CN103641746A - N-methyl-N'nitroguanidine synthesis process - Google Patents
N-methyl-N'nitroguanidine synthesis process Download PDFInfo
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- CN103641746A CN103641746A CN201310590138.7A CN201310590138A CN103641746A CN 103641746 A CN103641746 A CN 103641746A CN 201310590138 A CN201310590138 A CN 201310590138A CN 103641746 A CN103641746 A CN 103641746A
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- CN
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- Prior art keywords
- methyl
- nitroguanidine
- methylthiourea
- nitro
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 24
- XCXKNNGWSDYMMS-UHFFFAOYSA-N 2-methyl-1-nitroguanidine Chemical compound CNC(N)=N[N+]([O-])=O XCXKNNGWSDYMMS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- MHRKBFJDSXKRPC-UHFFFAOYSA-N 1-methyl-1-nitrothiourea Chemical compound NC(=S)N(C)[N+]([O-])=O MHRKBFJDSXKRPC-UHFFFAOYSA-N 0.000 claims abstract description 22
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000967 suction filtration Methods 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000010813 municipal solid waste Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000575 pesticide Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- NNBBQNFHCVVQHZ-UHFFFAOYSA-N methyl carbamimidothioate;sulfuric acid Chemical compound CSC(N)=N.OS(O)(=O)=O NNBBQNFHCVVQHZ-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- NWWZPOKUUAIXIW-DHZHZOJOSA-N (E)-thiamethoxam Chemical compound [O-][N+](=O)/N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-DHZHZOJOSA-N 0.000 description 3
- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 description 2
- 229930014345 anabasine Natural products 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- -1 carboxylamine lipid Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000003992 organochlorine insecticide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of pesticide intermediates, and relates to a N-methyl-N'nitroguanidine synthesis process, which comprises: (1) pouring fuming nitric acid and concentrated sulfuric acid into a reaction bottle, and adding S-methyl isothiourea sulfate under a stirring condition; (2) after completing the reaction, adding ice, carrying out suction filtration, and carrying out vacuum drying to obtain N-nitro methylthiourea powder; (3) pouring methanol into the reaction bottle, adding the dried N-nitro methylthiourea, and adding a methylamine alcohol solution in a dropwise manner at a room temperature; and (4) carrying out a reaction for 3 h at a temperature of 80 DEG C, filtering while hot, cooling, carrying out suction filtration, and carrying out vacuum drying on the filter cake to obtain the N-methyl-N'nitroguanidine solid. According to the process, the reaction condition is optimized, the cost is saved, and the total yield is increased to 85%.
Description
?
Technical field
The invention belongs to pesticide intermediate technical field, be specifically related to a kind of synthesis technique of N-methyl-N ' nitroguanidine.
Background technology
The mechanism of action of the s-generation anabasine insecticide that the Diacloden of take is representative is similar to first-generation anabasine insecticide, but have that consumption is lower, insecticidal spectrum is wider, security is higher, the residual feature such as low, environmentally friendly, is the improved seeds that replace organophosphorus, carboxylamine lipid, organochlorine insecticides.N-methyl-N ' nitroguanidine is the necessary intermediate of synthetic Diacloden, and its yield height directly has influence on the synthetic of Diacloden.
Summary of the invention
In order to improve the productive rate of N-methyl-N ' nitroguanidine, the invention provides a kind of synthesis technique of N-methyl-N ' nitroguanidine.
A synthesis technique for N-methyl-N ' nitroguanidine, this technique comprises following production stage:
(1) in reaction flask, drop into nitrosonitric acid and the vitriol oil, be cooled to-10 ℃, under agitation condition, add S-methyl-isourea, maintain liquid temperature-10～-7 ℃, continuation adds the S-methyl-isourea of equivalent under agitation condition again, maintain 0～5 ℃ of liquid temperature, add rear continuation reaction 10min;
(2) after reaction finishes, add trash ice, wait to separate out tiny product particle, suction filtration, cold water cleans twice, and vacuum-drying at 80～85 ℃ of temperature, obtains N-nitro methylthiourea powder;
(3) in reaction flask, first drop into methyl alcohol, add dry N-nitro methylthiourea, the mol ratio of methyl alcohol and N-nitro methylthiourea is 2:1, under room temperature, drips methylamine alcohol solution, and 45～60min drips off, and continues to stir 1 h;
(4) then at 80 ℃, react 3 h, the thiomethyl alcohol of effusion absorbs with 30%NaOH solution, filtered while hot, and hot filtrate is slowly cooled to 0 ℃, and adularescent crystallized product is separated out, suction filtration, filter cake vacuum-drying, obtains N-methyl-N ' nitroguanidine solid.
Further, the volume ratio of described step (1) nitrosonitric acid and the vitriol oil is 1:3～5.
Further, to add the mass ratio of S-methyl-isourea and nitrosonitric acid be 1:22～25 to described step (1).
Further, the mass ratio of described step (3) N-nitro methylthiourea and methylamine alcohol is 1:1～1.5.
This process using the method for first nitrated reamination, and reaction conditions is optimized, make overall yield bring up to 85%, saved cost, industrial prospect is wide.
Embodiment
Embodiment 1
A synthesis technique for N-methyl-N ' nitroguanidine, this technique comprises following production stage:
(1) in reaction flask, drop into nitrosonitric acid and the vitriol oil, the volume ratio of nitrosonitric acid and the vitriol oil is 1:3, be cooled to-10 ℃, under agitation condition, add S-methyl-isourea, the mass ratio of S-methyl-isourea and nitrosonitric acid is 1:22, maintains liquid temperature-10～-7 ℃, continues to add the S-methyl-isourea of equivalent under agitation condition again, maintain 3～5 ℃ of liquid temperatures, add rear continuation reaction 10min;
(2) after reaction finishes, add trash ice, wait to separate out tiny product particle, suction filtration, cold water cleans twice, and vacuum-drying at 80～85 ℃ of temperature, obtains N-nitro methylthiourea powder;
(3) in reaction flask, first drop into methyl alcohol, add dry N-nitro methylthiourea, the mol ratio of methyl alcohol and N-nitro methylthiourea is 2:1, under room temperature, drip methylamine alcohol solution, the mass ratio of N-nitro methylthiourea and methylamine alcohol is 1:1, and 45min drips off, and continues to stir 1 h;
(4) then at 80 ℃, react 3 h, the thiomethyl alcohol of effusion absorbs with 30%NaOH solution, filtered while hot, and hot filtrate is slowly cooled to 0 ℃, and adularescent crystallized product is separated out, suction filtration, filter cake vacuum-drying, obtains N-methyl-N ' nitroguanidine solid.
The productive rate of the N-methyl-N ' nitroguanidine obtaining by this technique is 85%.
Embodiment 2
A synthesis technique for N-methyl-N ' nitroguanidine, this technique comprises following production stage:
(1) in reaction flask, drop into nitrosonitric acid and the vitriol oil, the volume ratio of nitrosonitric acid and the vitriol oil is 1:5, be cooled to-10 ℃, under agitation condition, add S-methyl-isourea, the mass ratio of S-methyl-isourea and nitrosonitric acid is 1:25, maintains liquid temperature-10～-7 ℃, continues to add the S-methyl-isourea of equivalent under agitation condition again, maintain 0～5 ℃ of liquid temperature, add rear continuation reaction 10min;
(2) after reaction finishes, add trash ice, wait to separate out tiny product particle, suction filtration, cold water cleans twice, and vacuum-drying at 80～82 ℃ of temperature, obtains N-nitro methylthiourea powder;
(3) in reaction flask, first drop into methyl alcohol, add dry N-nitro methylthiourea, the mol ratio of methyl alcohol and N-nitro methylthiourea is 2:1, under room temperature, drip methylamine alcohol solution, the mass ratio of N-nitro methylthiourea and methylamine alcohol is 1:5, and 60min drips off, and continues to stir 1 h;
(4) then at 80 ℃, react 3 h, the thiomethyl alcohol of effusion absorbs with 30%NaOH solution, filtered while hot, and hot filtrate is slowly cooled to 0 ℃, and adularescent crystallized product is separated out, suction filtration, filter cake vacuum-drying, obtains N-methyl-N ' nitroguanidine solid.
The productive rate of the N-methyl-N ' nitroguanidine obtaining by this technique is 83.5%.
Embodiment 3
A synthesis technique for N-methyl-N ' nitroguanidine, this technique comprises following production stage:
(1) in reaction flask, drop into nitrosonitric acid and the vitriol oil, the volume ratio of nitrosonitric acid and the vitriol oil is 1:4, be cooled to-10 ℃, under agitation condition, add S-methyl-isourea, the mass ratio of S-methyl-isourea and nitrosonitric acid is 1:23, maintains liquid temperature-10～-7 ℃, continues to add the S-methyl-isourea of equivalent under agitation condition again, maintain 0～5 ℃ of liquid temperature, add rear continuation reaction 10min;
(2) after reaction finishes, add trash ice, wait to separate out tiny product particle, suction filtration, cold water cleans twice, and vacuum-drying at 82～85 ℃ of temperature, obtains N-nitro methylthiourea powder;
(3) in reaction flask, first drop into methyl alcohol, add dry N-nitro methylthiourea, the mol ratio of methyl alcohol and N-nitro methylthiourea is 2:1, under room temperature, drip methylamine alcohol solution, the mass ratio of N-nitro methylthiourea and methylamine alcohol is 1:1.2, and 50min drips off, and continues to stir 1 h;
(4) then at 80 ℃, react 3 h, the thiomethyl alcohol of effusion absorbs with 30%NaOH solution, filtered while hot, and hot filtrate is slowly cooled to 0 ℃, and adularescent crystallized product is separated out, suction filtration, filter cake vacuum-drying, obtains N-methyl-N ' nitroguanidine solid.
The productive rate of the N-methyl-N ' nitroguanidine obtaining by this technique is 84%.
Claims (4)
1. a synthesis technique for N-methyl-N ' nitroguanidine, is characterized in that, this technique comprises following production stage:
(1) in reaction flask, drop into nitrosonitric acid and the vitriol oil, be cooled to-10 ℃, under agitation condition, add S-methyl-isourea, maintain liquid temperature-10～-7 ℃, continuation adds the S-methyl-isourea of equivalent under agitation condition again, maintain 0～5 ℃ of liquid temperature, add rear continuation reaction 10min;
(2) after reaction finishes, add trash ice, wait to separate out tiny product particle, suction filtration, cold water cleans twice, and vacuum-drying at 80～85 ℃ of temperature, obtains N-nitro methylthiourea powder;
(3) in reaction flask, first drop into methyl alcohol, add dry N-nitro methylthiourea, the mol ratio of methyl alcohol and N-nitro methylthiourea is 2:1, under room temperature, drips methylamine alcohol solution, and 45～60min drips off, and continues to stir 1 h;
(4) then at 80 ℃, react 3 h, the thiomethyl alcohol of effusion absorbs with 30%NaOH solution, filtered while hot, and hot filtrate is slowly cooled to 0 ℃, and adularescent crystallized product is separated out, suction filtration, filter cake vacuum-drying, obtains N-methyl-N ' nitroguanidine solid.
2. the synthesis technique of a kind of N-methyl-N ' nitroguanidine according to claim 1, is characterized in that, the volume ratio of step (1) nitrosonitric acid and the vitriol oil is 1:3～5.
3. the synthesis technique of a kind of N-methyl-N ' nitroguanidine according to claim 1, is characterized in that, it is 1:22～25 that step (1) adds the mass ratio of S-methyl-isourea and nitrosonitric acid.
4. the synthesis technique of a kind of N-methyl-N ' nitroguanidine according to claim 1, is characterized in that, the mass ratio of step (3) N-nitro methylthiourea and methylamine alcohol is 1:1～1.5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310590138.7A CN103641746B (en) | 2013-11-22 | 2013-11-22 | A kind of synthesis technique of N-methyl-N ' nitroguanidine |
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| CN201310590138.7A CN103641746B (en) | 2013-11-22 | 2013-11-22 | A kind of synthesis technique of N-methyl-N ' nitroguanidine |
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| CN103641746A true CN103641746A (en) | 2014-03-19 |
| CN103641746B CN103641746B (en) | 2016-03-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317152A (en) * | 2019-06-18 | 2019-10-11 | 武汉青江化工黄冈有限公司 | A kind of O- methyl-N methyl-N '-nitro isourea production method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059719A (en) * | 1990-08-17 | 1992-03-25 | 武田药品工业株式会社 | Novel substituted guanidine derivatives and preparation thereof and application |
| CN1163888A (en) * | 1996-03-25 | 1997-11-05 | 拜尔公司 | Process for preparing N-methyl-N'-nitroguanidine |
| CN1197064A (en) * | 1997-03-31 | 1998-10-28 | 三井化学株式会社 | Preparation process of nitroguanidine derivatives |
| TWI291947B (en) * | 2000-01-12 | 2008-01-01 | Bayer Ag | Process for the preparation of n-methyl-n'-nitroguanidine |
-
2013
- 2013-11-22 CN CN201310590138.7A patent/CN103641746B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059719A (en) * | 1990-08-17 | 1992-03-25 | 武田药品工业株式会社 | Novel substituted guanidine derivatives and preparation thereof and application |
| CN1163888A (en) * | 1996-03-25 | 1997-11-05 | 拜尔公司 | Process for preparing N-methyl-N'-nitroguanidine |
| CN1197064A (en) * | 1997-03-31 | 1998-10-28 | 三井化学株式会社 | Preparation process of nitroguanidine derivatives |
| TWI291947B (en) * | 2000-01-12 | 2008-01-01 | Bayer Ag | Process for the preparation of n-methyl-n'-nitroguanidine |
Non-Patent Citations (1)
| Title |
|---|
| LAWRENCE FISHBEIN，JOHN A. GALLAGHAN: "The Preparation and Reactions of 2-Alkyl-1-(or 3)-nitro-2-thiopseudourea. Part I. Reaction with Amines", 《J. AM. CHEM. SOC.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317152A (en) * | 2019-06-18 | 2019-10-11 | 武汉青江化工黄冈有限公司 | A kind of O- methyl-N methyl-N '-nitro isourea production method |
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| CN103641746B (en) | 2016-03-30 |
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Inventor after: Su Jianli Inventor before: Zhang Yafeng |
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Effective date of registration: 20151207 Address after: 266061 Shandong, Laoshan, Hongkong East Road, No. Pioneering Park, biological park, room 248, No. 239 Applicant after: Qingdao Wenchuang Science & Technology Co., Ltd. Address before: 266071 Shandong province Qingdao City High Road No. 12 four unit 604 Applicant before: Zhang Yafeng |
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Effective date of registration: 20181204 Address after: 401120 Chongqing Yubei District Longxi Street Jinlong Road 259 Finance and Information City International 4 1-6 Patentee after: Chongqing Haoting Zhongtuo Environmental Technology Co., Ltd. Address before: 266061 Qingdao Hongkong Laoshan road 248, Pioneer Park, 239 Biological Park 239 Patentee before: Qingdao Wenchuang Science & Technology Co., Ltd. |
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Effective date of registration: 20201119 Address after: 274600 west of north section of Huaxu road and north side of Changcheng street, juancheng County, Heze City, Shandong Province Patentee after: JUANCHENG DINGSHENG CHEMICAL TECHNOLOGY Co.,Ltd. Patentee after: JUANCHENG RUIDING TECHNOLOGY Co.,Ltd. Address before: 401120 Chongqing Yubei District Longxi Street Jinlong Road 259 Finance and Information City International 4 1-6 Patentee before: Chongqing Haoting Zhongtuo Environmental Technology Co.,Ltd. |