CN106518797A - Pentazole composite salt and preparation method thereof - Google Patents
Pentazole composite salt and preparation method thereof Download PDFInfo
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- CN106518797A CN106518797A CN201610689258.6A CN201610689258A CN106518797A CN 106518797 A CN106518797 A CN 106518797A CN 201610689258 A CN201610689258 A CN 201610689258A CN 106518797 A CN106518797 A CN 106518797A
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- pentazole
- methanol
- salt
- ferrous
- substituted phenyl
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- WUHLVXDDBHWHLQ-UHFFFAOYSA-N pentazole Chemical compound N=1N=NNN=1 WUHLVXDDBHWHLQ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 150000003839 salts Chemical class 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 pentazolate anion Chemical class 0.000 claims abstract description 39
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims abstract description 34
- KMRDNOKWDDOCNT-UHFFFAOYSA-N 1-phenylpentazole Chemical class C1=CC=CC=C1N1N=NN=N1 KMRDNOKWDDOCNT-UHFFFAOYSA-N 0.000 claims abstract description 23
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 264
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 102
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 239000012046 mixed solvent Substances 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- GIPOFCXYHMWROH-UHFFFAOYSA-L 2-aminoacetate;iron(2+) Chemical compound [Fe+2].NCC([O-])=O.NCC([O-])=O GIPOFCXYHMWROH-UHFFFAOYSA-L 0.000 claims description 7
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 7
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000859 α-Fe Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 239000003223 protective agent Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 description 50
- 239000000243 solution Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- JTFZBQMSQKUMPP-UHFFFAOYSA-N 1-(4-methoxyphenyl)pentazole Chemical compound C1=CC(OC)=CC=C1N1N=NN=N1 JTFZBQMSQKUMPP-UHFFFAOYSA-N 0.000 description 5
- KWUMDXKCORHVHH-UHFFFAOYSA-N 2,6-dimethyl-4-(pentazol-1-yl)phenol Chemical compound CC=1C=C(C=C(C=1O)C)N1N=NN=N1 KWUMDXKCORHVHH-UHFFFAOYSA-N 0.000 description 5
- XAHWJGTVXSJSAG-UHFFFAOYSA-N 2-methyl-4-(pentazol-1-yl)phenol Chemical compound CC=1C=C(C=CC=1O)N1N=NN=N1 XAHWJGTVXSJSAG-UHFFFAOYSA-N 0.000 description 5
- CGPNKUBKCFFUHB-UHFFFAOYSA-N 4-(pentazol-1-yl)phenol Chemical compound C1=CC(O)=CC=C1N1N=NN=N1 CGPNKUBKCFFUHB-UHFFFAOYSA-N 0.000 description 5
- OICBARXSRMXZPL-UHFFFAOYSA-N 4-dimethylaminophenylpentazole Chemical compound C1=CC(N(C)C)=CC=C1N1N=NN=N1 OICBARXSRMXZPL-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 238000005474 detonation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000002204 nitrogen-15 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D259/00—Heterocyclic compounds containing rings having more than four nitrogen atoms as the only ring hetero atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a pentazole composite salt and a preparation method thereof. By cutting off a C-N bond of substituted phenyl pentazole, a pentazolate anion is prepared. By adopting m-chloroperoxybenzoic acid and a ferrous salt as an oxidizing agent and a protective agent, respectively, a pentazolate-anion-containing composite salt [(N5)6(H3O)3(NH4)4Cl] is prepared. According to the invention, the pentazolate-anion-containing composite salt is achieved by cutting off the C-N bond of the substituted phenyl pentazole and successfully separating out the pentazolate anion. Also the synthesized pentazole composite salt can stably exist at normal temperature, and has great application values in the field of energetic materials.
Description
Technical Field
The invention relates toA pentazole composite salt and a preparation method thereof, in particular to a composite salt [ (N) containing pentazole anion5)6(H3O)3(NH4)4Cl]And a preparation method thereof, belonging to the technical field of energetic materials.
Background
Because of the remarkable advantages of the total nitrogen compound in detonation performance compared with the traditional energetic material, the research focus in the field of domestic and foreign energetic materials is gradually shifting from the traditional energetic material to the novel total nitrogen compound. The most remarkable characteristic of the total nitrogen compound is that molecules contain a large number of N-N and N ═ N bonds, huge energy is released in the process of decomposing into nitrogen, and meanwhile, the electronegativity of nitrogen is second to that of F and O elements, so that a strong chemical bond can be formed, namely, the total nitrogen derivative which is wholly or partially composed of nitrogen elements has certain stability. Compared with the traditional energetic material, the full-nitrogen material has the advantages of high density, high formation enthalpy, ultrahigh energy, clean detonation products and the like, so that the full-nitrogen material is expected to be applied to the fields of explosives, propellant powder, propellant, gas generating agent and the like as a new generation of ultrahigh energy energetic material.
As an important component of total nitrogen compounds, the milestone breakthrough of experimental research on total nitrogen ion compounds was reported in 1999 as N5 +And (4) synthesizing. Its discovery has created new promise by scientists for the synthesis of total nitrogen high energy density materials. N is a radical of5 +The ions being present in salt form (e.g. N)5SnF3Or N5SbF6) But due to N5 +The thermal stability of these salts is low, resulting in low thermal stability of these salts. Therefore, many experimental studies are conducted to find a suitable anion and N5 +Formation of salts with ionic composition to increase N5 +Stability of the ions. Wherein N is5 +N5 -The combination is a very ideal target molecule, but this requires the search for synthetic N5 -A method of ionizing, andwith respect to N5 -Ion, the synthesis of which is currently reported in only a small number of documents.
In 2002, Vij et al bombarded the central C-N bond in arylpentazole by using high-energy cracking energy in a mass spectrometer, and captured N in secondary mass spectrum for the first time5 -Fragmentation signal of cyclic anion [ Angew. chem.114, 3177-3180 (2002)]This finding gave the experimenter the separation of N from arylpentazoles5 -Bringing great hopes. However, the experimental studies have not made a major breakthrough, and the search for various means for cleaving the C-N bond of the arylpentazoles has been essentially stopped. In 2003, Butler et al reported that N was first obtained in experiments by cleaving the C-N bond of aryl pentazole with Cerium Ammonium Nitrate (CAN) in acetonitrile solution5 -[Chem.Commun.8,1016–1017(2003)]. In 2005, Schroer repeated Butler's experiment and confirmed that N was not obtained by cleaving C-N bond5 -[Chem.Commun.12,1607–1609(2005)]. In 2007, Butler re-studied his own experiments and finally concluded that there was no direct evidence of N being obtained5 -[J.Org.Chem.73,1354–1364(2008)]. Thereafter with respect to N5 -There have been no progress reported, only some theoretical calculations have been reported, 2016, 7 months, Haas reported the use of sodium metal as a starting material, the cleavage of the phenylpentazole by a free radical mechanism, and the detection of N below-40 ℃ using a mass spectrometer5 -[Angew.Chem.128,1–4(2016)]。
In summary, N is the same as5 -The technical problem of synthesis is shown in the prior literature report N5 -Very few of the N can be successfully synthesized, and the N which can stably exist at normal temperature can not be successfully synthesized at present5 -Report of complex salts.
Disclosure of Invention
Aiming at N stably existing at normal temperature in the prior art5 -The invention provides a compound salt of pentazole and a preparation method thereof,the pentazole anion is prepared by cutting off the C-N bond of the substituted phenyl pentazole, and the composite salt [ (N) containing the pentazole anion is successfully prepared by respectively adopting m-chloroperoxybenzoic acid and ferrous salt as an oxidant and a protective agent5)6(H3O)3(NH4)4Cl]。
The technical scheme of the invention is as follows:
a compound salt of pentazole has a molecular formula of (N)5)6(H3O)3(NH4)4Cl, wherein N5 -Is a cyclic N5 -。
The preparation method of the pentazole composite salt comprises the following synthetic route:
wherein,is substituted phenyl pentazole, Fe2+Is ferrous salt, mCPBA is m-chloroperoxybenzoic acid,is a pentazole complex salt (N)5)6(H3O)3(NH4)4Cl。
The substituent group in the substituted phenyl pentazole is an electric supply group.
The substituted phenyl pentazole can be para-position mono-substituted phenyl pentazole, and the substituent group is an electricity supply group and is selected from hydroxyl, methyl, methoxyl, tert-butyl, dimethylamino and the like.
The substituted phenyl pentazole can be para-position and meta-position disubstituted phenyl pentazole, and the substituted group is an electric supply group and is selected from hydroxyl, methyl, methoxyl, tert-butyl, dimethylamino and the like.
The substituted phenyl pentazole can be p-and m-substituted phenyl pentazoles, and the substituent group is an electron donating group selected from hydroxyl, methyl, methoxy, tert-butyl, dimethylamino and the like.
The ferrous salt is selected from ferrous sulfate, ferrous glycinate, ferrous oxalate, ferrous acetate, ferrous chloride and the like.
The preparation method of the pentazole composite salt comprises the following specific steps:
dissolving substituted phenyl pentazole in a mixed solvent of methanol and acetonitrile at the temperature of below-30 ℃, adding a methanol water solution of ferrous salt, stirring and mixing uniformly, then adding a methanol solution of m-chloroperoxybenzoic acid, reacting for more than 24h, heating to room temperature, filtering, performing rotary evaporation to remove the solvent, dissolving the obtained product in an organic solvent, adding water for liquid separation and extraction, combining water phases, and performing rotary evaporation to pass through a column to obtain the pentazole composite salt (N)5)6(H3O)3(NH4)4Cl。
In the mixed solvent of methanol and acetonitrile, the volume ratio of methanol to acetonitrile is 1: 0.8-1.2, preferably 1: 1.
The volume ratio of methanol to water in the methanol-water solution of ferrous salt is 1: 4-6, preferably 1: 5.
The molar ratio of the substituted phenyl pentazole to the ferrous salt to the m-chloroperoxybenzoic acid is 1: 1-5: 2-10, and preferably 1:2: 4.
The reaction time is preferably 36 hours or more.
The organic solvent is selected from ethyl acetate or diethyl ether, and diethyl ether is preferred.
The method provided by the invention firstly cuts off the C-N bond of the substituted phenyl pentazole and successfully separates the pentazole anion to obtain the pentazole anion-containing composite salt, and the synthesized pentazole composite salt can stably exist at normal temperature, so that the method has a great application value in the field of energetic materials.
Drawings
FIG. 1 is a diagram of a pentazole complex salt of the present invention1H-NMR spectrum.
FIG. 2 is a diagram of a pentazole complex salt of the present invention15N-NMR spectrum.
FIG. 3 is an ESI-MS spectrum of a pentazole complex salt of the present invention.
FIG. 4 is an IR spectrum of a pentazole complex salt of the present invention.
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 substituted phenyl pentazoles and ferrous salts.
Example 1
4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, and under the reaction condition of-45 ℃, methanol aqueous solution (v/v,1/4) of ferrous glycinate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ethyl acetate, adding water, separating, extracting, combining water phases, and rotary evaporating to pass through a column to obtain the compound pentazole salt 21.2mg with the yield of 12.08%.
Example 2
4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃, an aqueous methanol solution (v/v,1/5) of ferrous sulfate heptahydrate (6mmol) is added (precooled to-45 ℃) and stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole 14.5mg with a yield of 8.26%.
Example 3
4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃, an aqueous methanol solution (v/v,1/6) of ferrous chloride tetrahydrate (6mmol) is added (precooled to-45 ℃) and stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ethyl acetate, adding water, separating, extracting, combining water phases, and rotary evaporating to pass through a column to obtain the compound pentazole salt 12.5mg with the yield of 7.12%.
Example 4
4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent (v/v,5/4) of methanol and acetonitrile in a single-neck flask, under the condition of-45 ℃ reaction, a methanol aqueous solution (v/v,1/5) of iron oxalate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole 10.8mg with a yield of 6.15%.
Example 5
4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,5/6) in a single-neck flask, under the condition of-45 ℃, an aqueous methanol solution (v/v,1/5) of ferrous acetate (6mmol) is added (precooled to-45 ℃) and stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole (9.7 mg) with a yield of 5.53%.
Example 6
4-methoxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the reaction condition of-45 ℃, methanol aqueous solution (v/v,1/5) of ferrous glycinate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole 22.4mg with a yield of 12.76%.
Example 7
4-methoxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃ reaction, a methanol aqueous solution (v/v,1/5) of ferrous sulfate heptahydrate (3mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole 15.2mg with a yield of 8.66%.
Example 8
4-methoxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃, a methanol aqueous solution (v/v,1/5) of tetrahydrate ferrous chloride (3mmol) is added (precooled to-45 ℃) and stirred for 30min, then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (6mmol) is added and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating liquid, extracting, combining water phases, and rotary evaporating to pass through a column to obtain 13.6mg of the pentazole composite salt with the yield of 7.75%.
Example 9
4-methoxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the reaction condition of-45 ℃, a methanol aqueous solution (v/v,1/5) of iron oxalate (15mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (24mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain 11.2mg of the pentazole complex salt with the yield of 6.38%.
Example 10
4-methoxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, and under the reaction condition of-45 ℃, a methanol aqueous solution (v/v,1/5) of ferrous acetate (12mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (30mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole 10.1mg with a yield of 5.75%.
Example 11
4-dimethylaminophenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the reaction condition of-30 ℃, a methanol aqueous solution (v/v,1/5) of ferrous glycinate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating liquid, extracting, combining water phases, and rotary evaporating to pass through a column to obtain the pentazole complex salt 24.5mg, wherein the yield is 13.96%.
Example 12
4-dimethylaminophenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-35 ℃ reaction, a methanol aqueous solution (v/v,1/5) of ferrous sulfate heptahydrate (6mmol) is added (precooled to-45 ℃) and stirred for 30min, then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole (17.6 mg) with a yield of 10.03%.
Example 13
4-dimethylaminophenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the reaction condition of-40 ℃, a methanol aqueous solution (v/v,1/5) of ferrous chloride tetrahydrate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole 14.6mg with a yield of 8.31%.
Example 14
4-dimethylaminophenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃ reaction, a methanol aqueous solution (v/v,1/5) of iron oxalate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for 24h reaction. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating liquid, extracting, combining water phases, and rotary evaporating to pass through a column to obtain the compound pentazole salt 12.6mg with the yield of 7.18%.
Example 15
4-dimethylaminophenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃ reaction, a methanol aqueous solution (v/v,1/5) of ferrous acetate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 30 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating liquid, extracting, combining water phases, and rotary evaporating to pass through a column to obtain 11.3mg of the pentazole composite salt with the yield of 6.44%.
Example 16 in a single-neck flask, 3-methyl-4-hydroxyphenyl pentazole (3mmol) was dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1), and an aqueous methanol solution (v/v,1/5) of ferrous glycinate (6mmol) was added under a-45 ℃ reaction condition (pre-cooled to-45 ℃), stirred for 30min, and then a methanol solution (pre-cooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) was added and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound pentazole salt 22.5mg with a yield of 12.82%.
Example 17
3-methyl-4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃ reaction, a methanol aqueous solution (v/v,1/5) of ferrous sulfate heptahydrate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating liquid, extracting, combining water phases, and rotary evaporating to pass through a column to obtain the pentazole complex salt 15.6mg with the yield of 8.89%.
Example 18
3-methyl-4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃, a methanol aqueous solution (v/v,1/5) of ferrous chloride tetrahydrate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating liquid, extracting, combining water phases, and rotary evaporating to pass through a column to obtain 13.7mg of the pentazole composite salt with the yield of 7.81%.
Example 19
3-methyl-4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃, an aqueous methanol solution (v/v,1/5) of iron oxalate (6mmol) is added (precooled to-45 ℃) and stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain 11.4mg of the pentazole complex salt with the yield of 6.49%.
Example 20
3-methyl-4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃, an aqueous methanol solution (v/v,1/5) of ferrous acetate (6mmol) is added (precooled to-45 ℃) and stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added and reacted for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole (9.9 mg) with a yield of 5.64%.
Example 21
3, 5-dimethyl-4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, and under the reaction condition of-45 ℃, methanol aqueous solution (v/v,1/5) of ferrous glycinate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole (26.8 mg), wherein the yield is 15.27%.
Example 22
3, 5-dimethyl-4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the condition of-45 ℃, an aqueous methanol solution (v/v,1/5) of ferrous sulfate heptahydrate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole 19.7mg with a yield of 11.22%.
Example 23
3, 5-dimethyl-4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the reaction condition of-45 ℃, a methanol aqueous solution (v/v,1/5) of ferrous chloride tetrahydrate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in ether, adding water, separating liquid, extracting, combining water phases, and rotary evaporating to pass through a column to obtain the pentazole complex salt 16.9mg with the yield of 9.63%.
Example 24
3, 5-dimethyl-4-hydroxyphenyl pentazole (3mmol) is dissolved in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, under the reaction condition of-45 ℃, a methanol aqueous solution (v/v,1/5) of ferrous oxalate (6mmol) is added (precooled to-45 ℃), stirred for 30min, and then a methanol solution (precooled to-45 ℃) of m-chloroperoxybenzoic acid (12mmol) is added for reaction for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain the compound salt of pentazole 14.9mg with a yield of 8.49%.
Example 25
Dissolving 3, 5-dimethyl-4-hydroxyphenyl pentazole (3mmol) in a mixed solvent of methanol and acetonitrile (v/v,1/1) in a single-neck flask, adding a methanol aqueous solution (v/v,1/5) of ferrous acetate (6mmol) under the condition of-45 ℃ reaction (precooling to-45 ℃), stirring for 30min, then adding a methanol solution (precooling to-45 ℃) of m-chloroperoxybenzoic acid (12mmol), and reacting for 36 h. Filtering, rotary evaporating to remove most of solvent, dissolving the obtained product in diethyl ether, adding water, separating, extracting, mixing water phases, and rotary evaporating to pass through a column to obtain 13.8mg of the pentazole complex salt with the yield of 7.86%.
FIG. 1 shows a pentazole complex salt [ (N)5)6(H3O)3(NH4)4Cl]The chemical shift of active hydrogen in the nuclear magnetic hydrogen spectrum of (2) is 7.17 ppm.
FIG. 2 shows a pentazole complex salt [ (N)5)6(H3O)3(NH4)4Cl]The nuclear magnetic nitrogen spectrum of (A) shows that the nitrogen spectrum chemical shift of the pentazole ring is about-70.68 to-70.74, and the nitrogen spectrum chemical shift of the ammonium radical is-358.50.
FIG. 3 shows a pentazole complex salt [ (N)5)6(H3O)3(NH4)4Cl]The mass number 70.09 of the mass spectrum of (A) is N5-molecular weight of (a).
FIG. 4 shows a pentazole complex salt [ (N)5)6(H3O)3(NH4)4Cl]Wherein 1223cm in the infrared spectrum of-1Is the infrared absorption of the pentazole ring.
Claims (10)
1. A compound salt of pentazole has a molecular formula of (N)5)6(H3O)3(NH4)4Cl, wherein N5 -Is a cyclic N5 -。
2. The method for preparing the pentazole complex salt of claim 1, wherein the synthetic route is as follows:
wherein,is substituted phenyl pentazole, wherein the substituted group in the substituted phenyl pentazole is an electron donating group, Fe2+Is ferrous salt, mCPBA is m-chloroperoxybenzoic acid,is a pentazole complex salt (N)5)6(H3O)3(NH4)4And Cl, the specific steps are as follows:
dissolving substituted phenyl pentazole in a mixed solvent of methanol and acetonitrile at the temperature of below-30 ℃, adding a methanol water solution of ferrous salt, stirring and mixing uniformly, then adding a methanol solution of m-chloroperoxybenzoic acid, reacting for more than 24h, heating to room temperature, filtering, performing rotary evaporation to remove the solvent, dissolving the obtained product in an organic solvent, adding water for liquid separation and extraction, combining water phases, and performing rotary evaporation to pass through a column to obtain the pentazole composite salt (N)5)6(H3O)3(NH4)4Cl。
3. The method for preparing the compound salt of pentazole of claim 2, wherein the substituted phenyl pentazole is p-monosubstituted phenyl pentazole, and the substituent group is selected from hydroxyl, methyl, methoxy, tert-butyl and dimethylamino.
4. The method for preparing a pentazole complex salt of claim 2, wherein the substituted phenyl pentazole is para-and meta-disubstituted phenyl pentazole, and the substituent group is selected from hydroxyl, methyl, methoxy, tert-butyl, dimethylamino.
5. The method for preparing a pentazole complex salt of claim 2, wherein the substituted phenyl pentazole is p-and m-substituted phenyl pentazole, and the substituent group is selected from hydroxyl, methyl, methoxy, tert-butyl, and dimethylamino.
6. A method for preparing a pentazole composite salt as claimed in any one of claims 2 to 5, wherein the ferrous salt is selected from ferrous sulfate, ferrous glycinate, ferrous oxalate, ferrous acetate and ferrous chloride.
7. The method for preparing the pentazole composite salt of claim 2, wherein in the mixed solvent of methanol and acetonitrile, the volume ratio of methanol to acetonitrile is 1: 0.8-1.2; the volume ratio of methanol to water in the methanol water solution of the ferrite is 1: 4-6; the molar ratio of the substituted phenyl pentazole to the ferrous salt to the m-chloroperoxybenzoic acid is 1: 1-5: 2-10.
8. The method for preparing a pentazole complex salt of claim 2, wherein in the mixed solvent of methanol and acetonitrile, the volume ratio of methanol to acetonitrile is 1: 1; the volume ratio of methanol to water of the methanol-water solution of the ferrous salt is 1: 5; the molar ratio of the substituted phenyl pentazole to the ferrous salt to the m-chloroperoxybenzoic acid is 1:2: 4.
9. The method for producing a pentazole complex salt according to claim 2, wherein the reaction time is 36 hours or more.
10. The method for preparing a pentazole complex salt of claim 2, wherein the organic solvent is selected from ethyl acetate or diethyl ether.
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| CN114436986A (en) * | 2022-01-20 | 2022-05-06 | 南京理工大学 | Preparation method of pentazole negative ions |
| CN115739161A (en) * | 2022-12-13 | 2023-03-07 | 南京理工大学 | Iron single-atom catalyst, preparation method thereof and application thereof in reaction for catalyzing and preparing pentazole anion salt |
| WO2023031552A1 (en) * | 2021-09-03 | 2023-03-09 | Arianegroup Sas | Method for producing the pentazolate anion using a hypervalent iodine oxidant |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098864A (en) * | 2017-05-12 | 2017-08-29 | 南京理工大学 | Pentazole sodium and the triazole cocrystalization compound of 4 amino 1,2,4 and preparation method thereof |
| CN107098864B (en) * | 2017-05-12 | 2024-01-30 | 南京理工大学 | Eutectic compound of sodium pentazole and 4-amino-1, 2, 4-triazole and preparation method thereof |
| CN113717119A (en) * | 2021-03-19 | 2021-11-30 | 吉林大学 | Pentazole compound material and preparation method thereof |
| WO2023031552A1 (en) * | 2021-09-03 | 2023-03-09 | Arianegroup Sas | Method for producing the pentazolate anion using a hypervalent iodine oxidant |
| FR3126708A1 (en) * | 2021-09-03 | 2023-03-10 | Arianegroup Sas | Process for making pentazolate anion using hypervalent iodine oxidant |
| CN114436986A (en) * | 2022-01-20 | 2022-05-06 | 南京理工大学 | Preparation method of pentazole negative ions |
| CN115739161A (en) * | 2022-12-13 | 2023-03-07 | 南京理工大学 | Iron single-atom catalyst, preparation method thereof and application thereof in reaction for catalyzing and preparing pentazole anion salt |
| CN115739161B (en) * | 2022-12-13 | 2024-07-02 | 南京理工大学 | Iron single-atom catalyst, preparation method thereof and application thereof in catalytic reaction for preparing tetrazole anion salt |
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