CN107365277B - Water-containing metal ion pentazole salt and preparation method thereof - Google Patents
Water-containing metal ion pentazole salt and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-containing metal ion pentazole salt, a preparation method and a preparation method thereof, wherein the chemical structural formula of the metal salt is M (N)5)x(H2O)yX =1 and y =4 when M is a monovalent metal of Li, Na, K or Ag, or x =2 and y =8 or 10 when M is a divalent metal of Fe, Co, Ni, Mg, Ca, Ba, Cu, Zn or Pb; the metal ion-containing arylpentazole is prepared by respectively adopting m-chloroperoxybenzoic acid and ferrous glycinate as a cutting reagent and an auxiliary agent, reacting with arylpentazole, selectively cutting off a C-N bond in an arylpentazole molecule by an oxidative cleavage method, and taking a salt containing metal ions as a capture reagent. The metal pentazole salt is successfully prepared, and has wide application in the field of energetic materials.
Description
Technical Field
The invention relates to a pentaconazole anion salt containing metal ions and a synthesis method thereof, belonging to the field of research of high-energy energetic materials.
Background
The chemical structural formula of the pentazole anion is as follows:
the novel ultra-high energy containing material is the key point of dispute and development of all military and strong countries in the world at present, is also an important mark of core military capability and military technology high point of the future country, and the all-nitrogen substance becomes a typical representative of a new generation of ultra-high energy containing material due to the advantages of high density, high enthalpy of formation, ultra-high energy, clean and pollution-free detonation products and the like, is expected to be applied to the fields of explosives, propellant and the like as the new generation of ultra-high energy containing material, and is always valued by all countries in the world.
The total nitrogen substances mainly comprise ionic total nitrogen, covalent total nitrogen and polymeric nitrogen, wherein the ionic total nitrogen substances are the most probably first applied substances because the ionic total nitrogen substances are ideal high-energy density materials and can also be used as substrates to obtain covalent total nitrogen materials and polymeric nitrogen through assembly. Except common energetic ions N3Other than, N5and-N5 ＋Is two kinds of total nitrogen ions which have been reported at present. And N5 ＋Ion phase ratio, N5The-ion has more electrons, stronger electronegativity and better stability. Theoretical studies have shown that in all N5Among the ionic isomers, the pentazole anion, which is an iso-electronic analogue of total nitrogen of cyclopentadiene anion having a cyclic structure, has the best stability due to good aromaticity, and has higher enthalpy and energy of formation, so that the pentazole anion is more likely to be utilized to synthesize other novel total nitrogen high-energy compoundsAngew Chem Int Ed,1999, 38(13-14): 2004-2009]. Thus, N5The synthesis of the-ion is always a research hotspot in the field of international energetic materials.
N5The ion is usually prepared using an arylpentazole compound. Because the arylpentazole usually only exists stably at low temperature (less than or equal to-40 ℃), the arylpentazole has poor stability, is easy to decompose and release nitrogen to be converted into an azide compound, and the bond energy of an N-N bond (82 KJ/mol) in the molecule of the arylpentazole is far less than that of a C-N bond (485)KJ/mol) so that the N-N bond of the arylpentazole molecule is far more susceptible to cleavage than the C-N bond, and direct cleavage of the C-N bond in the arylpentazole molecule results in fragmentation of the pentazole ring and failure to obtain N5The ion, in addition to N5The stability of the ion is poor, and therefore, N is obtained by cleaving the C-N bond in the arylpentazole molecule by a conventional method5The ion is very difficult. In 2002, Vij et al bombarded arylpentazoles in a mass spectrometer with high-energy electron beams, and captured N in a secondary mass spectrum for the first time5Fragment signal of-ring anionAngew Chem Int Ed,2002, 41(16): 3051-3054]. However, only N can be demonstrated with this approach5The presence of an ion makes it impossible to obtain N5The practical species of the-ion, and the experimental studies thereafter, have essentially stopped seeking various means for cleaving the C-N bond in the arylpentazole molecule. In 2003, Butler et al used ammonium ceric nitrate to react with p-methoxyphenyl pentazole, oxidized and cleaved C-N bonds in substrate molecules by the oxidation of high-valent cerium ions, and claimed that N was detected by NMR analysis5Alpha-ion 2Chem Commun, 2003,8: 1016-1017]. In 2005, Schroer et al repeated the Butler experiment without obtaining N5Ion and confirm N in the nuclear magnetic nitrogen spectrogram reported by Butler et al5The signal is NO added during the experiment3Produced other than N-5ˉ[Chem Commun, 2005, 12: 1607–1609]. In 2008, Butler et al repeated their own experiments and found that there was indeed no direct evidence that the C-N bond in the arylpentazole molecule was cleaved and the N captured5Alpha-ion 2J Org Chem,2008, 73(4): 1354-1364]. Thereafter with respect to N5No progress was reported, only some theoretical calculations reported, until 2016, Haas et al reported that selective cleavage of C-N bond in arylpentazole molecule by reductive cleavage using metallic sodium as cleavage reagent at low temperature, and N was first detected in primary mass spectrum5The signal of-confirms N5The ion may be present in the solution at a low temperature (. ltoreq. -40 ℃ C.)Angew Chem Int Ed,2016, 55(42), 13233-13235]。
Disclosure of Invention
The invention aims to provide a method for preparing a metal ion-containing pentazole salt by cutting off a C-N bond of substituted phenyl pentazole, which comprises the steps of dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole in a mixed solvent of methanol and acetonitrile, selectively cutting off the C-N bond of aryl pentazole by taking ferrous glycinate and m-chloroperoxybenzoic acid as cutting-off reagents, and further capturing pentazole anions by using metal salt to successfully prepare the metal pentazole salt.
The technical solution for realizing the purpose of the invention is as follows:
a metal ion pentazole salt with chemical structural formula of M (N)5)x(H2O)yWhen M is a monovalent metal, Li, Na, K or Ag, x =1, y =4; when M is a divalent metal Fe, Co, Ni, Mg, Ca, Ba, Cu, Zn or Pb, x =2, y =8 or 10.
Wherein, when the metal ion pentazole salt is Co (N)5)2(H2O)8The crystal data are as follows:
the molecular formula is as follows: co (N)5)2(H2O)8；
Molecular weight: 343.16, respectively;
the crystal form is as follows: orthogonal;
unit cell parameters a = 12.1536 Å, b =17.1485 Å, c =6.4578 Å, α = β = γ = 90;
unit cell volume 1345.91 Å3；
Z：4。
Wherein, when the metal ion pentazolate is Mg (N)5)2(H2O)10The crystal data are as follows:
the molecular formula is as follows: mg (N)5)2(H2O)10；
Molecular weight: 344.57, respectively;
the crystal form is as follows: three-oblique;
unit cell parameters a =7.1463 Å, b =7.1973 Å, c =9.2237 Å =90.939 °, β = 106.774 °, γ =117.603 °;
unit cell volume 396.18 Å3；
Z：1。
The metal ion pentazole salt is prepared by respectively adopting m-chloroperoxybenzoic acid and ferrous glycinate as a cutting reagent and an auxiliary agent, reacting with aryl pentazole, selectively cutting off a C-N bond in an aryl pentazole molecule by an oxidative cleavage method, and taking a salt containing metal ions as a capture reagent.
Compared with the prior art, the invention has the following remarkable advantages:
according to the invention, ferrous glycinate and m-chloroperoxybenzoic acid are used as cutting reagents to selectively cut off C-N bonds of aryl pentazole, and metal salt is used for capturing pentazole anions obtained by cutting off, so that metal pentazole salt is successfully prepared, and the metal pentazole salt is widely applied to the field of energetic materials.
The present invention is described in further detail below with reference to the attached drawing figures.
Drawings
FIG. 1 is a process flow diagram of the process for the preparation of metal pentazole salts of the present invention.
FIG. 2 is ESI-MS spectrum of pentazole of the present invention.
FIG. 3 is the product Co (N)5)2(H2O)8Crystal structure of (2).
FIG. 4 is the product Mg (N)5)2(H2O)10Crystal structure of (2).
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. The present invention includes, but is not limited to, the following metal salts.
Taking metal magnesium and cobalt as examples, the reaction equation of the compound pentazole salt provided by the invention is as follows:
the following examples were carried out as described in FIG. 1.
The ESI-MS spectrogram of the pentazole compound adopted by the invention is shown in figure 2.
Example 1: in a single-neck flask, add 3, 5-bisMethyl-4-hydroxyphenyl pentazole (3 mmol) is dissolved in a mixed solvent of methanol and acetonitrile, and under the reaction condition of-45 ℃, a methanol water solution of ferrous glycinate (6 mmol) is added (precooled to-45 ℃), stirred for 30 min, and then a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) is added (precooled to-45 ℃), and the reaction is carried out for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobalt chloride hexahydrate (3 mmol), stirring at 25 deg.C for reaction for 3 hr, and rotary evaporating to obtain 58.4 mg of pentazole metal salt Co (N)5)2(H2O)8The yield was 11.35%.
Example 2: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobalt nitrate hexahydrate (6 mmol), stirring at 25 deg.C for reaction for 6h, and rotary evaporating to obtain 63.1 mg of pentazole metal salt Co (N)5)2(H2O)8The yield was 12.26%.
Example 3: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobaltous sulfate heptahydrate (9 mmol), stirring at 30 deg.C for reaction for 6h, and rotary evaporating to obtain 56.4 mg of pentazole metal salt Co (N)5)2(H2O)8The yield was 10.96%.
Example 4: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, and adding glycerol under the reaction condition of-45 DEG CFerrous amino acid (6 mmol) in methanol water solution (precooled to-45 ℃), stirring for 30 min, then adding m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) in methanol (precooled to-45 ℃) and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobalt nitrate hexahydrate (6 mmol), stirring at 25 deg.C for reaction for 3 hr, and rotary evaporating to obtain 61.2 mg of pentazole metal salt Co (N)5)2(H2O)8The yield was 11.89%.
Example 5: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobalt nitrate hexahydrate (6 mmol), stirring at 25 deg.C for reaction for 9 h, and rotary evaporating to obtain 61.8 mg of pentazole metal salt Co (N)5)2(H2O)8The yield was 12.01%.
Example 5: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobalt nitrate hexahydrate (6 mmol), stirring at 20 deg.C for reaction for 6h, and rotary evaporating to obtain 60.8 mg of pentazole metal salt Co (N)5)2(H2O)8The yield was 11.82%.
Example 6: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding methanol water solution of ferrous glycinate (6 mmol) under the reaction condition of-45 ℃ (precooling to-45 ℃), stirring for 30 min, and then adding m-chloroperoxybenzoic acid (W)t 85%) (12 mmol) in methanol (precooled to-45 ℃ C.) was reacted for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobalt nitrate hexahydrate (6 mmol), stirring at 30 deg.C for reaction for 6h, and rotary evaporating to obtain 62.2 mg of pentazole metal salt Co (N)5)2(H2O)8The yield was 12.09%.
Example 7: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding magnesium chloride hexahydrate (6 mmol), stirring at 30 deg.C for reaction for 9 hr, and rotary evaporating to obtain 39.4 Mg of metal salt Mg (N) of pentazole5)2(H2O)10The yield was 7.63%.
Example 8: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid, extracting, mixing water phases, adding magnesium nitrate hexahydrate (3 mmol), stirring at 25 deg.C for 6 hr, and rotary evaporating to obtain 43.2 Mg of metal salt Mg (N) of pentazole5)2(H2O)10The yield was 8.37%.
Example 9: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most of solvent, separating liquid, and extractingCollecting, mixing water phases, adding magnesium sulfate heptahydrate (3 mmol), stirring at 25 deg.C for 9 hr, and rotary evaporating to obtain 40.8 Mg of metal salt Mg (N) of pentazole5)2(H2O)10The yield was 7.91%.
Example 10: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobalt nitrate hexahydrate (6 mmol), stirring at 25 deg.C for reaction for 3 hr, and rotary evaporating to obtain 41.5 Mg of metal salt Mg (N) of pentazole5)2(H2O)10The yield was 8.04%.
Example 11: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding cobalt nitrate hexahydrate (6 mmol), stirring at 20 deg.C for reaction for 6h, and rotary evaporating to obtain 41.9 Mg of pentazole metal salt Mg (N)5)2(H2O)10The yield was 8.12%.
Example 12: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid, extracting, mixing water phases, adding magnesium nitrate hexahydrate (6 mmol), stirring at 30 deg.C for reaction for 6 hr, and rotary evaporating to obtain 42.4 mg pentazoleMetal salt Mg (N)5)2(H2O)10The yield was 8.22%.
Example 13: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding nickel sulfate hexahydrate (9 mmol), stirring at 25 deg.C for reaction for 6h, and rotary evaporating to obtain 53.8 mg metal pentazolate Ni (N)5)2(H2O)8The yield was 10.46%.
Example 14: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding nickel bromide (9 mmol), stirring at 25 deg.C for 4 hr, and rotary evaporating to obtain 55.3 mg metal pentazolate Ni (N)5)2(H2O)8The yield was 10.75%.
Example 15: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding ferrous sulfate heptahydrate (6 mmol), stirring at 25 deg.C for 8 hr, and rotary evaporating to obtain 51.2 mg metal pentazolate Fe (N)5)2(H2O)8The yield was 10.04%.
Example 16: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding ferrous chloride tetrahydrate (6 mmol), stirring at 20 deg.C for reaction for 6 hr, and rotary evaporating to obtain 52.9 mg metal pentazolate Fe (N)5)2(H2O)8The yield was 10.37%.
Example 17: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid, extracting, mixing water phases, adding lithium chloride (3 mmol), stirring at 30 deg.C for 6 hr, and rotary evaporating to obtain 44.2 mg metal pentazolate LiN5(H2O)4Yield 9.89%.
Example 18: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary distilling to remove most solvent, separating liquid and extracting, mixing water phases, adding lithium nitrate (6 mmol), stirring at 30 deg.C for reaction for 3 h, and rotary distilling to obtain 45.7 mg metal pentazolyl salt LiN5(H2O)4The yield was 10.22%.
Example 19: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, and reacting at-45 DEG CThen, a methanol aqueous solution of ferrous glycinate (6 mmol) was added (precooled to-45 ℃ C.), stirred for 30 min, and then a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) was added (precooled to-45 ℃ C.), and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, separating liquid and extracting, mixing water phases, adding sodium fluoride (9 mmol), stirring at 20 deg.C for reaction for 9 h, and rotary evaporating to obtain 55.7 mg metal pentazolate NaN5(H2O)4The yield was 11.25%.
Example 20: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most of solvent, separating liquid, extracting, mixing water phases, adding sodium iodide (6 mmol), stirring at 25 deg.C for reaction for 3 hr, and rotary evaporating to obtain 54.7 mg metal pentazolate NaN5(H2O)4The yield was 11.05%.
Example 21: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most of solvent, separating liquid, extracting, mixing water phases, adding potassium bicarbonate (6 mmol), stirring at 30 deg.C for 9 hr, and rotary evaporating to obtain 73.4 mg metal pentazolate KN5(H2O)4Yield 13.52%.
Example 22: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the reaction condition of-45 ℃ (precooling to-45 ℃), stirring for 30 min, and then adding a methanol solution (precooled to-12 mmol) of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) in the mixed solventTo-45 ℃ for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding potassium hydrogen phosphate (9 mmol), stirring at 25 deg.C for 6 hr, and rotary evaporating to obtain 71.8 mg metal pentazolate KN5(H2O)4The yield was 13.22%.
Example 23: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding silver nitrate (3 mmol), stirring at 20 deg.C for reaction for 6 hr, and rotary evaporating to obtain 73.3 mg metal pentazolate AgN5(H2O)4Yield 9.77%.
Example 24: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding silver fluoride (6 mmol), stirring at 25 deg.C for 6 hr, and rotary evaporating to obtain 74.9 mg metal pentazolate AgN5(H2O)4The yield was 9.99%.
Example 25: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid, extracting, mixing water phases, adding calcium nitrate (3 mmol), stirring at 20 deg.C for 6 hr, and rotary evaporating to obtain 427 mg of metal pentazolate Ca (N)5)2(H2O)8The yield was 8.79%.
Example 26: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid, extracting, mixing water phases, adding calcium chloride (3 mmol), stirring at 30 deg.C for 6 hr, and rotary evaporating to obtain 45.9 mg metal pentazolate Ca (N)5)2(H2O)8Yield 9.44%.
Example 27: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid, extracting, mixing water phases, adding barium nitrate (6 mmol), stirring at 25 deg.C for 6 hr, and rotary evaporating to obtain 57.6 mg metal pentazolate Ba (N)5)2(H2O)8Yield 9.12%.
Example 28: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid, extracting, mixing water phases, adding barium bromide (9 mmol), stirring at 25 deg.C for 3 hr, and rotary evaporating to obtain 54.8 mg metal pentazolate Ba (N)5)2(H2O)8The yield was 8.68%.
Example of the implementation29: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid, extracting, mixing water phases, adding copper sulfate pentahydrate (3 mmol), stirring at 30 deg.C for 6 hr, and rotary evaporating to obtain 46.8 mg metal pentazolate Cu (N)5)2(H2O)8The yield was 8.96%.
Example 30: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding copper nitrate (6 mmol), stirring at 25 deg.C for 6 hr, and rotary evaporating to obtain 47.3 mg metal pentazolate Cu (N)5)2(H2O)8Yield 9.06%.
Example 31: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding zinc chloride (9 mmol), stirring at 25 deg.C for 6 hr, and rotary evaporating to obtain 48.9 mg metal pentazolate Zn (N)5)2(H2O)8Yield 9.34%.
Example 31: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, and reacting at-45 DEG CUnder the condition, a methanol aqueous solution (precooled to-45 ℃) of ferrous glycinate (6 mmol) is added, stirring is carried out for 30 min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding zinc nitrate hexahydrate (3 mmol), stirring at 20 deg.C for reaction for 6 hr, and rotary evaporating to obtain 49.7 mg metal pentazolate Zn (N)5)2(H2O)8Yield 9.49%.
Example 32: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating, extracting, mixing water phases, adding lead sulfate (6 mmol), stirring at 25 deg.C for 9 hr, and rotary evaporating to obtain 73.2 mg metal pentazolate Pb (N)5)2(H2O)8The yield was 9.94%.
Example 33: dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3 mmol) in a mixed solvent of methanol and acetonitrile in a single-neck flask, adding a methanol water solution of ferrous glycinate (6 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30 min, then adding a methanol solution of m-chloroperoxybenzoic acid (Wt 85%) (12 mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), and reacting for 36 h. Filtering, rotary evaporating to remove most solvent, separating liquid and extracting, mixing water phases, adding lead nitrate (6 mmol), stirring at 25 deg.C for 6 hr, and rotary evaporating to obtain 71.3 mg metal pentazolate Pb (N)5)2(H2O)8Yield 9.68%.
Claims (6)
1. The water-containing metal ion pentazolate is characterized in that the chemical structural formula of the water-containing metal ion pentazolate is M (N)5)x(H2O)yWhen M is a monovalent metal Li, Na, K or Ag, x =1 and y =4, and when M is a divalent metal Fe, Co, Ni, Mg, B,Ca. Ba, Cu, Zn or Pb, x =2 and y = 8.
2. The aqueous metal ion pentazole salt of claim 1, wherein the pentazole salt is Co (N)5)2(H2O)8。
3. The method for preparing an aqueous metal ion pentazole salt according to claim 1 or 2, wherein m-chloroperoxybenzoic acid and ferrous glycinate are respectively used as a cutting reagent and an auxiliary agent, the m-chloroperoxybenzoic acid and the ferrous glycinate are reacted with the arylpentazole, the C-N bond in the molecule of the arylpentazole is selectively cut off by an oxidative cleavage method, and a salt containing metal ions is used as a capture reagent.
4. The production method according to claim 3, characterized in that: the molar ratio of the reaction materials in the cutting reaction is aryl pentazole: the salt containing metal ions = 1: 1-3.
5. The production method according to claim 3, characterized in that: the reaction temperature is 20-30 ℃.
6. The production method according to claim 3, characterized in that: the reaction time is 3-9 h.
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| A Symmetric Co(N5)2(H2O)4•4H2O High-Nitrogen Compound Formed by Cobalt(II) Cation Trapping of a Cyclo-N5- Anion;Chong Zhang等;《Angew. Chem. Int. Ed.》;20170322;第56卷(第16期);Supporting information第1-6页 * |
| Investigation on the Stability of Multisubstituted Arylpentazoles and the Influence on the Generation of Pentazolate Anion;Zhang, Chong等;《Journal of Energetic Materials》;20151116;第34卷(第1期);103-111 * |
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