CN104815692A - Copper catalyst and composition thereof, and applications of copper catalyst and composition - Google Patents
Copper catalyst and composition thereof, and applications of copper catalyst and composition Download PDFInfo
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- CN104815692A CN104815692A CN201510160637.1A CN201510160637A CN104815692A CN 104815692 A CN104815692 A CN 104815692A CN 201510160637 A CN201510160637 A CN 201510160637A CN 104815692 A CN104815692 A CN 104815692A
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- copper catalyst
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- 0 C(C*1)C*2C1CCCCC2 Chemical compound C(C*1)C*2C1CCCCC2 0.000 description 1
- CIUYJYRQKYGNQP-UHFFFAOYSA-N NCc1cc([N+]([O-])=O)ccc1 Chemical compound NCc1cc([N+]([O-])=O)ccc1 CIUYJYRQKYGNQP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a copper catalyst, which is a coordination compound formed from copper atoms and/or cuprous ions and a ligand, wherein ligand is an organic amine ligand. The invention further relates to a composition formed from the copper catalyst and a nitrating reagent, wherein the composition has characteristics of simple composition, wide application range, mild reaction conditions, less reaction steps, and simple operation, and is especially for industrial production of nitrobenzene, particularly 4-nitroanisole.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind of copper catalyst and composition thereof and purposes.
Background technology
Nitrobenzene is the important intermediate of synthetic drug, dyestuff and plastics.At present, industrial with in laboratory, usually adopt benzene and excessive nitric acid, sulfuric acid generation nitration reaction to obtain nitrobenzene.But this synthetic method must consume a large amount of nitric acid, sulfuric acid, and course of reaction thermal discharge is large, produces a large amount of spent acid, causes severe contamination to environment.Having bibliographical information, under palladium chtalyst effect, is that nitrobenzene prepared by raw material with halogeno-benzene, due to palladium catalyst costly, make the method be only limitted to the production scale in laboratory, be not suitable for industrial production." Copper-catalyzed coupling of aryl halides and nitrite salts:a mild Ullmann-type synthesis of aromatic nitro compounds ", TetrahedronLetters, 2005,46,4715 – 4717 disclose a kind of with 4-iodanisol or 4-bromoanisole for raw material, under the effect of copper and organic amine part, preparation 4-Nitroanisole.But, 4-iodanisol or 4-bromoanisole source less, price costly, make above-mentioned composition can not large-scale application in industrial production, limit its range of application.
Therefore, study a kind of form simple, reaction condition is gentle, reactions steps is few, easy and simple to handle, the copper catalyst prepared for nitration reaction, particularly nitrobenzene that is suitable for suitability for industrialized production and composition thereof have very important significance.
Summary of the invention
The raw material sources had for the preparation method solving nitrobenzene in prior art are less, reaction condition is violent, synthetic route is long, be unsuitable for the shortcomings such as suitability for industrialized production, the invention provides a kind of copper catalyst for nitration reaction and composition thereof, more preferably, a kind of copper catalyst of preparing for nitrobenzene and composition thereof is provided.
For solving the problems of the technologies described above, the invention provides a kind of copper catalyst, described copper catalyst is the complex that copper atom and/or cuprous ion and part are formed; Described part is organic amine part.
In the above-mentioned copper catalyst of the present invention, described part is selected from
in at least one.
In the above-mentioned copper catalyst of the present invention, the mol ratio of the mol ratio of the copper atom in described copper catalyst and/or cuprous ion and described part is 0.02 ~ 0.100:0.03 ~ 0.20.
In the above-mentioned copper catalyst of the present invention, the mol ratio of the mol ratio of the copper atom in described copper catalyst and/or cuprous ion and described part is 0.05 ~ 0.075:0.05 ~ 0.15.
The purposes of the above-mentioned copper catalyst of the present invention in nitration reaction, described nitration reaction is,
Comprise a composition for the above-mentioned copper catalyst of the present invention, also comprise nitrating agent.
In above-mentioned composition of the present invention, described nitrating agent is selected from natrium nitrosum, potassium nitrite, at least one in calcium nitrite, magnesium nitrite, barium nitrite, strontium nitrite, normal-butyl ammonium nilrite.
In above-mentioned composition of the present invention, the mol ratio of the copper atom in described copper catalyst and/or cuprous ion, described part and described nitrating agent is 0.02 ~ 0.100:0.03 ~ 0.20:0.5 ~ 2.0.
In above-mentioned composition of the present invention, the mol ratio of the copper atom in described copper catalyst and/or cuprous ion, described part and described nitrating agent is 0.05 ~ 0.075:0.05 ~ 0.15:1 ~ 1.5.
The purposes of above-mentioned composition of the present invention in nitration reaction, described nitration reaction is,
In the above-mentioned purposes in nitration reaction of the present invention, R is H, (C
1-C
10)-alkyl, OR
1, NR
2r
3, NHCOR
4, NO
2, COOR
5;
R
1for H, (C
1-C
10)-alkyl, aryl;
R
2, R
3be H, (C with being mutually independent
1-C
10)-alkyl, aryl;
R
4for (C
1-C
10)-alkyl, aryl;
R
5for (C
1-C
10)-alkyl, aryl.
In the above-mentioned purposes in nitration reaction of the present invention, R is (C
1-C
4)-alkyl, OR
1, NR
2r
3, NHCOR
4, COOR
5;
R
1for (C
1-C
4)-alkyl;
R
2, R
3be (C with being mutually independent
1-C
4)-alkyl;
R
4for (C
1-C
4)-alkyl;
R
5for (C
1-C
4)-alkyl.
In the above-mentioned purposes in nitration reaction of the present invention, described chlorobenzene is
In the above-mentioned purposes in nitration reaction of the present invention, copper atom in described chlorobenzene and described copper catalyst and/or the mol ratio of cuprous ion are 1:0.02 ~ 0.100, the mol ratio of described chlorobenzene and described nitrating agent is 1:0.5 ~ 2.0, the mol ratio of described chlorobenzene and described part is 1:0.03 ~ 0.20, reaction temperature is 50 ~ 150 DEG C, and the reaction time is 4 ~ 40 hours.
In the above-mentioned purposes in nitration reaction of the present invention, copper atom in described chlorobenzene and described copper catalyst and/or the mol ratio of cuprous ion are 1:0.05 ~ 0.075, the mol ratio of described chlorobenzene and described nitrating agent is 1:1 ~ 1.5, the mol ratio of described chlorobenzene and described part is 1:0.05 ~ 0.15, described reaction temperature is 70 ~ 100 DEG C, and the described reaction time is 12 ~ 20 hours.
In the above-mentioned purposes in nitration reaction of the present invention, copper atom in described chlorobenzene and described copper catalyst or the mol ratio of cuprous ion are 1:0.05, the mol ratio of described chlorobenzene and described nitrating agent is 1:1.2, the mol ratio of described chlorobenzene and described part is 1:0.1, described reaction temperature is 80 DEG C, and the described reaction time is 12 hours.
In the above-mentioned purposes in nitration reaction of the present invention, also comprise the step adopting isolation and purification method described nitrobenzene to be carried out to separation and purification treatment.
In the above-mentioned purposes in nitration reaction of the present invention, described isolation and purification method is selected from least one in filtration, extraction, recrystallization, distillation, column chromatography, thin-layer chromatography, freeze drying.
Technique scheme of the present invention has the following advantages compared to existing technology:
According to the record of " Copper-catalyzed coupling of aryl halides and nitrite salts:a mildUllmann-type synthesis of aromatic nitro compounds ", under the existence of nitrating agent and copper catalyst, the productive rate preparing 4-Nitroanisole for raw material with 4-bromoanisole well below with 4-iodanisol for the productive rate of 4-Nitroanisole prepared by raw material.And be known in those skilled in the artly, in Ullmann reaction, reactivity is :-I>-Br>Cl, namely comparatively 4-iodanisol, 4-bromoanisole reactivity are poorer for 4-chloroanisole, instruct according to above-mentioned technology, those skilled in the art can be expected that, under the existence of nitrating agent and copper catalyst, 4-chloroanisole prepares the productive rate of 4-Nitroanisole will be lower.Therefore, instruct according to above-mentioned technology, those skilled in the art can not select the worse 4-chloroanisole of reactivity to be raw material, under the existence of nitrating agent and copper catalyst, and preparation 4-Nitroanisole; Also would not take chlorobenzene as raw material, under the existence of nitrating agent and copper catalyst, prepare nitrobenzene.
A kind of copper catalyst of the present invention, described copper catalyst is the complex that copper atom and/or cuprous ion and part are formed; Described part is organic amine part; Comprise the composition of this copper catalyst of power, also comprise nitrating agent.The present invention is by optimizing concrete kind, the concrete kind of nitrating agent, the concrete kind of copper catalyst, the particular type of nitration reaction, the concrete kind of non-protonic solvent of organic amine part, go forward side by side the mol ratio of one-step optimization chlorobenzene and nitrating agent, copper catalyst and part, reaction temperature and reaction time, make that chlorobenzene can next step prepares nitrobenzene in the catalysis of copper catalyst.Said composition, composition (nitrating agent and copper catalyst) is simple, applied widely, and reaction condition (50 ~ 150 DEG C) is gentle, and reactions steps is few, easy and simple to handle, be suitable for the suitability for industrialized production of nitrobenzene particularly 4-Nitroanisole.
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the HPLC figure of 4-Nitroanisole in the embodiment of the present invention 1;
Fig. 2 is the IR figure of the pellet technique of 4-Nitroanisole in the embodiment of the present invention 1;
Fig. 3 is 4-Nitroanisole in the embodiment of the present invention 1
1hNMR schemes;
The concrete testing conditions of Fig. 1 is as follows: HPLC column: Inertsil ODS-35 μm 4.6 × 250m; Determined wavelength: 254nm; Mobile phase: methyl alcohol: water=3:1; Sample introduction concentration: 5mg/mL.
Detailed description of the invention
1, instrument
High performance liquid chromatograph: KNAUER HPLC PUMP K-501, KNAUER UVDETECTOR K-2501;
Infrared spectrometer: BRUKER TENSOR 27;
NMR: BRUKER AVANCE III.
2, reagent
TDA tri-[2-(2-methoxy ethoxy) ethyl] amine, structural formula is:
N, N '-dimethyl ethylenediamine, structural formula is:
DMF DMF.
Source chemicals used in following examples and solvent are commercially available product, and purity is pure for analyzing.
embodiment 1 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 42.8g (1.0mmol)
20.7g (1.2mmol) natrium nitrosum, 1.0g (0.05mmol) copper powder, 4.8g (0.05mmol)
2.6g (0.1mmol)
with 500mL DMF, 80 DEG C are reacted 12 hours, and cooling, reactant liquor is poured in 1500mL water, filters to obtain product
12.7g, yield is 83.0%.
Fusing point m.p.51.3 ~ 52.7 DEG C, HPLC purity is greater than 98%.
1H-NMR(DMSO-d
6，400MHz)δ：8.21(d，J＝8.0Hz，2H)，7.15(d，J＝8.0Hz，2H)，3.90(s，3H)。
embodiment 2 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 42.8g (1.0mmol)
17.25g (1.0mmol) potassium nitrite, 1.5g (0.075mmol) copper powder, 7.2g (0.075mmol)
1.3g (0.05mmol)
with 500mL dimethyl sulfoxide (DMSO), 70 DEG C are reacted 20 hours, and cooling, freeze drying must obtain product
13.1g, yield is 85.6%.
embodiment 3 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 42.8g (1.0mmol)
25.88g (1.5mmol) normal-butyl ammonium nilrite, 1.2g (0.06mmol) copper powder, 5.8g (0.06mmol)
3.9g (0.15mmol)
500mL toluene, 100 DEG C are reacted 15 hours, and cooling, extracts to obtain product
13.5g, yield is 88.2%.
embodiment 4 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 1.0mmol
1.5mmol calcium nitrite, 0.06mmol copper powder, 0.06mmol
0.15mmol
500mL benzene, 100 DEG C are reacted 15 hours, and cooling, column chromatography obtains product
embodiment 5 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 1.0mmol
1.0mmol magnesium nitrite, 0.075mmol cuprous iodide, 0.075mmol
0.05mmol
500mL acetonitrile, 70 DEG C are reacted 20 hours, and cooling, column chromatography obtains product
embodiment 6 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 1.0mmol
1.2mmol strontium nitrite, 0.05mmol cuprous iodide, 0.05mmol
0.1mmol
500mL carbon tetrachloride, 80 DEG C are reacted 12 hours, and cooling, be recrystallized to obtain product
embodiment 7 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 1.0mmol
1.5mmol calcium nitrite, 0.06mmol copper powder, 0.06mmol
0.15mmol
500mL benzene, 100 DEG C are reacted 15 hours, and cooling, column chromatography obtains product
embodiment 8 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 1.0mmol
1.2mmol strontium nitrite, 0.05mmol cuprous iodide, 0.05mmol
0.1mmol
500mL carbon tetrachloride, 80 DEG C are reacted 12 hours, and cooling, reactant liquor is poured in 1500mL water, filters to obtain product
embodiment 9 preparation
In the 1000mL round-bottomed flask that agitating device is housed, add 1.0mmol
1.2mmol natrium nitrosum, 0.05mmol copper powder, 0.05mmol
0.1mmol
500mL DMF, 80 DEG C are reacted 12 hours, and cooling, reactant liquor is poured in 1500mL water, and freeze drying obtains product
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. a copper catalyst, is characterized in that, described copper catalyst is the complex that copper atom and/or cuprous ion and part are formed; Described part is organic amine part.
2. copper catalyst according to claim 1, is characterized in that,
Described part is selected from
in at least one.
3. copper catalyst according to claim 1 and 2, is characterized in that, the mol ratio of the mol ratio of the copper atom in described copper catalyst and/or cuprous ion and described part is 0.02 ~ 0.100:0.03 ~ 0.20.
4. the copper catalyst according to any one of claim 1-3, is characterized in that, the mol ratio of the mol ratio of the copper atom in described copper catalyst and/or cuprous ion and described part is 0.05 ~ 0.075:0.05 ~ 0.15.
5. the purposes of the copper catalyst described in any one of claim 1-4 in nitration reaction.
6. comprise a composition for the copper catalyst described in any one of claim 1-4, it is characterized in that, also comprise nitrating agent.
7. composition according to claim 6, is characterized in that, described nitrating agent is selected from natrium nitrosum, potassium nitrite, at least one in calcium nitrite, magnesium nitrite, barium nitrite, strontium nitrite, normal-butyl ammonium nilrite.
8. the composition according to claim 6 or 7, is characterized in that, the mol ratio of the copper atom in described copper catalyst and/or cuprous ion, described part and described nitrating agent is 0.02 ~ 0.100:0.03 ~ 0.20:0.5 ~ 2.0.
9. composition according to claim 8, is characterized in that, the mol ratio of the copper atom in described copper catalyst and/or cuprous ion, described part and described nitrating agent is 0.05 ~ 0.075:0.05 ~ 0.15:1 ~ 1.5.
10. the purposes of the composition described in any one of claim 6-9 in nitration reaction.
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|---|---|---|---|
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|---|---|---|---|
| CN201510160637.1A CN104815692A (en) | 2015-04-03 | 2015-04-03 | Copper catalyst and composition thereof, and applications of copper catalyst and composition |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605777A (en) * | 1984-06-13 | 1986-08-12 | Nobel Kemi Ab | Method of manufacturing o- and p-nitrobenzaldehyde |
| CN1089522A (en) * | 1993-01-14 | 1994-07-20 | 华东师范大学 | Chiral copper catalyst ligand and synthetic method thereof |
| JP2006028140A (en) * | 2004-07-21 | 2006-02-02 | Science Univ Of Tokyo | Synthetic method of aromatic nitro compound |
| CN101563313A (en) * | 2006-12-21 | 2009-10-21 | 纳幕尔杜邦公司 | Process for the synthesis of ethers of aromatic acids |
| CN102180794A (en) * | 2011-03-16 | 2011-09-14 | 清华大学 | Method for synthesizing nitrobenzene compounds |
| CN102399164A (en) * | 2011-12-21 | 2012-04-04 | 武汉武药科技有限公司 | Method for synthesizing chloramphenicol from nitromethane |
-
2015
- 2015-04-03 CN CN201510160637.1A patent/CN104815692A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605777A (en) * | 1984-06-13 | 1986-08-12 | Nobel Kemi Ab | Method of manufacturing o- and p-nitrobenzaldehyde |
| CN1089522A (en) * | 1993-01-14 | 1994-07-20 | 华东师范大学 | Chiral copper catalyst ligand and synthetic method thereof |
| JP2006028140A (en) * | 2004-07-21 | 2006-02-02 | Science Univ Of Tokyo | Synthetic method of aromatic nitro compound |
| CN101563313A (en) * | 2006-12-21 | 2009-10-21 | 纳幕尔杜邦公司 | Process for the synthesis of ethers of aromatic acids |
| CN102180794A (en) * | 2011-03-16 | 2011-09-14 | 清华大学 | Method for synthesizing nitrobenzene compounds |
| CN102399164A (en) * | 2011-12-21 | 2012-04-04 | 武汉武药科技有限公司 | Method for synthesizing chloramphenicol from nitromethane |
Non-Patent Citations (2)
| Title |
|---|
| GUOBING YAN等: "Recent advances in the synthesis of aromatic nitro compounds", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
| SHINICHI SAITO等: "Copper-catalyzed coupling of aryl halides and nitrite salts: a mild Ullmann-type synthesis of aromatic nitro compounds", 《TETRAHEDRON LETTERS》 * |
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