CN100551904C - The N-methyl N '-preparation method of nitroguanidine - Google Patents
The N-methyl N '-preparation method of nitroguanidine Download PDFInfo
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- CN100551904C CN100551904C CNB2007100235897A CN200710023589A CN100551904C CN 100551904 C CN100551904 C CN 100551904C CN B2007100235897 A CNB2007100235897 A CN B2007100235897A CN 200710023589 A CN200710023589 A CN 200710023589A CN 100551904 C CN100551904 C CN 100551904C
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- nitroguanidine
- methylamine
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Abstract
A kind of N-methyl N '-synthetic method of nitroguanidine, belong to the pesticide intermediate technical field.May further comprise the steps: A) prepare Compound I,, boil off water and get the fused methylamine nitrate, add the Dyhard RU 100 reaction again and make Compound I (N-methyl N '-Guanidinium nitrate) by in the nitric acid and methylamine with Dyhard RU 100 and methylamine nitrate; B) prepare Compound I I by Compound I, with Compound I in the vitriol oil, react Compound I I (N-methyl N '-nitroguanidine).Advantage: reduced raw materials cost, the reaction yield height, industrial equipments is simple, and yield can reach 90%, and content is more than 98%, for industrial mass manufacture provides guarantee.
Description
Technical field:
The present invention relates to the N-methyl N '-synthetic method of nitroguanidine, belong to the pesticide intermediate technical field.
Background technology:
The N-methyl N '-nitroguanidine is a kind of important pesticide intermediate, is the important source material that is used for medicines such as synthetic thiophene worm piperazine.Its structural formula is as follows:
At present, synthetic N-methyl N '-traditional technology (CN1163888A, application number 97104941.6) of nitroguanidine is to make Compound I I with nitroguanidine and aqueous methylamine solution 0-40 ℃ of reaction.This technological reaction raw material nitroguanidine cost is higher, and yield is lower.Synthetic route is as follows:
Other has technology (CN1251089A, the applying date 98803645.2) is to use in the nitric acid and methylamine, and with the cyanamide reaction, dehydration forms Compound I I again.This technology shortcoming is that reaction needs autoclave, and needs propyl carbinol to make solvent, and the equipment requirements height needs autoclave, the raw materials cost height.Synthetic route is as follows:
Summary of the invention:
The object of the present invention is to provide a kind of N-methyl N '-synthetic method of nitroguanidine, this method yield height, equipment requirements is simple, and preparation cost is low, is suitable for suitability for industrialized production.
The objective of the invention is to reach so a kind of N-methyl N '-preparation method of nitroguanidine, it may further comprise the steps:
A) prepare Compound I with Dyhard RU 100 and methylamine nitrate,, boil off water and get the fused methylamine nitrate, add the Dyhard RU 100 reaction again and make Compound I (N-methyl N '-Guanidinium nitrate) by in the nitric acid and methylamine;
B) prepare Compound I I by Compound I, with Compound I in the vitriol oil, react Compound I I (N-methyl N '-nitroguanidine).
Temperature of reaction when Dyhard RU 100 steps A in one embodiment of the invention) and methylamine nitrate prepare Compound I is 90-140 ℃.
In another embodiment of the present invention, step B) vitriol oil described in and the mass ratio of Compound I are 1.6-4: 1, and temperature of reaction is 15-35 ℃.
Preparation method disclosed in this invention since selected for use Dyhard RU 100 and methylamine nitrate prepare Compound I in the vitriol oil, react again the N-methyl N '-nitroguanidine, therefore compared with the prior art, reduced raw materials cost, the reaction yield height, industrial equipments is simple, yield can reach 90%, and content is more than 98%, for industrial mass manufacture provides guarantee.
Embodiment
The reaction formula of the synthetic method that the present invention recommended is as follows:
Compound I Compound I I
Embodiment 1:
A) in the 1000L enamel reaction still, add 40% aqueous methylamine solution 600Kg, under the icy salt solution freezing conditions, the 500Kg98% concentrated nitric acid is added drop-wise in the aqueous solution of methylamine, mol ratio is 1: 1, and dropping temperature control is no more than 40 ℃, drips off intensification, vacuum distilling dehydration, concentrate do the molten state methylamine nitrate.
The 330Kg Dyhard RU 100 is added in the above gained molten state methylamine nitrate in batches, Dyhard RU 100 and methylamine nitrate mol ratio 1: 2,120 ℃ of temperature of reaction were reacted 6 hours, the cooling lump Compound I crude product 1000Kg.
B) produce Compound I I by Compound I, in the 1000L enamel reaction still, add 98% vitriol oil 400Kg, will be by steps A) the Compound I 200Kg of gained joining in the vitriol oil below 25 ℃ in batches, add back 30 ℃ of reactions 4 hours, under freezing conditions be put in the frozen water of 1200Kg, separate out Compound I I, centrifuge dewatering, rinsing, the wet product of Compound I I, dry 158Kg Compound I I (content is more than 98%), i.e. N-methyl N '-nitroguanidine;
Embodiment 2:
Only with steps A) in temperature of reaction change 100 ℃ into by 120 ℃, the reaction times by became 10 hours in 6 hours finished product 147Kg (content is more than 98%).All the other are with the description to embodiment 1.
Embodiment 3:
Only with steps A) in temperature of reaction change 140 ℃ into by 120 ℃, the reaction times by became 5 hours in 6 hours finished product 135Kg (content is more than 98%).All the other are all with the description to embodiment 1.
Embodiment 4:
Only with step B) in vitriol oil 400Kg change 320Kg into, finished product 138Kg (content is more than 98%).All the other are with the description to embodiment 1.
Embodiment 5:
Only with step B) in vitriol oil 400Kg change 600Kg into, finished product 155Kg (content is more than 98%).All the other are with the description to embodiment 1.
Embodiment 6:
Only with step B) in temperature of reaction change 15 ℃ into for 30 ℃, the reaction times became 8 hours by 4 hours, finished product 150Kg (content is more than 98%).All the other are with the description to embodiment 1.
Embodiment 7:
Only with step B) in temperature of reaction change 35 ℃ into for 30 ℃, finished product 153Kg (content is more than 98%).All the other are with the description to embodiment 1.
Claims (1)
1, a kind of N-methyl N '-preparation method of nitroguanidine, it is characterized in that it may further comprise the steps:
A) prepare compound N-methyl N with Dyhard RU 100 and methylamine nitrate '-Guanidinium nitrate, by in the nitric acid and methylamine, boil off water and get the fused methylamine nitrate, add the Dyhard RU 100 reaction again and make compound N-methyl N '-Guanidinium nitrate;
B) '-Guanidinium nitrate prepare compound N-methyl N '-nitroguanidine by compound N-methyl N, '-Guanidinium nitrate in the vitriol oil, react compound N-methyl N '-nitroguanidine with compound N-methyl N, wherein: the mol ratio of Dyhard RU 100 and methylamine nitrate is 1: 2, described Dyhard RU 100 and methylamine nitrate prepare compound N-methyl N '-temperature of reaction during Guanidinium nitrate is 90-140 ℃, the described vitriol oil and compound N-methyl N '-mass ratio of Guanidinium nitrate is 1.6-4: 1, and temperature of reaction is 15-35 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100235897A CN100551904C (en) | 2007-06-11 | 2007-06-11 | The N-methyl N '-preparation method of nitroguanidine |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100235897A CN100551904C (en) | 2007-06-11 | 2007-06-11 | The N-methyl N '-preparation method of nitroguanidine |
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| CN101066939A CN101066939A (en) | 2007-11-07 |
| CN100551904C true CN100551904C (en) | 2009-10-21 |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101565392A (en) * | 2008-04-21 | 2009-10-28 | 南通天泽化工有限公司 | Methyl nitroguanidine and preparation method thereof |
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2007
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Non-Patent Citations (6)
| Title |
|---|
| 1-(4-氯苄基)-2-硝基亚氨基-咪唑烷的合成及其生物活性初步研究. 梁英.江西化工，第2期. 2002 |
| 1-(4-氯苄基)-2-硝基亚氨基-咪唑烷的合成及其生物活性初步研究. 梁英.江西化工，第2期. 2002 * |
| 双氰胺及其下游产品. 胡培忠.化工设计，第2期. 1997 |
| 双氰胺及其下游产品. 胡培忠.化工设计，第2期. 1997 * |
| 硝酸胍的精制. 吴和明等.江苏化工，第23卷第4期. 1995 |
| 硝酸胍的精制. 吴和明等.江苏化工，第23卷第4期. 1995 * |
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| CN101066939A (en) | 2007-11-07 |
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Assignee: Nantong Tendenci Chemical Co., Ltd. Assignor: Jiangsu Tianze Chemical Co., Ltd. Contract fulfillment period: 2007.6.20 to 2017.6.19 Contract record no.: 2009320001448 Denomination of invention: Process for preparing N- methyl N- nitro guanidine Granted publication date: 20091021 License type: Exclusive license Record date: 2009.8.10 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.6.20 TO 2017.6.19; CHANGE OF CONTRACT Name of requester: NANTONG TENDENCI CHEMICAL CO., LTD. Effective date: 20090810 |
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Effective date of registration: 20130828 Address after: 226531 Jiangsu city of Nantong province Rugao city Yongxing Stone Town neighborhood (Rugao Port Development Zone, fine chemical industry park riverside papermaking factory) Patentee after: Nantong Tendenci Chemical Co., Ltd. Address before: 215500 Changshou City province Jiangsu Yushan Town Ditch Village Patentee before: Jiangsu Tianze Chemical Co., Ltd. |
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