WO2017126197A1 - 2-アミノニコチン酸ベンジルエステル誘導体の製造方法 - Google Patents
2-アミノニコチン酸ベンジルエステル誘導体の製造方法 Download PDFInfo
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- 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
- C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- 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
- C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Definitions
- the present invention relates to a method for producing a 2-aminonicotinic acid benzyl ester derivative. Specifically, the present invention provides 2-aminonicotinic acid benzyl ester derivative, which is a useful compound as an active ingredient of agricultural fungicides, in high yield and high purity, and has high volumetric efficiency and little impact on the environment.
- the present invention relates to an industrial manufacturing method.
- a carboxylic acid derivative is converted to an acid chloride using a halogenating agent and reacted with an alcohol derivative in an organic solvent in the presence of a base, or a carboxylic acid derivative and an alcohol derivative are reacted.
- a method of reacting with a condensing agent in an organic solvent is known.
- Patent Document 1 discloses a method for producing a 2-aminonicotinic acid ester derivative represented by the following reaction formula as a method for producing a 2-aminonicotinic acid ester derivative.
- M is an alkali metal
- X is a halogen atom.
- the method of Patent Document 1 can produce a 2-aminonicotinic acid ester derivative with high yield and high purity, the viscosity of the reaction solution tends to increase, and the volumetric efficiency of production is increased to 10% or more. Difficult to do.
- a polar solvent that is soluble in water it is not possible to wipe away environmental concern materials in solvent recycling and waste liquid treatment after the reaction.
- Patent Document 1 It has been described in Patent Document 1 that a conventional method for producing an ester derivative is not preferable in the production of a 2-aminonicotinic acid ester derivative in the prior art. That is, when the 2-aminonicotinic acid derivative is converted to acid chloride, the reaction solution turns brown, the target reaction hardly proceeds, and the amount of by-products increases. Further, the reaction using a condensing agent is not completed.
- the method described in Patent Document 1 is not necessarily an optimal manufacturing method because of low volumetric efficiency and environmental impact. Therefore, in addition to obtaining the target product with high yield and high purity, it has been desired to develop an industrial production method with high volumetric efficiency and less environmental impact.
- the present inventors have used 2-aminonicotinic acid derivatives and benzyl derivatives using an aromatic hydrocarbon solvent in the presence of a phase transfer catalyst or a catalytic amount of a tertiary amine.
- the present inventors have found a method of reacting at a high concentration and have reached the present invention.
- the present invention provides the following formula [I]: (Wherein R 1 represents a hydrogen atom or a C 1 -C 4 alkyl group, M represents hydrogen or an alkali metal), and the following formula [II]: (Wherein R 2 represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group or a C 1 -C 4 alkoxy group, A represents a nitrogen atom or a methine group (CH), and X represents a hydroxyl group or Represents a halogen atom, and Y represents an oxygen atom, a methylene group (CH 2 ) or a methyleneoxy group (OCH 2 ).
- the volumetric efficiency and the burden on the environment are reduced as compared with the conventional technique. That is, by using an aromatic hydrocarbon solvent, which is a poor solvent, compared to a polar solvent, the viscosity does not increase even in a high concentration slurry, the stirrability is maintained, and the productivity when using the same manufacturing apparatus is increased. improves.
- aromatic hydrocarbon solvents are easy to reuse, they are also useful for reducing the environmental burden.
- examples of the C 1 -C 4 alkyl group represented by R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
- halogen atom represented by R 2 and X for example, fluorine atom, chlorine atom, bromine atom, iodine atom
- C 1 -C 4 alkoxy group represented by R 2 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, A tert-butoxy group is exemplified, and examples of the alkali metal represented by M include sodium and potassium.
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used in an aromatic hydrocarbon solvent such as benzene, toluene or xylene.
- a base or alkali metal carbonate such as sodium carbonate or potassium carbonate is added to the above formula [I], for example, 1 to 10 times mol, preferably 1 to 5 times mol, for example, 0 to 100 ° C. For 1 to 1 hour, preferably at 20 to 60 ° C. for 5 to 30 minutes.
- X in the above formula [II] is a hydroxyl group, it is thionyl chloride in an aromatic hydrocarbon solvent such as benzene, toluene or xylene.
- the halogenating agent such as thionyl bromide or phosphorus oxychloride is, for example, 1.0-fold mol to 3.0-fold mol, preferably 1.0-fold mol to 1.times.
- Add 5 times mole Te for example, 5 minutes to 1 hour at -5 ⁇ 30 ° C., preferably may include a step of stirring for 10 minutes to 40 minutes at 0 ⁇ 25 ° C..
- a tertiary amine such as [2,2,2] octane is, for example, 0.001 mole to 0.1 mole, preferably 0.005 mole to 0.00 moles with respect to the compound of the formula [I]. Add 5 moles and add 5 to 10 hours at 0 to 130 ° C. Preferably, the mixture is stirred at 70 to 120 ° C.
- the reaction solution is distilled under reduced pressure to distill off the organic solvent, for example, 10 to 100%, and ice water is poured into the reaction solution.
- the amount of the aromatic hydrocarbon solvent used may be, for example, 3 to 5 times the maximum theoretical value that can be obtained for the target compound, and the volumetric efficiency is as high as about 20 to 35%.
- the aromatic hydrocarbon solvent can be easily distributed with water by distillation of the reaction solution or filtrate under reduced pressure, and the environmental burden can be reduced by reusing it.
- an aromatic hydrocarbon solvent used in the reaction of a compound in which M in the formula [I] is hydrogen and an alkali metal hydroxide, a compound of the formula [II] and a halogenating agent may be the same or different, but are preferably the same.
- the nicotinic acid derivative represented by the above formula [I] used in the production method of the present invention can be immediately synthesized from a known compound according to, for example, the method described in JP 2010-038661 A.
- the alcohol derivative in which X in the above formula [II] used in the production method of the present invention is a hydroxyl group is, for example, according to the method described in Journal of Medicinal Chemistry, 43, 1826 (2000), It can be synthesized immediately from known compounds.
- the compound of the above formula [III] produced in the production method of the present invention is useful as an agricultural fungicide.
- Table 1 below shows the data of the compounds 1 and 3 to 8 of the present invention produced by the same method as in Example 1 together with the compound 2 of the present invention.
- the production method of the present invention is a production method with high industrial value of 2-aminonicotinic acid benzyl ester derivative which is an agricultural fungicide.
Abstract
Description
で表されるベンジル誘導体を、
a)上記式[I]において、Mが水素の場合は塩基を用いて
b)上記式[II]において、Xが水酸基の場合はハロゲン化剤を用いて
反応させた後、相関移動触媒または三級アミン存在下、芳香族炭化水素溶媒中で反応させて、下式[III]:
上記式[I]、[II]および[III]において、R1およびR2で示されるC1~C4のアルキル基としては、例えば、メチル基や、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基などが挙げられ、R2およびXで示されるハロゲン原子としては、例えば、フッ素原子や、塩素原子、臭素原子、ヨウ素原子が挙げられ、R2で示されるC1~C4のアルコキシ基としては、例えば、メトキシ基や、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基が挙げられ、Mで示されるアルカリ金属としては、例えば、ナトリウムまたはカリウムが挙げられる。
本発明の製造方法において使用される上記式[II]のXが水酸基で表されるアルコール誘導体は、例えば、Journal of Medicinal Chemistry, 43巻, 1826頁(2000)に記載された方法に準じて、公知化合物から直ちに合成することができる。
本発明の製造方法において製造される上記式[III]の化合物は、農業用殺菌剤として有用である。
2-アミノ-6-メチルニコチン酸-4-フェノキシベンジルの合成
2-アミノ-6-メチルニコチン酸カリウム(0.95g)をトルエン(5mL)に懸濁し、(1-クロロメチル)-4-フェノキシベンゼン(1.10g)と18-クラウン-6エーテル(40mg)を加えて、105℃で6時間加熱撹拌した。反応液を室温まで冷却し、減圧下でトルエンを約80%留去した。残渣に氷水を加えて室温で20分間撹拌した。析出した結晶をろ取、乾燥して、目的物(表1記載の化合物2)1.52g(収率91.6%,容積効率33.4%)を得た。
1H-NMR (CDCl3) δppm: 2.38 (3H,s), 5.25 (2H,s), 6.06-6.72 (2H.br), 6.44 (1H,d), 6.99-7.04 (4H,m), 7.12 (1H,t), 7.31-7.41 (4H,m), 8.04 (1H,d)
2-アミノ-6-メチルニコチン酸-4-フェノキシベンジルの合成
2-アミノ-6-メチルニコチン酸カリウム(0.95g)をm-キシレン(5mL)に懸濁し、(1-クロロメチル)-4-フェノキシベンゼン(1.10g)とテトラメチルエチレンジアミン(19mg)を加えて、110℃で6時間加熱撹拌した。反応液を室温まで冷却し、減圧下でm-キシレンを約80%留去した。残渣に氷水を加えて室温で20分間撹拌した。析出した結晶をろ取、乾燥して、目的物(表1記載の化合物2)1.41g(収率84.4%,容積効率33.4%)を得た。
2-アミノ-6-メチルニコチン酸-4-フェノキシベンジルの合成
2-アミノ-6-メチルニコチン酸カリウム(0.95g)をm-キシレン(5mL)に懸濁し、(1-クロロメチル)-4-フェノキシベンゼン(1.10g)とテトラブチルアンモニウムブロミド(49mg)を加えて、110℃で6時間加熱撹拌した。反応液を室温まで冷却し、減圧下でm-キシレンを約90%留去した。残渣に氷水を加えて室温で20分間撹拌した。析出した結晶をろ取、乾燥して、目的物(表1記載の化合物2)1.55g(収率92.8%,容積効率33.4%)を得た。
2-アミノ-6-メチルニコチン酸-4-フェノキシベンジルの合成
2-アミノ-6-メチルニコチン酸(2.28g)をm-キシレン(15mL)に懸濁し、水酸化ナトリウム(1.20g)を加えて、40℃で30分間撹拌し、溶液1とした。一方、(4-フェノキシフェニル)メタノール(3.00g)をm-キシレン(5mL)に溶解し、氷冷下で塩化チオニル(1.1mL)を滴下し、室温に戻しながら30分間撹拌した。その反応液を溶液1に加え、テトラブチルアンモニウムブロミド(145mg)を加えて、110℃で6時間加熱撹拌した。反応液を室温まで冷却し、減圧下でm-キシレンを約90%留去した。残渣に氷水を加えて室温で30分間撹拌した。析出した結晶をろ取、乾燥して、目的物(表1記載の化合物2)4.17g(収率83.2%,容積効率20%)を得た。
2-アミノ-6-メチルニコチン酸-4-フェノキシベンジルの合成
2-アミノ-6-メチルニコチン酸(3.04g)をm-キシレン(20mL)に懸濁し、炭酸カリウム(4.15g)を加えて、40℃で30分間撹拌し、溶液1とした。一方、(4-フェノキシフェニル)メタノール(4.00g)をm-キシレン(7mL)に溶解し、氷冷下で塩化チオニル(1.46mL)を滴下し、室温に戻しながら30分間撹拌した。その後,系内の塩化水素,二酸化硫黄および塩化チオニルを留去し,溶液1に加え、テトラブチルアンモニウムブロミド(194mg)を加えて、110℃で4時間加熱撹拌した。反応液を室温まで冷却し、減圧下でm-キシレンを約95%留去した。残渣に氷水を加えて室温で30分間撹拌した。析出した結晶をろ取、乾燥して、目的物(表1記載の化合物2)6.39g(収率95.7%,容積効率25%)を得た。
Claims (3)
- 下式[I]:
で表されるベンジル誘導体を、
a)上記式[I]において、Mが水素の場合は塩基を用いて
b)上記式[II]において、Xが水酸基の場合はハロゲン化剤を用いて
反応させた後、相関移動触媒または三級アミン存在下、芳香族炭化水素溶媒中で反応させて、下式[III]:
- 下式[I]:
)で表される2-アミノニコチン酸無機塩誘導体、および、下式[II]:
- 下式[VI]:
で表される2-アミノニコチン酸誘導体、および、下式[VII]:
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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JP2017562446A JP6771775B2 (ja) | 2016-01-21 | 2016-11-08 | 2−アミノニコチン酸ベンジルエステル誘導体の製造方法 |
CN201680076095.2A CN108473431B (zh) | 2016-01-21 | 2016-11-08 | 2-氨基烟酸苄酯衍生物的制造方法 |
RU2018130080A RU2702121C1 (ru) | 2016-01-21 | 2016-11-08 | Способ получения производного бензилового эфира 2-аминоникотиновой кислоты |
BR112018013541-0A BR112018013541B1 (pt) | 2016-01-21 | 2016-11-08 | Método para produzir um derivado do éster benzílico do ácido 2-aminonicotínico |
US15/781,302 US10442768B2 (en) | 2016-01-21 | 2016-11-08 | Method for producing 2-aminonicotinic acid benzyl ester derivative |
KR1020187023670A KR102157528B1 (ko) | 2016-01-21 | 2016-11-08 | 2-아미노니코틴산 벤질에스테르 유도체의 제조 방법 |
EP16886436.1A EP3406595B1 (en) | 2016-01-21 | 2016-11-08 | Method for producing 2-aminonicotinic acid benzyl ester derivative |
ZA2018/05438A ZA201805438B (en) | 2016-01-21 | 2018-08-15 | Method for producing 2-aminonicotinic acid benzyl ester derivative |
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EP (1) | EP3406595B1 (ja) |
JP (1) | JP6771775B2 (ja) |
KR (1) | KR102157528B1 (ja) |
CN (1) | CN108473431B (ja) |
RU (1) | RU2702121C1 (ja) |
TW (1) | TWI631104B (ja) |
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ZA (1) | ZA201805438B (ja) |
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WO2014006945A1 (ja) * | 2012-07-04 | 2014-01-09 | アグロカネショウ株式会社 | 2-アミノニコチン酸エステル誘導体およびこれを有効成分とする殺菌剤 |
JP2015030693A (ja) * | 2013-08-01 | 2015-02-16 | アグロカネショウ株式会社 | 2−アミノニコチン酸ベンジル誘導体およびこれを有効成分とする殺菌剤 |
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2016
- 2016-11-08 RU RU2018130080A patent/RU2702121C1/ru active
- 2016-11-08 EP EP16886436.1A patent/EP3406595B1/en active Active
- 2016-11-08 JP JP2017562446A patent/JP6771775B2/ja active Active
- 2016-11-08 CN CN201680076095.2A patent/CN108473431B/zh active Active
- 2016-11-08 WO PCT/JP2016/083100 patent/WO2017126197A1/ja active Application Filing
- 2016-11-08 US US15/781,302 patent/US10442768B2/en active Active
- 2016-11-08 KR KR1020187023670A patent/KR102157528B1/ko active IP Right Grant
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- 2017-01-18 TW TW106101633A patent/TWI631104B/zh active
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JPH04108793A (ja) * | 1990-08-28 | 1992-04-09 | Yodogawa Seiyaku Kk | ペニシリン類のエステル化方法 |
JP2001501630A (ja) * | 1996-10-04 | 2001-02-06 | ハー・ルンドベック・アクティーゼルスカブ | 3―アルコキシイソオキサゾール―4―イル―置換された2―アミノカルボン酸化合物 |
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KR20180099888A (ko) | 2018-09-05 |
JP6771775B2 (ja) | 2020-10-21 |
ZA201805438B (en) | 2019-06-26 |
TW201726624A (zh) | 2017-08-01 |
JPWO2017126197A1 (ja) | 2018-11-15 |
EP3406595A4 (en) | 2019-06-12 |
BR112018013541A2 (ja) | 2018-12-04 |
US20180362464A1 (en) | 2018-12-20 |
EP3406595B1 (en) | 2020-04-01 |
EP3406595A1 (en) | 2018-11-28 |
CN108473431A (zh) | 2018-08-31 |
CN108473431B (zh) | 2021-08-10 |
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