CN110156714B - Preparation method of iodosulfuron-methyl sodium intermediate - Google Patents
Preparation method of iodosulfuron-methyl sodium intermediate Download PDFInfo
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- CN110156714B CN110156714B CN201910407728.9A CN201910407728A CN110156714B CN 110156714 B CN110156714 B CN 110156714B CN 201910407728 A CN201910407728 A CN 201910407728A CN 110156714 B CN110156714 B CN 110156714B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
- C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
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Abstract
The invention discloses a preparation method of an iodosulfuron-methyl sodium salt intermediate, which is obtained by one-step reaction of 6-aminosaccharin and potassium iodide in the presence of alkyl nitrite and acetic acid; the molar ratio of potassium iodide to 6-aminosaccharin is 1: 1-1.2: 1; the molar ratio of the alkyl nitrite to the 6-aminosaccharin is 0.95: 1-1: 1; the alkyl nitrite is ethyl nitrite, isopropyl nitrite, n-butyl nitrite and isoamyl nitrite; the molar ratio of the acetic acid to the 6-saccharin is 1: 1-1.2: 1. According to the method, alkyl nitrite is adopted for diazotization, and potassium iodide is added at the same time, so that the decomposition and hydrolysis of diazonium salt can be avoided, and the reaction yield is greatly improved; moreover, the method of the present invention does not require a large amount of water as a solvent, and only a small amount of water is used for washing the organic layer in the post-treatment, so that the amount of the target product in the waste water produced by the method of the present invention is not more than 2 times by weight.
Description
Technical Field
The invention belongs to the technical field of pesticide intermediate preparation, and particularly relates to a preparation method of an iodosulfuron-methyl sodium intermediate 6-iodosaccharin.
Background
Iodosulfuron-methyl sodium (Iodosulfuron-methyl sodium) is a sulfonylurea herbicide developed by bayer corporation. Iodosulfuron-methyl sodium is an acetolactate synthase (ALS) inhibitor. Mainly expressed in inhibiting the synthesis of valine and isoleucine in organisms, thus hindering cell division and plant growth, and selectively eliminating weeds in rice. The iodosulfuron-methyl sodium is used for preventing and killing broad-leaved weeds and part of gramineous weeds in cereal crop fields, such as cleavers, chamomile, aeolian weeds, wild oats, bluegrass and the like.
6-iodosaccharin is an important intermediate for synthesizing iodosulfuron-methyl sodium, and the existing preparation methods of 6-iodosaccharin basically prepare 6-iodosaccharin by reacting 6-saccharin with sodium nitrite to prepare diazonium salt, and then reacting the diazonium salt with an iodine-containing reagent (such as potassium iodide) (see literature 1 and literature 2), wherein the reaction formula is as follows:
the method mainly has the following two problems:
(1) the diazonium salt is not only easy to decompose, but also easy to hydrolyze due to the presence of water, so that more impurities are generated and the reaction yield is low.
The yield of reference 2 is 70.8%, and the yield of reference 1 is more preferably 46.5%.
The diazonium salt decomposes the impurities as follows:
the diazonium salt hydrolysis impurities are as follows:
(2) the method needs a large amount of organic acid and water as solvents, so that the produced salt-containing wastewater is more, the cost for treating the wastewater is higher, and the method does not accord with the environmental protection requirement and the economic requirement.
Document 2 produces wastewater about 16 times the weight of the target product, and more document 1 produces wastewater about 40 times the weight of the target product.
Document 1: chinese patent document CN1702064A, published 2005, 11/30/month.
Document 2: xinhong Cai et al, "A convention Synthesis of 2-Methoxycarbonyl-5-iodobenzene sulfonium", "Asian Journal of Chemistry", 2017, vol.29, No. 7, p.1622-.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of an iodosulfuron-methyl sodium salt intermediate which is environment-friendly and particularly has high reaction yield.
The technical scheme for realizing the purpose of the invention is as follows: a process for preparing the intermediate of iodosulfuron-methyl sodium salt includes one-step reaction between 6-aminosaccharin and potassium iodide in the presence of alkyl nitrite and acetic acid.
The molar ratio of the potassium iodide to the 6-saccharin is 1: 1-1.2: 1.
The molar ratio of the alkyl nitrite to the 6-saccharin is 0.95: 1-1: 1.
The alkyl nitrite is ethyl nitrite, isopropyl nitrite, n-butyl nitrite, isoamyl nitrite, preferably isoamyl nitrite.
The molar ratio of the acetic acid to the 6-saccharin is 1: 1-1.2: 1.
The above reaction is carried out in an organic solvent; the organic solvent is toluene, ethanol, isoamyl alcohol, isopropanol or n-butanol, and preferably toluene.
The reaction temperature is 0 to 40 ℃, preferably 0 to 20 ℃.
The reaction time is 1 to 4 hours, preferably 1 to 2 hours.
The invention has the following positive effects:
(1) the method adopts alkyl nitrite for diazotization, and simultaneously adds potassium iodide, thereby avoiding the decomposition and hydrolysis of diazonium salt and greatly improving the reaction yield.
(2) The process of the present invention does not require a large amount of water as a solvent, and only a small amount of water is used for washing the organic layer in the post-treatment, so that the amount of the target product in the waste water produced by the process of the present invention is not more than 2 times the weight of the waste water, which is far lower than that of the prior art process.
(3) The method has the advantages of simple process, high product yield, less waste water, environmental protection and low cost, and is suitable for industrial production.
Detailed Description
(example 1)
The reaction formula of this example is as follows:
the specific method of this example is as follows:
a500 mL reaction flask was charged with 20g (0.101 mol) of 6-aminosaccharin, 17.6g (0.106 mol) of potassium iodide, 6.4g (0.107 mol) of acetic acid and 100g of toluene, 11.8g (0.101 mol) of isoamyl nitrite was added dropwise at about 10 ℃ and reacted at 20 ℃ for 2 hours, then 20g of water was added thereto, stirred for 10 minutes, allowed to stand for delamination, 15g of a 10wt% aqueous solution of sodium carbonate was added to the organic layer, stirred for 10 minutes, allowed to stand for delamination and desolventized in the organic layer, whereby 28.1g of 6-iodosaccharin was obtained, the content was 96% and the yield was 90.0%.
(example 2)
The reaction formula of this example is as follows:
the specific method of this example is as follows:
a500 mL reaction flask was charged with 20g (0.101 mol) of 6-aminosaccharin, 17.6g (0.106 mol) of potassium iodide, 6.4g (0.107 mol) of acetic acid and 100g of toluene, 10.4g (0.101 mol) of n-butyl nitrite was added dropwise at about 10 ℃ and reacted at 20 ℃ for 2 hours, then 20g of water was added thereto, the mixture was stirred for 10 minutes, the mixture was allowed to stand for separation, 15g of a 10wt% aqueous solution of sodium carbonate was added to the organic layer, the mixture was stirred for 10 minutes, the mixture was allowed to stand for separation, and the organic layer was desolventized to obtain 27.5g of 6-iodosaccharin, the content of which was 95%, and the yield was 88.1%.
(example 3)
The reaction formula of this example is as follows:
the specific method of this example is as follows:
adding 20g (0.101 mol) of 6-aminosaccharin, 17.6g (0.106 mol) of potassium iodide, 6.4g (0.107 mol) of acetic acid and 100g of toluene into a 500mL reaction bottle, dropwise adding 9.0g (0.101 mol) of isopropyl nitrite at about 10 ℃, reacting at 20 ℃ for 2 hours after dropwise adding, then adding 20g of water, stirring for 10 minutes, standing for layering, adding 15g of 10wt% sodium carbonate aqueous solution into an organic layer, stirring for 10 minutes, standing for layering, and desolventizing the organic layer to obtain 26.5g of 6-iodosaccharin, wherein the content is 95%, and the yield is 84.9%.
Claims (10)
1. A process for preparing the intermediate of iodosulfuron-methyl sodium salt includes one-step reaction between 6-aminosaccharin and potassium iodide in the presence of alkyl nitrite and acetic acid.
2. The process for producing an iodosulfuron sodium intermediate according to claim 1, characterized in that: the molar ratio of the potassium iodide to the 6-saccharin is 1: 1-1.2: 1.
3. The process for producing an iodosulfuron sodium intermediate according to claim 1, characterized in that: the molar ratio of the alkyl nitrite to the 6-saccharin is 0.95: 1-1: 1.
4. The process for producing an iodosulfuron sodium intermediate according to claim 1, characterized in that: the alkyl nitrite is ethyl nitrite, isopropyl nitrite, n-butyl nitrite and isoamyl nitrite.
5. The process for producing an iodosulfuron sodium intermediate according to claim 4, characterized in that: the alkyl nitrite is isoamyl nitrite.
6. The process for producing an iodosulfuron sodium intermediate according to claim 1, characterized in that: the molar ratio of the acetic acid to the 6-saccharin is 1: 1-1.2: 1.
7. The process for producing an iodosulfuron sodium intermediate according to claim 1, characterized in that: the above reaction is carried out in an organic solvent; the organic solvent is toluene, ethanol, isoamyl alcohol, isopropanol or n-butanol.
8. The process for producing an iodosulfuron sodium intermediate according to claim 7, characterized in that: the organic solvent is toluene.
9. The process for producing an iodosulfuron sodium intermediate according to claim 1, characterized in that: the reaction temperature is 0-40 ℃, and the reaction time is 1-4 h.
10. The process for producing an iodosulfuron sodium intermediate according to claim 9, characterized in that: the reaction temperature is 0-20 ℃, and the reaction time is 1-2 h.
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