CN106588687B - A kind of process for reductive dehalogenation of organohalogen compounds - Google Patents
A kind of process for reductive dehalogenation of organohalogen compounds Download PDFInfo
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Abstract
The invention discloses a kind of process for reductive dehalogenation of organohalogen compounds, under atmosphere of inert gases, in the presence of catalyst, alkali and solvent, reaction temperature control is at 90-100 DEG C, organic compound shown in organohalogen compounds reductive dehalogenation production (III) shown in formula (I) or formula (II) or formula (IV):
Description
Technical field
The present invention relates to a kind of dehalogenation methods, and in particular to a kind of process for reductive dehalogenation of organohalogen compounds belongs to chemistry
Technical field.
Background technique
Because organohalogen compounds are to environment, there are potential persistence to endanger, the reduction dehalogenation reaction of organohalogen compounds
Organic synthesis, biochemistry and in terms of have important application, realized especially by selective dehalogenation reaction
The degradation of environmental contaminants is in Environmental Chemistry, organic synthesis increasingly by the attention of researcher.
Also there is great theoretical and practical application meaning just because of the reduction dehalogenation reaction of organohalogen compounds, in recent years messenger
A large amount of further investigation has been carried out to the reduction dehalogenation reaction of such compound, many progress continue to bring out, such as:
Yasunari Monguchi et al. (" Pd/C-Et3N-mediated catalytic
Hydrodechlorination of aromatic chlorides under mild conditions ", Tetrahedron,
2006,62,7926-7933) one kind is disclosed under palladium/carbon catalysis, and aryl halide is carried out as hydrogen source using molecular hydrogen to add hydrogen
The method of dehalogenation, reaction equation are as follows:
Jingbo Chen et al. (" A practical palladium catalyzed dehalogenation of
Aryl halides and a-haloketones ", Tetrahedron, 2007,63,4266-4270) a kind of palladium is disclosed to urge
Change, to the method that aryl halide and α-halogenatedketone carry out catalysis dehalogenation, reaction equation is as follows:
Waldemar Maximilian Czaplik et al. (" Practical iron-catalyzed
Dehalogenation of aryl halides ", Chem.Commun, 2010,46,6350-6352) a kind of iron is disclosed to urge
Change, to the method for halogenated aryl hydrocarbon reductive dehalogenation, reaction equation is as follows:
Ken-ichi Fujita et al. (" Chemoselective transfer hydrodechlorination of
Aryl chlorides catalyzed by Cp*Rh complexes ", Chem.Commun, 2002,2964-2965) it is open
Under the conditions of a kind of rhodium catalysis, to the method for chlorinated aromatic hydrocarbons transfer hydrogenation dechlorination, reaction equation is as follows:
Ayoung Pyo et al. (" Palladium-catalyzed hydrodehalogenation of aryl
Halides using paraformaldehyde as the hydride source:high-throughput
Screening by paper-based colorimetric iodide sensor ", Tetrahedron Lett, 2013,
It 54,5207-5210.) is side of the hydrogen source to aryl halide catalysis dehalogenation using paraformaldehyde under the conditions of disclosing a kind of palladium chtalyst
Method, reaction equation are as follows:
Although these methods are still deposited as described above, disclosing a variety of methods of organohalogen compounds dehalogenation in the prior art
In numerous defects, such as: it needs to use hydrogen as hydrogen source, yield is too low, catalyst is prohibitively expensive or needs additional phosphorus ligand, anti-
Answer that process is excessively cumbersome, substrate spectrum is limited etc..
Therefore, for the new and effective method of organohalogen compounds dehalogenation, there are still the necessity for continuing research, in environmental science
Still there is important research meaning with organic synthesis field, this be also where the power that is accomplished of the present invention and basis institute according to.
Summary of the invention
To solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of reductive dehalogenation sides of organohalogen compounds
Method, the process for reductive dehalogenation both do not need addition hydrogen as hydrogen source, do not need additional phosphorus ligand, simultaneous reactions process letter yet
List, yield are higher, and being amplified to gram-grade reaction still can obtain the yield of near quantitative.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
The process for reductive dehalogenation of organohalogen compounds shown in a kind of formula (I) or formula (II), which is characterized in that in inert gas atmosphere
Under enclosing, in the presence of catalyst, alkali and solvent, reaction temperature is controlled at 90-100 DEG C,
Organic compound shown in organohalogen compounds reductive dehalogenation production (III) shown in formula (I):
Organic compound shown in organohalogen compounds reductive dehalogenation production (IV) shown in formula (II):
Wherein, Ar be aromatic ring or heteroaromatic containing various substituent groups,
X be chlorine, bromine, iodine,
R1、R2For aryl or alkyl,
Y be oxygen or nitrogen,
Aforementioned solvents provide hydrogen, be in isopropanol, water, ethyl alcohol, formic acid and triethylamine any one or it is any several
Mixture, most preferably isopropanol, the dosage of solvent there is no stringent restriction, those skilled in the art can according to the actual situation into
Row is suitably selected and is determined, dosage size facilitates reaction to carry out and post-process, and is no longer described in detail herein.
Process for reductive dehalogenation above-mentioned, which is characterized in that aforementioned catalytic agent is dichloro (p-Methylisopropylbenzene) ruthenium dimer
Or diiodo- (p-cymene) ruthenium dimer.
Process for reductive dehalogenation above-mentioned, which is characterized in that aforementioned catalytic agent is dichloro (p-Methylisopropylbenzene) ruthenium dimer.
Process for reductive dehalogenation above-mentioned, which is characterized in that organohalogen compounds shown in formula (I) or formula (II) and catalyst rub
You are than being 1:0.005-0.025.
Process for reductive dehalogenation above-mentioned, which is characterized in that aforementioned bases be cesium acetate, potassium carbonate, sodium acetate, potassium hydroxide,
Any one in triethylamine, dipotassium hydrogen phosphate, potassium phosphate, potassium tert-butoxide, cesium carbonate and sodium tert-butoxide, most preferably cesium acetate or
Potassium tert-butoxide.
Process for reductive dehalogenation above-mentioned, which is characterized in that aforementioned bases are cesium acetate or potassium tert-butoxide.
Process for reductive dehalogenation above-mentioned, which is characterized in that the molar ratio of organohalogen compounds and alkali shown in formula (I) or formula (II)
For 1:1.2.
The invention has the beneficial effects that:
(1) by suitable substrates, temperature, catalyst and alkali Integrated Selection with cooperate with, expanded the range of substrate；
(2) catalyst used in is not necessarily to additional phosphorus ligand, relative low price, and dosage can be significantly reduced to
0.1mol%；
(3) solvent used in is used as hydrogen source to participate in reaction simultaneously, easy to operate, and many reactions are all up quantitative receipts
Rate, being amplified to gram-grade reaction still can obtain the yield of near quantitative.
Specific embodiment
Below in conjunction with detailed description of the invention by specific embodiments, but these are not to of the invention with embodiment
Real protection scope constitutes any type of any restriction, more non-that protection scope of the present invention is confined to this.
Embodiment 1
At room temperature, compound, 0.005mmol shown in 0.2mmol formula (I-1) are added in the reaction tube equipped with stirring magneton
Catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol cesium acetate, then nitrogen is blown
It sweeps, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts 12h at such a temperature.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is by flash column chromatography (petrol ether/ethyl acetate, the two volume ratio are 1:1) purification, to obtain formula
(III-1) target dehalogenated product shown in.It is computed, yield 88%.
Nuclear magnetic resonance:1H NMR (entry 1,500MHz, CDCl3) δ 7.82 (d, J=7.2Hz, 2H), 7.52 (t, J=
7.4Hz, 1H), 7.44 (t, J=7.6Hz, 2H), 6.29 (bs, 2H).
13C NMR (entry 1,125MHz, CDCl3) δ 169.7,133.5,132.0,128.6,127.4.
Embodiment 2
At room temperature, compound, 0.005mmol shown in 0.2mmol formula (I-2) are added in the reaction tube equipped with stirring magneton
Catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol cesium acetate, then nitrogen is blown
It sweeps, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts 20h at such a temperature.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is by flash column chromatography (petrol ether/ethyl acetate, the two volume ratio are 1:1) purification, to obtain formula
(III-2) target dehalogenated product shown in.It is computed, yield 98%.
Nuclear magnetic resonance:1H NMR (entry 1,500MHz, CDCl3) δ 7.82 (d, J=7.2Hz, 2H), 7.52 (t, J=
7.4Hz, 1H), 7.44 (t, J=7.6Hz, 2H), 6.29 (bs, 2H).
13C NMR (entry 1,125MHz, CDCl3) δ 169.7,133.5,132.0,128.6,127.4.
Embodiment 3
At room temperature, compound, 0.005mmol shown in 0.2mmol formula (I-3) are added in the reaction tube equipped with stirring magneton
Catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol cesium acetate, then nitrogen is blown
It sweeps, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts at such a temperature for 24 hours.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is by flash column chromatography (petrol ether/ethyl acetate, the two volume ratio are 5:1) purification, to obtain formula
(III-3) target dehalogenated product shown in.It is computed, yield 93%.
Nuclear magnetic resonance:1H NMR (500MHz, CDCl3) δ 10.81 (bs, 1H), 7.92 (d, J=8.9Hz, 2H), 7.41 (d,
J=7.5Hz, 1H), 7.35 (t, J=7.5Hz, 1H), 2.42 (s, 3H).
13C NMR (125MHz, CDCl3) δ 172.6,138.3,134.6,130.7,129.3,128.4,127.4,21.3.
Embodiment 4
At room temperature, compound, 0.005mmol shown in 0.2mmol formula (I-4) are added in the reaction tube equipped with stirring magneton
Catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol cesium acetate, then nitrogen is blown
It sweeps, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts at such a temperature for 24 hours.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is by flash column chromatography (petrol ether/ethyl acetate, the two volume ratio are 3:1) purification, to obtain formula
(III-4) target dehalogenated product shown in.It is computed, yield 78%.
Nuclear magnetic resonance:1H NMR (500MHz, d6- DMSO) δ 9.08 (t, J=5.7Hz, 1H), 7.91 (d, J=7.5Hz,
2H), 7.54 (t, J=7.3Hz, 1H), 7.48 (t, J=7.5Hz, 2H), 7.33 (d, J=4.4Hz, 4H), 7.26-7.22 (m,
1H), 4.50 (d, J=6.0Hz, 2H).
13C NMR (125MHz, d6- DMSO) δ 166.2,140.0,134.3,131.2,128.3,128.3,127.2,
127.2,126.7,42.6.
Embodiment 5
At room temperature, compound, 0.005mmol shown in 0.2mmol formula (I-5) are added in the reaction tube equipped with stirring magneton
Catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol cesium acetate, then nitrogen is blown
It sweeps, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts at such a temperature for 24 hours.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is by flash column chromatography (petrol ether/ethyl acetate, the two volume ratio are 4:1) purification, to obtain formula
(III-5) target dehalogenated product shown in.It is computed, yield 72%.
Nuclear magnetic resonance:1H NMR (500MHz, d6- DMSO) δ 10.70 (s, 1H), 6.96-6.89 (m, 4H), 4.56 (s,
2H)。
13C NMR (125MHz, d6- DMSO) δ 164.9,143.2,127.2,123.0,122.3,116.1,115.8,
66.7。
Embodiment 6
At room temperature, compound, 0.005mmol shown in 0.2mmol formula (I-6) are added in the reaction tube equipped with stirring magneton
Catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol potassium tert-butoxide, then nitrogen is blown
It sweeps, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts at such a temperature for 24 hours.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is purified by flash column chromatography (petroleum ether), to obtain target dehalogenated product shown in formula (III-6).
It is computed, yield is greater than 99%.
Nuclear magnetic resonance:1H NMR (500MHz, CDCl3) δ 7.77 (d, J=7.5Hz, 2H), 7.52 (d, J=7.4Hz, 2H),
7.35 (t, J=7.5Hz, 2H), 7.28 (t, J=7.4Hz, 2H), 3.87 (s, 2H).
13C NMR (125MHz, CDCl3) δ 143.3,141.7,126.8,125.1,119.9,37.0.
Embodiment 7
At room temperature, compound shown in 10mmol formula (I-7) is added in the reaction tube equipped with stirring magneton, 0.1mmol is urged
Agent dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 12mmol potassium tert-butoxide, then nitrogen purge,
1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts at such a temperature for 24 hours.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is purified by flash column chromatography (petroleum ether), to obtain target dehalogenated product shown in formula (III-7).
It is computed, yield 97%.
Nuclear magnetic resonance:1H NMR (entry 36,500MHz, CDCl3) δ 7.59 (d, J=7.4Hz, 4H), 7.43 (t, J=
7.7Hz, 4H), 7.33 (t, J=7.4Hz, 2H).
13C NMR (entry 36,125MHz, CDCl3) δ 141.3,128.8,127.3,127.2.
Embodiment 8
At room temperature, equipped with stirring magneton reaction tube in be added 0.2mmol formula (II -1) shown in compound,
0.005mmol catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol cesium acetate, so
Nitrogen purges afterwards, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts at such a temperature for 24 hours.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is by flash column chromatography (petrol ether/ethyl acetate, the two volume ratio are 4:1) purification, to obtain formula
Target dehalogenated product shown in (IV -1).It is computed, yield 78%.
Nuclear magnetic resonance:1H NMR (500MHz, CDCl3) δ 7.30 (t, J=7.5Hz, 2H), 7.21-7.25 (m, 3H), 4.28
(t, J=7.1Hz, 2H), 2.93 (t, J=7.1Hz, 2H), 2.27 (t, J=7.5Hz, 2H), 1.62-1.56 (m, 2H), 1.32-
1.22 (m, 4H), 0.88 (t, J=7.0Hz, H).
13C NMR (125MHz, CDCl3) δ 173.8,137.9,128.9,128.5,126.5,64.7,35.2,34.3,
31.3,24.6,22.3,13.9.
Embodiment 9
At room temperature, equipped with stirring magneton reaction tube in be added 0.2mmol formula (II -2) shown in compound,
0.005mmol catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol cesium acetate, so
Nitrogen purges afterwards, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts 20h at such a temperature.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is by flash column chromatography (petrol ether/ethyl acetate, the two volume ratio are 40:1) purification, to obtain
Target dehalogenated product shown in formula (IV -2).It is computed, yield 67%.
Nuclear magnetic resonance:1H NMR (500MHz, CDCl3) δ 7.24-7.17 (m, 5H), 4.29 (t, J=7.1Hz, 2H), 2.94
(t, J=7.0Hz, 2H), 2.31 (q, 7.6Hz, 2H), 1.12 (t, J=7.6Hz, 3H).
13C NMR (125MHz, CDCl3) δ 174.4,137.9,128.9,128.5,126.5,64.8,35.2,27.6,
9.1。
Embodiment 10
At room temperature, equipped with stirring magneton reaction tube in be added 0.2mmol formula (II -3) shown in compound,
0.005mmol catalyst dichloro (p-Methylisopropylbenzene) ruthenium dimer ([RuCl2(cymene)]2), 0.24mmol potassium carbonate, so
Nitrogen purges afterwards, 1mL isopropanol is added under nitrogen protection, stirring is warming up to 100 DEG C, and reacts at such a temperature for 24 hours.
After reaction, reaction solution is cooled to room temperature, and is filtered with the funnel for being covered with one layer of silica gel, is then evaporated under reduced pressure
Solvent is removed, residue is by flash column chromatography (petrol ether/ethyl acetate, the two volume ratio are 4:1) purification, to obtain formula
Target dehalogenated product shown in (IV -3).It is computed, yield 82%.
Nuclear magnetic resonance:1H NMR (500MHz, CDCl3) δ 7.42 (t, J=7.5Hz, 2H), 7.34 (t, J=7.2Hz, 1H),
7.19 (d, J=7.6Hz, 2H), 3.27 (s, 3H), 1.87 (s, 3H).
13C NMR (125MHz, CDCl3) δ 170.5,144.7,129.7,127.7,127.1,37.1,22.3.
Embodiment 11
Except catalyst is replaced with three (triphenylphosphine) ruthenous chlorides by dichloro (p-Methylisopropylbenzene) ruthenium dimer
((Ph3P)3RuCl2) outside, other operations are constant, repeat embodiment 1 and obtain embodiment 11.It is computed, yield 24%.
Embodiment 12
Except catalyst is replaced with diiodo- (p-cymene) ruthenium dimer by dichloro (p-Methylisopropylbenzene) ruthenium dimer
([RuI2(cymene)]2) outside, other operations are constant, repeat embodiment 1 and obtain embodiment 12.It is computed, yield 65%.
Embodiment 13
Except by catalyst by dichloro (p-Methylisopropylbenzene) ruthenium dimer (adjacent luxuriant and rich with fragrance hello of 4,7- biphenyl -1,10- that replace with three
Quinoline) outside ruthenous chloride, other operations are constant, repeat embodiment 1 and obtain embodiment 13.It is computed, yield 0 is that is, reactionless.
Embodiment 14
In addition to being omitted catalyst, other operations are constant, repeat embodiment 1 and obtain embodiment 14.It is computed, produces
Rate is 0, i.e., reactionless.
It can be seen that reduction dehalogenation reaction must be completed under the catalysis of catalyst.Three (the adjacent luxuriant and rich with fragrance hello of 4,7- biphenyl -1,10-
Quinoline) ruthenous chloride is unable to complete this reaction, three (triphenylphosphine) ruthenous chloride ((Ph3P)3RuCl2) catalytic effect it is very poor, with
Very similar diiodo- (p-cymene) ruthenium the dimer ([RuI of dichloro (p-Methylisopropylbenzene) ruthenium dimer2(cymene)]2)
The reaction can be made to carry out and obtain moderate yield.
Embodiment 15
In addition to alkali is replaced with potassium carbonate by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment 15.
It is computed, yield 79%.
Embodiment 16
In addition to alkali is replaced with sodium acetate by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment 16.
It is computed, yield 37%.
Embodiment 17
In addition to alkali is replaced with potassium hydroxide by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment
17.It is computed, yield 58%.
Embodiment 18
In addition to alkali is replaced with triethylamine by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment 18.
It is computed, yield 64%.
Embodiment 19
In addition to alkali is replaced with dipotassium hydrogen phosphate by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment
19.It is computed, yield 40%.
Embodiment 20
In addition to alkali is replaced with potassium phosphate by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment 20.
It is computed, yield 25%.
Embodiment 21
In addition to alkali is replaced with potassium tert-butoxide by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment
21.It is computed, yield 70%.
Embodiment 22
In addition to alkali is replaced with cesium carbonate by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment 22.
It is computed, yield 31%.
Embodiment 23
In addition to alkali is replaced with sodium tert-butoxide by cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment
23.It is computed, yield 71%.
Embodiment 24
In addition to being omitted cesium acetate, other operations are constant, repeat embodiment 1 and obtain embodiment 24.It is computed, produces
Rate is 0, i.e., reactionless.
It can be seen that in the method for the invention, the type of alkali and whether there is or not have significant impact for reaction.Acetic acid
The effect of the alkali such as sodium, dipotassium hydrogen phosphate, potassium phosphate is poor.The effect of the alkali such as potassium carbonate, potassium tert-butoxide, sodium tert-butoxide is also fine.
When alkali is not present, reaction can not be carried out.
In fact, selecting weak base cesium acetate effect best the substrate for being similar to embodiment 1-5 and embodiment 8-10
(alkali used in embodiment 10 is potassium carbonate)；And the substrate for being similar to embodiment 6 and 7, select the effect of highly basic potassium tert-butoxide
Most preferably.Those skilled in the art suitably can be selected and be determined according to the actual situation.
Embodiment 25
In addition to solvent (hydrogen source) is replaced with tert-pentyl alcohol by isopropanol, other operations are constant, repeat embodiment 1 and obtain reality
Apply example 25.It is computed, yield 0 is that is, reactionless.
Embodiment 26
In addition to solvent (hydrogen source) is replaced with water by isopropanol, other operations are constant, repeat embodiment 1 and obtain embodiment
26.It is computed, yield 0 is that is, reactionless.
Embodiment 27
In addition to the mixture (volume ratio 1:1) that solvent (hydrogen source) is replaced with isopropyl alcohol and water by isopropanol, other operations
It is constant, it repeats embodiment 1 and obtains embodiment 27.It is computed, yield 49%.
Embodiment 28
In addition to solvent (hydrogen source) is replaced with ethyl alcohol by isopropanol, other operations are constant, repeat embodiment 1 and implemented
Example 28.It is computed, yield 33%.
Embodiment 29
In addition to the mixture (molar ratio 1:1) that solvent (hydrogen source) is replaced with water and formic acid by isopropanol, other operations are equal
It is constant, it repeats embodiment 1 and obtains embodiment 29.It is computed, yield 68%.
Embodiment 30
In addition to the mixture (molar ratio 5:2) that solvent (hydrogen source) is replaced with water and triethylamine by isopropanol, other operations
It is constant, it repeats embodiment 1 and obtains embodiment 30.It is computed, yield 46%.
It can be seen that the type selection of solvent (hydrogen source) is most important, isopropanol effect is best.When selection tert-pentyl alcohol or water
When doing solvent (hydrogen source), it is unable to get product.When with the mixture of ethyl alcohol or isopropyl alcohol and water, effect is poor.Water and formic acid/
The system of triethylamine can also complete the reaction, and effect is relatively weaker.
In conclusion the process for reductive dehalogenation of organohalogen compounds provided by the invention:
(1) by suitable substrates, temperature, catalyst and alkali Integrated Selection with cooperate with, expanded the range of substrate；
(2) catalyst used in is not necessarily to additional phosphorus ligand, relative low price, and dosage can be significantly reduced to
0.1mol%；
(3) solvent used in is used as hydrogen source to participate in reaction simultaneously, easy to operate, and many reactions are all up quantitative receipts
Rate, being amplified to gram-grade reaction still can obtain the yield of near quantitative.
So process for reductive dehalogenation of the invention has a good application prospect in the fields such as Environmental Chemistry, organic chemistry
And researching value, also new reference is provided for generic reaction research.
It should be noted that the above embodiments do not limit the invention in any form, it is all to use equivalent replacement or equivalent change
The mode changed technical solution obtained, falls within the scope of protection of the present invention.
Claims (4)
1. a kind of process for reductive dehalogenation of organohalogen compounds shown in formula (I), which is characterized in that under atmosphere of inert gases, in urging
In the presence of agent, alkali and solvent, reaction temperature is controlled at 90-100 DEG C,
Organic compound shown in organohalogen compounds reductive dehalogenation production (III) shown in formula (I):
Wherein, Ar be aromatic ring or heteroaromatic,
X be chlorine, bromine, iodine,
R1For aryl or alkyl,
The catalyst is dichloro (p-Methylisopropylbenzene) ruthenium dimer；
The alkali is cesium acetate；
The solvent is isopropanol.
2. a kind of process for reductive dehalogenation of organohalogen compounds shown in formula (II), which is characterized in that under atmosphere of inert gases, in urging
In the presence of agent, alkali and solvent, reaction temperature is controlled at 90-100 DEG C,
Organic compound shown in organohalogen compounds reductive dehalogenation production (IV) shown in formula (II):
Wherein, X be chlorine, bromine, iodine,
R1、R2For aryl or alkyl,
Y be oxygen or nitrogen,
The catalyst is dichloro (p-Methylisopropylbenzene) ruthenium dimer；
The alkali is cesium acetate；
The solvent is isopropanol.
3. process for reductive dehalogenation according to claim 1 or 2, which is characterized in that organic halogenation shown in formula (I) or formula (II)
The molar ratio of object and catalyst is 1:0.005-0.025.
4. process for reductive dehalogenation according to claim 1 or 2, which is characterized in that organic halogenation shown in formula (I) or formula (II)
The molar ratio of object and alkali is 1:1.2.
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