CN103626690B - Method for directly synthesizing nitrogenous heterocyclic aromatic hydrocarbon compound with aromatic hydrocarbon compound - Google Patents
Method for directly synthesizing nitrogenous heterocyclic aromatic hydrocarbon compound with aromatic hydrocarbon compound Download PDFInfo
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- CN103626690B CN103626690B CN201310669687.3A CN201310669687A CN103626690B CN 103626690 B CN103626690 B CN 103626690B CN 201310669687 A CN201310669687 A CN 201310669687A CN 103626690 B CN103626690 B CN 103626690B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a method for directly synthesizing a nitrogenous heterocyclic aromatic hydrocarbon compound with an aromatic hydrocarbon compound. The method comprises the steps that under a normal temperature discharge condition, an inorganic nitrogen compound serves as a nitrogen source, the aromatic hydrocarbon compound serves as a raw material, and the nitrogenous heterocyclic aromatic hydrocarbon compound is generated through reaction of benzene and a nitrogenous compound radical in an open or sealed reaction kettle. According to the method, a pyridine compound can be generated directly under the discharge condition through interaction of benzene and the inorganic nitrogen compound at normal temperature and pressure; with the adoption of the reaction condition of the method, methylbenzene can be directly converted into 3-picoline, dimethylbenzene can generate dimethyl pyridine, and naphthalene can generate isoquinoline; and the method has the advantages that the method is easy and simple to operate, mild in condition and high in selectivity, and the raw material is easy to obtain.
Description
Technical field
The present invention relates to the synthesis of nitrogen heterocyclic ring aromatic hydroxy compound, relating in particular to a kind of is raw material with aromatic hydroxy compound, is directly synthesized the method for nitrogen-containing heterocycle compound under electrion condition by the free radical reaction with inorganic nitride.
Technical background
Nitrogen heterocyclic ring aromatic hydroxy compound is the compound that a class is formed by carbon atom one or more on nitrogen-atoms substituted arene.Owing to having unique chemical physics performance, be widely used as denaturing agent, dyeing auxiliaries, be also used as the initial reactant synthesizing a series of product simultaneously, comprise medicine, sterilizing agent, dyestuff, food dressing, tackiness agent, explosive etc.Now, the preparation of nitrogen heterocyclic ring aromatic hydroxy compound can directly obtain from crude coal tar, but its content is lower, and need purify through multistage fractionation, therefore efficiency comparison is low; Also obtain by various chemosynthesis approach, as prepared, its step more loaded down with trivial details [Ullmann's Encyclopedia of Industrial Chemistry557-589 (2000)] by catalysis pyroreaction by aldehyde, ketone compounds and nitrogenous compound.Can as apparent from the structure of nitrogen heterocyclic ring aromatic hydroxy compound, it is the compound that instead of one or more carbon atom on aromatic hydrocarbons by nitrogen-atoms and formed that its structure forms the difference maximum with aromatic hydroxy compound.Therefore, effectively can simplify synthesis step as directly nitrogen heterocyclic ring aromatic hydroxy compound can be synthesized by the carbon atom of nitrogen-atoms substituted arene compound, improve combined coefficient.
Benzene as the simplest aromatic hydroxy compound, due to the compound stability of uniqueness, the carbon atom in its structure be difficult to activated and by other heteroatoms by substitution reaction synthesizing heterocyclic compounds.Although existing many about benzene and the interactional bibliographical information of other heteroatoms now, as atom N [J Phys.Chem.A103, 4261-4269 (1999), Chem.Phys.Lett.346, 35-40 (2001), Int.J.Mass Spectrom.230, 1-9 (2003), J.Chem.Phys.119, 1978-1985 (2003), Chem.Phys.302, 295-308 (2004), J.Chem.Phys.131 (2009)], O atom [J.Phys.Org.Chem.14, 300-309 (2001), Science295, 105-107 (2002), J.Phys.Chem.A110, 7841-7847 (2006)], Si atom [J.Am.Chem.Soc.99, 2943-2948 (1977), J.Am.Chem.Soc.114, 2802-2806 (1992)] and P atom [J.Am.Chem.Soc.114, 7582-7584 (1992), Sulfur Silicon Relat.Elem.149, 23-28 (1999)], but interacting to give birth to about benzene and heteroatoms directly becomes the Experimental report of heterocyclic arene compound less.Before a unique example can be returned and be traced back 20 years, the people such as Muedas are by benzene and PI
3interaction generate seven member ring heterocyclic compounds thing C
6h
6the report [J.Am.Chem.Soc.114,7582-7584 (1992)] of P.However, directly not yet there is report up to now by generating hexa-atomic aromatic hydroxy compound with the interaction of heteroatoms (as atom N) by benzene, particularly directly generating heterocycles, pyridines by benzene.As everyone knows, benzene, due to the chemically stable phase of uniqueness, it is conventionally believed that and directly can not generate pyridine by benzene.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, a kind of aromatic hydroxy compound is the object of the present invention is to provide directly to synthesize the method for nitrogen heterocyclic ring aromatic hydroxy compound, at normal temperatures and pressures, benzene, by the interaction with inorganic nitrogen-containing compound, directly can generate pyridine compounds under discharging condition; Meanwhile, utilize reaction conditions provided by the invention, toluene can be made to be converted into 3-picoline, dimethylbenzene generation lutidine, naphthalene generation isoquinoline 99.9 etc.; The method has easy and simple to handle, mild condition, and raw material is easy to get, selectivity advantages of higher.
For achieving the above object, technical scheme of the present invention is as follows:
Aromatic hydroxy compound directly synthesizes the method for nitrogen heterocyclic ring aromatic hydroxy compound, under normal temperature discharging condition, take inorganic nitrogen compound as nitrogenous source, take aromatic hydroxy compound as raw material, in open type or sealed reactor, generate nitrogen heterocyclic ring aromatic hydroxy compound by the reaction of benzene and nitrogenous compound free radical, reaction formula is as follows:
Wherein:
In reaction formula, substituent R can be hydrogen atom, alkyl group or aromatic yl group;
The nitrogenous source of described inorganic nitrogen compound is nitrogen protoxide, nitrogen peroxide, nitrogen or air, and inorganic nitrogen-sourced gas flow rate can be 0.1 ~ 50L/min;
Discharging condition is high direct voltage electric discharge or exchanges discharge of plasma in low temperature;
Reaction system can be open type electric discharge system or sealed electric discharge system;
Reaction times is: 5 seconds were by 20 hours;
Temperature of reaction is: 0 ~ 100 DEG C;
Described aromatic hydroxy compound can be technical pure or analytical pure or guaranteed reagent, comprises benzene,toluene,xylene and its substituent.
The present invention has the following advantages:
1. this reaction system a step preparation can generate nitrogen-containing heterocycle compound, without the need to being repeatedly separated, purifying reacting.
2. this reaction system is without the need to adding any catalyzer, directly can carry out under discharging condition.Adopt this reaction system, without the need to preparation, screening, optimization of catalysts, directly can directly generate nitrogen heterocyclic ring aromatic hydroxy compound by the exoelectrical reaction of aromatic hydroxy compound and inorganic nitrogen-containing compound.Electric energy is adopted to have green, environmental protection, stability high as activation aromatic hydrocarbons and inorganic nitride.
3. reaction conditions is gentle.Under normal temperature discharging condition, being interacted by stable aromatic hydroxy compound and inorganic nitrogenize, without the need to introducing strong acid, highly basic or catalyzer, can directly generate heterocyclic arene compound.
4. good reaction selectivity.The present invention under given conditions, directly can generate pyridine by benzene or directly generate 3-picoline by toluene, the position of nitrogen-atoms carbon atom on substituted benzene ring has unique selectivity.
Product analysis: can adopt the analysis of mass spectrum on-line monitoring or collecting reaction product, adopts GC/MS technology to analyze.
The present invention is easy and simple to handle, mild condition, and raw material is easy to get, selectivity high.
Accompanying drawing explanation
Fig. 1 (A) is reaction of low temperature plasma device; Fig. 1 (B) is the GC/MS spectrogram that embodiment one collects product.
Fig. 2 (A) is online reaction of low temperature plasma device; Fig. 2 (B) is the GC spectrogram collecting product; Fig. 2 (C) is the MS/MS spectrogram collecting parent ion m/z80 in product; Fig. 2 (D) is the MS/MS spectrogram of standard pyridine compounds parent ion m/z80.
Fig. 3 generates the reaction unit of pyridine by benzene under direct-current discharge system: Fig. 3 (A) take paper as the reaction unit of matrix; Fig. 3 (B) take acupuncture needle as the reaction unit of matrix.
Fig. 4 is the confirmation being generated 3-picoline structure under direct-current discharge system by toluene: Fig. 4 (A) is the MS/MS mass spectrum generating parent ion m/z94 under benzene discharging condition; Fig. 4 (B) is the MS/MS mass spectrum that 2-picoline generates parent ion m/z94; Fig. 4 (C) is the MS/MS mass spectrum that 3-picoline generates parent ion m/z94; Fig. 4 (D) is the MS/MS mass spectrum that 4-picoline generates parent ion m/z94.
Embodiment
Below by embodiment in detail the present invention is described in detail; But the present invention is not limited to following embodiment.
Embodiment one
By the direct pyridine synthesis of benzene under low-temperature plasma concrete conditions in the establishment of a specific crime
Under room temperature, in 50mL round-bottomed flask, add 5mL benzene (chromatographically pure), pass into 1%NO/N with the flow velocity of 0.15mL/min
2gas, adopts Figure 1A device, and Figure 1A is a reaction of low temperature plasma device, comprises nitrogenous source air flow system, low-temperature plasma surface dielectric barrier discharge electrode and magnetic agitation system, and under magnetic stirring, applying 5W frequency is 3.0kHz, 2.5kV
p-pvoltage of alternating current, reaction 8h, collect product, GC/MS analyze, result is as Figure 1B.Can be found out by Figure 1B, utilize reaction unit 1A, through 1%NO/N
2the reaction of gas and benzene, collects product and contains a certain amount of pyridine reaction product, describe and directly can generate pyridine compounds by the reaction of benzene and nitrogenous compound.
Embodiment two
By the direct pyridine synthesis of benzene under low-temperature plasma concrete conditions in the establishment of a specific crime
As Fig. 2 A reaction of low temperature plasma device, comprise nitrogenous source air flow system, sample pool, medium blocking discharge electrode and mass spectrometric detection system, add 5mL benzene (chromatographically pure), pass into 1%NO/N with the flow velocity of 0.40mL/min
2gas, be 3.0kHz in applying 5W frequency, voltage is 2.5kV
p-pvoltage of alternating current, directly analyzed product by mass spectrum, result is as Fig. 2 B-C.Can be found out by Fig. 2 B, a step can generate pyridine compounds C by benzene
5h
6n (m/z80.0494).Collect the second order ms figure of parent ion m/z80 and the second order ms figure of standard pyridine sample parent ion m/z80 in product by comparing, and then illustrate that reaction product has the structure of pyridine compounds.
Embodiment three
By the direct pyridine synthesis of benzene under low-temperature plasma concrete conditions in the establishment of a specific crime
As Fig. 2 A reaction of low temperature plasma device, add 5mL benzene (chromatographically pure), pass into N with the flow velocity of 0.40mL/min
2gas.Be 3.0kHz, 2.5kV in applying 5W frequency
p-pvoltage of alternating current, directly can be found out the generation of pyridine compounds to the analysis of product by mass spectrum.
Embodiment four
By the direct pyridine synthesis of benzene under low-temperature plasma concrete conditions in the establishment of a specific crime
As Fig. 2 A reaction of low temperature plasma device, adding 5mL benzene (chromatographically pure), pass into air with the flow velocity of 0.40mL/min, is 3.0kHz, 2.5kV in applying 5W frequency
p-pvoltage of alternating current, directly can be found out the generation of pyridine compounds to the analysis of product by mass spectrum.
Embodiment five
By the direct pyridine synthesis of benzene under direct-current discharge condition
As Fig. 3 reaction unit, comprise high-voltage power supply, sample carrying trilateral paper substrate or contain polymer-like QC wiry and mass spectrometric detection system, chromatographic paper matrix or containing the pipe of polymkeric substance wiry in add the benzene reactant of 50 μ L, under atmospheric conditions, using air as nitrogenous source, apply the volts DS of 4.0kV, directly adopt mass spectrum to analyze product, find that benzene one step can generate pyridine compounds.
Embodiment six
3-picoline is directly synthesized by toluene under direct-current discharge condition
As Fig. 3 A reaction unit, chromatographic paper matrix adds the toluene reactant of 30 μ L, under atmospheric conditions, using air as nitrogenous source, apply the volts DS of 4.0kV, directly adopt mass spectrum to analyze product, find that toluene one-step can generate 3-methyl-pyridyl compound, result is as Fig. 4.Can be found out by this figure, the MS/MS spectrogram adopting benzene reaction system to generate the parent ion peak of m/z94 mates completely with the MS/MS spectrogram of the parent ion peak of standard model 3-picoline m/z94, illustrates that product has the structure of 3-picoline.
Embodiment seven
By the direct synthesization of dimethyl pyridine of o-Xylol under direct-current discharge condition
As Fig. 3 A reaction unit, chromatographic paper matrix adds the o-Xylol reactant of 30 μ L, under atmospheric conditions, using air as nitrogenous source, apply the volts DS of 4.0kV, directly adopt mass spectrum to analyze product, find that o-Xylol one step can generate dimethyl pyrazole acridine compound.
Embodiment eight
By the direct synthesis of quinoline of naphthalene under direct-current discharge condition
As Fig. 2 A reaction unit, in reaction system, add naphthalene reactant, pass into air with the flow velocity of 0.40mL/min.Be 3.0kHz, 2.5kV in applying 5W frequency
p-pvoltage of alternating current, directly can be found out the generation of quinoline compound to the analysis of product by mass spectrum.
Claims (1)
1. aromatic hydroxy compound directly synthesizes the method for nitrogen heterocyclic ring aromatic hydroxy compound, it is characterized in that, under normal temperature discharging condition, take inorganic nitrogen compound as nitrogenous source, take aromatic hydroxy compound as raw material, in open type or sealed reactor, generate nitrogen heterocyclic ring aromatic hydroxy compound by the reaction of benzene and nitrogenous compound free radical, reaction formula is as follows:
Wherein:
The nitrogenous source of described inorganic nitrogen compound is nitrogen protoxide, nitrogen peroxide, nitrogen or air, and inorganic nitrogen-sourced gas flow rate can be 0.1 ~ 50L/min;
Discharging condition is high direct voltage electric discharge or exchanges discharge of plasma in low temperature;
Reaction system can be open type electric discharge system or sealed electric discharge system;
Reaction times is: 5 seconds were by 20 hours;
Described aromatic hydroxy compound is benzene,toluene,xylene and naphthalene.
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