CN102241640A - Synthesis method of tris-(4-tetrazolyl-phenyl)amine - Google Patents
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- CN102241640A CN102241640A CN201110133812XA CN201110133812A CN102241640A CN 102241640 A CN102241640 A CN 102241640A CN 201110133812X A CN201110133812X A CN 201110133812XA CN 201110133812 A CN201110133812 A CN 201110133812A CN 102241640 A CN102241640 A CN 102241640A
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Abstract
The invention relates to a synthesis method of tris-(4-tetrazolyl-phenyl)amine, belonging to the field of material chemistry. The technical scheme of the invention is as follows: reacting diphenylamine with halo-benzene under a basic condition to obtain triphenylamine, carrying out substitution reaction on triphenylamine with iodine to generate tris-(4-iodophenyl)amine, then reacting tris-(4-iodophenyl)amine with CuCN to generate tris-(4-cyanophenyl)amine, and finally reacting tris-(4-cyanophenyl)amine with sodium azide to generate tris-(4-tetrazolyl-phenyl)amine. The porous material built by reacting obtained tris-(4-tetrazolyl-phenyl)amine with a metal has the stability of carboxylic acid porous frames, achieves intra-pore functionalization, and has pores in a mesoporous size. The adsorption capacity with respect to specific sulfur-containing small molecules shows that the porous material has potential application value in developing high-performance petrochemical products.
Description
Technical field
The invention belongs to the materials chemistry field, particularly the synthetic method of the intermediate of preparation one class functional porous material.
Background technology
Exhaust environment pollution problem, serious harm be to ecotope and human life and health, become in the world one of serious environmental problem at present.And being the burning of fossil energy, the main source of topsoil causes.At present, fossil energy utilize mode still based on burning, and will continue a very long time.Deleterious S, N, F, As, P(all contain lone-pair electron to) etc. be converted into the compound-SO of oxidation state
x, NO
x, P
2O
5, etc.And SO
x, NO
xA large amount of dischargings make air quality gather deterioration, form acid rain, environment for human survival and mankind itself are produced huge harm; Very serious to buildings and all kinds of facility corrosion harmfulness.And the non-burn application of fossil oil (chemical and industrial chemicals) mainly contains the then corresponding H of being converted into of harmful substances
2S, organosulfur, NH
3, HF, PH
3, AsH
3These objectionable impuritiess have toxic action to the catalyzer of the deep-processing process of oil.At this moment because: most of nitride, sulfide, there are lone-pair electron in phosphide, with the surface of metal catalyst very strong bonding action is arranged, and compares with reactant, has bigger adsorption index.The absorption of these objectionable impuritiess on catalyzer has stoped the diffusion of reactant to the active centre, thereby makes catalyzer lose effectiveness.Therefore, in Chemical Manufacture and fuel oil use, must carry out purifying treatment to raw material.
How remove these objectionable constituent from the source: mainly be N, P, the S pollutent is produced clean fuel oil, just has very much meaning.And main focus is how to reduce the content of sulphur from gasoline or diesel oil.At present, and United States Department Of Transportation the latest requirement of gasoline and diesel oil sulphur content be respectively be less than 30 and 15ppm(
Official J. Eur. Communities2003
, L76,10.).And the sulphur content of widely used gasoline of China and diesel oil is too high: domestic gasoline sulfure content is generally at 300 ~ 800ppm, even higher, to all being very disadvantageous on environment and the energy consumption.And the washing of traditional strong oxidizer, rectificating method is difficult to realize the purpose of this deep desulfuration.Simultaneously, there is high security risk especially in the strong oxidizer desulfurization.To all being adverse factors on environment and the energy consumption: the too high gasoline combustion of sulphur content can cause the Pd of purifying vehicle exhaust treatment system, and noble metal catalysts such as Pt are poisoned, thereby cause a large amount of environmental pollution gas NO
xDirectly discharging enters atmosphere.
Ralph T. Yang is based on Cu
IAnd Ag
IThe adsorption experiment of the porous material that Y type cation zeolites is constructed finds that this material is extremely strong to the absorption of the thiophenic sulfur in the fuel oil at normal temperatures and pressures, can realize that sulphur content is from 430 ppm → 0.2 ppm in the fuel oil, (R. T. Yang, A. J. Hern á ndez-Maldonado, F. H. Yang
Science.2003
, 301,79-81.). the desulphurizing ability of this degree of depth is to come from cationic metal center S → M coordination and M → π effect in thiophenic sulfur molecule and this loose structure; The main component of gasoline and diesel oil is each family's hydro carbons; The metal center of porous material is to its almost not effect; And sulphur atom is had certain weak coordination; Therefore can realize the adsorption and enrichment to sulfurous organic compound in the liquid phase; Reach purpose (the C. Laborde-Boutet of reduce fuel oil sulfur content; G. Joly; A. Nicolaos; M. Thomas; P. Magnoux Ind Eng. Chem. Res.2006
, 45,6758-6764).Yet because the too small limitation of this inorganic zeolitic material duct size (easy plugging hole road junction behind the adsorbed molecules) and regeneration capabilities limits (destruction that too high temperature regeneration causes material structure self) make it be difficult to the industrial application of reality.
So, seek a kind of porous material that has macropore size more and have a metal function site and just seem very important.
Contain more macropore for how to construct, traditional inorganic porous material (mainly being zeolite, molecular sieve) is to be difficult to realize.And Yaghi etc. utilize the fragrant polyacid and the metal ion (hybrid inorganic-organic materials) of rigidity and better heat stability, by the solvent thermal technology, the carboxylic acid of selecting different size is as connected body, though the size in duct from 3.8 to 28.8 in the realization polymkeric substance, the hole free volume has reached the porous material (MOFs) of 91.1% hybrid inorganic-organic of material cumulative volume when maximum
(A) M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O ' Keefe, O.M. Yaghi,
Science2002
, 295,469; B) Yaghi, O. M.; O ' Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J.
Nature2003
, 423,705; C) H. K. chae, D. Y. Siberio-Perez, J. Kim, Y. Go, M. Eddaoudi, A. J. Matzger, M. O ' Keeffe, O. M. Yaghi,
Nature, 2004
, 427,523.
)But, but be difficult to the metal site functionalization in its duct of realization.Therefore, do not possess the application of this aspect yet.
Because the immobilized hybrid inorganic-organic materials in vesicular structure of metal center has many advantages:
(1) metal active center and duct size can be controlled design, and the duct size can be enough big, can be because of not stopping up the duct behind the adsorbed molecules;
(2) metal center homodisperse, contact area is big, and loading capacity is big;
(3) the hybrid inorganic-organic crystalline material is insoluble to fuel oil, and reaction is easy to handle, and the easy-to-use alcoholic solvent of material carries out low-temp recovery.Realize reusing, this has more realistic meaning in industrial application.
The contriver makes a kind of Cu-UMCs-MOFs porous cubic system material that can be used for deep desulfurization of fuel oil by the synthetic method, this material has the scope of application of broad, this material is extremely strong to the absorption of the thiophene sulphur in the fuel oil at normal temperatures and pressures, can realize that desulfurization content is reduced to below the 10ppm in the fuel oil.And the intermediate of synthetic this material---three-(4-tetrazole base phenyl) amine are one of keys.
Summary of the invention
The object of the invention is to propose a kind of synthetic method of three-(4-tetrazole base phenyl) amine.
Technical solution of the present invention is: under alkaline condition, pentanoic and halobenzene reaction are obtained triphenylamine, generate three-(4-iodobenzene) amine through the elemental iodine substitution reaction, generate three-(4-itrile group phenyl) amine with the CuCN reaction again, last and reaction of sodium azide generates three-(4-tetrazole base phenyl) amine.
The present invention is the core parent with the triphenylamine, synthesizes to have three structures, the larger-size tetrazole of part.By its further with metal Cu (I or II) ion, utilize the solvent thermal technology, synthetic metal dots is exposed to the crystalline state porous material of the hybrid inorganic-organic on " wall " in the material duct.Realized the large-size in material duct, in the duct, utilize the bare metal active sites realize to the micromolecular absorption of thiophene-based sulfur-bearing in the fuel oil with separate, thereby realized deep desulfurization of fuel oil.
The porous material that three-(the 4-tetrazole base phenyl) amine of making by the present invention and the reaction of metal are constructed not only possesses the bone porous stability of carboxylic-acid, also realized the functionalization in the duct, and the duct size can reach mesoporous size.The micromolecular adsorptive power of specific sulfur-bearing has more been shown its potential using value, and to exploitation high-performance petrochemicals, the environmental pollution that reduces the fuel oil generation all has crucial strategic importance.
In addition, the present invention under alkaline condition, is dissolved in pentanoic in the solvent when the preparation triphenylamine, in 100～150 ℃ of temperature condition down with the halobenzene reaction, make the triphenylamine crude product, the aniline crude product carries out recrystallization through alkane solvent repeatedly, gets triphenylamine; The molar ratio of described pentanoic, halobenzene, alkali is 1 ︰, 1～1.5 ︰ 1.5～4; Described alkali is any one among sodium tert-butoxide, potassium tert.-butoxide, NaH, the LiH, and the solvent in described when reaction is N, dinethylformamide, N, in N-diethylformamide, N,N-dimethylacetamide or the methyl-sulphoxide at least any one; Solvent during described recrystallization is C
3～C
8The alkane of straight or branched or naphthenic hydrocarbon in a kind of.
The molar ratio of described pentanoic, halobenzene, alkali is preferably 1 ︰, 1～1.2 ︰ 2～3.
When preparation three-(4-iodobenzene) amine, triphenylamine is dissolved in anhydrous methanol or the ethanol, under the catalysis of red precipitate, the following and elemental iodine reaction in 0-80 ℃ of temperature condition, the molar ratio of described triphenylamine, elemental iodine and red precipitate is 1 ︰, 3～6 ︰ 3 ~ 6; Reaction finishes after distillation concentrates, and recrystallization gets three-(4-iodobenzene) amine; The solvent of described recrystallization be in benzene,toluene,xylene or the trimethylbenzene at least any one.
The molar ratio of described triphenylamine, elemental iodine and red precipitate is 1 ︰, 4 ~ 4.5 ︰ 4 ~ 4.5.
When preparation three-(4-itrile group phenyl) amine, with three-(4-iodobenzene) amine solvents in solvent, under 100-180 ℃ of temperature condition, under the catalysis of HMPA, with the CuCN reaction, obtain three-(4-itrile group phenyl) amine through diluting solvent dilution, filtration, washing, separation successively then; The molar ratio of described three-(4-iodobenzene) amine and CuCN is 1 ︰ 3～6; The solvent of described dissolving three-(4-iodobenzene) amine is N, dinethylformamide, N, in N-diethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or the HMPA at least any one; Described diluting solvent is with ethyl acetate, methylene dichloride, chloroform or C
2～C
8The alkane, naphthenic hydrocarbon, hydrochloric ether of straight or branched at least any one.
The molar ratio of described three-(4-iodobenzene) amine and CuCN is preferably 1 ︰ 4～4.5.
When preparation three-(4-tetrazole base phenyl) amine, with three-(4-itrile group phenyl) amine solvents in solvent, under 100～180 ℃ of temperature condition, under the catalysis of quaternary ammonium salt, with reaction of sodium azide, pH value with reaction mixture is adjusted to 1.0-4.0 then, gets the solid of separating out, and obtains three-(4-tetrazole base phenyl) amine through the cleaning solvent washing; The solvent of described dissolving three-(4-itrile group phenyl) amine is N, dinethylformamide, N, in N-diethylformamide, N,N-dimethylacetamide or the methyl-sulphoxide at least any one; Described quaternary ammonium salt is a kind of in ammonium chloride, brometo de amonio, ammonium iodide, zinc chloride, zinc bromide or the zinc iodide; The molar ratio of described three-(4-itrile group phenyl) amine, sodiumazide and quaternary ammonium salt is 1 ︰, 3～6 ︰ 3～6; Described cleaning solvent is at least a arbitrarily in water, methyl alcohol, ethanol or the acetone.
The molar ratio of described three-(4-itrile group phenyl) amine, sodiumazide and quaternary ammonium salt is preferably 1 ︰, 4～5 ︰ 4～5.
Described pH value preferably is adjusted to 1.0～4.0.
Embodiment
One, preparation method:
Following example just illustrates technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.
Step 1:Synthesizing of triphenylamine
Under 120 ℃ of nitrogen protections, with pentanoic 51 grams and t-BuOK 86 grams and anhydrous 2000 mL DMF stirring 3h.Bromobenzene 71 grams slowly add in the reaction system, stir 72h at 140 ℃.Then, the reaction mixture underpressure distillation, NaHCO is used in cooling
3(10%) washing extracts with sherwood oil.Organic phase is adjusted to neutral pH, uses MgSO
4Drying is filtered, and steams solvent.Obtain residue white crystal shape product---triphenylamine, output 59 grams, yield 80%.
Step 2:Synthesizing of three-(4-iodobenzene) amine
At room temperature, with triphenylamine 24.5 gram and dehydrated alcohol 300mL, and red precipitate 70 grams add in the reaction system stirring at room 1h.Then, add elemental iodine 80 grams, keep room temperature reaction 12h.Ethanol is reclaimed in the reaction mixture underpressure distillation.Solid phase adds benzene 300mL and carries out recrystallization.Obtain white crystal shape product---three-(4-iodobenzene) amine, output 56 grams, yield 90%.
Step 3:Synthesizing of three-(4-itrile group phenyl) amine
Under the nitrogen protection, three-(4-iodobenzene) amine, 6.23 grams and CuCN 4.5 are restrained in the four-hole bottle of putting into 250 milliliters.Add 100 milliliters of HMPA then.Carried out reacting by heating 12 hours at 160 ℃.After 12 hours, go out HMPA with oily underpressure distillation.Naturally cooling then.To the Na that wherein adds saturated 50mL
2CO
3The aqueous solution and the CH of 100ml
2Cl
2Extract.Separatory then.Obtaining organic phase washes once more.Methylene dichloride is reclaimed in air distillation.Crude product carries out flash column chromatography with methylene dichloride, obtains light yellow solid---three-(4-itrile group phenyl) amine, output 2.57 grams, yield 84%.
Step 4:Synthesizing of three-(4-tetrazole base phenyl) amine
Under the nitrogen protection, with three-(4-itrile group phenyl) amine, 16 gram and NaN
314.6 gram and NH
4Cl 13 restrains in the four-hole bottle of putting into 500 milliliters.Add 200 milliliters of DMF then.Reflux 24h.Stopped reaction, naturally cooling then.Carry out underpressure distillation and go out the DMF solvent.Residuum is poured in the frozen water, and regulates PH=1 with hydrochloric acid, separates out a large amount of light solids.Filter water washing, drying under reduced pressure.Obtain white three-(4-tetrazole base phenyl) amine, 18.5 grams, yield 85%.
Above step 1 is as follows to 4 concrete synthetic route:
Two, use:The preparation of porous crystalline material
In the 100mL stainless steel autoclave, add three-(4-tetrazole base phenyl) amine, 4.4 grams and cuprous chloride 9 grams.The water that adds 50 milliliters of DMF and 10mL then.After airtight, keep 140 ℃ of 72h in the baking oven.Program is reduced to room temperature then, filters water washing, methanol wash, drying under reduced pressure.Obtain light green three-(4-tetrazole base phenyl) amine polyhedral crystal 4 .0 gram.
Claims (10)
1. the synthetic method of three-(4-tetrazole base phenyl) amine, it is characterized in that: under alkaline condition, pentanoic and halobenzene reaction are obtained triphenylamine, generate three-(4-iodobenzene) amine through the elemental iodine substitution reaction, generate three-(4-itrile group phenyl) amine with the CuCN reaction again, last and reaction of sodium azide generates three-(4-tetrazole base phenyl) amine.
2. according to the synthetic method of described three-(the 4-tetrazole base phenyl) amine of claim 1, it is characterized in that: when the preparation triphenylamine, under alkaline condition, pentanoic is dissolved in the solvent, following and the halobenzene reaction in 100～150 ℃ of temperature condition, make the triphenylamine crude product, the aniline crude product carries out recrystallization through alkane solvent repeatedly, gets triphenylamine; The molar ratio of described pentanoic, halobenzene, alkali is 1 ︰, 1～1.5 ︰ 1.5～4; Described alkali is any one among sodium tert-butoxide, potassium tert.-butoxide, NaH, the LiH, and the solvent in described when reaction is N, dinethylformamide, N, in N-diethylformamide, N,N-dimethylacetamide or the methyl-sulphoxide at least any one; Solvent during described recrystallization is C
3～C
8The alkane of straight or branched or naphthenic hydrocarbon in a kind of.
3. according to the synthetic method of described three-(the 4-tetrazole base phenyl) amine of claim 2, it is characterized in that: the molar ratio of described pentanoic, halobenzene, alkali is 1 ︰, 1～1.2 ︰ 2～3.
4. according to the synthetic method of described three-(the 4-tetrazole base phenyl) amine of claim 1, it is characterized in that: when preparation three-(4-iodobenzene) amine, triphenylamine is dissolved in anhydrous methanol or the ethanol, under the catalysis of red precipitate, following and the elemental iodine reaction in 0-80 ℃ of temperature condition, the molar ratio of described triphenylamine, elemental iodine and red precipitate is 1 ︰, 3 ~ 6 ︰ 3 ~ 6; Reaction finishes after distillation concentrates, and recrystallization gets three-(4-iodobenzene) amine; The solvent of described recrystallization be in benzene,toluene,xylene or the trimethylbenzene at least any one.
5. according to the synthetic method of described three-(the 4-tetrazole base phenyl) amine of claim 4, it is characterized in that: the molar ratio of described triphenylamine, elemental iodine and red precipitate is 1 ︰, 4～4.5 ︰ 4～4.5.
6. according to the synthetic method of described three-(the 4-tetrazole base phenyl) amine of claim 1, it is characterized in that: when preparation three-(4-itrile group phenyl) amine, with three-(4-iodobenzene) amine solvents in solvent, under 100～180 ℃ of temperature condition, under the catalysis of HMPA, with the CuCN reaction, obtain three-(4-itrile group phenyl) amine through diluting solvent dilution, filtration, washing, separation successively then; The molar ratio of described three-(4-iodobenzene) amine and CuCN is 1 ︰ 3～6; The solvent of described dissolving three-(4-iodobenzene) amine is N, dinethylformamide, N, in N-diethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or the HMPA at least any one; Described diluting solvent is with ethyl acetate, methylene dichloride, chloroform or C
2～C
8The alkane, naphthenic hydrocarbon, hydrochloric ether of straight or branched at least any one.
7. according to the synthetic method of described three-(the 4-tetrazole base phenyl) amine of claim 6, it is characterized in that: the molar ratio of described three-(4-iodobenzene) amine and CuCN is 1 ︰ 4～4.5.
8. according to the synthetic method of described three-(the 4-tetrazole base phenyl) amine of claim 1, it is characterized in that: when preparation three-(4-tetrazole base phenyl) amine, with three-(4-itrile group phenyl) amine solvents in solvent, under 100～180 ℃ of temperature condition, under the catalysis of quaternary ammonium salt, with reaction of sodium azide, the pH value with reaction mixture is adjusted to 1.0-4.0 then, get the solid of separating out, obtain three-(4-tetrazole base phenyl) amine through the cleaning solvent washing; The solvent of described dissolving three-(4-itrile group phenyl) amine is N, dinethylformamide, N, in N-diethylformamide, N,N-dimethylacetamide or the methyl-sulphoxide at least any one; Described quaternary ammonium salt is a kind of in ammonium chloride, brometo de amonio, ammonium iodide, zinc chloride, zinc bromide or the zinc iodide; The molar ratio of described three-(4-itrile group phenyl) amine, sodiumazide and quaternary ammonium salt is 1 ︰, 3～6 ︰ 3～6; Described cleaning solvent is at least a arbitrarily in water, methyl alcohol, ethanol or the acetone.
9. the synthetic method of described according to Claim 8 three-(4-tetrazole base phenyl) amine is characterized in that: the molar ratio of described three-(4-itrile group phenyl) amine, sodiumazide and quaternary ammonium salt is 1 ︰, 4～5 ︰ 4～5.
10. the synthetic method of described according to Claim 8 three-(4-tetrazole base phenyl) amine is characterized in that: described pH value is adjusted to 1.0～4.0.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532160A (en) * | 2011-11-28 | 2012-07-04 | 中国科学技术大学 | Catalytic synthesis method of conductive polymer monomer |
| CN105233652A (en) * | 2015-10-13 | 2016-01-13 | 李宇花 | Treatment agent for removing sulfide from oil-fired boiler tail gas |
| CN105289556A (en) * | 2015-11-18 | 2016-02-03 | 中国科学技术大学苏州研究院 | Metal functionalized nano-porous material and preparation method thereof |
| CN105461547A (en) * | 2015-12-12 | 2016-04-06 | 常州大学 | Method for synthesizing periodide |
| CN106608871A (en) * | 2015-10-27 | 2017-05-03 | 南京理工大学 | Preparation method of 3-amino-4-(5-tetrazole)furazan |
| CN108384020A (en) * | 2018-03-09 | 2018-08-10 | 河海大学 | It is a kind of novel containing the metal organic framework for not being coordinated tetrazole group and its synthetic method and application |
-
2011
- 2011-05-23 CN CN201110133812XA patent/CN102241640A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532160A (en) * | 2011-11-28 | 2012-07-04 | 中国科学技术大学 | Catalytic synthesis method of conductive polymer monomer |
| CN105233652A (en) * | 2015-10-13 | 2016-01-13 | 李宇花 | Treatment agent for removing sulfide from oil-fired boiler tail gas |
| CN106608871A (en) * | 2015-10-27 | 2017-05-03 | 南京理工大学 | Preparation method of 3-amino-4-(5-tetrazole)furazan |
| CN105289556A (en) * | 2015-11-18 | 2016-02-03 | 中国科学技术大学苏州研究院 | Metal functionalized nano-porous material and preparation method thereof |
| CN105461547A (en) * | 2015-12-12 | 2016-04-06 | 常州大学 | Method for synthesizing periodide |
| CN108384020A (en) * | 2018-03-09 | 2018-08-10 | 河海大学 | It is a kind of novel containing the metal organic framework for not being coordinated tetrazole group and its synthetic method and application |
| CN108384020B (en) * | 2018-03-09 | 2020-09-11 | 河海大学 | Metal organic framework containing uncoordinated tetrazole group and synthesis method and application thereof |
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Application publication date: 20111116 |