JPH03287576A - Production of quinolinic acid - Google Patents
Production of quinolinic acidInfo
- Publication number
- JPH03287576A JPH03287576A JP8943990A JP8943990A JPH03287576A JP H03287576 A JPH03287576 A JP H03287576A JP 8943990 A JP8943990 A JP 8943990A JP 8943990 A JP8943990 A JP 8943990A JP H03287576 A JPH03287576 A JP H03287576A
- Authority
- JP
- Japan
- Prior art keywords
- quinoline
- acid
- reaction
- chlorate
- aqueous medium
- 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.)
- Pending
Links
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 60
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims abstract description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012736 aqueous medium Substances 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 239000002253 acid Substances 0.000 abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000002609 medium Substances 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 230000011514 reflex Effects 0.000 abstract 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000004155 Chlorine dioxide Substances 0.000 description 9
- 235000019398 chlorine dioxide Nutrition 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- -1 vanadium ions Chemical class 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 4
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 229960003540 oxyquinoline Drugs 0.000 description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000004325 8-hydroxyquinolines Chemical class 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229940005989 chlorate ion Drugs 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LGDFHDKSYGVKDC-UHFFFAOYSA-N 8-hydroxyquinoline-5-sulfonic acid Chemical compound C1=CN=C2C(O)=CC=C(S(O)(=O)=O)C2=C1 LGDFHDKSYGVKDC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、感圧色素、医薬、農薬等に有用な中間体であ
るキノリン＃１．（別名２．３−ピリジンジカルボン酸
〉の新規の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides quinoline #1. This invention relates to a new method for producing 2,3-pyridinedicarboxylic acid (also known as 2,3-pyridinedicarboxylic acid).
（従来の技術）
キノリン酸の一般的合戒法としては、キノリン若しくは
そのベンゼン環部位を活性化した８−ヒドロキシキノリ
ン誘導体を酸化して得る方法がある。しかしながらこれ
までの合成法には種々の問題があった。(Prior Art) As a general method for producing quinolinic acid, there is a method of obtaining it by oxidizing quinoline or an 8-hydroxyquinoline derivative with its benzene ring moiety activated. However, conventional synthesis methods have had various problems.
例えばキノリンをアルカリ媒体中過マンガン酸カリウム
で酸化する方法（Ｂｅｒ、Ｄｔｓｃｈ、Ｃｈｅｍ、Ｇｅ
ｓ、 。For example, oxidation of quinoline with potassium permanganate in an alkaline medium (Ber, Dtsch, Chem, Ge
s.
土！、７４７ （１８７９））は、反応条件が厳しく、
選択性が非常に低く、多量の副生成物が生じるという欠
点がある。soil! , 747 (1879)), the reaction conditions were harsh;
The disadvantage is that the selectivity is very low and a large amount of by-products are produced.
キノリンを銅イオン存在下過酸化水素で酸化する方法（
Ｃｈｅ＋ｍ、Ｂｅｒ、、 ６５ 、１１ （１９３２
））は、操作が極めて困難な上過剰の酸化剤を用いるに
も拘わらず収率が十分でない。Method of oxidizing quinoline with hydrogen peroxide in the presence of copper ions (
Che+m, Ber, 65, 11 (1932
)) is extremely difficult to operate, and even though an excess of oxidizing agent is used, the yield is insufficient.
キノリンをルテニウム化合物存在下塩基性水媒体中次亜
塩素酸塩で酸化する方法（特開昭６０−８４２７０及び
特開昭６ｌ−２１２５６３）では工業的に人手容易な次
亜塩素酸ナトリウムを用いるが、その濃度５〜１５％と
希薄なことから、収量当りの反応容積が大きくなるとい
う欠点がある。In the method of oxidizing quinoline with hypochlorite in a basic aqueous medium in the presence of a ruthenium compound (JP-A-60-84270 and JP-A-6L-212563), sodium hypochlorite, which is industrially easy to handle, is used. , since its concentration is dilute at 5 to 15%, it has the disadvantage that the reaction volume per yield is large.
キノリンをバナジウムイオン等の陽イオンの存在下酸性
水媒体中過酸化水素で予備酸化した後塩素酸塩又は亜塩
素酸塩で酸化する方法（特開昭６Ｏ−１５６６７３）は
、反応の温度制御が極めて難しい上に、二段階の酸化が
必要で操作が面倒である。A method in which quinoline is pre-oxidized with hydrogen peroxide in an acidic aqueous medium in the presence of cations such as vanadium ions, and then oxidized with chlorate or chlorite (Japanese Patent Application Laid-open No. 6O-156673), allows temperature control of the reaction. In addition to being extremely difficult, it requires two stages of oxidation and is cumbersome to operate.
キノリンを酸性水媒体中塩素酸塩で酸化する方法（特開
昭６２−２０９０６３）は銅イオンの非存在下では収率
が低く、工業的に価値ある収率を得るためには、銅イオ
ン存在下で行わなければならない、従って、キノリン酸
は銅塩の形で得られるため、銅塩の分解工程が必要とな
る。The method of oxidizing quinoline with chlorate in an acidic aqueous medium (Japanese Unexamined Patent Publication No. 62-209063) has a low yield in the absence of copper ions, and in order to obtain an industrially valuable yield, it is necessary to Therefore, since quinolinic acid is obtained in the form of copper salts, a copper salt decomposition step is required.
８−ヒドロキシキノリン誘導体を酸化する方法としては
、８−ヒドロキシキノリンを硝酸で酸化する方法（Ｃｈ
ｅｓ、Ｂｅｒ、、 ８０．５０５ （１９４７））。As a method of oxidizing 8-hydroxyquinoline derivatives, a method of oxidizing 8-hydroxyquinoline with nitric acid (Ch
es, Ber, 80.505 (1947)).
８−ヒドロキシキノリンをバナジウムイオン存在下酸性
水媒体中塩素酸イオンで酸化する方法（特開昭５８−１
０５９６４）、８−ヒドロキシキノリン−５−スルホン
酸をバナジウムイオン存在下、亜塩素酸ナトリウムで酸
化する方法（西独特許９４５１４７）、８−ヒドロキシ
キノリンを塩基性水媒体中で過酸化水素を用いて酸化す
る方法（特開昭６３−１１９４６６）、８−ヒドロキシ
キノリンを塩基性水媒体中で過酸化水素で予備酸化した
後、ｐＨ調整後次亜塩素酸塩で酸化する方法（特開平１
−２６８６７７）等が挙げられる。しかしながら、これ
らは原料の入手が容易でない上に高価であるため工業的
に価値ある方法とはいえない。A method of oxidizing 8-hydroxyquinoline with chlorate ions in an acidic aqueous medium in the presence of vanadium ions (JP-A-58-1
05964), a method for oxidizing 8-hydroxyquinoline-5-sulfonic acid with sodium chlorite in the presence of vanadium ions (West German patent 945147), oxidizing 8-hydroxyquinoline with hydrogen peroxide in a basic aqueous medium A method in which 8-hydroxyquinoline is preoxidized with hydrogen peroxide in a basic aqueous medium, and then oxidized with hypochlorite after adjusting the pH (Japanese Patent Application Laid-Open No. 1983-11946)
-268677), etc. However, these methods are not industrially valuable because the raw materials are not easily available and are expensive.
（発明が解決しようとする課！す
本発明者らは、上記の欠点を改善するため、安価で容易
に入手できる出発物質から温和な条件下、高収率にキノ
リン酸を製造する目的で鋭意検討した。その結果、酸性
水媒体中でキラリンにメタノールと塩素酸塩とを添加し
て、反応系中で発生する二酸化塩素を真の酸化剤として
作用させることによってベンゼン環部位を活性化せずと
もキノリン酸が選択性よく得られることを見出し、本発
明ルと塩素酸塩とを添加して該キノリンを酸化すること
を特徴とするキノリン酸の製造法である。(Issues to be Solved by the Invention!) In order to improve the above-mentioned drawbacks, the present inventors have worked diligently to produce quinolinic acid in high yield under mild conditions from inexpensive and easily available starting materials. As a result, methanol and chlorate were added to chiralin in an acidic aqueous medium, and the chlorine dioxide generated in the reaction system acted as a true oxidizing agent, without activating the benzene ring moiety. It has been discovered that quinolinic acid can be obtained with good selectivity, and this method is characterized in that the quinoline of the present invention and a chlorate are added to oxidize the quinoline.
また本発明は、ルテニウム化合物存在下で該酸化反応を
行う方法である。Further, the present invention is a method of carrying out the oxidation reaction in the presence of a ruthenium compound.
酸化剤として塩素酸イオンを用いる方法としては、既に
キノリンを酸性水媒体中、塩素酸イオンで酸化する方法
（特開昭６２−２０９０６３号公報参照、）が開示され
ているが、本発明はメタノールと塩素酸塩とを用いるこ
とにより、反応式（１）％式％
に従って反応系内に発生した二酸化塩素が酸化剤として
作用するので、塩素酸イオンを単独で用いた場合より高
い選択性が得られるものと考えられる。As a method using chlorate ions as an oxidizing agent, a method has already been disclosed in which quinoline is oxidized with chlorate ions in an acidic aqueous medium (see Japanese Patent Application Laid-Open No. 62-209063). By using chlorate and chlorate, the chlorine dioxide generated in the reaction system acts as an oxidizing agent according to reaction formula (1)% formula %, so higher selectivity can be obtained than when chlorate ion is used alone. It is considered that the
本発明に用いる塩素酸イオンの供給源としては、通常の
水溶性塩素酸金属塩類を使用することができる。金属塩
の種類には何等制限されないが、−般にリチウム、カリ
ウム、ナトリウム等のアルカリ金属塩、特に工業的に安
価に入手できる塩素酸ナトリウムが適している。As a source of chlorate ions used in the present invention, common water-soluble chlorate metal salts can be used. Although the type of metal salt is not limited in any way, alkali metal salts such as lithium, potassium, and sodium are generally suitable, particularly sodium chlorate, which is industrially available at low cost.
塩素酸塩の使用量は、キノリン１モルに対して３〜１０
モル、好ましくは４〜７モルである。３モル未満では反
応の転化率が低く大量の未反応キノリンが回収される。The amount of chlorate used is 3 to 10 per mole of quinoline.
mol, preferably 4 to 7 mol. If it is less than 3 moles, the reaction conversion rate will be low and a large amount of unreacted quinoline will be recovered.
逆に１０モルを超えると、二酸化塩素の発生が激しくな
り、塩素酸塩が無為に消費されるだけであり、増量に見
合うだけの収２率向上は見られない。On the other hand, if the amount exceeds 10 moles, chlorine dioxide will be generated intensely, chlorate will be wasted, and the yield will not improve to the extent that the increase in amount corresponds to the increase.
メタノールの使用量は、好ましくは塩素酸塩の使用量の
０．１５〜０．３５倍モル、より好ましくは０．２〜０
．３倍モルである。０．１５倍モル未満では二酸化塩素
の発生量が少なくてメタノールを添加する効果が小さく
、また０、３５倍モルを超える量を添加するとべ応式（
２）
％式％
に従って塩素の発生量が次第に多くなり、転化率。The amount of methanol used is preferably 0.15 to 0.35 times the amount of chlorate used, more preferably 0.2 to 0.
．． It is 3 times the mole. If it is less than 0.15 times the mole, the amount of chlorine dioxide generated is small and the effect of adding methanol is small, and if it is added in an amount exceeding 0.35 times the mole, the
2) The amount of chlorine generated gradually increases according to the % formula, the conversion rate.
選択性がいずれも減少し副生酸物が多くなってくるので
好ましくない。Both are unfavorable because the selectivity decreases and the amount of by-product acids increases.
尚塩素酸塩の水溶液とメタノールを混合しても特に反応
は起らないので、キノリンの酸性水媒体中に予め塩素酸
塩の水溶液とメタノールとを混合した液を添加するか、
キノリンの酸性水媒体中に塩素酸塩の水溶液とメタノー
ルを同時に別々に添加するかのいずれの方法も適用可能
である。Note that no particular reaction occurs when an aqueous solution of chlorate and methanol are mixed, so either a mixture of an aqueous solution of chlorate and methanol is added in advance to the acidic aqueous medium of quinoline, or
Any method of simultaneously and separately adding an aqueous solution of chlorate and methanol to an acidic aqueous medium of quinoline is applicable.
また、反応系外で発生させた二酸化塩素を系内に導入す
る方法でも反応は進行するものの、二酸化塩素の反応液
中への吸収速度が遅い（特に５０℃以上の反応液の場合
、）ので、本発明の方法より転化率が小さくなり好まし
くない。In addition, although the reaction proceeds by introducing chlorine dioxide generated outside the reaction system into the system, the absorption rate of chlorine dioxide into the reaction solution is slow (especially in the case of a reaction solution at 50°C or higher). , the conversion rate is lower than that of the method of the present invention, which is not preferable.
本発明の酸性水媒体に用いる酸としては、硝酸。The acid used in the acidic aqueous medium of the present invention is nitric acid.
燐酸、特に硫酸のような鉱酸が適している。但し、塩酸
は塩素酸塩と反応して塩素を生じるので好ましくない。Mineral acids such as phosphoric acid and especially sulfuric acid are suitable. However, hydrochloric acid is not preferred because it reacts with chlorate to produce chlorine.
酸の使用量はキノリン１モルに対して３〜１０の酸当量
、好ましくは５〜７の酸当量である。また酸性水媒体の
酸濃度は３〜１３規定が好ましい。これらの範囲外では
反応率が低下する。The amount of acid used is 3 to 10 acid equivalents, preferably 5 to 7 acid equivalents per mole of quinoline. Moreover, the acid concentration of the acidic aqueous medium is preferably 3 to 13 normal. Outside these ranges, the reaction rate decreases.
本発明の反応は、好ましくは４０℃から反応液の還流温
度まで、より好ましくは５０℃から８０℃までの温度範
囲で行われる。４０℃未満では反応速度が非常に遅くな
り実用的でなく、また選択性も殆んど向上しない。一方
温度を上げるに従って反応速度は速くなり、二酸化塩素
の発生速度も速くなるものの二酸化塩素の過剰分の溶解
度が低下するので、転化率は徐々に下ってくる。従って
前記の反応温度範囲が好ましい。本発明の反応は、特に
加圧又は減圧で行う必要はない。The reaction of the present invention is preferably carried out at a temperature ranging from 40°C to the reflux temperature of the reaction solution, more preferably from 50°C to 80°C. If it is lower than 40°C, the reaction rate becomes extremely slow and is not practical, and the selectivity is hardly improved. On the other hand, as the temperature increases, the reaction rate increases and the rate of generation of chlorine dioxide also increases, but the solubility of excess chlorine dioxide decreases, so the conversion rate gradually decreases. Therefore, the above reaction temperature range is preferred. The reaction of the present invention does not particularly need to be carried out under elevated or reduced pressure.
本発明は触媒なしでも十分高い収率で反応することがで
きるが、ルテニウム化合物を存在させるのが望ましい、
ルテニウム化合物の存在により、反応の転化率を向上さ
せることができ、１バフチ当りの収量が更に向上する。Although the present invention can perform the reaction in sufficiently high yield without a catalyst, it is desirable to have a ruthenium compound present.
The presence of the ruthenium compound can improve the conversion rate of the reaction and further improve the yield per batch.
本発明に触媒として用いるルテニウム化合物の例として
は、四酸化ルテニウム、三塩化ルテニウム、二酸化ルテ
ニウムを挙げることができる。ルテニウム化合物の使用
量はキノリン１モルに対して１０４〜１０４モル、好ま
しくは１０−４〜１Ｏ−３モルである。１０−’モル未
満では触媒添加の効果が小さい、１０−”モルを超える
使用量は勿論−層早い反応速度が得られるが、コスト面
で問題となる。Examples of the ruthenium compound used as a catalyst in the present invention include ruthenium tetroxide, ruthenium trichloride, and ruthenium dioxide. The amount of the ruthenium compound used is 104 to 104 mol, preferably 10-4 to 10-3 mol, per 1 mol of quinoline. If the amount is less than 10-' mole, the effect of the addition of the catalyst is small; if it is more than 10-' mole, a faster reaction rate can be obtained, but this poses a problem in terms of cost.
本発明の更に有利な点は、反応副生成物が非常に少ない
ので、反応終了時にキノリン酸の結晶が比較的高い純度
で反応液より晶出し、必要に応じて溶媒による洗浄、再
結晶等の通常の精製手段により高純度にできる点である
。これは塩素酸塩を用いる従来技術（特開昭６０−１５
６６７３．特開昭６２−２０９０６３号公報参照。）と
大きく異なる点である。A further advantage of the present invention is that since there are very few reaction by-products, quinolinic acid crystals with relatively high purity are crystallized from the reaction solution at the end of the reaction, and if necessary, washing with a solvent, recrystallization, etc. The point is that high purity can be obtained by ordinary purification means. This is a conventional technique using chlorate (Japanese Unexamined Patent Publication No. 60-15
6673. See Japanese Patent Application Laid-Open No. 62-209063. ) is very different.
（発明の効果） 本発明は次の如き特徴を有するものである。(Effect of the invention) The present invention has the following features.
（１）原料には安価で入手容易なキノリンを用いること
ができる。ヘンゼン核に特定の活性基を予め導入する必
要がない。(1) Quinoline, which is inexpensive and easily available, can be used as a raw material. There is no need to introduce specific active groups into the Hensen nucleus in advance.
（２）本発明では、キノリンにメタノールと塩素酸塩と
を添加することにより反応系内に生成する二酸化塩素が
酸化剤として作用するので、簡単な操作で短時間に添加
することができる。(2) In the present invention, since chlorine dioxide produced in the reaction system by adding methanol and chlorate to quinoline acts as an oxidizing agent, it can be added in a short time with a simple operation.
（３）塩素酸イオンを単独で用いた場合に比べて本発明
の反応の選択性は非常に高く副生ｒｌｉ物が少ない。(3) Compared to the case where chlorate ion is used alone, the selectivity of the reaction of the present invention is very high and the amount of by-product rli products is small.
（４）本発明の反応は、急激な発熱反応が起らず、温度
制御が極めて容易である。(4) In the reaction of the present invention, rapid exothermic reaction does not occur, and temperature control is extremely easy.
（５） ルテニウム化合物を用いる場合もその使用量
は極微量で有効である。(5) When using a ruthenium compound, it is effective even if the amount used is extremely small.
このように本発明は工業的製法として極めて有利な方法
ということができる。As described above, the present invention can be said to be an extremely advantageous industrial manufacturing method.
（実施例）
以下本発明を更に具体的に実施例で詳細に説明する。な
お、例中濃度％はいずれも重量基準である。(Example) The present invention will now be described in more detail with reference to Examples. In addition, all concentration percentages in the examples are based on weight.
実施例１
キノリン１６．３ｇ（１２６ミリモル）、濃硫酸３８、
６ ｇ及び水１２５ｍｌを含む溶液を５０℃に加温し、
゛これにメタノール５．１ｇ（１６０ミリモル）と４４
％塩素酸ナトリウム水溶液１５５ｇ（６４０ｚリモル）
の混合液を滴下し、同温度で３時間撹拌した０次に、徐
々に温度を上げ３時間還流させた。Example 1 16.3 g (126 mmol) of quinoline, 38 g of concentrated sulfuric acid,
A solution containing 6 g and 125 ml of water was heated to 50°C,
゛To this, 5.1 g (160 mmol) of methanol and 44
% sodium chlorate aqueous solution 155g (640z remol)
The mixture was added dropwise and stirred at the same temperature for 3 hours.Then, the temperature was gradually raised and the mixture was refluxed for 3 hours.
室温まで放冷後２０％水酸化ナトリウム水溶液でｐＨ１
１に調整し、遊離した未反応キノリンを四塩化炭素で抽
出単離した。水層中のキノリン酸は液体クロマトグラフ
（カラムはハミルトン社製ｒＰＲＰ−１カラム」を使用
、）により定量し、転化率（％）及び選択率（％）は夫
々次式に拠り求めた。After cooling to room temperature, adjust the pH to 1 with 20% sodium hydroxide aqueous solution.
1, and the liberated unreacted quinoline was extracted and isolated with carbon tetrachloride. Quinolinic acid in the aqueous layer was quantified by liquid chromatography (using an rPRP-1 column manufactured by Hamilton Co.), and the conversion rate (%) and selectivity (%) were determined according to the following formulas.
その結果回収キノリンは６．３ｇ（転化率６１．３％〉
、生成したキノリン酸は１１．６ｇ（選択率８９．６％
）であった。As a result, the recovered quinoline was 6.3g (conversion rate 61.3%)
, the produced quinolinic acid was 11.6g (selectivity 89.6%
)Met.
実施例２
キノリン１６．２ｇ（１２５′Ｓリモル）、Ｉｉｉ酸３
８、６ ｇ及び水１２５ｍｌを含む溶液に４．６×１Ｏ
−３モル／ｌ三塩化ルテニウム水溶液１．３ ｍ Ｊ（
０，０６０１リモル）を添加し、撹拌しながら５０℃に
加温した。これにメタノール５．０ｇ〈１５５ξリモル
〉と４４％塩素酸ナトリウム水溶液１５０ｇ （６２０
ξリモル）の混合液を滴下し、同温度で３時間撹拌した
０次に、徐々に温度を上げ３時間還流させた。室温まで
放冷後実施例１と同様に処理した結果、１回収キノリン
は２．７２ｇ（転化率８３．２％〉、生成したキノリン
酸は１６．１ｇ（選択率９２．２％）であった。Example 2 16.2 g of quinoline (125'S remol), III acid 3
8.6 x 1O in a solution containing 6 g and 125 ml of water.
-3 mol/l ruthenium trichloride aqueous solution 1.3 m J (
0.0601 lmol) was added thereto, and the mixture was heated to 50° C. with stirring. To this, 5.0 g of methanol (155 ξ mol) and 150 g of 44% sodium chlorate aqueous solution (620
A mixed solution of ξ mol) was added dropwise, and the mixture was stirred at the same temperature for 3 hours.Then, the temperature was gradually raised and the mixture was refluxed for 3 hours. After cooling to room temperature, it was treated in the same manner as in Example 1. As a result, 1 recovered quinoline was 2.72 g (conversion rate 83.2%) and quinolinic acid produced was 16.1 g (selectivity 92.2%). .
比較例１
キノリン１６．８ｇ（１３０ミリモル）、濃硫酸３８、
６ ｇ及び水１２５ｍｊを含む溶液を５０℃に加温し４
４％塩素酸ナトリウム水溶液１５０ｇ（６２０ξリモル
）を滴下し、同温度で３時間撹拌した０次に徐々に温度
を上げ３時間還流させた。Comparative Example 1 16.8 g (130 mmol) of quinoline, 38 g of concentrated sulfuric acid,
A solution containing 6 g and 125 mj of water was heated to 50°C and 4
150 g (620 ξ mol) of a 4% aqueous sodium chlorate solution was added dropwise, and the mixture was stirred at the same temperature for 3 hours.Then, the temperature was gradually raised and the mixture was refluxed for 3 hours.
室温まで放冷後実施例１と同様に処理した結果、回収キ
ノリンは４．０ｇ＜転化率７６％）、生成したキノリン
酸は９ｇ（選択率４８％）であった。After cooling to room temperature, the mixture was treated in the same manner as in Example 1. As a result, the recovered quinoline was 4.0 g (conversion rate 76%) and the produced quinolinic acid was 9 g (selectivity 48%).
Claims (2)
とを添加して該キノリンを酸化することを特徴とするキ
ノリン酸の製造法。(1) A method for producing quinolinic acid, which comprises adding methanol and a chlorate to quinoline in an acidic aqueous medium to oxidize the quinoline.
ノリン酸の製造法。(2) The method for producing quinolinic acid according to claim 1, which is carried out in the presence of a ruthenium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8943990A JPH03287576A (en) | 1990-04-03 | 1990-04-03 | Production of quinolinic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8943990A JPH03287576A (en) | 1990-04-03 | 1990-04-03 | Production of quinolinic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03287576A true JPH03287576A (en) | 1991-12-18 |
Family
ID=13970714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8943990A Pending JPH03287576A (en) | 1990-04-03 | 1990-04-03 | Production of quinolinic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03287576A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6900330B1 (en) | 2002-12-10 | 2005-05-31 | Hebei Sinochem Fuheng Co., Ltd. | Process for producing 2,3-pyridinedicarboxylic acid |
| US7157583B2 (en) | 2002-11-07 | 2007-01-02 | Sumikin Air Water Chemical Inc. | Process for producing high-purity 2,3-pyridinedicarboxylic acid |
| CN111004175A (en) * | 2019-12-24 | 2020-04-14 | 沈阳化工研究院有限公司 | Method for preparing nitrogen-containing six-membered ring dicarboxylic acid |
-
1990
- 1990-04-03 JP JP8943990A patent/JPH03287576A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7157583B2 (en) | 2002-11-07 | 2007-01-02 | Sumikin Air Water Chemical Inc. | Process for producing high-purity 2,3-pyridinedicarboxylic acid |
| US6900330B1 (en) | 2002-12-10 | 2005-05-31 | Hebei Sinochem Fuheng Co., Ltd. | Process for producing 2,3-pyridinedicarboxylic acid |
| CN111004175A (en) * | 2019-12-24 | 2020-04-14 | 沈阳化工研究院有限公司 | Method for preparing nitrogen-containing six-membered ring dicarboxylic acid |
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