CN106588693B - A kind of synthetic method of aryl azide compound - Google Patents
A kind of synthetic method of aryl azide compound Download PDFInfo
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Abstract
The invention discloses a kind of synthetic methods of aryl azide compound, specific steps are as follows: by iodo aryl class compound, sodium azide, 1,11 carbon -7- alkene of 8- diazabicylo [5.4.0] and catalyst are added in the reaction vessel equipped with solvent, reaction mixture is stirred to react in 60-105 DEG C again, TLC tracing detection is to fully reacting, ammonium hydroxide is added into reaction mixture again, then it is extracted with ethyl acetate 3 times, and it is washed 1 time with saturated common salt, take organic phase dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product.Raw material used in the present invention is simple and easy to get, and the range of choice of catalyst copper source is wide, and reaction condition is mild, and easy to operate, yield is relatively high.
Description
Technical field
The invention belongs to the synthesis technical fields of azide compounds, and in particular to a kind of conjunction of aryl azide compound
At method.
Background technique
Aryl azide compound contains azido high energy active function groups, is a kind of important chemical synthesis intermediate,
It is widely used in the numerous areas such as organic synthesis, chemical biology, functional material and clinical medicine.In addition, by folded
The introducing of nitrogen base, can also realize the conversion reaction of some important functional groups, for example, famous " Click " reaction and
Staudinger reaction etc..In recent years, as people are to the full appreciation of azide property and its mentioning for experiment safety technology
Height, such compound regain the attention of researcher, especially beginning of this century Sharpless etc. for azido compound and Terminal Acetylenes
1,3- dipole-diople interaction develop into " click " reaction since, aryl azide chemical combination object synthesize 1,2,3- triazole compounds
Application development etc. numerous related fieldss is especially rapid, causes the extensive concern of people.At present about aryl azide class chemical combination
There are many synthetic method of object, generally have following several: (1) aryl primary amine diazo-reaction: preparing virtue using arylamine diazo-reaction
Base azido compound is the classical way of such compound synthesis, and reaction is often carried out in two steps, and the first step is that arylamine aoxidizes to obtain
Diazonium salt carries out in strong acidic environment often using sodium nitrite as oxidant, and second step is the decomposition of diazonium salt and further
Azide obtains target product, and the method has many advantages, such as that low in cost, reaction is efficient, the disadvantage is that needing under strong acidic environment
It carries out, will affect the structure of substrate and the compatibility of functional group sometimes；(2) the direct nucleophilic displacement of fluorine of short of electricity virtue halogen: electron deficient aromatic ring
Fragrant halogen key be activated, a variety of nucleophilic substitutions easily occur for electrophilicity enhancing, and Wilson etc. uses the carbon-halogen bond containing activation
2- chloropyridine system class compound and sodium azide directly occur nucleophilic substitution and obtain aryl azide compound, contained to take
Be more advantageous to when Dai Jiwei electron-withdrawing group reaction progress (J. Org. Chem., 1990, 55(12): 3755-3761)；
(3) halogenated hydrocarbons catalytic coupling: Ma etc. is even by the catalysis of halogenated hydrocarbons and Sodium azide using cuprous iodide/L-PROLINE as catalyst
The obtained organic azide of connection reaction (Chem. Commun., 2004, 888-889)；(4) organic boronic catalytic coupling:
The discovery aryl boric acid such as Guo and sodium azide can smoothly react under catalysis of cupric sulphate, generate aryl azide chemical combination object.This is anti-
The advantages of answering is mild condition, can be carried out at room temperature, and a variety of functional groups are unaffected, and " copper source " can use in extensive range and vertical
Body it is selectively good (Tetrahedron Lett., 2007, 48, 3525-3529)；(5) phenylhydrazine is in triphenylphosphine, bromine water and four
Under the action of butyl inferior ammonium nitrate reaction generate aryl azide chemical combination object (Tetrahedron Lett., 2008, 49, 4242-
4244).But there are still many defects for the above method, it is more demanding to pH when such as diazotising, it is not easy to control, material toxicity compared with
Greatly, it is easy to generate by-product, yield is lower, and the scope of application is small, and limitation is larger, and condition is harsh, therefore limits it further
Using.
Summary of the invention
The technical problem to be solved by the present invention is to provide it is a kind of it is easy to operate, be easy to control and the higher aryl azide of yield
The synthetic method of class compound.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of synthesis side of aryl azide compound
Method, it is characterised in that specific steps are as follows: by iodo aryl class compound, sodium azide, 1,8- diazabicylo [5.4.0] 11
Carbon -7- alkene (DBU) and catalyst are added in the reaction vessel equipped with solvent, then reaction mixture is anti-in 60-105 DEG C of stirring
It answers, TLC tracing detection to fully reacting, then ammonium hydroxide is added into reaction mixture, be then extracted with ethyl acetate 3 times, be used in combination
Saturated common salt is washed 1 time, is taken organic phase dry, is filtered, and rotation removes solvent, and column chromatographic purifying obtains target product, the iodo
Aryl class compound be iodobenzene, to methyl iodobenzene, to methoxyl group iodobenzene, to bromo-iodobenzene, to ethyoxyl iodobenzene, 3,4- dimethyl iodine
Benzene, bromo-iodobenzene, chloroiodobenzone, adjacent methyl iodobenzene, 2,4,6- trimethyl iodobenzene, adjacent chloroiodobenzone, adjacent hydroxy-iodobenzene, adjacent fluorine iodine
Benzene, 2- iodine trifluoromethylbenzene or between nitro iodobenzene methyl, the catalyst is copper acetate, copper sulphate, copper chloride, bromination
Copper, acetylacetone copper, cuprous iodide, stannous chloride, cuprous bromide or cuprous oxide, the solvent dimethyl sulfoxide or N, N-
Dimethylformamide.
Further preferably, the iodo aryl class compound, sodium azide, 1,8- diazabicylo [5.4.0] 11
The molar ratio of carbon -7- alkene and catalyst is 1:1.2:0.05-0.3:0.05-0.1.
Raw material used in the present invention is simple and easy to get, and the range of choice of catalyst copper source is wide, and reaction condition is mild, operation letter
Single, yield is relatively high.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
Using different mantoquitas as catalyst, by 1.0mmol iodobenzene, 1.2mmol sodium azide, 0.2mmol DBU and
0.1mmol catalyst is added sequentially in the reaction flask equipped with 3.0mL dimethyl sulfoxide, and reaction mixture is anti-in 95 DEG C of stirrings
It answers, a few drop ammonium hydroxide are added into reaction mixture for TLC tracking reaction to fully reacting, be then extracted with ethyl acetate (10mL ×
3) it, then with saturated common salt washes 1 time, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, different catalysts pair
The influence of reaction yield is shown in Table 1.
Influence of 1 different catalysts of table to reaction yield
| Group | Catalyst | Reaction time (h) | Yield (%) |
| 1 | Cu(OAc)2·H2O | 1.5 | 91 |
| 2 | CuSO4·5H2O | 1.5 | 84 |
| 3 | CuCl2·2H2O | 2.0 | 83 |
| 4 | CuBr2 | 2.0 | 83 |
| 5 | Cu(acac)2 | 5.0 | 50 |
| 6 | CuI | 2.5 | 90 |
| 7 | CuBr | 3.0 | 85 |
| 8 | CuCl | 3.0 | 85 |
| 9 | Cu2O | 2.5 | 87 |
Embodiment 2
1.0mmol iodobenzene, 1.2mmol sodium azide, 0.2mmol DBU and 0.1mmol copper acetate are added sequentially to fill
In the reaction flask for having 3.0mL solvent, reaction mixture is stirred to react in 95 DEG C, TLC tracking reaction is to fully reacting, to reaction
A few drop ammonium hydroxide are added in mixture, are then extracted with ethyl acetate (10mL × 3), then are washed 1 time with saturated common salt, it is dry, it takes out
Filter, rotation remove solvent, and column chromatographic purifying obtains target product, and influence of the different solvents to reaction yield is shown in Table 2.
Influence of 2 different solvents of table to reaction yield
| Group | Solvent | Reaction time (h) | Yield (%) |
| 1 | DMSO | 1.5 | 93 |
| 2 | DMF | 5.0 | 80 |
| 3 | MeOH | 8.0 | 45 |
| 4 | EtOH | 8.0 | 40 |
| 5 | H2O | 9.0 | 20 |
| 6 | EtOH/H2O (7:3) | 10.0 | 40 |
Embodiment 3
1.0mmol iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate are added sequentially to fill
In the reaction flask for having 3mL dimethyl sulfoxide, reaction mixture is stirred to react 1.5h in 95 DEG C, TLC tracking reaction is to having reacted
Entirely, a few drop ammonium hydroxide are added into reaction mixture, are then extracted with ethyl acetate (10mL × 3), then wash 1 with saturated common salt
It is secondary, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 92%.
The data characterization of aziminobenzene: light yellow liquid；1H NMR (400 MHz, CDCl3) δ: 7.38-7.34 (m,
2H), 7.15 (t, J = 8.0 Hz, 1H), 7.04 (d, J = 8.0 Hz, 2H). 13C NMR (100 MHz,
CDCl3) δ: 140.0, 129.8, 124.9, 119.0。
Embodiment 4
1.0mmol iodobenzene, 1.2mmol sodium azide, 0.05mmol DBU and 0.05mmol cupric sulfate pentahydrate are successively added
Enter into the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 1.5h in 95 DEG C, TLC tracking reaction is extremely
A few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use saturated common salt for fully reacting
Washing 1 time, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 60%.
Embodiment 5
1.0mmol iodobenzene, 1.2mmol sodium azide, 0.3mmol DBU and 0.1mmol copper chloride are added sequentially to fill
In the reaction flask for having 3mL dimethyl sulfoxide, reaction mixture is stirred to react 13h in 60 DEG C, TLC tracking reaction is to having reacted
Entirely, a few drop ammonium hydroxide are added into reaction mixture, are then extracted with ethyl acetate (10mL × 3), then wash 1 with saturated common salt
It is secondary, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 80%.
Embodiment 6
1.0mmol iodobenzene, 1.2mmol sodium azide, 0.3mmol DBU and 0.1mmol copper bromide are added sequentially to fill
In the reaction flask for having 3mL dimethyl sulfoxide, reaction mixture is stirred to react 2h in 105 DEG C, TLC tracking reaction is to having reacted
Entirely, a few drop ammonium hydroxide are added into reaction mixture, are then extracted with ethyl acetate (10mL × 3), then wash 1 with saturated common salt
It is secondary, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 78%.
Embodiment 7
Successively by 1.0 mmol iodobenzenes, 1.2 mmol sodium azide, 0.15 mmol DBU and 0.1mmol acetylacetone copper
It is added in the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 2h in 95 DEG C, TLC tracking reaction is extremely
A few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use saturated common salt for fully reacting
Washing 1 time, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 40%.
Embodiment 8
Successively to methyl iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol cuprous iodide by 1.0mmol
Be added in the reaction flask equipped with 3mL n,N-Dimethylformamide, reaction mixture be stirred to react 3.5h in 95 DEG C, TLC with
Track is reacted to fully reacting, and a few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use
Saturated common salt is washed 1 time, dry, is filtered, and rotation removes solvent, and column chromatographic purifying obtains target product, yield 87%.
The data characterization of p-methylphenyl nitrine: light yellow liquid；1H NMR (400 MHz, CDCl3) δ: 7.16
(d, J = 8.0 Hz, 2H), 6.93 (d, J = 8.0 Hz, 2H), 2.34 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ: 137.1, 134.6, 130.4, 118.9, 20.7。
Embodiment 9
Successively to methoxyl group iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate by 1.0mmol
It is added in the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 3.5h, TLC tracking reaction in 95 DEG C
To fully reacting, a few drop ammonium hydroxide are added into reaction mixture, are then extracted with ethyl acetate (10mL × 3), then is eaten with saturation
Salt is washed 1 time, dry, is filtered, and rotation removes solvent, and column chromatographic purifying obtains target product, yield 85%.
The data characterization of p-methoxyphenyl nitrine: yellow liquid；1H NMR (400 MHz, CDCl3) δ: 6.96
(d, J = 8.0 Hz, 2H), 6.89 (d, J = 8.0 Hz, 2H), 3.80 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ: 157.0, 132.3, 120.0, 115.1, 55.6。
Embodiment 10
1.0mmol sequentially adds bromo-iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate
Into the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 2h, TLC tracking reaction to reaction in 95 DEG C
Completely, a few drop ammonium hydroxide are added into reaction mixture, are then extracted with ethyl acetate (10mL × 3), then wash 1 with saturated common salt
It is secondary, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 88%.
The data characterization of p-bromophenyl nitrine: off-white powder；1H NMR (400 MHz, CDCl3) δ: 7.56-7.58
(m, 2H), 7.41-7.43 (m, 2H). 13C NMR (100 MHz, CDCl3) δ: 138.9, 132.0, 128.4,
121.9。
Embodiment 11
Successively to ethyoxyl iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate by 1.0mmol
It is added in the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 4h in 95 DEG C, TLC tracking reaction is extremely
A few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use saturated common salt for fully reacting
Washing 1 time, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 80%.
To the data characterization of ethoxyl phenenyl nitrine: light yellow liquid；1H NMR (400 MHz, CDCl3) δ: 6.94-
6.96 (m, 2H), 6.87-6.89 (m, 2H), 4.01 (q, J = 7.0 Hz, 2H), 1.42 (t, J = 7.0
Hz, 3H). 13C NMR (100 MHz, CDCl3) δ: 156.3, 132.1, 119.9, 115.7, 63.8, 14.8。
Embodiment 12
By 1.0mmol 3,4- dimethyl iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate
It is added sequentially in the reaction flask equipped with 3mL dimethyl sulfoxide, by reaction mixture in 95 DEG C of stirring 2.5h, TLC tracking reactions
To fully reacting, a few drop ammonium hydroxide are added into reaction mixture, are then extracted with ethyl acetate (10mL × 3), then is eaten with saturation
Salt is washed 1 time, dry, is filtered, and rotation removes solvent, and column chromatographic purifying obtains target product, yield 90%.
The data characterization of 3,4- 3,5-dimethylphenyl nitrine: green yellow liquid；1H NMR (400 MHz, CDCl3) δ:
7.10 (d, J = 8.0 Hz, 1H), 6.81 (s, 1H), 6.77 (d, J = 8.0 Hz, 1H), 2.25 (s,
3H), 2.24 (s, 3H). 13C NMR (100 MHz, CDCl3) δ: 138.3, 137.3, 133.4, 130.8,
120.0, 116.3, 19.9, 19.2。
Embodiment 13
Bromo-iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate between 1.0mmol are successively added
Enter into the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 4.5h in 95 DEG C, TLC tracking reaction is extremely
A few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use saturated common salt for fully reacting
Washing 1 time, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 85%.
The data characterization of m-bromophenyl nitrine: light yellow liquid；1H NMR (400 MHz, CDCl3) δ: 7.70 (s,
1H), 7.46-7.51 (m, 2H), 7.30-7.34 (m, 1H). 13C NMR (100 MHz, CDCl3) δ: 141.8,
130.8, 130.4, 130.2, 125.8, 123.0。
Embodiment 14
Chloroiodobenzone, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate between 1.0mmol are successively added
Enter into the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is placed in 95 DEG C and is stirred to react 4.5h, TLC tracking reaction
To fully reacting, a few drop ammonium hydroxide are added into reaction mixture, are then extracted with ethyl acetate (10mL × 3), then is eaten with saturation
Salt is washed 1 time, dry, is filtered, and rotation removes solvent, and column chromatographic purifying obtains target product, yield 85%.
The data characterization of m-chloro aziminobenzene: light yellow liquid；1H NMR (400 MHz, CDCl3) δ: 7.30-7.26
(m, 1H), 7.12 (d, J = 8.0 Hz, 1H), 7.03 (t, J = 2.0 Hz, 1H), 6.93 (dd, J =
8.1, 2.1 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 141.5, 135.4, 130.7, 125.1,
119.3, 117.2。
Embodiment 15
1.0mmol neighbour's methyl iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate are successively added
Enter into the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is placed in 95 DEG C and is stirred to react 5.0h, TLC tracking reaction
To fully reacting, a few drop ammonium hydroxide are added into reaction mixture, are then extracted with ethyl acetate (10mL × 3), then is eaten with saturation
Salt is washed 1 time, dry, is filtered, and rotation removes solvent, and column chromatographic purifying obtains target product, yield 75%.
The data characterization of o-methyl-phenyl nitrine: light yellow liquid；1H NMR (400 MHz, CDCl3) δ: 7.24-
7.20 (m, 1H), 7.16-7.09 (m, 2H), 7.05-7.01 (m,1H), 2.20 (s, 3H). 13C NMR (100
MHz, CDCl3) δ: 138.4, 131.2, 129.6, 127.1, 124.6, 117.9, 17.3。
Embodiment 16
By 1.0mmol 2,4,6- trimethyl iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol acetic acid
Copper is added sequentially in the reaction flask equipped with 3mL dimethyl sulfoxide, and reaction mixture is placed in 95 DEG C and is stirred to react 2h, TLC with
Track is reacted to fully reacting, and a few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use
Saturated common salt is washed 1 time, dry, is filtered, and rotation removes solvent, and column chromatographic purifying obtains target product, yield 78%.
The data characterization of 3,4,6- trimethylphenyl nitrine: light yellow liquid；1H NMR (400 MHz, CDCl3) δ:
6.86 (s, 2H), 2.35 (s, 6H), 2.28 (s, 3H). 13C NMR (100 MHz, CDCl3) δ: 135.3,
134.4, 131.9, 129.5, 20.7, 18.1。
Embodiment 17
1.0mmol neighbour's chloroiodobenzone, 1.2mmol sodium azide, 0.15 mmol DBU and 0.1mmol copper acetate are successively added
Enter into the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 3.5h in 95 DEG C, TLC tracking reaction is extremely
A few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use saturated common salt for fully reacting
Washing 1 time, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 75%.
The data characterization of Chloro-O-Phenyl nitrine: colourless oil liquid；1H NMR (400 MHz, CDCl3) δ: 7.37
(d, J = 8.0 Hz, 1H), 7.31-7.28(m, 1H), 7.17 (d, J = 8.0 Hz, 1H), 7.08 (t, J =
8.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 137.2, 130.8, 127.9, 125.6, 125.0,
119.7。
Embodiment 18
1.0mmol neighbour's hydroxy-iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate are successively added
Enter into the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 3.5h in 95 DEG C, TLC tracking reaction is extremely
A few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use saturated common salt for fully reacting
Washing 1 time, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 71%.
The data characterization of o-hydroxy-phenyl nitrine: dark red solution；1H NMR (400 MHz, CDCl3) δ: 7.08-
7.03 (m, 2H), 6.93 (t, J = 7.8 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ: 147.4,
126.0, 126.0, 121.2, 118.4, 116.0。
Embodiment 19
1.0mmol neighbour's fluorine iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1 mmol copper acetate are successively added
Enter into the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is stirred to react 3.5h in 95 DEG C, TLC tracking reaction is extremely
A few drop ammonium hydroxide are added into reaction mixture, (10mL × 3) are then extracted with ethyl acetate, then use saturated common salt for fully reacting
Washing 1 time, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 71%.
The data characterization of o-fluorophenyl nitrine: dark red solution；1H NMR (400 MHz, CDCl3) δ: 7.14-7.05
(m, 4H). 13C NMR (100 MHz, CDCl3) δ: 156.1, 125.8, 125.7, 124.9, 124.8, 121.0,
116.8, 116.6。
Embodiment 20
By 1.0mmol 2- iodine trifluoromethylbenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol copper acetate
It is added sequentially in the reaction flask equipped with 3mL dimethyl sulfoxide, reaction mixture is placed in 95 DEG C and is stirred to react 4h, TLC tracking
Reaction a few drop ammonium hydroxide is added into reaction mixture, are then extracted with ethyl acetate (10mL × 3) to fully reacting, then with satisfying
It is washed 1 time with salt, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 72%.
The data characterization of 2- (trifluoromethyl) aziminobenzene: yellow-brown solid；1H NMR (400 MHz, CDCl3) δ:
7.63 (d, J = 8.0 Hz, 1H), 7.58 (t, J = 8.0Hz, 1H), 7.30 (d, J = 8.0 Hz, 1H),
7.22 (t, J = 8.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ: 138.5, 133.1, 127.4,
124.5, 124.3, 121.6, 119.5。
Embodiment 21
By 1.0mmol between nitro iodobenzene, 1.2mmol sodium azide, 0.15mmol DBU and 0.1mmol acetic acid methyl
Copper is added sequentially in the reaction flask equipped with 3mL dimethyl sulfoxide, and reaction mixture is stirred to react 4h, TLC tracking in 95 DEG C
Reaction a few drop ammonium hydroxide is added into reaction mixture, are then extracted with ethyl acetate (10mL × 3) to fully reacting, then with satisfying
It is washed 1 time with salt, it is dry, it filters, rotation removes solvent, and column chromatographic purifying obtains target product, yield 70%.
To the data characterization of methyl m-nitro base nitrine: yellow-brown solid；1H NMR (400 MHz, CDCl3) δ:
7.63 (s, 1H), 7.33 (d, J = 8.0 Hz, 1H), 7.16 (d, J = 8.0 Hz, 1H), 2.57 (s,
3H). 13C NMR (100 MHz, CDCl3) δ: 149.7, 139.3, 134.1, 130.0, 123.4, 115.2,
20.0。
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. a kind of synthetic method of aryl azide compound, it is characterised in that specific steps are as follows: by iodo aryl class compound,
Sodium azide, 1,8- diazabicylo [5 .4 .0] 11 carbon -7- alkene and catalyst are added to the reaction equipped with dimethyl sulfoxide
In container, then reaction mixture is stirred to react in 60-105 DEG C, TLC tracing detection to fully reacting, then to reaction mixture
Then middle addition ammonium hydroxide is extracted with ethyl acetate 3 times, and washed 1 time with saturated common salt, takes organic phase dry, filters, rotation is except molten
Agent, column chromatographic purifying obtain target product, the iodo aryl class compound be iodobenzene, to methyl iodobenzene, to methoxyl group iodine
Benzene, to bromo-iodobenzene, to ethyoxyl iodobenzene, 3,4- dimethyl iodobenzene, bromo-iodobenzene, chloroiodobenzone, adjacent methyl iodobenzene, 2,4,
6- trimethyl iodobenzene, adjacent chloroiodobenzone, adjacent hydroxy-iodobenzene, adjacent fluorine iodobenzene, 2- iodine trifluoromethylbenzene or between nitro iodobenzene methyl, institute
The catalyst stated is copper acetate.
2. the synthetic method of aryl azide compound according to claim 1, it is characterised in that: the iodo aryl
Compound, sodium azide, 1,8- diazabicylo [5 .4 .0] 11 carbon -7- alkene and catalyst molar ratio be 1:
1.2:0.05-0.3:0.05-0.1。
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| CN110105408B (en) * | 2019-05-09 | 2022-11-08 | 上海药明康德新药开发有限公司 | Synthetic method of On-DNA aryl azide in construction of DNA coding compound library |
| CN116478064A (en) * | 2023-04-21 | 2023-07-25 | 平顶山学院 | 2-azido-2, 2-difluoro-N-aryl acetamide and synthesis method and application thereof |
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| CN103012195B (en) * | 2012-12-03 | 2015-04-22 | 浙江工业大学 | Preparation method of aryl azide compound |
| CN103113313A (en) * | 2013-03-07 | 2013-05-22 | 同济大学 | Synthetic method of aliphatic 1-substitution-1,2,3-triazole |
| WO2015022335A1 (en) * | 2013-08-12 | 2015-02-19 | Katholieke Universiteit Leuven | Vancomycin analogs |
| CN104945341B (en) * | 2015-07-15 | 2018-03-02 | 河南师范大学 | A kind of method of the triazole compound of three components one pot process 1,2,3 |
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