WO2015053576A1 - Procédé pour la préparation de 3-alkylthio-2-bromopyridine - Google Patents

Procédé pour la préparation de 3-alkylthio-2-bromopyridine Download PDF

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Publication number
WO2015053576A1
WO2015053576A1 PCT/KR2014/009508 KR2014009508W WO2015053576A1 WO 2015053576 A1 WO2015053576 A1 WO 2015053576A1 KR 2014009508 W KR2014009508 W KR 2014009508W WO 2015053576 A1 WO2015053576 A1 WO 2015053576A1
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WO
WIPO (PCT)
Prior art keywords
dienenitrile
penta
formula
alkyl
phenyl
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Application number
PCT/KR2014/009508
Other languages
English (en)
Inventor
Sei Chang Ahn
Sook Hee Kim
Sadaiah KADIVENDI
Seo Yeon Lee
Ki Dae Kim
In Ae RYU
Original Assignee
Lg Life Sciences Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lg Life Sciences Ltd. filed Critical Lg Life Sciences Ltd.
Priority to CN201480054868.8A priority Critical patent/CN105636938B/zh
Priority to JP2016521955A priority patent/JP6257115B2/ja
Publication of WO2015053576A1 publication Critical patent/WO2015053576A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/32—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to an acyclic carbon atom of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/32—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings

Definitions

  • the present invention relates to a novel method for the preparation of a key intermediate pyridine compound for producing fluoroalkylpyridine-sulfonyl urea derivatives showing superior herbicidal activity, novel alkylthioolefin derivatives used in the preparation and a method for the preparation thereof.
  • A represents C 3 -C 5 -alkyl or C 3 -C 6 -cycloalkyl, or represents benzyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy.
  • the compound of Formula 1 can be prepared by reacting the compound of Formula 3 with a strong base of lithium amides of Formula 4 and then with the electrophile compound of Formula 5.
  • n 0 or 3
  • A represents C 3 -C 5 -alkyl or C 3 -C 6 -cycloalkyl, or represents benzyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy, and
  • X represents chlorine or S-A.
  • the compound of Formula 5 is the following disulfide compound of Formula 5a having a symmetrical structure.
  • the reaction of the strong base of lithium amides of Formula 4 has a problem requiring ultralow temperature condition of -78°C or lower. Furthermore, when the strong base reacts with the pyridine ring, it removes not only 3-position hydrogen atom but also 4-position hydrogen atom in the pyridine ring to produce the side product of Formula 6 having electrophiles in both 3-position and 4-position in the amount of 5-10%.
  • EWG represents an electron-withdrawing group, specifically an alkylester, cyano or alkylsulfone group.
  • A represents C 3 -C 5 -alkyl or C 3 -C 6 -cycloalkyl, or represents benzyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy.
  • the present inventors have intensively studied the method of using the less-reactive alkylthioacetonitrile of Formula 14 without using a cryogenic reactor to conveniently prepare the key intermediate compound of Formula 1 of high purity for producing flucetosulfuron. Consequently, the present inventors have conceived successfully the process to synthesize the pyridine derivative of Formula 1 having an alkylthio substituent at 3-position of pyridine ring by reacting a novel alkylthioolefin derivative with hydrogen bromide without ultralow temperature condition. The present inventors have also developed the method of preparing the novel compound, which has weak electron-withdrawing strength so that it could not be produced by a known method, to complete the present invention.
  • the object of the present invention is to provide a novel method for the preparation of a key intermediate compound for producing flucetosulfuron showing superior herbicidal activity.
  • Another object of the present invention is to provide novel alkylthioolefin derivatives used in the preparation of the intermediate compound and a method for the preparation thereof.
  • the present invention provides alkylthioolefin derivatives of Formula 2 for the preparation of a key intermediate pyridine derivative of the following Formula 1 for producing flucetosulfuron.
  • A represents C 3 -C 5 -alkyl or C 3 -C 6 -cycloalkyl, or represents benzyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy,
  • X represents cyclic secondary amine or the secondary amine of R 1 R 2 N, wherein each of R 1 and R 2 represents independently C 1 ⁇ C 3 alkyl, or represents phenyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy.
  • the cyclic secondary amine is selected from pyrrolidine, piperidine and morpholine, and each of R 1 and R 2 is independently selected from methyl, ethyl, propyl and phenyl, or selected from phenyl which is 1- to 5-substituted with substituents selected from methyl, ethyl, methoxy and ethoxy.
  • Examples of preferable compounds of Formula 2 are 2-(benzylsulfanyl)-5-[methyl(phenyl)amino]penta-2,4-dienenitrile, 2-(t-butylsulfanyl)-5-[methyl(phenyl) amino]penta-2,4-dienenitrile, 5-[methyl(phenyl)amino]-2-(propan-2-ylsulfanyl)penta-2,4-dienenitrile, 5-[methyl(4-methoxyphenyl)amino]-2-(propan-2-ylsulfanyl)penta-2,4-dienenitrile, 5-[methyl(4-ethoxyphenyl)amino]-2-(propan-2-ylsulfanyl)penta-2,4-dienenitrile, 2-(benzylsulfanyl)-5-[ethyl(phenyl)amino]penta-2,4-dienenitrile, 2-
  • Examples of more preferable compounds of Formula 2 are 5-[methyl(phenyl)amino]-2-(propan-2-ylsulfanyl)penta-2,4-dienenitrile, 5-(piperidin-1-yl)-2-(propan-2-ylsulfanyl)penta-2,4-dienenitrile, 5-(dimethylamino)-2-(propan-2-ylsulfanyl)penta-2,4-dienenitrile and 5-(morpholin-4-yl)-2-(propan-2-ylsulfanyl)penta-2,4-dienenitrile.
  • the compounds of Formula 2 according to the present invention are prepared by reacting the compound of the following Formula 14 and the compound of Formula 15 with an organic acid and organic base concurrently in the presence of a solvent.
  • A represents C 3 -C 5 -alkyl or C 3 -C 6 -cycloalkyl, or represents benzyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy,
  • X represents cyclic secondary amine or the secondary amine of R 1 R 2 N, wherein each of R 1 and R 2 represents independently C 1 ⁇ C 3 alkyl, or represents phenyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy.
  • the compound of Formula 2 according to the present invention which cannot be obtained by the methods of the above Reaction Schemes 1 or 2 because the electron-withdrawing strength of the alkylthio radical in the compound of Formula 14 is very weak, may be obtained by direct Knovenagel condensation reaction with the acrolein derivative of Formula 15.
  • the key intermediate pyridine derivatives of the following Formula 1 for producing flucetosulfuron are prepared by reacting the compound of Formula 2 with hydrogen bromide in the presence of a solvent according to the present invention.
  • A represents C 3 -C 5 -alkyl or C 3 -C 6 -cycloalkyl, or represents benzyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy,
  • X represents cyclic secondary amine or the secondary amine of R 1 R 2 N, wherein each of R 1 and R 2 represents independently C 1 -C 3 alkyl, or represents phenyl which is unsubstituted or 1- to 5-substituted with substituents selected from C 1 -C 2 -alkyl and C 1 -C 2 -alkoxy.
  • the intermediate pyridine derivatives of the following Formula 1 for producing flucetosulfuron are prepared by reacting the compound of Formula 2 with hydrogen bromide in the presence of a solvent according to the present invention.
  • the reaction is described in the following reaction scheme.
  • hydrogen bromide may be used as hydrogen bromide gas in an appropriate solvent or as a hydrogen bromide solution dissolved in acetic acid. Hydrogen bromide is preferably used in excess and more preferably in an amount of 3 to 5 equivalents.
  • the reaction can be carried out at a temperature ranging from 0 to 40°C, preferably at a temperature of 5 to 25°C, more preferably at a temperature of 5 to 15°C.
  • hydrogen bromide gas When hydrogen bromide gas is used in the reaction, hydrogen bromide gas is passed through the solution in which the compound of Formula 2 is dissolved.
  • hydrogen bromide solution When hydrogen bromide solution is used, hydrogen bromide/acetic acid solution is added to the solution in which the compound of Formula 2 is dissolved. Alternatively, the solution in which the compound of Formula 2 is dissolved may be added to the hydrogen bromide/acetic acid solution.
  • any conventional solvent which does not participate in the reaction can be used in the reaction.
  • Preferable solvents are alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene, toluene and xylene; tetrahydrofuran or dichloromethane.
  • the solvent used in the preparation of the starting material of Compound 2 may also be used in the reaction without change.
  • the compound of Formula 2 which is used for the preparation of the compound of Formula 1 is a novel alkylthioolefin derivative.
  • the present invention provides the compound of Formula 1 and a method of preparing the same.
  • the compound of Formula 2 according to the present invention can be prepared through Knovenagel condensation reaction by reacting the compound of Formula 14 and the compound of Formula 15 along with an organic acid and organic base under the condition of solvent reflux (Name Reactions and Reagents in Organic Synthesis, Mundy, B.P.; Ellerd, M.G., John Wiley & Sons, Inc. 1988). The reaction is described in the following reaction scheme.
  • the detailed reaction condition is as follows. Any conventional solvent which does not participate in the reaction can be used in the reaction.
  • Preferable solvents are aromatic hydrocarbons such as benzene, toluene and xylene.
  • the reaction temperature is maintained to remove water under the condition of solvent reflux.
  • a combination of an organic acid such as acetic acid, benzoic acid or propanoic acid and a secondary amine organic base such as morpholine, pyrrolidine, piperidine, dimethylamine, diethylamine or N-methylaniline is used in the reaction.
  • the organic acid can be used in a catalytic amount of 0.01 equivalent to an amount of 3 equivalents, preferably in an amount of 0.1 to 2 equivalents.
  • the organic base can be used in a catalytic amount of 0.01 equivalent to an amount of 3 equivalents, preferably in an amount of 0.2 to 2 equivalents.
  • the reaction is carried out at a temperature ranging from 100 to 150°C under reflux while the side product water is removed.
  • the compound of Formula 14 for the preparation of the compound of Formula 2 according to the present invention can be commercially obtained or can be simply prepared through a conventional nucleus substitution reaction by reacting the compound of Formula 16 with chloroacetonitrile.
  • the compound of Formula 15 is a known compound which can be commercially obtained or can be prepared by using a conventional synthetic process ( Helv. Chim. Acta. 1999, 82, 326; Justus Liebigs Annalen der Chemie , 1950, 568 34).
  • the key intermediate of Formula 1 for producing flucetosulfuron can be prepared through a simple processing step without using ultralow temperature condition, with a yield equivalent or superior to those of conventional methods.
  • Example 1-1 After 5-[methyl(phenyl)amino]-2-(propan-2-ylsulfanyl)penta-2,4-dienenitrile (14.9 g, 57.8 mmol) obtained in Example 1-1 was dissolved in the mixture of toluene (50 mL) and ethanol (50 mL), hydrogen bromide gas was introduced thereto at room temperature for 2 hours while stirring the mixture. After the termination of the reaction, nitrogen gas was introduced for 1 hour to remove the excess hydrogen bromide gas. After water (70 mL) was added to the mixture to separate layers, the organic layer was washed sequentially with 20% sodium hydroxide solution and water, and then distilled under reduced pressure. The resultant was purified by silica gel column chromatography to obtain the title compound (10.7 g, 80% yield).
  • the compound of Formula 1 can be prepared, through a simple processing step, with a yield equivalent or superior to those of conventional methods.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur un nouveau procédé pour la préparation d'un composé pyridine intermédiaire clé pour la production de dérivés de fluoroalkylpyridine-sulfonylurée présentant une activité herbicide supérieure, sur de nouveaux dérivés d'alkylthiooléfine utilisés dans la préparation et sur un procédé pour la préparation de ceux-ci. Selon le présent procédé utilisant les nouveaux dérivés d'alkylthiooléfine de formule 2, le composé intermédiaire de formule 1 pour la production de flucétosulfuron peut être préparé, grâce à une étape de traitement simple, avec un rendement équivalent ou supérieur à ceux de procédés classiques.
PCT/KR2014/009508 2013-10-11 2014-10-10 Procédé pour la préparation de 3-alkylthio-2-bromopyridine WO2015053576A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201480054868.8A CN105636938B (zh) 2013-10-11 2014-10-10 制备3-烷硫基-2-溴吡啶的方法
JP2016521955A JP6257115B2 (ja) 2013-10-11 2014-10-10 ３−アルキルチオ−２−ブロモピリジンの製造方法

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KR10-2013-0121556 2013-10-11
KR20130121556 2013-10-11

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WO2015053576A1 true WO2015053576A1 (fr) 2015-04-16

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KR (1) KR101603324B1 (fr)
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CN106866515B (zh) * 2017-02-10 2019-05-28 山东师范大学 一种磺酰基吡啶衍生物及其合成方法
CN106866514B (zh) * 2017-02-10 2019-05-28 山东师范大学 一种水相法合成2-卤代-3-取代烃基磺酰基吡啶及其中间体的方法

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KR101603324B1 (ko) 2016-03-14
JP2016538251A (ja) 2016-12-08
CN105636938B (zh) 2018-09-07
CN105636938A (zh) 2016-06-01
JP6257115B2 (ja) 2018-01-10
KR20150042736A (ko) 2015-04-21

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