CN103012195B - Preparation method of aryl azide compound - Google Patents
Preparation method of aryl azide compound Download PDFInfo
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- CN103012195B CN103012195B CN201210521317.0A CN201210521317A CN103012195B CN 103012195 B CN103012195 B CN 103012195B CN 201210521317 A CN201210521317 A CN 201210521317A CN 103012195 B CN103012195 B CN 103012195B
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- VTWDWDYHAAZREM-UHFFFAOYSA-N Cc(cc1)ccc1[NH+](C)[O-] Chemical compound Cc(cc1)ccc1[NH+](C)[O-] VTWDWDYHAAZREM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of an aryl azide compound. The method comprises: mixing an iodo-aryl compound shown in formula (II) with sodium azide, an alkaline substance, and a ligand in a solvent, leaving them to react at 60-100DEG C under the catalysis of porous copper, conducting TLC tracking detection till the end of a complete reaction, subjecting the reaction solution to aftertreatment so as to obtain the aryl azide compound shown in formula (I). The ligand is L-proline, pyrrolidine, L-glutamic acid, L-threonine or L-alanine. The solvent is dimethyl sulfoxide, dimethylformamide, water or a mixed solvent of dimethyl sulfoxide and water. The method disclosed in the invention adopts porous copper as the catalyst, and the preparation can be complete through a one-pot technique. The method has the advantages of mild reaction conditions, convenient operation, good product quality, and high yield.
Description
(1) technical field
The present invention relates to a kind of preparation method of aryl azide compound.
(2) background technology
Aryl azide compound, as important chemosynthesis intermediate, is widely used in organic chemical synthesis.A lot of about the synthetic method of aryl azide compound at present, generally have following several: 1. one-level arylamines is under the effect of mineral acid and Sodium Nitrite, the diazonium compound generated and sodiumazide obtain aryl azide compound (Ina Wilkening through replacement(metathesis)reaction, Giuseppe del Signore and Christian P. R. Hackenberger, Chem. Commun., 2011,47,349-351).2. halogeno-benzene and trinitride obtain aryl azide compound (Wei Zhua and Dawei Ma, Chem.Commun., 2004,888 – 889) through linked reaction.3. phenylhydrazine is at triphenyl phosphorus, and under the effect of bromine water and tetrabutyl inferior ammonium nitrate, reaction generates aryl azide compound (Nasser Iranpoor, Habib Firouzabadi, Najmeh Nowrouzi, Tetrahedron Letters, 2008,49,4242 – 42444).4. aromatic yl acid salt and sodiumazide generate nitrine aryl compound (Liang Wang under the catalysis of Cu (I), Chun Cai, Green Chemistry Letters and Reviews, 2010,3 (2), 121-125).But above-mentioned preparation method still exists a lot of defect: as higher to the requirement of pH during diazotization, be not easy to control, material toxicity is comparatively large, and easily generate by product, yield is not high, and the scope of application is wideless, and limitation is comparatively large, and condition is harsh, because which limit its applicability.
(3) summary of the invention
The present invention seeks to improve the various defects of prior art, provide a kind of catalyzer to be easy to get, can repeatedly reuse, mild condition, easy and simple to handle, easily control and the chemical synthesis process of aryl azide compound that yield is higher.
The technical solution used in the present invention is:
The preparation method of the nitrine aryl compounds shown in a kind of formula I, described method for: by the iodo aryl compound shown in formula II and sodiumazide, alkaline matter, part in solvent, under the katalysis of Porous Cu, react at 60 ~ 100 DEG C of temperature, TLC tracing detection is to reacting completely, and reaction solution aftertreatment obtains the aryl azide compound shown in formula I; Described part is L-PROLINE, tetramethyleneimine, Pidolidone, L-threonine or ALANINE; Described solvent is dimethyl sulfoxide (DMSO) (be called for short DMSO), the mixed solvent of dimethyl formamide (being called for short DMF), water or dimethyl sulfoxide (DMSO) and water;
In formula I or formula (II), R is to methoxyl group (p-OCH
3), O-methoxy (o-OCH
3), to methyl (p-CH
3), to oxyethyl group (p-OC
2h
5), to amino (p-NH
2), acetparaminosalol (p-NHCOCH
3), to bromo (p-Br), to chloro (p-Cl) or to trifluoromethyl (p-CF
3), be preferably to methoxyl group, to methyl, to oxyethyl group, to amino, to bromo or to chloro.
Described alkaline matter is NaOH, KOH, LiOH, Na
2cO
3, NaHCO
3, Cs
2cO
3, CH
3cOOCs, CH
3cOONa, K
3pO
43H
2o, triethylamine, Diisopropylamine, diethylamine or quadrol, be preferably NaOH, LiOH, Na
2cO
3, Cs
2cO
3, CH
3cOOCs, CH
3cOONa, K
3pO
43H
2o, triethylamine or Diisopropylamine, most preferably be Diisopropylamine.
Described part is preferably L-PROLINE, L-threonine or ALANINE, most preferably is L-PROLINE.
Described solvent is dimethyl sulfoxide (DMSO) (be called for short DMSO), the mixed solvent of dimethyl formamide (being called for short DMF), water or dimethyl sulfoxide (DMSO) and water, and in the mixed solvent of wherein dimethyl sulfoxide (DMSO) and water, the volume ratio of dimethyl sulfoxide (DMSO) and water is generally 1:0.1 ~ 9.
Described solvent is preferably DMSO.
The ratio of the amount of substance that feeds intake of the iodo aryl compound shown in described formula II, sodiumazide, alkaline matter, part is 1:1.1 ~ 2:0.2 ~ 0.3:0.05 ~ 0.2, is preferably 1:2:0.2:0.2.
The aperture of described Porous Cu is 5 ~ 150 μm, is preferably 5 μm.Described Porous Cu directly buys acquisition by commercial goods.
1 ~ 10% of the amount of substance that the amount of substance consumption of described Porous Cu is the iodo aryl compound shown in formula II, is preferably 5 ~ 10%, most preferably is 5%.
The volumetric usage of described solvent counts 2 ~ 10mL/mmol with the amount of substance of the iodo aryl compound shown in formula II, is preferably 2mL/mmol.
The temperature of reaction of the present invention is preferably 80 ~ 100 DEG C, most preferably 80 DEG C.
The present invention's reaction is by TLC tracing detection to reacting completely, and the usual reaction times is 10 ~ 80h, is preferably 14 ~ 80h.
Reaction solution post-treating method of the present invention is: after reaction terminates, reaction solution is extracted with ethyl acetate, and with saturated sodium-chloride water solution washing, get organic phase drying, concentrated after through column chromatography for separation, using sherwood oil as developping agent, collect R
fthe elutriant of value 0.7 ~ 0.8, the underpressure distillation of gained elutriant, dry, obtained aryl azide compound shown in described formula I.
Further, the preparation method of aryl azide compound of the present invention recommends to carry out according to following steps: described method is carried out according to the following steps: mixed in a solvent with sodiumazide, alkaline matter, part by the iodo aryl compound shown in formula II, add the Porous Cu catalyzer in 5 μm, aperture, react at 80 DEG C of temperature, TLC tracing detection is to reacting completely, reaction solution is extracted with ethyl acetate, and wash with saturated sodium-chloride water solution, get organic phase drying, concentrated after through column chromatography for separation, using sherwood oil as developping agent, collect R
fthe elutriant of value 0.7 ~ 0.8, the underpressure distillation of gained elutriant, dry, obtained aryl azide compound shown in described formula I; Described alkaline matter is Diisopropylamine; Described part is L-PROLINE; Described solvent is dimethyl sulfoxide (DMSO); The ratio of the amount of substance that feeds intake of the iodo aryl compound shown in described formula II, sodiumazide, Diisopropylamine, L-PROLINE is 1:2:0.2:0.2; 5% of the amount of substance that the amount of substance consumption of described Porous Cu is the iodo aryl compound shown in formula II; The volumetric usage of described solvent counts 2mL/mmol with the amount of substance of the iodo aryl compound shown in formula II.
The preparation method of aryl azide compound provided by the invention, its key is to have selected Porous Cu to make catalyzer, can prepare by one kettle way.Its advantage is: (1), mild condition, easy to operate, and product quality is good, and yield is higher; (2), one kettle way preparation, reaction process is safe and reliable; (3), catalyzer Porous Cu is cheaply easy to get, and do not need process just can reuse repeatedly and on reaction effect without any impact.(4), this reaction meets atom economy principle, and have higher regioselectivity and Atom economy, raw material availability is high.In view of aryl azide compound is as important chemosynthesis intermediate, therefore the present invention has prospects for commercial application widely.
(4) embodiment
Below will the present invention is further illustrated by embodiment, but protection scope of the present invention is not limited thereto.
The Porous Cu used in embodiment is produced by Changsha Liyuan New Material Co., Ltd., 5 μm, aperture.
Embodiment 1:
1-nitrine-4-methyl-phenoxide
By paraiodoanisole (II-1) (468.1mg, 2mmol), sodiumazide (260.0mg, 4mmol), L-PROLINE (46.1mg, 0.4mmol), Diisopropylamine (56 μ l, 0.4mmol), Porous Cu (6.4mg, 0.1mmol) mixing in DMSO (4mL), stirring reaction in 80 DEG C of oil baths, TLC follows the tracks of reaction to reacting completely, reaction times 26.5h.After reaction terminates, with ethyl acetate (10mL × 3) extraction, saturated common salt water washing, merges organic phase, anhydrous sodium sulfate drying, filters, and filtrate concentrates, and through column chromatography for separation, take sherwood oil as developping agent, collects R
fthe elutriant of value 0.7 ~ 0.8, the underpressure distillation of gained elutriant, dry, obtain target compound (I-1) 286.3mg, yield is 95.97%, yellow oily liquid.
1H NMR (500MHz, CDCl
3): δ=6.98(d, J=9.0 Hz, 2H), 6.91(d, J=9.0 Hz, 2H), 3.81(s, 3H).
Embodiment 2:
Change Diisopropylamine into NaOH(0.0160g, 0.4mmol), the reaction times is 30h, and other operations are with embodiment 1, and yield is 79.50%.
Embodiment 3:
Change Diisopropylamine into KOH(0.0224g, 0.4mmol), the reaction times is 62.5h, and other operations are with embodiment 1, and yield is 15.47%.
Embodiment 4:
Change Diisopropylamine into LiOH(0.0168g, 0.4mmol), the reaction times is 79h, and other operations are with embodiment 1, and yield is 62.48%.
Embodiment 5:
Change Diisopropylamine into Na
2cO
3(0.0424g, 0.4mmol), the reaction times is 50.5h, and other operations are with embodiment 1, and yield is 66.94%.
Embodiment 6:
Change Diisopropylamine into NaHCO
3(0.0336g, 0.4mmol), the reaction times is 46h, and other operations are with embodiment 1, and yield is 46.50%.
Embodiment 8:
Change Diisopropylamine into Cs
2cO
3(0.1303g, 0.4mmol), the reaction times is 54h, and other operations are with embodiment 1, and yield is 74.26%.
Embodiment 9:
Change Diisopropylamine into CH
3cOOCs(0.0768g, 0.4mmol), the reaction times is 35.5h, and other operations are with embodiment 1, and yield is 71.76%.
Embodiment 10:
Change Diisopropylamine into CH
3cOONa(0.0328g, 0.4mmol), the reaction times is 28h, and other operations are with embodiment 1, and yield is 76.40%.
Embodiment 11:
Change Diisopropylamine into K
3pO
43H
2o(0.1065g, 0.4mmol), the reaction times is 34h, and other operations are with embodiment 1, and yield is 62.50%.
Embodiment 12:
Diisopropylamine is changed into triethylamine (0.0405g, 0.4mmol), the reaction times is 28.5h, and other operations are with embodiment 1, and yield is 81.78%.
Embodiment 13:
Diisopropylamine is changed into diethylamine (0.0293g, 0.4mmol), the reaction times is 38h, and other operations are with embodiment 1, and yield is 49.30%.
Embodiment 14:
Diisopropylamine is changed into quadrol (0.0240g, 0.4mmol), the reaction times is 38h, and other operations are with embodiment 1, and yield is 54.00%.
Embodiment 15:
Change ligand L-proline(Pro) into tetramethyleneimine (0.0284g, 0.4mmol), the reaction times is 29h, and other operations are with embodiment 1, and yield is 28.53%.
Embodiment 16:
Change ligand L-proline(Pro) into Pidolidone (0.0589g, 0.4mmol), the reaction times is 29h, and other operations are with embodiment 1, and yield is 15.98%.
Embodiment 17:
Change ligand L-proline(Pro) into L-threonine (0.0476g, 0.4mmol), the reaction times is 17h, and other operations are with embodiment 1, and yield is 80.79%.
Embodiment 18:
Change ligand L-proline(Pro) into ALANINE (0.0356g, 0.4mmol), the reaction times is 17h, and other operations are with embodiment 1, and yield is 79.32%.
Embodiment 19:
Change solvent DMSO into DMF(4mL), the reaction times is 28.5h, and other operations are with embodiment 1, and yield is 55.06%.
Embodiment 20:
Solvent DMSO is changed into deionized water (4mL), the reaction times is 65h, and other operations are with embodiment 1, and yield is 64.71%.
Embodiment 21:
Solvent is changed into 4mL DMSO:H
2the mixed solvent of O volume ratio 9:1, the reaction times is 40h, and other operations are with embodiment 1, and yield is 63.38%.
Embodiment 22:
Solvent is changed into 4mL DMSO:H
2the mixed solvent of O volume ratio 3:1, the reaction times is 730h, and other operations are with embodiment 1, and yield is 29.77%.
Embodiment 23:
Solvent is changed into 4mL DMSO:H
2the mixed solvent of O volume ratio 1:1, the reaction times is 73h, and other operations are with embodiment 1, and yield is 30.02%.
Embodiment 24:
Solvent is changed into 4mL DMSO:H
2the mixed solvent of O volume ratio 1:3, the reaction times is 73h, and other operations are with embodiment 1, and yield is 44.28%.
Embodiment 25:
Solvent is changed into 4mL DMSO:H
2the mixed solvent of O volume ratio 1:9, the reaction times is 47.5h, and other operations are with embodiment 1, and yield is 54.94%.
Embodiment 26:
The amount of L-PROLINE is reduced to 23.0mg (0.2mmol), the reaction times is 21.5h, and other operations are with embodiment 1, and yield is 76.15%.
Embodiment 27:
The amount of L-PROLINE is reduced to 11.5mg (0.1mmol), the reaction times is 22.5h, and other operations are with embodiment 1, and yield is 68.01%.
Embodiment 28:
The amount of L-PROLINE is reduced to 0, and the reaction times is 62.5h, and other operations are with embodiment 1, and yield is 23.32%.
Embodiment 29:
The amount of Porous Cu is reduced to 1.28mg (0.02mmol), the reaction times is 48h, and other operations are with embodiment 1, and yield is 61.68%.
Embodiment 30:
The amount of Porous Cu is increased to 12.8mg (0.2mmol), the reaction times is 19.5h, and other operations are with embodiment 1, and yield is 80.14%.
Embodiment 31:
Temperature of reaction is reduced to 60 DEG C, the reaction times is 48h, and other operations are with embodiment 1, and yield is 4.14%.
Embodiment 32:
Temperature of reaction is elevated to 100 DEG C, the reaction times is 16.5h, and other operations are with embodiment 1, and yield is 52.70%.
Embodiment 33:
1-nitrine-2-methyl-phenoxide
Substitute paraiodoanisole with 468.1mg (2mmol) 2-phenyl-iodide methyl ether (II-2), other operations are with embodiment 1, and obtain target product (I-2) 55.2mg, yield is 18.5%, colourless oil liquid.
1H NMR (500MHz, CDCl
3) δ=7.14–7.10(m, 1H), 7.04-7.03(m, 1H), 6.97–6.90(m, 2H), 3.89 (s, 3H).
Embodiment 34:
(Ⅰ-3) (Ⅱ-3)
Substitute paraiodoanisole with 436.1mg (2mmol) 4-iodo toluene (II-3), other operations are with embodiment 1, and obtain target product (I-3) 177.0mg, yield is 66.46%, colourless oil liquid.
1HNMR(500MHz, CDCl
3):δ=7.17(d, J=8.0, 2H), 6.94(d, J=8.0, 2H).
Embodiment 35:
Substitute paraiodoanisole with 496.1mg (2mmol) 4-phenyl-iodide ether (II-4), other operations are with embodiment 1, and obtain target product (I-4) 282.9mg, yield is 86.68%, yellow oily liquid.
1H NMR (500MHz, CDCl
3) δ=6.98–6.94 (m, 2H), 6.91–6.88 (m, 2H), 4.02 (q, J=7.0 Hz, 2H), 1.43 (t, J=7.0 Hz, 3H).
Embodiment 36:
Substitute paraiodoanisole with 438.0mg (2mmol) 4-iodo aniline (II-5), other operations are with embodiment 1, and obtain target product (I-5) 257.8mg, yield is 96.11%, yellow oily liquid.
1HNMR(500MHz, CDCl
3):δ=6.85(d, J=8.7, 2H), 6.69(d, J=8.7, 2H), 3.66(s, 2H).
Embodiment 37:
Substitute paraiodoanisole with 522.1mg (2mmol) 1-carbamyl-4-phenyl-iodide (II-6), other operations are with embodiment 1, and obtain target product (I-6) 169.0mg, yield is 47.95%, white solid.
1HNMR(500MHz, CDCl
3):δ=7.51(d,J=8.8,2H), 7.30(s,1H), 6.99(d,J=8.8,2H), 2.19(s,3H).
Embodiment 38:
Substitute paraiodoanisole with 565.8mg (2mmol) 4-iodo bromobenzene (II-7), other operations are with embodiment 1, and obtain target product (I-7) 346.5mg, yield is 87.50%, yellow oily liquid.
1H NMR (500MHz, CDCl
3) δ=7.4–7.46(m, 2H), 6.93–6.90(m, 2H).
Embodiment 39:
Substitute paraiodoanisole with 476.9mg (2mmol) 4-iodo chlorobenzene (II-8), other operations are with embodiment 1, and obtain target product (I-8) 173.5mg, yield is 56.50%, yellow oily liquid.
1H NMR (500MHz, CDCl
3) δ=7.34–7.31(m, 2H), 6.98–6.95(m, 2H).
Embodiment 40:
Substitute paraiodoanisole with 544.0mg (2mmol) 4-iodo trifluoromethylbenzene (II-9), other operations are with embodiment 1, and obtain target product (I-9) 64.0mg, yield is 17.09%, colourless oil liquid.
1HNMR(500MHz, CDCl
3):δ=7.55(d, J=8.5, 2H), 7.72(d, J=8.5, 2H).
Claims (3)
1. the preparation method of the aryl azide compound shown in a formula I, described method for: by the iodo aryl compound shown in formula II and sodiumazide, alkaline matter, part in solvent, under the katalysis of Porous Cu, react at 80 DEG C of temperature, TLC tracing detection is to reacting completely, and reaction solution aftertreatment obtains the aryl azide compound shown in formula I; Described part is L-PROLINE; Described solvent is dimethyl sulfoxide (DMSO); The aperture of described Porous Cu is 5 μm; The ratio of the amount of substance that feeds intake of the iodo aryl compound shown in described formula II, sodiumazide, alkaline matter, part is 1:2:0.2:0.2; 5% of the amount of substance that the amount of substance consumption of described Porous Cu is the iodo aryl compound shown in formula II;
In formula I or formula (II), R be to methoxyl group, O-methoxy, to methyl, to oxyethyl group, to amino, acetparaminosalol, to bromo, to chloro or to trifluoromethyl;
Described alkaline matter is Diisopropylamine.
2. the method for claim 1, is characterized in that described reaction solution post-treating method is: after reaction terminates, reaction solution is extracted with ethyl acetate, and wash with saturated sodium-chloride water solution, get organic phase drying, concentrated after through column chromatography for separation, using sherwood oil as developping agent, collect R
fthe elutriant of value 0.7 ~ 0.8, the underpressure distillation of gained elutriant, dry, obtained aryl azide compound shown in described formula I.
3. the method for claim 1, it is characterized in that described method is carried out according to the following steps: mixed in a solvent with sodiumazide, alkaline matter, part by the iodo aryl compound shown in formula II, add the Porous Cu catalyzer in 5 μm, aperture, react at 80 DEG C of temperature, TLC tracing detection is to reacting completely, reaction solution is extracted with ethyl acetate, and wash with saturated sodium-chloride water solution, get organic phase drying, concentrated after through column chromatography for separation, using sherwood oil as developping agent, collect R
fthe elutriant of value 0.7 ~ 0.8, the underpressure distillation of gained elutriant, dry, obtained aryl azide compound shown in described formula I; Described alkaline matter is Diisopropylamine; Described part is L-PROLINE; Described solvent is dimethyl sulfoxide (DMSO); The ratio of the amount of substance that feeds intake of the iodo aryl compound shown in described formula II, sodiumazide, Diisopropylamine, L-PROLINE is 1:2:0.2:0.2; 5% of the amount of substance that the amount of substance consumption of described Porous Cu is the iodo aryl compound shown in formula II; The volumetric usage of described solvent counts 2mL/mmol with the amount of substance of the iodo aryl compound shown in formula II.
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Citations (3)
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| DE4240193A1 (en) * | 1992-10-07 | 1994-06-01 | Nat Res Dev | Dihalo-dimethyl-monoazido-mononitro-benzenes, photoresist compositions based thereon, processes for their preparation and their use |
| CN101948405A (en) * | 2010-09-09 | 2011-01-19 | 同济大学 | Method for preparing bromoaryl azide |
| CN102603660A (en) * | 2012-02-10 | 2012-07-25 | 浙江工业大学 | Preparation method of 1H-1,2,3-triazole compound |
-
2012
- 2012-12-03 CN CN201210521317.0A patent/CN103012195B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4240193A1 (en) * | 1992-10-07 | 1994-06-01 | Nat Res Dev | Dihalo-dimethyl-monoazido-mononitro-benzenes, photoresist compositions based thereon, processes for their preparation and their use |
| CN101948405A (en) * | 2010-09-09 | 2011-01-19 | 同济大学 | Method for preparing bromoaryl azide |
| CN102603660A (en) * | 2012-02-10 | 2012-07-25 | 浙江工业大学 | Preparation method of 1H-1,2,3-triazole compound |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis of aryl azides and vinyl azides via proline-promoted CuI-catalyzed coupling reactions";Wei Zhu and Dawei Ma;《Chem.Commun.》;20040305;888-889 * |
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Effective date of registration: 20191225 Address after: 314400 in huangwan town government, Haining City, Jiaxing City, Zhejiang Province Patentee after: Haining huangwan town Asset Management Co.,Ltd. Address before: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20191225 Address after: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: The city Zhaohui six districts Chao Wang Road Hangzhou City, Zhejiang province 310014 18 Patentee before: Zhejiang University of Technology |
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