CN105669357A - Green preparation technique of 1,4-diiodo-benzene - Google Patents
Green preparation technique of 1,4-diiodo-benzene Download PDFInfo
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- CN105669357A CN105669357A CN201610129881.6A CN201610129881A CN105669357A CN 105669357 A CN105669357 A CN 105669357A CN 201610129881 A CN201610129881 A CN 201610129881A CN 105669357 A CN105669357 A CN 105669357A
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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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- 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 invention relates to a green preparation technique of 1,4-diiodo-benzene. The technique comprises the following steps: carrying out electrophilic substitution reaction on a simple substance iodine and aniline in a weakly alkaline medium solution, separating, and drying to obtain a paraiodoaniline crude product; carrying out diazo-reaction on the paraiodoaniline crude product and a sodium nitrate solution to prepare a diazonium salt, and removing excess sodium nitrate in the system; adding chloroform and a potassium iodide solution into the reaction system, reacting for 3-6 hours while keeping the temperature at -5 to -10 DEG C, slowly heating to room temperature, continuing reacting for 2-6 hours, and carrying out separation and purification on the reaction product to obtain the 1,4-diiodo-benzene. The technique has the advantage of high product purity, and obviously lowers the production cost. The technique implements comprehensive utilization of the potassium iodide waste solution resources, thereby lowering the production cost. The technique simplifies the operation engineering, and enhances the yield of the product.
Description
Technical field
The present invention relates to the green preparation process of a kind of 1,4-bis-iodine benzene.
Background technology
1,4-bis-iodine benzene is a kind of important organic intermediate, synthesizes multiple replacement functional compounds with different activities radical reaction, and in field extensive application such as medicine, agricultural chemicals and materials, its Synthesis and application has researching value.
The synthetic method of 1,4-bis-iodine benzene has multiple, and wherein the diazotization iodination of arylamine is comparatively common method. This kind of method is mainly divided into following several.
Para-phenylene diamine dihydrochloride diazotization, then carry out replacement(metathesis)reaction with potassiumiodide, the amino of pentanoic is replaced by iodine, obtains 1,4-bis-iodine benzene. Owing to raw material Ursol D is through twice diazotization, diazotization receipts rate is lower; In addition, in product, the content of 4-chlorine benzene iodide and benzene iodide is very high, it is difficult to separation.
In order to simplify reactions steps, chemist adopts paraiodoaniline diazotization, then carries out replacement(metathesis)reaction with potassiumiodide, obtains product 1,4-bis-iodine benzene. Owing to paraiodoaniline source is rare, not easily preservation and price are higher, it is difficult to mass-producing application in the industry.
At present, the usual aniline of producing of 1,4-bis-iodine benzene carries out phenyl ring electrophilic substitution iodate in weakly alkaline sodium bicarbonate medium, through Sodium Nitrite and acetic acid as diazo reagent, cuprous iodide and hydroiodic acid HI as displacer reagent. Owing to the zero pour of acetic acid is 16.6 DEG C, easily solidify during low temperature diazotization and cause reaction insufficient. In addition, the price of cuprous iodide and hydroiodic acid HI is relatively high, and the consumption of hydroiodic acid HI is big so that reaction cost is higher.
Summary of the invention
It is an object of the invention to the deficiency for solving the problems of the technologies described above, it provides the preparation method of the 1,4-bis-iodine benzene of a kind of low cost and environmental protection, the method raw material is easy to get, and product rate height, is adapted to commercial scale production.
The present invention solves the problems of the technologies described above the technical scheme adopted: the green preparation process of a kind of 1,4-bis-iodine benzene, and the method comprises:
(1) iodine and aniline are carried out electrophilic substitution reaction in the solution of weak alkaline medium, it is separated dry the thick product of paraiodoaniline; Liquid is the liquor kalii iodide that reaction generates, and is directly used in follow-up iodine replacement(metathesis)reaction;
(2) by thick for paraiodoaniline product and sodium nitrite solution and concentrated acid generation diazotization reaction, obtained diazonium salt, Sodium Nitrite unnecessary in removing system;
(3) adding chloroform and liquor kalii iodide in reaction system, keep-5～-10 DEG C of reactions after 3～6 hours, slowly rise to room temperature, continue reaction 2～6 hours, from reaction product, separation and purification obtains 1,4-bis-iodine benzene.
By such scheme, described weak alkaline medium is the aqueous solution of saleratus.
By such scheme, the concentration of aqueous solution of saleratus is 5%～20% (w/w).
By such scheme, step 1) described in aniline and the molar ratio of iodine be 1:1.0～1.1, temperature of reaction is 5～10 DEG C, 3～8 hours reaction times.
By such scheme, the feed postition of described iodine adds after pulverizing in batches.
By such scheme, step 2) described in concentrated acid be concentrated hydrochloric acid or the vitriol oil.
By such scheme, step 2) described in concentrated acid and the molar ratio of paraiodoaniline be 5～20:1.
By such scheme, step 2) described in Sodium Nitrite and the mol ratio of paraiodoaniline be 1.05～1.2:1, the temperature of reaction of described diazotization reaction is-10～-5 DEG C, 3～6 hours reaction times.
By such scheme, the feed postition of Sodium Nitrite adds for slowly dripping, and drips that to add the time be 15～120 minutes.
By such scheme, described liquor kalii iodide is the liquor kalii iodide recycled.
Comparing existing material and technology, tool of the present invention has the following advantages and useful effect:
(1) under optimal conditions iodine raw material availability be close to 100%, product purity height, significantly reduce production cost;
(2) course of iodization of aniline adopt saleratus to substitute sodium bicarbonate, coproduction liquor kalii iodide. The liquor kalii iodide that reaction generates, without the need to any process, is directly used in subsequent reactions step and generates product 1,4-bis-iodine benzene, reduces the generation of waste liquid in reaction pilot process greatly, it is achieved the comprehensive utilization of potassiumiodide waste liquid resource, reduces production cost;
(3) intermediate that in the middle of the reaction of the present invention, each step generates all does not need to purify and just can be directly used in next step synthesis, simplification operates engineering, it is to increase the product rate of product.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of 1,4-bis-iodine benzene;
Fig. 2 is separated the paraiodoaniline nucleus magnetic hydrogen spectrum spectrogram obtained in embodiment 1;
Fig. 3 is separated the 1,4-bis-iodine benzene nucleus magnetic hydrogen spectrum spectrogram obtained in embodiment 1.
Embodiment
The synthesis of 1,4-bis-iodine benzene of the present invention is further described by following specific examples. But protection domain of the presently claimed invention is not limited to the scope involved by embodiment.
Embodiment 1
Such as Fig. 1 technical process, 9.3g aniline (0.1mol) is joined in the potassium bicarbonate solution of 110 milliliter 10% (w/w), then add the 26.7g iodine of the iodine pulverized and aniline mol ratio 1.05:1 in 15～20 minutes in batches, carry out electrophilic substitution reaction at 5～10 DEG C 4 hours, filter after having reacted. Liquid is the liquor kalii iodide that reaction generates, the iodine replacement(metathesis)reaction being directly used in. Paraiodoaniline 21.0g, product rate 95.8% is obtained after solid drying. Such as Fig. 2, proton nmr spectra analytical results:1HNMR (CDCl3,270MHz), 7.40 (d, 2H), 6.47 (d, 2H), 3.38 (s, 2H), nucleus magnetic resonance test is indicated as target product.
21.0g paraiodoaniline (0.096mol) is joined in 400 ml waters, control temperature of reaction is less than 0 DEG C, add the concentrated hydrochloric acid of 90 milliliter 36.5% (w/w) of hydrochloric acid and paraiodoaniline mol ratio 11.1:1, it is quickly cooled to-10 DEG C to precipitate out superfine white crystal, then drip in 15～20 minutes and add Sodium Nitrite and paraiodoaniline mol ratio is the sodium nitrite solution 33 milliliters of 20% (w/w) of 1.15:1, react 4 hours at-10～-5 DEG C, obtained diazonium salt, unnecessary Sodium Nitrite is with a small amount of urea cancellation;Keeping the temperature of reaction of-10 DEG C, add 150 milliliters of chloroforms in above-mentioned obtained diazonium salt solution, then add the liquor kalii iodide 110 milliliters of recovery, low-temp reaction 4 hours, slowly rises to room temperature, reacts 2 hours. Reaction mixture layering, organic phase sodium sulfite solution is washed till orange, more respectively with sodium carbonate solution, water washing, anhydrous magnesium sulfate drying, underpressure distillation is reclaimed chloroform and obtained faint yellow solid 28.39g. Such as Fig. 3, proton nmr spectra analytical results:1HNMR (CDCl3,270MHz), 7.45 (d, 2H), nucleus magnetic resonance test is indicated as target product.
This synthetic method is in aniline, and molar yield is 80.0%, and purity is 93%, fusing point 127～133 DEG C.
Embodiment 2
13.95g aniline (0.15mol) is joined in the potassium bicarbonate solution of 110 milliliter 15% (w/w), then add the 40.0g iodine of the iodine pulverized and aniline mol ratio 1.05:1 in 15～20 minutes in batches, carry out electrophilic substitution reaction at 5～10 DEG C 4 hours, filter after having reacted. Liquid is the liquor kalii iodide that reaction generates, the iodine replacement(metathesis)reaction being directly used in. Obtaining paraiodoaniline crude product 31.1g after solid drying, product rate 94.5%, nucleus magnetic resonance test is indicated as target product.
31.1g paraiodoaniline (0.142mol) is joined in 600 ml waters, control temperature of reaction is less than 0 DEG C, add sulfuric acid and paraiodoaniline mol ratio is the vitriol oil of 40.5 milliliter 98% (w/w) of 5.25:1, it is quickly cooled to-10 DEG C to precipitate out superfine white crystal, then drip in 15～20 minutes and add Sodium Nitrite and paraiodoaniline mol ratio is the sodium nitrite solution 50 milliliters of 20% (w/w) of 1.18:1, react 4 hours at-10～-5 DEG C, obtained diazonium salt, unnecessary Sodium Nitrite is with a small amount of urea cancellation; Keeping the temperature of reaction of-10 DEG C, add 200 milliliters of chloroforms in above-mentioned obtained diazonium salt solution, then add the liquor kalii iodide 110 milliliters of recovery, low-temp reaction 4 hours, slowly rises to room temperature, reacts 2 hours. Reaction mixture layering, organic phase sodium sulfite solution is washed till orange, more respectively with sodium carbonate solution, water washing, anhydrous magnesium sulfate drying, underpressure distillation is reclaimed chloroform and obtained faint yellow solid 40.3g, and nucleus magnetic resonance test is indicated as target product.
This synthetic method is in aniline, and molar yield is 75.0%, and purity is 92.1%, fusing point 126～133 DEG C.
Embodiment 3
1.86kg aniline (20mol) is joined in the potassium bicarbonate solution of 20 liter 10% (w/w), then add the 5.34kg iodine (21mol) of the iodine pulverized and aniline mol ratio 1.05:1 in 40 minutes in batches, carry out electrophilic substitution reaction at 5～10 DEG C 6 hours, filter after having reacted. Liquid is the liquor kalii iodide that reaction generates, the iodine replacement(metathesis)reaction being directly used in. Obtaining paraiodoaniline 4.07kg after solid drying, nucleus magnetic resonance test is indicated as target product, product rate 93.0%.
4.07kg paraiodoaniline (18.6mol) is joined in 80 premium on currency, control temperature of reaction is less than 0 DEG C, add the concentrated hydrochloric acid of 20 liter 36.5% (w/w) of hydrochloric acid and paraiodoaniline mol ratio 12.8:1, it is quickly cooled to-10 DEG C to precipitate out superfine white crystal, then drip in 60 minutes and add Sodium Nitrite and paraiodoaniline mol ratio is the sodium nitrite solution 6.6 liters of 20% (w/w) of 1.19:1, react 5 hours at-10～-5 DEG C, obtained diazonium salt, unnecessary Sodium Nitrite is with a small amount of urea cancellation; Keeping the temperature of reaction of-10 DEG C, add 30 liters of chloroforms in above-mentioned obtained diazonium salt solution, then add the liquor kalii iodide 20 liters of recovery, low-temp reaction 5 hours, slowly rises to room temperature, reacts 4 hours.Reaction mixture layering, organic phase sodium sulfite solution is washed till orange, more respectively with sodium carbonate solution, water washing, anhydrous magnesium sulfate drying, underpressure distillation is reclaimed chloroform and obtained faint yellow solid 5.4kg, and nucleus magnetic resonance test is indicated as target product.
This synthetic method is in aniline, and molar yield is 74.2%, and purity is 90.5%, fusing point 125～133 DEG C.
Embodiment 4
2.79kg aniline (30mol) is joined in the potassium bicarbonate solution of 22 liter 15% (w/w), then add the 8.1kg iodine (31.9mol) of the iodine pulverized and aniline mol ratio 1.06:1 in 40 minutes in batches, carry out electrophilic substitution reaction at 5～10 DEG C 6 hours, filter after having reacted. Liquid is the liquor kalii iodide that reaction generates, the iodine replacement(metathesis)reaction being directly used in. Obtaining paraiodoaniline 6.07kg after solid drying, nucleus magnetic resonance test is indicated as target product, product rate 92.2%.
6.07kg paraiodoaniline (27.7mol) is joined in 120 premium on currency, control temperature of reaction is less than 0 DEG C, add the vitriol oil of 20 liter 98% (w/w) of sulfuric acid and paraiodoaniline mol ratio 13.3:1, it is quickly cooled to-10 DEG C to precipitate out superfine white crystal, then the sodium nitrite solution 10 liters of 20% (w/w) adding Sodium Nitrite and paraiodoaniline mol ratio 1.2:1 is dripped in 60 minutes, react 5 hours at-10～-5 DEG C, obtained diazonium salt, unnecessary Sodium Nitrite is with a small amount of urea cancellation; Keeping the temperature of reaction of-10 DEG C, add 40 liters of chloroforms in above-mentioned obtained diazonium salt solution, then add the liquor kalii iodide 22 liters of recovery, low-temp reaction 5 hours, slowly rises to room temperature, reacts 4 hours. Reaction mixture layering, organic phase sodium sulfite solution is washed till orange, more respectively with sodium carbonate solution, water washing, anhydrous magnesium sulfate drying, underpressure distillation is reclaimed chloroform and obtained faint yellow solid 7.92kg, and nucleus magnetic resonance test is indicated as target product.
This synthetic method is in aniline, and molar yield is 71.6%, and purity is 89.5%, fusing point 125～133 DEG C.
Claims (10)
1. a preparation method for 1,4-bis-iodine benzene, the method comprises:
(1) iodine and aniline are carried out electrophilic substitution reaction in the solution of weak alkaline medium, it is separated dry the thick product of paraiodoaniline;
(2) by thick for paraiodoaniline product and sodium nitrite solution and concentrated acid generation diazotization reaction, obtained diazonium salt, Sodium Nitrite unnecessary in removing system;
(3) adding chloroform and liquor kalii iodide in reaction system, keep-5～-10 DEG C of reactions after 3～6 hours, slowly rise to room temperature, continue reaction 2～6 hours, from reaction product, separation and purification obtains 1,4-bis-iodine benzene.
2. preparation method according to claim 1, it is characterised in that described weak alkaline medium is the aqueous solution of saleratus.
3. preparation method according to claim 2, it is characterised in that the concentration of aqueous solution of saleratus is 5%～20% (w/w).
4. preparation method according to claim 1, it is characterised in that, step 1) described in aniline and the molar ratio of iodine be 1:1.0～1.1, temperature of reaction is 5～10 DEG C, 3～8 hours reaction times.
5. preparation method according to claim 1, it is characterised in that the feed postition of described iodine adds after pulverizing in batches.
6. preparation method according to claim 1, it is characterised in that, step 2) described in concentrated acid be concentrated hydrochloric acid or the vitriol oil.
7. preparation method according to claim 1, it is characterised in that, step 2) described in concentrated acid and the molar ratio of paraiodoaniline be 5～20:1.
8. preparation method according to claim 1, it is characterised in that, step 2) described in Sodium Nitrite and the mol ratio of paraiodoaniline be 1.05～1.2:1, the temperature of reaction of described diazotization reaction is-10～-5 DEG C, 3～6 hours reaction times.
9. preparation method according to claim 1, it is characterised in that the feed postition of Sodium Nitrite adds for slowly dripping, drips that to add the time be 15～120 minutes.
10. preparation method according to claim 1, it is characterised in that described liquor kalii iodide is the liquor kalii iodide recycled.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542958A (en) * | 2016-11-02 | 2017-03-29 | 贵州大学 | A kind of preparation method of adjacent Iodoaniline |
| CN113149835A (en) * | 2021-05-10 | 2021-07-23 | 广西师范大学 | Preparation method for quickly generating alpha-keto ester by iodine-mediated oxidation of alpha-diazo ester |
| 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 |
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| 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 |
|---|
| LESTER FRIEDM等: "Aprotic Diazotization of Aniline in the Presence of Iodine", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| 郭敬等: "对溴碘苯的合成研究", 《化学与粘合》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542958A (en) * | 2016-11-02 | 2017-03-29 | 贵州大学 | A kind of preparation method of adjacent Iodoaniline |
| 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 |
| CN113149835A (en) * | 2021-05-10 | 2021-07-23 | 广西师范大学 | Preparation method for quickly generating alpha-keto ester by iodine-mediated oxidation of alpha-diazo ester |
| 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 |
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