JPH03181464A - Nicotinic acid derivative having substituted group and production thereof - Google Patents
Nicotinic acid derivative having substituted group and production thereofInfo
- Publication number
- JPH03181464A JPH03181464A JP32050689A JP32050689A JPH03181464A JP H03181464 A JPH03181464 A JP H03181464A JP 32050689 A JP32050689 A JP 32050689A JP 32050689 A JP32050689 A JP 32050689A JP H03181464 A JPH03181464 A JP H03181464A
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- formula
- formulas
- tables
- general formula
- same meaning
- 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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Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical class OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 3
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims abstract description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000002363 herbicidal effect Effects 0.000 abstract description 4
- 239000004009 herbicide Substances 0.000 abstract description 4
- 239000012046 mixed solvent Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 2
- HUYBFOHLVMQBPF-UHFFFAOYSA-N 2-methyl-6-methylsulfanylpyridine-3-carboxylic acid Chemical compound CSC1=CC=C(C(O)=O)C(C)=N1 HUYBFOHLVMQBPF-UHFFFAOYSA-N 0.000 description 1
- -1 2-methyl-6-methylsulfonylnicotinic acid ethyl ester Chemical compound 0.000 description 1
- FOSKDLKQVBAAKP-UHFFFAOYSA-N 2-methyl-6-methylsulfonylpyridine-3-carboxylic acid Chemical compound CC1=C(C(=O)O)C=CC(=N1)S(=O)(=O)C FOSKDLKQVBAAKP-UHFFFAOYSA-N 0.000 description 1
- XOGTZOOQQBDUSI-UHFFFAOYSA-M Mesna Chemical compound [Na+].[O-]S(=O)(=O)CCS XOGTZOOQQBDUSI-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical class O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QTQNOBVKWYIKMP-UHFFFAOYSA-N ethyl 2-methyl-1-oxidopyridin-1-ium-3-carboxylate Chemical compound CCOC(=O)C1=CC=C[N+]([O-])=C1C QTQNOBVKWYIKMP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960004635 mesna Drugs 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
農医薬中間体、特に除草剤の中間体として有用な新規な
化合物及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel compound useful as an agrochemical intermediate, particularly a herbicide intermediate, and a method for producing the same.
〔従来の技術及び発明が解決しようとする課題〕１．３
−シクロヘキサンジオンｌｊ”１３体（例えばＢＰ−３
１６４９１など）、が除草剤として有用であることが知
られており、置換ピコリン酸が中間体として用いられて
いる。[Problems to be solved by conventional technology and invention] 1.3
-13 cyclohexanedione lj'' bodies (e.g. BP-3
16491) are known to be useful as herbicides, and substituted picolinic acids are used as intermediates.
本発明者等は上記、置換ピコリン酸のかわりに置換ニコ
チン酸を中間体として用い、同様のｌ、３−シクロヘキ
サンジオン誘導体を製造した場合、公知化合物より優れ
た除草活性があることを見い出した。The present inventors have found that when a similar 1,3-cyclohexanedione derivative is produced by using substituted nicotinic acid as an intermediate instead of the above-mentioned substituted picolinic acid, it has a herbicidal activity superior to that of known compounds.
本発明は、
（＋） 一般弐（１）
Ｒ＋
〔式中、Ｒは水素又はアルキル、旧はシアノ、−ｚ−Ｒ
ｔ （ここでＺは酸素又は−３（０）ｍ−を示し、Ｒ
ｔはアルキル、アルケニル、フェニル、置換フェニル、
ベンジル、置換へテロ環、アルコキシアルキル、又はア
ルキルチオアルキルを、ｍは０、ｌ又は２を示す、）を
示す、〕で表わされる化合物及びその製造方法である。The present invention provides (+) General 2 (1) R+ [wherein R is hydrogen or alkyl, formerly cyano, -z-R
t (where Z represents oxygen or -3(0)m-, R
t is alkyl, alkenyl, phenyl, substituted phenyl,
benzyl, substituted heterocycle, alkoxyalkyl, or alkylthioalkyl, m represents 0, 1, or 2), and a method for producing the same.
本発明の化合物は次のようにして製造される。The compound of the present invention is produced as follows.
（１）
（旧 （ＩＩＩ） （１’）Ｘはハロゲ
ン、又はシアノ、Ｍはアルカリ金属を示し、Ｒ，Ｒｘ
、Ｚは前記と同じ意味を示す。(1) (Old (III) (1') X is halogen or cyano, M is alkali metal, R, Rx
, Z have the same meanings as above.
溶媒としてはＤＭＦ、低級アルコール等の水と混和する
溶媒もしくはそれらと水との混合溶媒中で０〜７０℃、
好ましくは室温で行われる。The solvent is 0 to 70°C in a water-miscible solvent such as DMF, lower alcohol, or a mixed solvent of these and water.
Preferably it is carried out at room temperature.
尚、本製造方法において、ＲとＲ１が異なる場合には、
エステル交換によりＲがＲ２に置換される場合もある。In addition, in this manufacturing method, if R and R1 are different,
In some cases, R is substituted with R2 by transesterification.
（２）
（ＴＶ） （Ｖ） （以下ＴＭＳＣＮと略す）
〔１”〕反応はトリエチルアミン等の塩基の存在下
アセトニトリル等の溶媒中加熱、好ましくは加熱還流下
行うか、Ｎ５Ｎ−ジメチルカルバモイルクロライドの存
在下塩化メチレン等の非水系溶媒中Ｏ〜室温好ましくは
室温で行われる。(2) (TV) (V) (hereinafter abbreviated as TMSCN)
[1”] The reaction is carried out in the presence of a base such as triethylamine in a solvent such as acetonitrile by heating, preferably under heating and reflux, or in the presence of N5N-dimethylcarbamoyl chloride in a non-aqueous solvent such as methylene chloride at 0 to room temperature, preferably at room temperature. It will be done.
（３） （ＩＶ） （Ｖｌ） （１”’ ） 「は低級アルキル、Ｒは前記と同じ意味を示す。(3) (IV) (Vl) (1”’) " is lower alkyl, and R has the same meaning as above.
（２）と同様な方法で製造される。It is manufactured in the same manner as (2).
〔■〕〔■４°〕
ｌはｌ又は２を、Ｒ，Ｒ，は前記と同じ意味を示す、過
酸化水素、過硫酸カリ（２ＫＨ３Ｏ。[■] [■4°] 1 stands for 1 or 2, R and R have the same meanings as above, hydrogen peroxide, potassium persulfate (2KH3O).
Ｋ ＨＳ Ｏ、・Ｋｇ Ｓ ０４ ） 、過酸等の酸化
剤の存在下、水もしくは酢酸等の水と混和する溶媒又は
これと水との混合溶媒中で室温〜８０°Ｃで行われる。K HSO, .Kg S 04 ), in the presence of an oxidizing agent such as peracid, in water, a water-miscible solvent such as acetic acid, or a mixed solvent of this and water at room temperature to 80°C.
（１”） 〔■１〕 ｒｏはアルキル、Ｒ１は前記と同し意味を示す。(1”) [■1] ro is alkyl, and R1 has the same meaning as above.
水又は含水系溶媒中、好ましくは室温でアルカリを作用
させて行われる。It is carried out in water or a water-containing solvent, preferably at room temperature, by the action of an alkali.
いずれの方法で反応した場合も反応終了後は、通常の後
処理を行うことにより目的物を得ることができる。Regardless of the reaction method used, after the reaction is completed, the desired product can be obtained by performing normal post-treatments.
本発明化合物の構造は、ＩＲ，ＮＭＲ，ＭＳ等から決定
した。The structure of the compound of the present invention was determined from IR, NMR, MS, etc.
次に実施例を挙げ、本発明を更に具体的に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１
（１） ２−メチル−６−クロロニトチン酸エチルエ
ステル（以下上という）４ｇ（０，０２モル）をｌＯｄ
のＤＭＦに溶かし、室温でＭｅＳＮａの１５％水溶液２
２ｇ（０，０４７モル）を滴下０滴下巾約２０℃の発熱
があった。室温で５時間攪拌後エステル交換Ｍ１で３回
抽出し、水、飽和食塩水で洗浄し、無水Ｍ ｇ Ｓ Ｏ
ａで乾燥した０Ｍｇ５Ｏａを濾過した後濾液を減圧留去
し、２−メチル−２−メチルメルカプトニドチン酸エチ
ルエステル（以下上という）を２．２ｇ得た。Example 1 (1) 4 g (0.02 mol) of 2-methyl-6-chloronitotinic acid ethyl ester (hereinafter referred to as above) was added to lOd
A 15% aqueous solution of MeSNa 2 dissolved in DMF at room temperature.
When 2 g (0,047 mol) was added dropwise, an exotherm of about 20° C. was generated. After stirring at room temperature for 5 hours, the mixture was extracted with transesterified M1 three times, washed with water and saturated brine, and then extracted with anhydrous MgSO.
After filtering the 0Mg5Oa dried in a, the filtrate was distilled off under reduced pressure to obtain 2.2 g of 2-methyl-2-methylmercaptonide tinic acid ethyl ester (hereinafter referred to as above).
（２） 粉末Ｍ６ｓＮａをＤＭＦ３０−に溶かし、土
７．９８ ｇ （０，０４モル）とＤＭＦ４０ｍの溶
液にＯ°〜５℃下滴下するように約２０分間で加えた。(2) Powdered M6sNa was dissolved in DMF30- and added dropwise to a solution of 7.98 g (0.04 mol) of soil and 40 m of DMF at 0° to 5° C. over about 20 minutes.
０℃で１時間撹拌後氷に反応ｆａ液をあけ酢酸エチルで
２回抽出した。＃酸エチル層を水で３回、飽和食塩水で
１回洗浄後、無水Ｍ ｇ Ｓ Ｏａで乾燥した後溶媒を
減圧留去し残渣８ｇ！得た。そのうち７ｇをカラムクロ
マトで清製し、目的物６．５ｇｇ得たｅ ｎ ”’ ”
１．５６１３ ＠実施例２
２−メチルニコチン酸エチルエステルＮ−オキシド（以
下上という）１７．６ｇ（９７ミリモルンをＣＨ，ＣＩ
□ （５０ｍに溶解し、９８％ＴＭＳＣＮ夏１．８ｇ（
１１７ミリモル）を加え、室温で５分間攪拌、さらにＭ
ｅ ｔ Ｎ ＣＯＣ１！ １２．６８（１１３４９モ
ル）を加え、室温で１８時ｌ？ｎ撹拌した。その後、５
℃に冷却し２０％に！ ｃｏ。After stirring at 0°C for 1 hour, the reaction fa solution was poured into ice and extracted twice with ethyl acetate. #After washing the ethyl acid layer three times with water and once with saturated brine, drying with anhydrous MgS Oa, the solvent was distilled off under reduced pressure, leaving 8 g of residue! Obtained. 7g of it was purified using column chromatography to obtain 6.5g of the target product.
1.5613 @Example 2 17.6 g of 2-methylnicotinic acid ethyl ester N-oxide (hereinafter referred to as above) (97 mmol was converted into CH, CI
□ (Dissolved in 50m, 98% TMSCN Summer 1.8g (
117 mmol), stirred at room temperature for 5 minutes, and further added M
et N COC1! 12.68 (11349 mol) was added and the solution was heated at room temperature for 18 hours. n stirred. After that, 5
Cool to ℃ to 20%! co.
水溶液１００ ｔａｌを加えた反応終了後、有機層を飽
和食塩水で洗浄し、無水ＪＳＯ，で乾燥後、溶媒で減圧
下除去した。残渣をカラムクロマトで精製し、２−メチ
ル−６−ジアツニコチン酸エチルエステル（以下土とい
う）１５．９ｇを得たａｍ９６５〜６６．５℃。After the reaction was completed by adding 100 tal of an aqueous solution, the organic layer was washed with saturated brine, dried over anhydrous JSO, and then removed with a solvent under reduced pressure. The residue was purified by column chromatography to obtain 15.9 g of 2-methyl-6-diatunicotinic acid ethyl ester (hereinafter referred to as soil) at 965-66.5°C.
実施例３
！ ３１ｇ（０，１７モル）とＣＨｔ ＣＩｔ Ｉ ５
０ｄの溶液にＣＩＣＣｌＣ０Ｎ １８．４ｇ （０，
１７モル）を加え、初め加熱し、その後１５分間室温で
攪拌した後氷水で冷却し７７％の（ＣＨｒ）ｓＳ ｉ
５ＣＨｓ ２７ ｇとｃｌ、ＣＩ、５０ｄｃＤ溶液を加
え、室温で１日撹拌した。氷−Ｋｇ Ｃｏ、水にあけ有
機層を水洗、ＭｇＳＯ４で乾燥ｆ＆溶媒を留去し、残渣
４２ｇを得た。残渣をカラムクロマトで精製し、目的物
８．５ｇを得た。 ｎ””１．５６１３゜
実施例４
ｉ８．５ ｇ （０，０４モル）をメタノール４００−
に溶かし、２ＫＨ３Ｏ−ＫＨ３Ｏ，・ＫａＳｏ。Example 3! 31 g (0.17 mol) and CHt CIt I 5
18.4 g of CICCClC0N (0,
17 mol) was added, first heated, then stirred at room temperature for 15 minutes, cooled with ice water, and diluted with 77% (CHr)sSi.
A solution of 27 g of 5CHs, Cl, CI, and 50 dcD was added, and the mixture was stirred at room temperature for one day. The organic layer was poured into ice-Kg Co and water, washed with water, dried with MgSO4, and the solvent was distilled off to obtain 42 g of a residue. The residue was purified by column chromatography to obtain 8.5 g of the target product. n''''1.5613゜Example 4 i8.5 g (0.04 mol) was dissolved in methanol 400-
2KH3O-KH3O, .KaSo.
４９、６ ｇの水層４００ｓｄの水溶液を１０℃で約！
時間かけて加えた。その後、室温まで昇温し、２時間半
攪拌した後、不溶物を濾過し、濾液を減圧下′ａ縮し、
酢酸エチルで抽出、有機層を水、飽和食塩水で洗浄した
後、Ｍ ｇ Ｓ Ｏａで乾燥した０Ｍｇ５０４を除去し
た後、溶媒を留去し、２−メチル−６−メチルスルホニ
ルニコチン酸エチルエステル（以下上という）９．０ｇ
を得た。ｎ１１１．５２２９゜
実施例５
２ ２．２ｇ（０，０１モル）を２Ｎ−ＮａＯＨ水溶液
中室温で２４時間加水分解した。その後、塩酸、酢酸で
酸性にし、酢酸エチルで抽出、有機層に飽和食塩水で洗
浄後無水Ｍ ｇ Ｓ Ｏａで乾燥ＭｇＳＯ４を除去した
後、溶媒を減圧下一部留去し、残液にヘキサンを加え、
析出した結晶を濾取し、２−メチル−６−メチルメルカ
プトニコチン酸１゜７ｇを得た。ｍｐ１８３．５〜１８
５°Ｃ０実施例６
ｉ １０ｇ（０，０４１モル）をメタノール４０−に溶
解し、９５％ＮａＯＨ２，６ｇ （６１，［１３リモル
）の水３０ｍ水溶液を室温で加え４時間攪拌した。メタ
ノールを減圧下除去し、酢酸エチルで洗浄した。水層を
塩酸で酸性にし、酢酸エチルで抽出し、水、飽和食塩水
で洗浄後Ｍ ｇ Ｓ Ｏａで乾燥し、溶媒を減圧下除去
し、２−メチル−６−メチルスルホニルニコチン酸７．
８ｇを得た。ｍｐ１４０〜１４２℃。49. 6 g of water layer 400 sd aqueous solution at 10℃ approx.!
I added it over time. After that, the temperature was raised to room temperature, and after stirring for 2 and a half hours, insoluble matter was filtered, and the filtrate was condensed under reduced pressure.
After extraction with ethyl acetate, the organic layer was washed with water and saturated brine, and after removing 0Mg504, which was dried over MgSOa, the solvent was distilled off, and 2-methyl-6-methylsulfonylnicotinic acid ethyl ester ( (hereinafter referred to as above) 9.0g
I got it. n111.5229° Example 5 2.2 g (0.01 mol) of 2 was hydrolyzed in a 2N aqueous NaOH solution at room temperature for 24 hours. Thereafter, it was made acidic with hydrochloric acid and acetic acid, extracted with ethyl acetate, the organic layer was washed with saturated brine, dried MgSO4 was removed with anhydrous MgS Oa, the solvent was partially distilled off under reduced pressure, and the remaining liquid was added with hexane. Add
The precipitated crystals were collected by filtration to obtain 1.7 g of 2-methyl-6-methylmercaptonicotinic acid. mp183.5-18
5°C0 Example 6 i 10g (0,041 mol) was dissolved in 40ml of methanol, a 30ml aqueous solution of 95% NaOH 2.6g (61, [13 mol)] was added at room temperature, and the mixture was stirred for 4 hours. Methanol was removed under reduced pressure and washed with ethyl acetate. The aqueous layer was acidified with hydrochloric acid, extracted with ethyl acetate, washed with water and saturated brine, dried over MgS Oa, the solvent was removed under reduced pressure, and 2-methyl-6-methylsulfonylnicotinic acid 7.
8g was obtained. mp140-142℃.
実施例７
新しく調製したナトリウムメトキシド２．３８ｇ（０，
０４４モル）を０ＭＦ２０ｄに溶解させ、土３．８ｇ（
０，０２モル）のＤＭＦ溶液１０−を室温で滴下した０
滴下後、室温で４時間攪拌した０反応終了後、反応液を
氷水に注入し、次いで得られた溶液を酢酸エチルで抽出
、有機層を水洗、次いでＭ ｇ Ｓ Ｏａで乾燦し、溶
媒を減圧下留去し、粗生成物を得た。シリカゲルカラム
クロマトにて精製し、油状の２−メチル−６−メドキシ
ニコチン酸メチルエステル（以下上という）２ｇ、ｎ”
１．５１５５を得た。Example 7 2.38 g of freshly prepared sodium methoxide (0,
044 mol) was dissolved in 0MF20d, and 3.8 g of soil (
0.02 mol) DMF solution 10- was added dropwise at room temperature.
After the dropwise addition, the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the reaction solution was poured into ice water, and the resulting solution was extracted with ethyl acetate. The organic layer was washed with water, and then dried with MgS Oa to remove the solvent. The residue was distilled off under reduced pressure to obtain a crude product. Purified with silica gel column chromatography to obtain oily 2-methyl-6-medoxynicotinic acid methyl ester (hereinafter referred to as above) 2g, n''
1.5155 was obtained.
実施例８
７０ｄのメタノールにナトリウム金属２．９ｇ（０，１
２６モル）を溶解させ、得られた溶液に土５ｇ（０，０
２５モル）のメタノール溶液３０ｍを室温で滴下した０
滴下後、室温で１０時間攪拌した０反応終了後、塩酸で
中和し、溶媒を減圧下留去した。残留物に水を加え、重
曹水で弱アルカリにし、酢酸エチルで抽出した。有機層
を飽和食塩水で洗浄、次いでＭｇ５Ｏ，にて乾燥した。Example 8 2.9 g of sodium metal (0,1
26 moles) and 5 g of soil (0,0
25 mol) of methanol solution was added dropwise at room temperature.
After the dropwise addition, the mixture was stirred at room temperature for 10 hours. After the reaction was completed, the mixture was neutralized with hydrochloric acid, and the solvent was distilled off under reduced pressure. Water was added to the residue, made weakly alkaline with aqueous sodium bicarbonate solution, and extracted with ethyl acetate. The organic layer was washed with saturated brine and then dried over Mg5O.
溶媒を減圧下留去し、油状物１．９７ ｇを得た。ＮＭ
Ｒ，ＴＬＣより実施例７に於いて得られた化合物上と一
敗した。The solvent was distilled off under reduced pressure to obtain 1.97 g of an oily substance. N.M.
R, TLC showed that the compound obtained in Example 7 was superior to that of the compound obtained in Example 7.
本発明化合物は工業的に有利に合成でき、農医薬中間体
、特に除草剤用中間体として有用である。The compounds of the present invention can be industrially advantageously synthesized and are useful as agricultural and pharmaceutical intermediates, particularly herbicide intermediates.
Claims (6)
−Ｚ−Ｒ＿２（ここでＺは酸素又は−Ｓ（Ｏ）ｍ−を示
し、Ｒ＿２はアルキル、アルケニル、フェニル、置換フ
ェニル、ベンジル、置換ヘテロ環、アルコキシアルキル
、又はアルキルチオアルキルを、ｍは０、１又は２を示
す。）を示す。〕で表わされる化合物。(1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R is hydrogen or alkyl, R_1 is cyano, or -Z-R_2 (here, Z is oxygen or -S( O) m-, R_2 represents alkyl, alkenyl, phenyl, substituted phenyl, benzyl, substituted heterocycle, alkoxyalkyl, or alkylthioalkyl, and m represents 0, 1 or 2.] Compound.
じ意味を示す。）で表わされる化合物と一般式〔III〕 Ｒ＿２−Ｚ−Ｍ〔III〕 （式中、Ｍはアルカリ金属を示し、Ｒ＿２は前記と同じ
意味を示す。）で表わされる化合物を反応させることか
らなる。 一般式〔 I ’〕 ▲数式、化学式、表等があります▼〔 I ’〕 （式中、Ｒ、Ｒ＿２、Ｚは前記と同じ意味を示す。）で
表われる化合物の製造方法。(2) General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, X represents halogen or cyano, and R has the same meaning as above.) Compounds and general formulas represented by [III] R_2-Z-M [III] (wherein M represents an alkali metal and R_2 has the same meaning as above) is reacted. General formula [I'] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I'] (In the formula, R, R_2, and Z have the same meanings as above.) A method for producing a compound represented by the following.
I ”〕 ▲数式、化学式、表等があります▼〔 I ’〕 （式中、Ｒは前記と同じ意味を示す。）で表わされる化
合物の製造方法。(3) General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] (In the formula, R has the same meaning as above) and the formula [V] (CH_3)_3SiCN[V] General formula consisting of reacting the compounds [
I ''] ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I'〕 (In the formula, R has the same meaning as above.) A method for manufacturing the compound represented by the formula.
物を反応させることからなる一般式〔 I ’”〕▲数式
、化学式、表等があります▼〔 I ’”〕 （式中、Ｒ、ｒは前記と同じ意味を示す。）で表わされ
る化合物の製造方法。(4) General formula [VI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] (In the formula, R has the same meaning as above.) and general formula [VI] (CH_3)_3Si-Sr [VI] (In the formula, r represents lower alkyl.) A general formula [ I '”] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I '”] (In the formula, R, r has the same meaning as above).
される化合物を酸化させることからなる一般式〔 I ”
〕 ▲数式、化学式、表等があります▼〔 I ＾４’〕 （式中、Ｒ、Ｒ＿２は前記と同じ意味を示し、ｌは１又
は２を示す。）で表われる化合物の製造方法。(5) General formula [VII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [VII] A general formula consisting of oxidizing the compound represented by (in the formula, R and R_2 have the same meanings as above) I”
] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ^4' ] (In the formula, R and R_2 have the same meanings as above, and l indicates 1 or 2.) A method for producing a compound represented by the formula.
す。）で表わされる化合物を加水分解することからなる
一般式〔 I ＾６’〕 ▲数式、化学式、表等があります▼〔 I ＾６’〕 （式中、Ｒ＿１は前記と同じ意味を示す。）で表わされ
る化合物の製造方法。(6) Compounds represented by the general formula [I ^5'] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I ^5'] (In the formula, r' is alkyl, and R_1 has the same meaning as above.) General formula [ I ^6'] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ^6'] (In the formula, R_1 has the same meaning as above.) Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32050689A JP2861157B2 (en) | 1989-12-12 | 1989-12-12 | Nicotinic acid derivative having substituent and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32050689A JP2861157B2 (en) | 1989-12-12 | 1989-12-12 | Nicotinic acid derivative having substituent and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03181464A true JPH03181464A (en) | 1991-08-07 |
| JP2861157B2 JP2861157B2 (en) | 1999-02-24 |
Family
ID=18122212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32050689A Expired - Fee Related JP2861157B2 (en) | 1989-12-12 | 1989-12-12 | Nicotinic acid derivative having substituent and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2861157B2 (en) |
-
1989
- 1989-12-12 JP JP32050689A patent/JP2861157B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2861157B2 (en) | 1999-02-24 |
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