CN101585519B - Method for preparing <15>N-hydroxylamine hydrochloride by hydrolyzing <15>N-nitromethane - Google Patents
Method for preparing <15>N-hydroxylamine hydrochloride by hydrolyzing <15>N-nitromethane Download PDFInfo
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- CN101585519B CN101585519B CN2008100376423A CN200810037642A CN101585519B CN 101585519 B CN101585519 B CN 101585519B CN 2008100376423 A CN2008100376423 A CN 2008100376423A CN 200810037642 A CN200810037642 A CN 200810037642A CN 101585519 B CN101585519 B CN 101585519B
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- nitromethane 99min
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- oxammonium hydrochloride
- preparation
- nitromethane
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 230000001035 methylating effect Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- -1 acids methyl esters Chemical class 0.000 claims description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical compound [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012022 methylating agents Substances 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003828 vacuum filtration Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- FUBFWTUFPGFHOJ-UHFFFAOYSA-N 2-nitrofuran Chemical class [O-][N+](=O)C1=CC=CO1 FUBFWTUFPGFHOJ-UHFFFAOYSA-N 0.000 description 1
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- DHJVLXVXNFUSMU-UHFFFAOYSA-N 3,7-dimethylnona-2,6-dienenitrile Chemical compound CCC(C)=CCCC(C)=CC#N DHJVLXVXNFUSMU-UHFFFAOYSA-N 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- BMMNWPYKMOFBBE-UHFFFAOYSA-N hydroxylamine;perchloric acid Chemical compound ON.OCl(=O)(=O)=O BMMNWPYKMOFBBE-UHFFFAOYSA-N 0.000 description 1
- VSNHCAURESNICA-LBPDFUHNSA-N hydroxyurea-15n Chemical compound NC(=O)[15NH]O VSNHCAURESNICA-LBPDFUHNSA-N 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing <15>N-hydroxylamine hydrochloride by hydrolyzing <15>N-nitromethane. The method adopts <15>N-nitrite as an isotope raw material to react with a methylating agent so as to obtain the <15>N-nitromethane, and the <15>N-nitromethan is hydrolyzed, condensed, crystallized and filtered to obtain the <15>N-hydroxylamine hydrochloride. Compared with the priorart, the invention has the advantages of reasonable and simple technology, easily obtained raw materials, high isotope conversion rate, product purity, abundance and yield, and the like, can prepare a great amount of <15>N-hydroxylamine hydrochloride with high purity and high abundance and is suitable for mass production.
Description
Technical field
The present invention relates to
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride.
Background technology
Oxammonium hydrochloride (Hydroxyamine) (molecular formula NH
2OHHCl, colourless needle crystal, 159 ℃ of fusing points) be important organic synthesis intermediate.Be used for sulfamethoxazole, VB in the pharmaceutical industry
6, VB
12, semisynthetic penicillin, Ibuprofen BP/EP and nitrofurans etc. synthetic, the chemical industry aspect is used for the synthetic of novel nitrile spices such as lemonile, jasmine nitrile, perchloric acid azanol etc.In addition, oxammonium hydrochloride also can be used as auxiliary agent, reductive agent, analytical reagent etc.
15N-oxammonium hydrochloride and derivative thereof as
15N-Suwannee River fulvic acid,
15N-hydroxyurea,
15N-fumarylacetone oxime and
15N-nylon etc. can be used as tracer agent, are used for the researchs such as metabolism of product synthesis mechanism and medicament production.
15N-oxammonium hydrochloride synthetic method mainly contains following two kinds:
(1) Chen Yaohuan etc. utilizes NaHSO
3-SO
2Reduction Na
15NO
2Preparation
15The N-oxammonium hydrochloride (Chen Yaohuan, Ceng Mingying, Xiang Lijuan etc.,
15The research I. important intermediate Na of N tagged compound
15NO
2With
15NH
2The preparation of OHHCl, chemical reagent, 1986,4:191-196);
(2) electrochemical reduction H such as Zhou Wenjuan
15NO
3Synthetic
15The N-oxammonium hydrochloride (Zhou Wenjuan, Ceng Mingying, Chen Yaohuan,
15N-nitric acid electrolytic reduction is synthetic
15The N-oxammonium hydrochloride, the 6th national stable isotope discussion collection of thesis, 1986,1-2).
Above-mentioned two kinds of methods all exist synthesis step complexity, highly energy-consuming, can't scale operation etc. shortcoming.
Summary of the invention
Purpose of the present invention provides for the defective that overcomes above-mentioned prior art and exist that a kind of technology is simple, product purity is high, be fit to scale operation
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride.
Purpose of the present invention can be achieved through the following technical solutions:
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride is characterized in that, this method may further comprise the steps:
(1)
15The preparation of N-Nitromethane 99Min.: with
15The N-nitrite is as the isotropic substance raw material, and with the methylating reagent reaction, after reacting completely, mixture obtains through rectifying in the aqueous solution of carbonate
15The N-Nitromethane 99Min.;
(2)
15The preparation of N-oxammonium hydrochloride:
15The reaction that is hydrolyzed of N-Nitromethane 99Min. and hydrolysing agent, after reacting completely, hydrolyzed solution is through concentrating, and crystallization is filtered, and obtains
15The N-oxammonium hydrochloride.
Described step (1) specifically comprises: with
15The N-Sodium Nitrite is the isotropic substance raw material, mixes with aqueous sodium carbonate,
15The weight ratio of N-Sodium Nitrite and yellow soda ash is 1.47～8.8: 1, and the temperature of this mixture is dropped to 0～15 ℃, adds the methylating reagent methyl-sulfate, methyl-sulfate with
15The mol ratio of N-Sodium Nitrite is 1～5: 1, and adding finishes, and is warmed up to 20～70 ℃, reaction 2～6h, and underpressure distillation separates, and obtains
15The N-Nitromethane 99Min..
Described step (2) specifically comprises: will
15The N-Nitromethane 99Min. mixes with the hydrolysing agent concentrated hydrochloric acid,
15The mol ratio of N-Nitromethane 99Min. and concentrated hydrochloric acid is 1: 1～5, back hydrolysis reaction 12～48h, and reaction finishes and obtains product, and this product cools off through concentrating, and crystallization is filtered, and drying obtains
15The N-oxammonium hydrochloride.
Described
15The N-nitrite also comprises
15The N-potassium nitrite.
The concentration of described aqueous sodium carbonate is 0.5g/10ml～3g/10ml.
Described methylating reagent also comprises Mono Chloro Acetic Acid, methyl iodide, toluenesulphonic acids methyl esters or sodium methylsulfate.
Described separation processes adopts water trap to separate.
Described refrigerative temperature is 0～10 ℃.
Described filtering process using 95% washing with alcohol is filtered.
Among the present invention, the isotropic substance raw material is
15The Sodium Nitrite of N mark, synthetic route is as follows:
The present invention adopts
15The Sodium Nitrite of N mark is as the isotropic substance raw material, with a kind of reaction acquisition in Mono Chloro Acetic Acid, methyl iodide, toluenesulphonic acids methyl esters, sodium methylsulfate or the methyl-sulfate
15The Nitromethane 99Min. of N mark, again through hydrolysis, concentrate, crystallization, filtration, obtain abundance and purity greater than 98%
15The N-oxammonium hydrochloride.
Compared with prior art, technology of the present invention rationally, simply has raw material and is easy to get, and isotopic transformation efficiency, product purity and abundance and yield advantages of higher can prepare a large amount of high purities and abundant
15The N-oxammonium hydrochloride is fit to scale operation.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
A kind of
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride, this method may further comprise the steps:
(1)
15The preparation of N-Nitromethane 99Min.
In the 500ml there-necked flask of magnetic agitation, thermometer and dropping funnel is housed, add the aqueous solution (the 2g anhydrous sodium carbonate is dissolved in the 20ml water) and the 8.8g (0.126mol) of anhydrous sodium carbonate
15The N-Sodium Nitrite drops to 10 ℃ with the temperature of this mixture, and powerful the stirring down dripped 12ml (0.126mol) methyl-sulfate in 30 minutes, dropwise, temperature is raised to 40 ℃, reaction 4h, heat up then and underpressure distillation, utilize water trap to separate distillatory liquid, lower floor is
15The N-Nitromethane 99Min.;
(2)
15The preparation of N-oxammonium hydrochloride
In being furnished with the 500ml there-necked flask of magnetic agitation, thermometer and reflux exchanger, add 6.83g (0.11mol) successively
15N-Nitromethane 99Min., 5ml water and 36ml (0.419mol) concentrated hydrochloric acid, oil bath is heated to boiling, controlled temperature is at 120 ℃, back flow reaction 24h, and reaction finishes, reaction solution is concentrated in vacuo to mass crystallization occurs, be cooled to 10 ℃, vacuum filtration is to doing, with twice of 95% cold washing with alcohol, 50 ℃ of oven dry obtain 4.93g
15The N-oxammonium hydrochloride, purity is no less than 98%, and abundance is greater than 98%.
Embodiment 2
A kind of
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride, this method may further comprise the steps:
(1)
15The preparation of N-Nitromethane 99Min.
In the 500ml there-necked flask of magnetic agitation, thermometer is housed, add the aqueous solution (the 2g anhydrous sodium carbonate is dissolved in the 20ml water) and the 8.8g (0.126mol) of anhydrous sodium carbonate
15The N-Sodium Nitrite drops to 5 ℃ with the temperature of this mixture, and powerful the stirring down added 24g (0.252mol) Mono Chloro Acetic Acid in 30 minutes, adding finishes, and temperature is raised to 20 ℃, reaction 6h, heat up then and underpressure distillation, utilize water trap to separate distillatory liquid, lower floor is
15The N-Nitromethane 99Min.;
(2)
15The preparation of N-oxammonium hydrochloride
In being furnished with the 500ml there-necked flask of magnetic agitation, thermometer and reflux exchanger, add 6.83g (0.11mol) successively
15N-Nitromethane 99Min., 5ml water and 9.4ml (0.11mol) concentrated hydrochloric acid, oil bath is heated to boiling, and controlled temperature is at 120 ℃, back flow reaction 24h, reaction finishes, reaction solution is concentrated in vacuo to mass crystallization occurs, be cooled to 10 ℃, vacuum filtration is to doing, with twice of 8 ℃ 95% washing with alcohol, each 10ml, 50 ℃ of oven dry obtain 5.38g
15The N-oxammonium hydrochloride, purity is no less than 98%, and abundance is greater than 98%.
Embodiment 3
A kind of
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride, this method may further comprise the steps:
(1)
15The preparation of N-Nitromethane 99Min.
In the 500ml there-necked flask of magnetic agitation, thermometer and dropping funnel is housed, add the aqueous solution (the 2g anhydrous sodium carbonate is dissolved in the 20ml water) and the 8.8g (0.126mol) of anhydrous sodium carbonate
15The N-Sodium Nitrite drops to 8 ℃ with the temperature of this mixture, and powerful the stirring down dripped 32ml (0.252mol) methyl iodide in 30 minutes, dropwise, temperature is raised to 70 ℃, reaction 2h, heat up then and underpressure distillation, utilize water trap to separate distillatory liquid, lower floor is
15The N-Nitromethane 99Min.;
(2)
15The preparation of N-oxammonium hydrochloride
In being furnished with the 500ml there-necked flask of magnetic agitation, thermometer and reflux exchanger, add 6.83g (0.11mol) successively
15N-Nitromethane 99Min., 5ml water and 24ml (0.279mol) concentrated hydrochloric acid, oil bath is heated to boiling, and controlled temperature is at 120 ℃, back flow reaction 28h, reaction finishes, reaction solution is concentrated in vacuo to mass crystallization occurs, be cooled to 5 ℃, vacuum filtration is to doing, with twice of 5 ℃ 95% washing with alcohol, each 15ml, 50 ℃ of oven dry obtain 6.02g
15The N-oxammonium hydrochloride, purity is no less than 98%, and abundance is greater than 98%.
Embodiment 4
A kind of
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride, this method may further comprise the steps:
(1)
15The preparation of N-Nitromethane 99Min.
In the 500ml there-necked flask of magnetic agitation, thermometer is housed, add the aqueous solution (the 1g anhydrous sodium carbonate is dissolved in the 20ml water) and the 8.8g (0.126mol) of anhydrous sodium carbonate
15The N-Sodium Nitrite drops to 0 ℃ with the temperature of this mixture, and powerful the stirring down added 84.47g (0.630mol) sodium methylsulfate in 30 minutes, adding finishes, and temperature is raised to 50 ℃, reaction 3h, heat up then and underpressure distillation, utilize water trap to separate distillatory liquid, lower floor is
15The N-Nitromethane 99Min.;
(2)
15The preparation of N-oxammonium hydrochloride
In being furnished with the 500ml there-necked flask of magnetic agitation, thermometer and reflux exchanger, add 6.83g (0.11mol) successively
15N-Nitromethane 99Min., 5ml water and 47ml (0.55mol) concentrated hydrochloric acid, oil bath is heated to boiling, and controlled temperature is at 120 ℃, back flow reaction 12h, reaction finishes, reaction solution is concentrated in vacuo to mass crystallization occurs, be cooled to 5 ℃, vacuum filtration is to doing, with twice of 3 ℃ 95% washing with alcohol, each 20ml, 40 ℃ of oven dry obtain 4.90g
15The N-oxammonium hydrochloride, purity is no less than 98%, and abundance is greater than 98%.
Embodiment 5
A kind of
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride, this method may further comprise the steps:
(1)
15The preparation of N-Nitromethane 99Min.
In the 500ml there-necked flask of magnetic agitation, thermometer and dropping funnel is housed, add the aqueous solution (the 6g anhydrous sodium carbonate is dissolved in the 20ml water) and the 8.8g (0.126mol) of anhydrous sodium carbonate
15The N-Sodium Nitrite drops to 15 ℃ with the temperature of this mixture, and powerful the stirring down dripped 48ml (0.318mol) toluenesulphonic acids methyl esters in 30 minutes, dropwise, temperature is raised to 60 ℃, reaction 3h, heat up then and underpressure distillation, utilize water trap to separate distillatory liquid, lower floor is
15The N-Nitromethane 99Min.;
(2)
15The preparation of N-oxammonium hydrochloride
In being furnished with the 500ml there-necked flask of magnetic agitation, thermometer and reflux exchanger, add 6.83g (0.11mol) successively
15N-Nitromethane 99Min., 5ml water and 28ml (0.33mol) concentrated hydrochloric acid, oil bath is heated to boiling, and controlled temperature is at 120 ℃, back flow reaction 48h, reaction finishes, reaction solution is concentrated in vacuo to mass crystallization occurs, be cooled to 0 ℃, vacuum filtration is to doing, with twice of 1 ℃ 95% washing with alcohol, each 25ml, 60 ℃ of oven dry obtain 6.12g
15The N-oxammonium hydrochloride, purity is no less than 98%, and abundance is greater than 98%.
Embodiment 6
A kind of
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride, this method may further comprise the steps:
(1)
15The preparation of N-Nitromethane 99Min.
In the 500ml there-necked flask of magnetic agitation, thermometer and dropping funnel is housed, add the aqueous solution (the 2g anhydrous sodium carbonate is dissolved in the 20ml water) and the 10.8g (0.126mol) of anhydrous sodium carbonate
15The N-potassium nitrite drops to 10 ℃ with the temperature of this mixture, and powerful the stirring down dripped 12ml (0.126mol) methyl-sulfate in 30 minutes, dropwise, temperature is raised to 40 ℃, reaction 4h, heat up then and underpressure distillation, utilize water trap to separate distillatory liquid, lower floor is
15The N-Nitromethane 99Min.;
(2)
15The preparation of N-oxammonium hydrochloride
In being furnished with the 500ml there-necked flask of magnetic agitation, thermometer and reflux exchanger, add 6.83g (0.11mol) successively
15N-Nitromethane 99Min., 5ml water and 36ml (0.419mol) concentrated hydrochloric acid, oil bath is heated to boiling, controlled temperature is at 120 ℃, back flow reaction 24h, and reaction finishes, reaction solution is concentrated in vacuo to mass crystallization occurs, be cooled to 10 ℃, vacuum filtration is to doing, with twice of 95% cold washing with alcohol, 50 ℃ of oven dry obtain 4.93g
15The N-oxammonium hydrochloride, purity is no less than 98%, and abundance is greater than 98%.
Claims (1)
1.
15N-Nitromethane 99Min. hydrolysis preparation
15The method of N-oxammonium hydrochloride is characterized in that, this method may further comprise the steps:
(1)
15The preparation of N-Nitromethane 99Min.: with
15The N-nitrite is as the isotropic substance raw material, and with the methylating reagent reaction, after reacting completely, mixture obtains through rectifying in the aqueous solution of carbonate
15The N-Nitromethane 99Min.;
(2)
15The preparation of N-oxammonium hydrochloride:
15The reaction that is hydrolyzed of N-Nitromethane 99Min. and hydrolysing agent, after reacting completely, hydrolyzed solution is through concentrating, and crystallization is filtered, and obtains
15The N-oxammonium hydrochloride;
Described step (1) specifically comprises: with
15The N-Sodium Nitrite or
15The N-potassium nitrite is the isotropic substance raw material, mixes with aqueous sodium carbonate,
15The weight ratio of N-Sodium Nitrite and yellow soda ash is 1.47～8.8: 1, and the temperature of this mixture is dropped to 0～15 ℃, adds methylating reagent methyl-sulfate or Mono Chloro Acetic Acid or methyl iodide or toluenesulphonic acids methyl esters or sodium methylsulfate, methyl-sulfate with
15The mol ratio of N-Sodium Nitrite is 1～5: 1, and adding finishes, and is warmed up to 20～70 ℃, reaction 2～6h, and underpressure distillation separates, and obtains
15The N-Nitromethane 99Min.;
Described step (2) specifically comprises: will
15The N-Nitromethane 99Min. mixes with the hydrolysing agent concentrated hydrochloric acid,
15The mol ratio of N-Nitromethane 99Min. and concentrated hydrochloric acid is 1: 1～5, back hydrolysis reaction 12～48h, and reaction finishes and obtains product, and this product cools off through concentrating, and crystallization is filtered, and drying obtains
15The N-oxammonium hydrochloride;
The concentration of described aqueous sodium carbonate is 0.5g/10ml～3g/10ml;
Described separation processes adopts water trap to separate;
Described refrigerative temperature is 0～10 ℃;
Described filtering process using 95% washing with alcohol is filtered.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100376423A CN101585519B (en) | 2008-05-20 | 2008-05-20 | Method for preparing <15>N-hydroxylamine hydrochloride by hydrolyzing <15>N-nitromethane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100376423A CN101585519B (en) | 2008-05-20 | 2008-05-20 | Method for preparing <15>N-hydroxylamine hydrochloride by hydrolyzing <15>N-nitromethane |
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| Publication Number | Publication Date |
|---|---|
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| CN101585519B true CN101585519B (en) | 2011-07-27 |
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| CN102659602B (en) * | 2012-04-13 | 2014-07-16 | 湖北远大富驰医药化工股份有限公司 | Novel method for producing nitromethane |
| CN105597354B (en) * | 2015-11-16 | 2020-10-30 | 山东宝源化工股份有限公司 | Nitromethane reduced pressure distillation system |
| CN108236945B (en) * | 2017-12-22 | 2021-01-08 | 北京凯瑞英科技有限公司 | Heteropolyacid slurry catalyst, preparation and application in hydroxylamine hydrochloride catalytic synthesis |
| CN108383082B (en) * | 2018-02-01 | 2020-10-16 | 北京凯瑞英科技有限公司 | Device and method for separating by-products generated in preparation of hydroxylamine hydrochloride by hydrolysis of nitromethane |
| CN109179350A (en) * | 2018-10-22 | 2019-01-11 | 江苏长青农化股份有限公司 | A kind of synthesis technology of hydroxylamine hydrochloride |
| CN109809376B (en) * | 2019-03-13 | 2022-08-12 | 湖北仙粼化工有限公司 | Hydroxylamine hydrochloride continuous production system and process thereof |
| CN110127640A (en) * | 2019-06-03 | 2019-08-16 | 北京凯瑞英科技有限公司 | The method and apparatus for refining hydroxylamine hydrochloride product |
-
2008
- 2008-05-20 CN CN2008100376423A patent/CN101585519B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 孙德乾等.提高硝基甲烷产品收率的工艺优化.《山东化工》.1999,(第2期),15-16. * |
| 程永钢.硝基甲烷制羟胺盐.《火炸药》.1993,(第4期),10-12. * |
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