CN106349295B - Half sandwich ruthenium complex, preparation method and the method that nitrobenzene compounds are reduced into amino benzenes compounds containing hydroxyl - Google Patents
Half sandwich ruthenium complex, preparation method and the method that nitrobenzene compounds are reduced into amino benzenes compounds containing hydroxyl Download PDFInfo
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- CN106349295B CN106349295B CN201610710340.2A CN201610710340A CN106349295B CN 106349295 B CN106349295 B CN 106349295B CN 201610710340 A CN201610710340 A CN 201610710340A CN 106349295 B CN106349295 B CN 106349295B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
Abstract
The invention discloses a kind of half sandwich ruthenium complex, preparation method and the method that nitrobenzene compounds are reduced into amino benzenes compounds containing hydroxyl, this contains shown in the structure such as formula (I) of half sandwich ruthenium complex of hydroxyl, wherein, in formula (I), X is halogen, the alkyl or halogen of R H, C1-C6.Half sandwich ruthenium complex of high yield can be prepared under the conditions of leniently by this method, and nitrobenzene compounds can be reduced into amino benzenes compounds under mild conditions by the half sandwich ruthenium complex,
Description
Technical field
The present invention relates to half sandwich ruthenium complexes, and in particular, to the half sandwich ruthenium complex containing hydroxyl,
Preparation method and the method that nitrobenzene compounds are reduced into amino benzenes compounds.
Background technique
Complex with ruthenium with half-sandwich structure has unique chemical stability, excellent optical property and abundant
Redox property, is the primary study content of the subjects such as inorganic chemistry, materials chemistry and Coordinative Chemistry, and is increasingly becoming the modern times
A very active field in chemical research.Complex with ruthenium with half-sandwich structure is in photochemistry, organic catalysis, alkene
Hydrocarbon double decomposition, electrochemistry, fluorescent ion probe, gas sensing etc. play important application.Therefore, it synthesizes and explores series
The application of complex with ruthenium with half-sandwich structure is very important research contents.But it is existing with half-sandwich
There are still some defects for the preparation method of the complex of ruthenium, and such as: the reaction time is longer, and yield is more low.
Aniline and its derivatives are a kind of basic Organic Chemicals, are widely used in medicine, pesticide, printing and dyeing and rubber
Etc. industries, be important Organic Ingredients.Currently, the most common preparation method of aniline and its derivatives is iron powder reducing method, because of it
The high requirements on the equipment in production process pollutes environment, and energy consumption is big, the drawbacks such as product separation trouble, the side of another kind preparation
Method is catalytic hydrogenation, and the major defect of the method is that reaction needs higher pressure, and production cost is higher.
Summary of the invention
The object of the present invention is to provide a kind of half sandwich ruthenium complex containing hydroxyl, preparation method and by nitrobenzene
The method that class compound is reduced into amino benzenes compounds can prepare the half of high yield by this method under the conditions of leniently
Sandwich ruthenium complex, and the half sandwich ruthenium complex can under mild conditions by nitrobenzene compounds also
Original is at amino benzenes compounds.
To achieve the goals above, the present invention provides a kind of half sandwich ruthenium complex containing hydroxyl, this contains
Shown in the structure such as formula (I) of the sandwich ruthenium complex of the half of hydroxyl,
Wherein, in formula (I), X is halogen, the alkyl or halogen of R H, C1-C6.
The present invention also provides a kind of preparation method of above-mentioned half sandwich ruthenium complex containing hydroxyl, features
Be, the preparation method comprises the following steps: protecting gas, organic solvent and in the presence of alkali compounds, will the structure as shown in formula (III) naphthalene
The presoma of base Schiff base ligand and the ruthenium of structure shown in formula (II) carries out complexation reaction so that the half sandwich ruthenium containing hydroxyl is made
Complex,
Wherein, in formula (II), X is halogen；In formula (III), the alkyl or halogen of R H, C1-C6.
Invention further provides a kind of method that nitrobenzene compounds are reduced into amino benzenes compounds, this method
Are as follows: in air atmosphere, using the sandwich ruthenium complex of half containing hydroxyl of claims 1 or 2 as catalyst, by formula (IV)
Shown in nitrobenzene compounds and reducing agent redox reaction is carried out in the polar solvent containing CATB to obtain formula (V)
Shown in nitre amino benzenes compounds,
Wherein, R1 is selected from the alkyl of H, halogen or C1-C6, and n is the positive integer of 1-4.
Through the above technical solutions, one aspect of the present invention is by under mild conditions will the structure as shown in formula (III)
Naphthalene Schiff base ligand and formula (II) shown in structure ruthenium presoma carry out complexation reaction be made the structure as shown in formula (I)
The sandwich ruthenium complex of half containing hydroxyl, the half sandwich ruthenium complex have excellent stability so as to
Presence stable in the air；On the other hand, the half sandwich ruthenium complex as made from above-mentioned complexation reaction is protected on ligand
Hydroxyl has been stayed, it can be quick, high in mild condition under polar solvent and CATB (cetyl trimethylammonium bromide) auxiliary
Nitrobenzene compounds are reduced into amino benzenes compounds by effect ground, so that this method has the prospect that can be widely popularized.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the preparation principle figure of the naphthalene Schiff base ligand of the structure as shown in formula (III)；
Fig. 2 is the X-ray single crystal diffraction figure of half sandwich ruthenium complex (I-3)；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of naphthalene Schiff base ligand (III-1)；
Fig. 4 is the carbon-13 nmr spectra figure of naphthalene Schiff base ligand (III-1)；
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of half sandwich ruthenium complex (I-3)；
Fig. 6 is the carbon-13 nmr spectra figure of half sandwich ruthenium complex (I-3).
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of half sandwich ruthenium complex containing hydroxyl, the half sandwich ruthenium coordination containing hydroxyl
Shown in the structure of compound such as formula (I),
Wherein, in formula (I), X is halogen, the alkyl or halogen of R H, C1-C6.
In the present invention, the specific group of X and R can select in above-mentioned range, it is contemplated that the cost of preparation
And yield, it is preferable that in formula (I), X is Cl or Br, R H, the alkyl of C1-C3, Cl or Br；It is highly preferred that at formula (I)
In, X Cl, R H, methyl or Cl.
The present invention also provides a kind of preparation method of above-mentioned half sandwich ruthenium complex containing hydroxyl, features
Be, the preparation method comprises the following steps: protecting gas, organic solvent and in the presence of alkali compounds, will the structure as shown in formula (III) naphthalene
The presoma of base Schiff base ligand and the ruthenium of structure shown in formula (II) carries out complexation reaction so that the half sandwich ruthenium containing hydroxyl is made
Complex,
Wherein, in formula (II), X is halogen；In formula (III), the alkyl or halogen of R H, C1-C6.
In the above preparation method, the specific group of X and R can select in above-mentioned range, it is contemplated that preparation
Cost and yield, it is preferable that in (II), X be Cl or Br；In formula (III), R H, the alkyl of C1-C3, Cl or Br；
It is highly preferred that in (II), X Cl；In formula (III), R H, methyl or Cl.
In the above preparation method, the actual conditions of complexation reaction can select in a wide range, but in order into one
Step improves the yield and preparation rate of product, it is preferable that complexation reaction at least meets the following conditions: reaction temperature 10-40
DEG C, reaction time 3-8h；It is highly preferred that reaction temperature is 20-30 DEG C, reaction time 4-6h.
Similarly, in the above preparation method, the dosage of each material can select in a wide range, but in order into one
Step improves the yield and preparation rate of product, it is preferable that relative to the presoma of 0.20mmol ruthenium, naphthalene Schiff base ligand
Dosage is 0.3-0.6mmol, and the dosage of alkali compounds is 0.4-1.0mmol, and the dosage of organic solvent is 10-20mL.
In addition, in the above preparation method, the specific type of alkali compounds can select in a wide range, but be
Further increase the yield of product, it is preferable that alkali compounds is selected from sodium acetate, potassium acetate, potassium carbonate, sodium carbonate and hydrogen-oxygen
Change one of sodium or a variety of, preferably potassium carbonate.
Similarly, in the above preparation method, the specific type of organic solvent can select in a wide range, but in order to
Further increase the yield of product, it is preferable that organic solvent is selected from one of methanol, ethyl alcohol and acetonitrile or a variety of, preferably
Methanol.
Similarly, in the above preparation method, protecting the specific type of gas can select in a wide range, but in order into
The yield of one step raising product, it is preferable that protection gas is nitrogen or argon gas.
Invention further provides a kind of method that nitrobenzene compounds are reduced into amino benzenes compounds, this method
Are as follows: in air atmosphere, using the sandwich ruthenium complex of half containing hydroxyl of claims 1 or 2 as catalyst, by formula (IV)
Shown in nitrobenzene compounds and reducing agent redox reaction is carried out in the polar solvent containing CATB to obtain formula (V)
Shown in nitre amino benzenes compounds,
Wherein, R1 is selected from the alkyl of H, halogen or C1-C6, and n is the positive integer of 1-4.
In the above preparation method, the specific group of R1 and n can select in above-mentioned range, but in order to further
Improve the yield of nitre amino benzenes compounds, it is preferable that R1 is selected from the alkyl of H, halogen or C1-C3, and n is the positive integer of 1-4；It is more excellent
Selection of land, R1 are selected from H, F, Cl, Br, I or methyl, and n is 1 or 2；It is further preferred that nitrobenzene compounds are selected from nitrobenzene, 4-
Fluoronitrobenzene, 4- nitro-chlorobenzene, 4- Nitrobromobenzene, 4- nitro iodobenzene, 4- nitrotoleune, 3- nitrotoleune, 2- nitrotoleune or
2,6- dimethyl nitrobenzene.
In the above-mentioned methods, the actual conditions of redox reaction can select in a wide range, but in order into one
Step improves the yield of product, it is preferable that redox reaction at least meets the following conditions: reaction temperature is 10-40 DEG C, when reaction
Between be 7-12h；Preferably, reaction temperature is 20-30 DEG C, reaction time 8-10h.
In the above-mentioned methods, the dosage of each material can select in a wide range, but in order to further increase product
Yield, it is preferable that relative to the nitrobenzene compounds of 0.3mmol, the dosage of reducing agent is 1-1.5mmol, catalyst
Dosage is 2 × 10-4-4×10-3The dosage of mmol, CATB are 1 × 10-4-2.5×10-4Mmol, the dosage of water are 1-4mL.
In addition, in the present invention, the specific type of polar solvent can select in a wide range, but in order to enable its
He can be fully contacted between material to improve the yield of product and reaction rate, it is preferable that polar solvent is selected from water, first
One of alcohol, ethyl alcohol and acetonitrile are a variety of, preferably water.
On the basis of above-mentioned content, the specific type of reducing agent can select in a wide range, but in order to make
Obtaining nitrobenzene compounds can sufficiently, efficiently be reduced, it is preferable that reducing agent is selected from sodium borohydride, lithium aluminium hydride reduction, hydration
It is one of in hydrazine and hydrogen or a variety of, preferably sodium borohydride.
In addition, in the present invention, the naphthalene Schiff base ligand of the structure as shown in formula (III) can be commercially available product, but be
It is further ensured that the purity of the drug, it is preferable that in the present invention by being voluntarily prepared, specific preparation route can be with
Referring to Fig. 1.
The present invention will be described in detail by way of examples below.Nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum are to pass through Switzerland
Bruker AV300MHz and Bruker AV 500MHz Nuclear Magnetic Resonance measures, and single crystal diffraction map is mono- by Bruker AXS
Brilliant diffractometer SMART APEX II is measured.
The presoma of the ruthenium of the structure as shown in formula (II-1), that is, 1- methyl -4- isopropyl cyclohexadiene ruthenous chloride dimer
([(p-Cymene)RuCl2)2]) be company, Shanghai Jing Chun biochemical technology limited liability company product, 2- hydroxyl-1-naphthalene Formaldehyde,
Ortho-Aminophenol, 2- amino -4- methylphenol, 2- amino -4- chlorophenol and potassium carbonate are the brilliant pure biochemical technology share in Shanghai
The product of Co., Ltd, nitrobenzene compounds, methanol and glacial acetic acid are Shanghai Jing Chun biochemical technology limited liability company public affairs
The product of department,
Preparation example 1
The preparation of the naphthalene Schiff base ligand of the structure as shown in formula (III-1):
2- hydroxyl-1-naphthalene Formaldehyde (0.5166g, 0.3mmol) and Ortho-Aminophenol are added in 50ml reaction tube
(0.3274g, 0.3mmol), adds 15ml anhydrous methanol and 0.1ml glacial acetic acid, and solution is heated to 75 DEG C of reflux 3h, then cold
But it to 25 DEG C, filtering, then is washed 3 times with dehydrated alcohol, obtains yellow solid 0.7606g, yield 96%.
The characterization result of product referring to Fig. 3 and Fig. 4, specifically:1H NMR(300MHz,DMSO-d6): δ 15.70 (d, J=
9.0Hz, 1H), 10.31 (s, 1H), 9.48 (d, J=9.0Hz, 1H), 8.37 (d, J=9.0Hz, 1H), 7.92 (d, J=
9.0Hz, 1H), 7.78 (d, J=9.0Hz, 1H), 7.65 (d, J=6.0Hz, 1H), 7.46 (t, J=6.0Hz, 1H), 7.24 (t,
J=6.0Hz, 1H), 7.09 (t, J=6.0Hz, 1H), 7.00~6.90 (m, 2H), 6.77 (d, J=9.0Hz, 1H)13C NMR
(75MHz,DMSO-d6):δ178.11,149.86,148.89,138.39,134.39,129.14,129.02,128.55,
127.18,126.29,125.57,123.48,120.27,120.18,118.03,116.41,108.15.IR(KBr cm-1):
3483(s),3033(m),1632(s),1585(m),1549(s),1514(s),1459(s),1360(s),1140(s),745
(s).
Preparation example 2
The preparation of the naphthalene Schiff base ligand of the structure as shown in formula (III-2):
It carries out that crocus solid 0.7930g, yield 95% is made according to the method for preparation example 1；Except that by 2-
Amino-phenol (0.3274g, 0.3mmol) is changed to 2- amino -4- methylphenol (0.3695g, 0.3mmol).
The characterization result of product are as follows:1H NMR(300MHz,DMSO-d6): δ 15.67 (d, J=9.0Hz, 1H), 10.05 (s,
1H), 9.45 (d, J=9.0Hz, 1H), 8.37 (d, J=9.0Hz, 1H), 7.76 (d, J=6.0Hz, 2H), 7.65 (d, J=
9.0Hz, 1H), 7.46 (t, J=6.0Hz, 1H), 7.24 (t, J=6.0Hz, 1H), 6.87 (s, 2H), 6.76 (d, J=
12.0Hz,1H),2.29(s,3H).13C NMR(75MHz,DMSO-d6):δ128.27,149.41,146.57,138.37,
134.44,129.44,129.26,128.49,127.63,126.26,125.67,123.43,120.12,118.14,118.10,
116.26,108.10,20.80.IR(KBr cm-1):3445(m),3022(m),2923(m),1621(vs),1593(s),1544
(s),1516(s),1459(m),1352(vs),1140(s),887(m),813(s),750(s).
Preparation example 3
The preparation of the naphthalene Schiff base ligand of the structure as shown in formula (III-3):
It carries out that crocus solid 0.8606g, yield 96% is made according to the method for preparation example 1；Except that by 2-
Amino-phenol (0.3274g, 0.3mmol) is changed to 2- amino -4- chlorophenol (0.4307g, 0.3mmol).
The characterization result of product are as follows:1H NMR(300MHz,DMSO-d6): δ 15.63 (d, J=9.0Hz, 1H), 10.54 (s,
1H), 9.51 (d, J=9.0Hz, 1H), 8.45 (d, J=9.0Hz, 1H), 8.10 (s, 1H), 7.81 (d, J=9.0Hz, 1H),
7.67 (d, J=9.0Hz, 1H), 7.47 (t, J=9.0Hz, 1H), 7.26 (t, J=9.0Hz, 1H), 7.10 (d, J=9.0Hz,
1H), 6.96 (d, J=6.0Hz, 1H), 6.79 (d, J=9.0Hz, 1H)13C NMR(75MHz,DMSO-d6):δ177.54,
150.66,147.93,138.64,134.24,130.70,129.44,128.56,126.50,126.45,125.12,124.09,
123.77,120.66,117.74,117.54,108.63.IR(KBr cm-1):3439(w),3060(m),1632(vs),1582
(m),1546(s),1505(m),1489(m),1349(m),1146(s),882(m),833(s),800(m),745(s).
Embodiment 1
The preparation of half sandwich ruthenium complex of the structure as shown in formula (I-1):
Under nitrogen protection, 1- methyl -4- isopropyl cyclohexadiene ruthenous chloride dimer [(p-cymene) is weighed
RuCl2]2122.4mg (0.20mmol), naphthalene Schiff base ligand (III-1) 131.5mg (0.50mmol), 96.5mg potassium carbonate
It is added in the reaction tube of 50ml, adds 15ml methanol, be stirred to react at 25 DEG C 4 hours；After recrystallization, with ethyl acetate and stone
Oily ether obtains dark red powder 185.8mg, yield 87% as eluant, eluent column separation.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3):δ8.53(s,1H),8.35(s,1H),7.64(d,J
=9.0Hz, 2H), 7.55 (d, J=6.0Hz, 1H), 7.33~7.26 (m, 2H), 7.17~6.98 (m, 5H), 5.45 (s, 2H),
4.95 (d, J=6.0Hz, 1H), 4.19 (d, J=3.0Hz, 1H), 2.76~2.67 (m, 1H), 2.18 (s, 3H), 1.24 (d, J
=6.0Hz, 3H), 1.14 (d, J=6.0Hz, 3H)13C NMR(125MHz,CDCl3):δ167.18,159.55,151.38,
146.13,137.05,135.12,129.26,128.83,128.03,127.04,125.24,124.45,122.73,119.81,
119.42,117.97,108.99,101.19,99.17,88.54,85.23,83.88,81.18,30.85,23.42,21.72,
18.77.Anal.Calcd.for C27H26NO2RuCl:C 60.84,H 4.92,N 2.63Found:C 60.80,H 4.93,N
2.68.IR(KBr cm-1):3458(m),3059(m),2961(s),2926(s),1614(s),1599(s),1576(s),1535
(vs),1354(s),1160(s),1093(m),820(s),746(vs),557(w).
Embodiment 2
The preparation of half sandwich ruthenium complex of the structure as shown in formula (I-2):
It carries out that dark red powder 182.0mg, yield 83% is made according to the method for embodiment 1；Except that by naphthalene
Base Schiff base ligand (III-1) 131.5mg (0.50mmol) is changed to except that by naphthalene Schiff base ligand (III-2)
138.5mg(0.50mmol)。
The characterization result of product are as follows:1H NMR(300MHz,CDCl3):δ8.52(s,1H),8.16(s,1H),7.64(t,J
=9.0Hz, 2H), 7.55 (d, J=9.0Hz, 1H), 7.31 (t, J=6.0Hz, 1H), 7.15~6.97 (m, 4H), 6.84 (s,
1H), 5.45 (d, J=3.0Hz, 2H), 4.96 (d, J=6.0Hz, 1H), 4.22 (d, J=6.0Hz, 1H), 2.76~2.67 (m,
1H), 2.38 (s, 3H), 2.18 (s, 3H), 1.25 (d, J=9.0Hz, 3H), 1.15 (d, J=9.0Hz, 3H)13C NMR
(125MHz,CDCl3):δ167.10,159.46,148.97,145.76,136.94,135.15,129.29,129.24,
129.15,127.97,127.04,125.26,124.82,122.67,119.45,117.65,108.98,101.19,99.07,
88.46,85.26,84.07,81.16,30.86,23.42,21.74,21.00,19.76.Anal.Calcd.for
C28H28NO2RuCl:C 61.48,H5.16,N 2.56Found:C 61.46,H 5.13,N 2.55.IR(KBr cm-1):3456
(s),3060(w),2967(w),2873(w),1615(s),1599(s),1579(m),1503(m),1464(vs),1371(m),
1190(w),830(s),750(s),671(m),580(w).
Embodiment 3
The preparation of half sandwich ruthenium complex of the structure as shown in formula (I-3):
It carries out that dark red powder 195.4mg, yield 86% is made according to the method for embodiment 1；Except that by naphthalene
Base Schiff base ligand (III-1) 131.5mg (0.50mmol) is changed to except that by naphthalene Schiff base ligand (III-3)
148.5mg(0.50mmol)。
The characterization result referring to fig. 2,5 and 6 of product, specifically:1H NMR(300MHz,CDCl3):δ8.48(s,2H),
7.65 (d, J=9.0Hz, 2H), 7.55 (d, J=6.0Hz, 1H), 7.36~7.23 (m, 3H), 7.19~7.11 (m, 2H),
7.04 (d, J=6.0Hz, 2H), 5.47 (d, J=3.0Hz, 2H), 5.00 (d, J=6.0Hz, 1H), 4.24 (d, J=6.0Hz,
1H), 2.76~2.67 (m, 1H), 2.18 (s, 3H), 1.25 (d, J=6.0Hz, 3H), 1.16 (d, J=9.0Hz, 3H)13C
NMR(125MHz,CDCl3):δ167.71,159.63,150.41,146.37,137.52,135.01,129.33,128.63,
128.20,127.08,125.18,124.28,124.24,122.95,119.38,119.08,108.92,101.58,99.18,
88.46,85.20,83.82,80.90,30.91,23.37,21.76,18.76.Anal.Calcd.for C27H25NO2RuCl2:C
57.15,H 4.44,N2.47Found:C 57.18,H 4.47,N 2.43.IR(KBr cm-1):3447(m),3059(m),
2926(m),2849(m),1617(s),1599(s),1576(s),1532(vs),1466(vs),1328(s),1282(s),
1190(s),904(w),827(s),746(s),672(s).
Application examples 1
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in reaction tube, half sandwich ruthenium complex is added
(I-3)3×10-4Mmol (0.1mol%), 0.3mmol nitrobenzene, 2ml (0.11mol) water, 80mg (2.2 × 10-4mol)CTAB
With 1.2mmol sodium borohydride, it is stirred to react 7 hours at 25 DEG C.After reaction, it is transferred in separatory funnel and ether extraction is added
It takes, stays supernatant, be spin-dried for rear pillar and chromatograph to obtain aniline (25mg, yield 90%).
The characterization result of product are as follows:1H NMR(300MHz,CDCl3):δ7.35(m,2H),6.95(m,1H),6.79(m,
2H),3.67(br,2H).
Application examples 2
It carries out that para-fluoroaniline (32mg, yield 97%) is made according to the method for application examples 1, except that nitrobenzene is changed
For p-fluoronitrobenzene.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3):δ6.89(m,2H),6.62(m,2H),3.55(br,
2H).
Application examples 3
It carries out that parachloroanilinum (36mg, yield 95%) is made according to the method for application examples 1, except that nitrobenzene is changed
For parachloronitrobenzene.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3): δ 7.10 (d, J=9.0Hz, 2H), 6.60 (d, J=
9.0Hz,2H),3.65(br,2H).
Application examples 4
It carries out that para-bromoaniline (48mg, yield 93%) is made according to the method for application examples 1, except that nitrobenzene is changed
For p-Nitrobromobenzene.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3): δ 7.23 (d, J=9.0Hz, 2H), 6.56 (d, J=
9.0Hz,2H),3.66(br,2H).
Application examples 5
It carries out that 4- amido iodobenzene (59mg, yield 90%) is made according to the method for application examples 1, except that by nitrobenzene
It is changed to 4- nitro base iodobenzene.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3): δ 7.40 (d, J=6.0Hz, 2H), 6.46 (d, J=
6.0Hz,2H),3.66(br,2H).
Application examples 6
It carries out that adjacent amido toluene (29mg, yield 92%) is made according to the method for application examples 1, except that by nitrobenzene
It is changed to ortho-methylnitrobenzene.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3): δ 7.10 (t, J=6.0Hz, 2H), 6.80-6.70
(m,2H),3.62(br,2H),2.22(s,3H).
Application examples 7
Amido toluene (30mg, yield 93%) between being made is carried out according to the method for application examples 1, except that by nitrobenzene
It is changed to meta-nitrotoluene.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3): δ 7.08 (t, J=6.0Hz, 1H), 6.62 (d, J=
6.0Hz, 1H), 6.53 (d, J=9.0Hz, 2H), 3.61 (br, 2H), 2.30 (s, 3H)
Application examples 8
It is made according to the method for application examples 1 to amido toluene (31mg, yield 95%), except that by nitrobenzene
It is changed to para-nitrotoluene.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3): δ 6.98 (d, J=9.0Hz, 2H), 6.62 (d, J=
9.0Hz,2H),3.53(br,2H),2.25(s,3H).
Application examples 9
It carries out that 2,6- dimethylaniline (31mg, yield 85%) is made according to the method for application examples 1, except that by nitre
Base benzene is changed to 2,6- dimethyl nitrobenzene.
The characterization result of product are as follows:1H NMR(300MHz,CDCl3): δ 6.98 (d, J=6.0Hz, 2H), 6.69 (d, J=
6.0Hz,1H),3.59(br,2H),2.22(s,6H).
Application examples 10
It carries out that parachloroanilinum (33mg, yield 90%) is made according to the method for application examples 3, except that by half sandwich ruthenium
Complex (I-3) dosage is changed to 3 × 10-3The dosage of mmol, CTAB are changed to 1.1 × 10-4mol.The characterization result of product is
It is consistent with the characterization result of application examples 3.
In addition, the method according to application examples 1 carries out, half sandwich ruthenium complex (I-3) is changed to half sandwich ruthenium and is coordinated
Compound (I-1) or half sandwich ruthenium complex (I-2), reduction reaction also have excellent yield.
Comparative example 1
It is carried out according to the method for application examples 3, except that half sandwich ruthenium complex (I-3) is not used, characterization knot
Fruit shows in product without parachloroanilinum.
Comparative example 2
Parachloroanilinum is carried out according to the method for application examples 3, except that not using CTAB, characterization result shows in product
Without parachloroanilinum.
Comparative example 3
It carries out obtaining parachloroanilinum (11mg, yield 30%) according to the method for application examples 3, except that by half sandwich ruthenium
Complex (I-3) is changed to 1- methyl -4- isopropyl cyclohexadiene ruthenous chloride dimer；The characterization result of product and application
The characterization result of example 3 is consistent.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (25)
1. a kind of half sandwich ruthenium complex containing hydroxyl, which is characterized in that the half sandwich ruthenium coordination containing hydroxyl
Shown in the structure of compound such as formula (I),
Wherein, in formula (I), X is halogen, the alkyl or halogen of R H, C1-C6.
2. half sandwich ruthenium complex according to claim 1, wherein in formula (I), X is Cl or Br, R H, C1-
Alkyl, Cl or the Br of C3.
3. half sandwich ruthenium complex according to claim 2, wherein in formula (I), X Cl, R H, methyl or
Cl。
4. a kind of preparation method of the half sandwich ruthenium complex as described in claim 1 containing hydroxyl, which is characterized in that
The preparation method is that: protecting gas, organic solvent and in the presence of alkali compounds, will the structure as shown in formula (III) naphthalene
The presoma of base Schiff base ligand and the ruthenium of structure shown in formula (II) carries out complexation reaction so that half folder containing hydroxyl is made
Heart ruthenium complex,
Wherein, in formula (II), X is halogen；In formula (III), the alkyl or halogen of R H, C1-C6.
5. the preparation method according to claim 4, wherein in (II), X is Cl or Br；In formula (III), R H,
Alkyl, Cl or the Br of C1-C3.
6. preparation method according to claim 5, wherein in (II), X Cl；In formula (III), R H, methyl or
Cl。
7. preparation method according to any one of claims 4 to 6, wherein the complexation reaction at least meets following item
Part: reaction temperature is 10-40 DEG C, reaction time 3-8h.
8. preparation method according to claim 7, wherein reaction temperature is 20-30 DEG C, reaction time 4-6h.
9. preparation method according to any one of claims 4 to 6, wherein the forerunner relative to ruthenium described in 0.20mmol
Body, the dosage of the naphthalene Schiff base ligand are 0.3-0.6mmol, and the dosage of the alkali compounds is 0.4-1.0mmol, institute
The dosage for stating organic solvent is 10-20mL.
10. preparation method according to any one of claims 4 to 6, wherein the alkali compounds be selected from sodium acetate,
One of potassium acetate, potassium carbonate, sodium carbonate and sodium hydroxide are a variety of.
11. preparation method according to claim 10, wherein the alkali compounds is potassium carbonate.
12. preparation method according to any one of claims 4 to 6, wherein the organic solvent is selected from methanol, ethyl alcohol
With one of acetonitrile or a variety of.
13. preparation method according to claim 12, wherein the organic solvent is methanol.
14. preparation method according to any one of claims 4 to 6, wherein the protection gas is nitrogen or argon gas.
15. a method of nitrobenzene compounds are reduced into amino benzenes compounds, which is characterized in that the method are as follows:
In air atmosphere, using half sandwich ruthenium complex described in any one of claim 1-3 containing hydroxyl as catalyst,
Nitrobenzene compounds shown in formula (IV) and reducing agent are carried out in the polar solvent containing CATB redox reaction with
Nitre amino benzenes compounds shown in formula (V) are obtained,
Wherein, R1 is selected from the alkyl of H, halogen or C1-C6, and n is the positive integer of 1-4.
16. according to the method for claim 15, wherein R1 is selected from the alkyl of H, halogen or C1-C3, and n is the just whole of 1-4
Number.
17. according to the method for claim 15, wherein R1 is selected from H, F, Cl, Br, I or methyl, and n is 1 or 2.
18. method described in any one of 5-17 according to claim 1, wherein the nitrobenzene compounds are selected from nitro
Benzene, 4- fluoronitrobenzene, 4- nitro-chlorobenzene, 4- Nitrobromobenzene, 4- nitro iodobenzene, 4- nitrotoleune, 3- nitrotoleune, 2- nitro first
Benzene or 2,6- dimethyl nitrobenzene.
19. method described in any one of 5-17 according to claim 1, wherein the redox reaction at least meet with
Lower condition: reaction temperature is 10-40 DEG C, reaction time 7-12h.
20. according to the method for claim 19, wherein reaction temperature is 20-30 DEG C, reaction time 8-10h.
21. method described in any one of 5-17 according to claim 1, wherein the nitrobenzene relative to 0.3mmol
Compound, the dosage of the reducing agent are 1-1.5mmol, and the dosage of the catalyst is 2 × 10-4-4×10-3Mmol, it is described
The dosage of CATB is 1 × 10-4-2.5×10-4Mmol, the dosage of the water are 1-4mL.
22. method described in any one of 5-17 according to claim 1, wherein the polar solvent is selected from water, methanol, second
One of pure and mild acetonitrile is a variety of.
23. according to the method for claim 22, wherein the polar solvent is water.
24. method described in any one of 5-17 according to claim 1, wherein the reducing agent is selected from sodium borohydride, hydrogenation
One of aluminium lithium, hydrazine hydrate and hydrogen are a variety of.
25. according to the method for claim 24, wherein the reducing agent is sodium borohydride.
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| WO2012071791A1 (en) * | 2010-12-01 | 2012-06-07 | 中国石油化工股份有限公司 | N ortho acyl substituted nitrogen-containing heterocyclic compound and process for preparing aminal iron (ii) complexes thereof |
| CN104876969A (en) * | 2015-05-11 | 2015-09-02 | 安徽师范大学 | Half-sandwich ruthenium coordination compounds, and preparation method and application thereof |
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| WO2012071791A1 (en) * | 2010-12-01 | 2012-06-07 | 中国石油化工股份有限公司 | N ortho acyl substituted nitrogen-containing heterocyclic compound and process for preparing aminal iron (ii) complexes thereof |
| CN104876969A (en) * | 2015-05-11 | 2015-09-02 | 安徽师范大学 | Half-sandwich ruthenium coordination compounds, and preparation method and application thereof |
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| Title |
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| Half-Sandwich Ruthenium Complexes with Schiff-Base Ligands:Syntheses, Characterization, and Catalytic Activities for the Reduction of Nitroarenes;Wei-Guo Jia等，;《Organometallics》;20160205;第35卷;第503-512页 |
| Synthesis, structures and catalytic activities of half-sandwich ruthenium complexes based on Schiff Base ligands;Wei-Guo Jia等，;《Inorganic Chemistry Communications》;20160203;第66卷;第15-18页，尤其是第16页方案1、第15页以及第16页、第17页表1 |
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