CN103880752B - The preparation of nitrogen heterocyclic metal-salt or its heterogeneous ring compound title complex - Google Patents
The preparation of nitrogen heterocyclic metal-salt or its heterogeneous ring compound title complex Download PDFInfo
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- CN103880752B CN103880752B CN201210563395.7A CN201210563395A CN103880752B CN 103880752 B CN103880752 B CN 103880752B CN 201210563395 A CN201210563395 A CN 201210563395A CN 103880752 B CN103880752 B CN 103880752B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
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Abstract
The present invention relates to a kind of for the preparation of the synthetic method of nitrogen heterocyclic metal-salt and nitrogen heterocyclic metal-salt heterogeneous ring compound title complex. In the absence of a solvent, by nitrogen heterocyclic and corresponding metal hydride mixing and ball milling, thus corresponding nitrogen heterocyclic metal-salt is obtained; In the absence of a solvent, by the mixture ball milling of a certain proportion of nitrogen heterocyclic, corresponding metal hydride and heterogeneous ring compound part, or by nitrogen heterocyclic metal-salt and a certain amount of heterogeneous ring compound ligand mixture ball milling, thus obtain nitrogen heterocyclic metal-salt heterogeneous ring compound title complex. Ball milling temperature is generally between-100°C to 300°C, and rotating speed is generally between 10 rpms to 500 rpms, and ball milling time general control is little between 300 hours 1. This preparation method have simple, without solvent, reaction without trim point, carry out thoroughly, reaction carries out degree and can monitor, the easily advantage of amplification.
Description
Technical field
The invention belongs to the preparation field of preparation method's technology and unknown compound, in particular to preparing nitrogen heterocyclic metal-salt (as: imidazole natrium) and heterogeneous ring compound title complex (as: imidazole natrium imidazoles) thereof based on ball milled.
Background technology
Nitrogen heterocyclic is the cyclic organic compounds containing nitrogen heteroatom in ring structure, has alkalescence more. The compound much with biological activity is all nitrogen heterocyclic, such as the nitrogenous base (ATCG) etc. of VITMAIN B1, Histidine, DNA. So nitrogen heterocyclic is the focus that organic synthesis and field of medicaments are paid close attention to always.
Nitrogen heterocyclic metal-salt is the intermediate that a class is often used in the process of synthesis of azacyclic compounds derivative, is especially widely used in alkyl substitution. The research of this compounds can be traced back to very early by people, just it is reacted such as " Americanized association can will " (JACS, 84 (1): 43-51.1962 and JACS, 90 (16): 4232-4238.1968) and character carried out report. The repercussion study participated in by this compounds at present is a lot, but its preparation is not all studied always in detail, the particularly report of not extensive preparation, so the price causing this similar drug remains high always, as the most common imidazole natrium is about 1300 yuan in the price of every 10 grams of Sigma-Aldrich company. The preparation of this compounds normally carries out in organic solvent, and for the sample expecting crystal form, this kind of method exists that solvent-oil ratio is big, operating process is loaded down with trivial details, length consuming time and reaction exist balance and be difficult to carry out the shortcoming such as completely.
Summary of the invention
It is an object of the invention to propose a kind of practical method being suitable for preparing various nitrogen heterocyclic metal-salt, to overcome, solvent-oil ratio in art methods is big, operating process is loaded down with trivial details, length consuming time and reaction exist balance and be difficult to carry out the shortcoming such as completely.
In order to realize above-mentioned purpose, present invention employs the technology of preparing based on ball milled, its concrete technical scheme is as follows:
In the absence of a solvent, being mixed according to certain mol proportion with one or more metal hydrides by one or more nitrogen heterocyclics, mechanical ball milling makes it have an effect, and this kind of effect can be considered as simple acid-base reaction. In the process of reaction, the mol ratio of nitrogen heterocyclic and metal hydride is between 1:20 to 20:1, speed of reaction can be controlled by the method for ball milling temperature and rotational speed of ball-mill, temperature of reaction general control is between-100 �� of C to 300 �� of C, and rotational speed of ball-mill is generally between 10 rpms to 500 rpms. Reaction is carried out degree and can be judged by the pressure change monitored in ball grinder, and ball milling time general control is little between 300 hours 1.
This method can be expanded, and for exploitation and the synthesis of nitrogen heterocyclic metal-salt this class novel cpd of heterogeneous ring compound title complex, the synthesis of this kind of compound cannot realize in traditional solvent reaction. Concrete technical scheme has the following two kinds:
Scheme one: in the absence of a solvent, one or more nitrogen heterocyclics are mixed with one or more metal hydrides, the mol ratio making nitrogen heterocyclic and metal hydride is between 1:20 to 20:1, add a certain amount of heterogeneous ring compound part simultaneously, the mol ratio making heterogeneous ring compound part and atoms metal is between 100:1 to 1:100, and mechanical ball milling makes it have an effect. In the process of reaction, it is possible to controlling speed of reaction by the method for ball milling temperature and rotational speed of ball-mill, temperature of reaction general control is within the scope of-100 �� of C to 300 �� of C, and rotational speed of ball-mill is generally between 10 rpms to 500 rpms. Reaction is carried out degree and can be judged by the pressure change monitored in ball grinder, and ball milling time general control is little between 300 hours 1.
Scheme two: first, prepares nitrogen heterocyclic metal-salt as stated above, and then adds a certain amount of heterogeneous ring compound part, and the mol ratio making heterogeneous ring compound part and atoms metal is between 100:1 to 1:100, and mechanical ball milling makes it have an effect. In the process of reaction, speed of reaction can be controlled by the method for ball milling temperature and rotational speed of ball-mill, temperature of reaction is generally between-100 �� of C to 300 �� of C, and rotational speed of ball-mill is generally between 10 rpms to 500 rpms, and ball milling time general control is little between 300 hours 1.
In described preparation scheme, material therefor is easy deliquescence or oxidizable material above, and therefore operation must operate under a dry, inert, such as N2Or in the glove box of Ar filling.
Nitrogen heterocyclic in this method is all nitrogen heterocyclics (comprising fused ring compound) and the derivative thereof that have reactive hydrogen on nitrogen heteroatom, such as one or more in imidazole and its derivants (such as glyoxal ethyline, 4-methylimidazole), pyrazoles and derivative, pyrroles and derivative, tetramethyleneimine and derivative, indoles and derivative, purine and derivative, carbazole and derivative thereof.
In this method, metal hydride can be one or more in alkalimetal hydride, alkaline earth metal hydride and transition metal hydride.
Alkalimetal hydride is one or more in lithium hydride, sodium hydride, potassium hydride KH.
Alkaline earth metal hydride is one or more in magnesium hydride, hydrolith.
Transition metal hydride is one or more in titanium hydride, zircoium hydride, zinc hydride.
In this method, heterogeneous ring compound part is have lone-pair electron, the heterogeneous ring compound (comprising nitrogen heterocyclic heterogeneous ring compound) that electronics carries out coordination can be provided, as: Furan and its derivatives, azoles and derivative thereof, different azoles and derivative thereof, pyrroles and derivative thereof, imidazole and its derivants, pyrazoles and derivative thereof, thiophene and derivatives, thiazole and derivative thereof, isothiazole and derivative thereof, pyridine and its derivatives, pyrans and derivative thereof, pyridazine and derivative thereof, pyrimidine and derivative thereof, pyrazine and derivative thereof, quinoline and its derivates, isoquinoline 99.9 and derivative thereof, pteridine and derivative thereof, acridine and derivative thereof, indoles and derivative thereof, purine and derivative thereof, one or more in carbazole and derivative thereof.
The feature of this method is: simple, without solvent, reaction without trim point, carry out thoroughly, react and carry out degree and can monitor, easily amplify.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the imidazole natrium of obtained imidazole natrium and standard.
Fig. 2 is the XRD spectra of obtained imidazoles lithium.
Fig. 3 is obtained pyrroles's sodium and the XRD spectra of pyrroles's lithium.
Fig. 4 is the XRD spectra according to the obtained imidazole natrium imidazoles of scheme one and imidazoles lithium imidazoles.
Fig. 5 is the XRD spectra according to the obtained imidazole natrium imidazoles of scheme two.
Specific embodiment
The present invention adopts above-mentioned ball milled to prepare various nitrogen heterocyclic metal-salt and heterogeneous ring compound title complex thereof. By the following examples the present invention is described in detail, it should be noted that the present invention is not limited to these embodiments.
Embodiment 1: the preparation of imidazole natrium
In glove box, take the imidazoles of 687mg and the sodium hydride of 252mg in same ball grinder. Noting, now two kinds of samples can not contact. After this ball grinder is sealed, carefully it is transferred on ball mill, when 50 �� of C, under 200rpm rotating speed, ball milling 5 hours. Reaction carries out degree can by monitoring that in ball grinder, pressure change realizes. Fig. 1 is X-ray diffraction (XRD) spectrogram of made sample, it can be seen that coincide with the imidazole natrium diffraction peak in database, proves that we have synthesized imidazole natrium, describe the feasibility of this preparation method.
Embodiment 2: the preparation of imidazoles lithium
In glove box, take the imidazoles of 687mg and the lithium hydride of 81mg in same ball grinder. Noting, now two kinds of samples can not contact. After this ball grinder is sealed, carefully it is transferred on ball mill, when 50 �� of C, under 200rpm rotating speed, ball milling 20 hours. Reaction carries out degree can by monitoring that in ball grinder, pressure change realizes. Fig. 2 is X-ray diffraction (XRD) spectrogram of made sample, it can be seen that the diffraction peak of imidazoles and lithium hydride disappears, and the substitute is one group of new diffraction peak, proves to define new species, i.e. our target product imidazoles lithium.
Embodiment 3: the preparation of pyrroles's sodium, pyrroles's lithium
In glove box, the sodium hydride (or 81mg lithium hydride) that takes 252mg, the pyrroles measuring 0.5ml are in same ball grinder. Noting, now two kinds of samples can not contact. After this ball grinder is sealed, carefully it is transferred on ball mill, when room temperature, under 150rpm rotating speed, ball milling 5 hours. Reaction carries out degree can by monitoring that in ball grinder, pressure change realizes. Fig. 3 is X-ray diffraction (XRD) spectrogram of made pyrroles's sodium and pyrroles's lithium powder sample.
Embodiment 4: the preparation (scheme one) of imidazole natrium imidazoles, imidazoles lithium imidazoles
In glove box, the sodium hydride (or 41mg lithium hydride) of the imidazoles (wherein 343.5mg imidazoles is as heterogeneous ring compound part) and 126mg that take 687mg is in same ball grinder. Noting, now two kinds of samples can not contact. After this ball grinder is sealed, carefully it is transferred on ball mill, when 50 �� of C, under 200rpm rotating speed, ball milling 5 hours (for imidazoles lithium imidazoles, ball milling 20h). Reaction carries out degree can by monitoring that in ball grinder, pressure change realizes. Fig. 3 is made imidazole natrium imidazoles and the X-ray diffraction (XRD) of imidazoles lithium imidazoles powdered sample, and they are the novel coordination compoundes of a class, yet there are no report, and we are called nitrogen heterocyclic metal-salt heterogeneous ring compound title complex.
Embodiment 5, the preparation (scheme two) of imidazole natrium imidazoles
In glove box, take imidazole natrium 450mg obtained in embodiment 1 and imidazoles 343.5mg(as heterogeneous ring compound part) in same ball grinder, after this ball grinder is sealed, carefully it is transferred on ball mill, when 50 �� of C, under 150rpm rotating speed, ball milling 5 hours. Fig. 5 is X-ray diffraction (XRD) spectrogram of made sample, it can be seen that coincide with imidazole natrium imidazoles diffraction peak obtained in embodiment 4.
Claims (8)
1. the preparation method of nitrogen heterocyclic metal-salt or its heterogeneous ring compound title complex, it is nitrogen heterocyclic metal-salt or the preparation of nitrogen heterocyclic metal-salt heterogeneous ring compound title complex, it is characterised in that:
Adopting ball milled, ball milling raw material is nitrogen heterocyclic and metal hydride, is mixed in proportion by ball milling raw material and carries out ball milling, obtains nitrogen heterocyclic metal-salt;
Or, adopting ball milled, ball milling raw material is nitrogen heterocyclic, metal hydride and heterogeneous ring compound part, or ball milling raw material is nitrogen heterocyclic metal-salt and heterogeneous ring compound part; Ball milling raw material is mixed in proportion and carries out ball milling, obtain nitrogen heterocyclic metal-salt heterogeneous ring compound title complex;
Raw material nitrogen heterocyclic is all nitrogen heterocyclics having reactive hydrogen on nitrogen heteroatom, raw material heterogeneous ring compound part be have lone-pair electron, the heterogeneous ring compound that electronics carries out coordination can be provided.
2. according to preparation method according to claim 1, it is characterised in that: ball milling temperature is between-100 DEG C to 300 DEG C.
3. according to the preparation method described in claim 1 or 2, it is characterised in that: rotational speed of ball-mill is between 10 rpms to 500 rpms.
4. according to the preparation method described in claim 1 or 2, it is characterised in that: the ball milling time is 1 little between 300 hours.
5. according to the preparation method described in claim 1 or 2, it is characterised in that:
Raw material nitrogen heterocyclic is all nitrogen heterocyclics having reactive hydrogen on nitrogen heteroatom, comprises fused ring compound;
Metal hydride can be one or two or more kinds in alkalimetal hydride, alkaline earth metal hydride and transition metal hydride;
Alkalimetal hydride is one or two or more kinds in lithium hydride, sodium hydride, potassium hydride KH;
Alkaline earth metal hydride is one or two or more kinds in magnesium hydride, hydrolith;
Transition metal hydride is one or two or more kinds in titanium hydride, zircoium hydride, zinc hydride.
6. according to the preparation method described in claim 1 or 2, it is characterised in that:
In nitrogen heterocyclic metal-salt preparation process, the mol ratio ratio of nitrogen heterocyclic and hydride is between 1:20 to 20:1.
7. according to the preparation method described in claim 1 or 2, it is characterised in that:
In the preparation process of nitrogen heterocyclic metal-salt heterogeneous ring compound title complex, the mol ratio of nitrogen heterocyclic and hydride is between 1:20 to 20:1, and heterogeneous ring compound part and atoms metal mol ratio are between 100:1 to 1:100.
8. according to the preparation method described in claim 1 or 2, it is characterised in that: the mol ratio of nitrogen heterocyclic metal-salt and heterogeneous ring compound part is between 100:1 to 1:100.
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| CN104356363B (en) * | 2014-11-10 | 2016-12-07 | 天津翔盛粉末涂料有限公司 | A kind of modified imidazole class latency Epoxy curing accelerators |
| CN108083986B (en) * | 2016-11-22 | 2020-08-04 | 中国科学院大连化学物理研究所 | Organic-inorganic hybrid material, preparation thereof and application thereof in hydrogen storage |
| CN112250582A (en) * | 2019-07-22 | 2021-01-22 | 中国科学院大连化学物理研究所 | Preparation method of amino metal compound and application of amino metal compound |
| CN111423618B (en) * | 2020-05-20 | 2021-07-06 | 中国科学技术大学 | Nitrogen heterocyclic aromatic amine-metal ion complex flame retardant and application thereof in preparation of flame-retardant epoxy resin |
| CN113620919B (en) * | 2021-06-18 | 2023-12-12 | 浙江工业大学 | Mechanical ball milling assisted synthesis method of 2-amino-3-cyano-4H-pyran compound |
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| US3808207A (en) * | 1967-06-05 | 1974-04-30 | Ethyl Corp | Complexes of beryllium hydride with tertiary amines |
| US20050148043A1 (en) * | 2002-04-09 | 2005-07-07 | Nicholas Dale | Biosensor for purines |
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Patent Citations (3)
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| US3808207A (en) * | 1967-06-05 | 1974-04-30 | Ethyl Corp | Complexes of beryllium hydride with tertiary amines |
| US20050148043A1 (en) * | 2002-04-09 | 2005-07-07 | Nicholas Dale | Biosensor for purines |
| CN102225748A (en) * | 2011-04-08 | 2011-10-26 | 沈阳师范大学 | Synthesis method for novel M-N-H (Mg(NH2)2-LiH) hydrogen storage material |
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