CN106518797B - A kind of pentazole complex salt and preparation method thereof - Google Patents
A kind of pentazole complex salt and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of pentazole complex salts and preparation method thereof; C-N key by cutting off substituted-phenyl pentazole is prepared for pentazole anion; using metachloroperbenzoic acid and ferrous salt respectively as oxidant and protective agent, it is prepared for the complex salt [(N containing pentazole anion5)6(H3O)3(NH4)4Cl].The present invention is by cutting off the C-N key of substituted-phenyl pentazole and being successfully separated out pentazole anion, the complex salt containing pentazole anion is obtained, and the pentazole complex salt synthesized can be stabilized at normal temperature, have huge application value in energetic material field.
Description
Technical field
The present invention relates to a kind of pentazole complex salts and preparation method thereof, and in particular to a kind of to contain the compound of pentazole anion
Salt [(N5)6(H3O)3(NH4)4Cl] and preparation method thereof, belong to energetic material technical field.
Background technique
Significant advantage of the whole nitrogen cpds due to its more traditional energetic material in terms of detonation property, domestic and international energetic material
The research emphasis in field is just gradually shifted from traditional energetic material to novel whole nitrogen cpds.Whole nitrogen cpds are most aobvious
The characteristic of work is that huge energy can be released during decomposition becomes nitrogen containing a large amount of N-N and N=N key in molecule
Amount, simultaneously because the electronegativity of nitrogen is only second to F and O element, can form stronger chemical bond, i.e., all or part of by nitrogen group
At full nitrogen analog derivative have certain stability.Relative to traditional energetic material, full nitrogen material has high density, Gao Sheng
The advantages that Cheng Han, superenergy and detonation product clean, thus be expected to be applied to as extrahigh energy energetic material of new generation explosive,
The fields such as propellant powder, propellant and gas generating agent.
As the important composition of whole nitrogen cpds, the milestone formula breakthrough of full Nitrogen ion compound experimental study is 1999
Year has reported N5 +Synthesis.Its discovery makes scientist be synthetically produced new hope for full nitrogen high-energy density materials.N5 +
Ion is existing (such as N in a salt form5SnF3Or N5SbF6), but due to N5 +Thermal stability it is very low, result in these
The thermal stability of salt is also very low.Therefore, many experimental studies hereafter are devoted to find a suitable anion and N5 +From
Son forms salt to improve N5 +The stability of ion.Wherein, N5 +N5 -Combination is exactly an ideal target molecule, but this is wanted
It asks and finds synthesis N5 -The method of ion, and about N5 -Ion, at present its synthesis of only a small amount of document report.
2002, Vij etc. was in a mass spectrometer with the center C-N key in high energy cracking energy bombardment aryl pentazole, for the first time
N is captured in second order ms5 -The fragment signal [Angew.Chem.114,3177-3180 (2002)] of cyclic annular anion, this
One discovery separates N from aryl pentazole to laboratory staff5 -Bring very big hope.However experimental study hereafter does not have but
Bigger breakthrough is stuck in substantially and seeks multiple means to cut off the C-N key of aryl pentazole.2003, the report benefit such as Butler
The C-N key for having cut off aryl pentazole in acetonitrile solution with ammonium ceric nitrate (CAN), obtains N in an experiment for the first time5 -
[Chem.Commun.8,1016–1017(2003)].2005, Butler experiment was repeated in Schroer, it was demonstrated that there is no cut off
C-N key obtains N5 -[Chem.Commun.12,1607–1609(2005)].2007, Butler restudied the reality of oneself
It tests, is finally concluded that no positive evidence shows to have obtained N5 -[J.Org.Chem.73,1354–1364(2008)].This
Afterwards about N5 -Report do not obtain any progress, the report of only some theoretical calculations, in July, 2016, Haas, which is reported, to be adopted
It uses metallic sodium as raw material, phenyl pentazole has been cut off by free radical mechanism, and detect N at -40 DEG C or less with mass spectrograph5 -
[Angew.Chem.128,1–4(2016)]。
In conclusion due to N5 -Synthesize existing technical problem, existing document report N5 -Few, the mesh that success synthesizes
It is preceding that there has been no successfully synthesize the N that can be stabilized at normal temperature5 -The report of complex salt.
Summary of the invention
For the N that can be stabilized under room temperature in the prior art5 -The blank of complex salt, the present invention provides a kind of pentazoles
Complex salt and preparation method thereof, the C-N key by cutting off substituted-phenyl pentazole is prepared for pentazole anion, using m-chloro peroxide benzene
Formic acid and ferrous salt are successfully prepared the complex salt [(N containing pentazole anion respectively as oxidant and protective agent5)6
(H3O)3(NH4)4Cl]。
Technical scheme is as follows:
A kind of pentazole complex salt, molecular formula are (N5)6(H3O)3(NH4)4Cl, wherein N5 -For cyclic n nitroso compound5 -。
The preparation method of above-mentioned pentazole complex salt, synthetic route are as follows:
Wherein,For substituted-phenyl pentazole, Fe2+For ferrous salt, mCPBA is metachloroperbenzoic acid,For pentazole complex salt (N5)6(H3O)3(NH4)4Cl。
Substituent group in the substituted-phenyl pentazole is power supplying groups.
The substituted-phenyl pentazole can be contraposition monosubstituted phenyl pentazole, and substituent group is power supplying groups, be selected from hydroxyl
Base, methyl, methoxyl group, tert-butyl, dimethylamino etc..
The substituted-phenyl pentazole can be contraposition and meta position disubstituted phenyl pentazole, and substituent group is power supplying groups,
Selected from hydroxyl, methyl, methoxyl group, tert-butyl, dimethylamino etc..
The substituted-phenyl pentazole can be contraposition and meta position tri-substituted phenyl pentazole, and substituent group is power supplying groups,
Selected from hydroxyl, methyl, methoxyl group, tert-butyl, dimethylamino etc..
The ferrous salt is selected from ferrous sulfate, ferrous bisglycinate chelate, ferrous oxalate, ferrous acetate, frerrous chloride etc..
The preparation method of above-mentioned pentazole complex salt, the specific steps are as follows:
At -30 DEG C hereinafter, substituted-phenyl pentazole to be dissolved in the in the mixed solvent of methanol and acetonitrile, the methanol of ferrous salt is added
Aqueous solution is uniformly mixed, and the methanol solution of metachloroperbenzoic acid is then added, and is reacted more than for 24 hours, after being warmed to room temperature,
Filtering, revolving remove solvent, obtained product are dissolved in organic solvent, and moisture liquid is added to extract, and merge water phase, rotate column and obtain
To pentazole complex salt (N5)6(H3O)3(NH4)4Cl。
The volume ratio of the in the mixed solvent of the methanol and acetonitrile, methanol and acetonitrile be 1:0.8~1.2, preferably 1:
1。
The volume ratio of the methanol aqueous solution of the ferrous salt, methanol and water is 1:4~6, preferably 1:5.
The molar ratio of the substituted-phenyl pentazole, ferrous salt and metachloroperbenzoic acid is 1:1~5:2~10, preferably
For 1:2:4.
The reaction time is preferably 36h or more.
The organic solvent is selected from ethyl acetate or ether, preferably ether.
The present invention cuts off the C-N key of substituted-phenyl pentazole for the first time and has been successfully separated out pentazole anion, is contained
The complex salt of pentazole anion, and the pentazole complex salt synthesized can be stabilized at normal temperature, be had in energetic material field
There is huge application value.
Detailed description of the invention
Fig. 1 is pentazole complex salt of the present invention1H-NMR spectrum.
Fig. 2 is pentazole complex salt of the present invention15N-NMR spectrogram.
Fig. 3 is the ESI-MS spectrogram of pentazole complex salt of the present invention.
Fig. 4 is the IR spectrogram of pentazole complex salt of the present invention.
Specific embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any way
The present invention.The present invention is including but not limited to following several substituted-phenyl pentazoles and ferrous salt.
Embodiment 1
In single-necked flask by 4- hydroxy phenyl pentazole (3mmol) be dissolved in methanol and acetonitrile in the mixed solvent (v/v,
1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/4) that ferrous bisglycinate chelate (6mmol) is added (is cooled to -45 in advance
DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, reacts 36h.
Filtering, revolving remove most of solvent, obtained product are dissolved in ethyl acetate, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 21.2mg, yield 12.08%.
Embodiment 2
In single-necked flask by 4- hydroxy phenyl pentazole (3mmol) be dissolved in methanol and acetonitrile in the mixed solvent (v/v,
1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) that ferrous sulfate heptahydrate (6mmol) is added (is cooled to -45 in advance
DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, reacts 36h.
Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, merge water phase, rotated column
Obtain pentazole complex salt 14.5mg, yield 8.26%.
Embodiment 3
In single-necked flask by 4- hydroxy phenyl pentazole (3mmol) be dissolved in methanol and acetonitrile in the mixed solvent (v/v,
1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/6) that four water frerrous chlorides (6mmol) are added (is cooled to -45 in advance
DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, reacts 36h.
Filtering, revolving remove most of solvent, obtained product are dissolved in ethyl acetate, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 12.5mg, yield 7.12%.
Embodiment 4
In single-necked flask by 4- hydroxy phenyl pentazole (3mmol) be dissolved in methanol and acetonitrile mixed solvent (v/v, 5/
4) in, under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) (being cooled to -45 DEG C in advance) of ferrous oxalate (6mmol) is added,
30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, reacts 36h.Filtering,
Revolving removes most of solvent, and obtained product is dissolved in ether, and moisture liquid is added to extract, and merges water phase, rotated column and obtain
Pentazole complex salt 10.8mg, yield 6.15%.
Embodiment 5
In single-necked flask by 4- hydroxy phenyl pentazole (3mmol) be dissolved in methanol and acetonitrile in the mixed solvent (v/v,
5/6), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) (being cooled to -45 DEG C in advance) of ferrous acetate (6mmol) is added,
30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, reacts 36h.Filtering,
Revolving removes most of solvent, and obtained product is dissolved in ether, and moisture liquid is added to extract, and merges water phase, rotated column and obtain
Pentazole complex salt 9.7mg, yield 5.53%.
Embodiment 6
4- methoxyphenyl pentazole (3mmol) is dissolved in the in the mixed solvent (v/ of methanol and acetonitrile in single-necked flask
V, 1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) that ferrous bisglycinate chelate (6mmol) is added (is cooled to -45 in advance
DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, reacts 36h.
Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, merge water phase, rotated column
Obtain pentazole complex salt 22.4mg, yield 12.76%.
Embodiment 7
4- methoxyphenyl pentazole (3mmol) is dissolved in the in the mixed solvent (v/ of methanol and acetonitrile in single-necked flask
V, 1/1), under -45 DEG C of reaction conditions, be added ferrous sulfate heptahydrate (3mmol) methanol aqueous solution (v/v, 1/5) (be cooled in advance -
45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol), reaction is then added
36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 15.2mg, yield 8.66%.
Embodiment 8
4- methoxyphenyl pentazole (3mmol) is dissolved in the in the mixed solvent (v/ of methanol and acetonitrile in single-necked flask
V, 1/1), under -45 DEG C of reaction conditions, be added four water frerrous chlorides (3mmol) methanol aqueous solution (v/v, 1/5) (be cooled in advance -
45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (6mmol) is then added, reacts 36h.
Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, merge water phase, rotated column
Obtain pentazole complex salt 13.6mg, yield 7.75%.
Embodiment 9
4- methoxyphenyl pentazole (3mmol) is dissolved in the in the mixed solvent (v/ of methanol and acetonitrile in single-necked flask
V, 1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) that ferrous oxalate (15mmol) is added (is cooled to -45 in advance
DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (24mmol) is then added, reacts 36h.
Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, merge water phase, rotated column
Obtain pentazole complex salt 11.2mg, yield 6.38%.
Embodiment 10
4- methoxyphenyl pentazole (3mmol) is dissolved in the in the mixed solvent (v/ of methanol and acetonitrile in single-necked flask
V, 1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) that ferrous acetate (12mmol) is added (is cooled to -45 in advance
DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (30mmol) is then added, reacts 36h.
Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, merge water phase, rotated column
Obtain pentazole complex salt 10.1mg, yield 5.75%.
Embodiment 11
4- dimethylamino phenyl pentazole (3mmol) is dissolved in the in the mixed solvent of methanol and acetonitrile in single-necked flask
Methanol aqueous solution (v/v, the 1/5) (pre-cooling of ferrous bisglycinate chelate (6mmol) is added under -30 DEG C of reaction conditions in (v/v, 1/1)
To -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol), reaction is then added
36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 24.5mg, yield 13.96%.
Embodiment 12
4- dimethylamino phenyl pentazole (3mmol) is dissolved in the in the mixed solvent of methanol and acetonitrile in single-necked flask
Methanol aqueous solution (v/v, the 1/5) (pre-cooling of ferrous sulfate heptahydrate (6mmol) is added under -35 DEG C of reaction conditions in (v/v, 1/1)
To -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol), reaction is then added
36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 17.6mg, yield 10.03%.
Embodiment 13
4- dimethylamino phenyl pentazole (3mmol) is dissolved in the in the mixed solvent of methanol and acetonitrile in single-necked flask
Methanol aqueous solution (v/v, the 1/5) (pre-cooling of four water frerrous chlorides (6mmol) is added under -40 DEG C of reaction conditions in (v/v, 1/1)
To -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol), reaction is then added
36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 14.6mg, yield 8.31%.
Embodiment 14
4- dimethylamino phenyl pentazole (3mmol) is dissolved in the in the mixed solvent of methanol and acetonitrile in single-necked flask
(v/v, 1/1), under -45 DEG C of reaction conditions, be added ferrous oxalate (6mmol) methanol aqueous solution (v/v, 1/5) (be cooled in advance -
45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol), reaction is then added
24h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 12.6mg, yield 7.18%.
Embodiment 15
4- dimethylamino phenyl pentazole (3mmol) is dissolved in the in the mixed solvent of methanol and acetonitrile in single-necked flask
(v/v, 1/1), under -45 DEG C of reaction conditions, be added ferrous acetate (6mmol) methanol aqueous solution (v/v, 1/5) (be cooled in advance -
45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol), reaction is then added
30h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 11.3mg, yield 6.44%.
3- methyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in methanol and acetonitrile in single-necked flask by embodiment 16
In the mixed solvent (v/v, 1/1), under -45 DEG C of reaction conditions, be added ferrous bisglycinate chelate (6mmol) methanol aqueous solution (v/v,
1/5) (be cooled to -45 DEG C in advance), stir 30min, then be added metachloroperbenzoic acid (12mmol) methanol solution (be cooled in advance -
45 DEG C), react 36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, close
And water phase, it rotated column and obtains pentazole complex salt 22.5mg, yield 12.82%.
Embodiment 17
3- methyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixed solvent of methanol and acetonitrile in single-necked flask
In (v/v, 1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) that ferrous sulfate heptahydrate (6mmol) is added is (pre-
It is cooled to -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, instead
Answer 36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, rotation
Steamed column obtains pentazole complex salt 15.6mg, yield 8.89%.
Embodiment 18
3- methyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixed solvent of methanol and acetonitrile in single-necked flask
In (v/v, 1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) that four water frerrous chlorides (6mmol) are added is (pre-
It is cooled to -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, instead
Answer 36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, rotation
Steamed column obtains pentazole complex salt 13.7mg, yield 7.81%.
Embodiment 19
3- methyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixed solvent of methanol and acetonitrile in single-necked flask
In (v/v, 1/1), under -45 DEG C of reaction conditions, be added ferrous oxalate (6mmol) methanol aqueous solution (v/v, 1/5) (pre-cooling
To -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol), reaction is then added
36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 11.4mg, yield 6.49%.
Embodiment 20
3- methyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixed solvent of methanol and acetonitrile in single-necked flask
In (v/v, 1/1), under -45 DEG C of reaction conditions, be added ferrous acetate (6mmol) methanol aqueous solution (v/v, 1/5) (pre-cooling
To -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol), reaction is then added
36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, revolving
It crosses column and obtains pentazole complex salt 9.9mg, yield 5.64%.
Embodiment 21
3,5- dimethyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixing of methanol and acetonitrile in single-necked flask
In solvent (v/v, 1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) of ferrous bisglycinate chelate (6mmol) is added
(being cooled to -45 DEG C in advance) stirs 30min, and the methanol solution that metachloroperbenzoic acid (12mmol) is then added (is cooled to -45 in advance
DEG C), react 36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, merge
Water phase rotated column and obtains pentazole complex salt 26.8mg, yield 15.27%.
Embodiment 22
3,5- dimethyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixing of methanol and acetonitrile in single-necked flask
In solvent (v/v, 1/1), under -45 DEG C of reaction conditions, be added ferrous sulfate heptahydrate (6mmol) methanol aqueous solution (v/v, 1/
5) (it is cooled to -45 DEG C in advance), stirs 30min, the methanol solution that metachloroperbenzoic acid (12mmol) is then added (is cooled to -45 in advance
DEG C), react 36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, merge
Water phase rotated column and obtains pentazole complex salt 19.7mg, yield 11.22%.
Embodiment 23
3,5- dimethyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixing of methanol and acetonitrile in single-necked flask
In solvent (v/v, 1/1), under -45 DEG C of reaction conditions, be added four water frerrous chlorides (6mmol) methanol aqueous solution (v/v, 1/
5) (it is cooled to -45 DEG C in advance), stirs 30min, the methanol solution that metachloroperbenzoic acid (12mmol) is then added (is cooled to -45 in advance
DEG C), react 36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, add moisture liquid to extract, merge
Water phase rotated column and obtains pentazole complex salt 16.9mg, yield 9.63%.
Embodiment 24
3,5- dimethyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixing of methanol and acetonitrile in single-necked flask
In solvent (v/v, 1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) that ferrous oxalate (6mmol) is added is (pre-
It is cooled to -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, instead
Answer 36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, rotation
Steamed column obtains pentazole complex salt 14.9mg, yield 8.49%.
Embodiment 25
3,5- dimethyl -4- hydroxy phenyl pentazole (3mmol) is dissolved in the mixing of methanol and acetonitrile in single-necked flask
In solvent (v/v, 1/1), under -45 DEG C of reaction conditions, the methanol aqueous solution (v/v, 1/5) that ferrous acetate (6mmol) is added is (pre-
It is cooled to -45 DEG C), 30min is stirred, the methanol solution (being cooled to -45 DEG C in advance) of metachloroperbenzoic acid (12mmol) is then added, instead
Answer 36h.Filtering, revolving remove most of solvent, obtained product are dissolved in ether, and moisture liquid is added to extract, and merge water phase, rotation
Steamed column obtains pentazole complex salt 13.8mg, yield 7.86%.
Fig. 1 is pentazole complex salt [(N5)6(H3O)3(NH4)4Cl] nucleus magnetic hydrogen spectrum, the as can be seen from the figure change of active hydrogen
Displacement study is 7.17ppm.
Fig. 2 is pentazole complex salt [(N5)6(H3O)3(NH4)4Cl] nuclear-magnetism nitrogen spectrum, the as can be seen from the figure nitrogen of pentazole ring
Composing chemical shift is -70.68~-70.74 or so, and the nitrogen spectrum chemical shift of ammonium root is -358.50.
Fig. 3 is pentazole complex salt [(N5)6(H3O)3(NH4)4Cl] mass spectrogram, as can be seen from the figure mass number 70.09
For N5 -Molecular weight.
Fig. 4 is pentazole complex salt [(N5)6(H3O)3(NH4)4Cl] infrared spectrum, wherein 1223cm-1For the red of pentazole ring
Outer absorption.
Claims (10)
1. a kind of pentazole complex salt, molecular formula is (N5)6(H3O)3(NH4)4Cl, wherein N5 -For cyclic n nitroso compound5 -。
2. the preparation method of pentazole complex salt as described in claim 1, which is characterized in that synthetic route is as follows:
Wherein,For substituted-phenyl pentazole, the substituent group in the substituted-phenyl pentazole is power supply base
Group, Fe2+For ferrous salt, mCPBA is metachloroperbenzoic acid,For pentazole complex salt (N5)6(H3O)3(NH4)4Cl, specifically
Step are as follows:
At -30 DEG C hereinafter, substituted-phenyl pentazole to be dissolved in the in the mixed solvent of methanol and acetonitrile, the methanol that ferrous salt is added is water-soluble
Liquid is uniformly mixed, and the methanol solution of metachloroperbenzoic acid is then added, and is reacted more than for 24 hours, after being warmed to room temperature, filtering,
Revolving removes solvent, and obtained product is dissolved in organic solvent, and moisture liquid is added to extract, and merges water phase, rotated column and obtain five
Azoles complex salt (N5)6(H3O)3(NH4)4Cl。
3. the preparation method of pentazole complex salt as claimed in claim 2, which is characterized in that the substituted-phenyl pentazole is pair
Position single-substituted base pentazole, substituent group are selected from hydroxyl, methyl, methoxyl group, tert-butyl, dimethylamino.
4. the preparation method of pentazole complex salt as claimed in claim 2, which is characterized in that the substituted-phenyl pentazole is pair
Position and meta position disubstituted phenyl pentazole, substituent group are selected from hydroxyl, methyl, methoxyl group, tert-butyl, dimethylamino.
5. the preparation method of pentazole complex salt as claimed in claim 2, which is characterized in that the substituted-phenyl pentazole is pair
Position and meta position tri-substituted phenyl pentazole, substituent group are selected from hydroxyl, methyl, methoxyl group, tert-butyl, dimethylamino.
6. the preparation method of the pentazole complex salt as described in claim 2 to 5 is any, which is characterized in that the ferrous salt choosing
From ferrous sulfate, ferrous bisglycinate chelate, ferrous oxalate, ferrous acetate, frerrous chloride.
7. the preparation method of pentazole complex salt as claimed in claim 2, which is characterized in that the mixing of the methanol and acetonitrile
In solvent, the volume ratio of methanol and acetonitrile is 1:0.8~1.2；The volume of the methanol aqueous solution of the ferrous salt, methanol and water
Than for 1:4~6；The molar ratio of the substituted-phenyl pentazole, ferrous salt and metachloroperbenzoic acid is 1:1~5:2~10.
8. the preparation method of pentazole complex salt as claimed in claim 2, which is characterized in that the mixing of the methanol and acetonitrile
In solvent, the volume ratio of methanol and acetonitrile is 1:1；The volume ratio of the methanol aqueous solution of the ferrous salt, methanol and water is 1:
5；The molar ratio of the substituted-phenyl pentazole, ferrous salt and metachloroperbenzoic acid is 1:2:4.
9. the preparation method of pentazole complex salt as claimed in claim 2, which is characterized in that the reaction time be 36h with
On.
10. the preparation method of pentazole complex salt as claimed in claim 2, which is characterized in that the organic solvent is selected from second
Acetoacetic ester or ether.
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