JPS6017790B2 - How to prepare benzimidazolone - Google Patents
How to prepare benzimidazoloneInfo
- Publication number
- JPS6017790B2 JPS6017790B2 JP55186986A JP18698680A JPS6017790B2 JP S6017790 B2 JPS6017790 B2 JP S6017790B2 JP 55186986 A JP55186986 A JP 55186986A JP 18698680 A JP18698680 A JP 18698680A JP S6017790 B2 JPS6017790 B2 JP S6017790B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- benzimidazolone
- selenium
- solvent
- phenylenediamine
- 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.)
- Expired
Links
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 title claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 229910052711 selenium Inorganic materials 0.000 claims description 16
- 239000011669 selenium Substances 0.000 claims description 16
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 150000008641 benzimidazolones Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- RQZJHKMUYSXABM-UHFFFAOYSA-N selanylidenemethanone Chemical compound O=C=[Se] RQZJHKMUYSXABM-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 235000018734 Sambucus australis Nutrition 0.000 description 1
- 244000180577 Sambucus australis Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- -1 alicyclic hydrocarbons Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical class [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 本発明はベンツイミダゾロンの製造方法に関する。[Detailed description of the invention] The present invention relates to a method for producing benzimidazolones.
ベンツイミダゾロンはよく知られているように染料、顔
料等の中間体や樹脂原料として広く用いられており、従
来はｏ−フェニレンジアミン塩酸塩をトルェン中でホス
ゲンと反応させる方法や、ｏ−フェニレンジアミンと尿
素を有機溶剤中又は水性溶剤中、１５ぴ０前後の温度で
反応させる方法によって製造されている。As is well known, benzimidazolones are widely used as intermediates for dyes, pigments, etc., and as raw materials for resins. It is produced by a method in which diamine and urea are reacted in an organic solvent or an aqueous solvent at a temperature of around 1500m.
しかし、これらの方法においては、上記のようにホスゲ
ンのような危険な反応教剤を用いる必要があったり、厳
しい反応条件を要したりするほか、一般に収率が低く、
且つ、得られるベンツィミダゾロンの純度も低い。本発
明は上記に鑑みてなされたものであって、ｏーフェニレ
ンジアミンから穏和な反応条件下で高収率で高純度のベ
ンツィミダゾロンを製造し得ると共に、触媒の回収、再
使用が容易であり、更に反応の後処理も簡単であるベン
ツィミダゾロンの製造方法を提供することを目的とする
。本発明のベンツィミダゾロンの製造方法は、ｏーフェ
ニレンジアミンを溶剤中にて塩基及びセレンの存在下で
一酸化炭素と反応させることを特徴とする。However, as mentioned above, these methods require the use of dangerous reaction materials such as phosgene, require harsh reaction conditions, and generally have low yields.
Moreover, the purity of the obtained benzimidazolone is also low. The present invention has been made in view of the above, and is capable of producing benzimidazolone with high yield and high purity from o-phenylenediamine under mild reaction conditions, and the catalyst can be easily recovered and reused. It is an object of the present invention to provide a method for producing benzimidazolone, which also allows easy post-treatment of the reaction. The method for producing benzimidazolone of the present invention is characterized by reacting o-phenylenediamine with carbon monoxide in a solvent in the presence of a base and selenium.
本発明においてｏ−フヱニレンジアミンは反応に有害な
影響を与えず、又は反応に関与して望ましくない副反応
を起こさないものであれば任意の不活性な置換基を有し
ていてもよく、これら置換基の例として脂肪族、脂環族
、芳香族炭化水素基、ヘテロ芳香族基、アルコキシ基、
アリロキシ基、塩素、臭素等のハロゲンを挙げることが
できる。In the present invention, o-phenylenediamine may have any inert substituent as long as it does not have a detrimental effect on the reaction or participate in the reaction and cause undesirable side reactions. Examples of these substituents include aliphatic, alicyclic, aromatic hydrocarbon groups, heteroaromatic groups, alkoxy groups,
Examples include an allyloxy group, halogens such as chlorine, and bromine.
本発明において用いるセレンは好ましくは粉末状のセレ
ンであって、一般の市販品をそのまま用いることができ
る。The selenium used in the present invention is preferably powdered selenium, and general commercially available products can be used as they are.
セレンはその使用量が多い程、反応速度は増すが、回収
の容易性等を考慮して、その使用量はｏ−フエニレンジ
アミン１モルに対してｏ．１〜５モル、好ましくは０．
２〜３モル、特に好ましくは０．５〜２モルである。５
モルを越えて多量に用いる必要は特にない。The reaction rate increases as the amount of selenium used increases, but in consideration of ease of recovery, etc., the amount of selenium used should be set to 0.000% per mole of o-phenylenediamine. 1 to 5 mol, preferably 0.
The amount is 2 to 3 mol, particularly preferably 0.5 to 2 mol. 5
There is no particular need to use a large amount exceeding the molar amount.
本発明は何ら理論に限定されるものではないが、セレン
は塩基の存在下に一酸化炭素と反応してセレン化カルボ
ニル（ＳｅＣＯ）を生成し、このセレン化カルボニルが
一方のアミノ基に挿入反応を行なって一ＮＨＣＯＳｅＨ
基を生じ、このカルボニル炭素がオルト位の窒素を求電
子的に攻撃、閉擬してへテロ環を形成すると共に、セレ
ン化水素を生じ、このセレン化水素は溶解しているとみ
られ、反応系は実質的に均一である。Although the present invention is not limited to any theory, it is believed that selenium reacts with carbon monoxide in the presence of a base to produce carbonyl selenide (SeCO), and this carbonyl selenide undergoes an insertion reaction into one of the amino groups. Perform 1NHCOSeH
This carbonyl carbon electrophilically attacks and closes the nitrogen at the ortho position to form a heterocycle, and hydrogen selenide is produced. This hydrogen selenide appears to be dissolved, and the reaction begins. The system is substantially homogeneous.
本発明においては、塩基としてはアルカリ金属及びアル
カリ士類金属の炭酸塩、重炭酸塩、水酸化物、酸化物、
アンモニア等の無機塩基、アミン類等の有機塩基が用い
られる。In the present invention, bases include carbonates, bicarbonates, hydroxides, oxides of alkali metals and alkali metals,
Inorganic bases such as ammonia and organic bases such as amines are used.
具体的には炭酸カリウム、炭酸ナトリウム、水酸化カリ
ウム、水酸化ナトリワム、トリエチルアミン、ピリジン
、ジメチルホルムアミド、Ｎ−メチルピロリジン等を挙
げることができるが、好ましくは有機塩基が用いられる
。塩基の使用量は特に制限はないが、普通、ｏーフェニ
レンジアミン１モルについて１〜１０モル、好まくは２
〜５モルである。本発明において用いる溶剤は水、水性
有機溶剤又は有機溶剤である。Specific examples include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine, pyridine, dimethylformamide, and N-methylpyrrolidine, but preferably an organic base is used. The amount of the base used is not particularly limited, but it is usually 1 to 10 mol, preferably 2 mol per mol of o-phenylenediamine.
~5 moles. The solvent used in the present invention is water, an aqueous organic solvent, or an organic solvent.
ここに有機溶剤としては反応に窓影響を与えないもの、
特に反応において還元されないものであれば任意であっ
てよく、例えば、エーテル類、アミド類、アミン類、芳
香族炭化水素類、脂肪族炭化水素類、脂環族炭化水素類
等の一種又は二種以上の混合物が任意に用いられる。具
体的にはテトラヒドロフラン、ジオキサン、ジエチルエ
ーテル、ジメチルホルムアミド、ジメチルアセトアミド
、トリエチルアミン、ピリジン、Ｎーメチルピロリジン
、ベンゼン、ヘキサン等が用いられるが、好ましくはこ
れらのうち、極性有機溶剤が用いられ、特に好ましくは
これらの水性溶剤が用いられる。尚、上記から明らかな
ように、本発明においては前記した塩基のうち、有機塩
基は溶剤を兼ねることができる。有機溶剤中の水含量は
通常、セレンに対して１〜１０び昔モルが用いられるが
、好ましくは２〜３０倍モルである。Here, organic solvents that do not have a window effect on the reaction,
In particular, any substance may be used as long as it is not reduced in the reaction, for example, one or two of ethers, amides, amines, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, etc. Mixtures of the above may be used arbitrarily. Specifically, tetrahydrofuran, dioxane, diethyl ether, dimethylformamide, dimethylacetamide, triethylamine, pyridine, N-methylpyrrolidine, benzene, hexane, etc. are used, and among these, polar organic solvents are preferably used, and particularly preferred. These aqueous solvents are used. Incidentally, as is clear from the above, in the present invention, among the above-mentioned bases, an organic base can also serve as a solvent. The water content in the organic solvent is usually 1 to 10 times the mole of selenium, preferably 2 to 30 times the mole of selenium.
しかし、この水含量は必らずしも臨界的ではない。本発
明の反応は一酸化炭素雰囲気下で行なわれ、その圧力は
通常１〜５０ｋｇ／の、好ましくは３〜３０ｋ９／めで
ある。圧力が高すぎると副反応が起こるので好ましくな
い。また、反応の温度は特に限定されないが、通常、室
温〜１００００、好ましくは５０〜８０ｑｏであり、反
応に要する時間は通常、１０時間以内であり、多くの場
合、４時間乃至５時間程度で反応が完了する。本発明の
方法においては、前記したように、通常、反応系は実質
的に溶液状態であるが、反応終了後にこの反応混合物に
空気を通じて、溶解しているセレン化合物を分解させる
と、赤色の無定形セレンを経て黒色の金属セレンが析出
する。However, this water content is not necessarily critical. The reaction of the present invention is carried out under a carbon monoxide atmosphere, and the pressure is usually 1 to 50 kg/m, preferably 3 to 30 k9/m. If the pressure is too high, side reactions will occur, which is not preferable. Further, the reaction temperature is not particularly limited, but is usually room temperature to 10,000 qo, preferably 50 to 80 qo, and the time required for the reaction is usually within 10 hours, and in many cases, the reaction takes about 4 to 5 hours. is completed. In the method of the present invention, as described above, the reaction system is usually in a substantially solution state, but when air is passed through the reaction mixture after the reaction is completed to decompose the dissolved selenium compound, a red color is formed. Black metallic selenium is precipitated via regular selenium.
この金属セレンを炉別し、洗糠後、この洗膝液と金属セ
レン炉別後の炉液とを合わせ、溶剤を留去すればベンツ
イミダゾロンを得る。このようにして得たベンツィミダ
ゾロンは通常、再結晶を要しない程度に高純度であるが
、必要ならば水等から再結晶する。本発明は以上のよう
に、ｏ−フェニレンジアミンに溶剤中で塩基及びセレン
の存在下に一酸化炭素を反応させるものであって、次の
ような利点を有する。This metallic selenium is separated in a furnace, and after washing, the washing liquid and the furnace liquid obtained after separating the metal selenium in the furnace are combined, and the solvent is distilled off to obtain benzimidazolone. The benzimidazolone thus obtained is usually of such high purity that it does not require recrystallization, but if necessary, it can be recrystallized from water or the like. As described above, the present invention involves reacting o-phenylenediamine with carbon monoxide in a solvent in the presence of a base and selenium, and has the following advantages.
｛ィｌ ｏ−フェニレンジアミンほか簡単な原料を用い
、好ましい場合にはほぼ定量的に高純度のベンツイミダ
ゾロンを製造することができる。In preferred cases, highly pure benzimidazolones can be produced almost quantitatively using o-phenylenediamine and other simple raw materials.
【ｏー 金属セレンは反応終了後、定量的に且つ容易に
回収され、更にそのままで循環再使用できる。し一 反
応系は実質的に均一系であり、反応操作及び反応終了後
の後処理も簡単である。[o- Metallic selenium can be quantitatively and easily recovered after the reaction is completed, and can be recycled and reused as is. The reaction system is substantially homogeneous, and the reaction operation and post-treatment after the reaction is simple.
〇 反応条件が穏和であり、反応に要する時間も短かし
、。〇 The reaction conditions are mild and the time required for the reaction is short.
以下に本発明の実施例を挙げる。Examples of the present invention are listed below.
実施例 １
ｏ−フヱニレンジアミン１．３５夕（１２．５ｍｍｏｌ
）、金属セレン粉末１．９７夕（１２．５ｍｍｏｌ）、
水１．６夕（８８．９ｍｍｏｌ）、トリエチルアミン５
夕（５０ｍｍｏｌ）及びテトラヒドロフラン１００舷を
２００肌容量のオートクレープに仕込み、一酸化炭素で
十分に置換した後、一酸化炭素圧を２０ｋ９／仇とした
。Example 1 1.35 o-phenylenediamine (12.5 mmol
), metallic selenium powder 1.97 mmol (12.5 mmol),
Water 1.6 (88.9 mmol), triethylamine 5
After charging 100 mmol of carbon dioxide and 100 mmol of tetrahydrofuran into an autoclave with a capacity of 200 m2 and thoroughly replacing the autoclave with carbon monoxide, the carbon monoxide pressure was set to 20 k9/m.
オートクレープ内を８０ｑｏに加溢し、３時間渡洋した
後、オートクレープを室温まで冷却し、一酸化炭素を除
去した。次いで、空気中にて約２び分間反応混合物を燈
拝して、金属セレンを析出させ、炉別し、メタノールで
洗絶した。炉液にこの洗糠液を合わせ、溶剤を留去して
、白色リン片状のベンツイミダゾロン１．６６夕（理論
収率９９．０％）を得た。このベンツィミダゾロンの純
度は高速液体クロマトグラフィーの結果、９５．６％で
あった。実施例 ２ｏーフエニレンジアミン１．３５夕
（１２．５肌ｍｏｌ）に対して金属セレン粉末０．９９
夕（６．３ｍｍｏｌ）を用いた以外は実施例１と全く同
様にして、ベンツイミダゾロン１．４６夕（理論収率８
８％）を得た。The inside of the autoclave was flooded with 80 qo and left at sea for 3 hours, then the autoclave was cooled to room temperature and carbon monoxide was removed. Next, the reaction mixture was heated in air for about 2 minutes to precipitate metallic selenium, separated in a furnace, and washed with methanol. This washing liquid was combined with the furnace liquid, and the solvent was distilled off to obtain 1.66 g of benzimidazolone in the form of white flakes (theoretical yield: 99.0%). The purity of this benzimidazolone was 95.6% as a result of high performance liquid chromatography. Example 2O-phenylenediamine 1.35 mol (12.5 mol) to metallic selenium powder 0.99
Benzimidazolone 1.46 mmol (theoretical yield: 8
8%).
実施例 ３水を添加しないで実施例１と同様にしてベン
ツィミダゾロン１．６３夕（理論収率９７．３％）を得
た。Example 3 1.63 hours of benzimidazolone (theoretical yield 97.3%) was obtained in the same manner as in Example 1 without adding water.
実施例 ４ｏ−フエニレンジアミン１．３５夕（１２．
５仇ｍｏｌ）、金属セレン粉末１．９７夕（１２．５ｍ
ｍｏｌ）、トリヱチルアミン４夕（４０ｍｍｏｌ）及び
テトラヒドロフラン１００の‘をオートクレープに仕込
み、一酸化炭素圧１０ｋ９／めで３０ｏｏで１餌時間反
応した。Example 4 o-Phenylenediamine 1.35 min (12.
5 moles), metal selenium powder 1.97 moles (12.5 m
mol), triethylamine (40 mmol), and tetrahydrofuran (100 mmol) were charged into an autoclave, and reacted for 1 hour at a carbon monoxide pressure of 10 k9/mole and 30 oo.
実施例１と同様に処理してベンツィミダゾロン１．４９
夕（理論収率８９％）を得た。実施例 ５
トルエチルアミンおよびテトラヒドロフランの代わりに
塩基兼溶剤としてピリジン１００のとを加え、実施例１
と全く同様にしてベンツィミダゾロン１．２１夕（理論
収率７２．３％）を得た。Benzimidazolone 1.49 was treated in the same manner as in Example 1.
A yield of 89% of theory was obtained. Example 5 Pyridine 100% was added as a base and solvent in place of toluethylamine and tetrahydrofuran, and Example 1
In exactly the same manner as above, 1.21 units of benzimidazolone (theoretical yield 72.3%) was obtained.
実施例 ６溶剤テトラヒドロフランの代わりに水１００
机を用いた以外実施例１と全く同機にしてベンツィミダ
ゾロン１．１３夕（理論収率６７．５％）を得た。Example 6 Water 100 instead of solvent tetrahydrofuran
1.13 hours of benzimidazolone (theoretical yield: 67.5%) was obtained using the same machine as in Example 1 except that a desk was used.
Claims (1)
ンの存在下で一酸化炭素と反応させることを特徴とする
ベンツイミダゾロンの製造方法。1. A method for producing benzimidazolone, which comprises reacting o-phenylenediamine with carbon monoxide in a solvent in the presence of a base and selenium.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55186986A JPS6017790B2 (en) | 1980-12-30 | 1980-12-30 | How to prepare benzimidazolone |
| FR8112252A FR2485012A1 (en) | 1980-06-23 | 1981-06-22 | PROCESS FOR THE MANUFACTURE OF BENZIMIDAZOLONES |
| US06/275,618 US4374250A (en) | 1980-06-23 | 1981-06-22 | Method of producing benzimidazolone |
| GB8119349A GB2080292A (en) | 1980-06-23 | 1981-06-23 | A Method of Producing Benzimidazolones |
| DE19813124618 DE3124618A1 (en) | 1980-06-23 | 1981-06-23 | METHOD FOR PRODUCING BENZIMIDAZOLONES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55186986A JPS6017790B2 (en) | 1980-12-30 | 1980-12-30 | How to prepare benzimidazolone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57112382A JPS57112382A (en) | 1982-07-13 |
| JPS6017790B2 true JPS6017790B2 (en) | 1985-05-07 |
Family
ID=16198192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55186986A Expired JPS6017790B2 (en) | 1980-06-23 | 1980-12-30 | How to prepare benzimidazolone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6017790B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151251B (en) * | 2014-08-07 | 2017-01-18 | 山东汇海医药化工有限公司 | Method for one-pot synthesis of 5-acetylacetamido-benzimidazolone |
-
1980
- 1980-12-30 JP JP55186986A patent/JPS6017790B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57112382A (en) | 1982-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1199642A (en) | Substituted phenylsulfonyloxybenzimidazolecarbamates, processes for their preparation and pharmaceutical compositions containing the same | |
| CN107417478B (en) | Method for synthesizing asymmetric disubstituted urea by catalytic oxidation carbonylation | |
| JPS6017790B2 (en) | How to prepare benzimidazolone | |
| CA1294625C (en) | Process for producing coarse-crystalline high-purity nicotinic acid | |
| US4374250A (en) | Method of producing benzimidazolone | |
| CN111100082B (en) | A kind of preparation method of 2-aryl benzotriazole compound | |
| JPS5940390B2 (en) | Method for producing aminobenzimidazolones | |
| JPS5940389B2 (en) | Method for producing benzimidazolone | |
| GB2080292A (en) | A Method of Producing Benzimidazolones | |
| JPS5940391B2 (en) | Method for producing benzimidazolone, benzoxazolone or benzthiazolone | |
| CN100430381C (en) | Method for preparing 3,5,6-trichloropyridin-2-alcohol sodium without solvent | |
| JPS5949217B2 (en) | Method for producing substituted diphenyl ether | |
| JPS60228452A (en) | Manufacture of pure 2,6-dichlorobenzonitrile | |
| JPS6041067B2 (en) | Method for producing benzoxazolone and benzthiazolone | |
| Babad et al. | Acylation of nitrogen heterocycles under the conditions of the schotten‐baumann reaction. III. Imidazoles | |
| JPH024758A (en) | Production of acylisocyanate | |
| JPH0551368A (en) | Production of benzazolones | |
| MXPA03003357A (en) | Processes for the production of methyl dithiocarbazinate. | |
| JPS62132849A (en) | Production of d-or l-n-t-butoxycarbonyl-o-benzylserine | |
| JPS6270344A (en) | Production of nitrophenoxyamine | |
| JPS6038385B2 (en) | Method for producing 2-benzothiazolones | |
| JPS5822022B2 (en) | Process for treating phenylenediamine isomer mixture | |
| JPS5811944B2 (en) | N-p-aminobenzyl-N'-p-aminophenyl urea and its production method | |
| JPS6267074A (en) | 1-hydroxypyrazole-4-carboxylic acid and manufacture | |
| JPH08208586A (en) | Process for producing 4'-cyanobiphenyl-4-ol |