CN105541785B - The post-processing approach of the dioxacyclohexanes of 2,2 dimethyl, 5 nitro, 5 nitroso 1,3 - Google Patents
The post-processing approach of the dioxacyclohexanes of 2,2 dimethyl, 5 nitro, 5 nitroso 1,3 Download PDFInfo
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- CN105541785B CN105541785B CN201610132876.0A CN201610132876A CN105541785B CN 105541785 B CN105541785 B CN 105541785B CN 201610132876 A CN201610132876 A CN 201610132876A CN 105541785 B CN105541785 B CN 105541785B
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
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Abstract
The invention discloses a kind of post-processing approach of the dioxacyclohexanes of 5 nitroso of 2,2 dimethyl, 5 nitro 1,3, comprise the following steps：In 10 DEG C~35 DEG C of temperature, the nitroso 1 of 2,2 dimethyl, 5 nitro 5 will be prepared, reaction solution obtained by 3 dioxacyclohexanes, add in the MOH aqueous solution that mass percent is 5%~50%, after stirring 1min~20min, liquid separation, organic phase is dry, obtains 2 after concentration, the dioxacyclohexanes of 2 dimethyl, 5 nitro, 5 nitroso 1,3, wherein 2, the mass ratio of the dioxacyclohexanes reaction solution of 2 dimethyl, 5 nitro, 5 nitroso 1,3 and MOH solution is 1:0.1~1, described MOH are NaOH or KOH.Present invention is mainly used for the last handling process of the dioxacyclohexanes of 2,2 dimethyl, 5 nitro, 5 nitroso 1,3.
Description
Technical field
The present invention relates to the post-processing approach of one kind 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes,
Belong to energetic material field.
Technical background
In recent years, Russian O.A.Luk ' yanov et al. combine-ONN- azoxies and nitre methyl, structure
A kind of novel high energy blast group：α-more nitre methyl oxidation azo base containing energy, the group have structure novelty, energy density
The advantages that height, oxygen balance calibration.O.A.Luk ' yanov et al. are introduced into furazan precursor structure containing energy, and design has synthesized series
Novel alpha-more nitre methyl oxidation azo furazano energetic compound, significantly improve the energy and density of this kind of compound.Wherein
Typical Representative has：3,3 '-two (trinitro- methyl-ONN) -4,4 '-azoxy furazan, calculating density are 2.04g/cm3, explosion velocity
For 9028m/s, detonation pressure 39.60G/Pa；3,3 '-two (fluorine geminal dinitro methyl-ONN) -4,4 '-two furazan ethers, calculate density
For 2.09g/cm3, explosion velocity 9229m/s, detonation pressure 41.13G/Pa.It is existing by the way that α-more nitre methyl oxidation azo group is introduced
Azepine precursor structure, the novel high-energy density energy-containing compound for synthesizing excellent performance can be designed.2,2- dimethyl -5- nitre
Base -5- nitroso -1,3- dioxacyclohexanes are the key intermediates for building the new group containing energy.Such as：N’-(α-
Acetoximinoalkyl)diazene-N-oxides and some of their transformations,
Russ.Chem.Bull., Int.Ed.1991,40 (1), 93 1 texts disclose one kind and prepare 2,2- dimethyl -5- nitros -5- Asias
The method of nitro -1,3- dioxacyclohexanes, synthetic route are as follows：
For this method with 2,2- dimethyl -5- nitro -1,3- dioxacyclohexanes sodium salts for raw material, dichloromethane is solvent,
Reaction obtains 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes under the nitrosification of dinitrogen tetroxide.Instead
After should terminating, its post-processing approach is：Filtering reacting liquid, insoluble solids are removed, filtrate is concentrated into half, using dichloromethane to wash
De- agent, after being purified by 3~4 pillar layer separations, 0.5h~1h is stored under cryogenic, is then washed through ether, filtered,
Air dries to obtain 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, yield 33.5%.The post processing side
Method step is complicated, cumbersome, and time-consuming longer, loss of product is more, and yield is relatively low.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of background technology and defect, there is provided simple to operate, yield
The post-processing approach of higher 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes.
The post-processing approach of 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes of the present invention, including with
Lower step：In -10 DEG C~35 DEG C of temperature, will prepare obtained by 2,2- dimethyl -5- nitro -5- nitrosos -1,3- dioxacyclohexanes
Reaction solution, add in the MOH aqueous solution that mass percent is 5%~50%, after stirring 1min~20min, liquid separation is organic relevant
2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes are obtained after dry, concentration, wherein 2,2- dimethyl -5- nitros -5-
The mass ratio of nitroso -1,3- dioxacyclohexanes reaction solution and MOH solution is 1:0.1~1, described MOH are NaOH or KOH.
The post-processing approach of currently preferred 2,2- dimethyl -5- nitros -5- nitroso -1,3- dioxacyclohexanes, bag
Include following steps：In 0 DEG C of temperature, it will prepare and reacted obtained by 2,2- dimethyl -5- nitro -5- nitrosos -1,3- dioxacyclohexanes
Liquid, add in the NaOH aqueous solution that mass percent is 30%, after stirring 5min, liquid separation, organic phase is dried, and concentration obtains 2,
2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, wherein 2,2- dimethyl -5- nitro -5- nitrosos -1,3- bis-
Oxygen hexamethylene reaction solution and the mass ratio of NaOH solution are 1:0.15.
2,2- dimethyl -5- nitros -5- nitroso -1,3- dioxacyclohexanes reaction solutions, are prepared according to following steps：
2,2- dimethyl -5- nitro -1,3- dioxacyclohexanes sodium salt is added in dichloromethane solution, in -35 DEG C of conditions
Under, while stirring, while instilling the dichloromethane solution of dinitrogen tetroxide, after -35 DEG C are reacted half an hour, warms naturally to 0-
5 DEG C, insoluble solids in system are filtered to remove, and obtain 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes are anti-
Liquid is answered, wherein the mol ratio of 2,2- dimethyl -5- nitro -1,3- dioxacyclohexanes sodium salts and dinitrogen tetroxide is 1:10.
Advantages of the present invention：
The post-processing approach operation letter of the 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes of the present invention
It is single, it is only necessary to alkali lye is washed, liquid separation, drying, four steps of concentration, and the post-processing operation in documents is complex, it is necessary to carry out more
Secondary concentration, silica gel filtering, washing operation, afterwards will also through Cord blood, ether washing, fast filtering, the step such as be air-dried,
Process is quite cumbersome；Using the post processing side of the 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes of the present invention
Method, finally gives the yield more a height of 52% of 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, and uses pair
It is more relatively low than the post-processing approach yield in file, finally give 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxocyclohex
The yield of alkane is only 33.5%.
Embodiment：
The present invention is described in further detail with reference to embodiments.
2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes reaction solution is according to document《N′-(α-
acetoximinoalkyl)diazene-N-oxides and some of their transformations》[J]
.Bulletin of the Academy of Sciences of the USSR,Division of chemical
science,1991,40(1):It is prepared by 93-98.
It should be noted that these embodiments are more typical examples, it is mainly used in understanding the present invention, but the present invention is unlimited
In these embodiments.
Embodiment 1：
In -10 DEG C of temperature, 2,2- dimethyl -5- nitro -5- nitroso -1, the 3- dioxacyclohexanes that will be obtained according to document
Reaction solution is instilled in the sodium hydroxide solution that 100mL mass percents are 10%, stirs 5min, liquid separation, organic phase is dry, concentration
2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, yield 50% are obtained afterwards.
Embodiment 2：
It is in 0 DEG C of temperature, 2,2- dimethyl -5- nitro -5- nitroso -1, the 3- dioxacyclohexanes obtained according to document are anti-
Answer drop to enter in the sodium hydroxide solution that 100mL mass percents are 30%, stir 5min, liquid separation, organic phase is dry, after concentration
Obtain 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, yield 52%.
Embodiment 3：
In 10 DEG C of temperature, 2,2- dimethyl -5- nitro -5- nitroso -1, the 3- dioxacyclohexanes that will be obtained according to document
Reaction solution is instilled in the potassium hydroxide solution that 100mL mass percents are 20%, stirring 10min, liquid separation, and organic phase is dry, dense
2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, yield 50% are obtained after contracting.
Embodiment 4：
In 35 DEG C of temperature, 2,2- dimethyl -5- nitro -5- nitroso -1, the 3- dioxacyclohexanes that will be obtained according to document
Reaction solution is instilled in the potassium hydroxide solution that 100mL mass percents are 50%, stirring 20min, liquid separation, and organic phase is dry, dense
2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, yield 43% are obtained after contracting.
Claims (2)
1. one kind 2, the post-processing approach of 2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, comprise the following steps：
In -10 DEG C~35 DEG C of temperature, reaction solution obtained by 2,2- dimethyl -5- nitro -5- nitrosos -1,3- dioxacyclohexanes will be prepared,
Add in the MOH aqueous solution that mass percent is 5%~50%, after stirring 1min~20min, liquid separation, organic phase is dry, concentration
2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes are obtained afterwards, wherein 2,2- dimethyl -5- nitro -5- nitrosos -
The mass ratio of 1,3- dioxacyclohexanes reaction solution and MOH solution is 1:0.1~1, described MOH are NaOH or KOH；The preparation
Reaction solution obtained by 2,2- dimethyl -5- nitro -5- nitrosos -1,3- dioxacyclohexanes, is prepared according to following steps：By 2,2- bis-
Methyl-5-nitro -1,3- dioxacyclohexanes sodium salt is added in dichloromethane solution, under the conditions of -35 DEG C, while stirring, on one side
The dichloromethane solution of dinitrogen tetroxide is instilled, after -35 DEG C are reacted half an hour, 0-5 DEG C is warmed naturally to, is filtered to remove system
Middle insoluble solids, that is, 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes reaction solutions are obtained, wherein 2,2- diformazans
The mol ratio of base -5- nitros -1,3- dioxacyclohexanes sodium salt and dinitrogen tetroxide is 1:10.
2. the post processing side of 2,2- dimethyl -5- nitros -5- nitroso -1,3- dioxacyclohexanes according to claim 1
Method, comprise the following steps：In 0 DEG C of temperature, will prepare obtained by 2,2- dimethyl -5- nitro -5- nitrosos -1,3- dioxacyclohexanes
Reaction solution, add in the NaOH aqueous solution that mass percent is 30%, after stirring 5min, liquid separation, organic phase is dried, and is concentrated and is produced
To 2,2- dimethyl -5- nitro -5- nitroso -1,3- dioxacyclohexanes, wherein 2,2- dimethyl -5- nitro -5- nitroso -1,
The mass ratio of 3- dioxacyclohexanes reaction solution and MOH solution is 1:0.15.
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| CN201610132876.0A CN105541785B (en) | 2016-03-09 | 2016-03-09 | The post-processing approach of the dioxacyclohexanes of 2,2 dimethyl, 5 nitro, 5 nitroso 1,3 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118776A (en) * | 1993-05-26 | 1996-03-20 | 罗纳·布朗克化学公司 | Preparation of nitro phenol |
| CN1262672A (en) * | 1996-07-12 | 2000-08-09 | 罗狄亚化学公司 | Nitrosation method of phenolic composition substituted by electro-attracting group and use thereof |
-
2016
- 2016-03-09 CN CN201610132876.0A patent/CN105541785B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118776A (en) * | 1993-05-26 | 1996-03-20 | 罗纳·布朗克化学公司 | Preparation of nitro phenol |
| CN1262672A (en) * | 1996-07-12 | 2000-08-09 | 罗狄亚化学公司 | Nitrosation method of phenolic composition substituted by electro-attracting group and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| N"-(a-Acetoxyiminoalkyl)diazene N-oxides and some of their Transformations;Luk"yanov, O. A.等;《Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya》;19911231(第1期);109-14 * |
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