process flow chart of 1,4- diiodo-benzenes；
Fig. 2 is paraiodoaniline nucleus magnetic hydrogen spectrum spectrogram isolated in embodiment 1；
Fig. 3 is 1,4- diiodo-benzene nucleus magnetic hydrogen spectrum spectrograms isolated in embodiment 1.
Specific embodiment
Example is further described the synthesis of 1,4- diiodo-benzenes of the present invention in detail below.But institute of the present invention
It is required that protection domain be not limited to range involved by embodiment.
Embodiment 1
Such as Fig. 1 technological processes, 9.3g aniline (0.1mol) is added to the potassium bicarbonate solution of 110 milliliter 10% (w/w)
In, the iodine pulverized and aniline molar ratio 1.05 are then added portionwise in 15~20 minutes：1 26.7g iodines, 5~10 DEG C
Lower progress electrophilic substitution reaction 4 hours, is filtered after the completion of reaction.Liquid is the liquor kalii iodide of reaction generation, is directly used in
Iodization reacts.Paraiodoaniline 21.0g, yield 95.8% are obtained after solid drying.Such as Fig. 2, nuclear magnetic resonance spectroscopy analysis result：1HNMR (CDCl3,270MHz), 7.40 (d, 2H), 6.47 (d, 2H), 3.38 (s, 2H), nuclear magnetic resonance test are shown to be target production
Object.
21.0g paraiodoanilines (0.096mol) are added in 400 milliliters of water, controlling reaction temperature is less than 0 DEG C, adds in salt
Acid and paraiodoaniline molar ratio 11.1：It is ultra-fine white to be quickly cooled to -10 DEG C of precipitations for the concentrated hydrochloric acid of 1 90 milliliter 36.5% (w/w)
Color crystal, it is 1.15 that sodium nitrite is then added dropwise in 15~20 minutes with paraiodoaniline molar ratio：The nitrous of 1 20% (w/w)
33 milliliters of acid sodium solution reacts 4 hours at -10~-5 DEG C, and diazol is made, and extra sodium nitrite is quenched with a small amount of urea
It goes out；- 10 DEG C of reaction temperature is kept, 150 milliliters of chloroforms are added in into diazonium salt solution obtained above, adds the iodine of recycling
Change 110 milliliters of potassium solution, low-temp reaction 4 hours is slowly increased to room temperature, reacts 2 hours.Reaction mixture is layered, and organic phase is used
Sodium sulfite solution is washed till orange colour, then respectively with sodium carbonate liquor, water washing, anhydrous magnesium sulfate drying, vacuum distillation recycling
Chloroform obtains faint yellow solid 28.39g.Such as Fig. 3, nuclear magnetic resonance spectroscopy analysis result：1HNMR (CDCl3,270MHz), 7.45 (d,
2H), nuclear magnetic resonance test is shown to be target product.
The synthetic method is in terms of aniline, molar yield 80.0%, purity 93%, 127~133 DEG C of fusing point.
Embodiment 2
13.95g aniline (0.15mol) is added in the potassium bicarbonate solution of 110 milliliter 15% (w/w), then 15~
The iodine pulverized and aniline molar ratio 1.05 are added portionwise in 20 minutes：1 40.0g iodines carry out electrophilic take at 5~10 DEG C
Generation reaction 4 hours is filtered after the completion of reaction.Liquid is the liquor kalii iodide of reaction generation, the iodization reaction being directly used in.Gu
Paraiodoaniline crude product 31.1g, yield 94.5% are obtained after soma is dry, nuclear magnetic resonance test is shown to be target product.
31.1g paraiodoanilines (0.142mol) are added in 600 milliliters of water, controlling reaction temperature is less than 0 DEG C, adds in sulphur
Acid is 5.25 with paraiodoaniline molar ratio：It is ultra-fine to be quickly cooled to -10 DEG C of precipitations for the concentrated sulfuric acid of 1 40.5 milliliter 98% (w/w)
White crystal, it is 1.18 that sodium nitrite is then added dropwise in 15~20 minutes with paraiodoaniline molar ratio：The Asia of 1 20% (w/w)
50 milliliters of sodium nitrate solution reacts 4 hours at -10~-5 DEG C, and diazol is made, and extra sodium nitrite is quenched with a small amount of urea
It goes out；- 10 DEG C of reaction temperature is kept, 200 milliliters of chloroforms are added in into diazonium salt solution obtained above, adds the iodine of recycling
Change 110 milliliters of potassium solution, low-temp reaction 4 hours is slowly increased to room temperature, reacts 2 hours.Reaction mixture is layered, and organic phase is used
Sodium sulfite solution is washed till orange colour, then respectively with sodium carbonate liquor, water washing, anhydrous magnesium sulfate drying, vacuum distillation recycling
Chloroform obtains faint yellow solid 40.3g, and nuclear magnetic resonance test is shown to be target product.
The synthetic method is in terms of aniline, molar yield 75.0%, purity 92.1%, 126~133 DEG C of fusing point.
Embodiment 3
1.86kg aniline (20mol) is added in the potassium bicarbonate solution of 20 liter 10% (w/w), is then divided in 40 minutes
It criticizes and adds in the iodine pulverized and aniline molar ratio 1.05：1 5.34kg iodines (21mol) carry out parental materials at 5~10 DEG C
Reaction 6 hours is filtered after the completion of reaction.Liquid is the liquor kalii iodide of reaction generation, the iodization reaction being directly used in.Solid
Paraiodoaniline 4.07kg is obtained after drying, nuclear magnetic resonance test is shown to be target product, yield 93.0%.
4.07kg paraiodoanilines (18.6mol) are added in 80 liters of water, controlling reaction temperature is less than 0 DEG C, adds in hydrochloric acid
With paraiodoaniline molar ratio 12.8：The concentrated hydrochloric acid of 1 20 liter 36.5% (w/w) is quickly cooled to -10 DEG C and superfine white crystalline substance is precipitated
Body, it is 1.19 that sodium nitrite is then added dropwise in 60 minutes with paraiodoaniline molar ratio：The sodium nitrite solution of 1 20% (w/w)
It 6.6 liters, is reacted 5 hours at -10~-5 DEG C, diazol is made, extra sodium nitrite is quenched with a small amount of urea；Keep -10
DEG C reaction temperature, 30 liters of chloroforms are added in into diazonium salt solution obtained above, add 20 liters of the liquor kalii iodide of recycling,
Low-temp reaction 5 hours is slowly increased to room temperature, reacts 4 hours.Reaction mixture is layered, and organic phase is washed till with sodium sulfite solution
Orange colour, then sodium carbonate liquor, water washing are used respectively, anhydrous magnesium sulfate drying, vacuum distillation recycling chloroform obtains faint yellow solid
5.4kg, nuclear magnetic resonance test are shown to be target product.
The synthetic method is in terms of aniline, molar yield 74.2%, purity 90.5%, 125~133 DEG C of fusing point.
Embodiment 4
2.79kg aniline (30mol) is added in the potassium bicarbonate solution of 22 liter 15% (w/w), is then divided in 40 minutes
It criticizes and adds in the iodine pulverized and aniline molar ratio 1.06：1 8.1kg iodines (31.9mol) carry out electrophilic take at 5~10 DEG C
Generation reaction 6 hours is filtered after the completion of reaction.Liquid is the liquor kalii iodide of reaction generation, the iodization reaction being directly used in.Gu
Paraiodoaniline 6.07kg is obtained after soma is dry, nuclear magnetic resonance test is shown to be target product, yield 92.2%.
6.07kg paraiodoanilines (27.7mol) are added in 120 liters of water, controlling reaction temperature is less than 0 DEG C, adds in sulfuric acid
With paraiodoaniline molar ratio 13.3：The concentrated sulfuric acid of 1 20 liter 98% (w/w) is quickly cooled to -10 DEG C and superfine white crystalline substance is precipitated
Then sodium nitrite and paraiodoaniline molar ratio 1.2 is added dropwise in body in 60 minutes：The sodium nitrite solution 10 of 1 20% (w/w)
It rises, is reacted 5 hours at -10~-5 DEG C, diazol is made, extra sodium nitrite is quenched with a small amount of urea；Kept for -10 DEG C
Reaction temperature adds in 40 liters of chloroforms into diazonium salt solution obtained above, adds 22 liters of the liquor kalii iodide of recycling, low temperature
Reaction 5 hours is slowly increased to room temperature, reacts 4 hours.Reaction mixture is layered, and organic phase is washed till orange with sodium sulfite solution
Color, then sodium carbonate liquor, water washing are used respectively, anhydrous magnesium sulfate drying, vacuum distillation recycling chloroform obtains faint yellow solid
7.92kg, nuclear magnetic resonance test are shown to be target product.
The synthetic method is in terms of aniline, molar yield 71.6%, purity 89.5%, 125~133 DEG C of fusing point.
Claims (9)
1. a kind of preparation method of Isosorbide-5-Nitrae-diiodo-benzene, this method include：
(1) iodine and aniline are subjected to electrophilic substitution reaction in the solution of weak alkaline medium, separation it is dry paraiodoaniline
Crude product；The weak alkaline medium is the aqueous solution of saleratus；
(2) diazo-reaction is occurred into for paraiodoaniline crude product and sodium nitrite solution and concentrated acid, diazol is made, remove system
In extra sodium nitrite；
(3) chloroform and liquor kalii iodide are added in into reaction system, after being kept for -5~-10 DEG C react 3~6 hours, is slowly increased to
Room temperature, the reaction was continued 2~6 hours, isolates and purifies to obtain Isosorbide-5-Nitrae-diiodo-benzene from reaction product.
2. preparation method according to claim 1, it is characterised in that the concentration of aqueous solution of saleratus is 5%~20%
(w/w)。
3. preparation method according to claim 1, which is characterized in that the molar ratio of aniline and iodine described in step 1)
Example is 1：1.0~1.1, reaction temperature is 5~10 DEG C, 3~8 hours reaction time.
4. preparation method according to claim 1, it is characterised in that the feed postition of the iodine is after pulverizing points
It criticizes and adds in.
5. preparation method according to claim 1, which is characterized in that the concentrated acid described in step 2) is concentrated hydrochloric acid or dense sulphur
Acid.
6. preparation method according to claim 1, which is characterized in that mole of concentrated acid and paraiodoaniline described in step 2)
Ratio is 5~20：1.
7. preparation method according to claim 1, which is characterized in that sodium nitrite and paraiodoaniline described in step 2)
Molar ratio is 1.05~1.2：1, the reaction temperature of the diazo-reaction is -10~-5,3~6 hours DEG C reaction time.
8. preparation method according to claim 1, it is characterised in that the feed postition of sodium nitrite is added dropwise to be slowly added dropwise
Time is 15~120 minutes.
9. preparation method according to claim 1, it is characterised in that the liquor kalii iodide is the iodate recycled
Potassium solution.
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| CN106542958B (en) * | 2016-11-02 | 2020-04-03 | 贵州大学 | Preparation method of o-iodoaniline |
| CN113929668A (en) * | 2020-06-29 | 2022-01-14 | 江苏恒瑞医药股份有限公司 | Preparation method of bicyclic substituted pyrazolone azo derivative |
| CN113149835B (en) * | 2021-05-10 | 2023-05-02 | 广西师范大学 | Preparation method for rapidly generating alpha-ketoester by iodine-mediated oxidation of alpha-diazo ester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004069772A1 (en) * | 2003-02-10 | 2004-08-19 | Mitsubishi Gas Chemical Company, Inc. | Process for production of iodine compounds and process for production of high-purity 5-iodo-2-methylbenzoic acid |
| CN103467306A (en) * | 2013-08-21 | 2013-12-25 | 浙江工业大学 | Synthetic method of iodo-aniline derivatives |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004069772A1 (en) * | 2003-02-10 | 2004-08-19 | Mitsubishi Gas Chemical Company, Inc. | Process for production of iodine compounds and process for production of high-purity 5-iodo-2-methylbenzoic acid |
| CN103467306A (en) * | 2013-08-21 | 2013-12-25 | 浙江工业大学 | Synthetic method of iodo-aniline derivatives |
Non-Patent Citations (2)
| Title |
|---|
| Aprotic Diazotization of Aniline in the Presence of Iodine;LESTER FRIEDM等;《The Journal of Organic Chemistry》;19680430;第33卷(第4期);第1636-1638页 * |
| 对溴碘苯的合成研究;郭敬等;《化学与粘合》;20091231;第31卷(第6期);第17-18页 * |
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