CN103073489A - Preparation method of Boscalid - Google Patents
Preparation method of Boscalid Download PDFInfo
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- CN103073489A CN103073489A CN2013100479026A CN201310047902A CN103073489A CN 103073489 A CN103073489 A CN 103073489A CN 2013100479026 A CN2013100479026 A CN 2013100479026A CN 201310047902 A CN201310047902 A CN 201310047902A CN 103073489 A CN103073489 A CN 103073489A
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- chlordiphenyl
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Abstract
The invention discloses a preparation method of Boscalid, which comprises the following steps that Suzuki coupling reaction occurs between o-iodoaniline and 4-chlorobenzene boronic acid to produce an intermediate product 4'-chlorinated biphenyl-2-amine under the catalytic effect of Pd/C by using methylbenzene and alkaline water as mixed solvent; and condensation reaction occurs between the 4'-chlorinated biphenyl-2-amine and 2-chloronicotinyl chloride to produce the Boscalid. The preparation method of the Boscalid has the advantages that the production cost is reduced, the yield of the intermediate product 4'-chlorinated biphenyl-2-amine is improved, the total yield of the two steps exceeds 84 percent and the industrial production is expected to be realized.
Description
Technical field
The present invention relates to the agricultural chemicals preparation field, specifically, relate to a kind of preparation method of sterilant.
Background technology
The full name of boscalid amine is N-(4 '-chloro-2-xenyl)-2-chloro-3-pyridyl methane amide, be a kind of efficient germicide.That German BASF and Japanese AG company are in more than 50 sterilant new variety that country registers such as Europe, the U.S. at first.Be mainly used to prevent and treat gray mold and the sclerotium diseases such as vegetables, beans.Its mechanism of action is that liquid permeates by the blade face through plant absorbing, then in plant, be transferred, can suppress mitochondrial succinate ester dehydrogenase activity, thereby hinder tricarboxylic acid cycle, make that amino acid, sugar lack, energy reduces, the division of interference cell and growth and fungicidal activity is arranged.The boscalid amine synthetic method of bibliographical information was divided into for two steps: the first step is the preparation of important intermediate 4 '-chlordiphenyl-2-amine; Second step is to prepare target product by 2-chloronicotinoyl chloride and 4 '-chlordiphenyl-2-amine condensation.Second step is relatively simple, and key is the Suzuki linked reaction of the first step.The method of synthetic 4 '-chlordiphenyl-2-amine had two classes in the past: the one, by o-Nitrochlorobenzene and 4-chlorobenzene boric acid Suzuki coupling, restore into amine.But this class reaction is two-step reaction, and except productive rate was low, the reduction of iron powder also brought the pollution of a large amount of iron mud, is not suitable for suitability for industrialized production.Another method is direct by adjacent Iodoaniline and the Suzuki coupling occurs 4-chlorobenzene boric acid, and the efficient of this class reaction is high, but bibliographical information is to adopt the high Pd (PPh of price
3)
4Be catalyzer, and need the harsh reaction conditions of anhydrous and oxygen-free, on economy and reaction conditions, all be not suitable for suitability for industrialized production.
Summary of the invention
Low, the shortcomings such as cost is high, severe reaction conditions of productive rate that exist in order to solve prior art, the invention provides a kind of preparation method of boscalid amine, reduced production cost and improved the productive rate of intermediate product 4 '-chlordiphenyl-2-amine, made overall yield surpass 84%.
The present invention relates to a kind of preparation method of boscalid amine, be achieved through the following technical solutions:
A kind of preparation method of boscalid amine may further comprise the steps:
,, under Pd/C catalysis, adjacent Iodoaniline and 4-chlorobenzene boric acid are carried out the Suzuki linked reaction generate intermediate product 4 '-chlordiphenyl-2-amine as mixed solvent with toluene and buck;
Described 4 '-chlordiphenyl-2-amine and 2-chloronicotinoyl chloride are carried out condensation reaction generation boscalid amine.
Described Suzuki linked reaction be with aqueous sodium carbonate as the alkali in the linked reaction, carry out the Suzuki linked reaction, the reaction formula of Suzuki linked reaction is as follows:
Described condensation reaction is under the catalysis of triethylamine, take ethylene dichloride as solvent, as the alkali in the condensation reaction, carries out condensation reaction with aqueous sodium carbonate, and the reaction formula of condensation reaction is as follows:
Compared with prior art, the present invention has the following advantages:
1, the present invention uses cheap Pd/C as catalyzer; Carry out the Suzuki linked reaction, with respect to the high Pd (PPh of available technology adopting price
3)
4Catalyzer has reduced production cost;
2, the present invention uses Pd/C as catalyzer, has further improved the productive rate of intermediate product 4 '-chlordiphenyl-2-amine;
3, use toluene and buck mixed solvent, be conducive to separation and the purification of product intermediate product 4 '-chlordiphenyl-2-amine.
Embodiment
Further describe the present invention by following examples, but should notice that scope of the present invention is not subjected to any restriction of these embodiment.In the following example, if no special instructions, " % " representation quality percentage ratio.
The preparation of embodiment 1:4 '-chlordiphenyl-2-amine
In the there-necked flask of 1L, add 4-chlorobenzene boric acid (31.3g, 200mmol), adjacent Iodoaniline (39.2g, 180mmol), Pd/C(0.3g, 5%) and toluene (300mL), then stirring at room 15 minutes adds Na
2CO
3The aqueous solution (300mL, 25%), then mixture heating up stirring and refluxing 30h is cooled to room temperature, standing demix.Inorganic layer merges organic layer with toluene extracting twice (50mL * 2), then washes three times (100mL * 3).The anhydrous MgSO of organic phase
4Drying, reclaim under reduced pressure toluene.Remaining oily matter is put into the freezing brown solid 34.2g of getting of 0～5 ° of C of refrigerator, productive rate: 93.2%.Mp:39-41 ° of C; (literature value CAS:1204-44-0, mp:42-44 ° of C).
According to the method described above, take adjacent Iodoaniline and 4-chlorobenzene boric acid as raw material, react under different solvents, different alkali, different catalyzer condition, wherein, the volume ratio of toluene and 25% aqueous sodium carbonate is 1:1; The mass ratio of the relatively described adjacent Iodoaniline of Pd/C catalyzer is 7.6 ‰, and concrete productive rate sees Table 1.
The productive rate of 4 '-chlordiphenyl under table 1. different condition-2-amine
Table 1 is the result show, under the condition of the same catalyst of identical alkali and same dose, the productive rate of 4 '-chlordiphenyl when solvent is toluene-2-amine is the highest; Under the condition of the same catalyst of identical solvent and same dose, the productive rate of 4 '-chlordiphenyl when alkali is aqueous sodium carbonate-2-amine is the highest; Under the condition of identical solvent and identical alkali, catalyzer is Pd/C, the productive rate of 4 '-chlordiphenyl-2-amine was the highest when catalytic amount was 300mg.Obviously, by above result as can be known, when solvent is that toluene, alkali are that aqueous sodium carbonate, catalyzer are Pd/C and catalytic amount when being 300mg, the productive rate of 4 '-chlordiphenyl-2-amine is the highest, and productive rate is 93.2%.
Embodiment 2: the preparation of boscalid amine
The 1mL triethylamine that in the 250mL of drying flask, adds ethylene dichloride (150mL), yellow soda ash (21.2g, 200mmol) and the catalytic amount of 4 '-chlordiphenyl-2-amine (20.4g, 100mmol), drying.Then frozen water is cooled to 10 ° of C, and minute 5 batches (every crowd of about 4g) adds 2-chloronicotinoyl chloride (19.36g, 110mmol), then continues reaction 4 hours under the room temperature.After reaction finished, hydrochloric acid (20mL, 10%) washing was used in first water (30mL) washing again, at last again water (30mL) washing.The anhydrous MgSO of organic phase
4Drying, solvent is reclaimed in air distillation, and remaining solid namely gets boscalid amine 31.2g, productive rate: 91.1% with alcohol and water mixed solvent (volume ratio is 1:1) recrystallization.Mp:143-144 ° of C; (literature value CAS:188425-85-6, mp:142-144 ° of C).
Claims (4)
1. the preparation method of a boscalid amine said method comprising the steps of:
,, under catalyst P d/C catalysis, adjacent Iodoaniline and 4-chlorobenzene boric acid are carried out the Suzuki linked reaction generate intermediate product 4 '-chlordiphenyl-2-amine as mixed solvent with toluene and buck;
Described 4 '-chlordiphenyl-2-amine and 2-chloronicotinoyl chloride are carried out condensation reaction generation boscalid amine.
2. the preparation method of boscalid amine according to claim 1 is characterized in that, described Suzuki linked reaction be with aqueous sodium carbonate as the alkali in the linked reaction, carry out the Suzuki linked reaction, the reaction formula of Suzuki linked reaction is as follows:
3. the preparation method of boscalid amine according to claim 1 is characterized in that, described condensation reaction is under the catalysis of triethylamine, take ethylene dichloride as solvent, as the alkali in the condensation reaction, carry out condensation reaction with aqueous sodium carbonate, the reaction formula of condensation reaction is as follows:
4. the preparation method of each described boscalid amine is characterized in that according to claim 1-3, and the volume ratio of described toluene and 25% aqueous sodium carbonate is 1:1; The mass ratio of the relatively described adjacent Iodoaniline of Pd/C catalyzer is 7.6 ‰.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554098A (en) * | 2013-10-31 | 2014-02-05 | 青岛农业大学 | One group of 2-chlorine-3-pyridine formyl compounds |
| CN103980192A (en) * | 2014-01-20 | 2014-08-13 | 泰州百力化学股份有限公司 | Selective synthesis method of cyprosulfamide with different crystal forms |
| CN104016915A (en) * | 2014-06-27 | 2014-09-03 | 重庆工商大学 | Preparation method of boscalid |
| WO2014174397A3 (en) * | 2013-04-25 | 2015-04-02 | Mandal Dr Swadhin K | Method of synthesis molecules using catalyst and composites thereof |
| CN104725303A (en) * | 2015-02-02 | 2015-06-24 | 西安近代化学研究所 | Synthetic method of 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide |
| CN105037172A (en) * | 2015-08-10 | 2015-11-11 | 张家港米西斯光电材料有限公司 | Preparation method of 2-(4'-chlorphenyl) aniline |
| CN106631812A (en) * | 2016-11-29 | 2017-05-10 | 浙江工业大学 | Preparation method of 4'-chloro-2-nitro-1,1'-biphenyl serving as boscalid intermediate |
| GB2552697A (en) * | 2016-08-04 | 2018-02-07 | Rotam Agrochem Int Co Ltd | Process for the preparation of boscalid |
| CN109476603A (en) * | 2016-08-04 | 2019-03-15 | 江苏龙灯化学有限公司 | The method for preparing Boscalid |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014174397A3 (en) * | 2013-04-25 | 2015-04-02 | Mandal Dr Swadhin K | Method of synthesis molecules using catalyst and composites thereof |
| CN103554098A (en) * | 2013-10-31 | 2014-02-05 | 青岛农业大学 | One group of 2-chlorine-3-pyridine formyl compounds |
| CN103554098B (en) * | 2013-10-31 | 2016-04-27 | 青岛农业大学 | One group of 2-chloro-3-pyridyl carbamoyl compound |
| CN103980192A (en) * | 2014-01-20 | 2014-08-13 | 泰州百力化学股份有限公司 | Selective synthesis method of cyprosulfamide with different crystal forms |
| CN104016915B (en) * | 2014-06-27 | 2016-03-30 | 重庆工商大学 | A kind of preparation method of boscalid amine |
| CN104016915A (en) * | 2014-06-27 | 2014-09-03 | 重庆工商大学 | Preparation method of boscalid |
| CN104725303A (en) * | 2015-02-02 | 2015-06-24 | 西安近代化学研究所 | Synthetic method of 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide |
| CN104725303B (en) * | 2015-02-02 | 2017-09-08 | 西安近代化学研究所 | The synthetic method of one kind 2 chlorine N (base of 4 ' chlordiphenyl 2) niacinamide |
| CN105037172A (en) * | 2015-08-10 | 2015-11-11 | 张家港米西斯光电材料有限公司 | Preparation method of 2-(4'-chlorphenyl) aniline |
| GB2552697A (en) * | 2016-08-04 | 2018-02-07 | Rotam Agrochem Int Co Ltd | Process for the preparation of boscalid |
| CN109476603A (en) * | 2016-08-04 | 2019-03-15 | 江苏龙灯化学有限公司 | The method for preparing Boscalid |
| CN109476604A (en) * | 2016-08-04 | 2019-03-15 | 江苏龙灯化学有限公司 | The method for being used to prepare Boscalid |
| GB2552697B (en) * | 2016-08-04 | 2021-03-10 | Rotam Agrochem Int Co Ltd | Process for the preparation of boscalid |
| CN106631812A (en) * | 2016-11-29 | 2017-05-10 | 浙江工业大学 | Preparation method of 4'-chloro-2-nitro-1,1'-biphenyl serving as boscalid intermediate |
| CN106631812B (en) * | 2016-11-29 | 2019-03-05 | 浙江工业大学 | A kind of Boscalid intermediate 4 '-chloro- 2- nitro -1,1 '-biphenyl preparation method |
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Application publication date: 20130501 |