CN103420779B - Preparation method of 2, 2'-diiodine-4, 4'-dibromobiphenyl - Google Patents
Preparation method of 2, 2'-diiodine-4, 4'-dibromobiphenyl Download PDFInfo
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Abstract
The invention provides a preparation method of 2, 2'-diiodine-4, 4'-dibromobiphenyl and aims to solve the problem that in the prior art, the preparation of the 2, 2'-diiodine-4, 4'-dibromobiphenyl is low in yield. The specific scheme comprises the following steps: (1) m-iodonitrobenzene is dissolved in an organic solvent and subjected to a backflow reaction under the action of a zinc and strong sodium hydroxide solution, an organic layer is washed through hydrobromic acid, the m-iodonitrobenzene is stirred for a reaction in a hydrobromic acid solution to remove undissolved substance through filtration, and then the hydrobromic acid solution is added to precipitate 2, 2'-diiodine-4, 4'-diaminodiphenyl hydrobromide; (2) the product in the first step is dissolved in water, the hydrobromic acid solution is added, a nitrous acid solution is dropwise added slowly for a diazo-reaction, a reaction solution is added into a hydrobromic acid and cuprous bromide solution and stirred, the temperature is raised to 30-60 DEG C, the reaction lasts 1-5 hours, organic solvents are used for extraction, and the 2, 2'-diiodine-4, 4'-dibromobiphenyl is obtained after purification. The preparation method is simple in operation condition, high in transforming rate, simple in aftertreatment, and suitable for industrial production.
Description
Technical field
The invention belongs to the synthetic field of chemical industry, relate in particular to a kind ofly 2,2'-bis-is iodo-4, the preparation method of 4'-'-dibromobiphenyl.
Background technology
Because the demand that solar energy resources is utilized is day by day urgent, increasing researcher transfers target in the field of efficient, cheap photovoltaic device.The polymkeric substance of take is compared with inorganic semiconductor material and is had unrivaled advantage as basic organic photovoltaic system.2,2'-bis-is iodo-4, and 4'-'-dibromobiphenyl is a kind of important intermediate of preparing block conjugated polymer.
At present the preparation method of this compound is in DMF solution, and it is bromo-2 that 2,5-, bis-bromo nitrobenzenes are prepared 4,4'-bis-under copper powder catalysis, 2'-dinitrobenzene biphenyl.4,4'-bis-is bromo-2, and 2'-dinitrobenzene biphenyl is under the effect of the reductive agents such as iron powder, glass putty, tin chloride, and reduction preparation 4,4'-bis-is bromo-2,2'-benzidine.Finally by diazotization, carry out iodo, 2,2'-bis-is iodo-4 in preparation, 4'-'-dibromobiphenyl.Its reaction process is as follows:
The method the first step is at high temperature reacted, and yield is low, and copper powder consumption is large, and the aftertreatment of reaction copper powder is more difficult.Finally carry out iodo, due to sterically hindered effect, yield is lower.Overall yield is in 20% left and right.Reaction final purification is processed and is difficult to, and only has by the method for column chromatography and purifies, and is difficult to carry out large-scale commercial production, has also limited the application of this product in industrial production simultaneously.
Summary of the invention
The present invention overcomes that in prior art, to prepare 2,2'-bis-iodo-4, and the problem that 4'-'-dibromobiphenyl yield is low provides a kind of 2, and 2'-bis-is iodo-4, the preparation method of 4'-'-dibromobiphenyl.The present invention is under the effect of zinc, sodium hydroxide, by a nitro iodobenzene, realize reduction and coupling one step and carry out, then passing through diazotization, bromo, to prepare 2,2'-bis-iodo-4,4'-'-dibromobiphenyl.The advantages such as it is simple that the method has operational condition, and transformation efficiency is high, and aftertreatment is simple, are applicable to carrying out suitability for industrialized production.
The technical solution adopted in the present invention is as follows: between (1) general, nitro iodobenzene is dissolved in organic solvent, back flow reaction 5～10h under the effect of zinc and strong caustic, form hydrodiazo benzene compound, the Hydrogen bromide that is 10～20wt.% by concentration washing organic layer, then in the hydrobromic acid solution that is 40～50wt.% in concentration, 0-40 ℃ of stirring reaction 3-10h, remove by filter insolubles, adding concentration is the hydrobromic acid solution of 40～50wt.%, separate out 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate;
(2) by 2,2 '-bis-iodo-4,4 '-benzidine hydrobromate is soluble in water, adding concentration is the hydrobromic acid solution of 40～50wt.%, slowly drip sodium nitrite solution, diazotization reaction 0.5-2h under-10-10 ℃ condition, after diazotization reaction, it is in the Hydrogen bromide of 40～50wt.% and the solution of cuprous bromide that reaction soln is joined to concentration, and-10-10 ℃ is stirred 1-3h, be warming up to 30-60 ℃, reaction 1-5h, organic solvent extraction, except desolventizing, from reaction product, collect target product crude product, crude product is carried out to purifying with organic solvent.Synthetic route is as follows:
Further, the described organic solvent of step (1) is a kind of in benzene, toluene, Benzene Chloride, dimethylbenzene, orthodichlorobenzene or sherwood oil, a nitro iodobenzene with the molecular volume of organic solvent than being 1:1～1.5mol/L.
Specifically, the described strong caustic concentration of step (1) is 30-50wt.%.
As preferably, the described strong caustic concentration of step (1) is 40wt.%.
Further, step (1) described between nitro iodobenzene and sodium hydroxide mol ratio be 1:1.5～2; Zinc powder and a nitro iodobenzene mol ratio are 3.0-4.0:1; Between step (1), nitro iodobenzene is 1:0.3～0.6mol/L with adding for the first time the molecular volume ratio of hydrobromic acid solution; Between nitro iodobenzene with the molecular volume that adds for the second time hydrobromic acid solution than being 1:0.8～1.2mol/L; Between nitro iodobenzene with the molecular volume that adds for the third time hydrobromic acid solution than being 1:0.5～0.8mol/L.
Further, in step (2), 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate: Sodium Nitrite: cuprous bromide=1.0:2.0-3.0:0.05-1.0(mol ratio); 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate: water=1.0:1-10(mass ratio); Described sodium nitrite solution concentration is 40～50wt.%; In step (2), 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate with the molecular volume that adds for the first time hydrobromic acid solution than being 1:0.2～0.5mol/L; 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate with the molecular volume that adds for the second time hydrobromic acid solution than being 1:0.15～0.4mol/L.。
As preferably, the described diazotization reaction temperature of step (2) is-5～5 ℃.
Specifically, the described extraction solvent of step (2) is a kind of in sherwood oil, ethyl acetate, methyl acetate, methylene dichloride or chloroform; Described purifying organic solvent used is one or more in methyl alcohol, ethanol, ethyl acetate, methyl acetate
Compared with prior art, beneficial effect is in the present invention:
1, reactions steps of the present invention is few, and yield is high, without pyroreaction, has effectively avoided at high temperature, and the side reaction of initiation, has improved transformation efficiency and product purity;
2, the reduction of reaction azo forms hydrobromate, without carrying out neutralizing treatment, directly drops into the next step;
3, react low for equipment requirements, aftertreatment is simple, and product can reach requirement by conventional purifying, and purifies without column chromatography;
4, reaction agents useful for same and raw material, convenient sources, low price, is convenient to suitability for industrialized production.
Embodiment
Embodiment 1
Nitro iodobenzene, 19.5g zinc powder between 24.9g, 30% sodium hydroxide solution 20g, 100mL sherwood oil, back flow reaction 5h, forms hydrazobenzene, with 10% Hydrogen bromide 30mL washing organic layer, then added in 80mL40% hydrobromic acid aqueous solution, 0 ℃ of stirring reaction 3h, removes by filter insolubles, add 48% Hydrogen bromide 50mL, separate out 2,2 '-bis-iodo-4,4 '-benzidine hydrobromate 20.92g.
By 2,2 '-bis-is iodo-4, in 4 '-benzidine hydrobromate 51.7g, adds water 52g, 48% Hydrogen bromide 20mL, slowly drips sodium nitrite solution (14.7g Sodium Nitrite/water 20g), under-10 ℃ of conditions, reacts 2h, after diazotization, join in the solution of cuprous bromide 14.4g/48% Hydrogen bromide 15mL ,-10 ℃ are stirred 3h, be warming up to 30 ℃, reaction 1h, ethyl acetate extraction, except desolventizing, 50mL dehydrated alcohol recrystallization for crude product, obtains product 33.84g.
Embodiment 2
Nitro iodobenzene, 26.0g zinc powder between 24.9g, 50% sodium hydroxide solution 16g, 100mL toluene, back flow reaction 10h, forms hydrazobenzene, with 20% Hydrogen bromide 60mL washing organic layer, then added in 120mL50% hydrobromic acid aqueous solution, 40 ℃ of stirring reaction 10h, remove by filter insolubles, add 48% Hydrogen bromide 80mL, separate out 2,2 '-bis-iodo-4,4 '-benzidine hydrobromate 23.92g.
By 2,2 '-bis-is iodo-4, in 4 '-benzidine hydrobromate 51.7g, adds water 500g, 48% Hydrogen bromide 50mL, slowly drips sodium nitrite solution (18.7g Sodium Nitrite/water 25g), under 10 ℃ of conditions, reacts 0.5h, after diazotization, join in the solution of cuprous bromide 0.72g/48% Hydrogen bromide 40mL, 10 ℃ are stirred 1h, be warming up to 60 ℃, reaction 5h, toluene extraction, except desolventizing, 50mL dehydrated alcohol recrystallization for crude product, obtains product 39.46g.
Embodiment 3
Nitro iodobenzene, 22.75g zinc powder between 24.9g, 40% sodium hydroxide solution 17.5g, 100mL dimethylbenzene, back flow reaction 8h, forms hydrazobenzene, with 15% Hydrogen bromide 50mL washing organic layer, then added in 100mL48% hydrobromic acid aqueous solution, 20 ℃ of stirring reaction 6h, remove by filter insolubles, add 48% Hydrogen bromide 50mL, separate out 2,2 '-bis-iodo-4,4 '-benzidine hydrobromate 25.39g.
By 2,2 '-bis-is iodo-4, in 4 '-benzidine hydrobromate 51.7g, adds water 150g, 48% Hydrogen bromide 20mL, slowly drips sodium nitrite solution (18.7g Sodium Nitrite/water 20g), under 0 ℃ of condition, reacts 1h, after diazotization, join in the solution of cuprous bromide 3.3g/48% Hydrogen bromide 25mL, 0 ℃ is stirred 1.5h, be warming up to 45 ℃, reaction 2.5h, methyl acetate extraction, except desolventizing, 50mL dehydrated alcohol recrystallization for crude product, obtains product 42.3g.
Embodiment 4
Nitro iodobenzene, 22.75g zinc powder between 24.9g, 40% sodium hydroxide solution 17.5g, 150mL benzene, back flow reaction 6h, forms hydrazobenzene, with 15% Hydrogen bromide 60mL washing organic layer, then added in 100mL48% hydrobromic acid aqueous solution, 20 ℃ of stirring reaction 4h, remove by filter insolubles, add 48% Hydrogen bromide 60mL, separate out 2,2 '-bis-iodo-4,4 '-benzidine hydrobromate 23.94g.
By 2,2 '-bis-is iodo-4, in 4 '-benzidine hydrobromate 51.7g, adds water 150g, 40% Hydrogen bromide 40mL, slowly drips sodium nitrite solution (13.8g Sodium Nitrite/water 20g), under 5 ℃ of conditions, reacts 1h, after diazotization, join in the solution of cuprous bromide 3.3g/40% Hydrogen bromide 30mL, 5 ℃ are stirred 1h, be warming up to 30 ℃, reaction 2.5h, dichloromethane extraction, except desolventizing, 50mL anhydrous methanol recrystallization for crude product, obtains product 36.7g.
Embodiment 5
Nitro iodobenzene, 26.0g zinc powder between 24.9g, 40% sodium hydroxide solution 17g, 120mL dimethylbenzene, back flow reaction 5h, forms hydrazobenzene, with 20% Hydrogen bromide 60mL washing organic layer, then added in 100mL48% hydrobromic acid aqueous solution, 40 ℃ of stirring reaction 8h, remove by filter insolubles, add 48% Hydrogen bromide 70mL, separate out 2,2 '-bis-iodo-4,4 '-benzidine hydrobromate 24.52g.
By 2,2 '-bis-is iodo-4, in 4 '-benzidine hydrobromate 51.7g, adds water 150g, 48% Hydrogen bromide 40mL, slowly drips sodium nitrite solution (13.8g Sodium Nitrite/water 20g), under 0 ℃ of condition, reacts 1.5h, after diazotization, join in the solution of cuprous bromide 5.0g/48% Hydrogen bromide 30mL, 0 ℃ is stirred 0.5h, be warming up to 50 ℃, reaction 5h, petroleum ether extraction, except desolventizing, 50mL anhydrous methanol recrystallization for crude product, obtains product 40.1g.
Embodiment 6
Nitro iodobenzene, 22.75g zinc powder between 24.9g, 40% sodium hydroxide solution 17.5g, 100mL benzene, back flow reaction 6h, forms hydrazobenzene, with 15% Hydrogen bromide 50mL washing organic layer, then added in 80mL48% hydrobromic acid aqueous solution, 20 ℃ of stirring reaction 4h, remove by filter insolubles, add 48% Hydrogen bromide 50mL, separate out 2,2 '-bis-iodo-4,4 '-benzidine hydrobromate 23.94g.
By 2,2 '-bis-is iodo-4, in 4 '-benzidine hydrobromate 51.7g, adds water 150g, 40% Hydrogen bromide 40mL, slowly drips sodium nitrite solution (13.8g Sodium Nitrite/water 20g), under 5 ℃ of conditions, reacts 1h, after diazotization, join in the solution of cuprous bromide 3.3g/40% Hydrogen bromide 40mL, 5 ℃ are stirred 1h, be warming up to 30 ℃, reaction 2.5h, methyl acetate extraction, except desolventizing, 50mL anhydrous methanol recrystallization for crude product, obtains product 36.7g.
Claims (8)
1. one kind 2,2'-bis-is iodo-4, and the preparation method of 4'-'-dibromobiphenyl, is characterized in that: concrete steps are as follows:
(1) between general, nitro iodobenzene is dissolved in organic solvent, back flow reaction 5～10h under the effect of zinc and strong caustic, form hydrodiazo benzene compound, the hydrobromic acid solution that is 10～20wt.% by concentration washing organic layer, in the hydrobromic acid solution that is then 40～50wt.% in concentration, 0-40 ℃ of stirring reaction 3-10h, remove by filter insolubles, adding concentration is the hydrobromic acid solution of 40～50wt.%, separates out 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate;
(2) by 2,2 '-bis-iodo-4,4 '-benzidine hydrobromate is soluble in water, adding concentration is the hydrobromic acid solution of 40～50wt.%, slowly drip sodium nitrite solution, diazotization reaction 0.5-2h under-10-10 ℃ condition, after diazotization reaction, it is in the Hydrogen bromide of 40～50wt.% and the solution of cuprous bromide that reaction soln is joined to concentration, and-10-10 ℃ is stirred 1-3h, be warming up to 30-60 ℃, reaction 1-5h, organic solvent extraction, except desolventizing, from reaction product, collect target product crude product, crude product is carried out to purifying with organic solvent.
2. according to claim 12,2'-bis-iodo-4, the preparation method of 4'-'-dibromobiphenyl, it is characterized in that: the described organic solvent of step (1) is a kind of in benzene, toluene, Benzene Chloride, dimethylbenzene, orthodichlorobenzene or sherwood oil, a nitro iodobenzene with the molecular volume of organic solvent than being 1:1～1.5mol/L.
3. according to claim 12,2'-bis-is iodo-4, and the preparation method of 4'-'-dibromobiphenyl, is characterized in that: the described strong caustic concentration of step (1) is 30-50wt.%.
4. according to claim 12,2'-bis-is iodo-4, and the preparation method of 4'-'-dibromobiphenyl, is characterized in that: the described strong caustic concentration of step (1) is 40wt.%.
5. according to claim 12,2'-bis-is iodo-4, and the preparation method of 4'-'-dibromobiphenyl, is characterized in that: step (1) described between nitro iodobenzene and sodium hydroxide mol ratio be 1:1.5～2; Zinc powder and a nitro iodobenzene mol ratio are 3.0-4.0:1;
Between step (1), nitro iodobenzene is 1:0.3～0.6mol/L with adding for the first time the molecular volume ratio of hydrobromic acid solution; Between nitro iodobenzene with the molecular volume that adds for the second time hydrobromic acid solution than being 1:0.8～1.2mol/L; Between nitro iodobenzene with the molecular volume that adds for the third time hydrobromic acid solution than being 1:0.5～0.8mol/L.
6. according to claim 12,2'-bis-is iodo-4, and the preparation method of 4'-'-dibromobiphenyl, is characterized in that: in step (2) 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate: Sodium Nitrite: cuprous bromide=1.0:2.0-3.0:0.05-1.0(mol ratio); 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate: water=1.0:1-10(mass ratio); Described sodium nitrite solution concentration is 40～50wt.%;
In step (2), 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate with the molecular volume that adds for the first time hydrobromic acid solution than being 1:0.2～0.5mol/L; 2,2 '-bis-is iodo-4,4 '-benzidine hydrobromate with the molecular volume that adds for the second time hydrobromic acid solution than being 1:0.15～0.4mol/L.
7. according to claim 12,2'-bis-is iodo-4, and the preparation method of 4'-'-dibromobiphenyl, is characterized in that: the described diazotization reaction temperature of step (2) is-5～5 ℃.
8. according to claim 12,2'-bis-is iodo-4, and the preparation method of 4'-'-dibromobiphenyl, is characterized in that: the described extraction solvent of step (2) is a kind of in sherwood oil, ethyl acetate, methyl acetate, methylene dichloride or chloroform; Described purifying organic solvent used is one or more in methyl alcohol, ethanol, ethyl acetate, methyl acetate.
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