JPS6317864A - Production of hydantoins - Google Patents
Production of hydantoinsInfo
- Publication number
- JPS6317864A JPS6317864A JP61162007A JP16200786A JPS6317864A JP S6317864 A JPS6317864 A JP S6317864A JP 61162007 A JP61162007 A JP 61162007A JP 16200786 A JP16200786 A JP 16200786A JP S6317864 A JPS6317864 A JP S6317864A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- hydantoin
- palladium
- carbon
- formula
- 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
- 150000001469 hydantoins Chemical class 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 28
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 229910052763 palladium Inorganic materials 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 150000001371 alpha-amino acids Chemical class 0.000 abstract description 2
- 235000008206 alpha-amino acids Nutrition 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000002778 food additive Substances 0.000 abstract description 2
- 235000013373 food additive Nutrition 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000000243 solution Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 11
- 229940091173 hydantoin Drugs 0.000 description 11
- UPDDIBZITPTASO-YVMONPNESA-N (5z)-5-[(4-hydroxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound C1=CC(O)=CC=C1\C=C/1C(=O)NC(=O)N\1 UPDDIBZITPTASO-YVMONPNESA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- GLLIXWMNULCIKR-UHFFFAOYSA-N 5-[(4-hydroxyphenyl)methyl]imidazolidine-2,4-dione Chemical compound C1=CC(O)=CC=C1CC1C(=O)NC(=O)N1 GLLIXWMNULCIKR-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000004811 liquid chromatography Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- -1 5-(2,4-dihydroxybenzylidene)hydantoin Chemical compound 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UDTSPKADQGPZFS-SOFGYWHQSA-N (5e)-5-benzylideneimidazolidine-2,4-dione Chemical compound N1C(=O)NC(=O)\C1=C/C1=CC=CC=C1 UDTSPKADQGPZFS-SOFGYWHQSA-N 0.000 description 3
- UDTSPKADQGPZFS-UHFFFAOYSA-N 1/7/3775 Natural products N1C(=O)NC(=O)C1=CC1=CC=CC=C1 UDTSPKADQGPZFS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YOFKIDCKEYKPNO-SOFGYWHQSA-N (5e)-5-[(2-methoxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound COC1=CC=CC=C1\C=C\1C(=O)NC(=O)N/1 YOFKIDCKEYKPNO-SOFGYWHQSA-N 0.000 description 1
- XLTKBDZXXGQCSC-RMKNXTFCSA-N (5e)-5-[(4-methoxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound C1=CC(OC)=CC=C1\C=C\1C(=O)NC(=O)N/1 XLTKBDZXXGQCSC-RMKNXTFCSA-N 0.000 description 1
- NKQBXYVAZTZVMV-YVMONPNESA-N (5z)-5-[(3,4-dimethoxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound C1=C(OC)C(OC)=CC=C1\C=C/1C(=O)NC(=O)N\1 NKQBXYVAZTZVMV-YVMONPNESA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QHJHCJJUSGPSNT-UHFFFAOYSA-N 1-[(4-hydroxyphenyl)methyl]imidazolidine-2,4-dione Chemical compound C1=CC(O)=CC=C1CN1C(=O)NC(=O)C1 QHJHCJJUSGPSNT-UHFFFAOYSA-N 0.000 description 1
- GXPDYJIBYGLMKU-UHFFFAOYSA-N 5-[(2-hydroxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound OC1=CC=CC=C1C=C1C(=O)NC(=O)N1 GXPDYJIBYGLMKU-UHFFFAOYSA-N 0.000 description 1
- JVIQAUUOTMODKJ-UHFFFAOYSA-N 5-[(2-methylphenyl)methylidene]imidazolidine-2,4-dione Chemical compound CC1=CC=CC=C1C=C1C(=O)NC(=O)N1 JVIQAUUOTMODKJ-UHFFFAOYSA-N 0.000 description 1
- BNLLHJGHQCBBLG-UHFFFAOYSA-N 5-[(3,4-dihydroxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound C1=C(O)C(O)=CC=C1C=C1C(=O)NC(=O)N1 BNLLHJGHQCBBLG-UHFFFAOYSA-N 0.000 description 1
- CVEPZWFFKVWAMM-UHFFFAOYSA-N 5-[(3-hydroxy-4-methoxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound C1=C(O)C(OC)=CC=C1C=C1C(=O)NC(=O)N1 CVEPZWFFKVWAMM-UHFFFAOYSA-N 0.000 description 1
- HZAHUPKFCIYWHZ-UHFFFAOYSA-N 5-[(3-hydroxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound OC1=CC=CC(C=C2C(NC(=O)N2)=O)=C1 HZAHUPKFCIYWHZ-UHFFFAOYSA-N 0.000 description 1
- NQFUGCKNXNBJNF-UHFFFAOYSA-N 5-[(3-methoxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound COC1=CC=CC(C=C2C(NC(=O)N2)=O)=C1 NQFUGCKNXNBJNF-UHFFFAOYSA-N 0.000 description 1
- UPDDIBZITPTASO-UHFFFAOYSA-N 5-[(4-hydroxyphenyl)methylidene]imidazolidine-2,4-dione Chemical compound C1=CC(O)=CC=C1C=C1C(=O)NC(=O)N1 UPDDIBZITPTASO-UHFFFAOYSA-N 0.000 description 1
- MDJFPRDVZHNPSA-UHFFFAOYSA-N 5-[(4-methylphenyl)methylidene]imidazolidine-2,4-dione Chemical compound C1=CC(C)=CC=C1C=C1C(=O)NC(=O)N1 MDJFPRDVZHNPSA-UHFFFAOYSA-N 0.000 description 1
- DBOMTIHROGSFTI-UHFFFAOYSA-N 5-benzylimidazolidine-2,4-dione Chemical compound O=C1NC(=O)NC1CC1=CC=CC=C1 DBOMTIHROGSFTI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000002747 voluntary effect Effects 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ヒダントイン類を工業的に有利に製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an industrially advantageous method for producing hydantoins.
本発明のヒダントイン類は、α−アミノ酸の中間原料と
して、また農薬、医薬、食品添加物の中間原料として有
用である。The hydantoins of the present invention are useful as intermediate raw materials for α-amino acids and for agricultural chemicals, medicines, and food additives.
（従来の技術）
既に５−アリーリデンヒダントインを還元してヒダント
イン類を製造する方法はいくつか報告されている。特開
昭６０−１１４５７では、５−ベンジリデンヒダントイ
ンをラネーニッケル触媒で還元し、５−ベンジルヒダン
トインを製造するに際し、アルカリ性水溶液中ラネーニ
ッケル触媒を５−ヘンジリデンヒダントインに対し、５
〜５０重量％使用している。(Prior Art) Several methods have already been reported for producing hydantoins by reducing 5-arylidenehydantoin. In JP-A-60-11457, 5-benzylidenehydantoin was reduced with a Raney nickel catalyst to produce 5-benzylhydantoin.
~50% by weight is used.
又、特開昭６０−２０４７５０では、パラジウム−炭素
触媒を５−ベンジリデンヒダントインに対し２１重量％
使用し、ＩＮ水酸化ナトリウム中室温にて還元している
。Furthermore, in JP-A-60-204750, palladium-carbon catalyst was added in an amount of 21% by weight based on 5-benzylidenehydantoin.
and reduced in IN sodium hydroxide at room temperature.
（発明が解決しようとする問題点）
前述の方法は、いずれも高価な触媒を多量に必要とする
ため、触媒コストが高く、経済的でないばかりか、反応
後触媒を除去する際大きな濾過機を要し、工業的には極
めて不利な欠点を有している。(Problems to be Solved by the Invention) All of the above-mentioned methods require a large amount of expensive catalyst, so the catalyst cost is high and not only is it uneconomical, but also requires a large filter to remove the catalyst after the reaction. Therefore, it has a drawback that is extremely disadvantageous from an industrial perspective.
（問題を解決するための手段）
本発明者らは、触媒量を低減すべく鋭意研究を重ねた結
果、パラジウム−炭素触媒において、触媒活性は反応温
度により著しく左右されることをつきとめ、特定の温度
条件下で還元することにより著しく触媒を低減できるこ
とを見出し、本発明を完成するにいたった。(Means for Solving the Problem) As a result of extensive research aimed at reducing the amount of catalyst, the present inventors found that in palladium-carbon catalysts, the catalytic activity is significantly affected by the reaction temperature, and It was discovered that the amount of catalyst can be significantly reduced by reduction under temperature conditions, leading to the completion of the present invention.
すなわち、本発明は一般式（Ｉ）
く式中、Ｒ３およびＲ２は、水素原子、水酸基、炭素数
１〜６のアルコキシ基及び炭素数１〜６のアルキル基を
示し、お互いに同一でも異なってもよい）で表される５
−了り−リデンヒダントインをパラジウム−炭素触媒の
存在下、３０〜１００℃の温度で水素により還元するこ
とを特徴とする一般式（式中、Ｒ９およびＲ２は一般式
（Ｉ）の場合と同じ意味である）で表されるヒダントイ
ン類の製造方法である。That is, the present invention provides general formula (I), in which R3 and R2 represent a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms, and may be the same or different from each other. 5 expressed as
-Complete- A general formula characterized in that lydenhydantoin is reduced with hydrogen in the presence of a palladium-carbon catalyst at a temperature of 30 to 100°C (wherein R9 and R2 are the same as in general formula (I)) This is a method for producing hydantoins represented by the following meanings.
本発明の方法において、原料として用いられる一般式（
りで表される５−アリーリデンヒダントインは、アルデ
ヒドとヒダントインとの縮合等によって容易に得られ、
例えば、５−ベンジリデンヒダントイン、５−（２−ヒ
ドロキシベンジリデン）ヒダントイン、５−（３−ヒド
ロキシベンジリデン）ヒダントイン、５−（４−ヒドロ
キシベンジリデン）ヒダントイン、５−（２−メトキシ
ベンジリデン）ヒダントイン、５−（３−メトキシベン
ジリデン）ヒダントイン、５− （４−メトキシベンジ
リデン）ヒダントイン、５− （２−メチルベンジリデ
ン）ヒダントイン、５− （３−メチルベンジリデン）
ヒダントイン、５− （４−メチルベンジリデン）ヒダ
ントイン、５− （２，４−ジヒドロキシベンジリデン
）ヒダントイン、５−（３，４−ジヒドロキシベンジリ
デン）ヒダントイン、５−（２−ヒドロキシ−３−メト
キシベンジリデン）ヒダントイン、５−（３−ヒドロキ
シ−４−メトキシベンジリデン）ヒダントイン、５−（
４−ヒドロキシ−３−メトキシベンジリデン）ヒダント
イン、５−（３，４−ジメトキシベンジリデン）ヒダン
トイン等があげられる。In the method of the present invention, the general formula (
5-arylidenehydantoin represented by is easily obtained by condensation of aldehyde and hydantoin, etc.
For example, 5-benzylidenehydantoin, 5-(2-hydroxybenzylidene)hydantoin, 5-(3-hydroxybenzylidene)hydantoin, 5-(4-hydroxybenzylidene)hydantoin, 5-(2-methoxybenzylidene)hydantoin, 5-( 3-Methoxybenzylidene)hydantoin, 5-(4-methoxybenzylidene)hydantoin, 5-(2-methylbenzylidene)hydantoin, 5-(3-methylbenzylidene)
Hydantoin, 5-(4-methylbenzylidene)hydantoin, 5-(2,4-dihydroxybenzylidene)hydantoin, 5-(3,4-dihydroxybenzylidene)hydantoin, 5-(2-hydroxy-3-methoxybenzylidene)hydantoin, 5-(3-hydroxy-4-methoxybenzylidene)hydantoin, 5-(
Examples include 4-hydroxy-3-methoxybenzylidene)hydantoin and 5-(3,4-dimethoxybenzylidene)hydantoin.
本発明の方法において、反応温度は３０〜１００℃の範
囲である０反応温度が３０℃未満では、反応速度は著し
く低下し、反応の進行を補うために多量の触媒を使用し
なければならない、又反応温度が１００℃を越えると、
副反応が進行し、ヒダントイン類の収率は低下する。In the method of the present invention, the reaction temperature is in the range of 30 to 100 °C. If the reaction temperature is less than 30 °C, the reaction rate will be significantly reduced, and a large amount of catalyst must be used to compensate for the progress of the reaction. Also, if the reaction temperature exceeds 100℃,
Side reactions proceed and the yield of hydantoins decreases.
反応温度が３０〜１００℃の範囲の場合、パラジウム−
炭素触媒は原料の５−了り−リデンヒダントインに対し
、パラジウム−炭素触媒中のパラジウム量として０．０
５〜０．３重量％、好ましくは０．１〜０．２５重量％
でよい、又この触媒は繰り返し使用が可能である。When the reaction temperature is in the range of 30 to 100°C, palladium-
The carbon catalyst has a palladium content of 0.0 as the amount of palladium in the palladium-carbon catalyst relative to the raw material 5-lydenhydantoin.
5-0.3% by weight, preferably 0.1-0.25% by weight
This catalyst can be used repeatedly.
パラジウム量が０．３重量％を越えるパラジウム−炭素
触媒を使用しても反応速度、収率の向上は見られず、経
済性の点から不利となる。Even if a palladium-carbon catalyst containing more than 0.3% by weight of palladium is used, no improvement in reaction rate or yield is observed, which is disadvantageous from an economic point of view.
本発明の方法において用いられるパラジウム−炭素触媒
に特に制限はな（、例えば、パラジウム含有率が５重量
％と１０重量％のパラジウム−炭素触媒などがあげられ
、これらは湿潤していても、乾燥していてもよい。The palladium-carbon catalyst used in the method of the present invention is not particularly limited (e.g., palladium-carbon catalysts with a palladium content of 5% and 10% by weight, etc.) may be wet or dry. You may do so.
本発明の方法において用いられる溶媒は、一般に接触還
元に用いられる溶媒を使用することができ、例えば、水
、メチルアルコール、エチルアルコール、テトラヒドロ
フラン、ジオキサン、ベンゼン、酢酸、水酸化ナトリウ
ムなどの金属アルカリ水溶液、アンモニア水溶液及びｎ
−ブチルアミンなどのアミン水溶液などを使用すること
ができる、しかし、溶媒によっては、原料または生成物
が溶解せず、結晶が析出することがあるが、反応には何
ら問題はない０反応後結晶が析出している場合、触媒を
分離する際は生成物が溶解する溶媒を加えて分離すれば
よい、操作性の観点から反応溶媒として生成物が溶解す
る溶媒を選択する方が好ましい。The solvent used in the method of the present invention can be a solvent generally used for catalytic reduction, such as water, methyl alcohol, ethyl alcohol, tetrahydrofuran, dioxane, benzene, acetic acid, a metal alkali aqueous solution such as sodium hydroxide, etc. , ammonia aqueous solution and n
-Aqueous solutions of amines such as butylamine can be used. However, depending on the solvent, the raw materials or products may not dissolve and crystals may precipitate, but this does not cause any problem with the reaction. No crystals appear after the reaction. If the catalyst is precipitated, it is sufficient to add a solvent in which the product can be dissolved to separate the catalyst. From the viewpoint of operability, it is preferable to select a solvent in which the product can be dissolved as the reaction solvent.
本発明に方法における水素圧力は、常圧でも、加圧でも
よいが、通常は常圧〜５０Ｋｇ／ｃｆｆｌＧの範囲でよ
い。The hydrogen pressure in the method of the present invention may be normal pressure or pressurized, but is usually in the range of normal pressure to 50 kg/cfflG.
反応の終了は、水素の吸収が止まるので容易に判断する
ことができ、通常、１〜１０時間で反応が完結する。The end of the reaction can be easily determined because hydrogen absorption stops, and the reaction is usually completed in 1 to 10 hours.
本発明に方法において、生成物のヒダントイン類を結晶
として取り出す場合は、触媒を分離後、濃縮または冷却
により析出した結晶を分離すればよい、又、溶媒に水酸
化ナトリウムなどの金属アルカリ水溶液を用いた場合に
は、塩酸、硫酸、トリエンスルホン酸などの酸により中
和し、析出した結晶を分離すればよい。In the method of the present invention, when the product hydantoins are extracted as crystals, the precipitated crystals may be separated by concentration or cooling after separating the catalyst, or an aqueous metal alkali solution such as sodium hydroxide may be used as the solvent. If so, it may be neutralized with an acid such as hydrochloric acid, sulfuric acid, or trienesulfonic acid, and the precipitated crystals may be separated.
（実施例）
以下、実施例によって、本発明の方法について更に具体
的に説明する。(Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
実施例１
攪拌機、温度計、水素導入管を備えた１２ガラス製耐圧
容器に５−（４−ヒドロキシベンジリデン）ヒダントイ
ン５０ｇ、５％パラジウム−炭素２．０ｇ（パラジウム
１５− （４−ヒドロキシベンジリデン）ヒダントイン
・０．２重量％）及び４重量％水酸化ナトリウム水溶液
４５０ｇを仕込み、４０℃、１０Ｋｇ／ａｊＧで水素化
反応を行った。水素の吸収は５時間で終了し、水素吸収
率は１０１％であった。触媒を濾別後反応液を液体クロ
マトグラフィーで分析したところ５−（４−ヒドロキシ
ベンジル）ヒダントインの収率９９％〔仕込み５−（４
−ヒドロキシベンジリデン）ヒダントインモル基準〕で
あった。Example 1 50 g of 5-(4-hydroxybenzylidene)hydantoin and 2.0 g of 5% palladium-carbon (palladium 15-(4-hydroxybenzylidene)hydantoin) were placed in a 12-glass pressure-resistant container equipped with a stirrer, a thermometer, and a hydrogen inlet tube.・0.2% by weight) and 450g of a 4% by weight aqueous sodium hydroxide solution were charged, and a hydrogenation reaction was carried out at 40°C and 10Kg/ajG. Hydrogen absorption was completed in 5 hours, and the hydrogen absorption rate was 101%. After filtering off the catalyst, the reaction solution was analyzed by liquid chromatography, and the yield of 5-(4-hydroxybenzyl)hydantoin was 99% [Preparation 5-(4
-hydroxybenzylidene)hydantoin molar basis].
反応液を塩酸にて中和し、析出した結晶を濾別後水洗乾
燥し、純度９９．５％の５−（４−ヒドロキシベンジル
）ヒダントイン４９．５ｇ （収率９８．５％）を得た
。The reaction solution was neutralized with hydrochloric acid, and the precipitated crystals were separated by filtration, washed with water, and dried to obtain 49.5 g of 5-(4-hydroxybenzyl)hydantoin with a purity of 99.5% (yield: 98.5%). .
実施例２
攪拌機、温度計、コンデンサー、水素導入管を備えたフ
ラスコに５−（４−ヒドロキシベンジリデン）ヒダント
イン１００ｇ、５％パラジウム−炭素２．０ｇ（パラジ
ウム１５− （４−ヒドロキシベンジリデン）ヒダント
イン・０．１重量％）及び８重量％水酸化ナトリウム水
溶液４５０ｇを仕込み、６０℃、常圧で水素化反応を行
った。水素の吸収は３時間で終了し、水素吸収峯は１０
０％であった。触媒を濾別後反応液を液体クロマトグラ
フィーで分析したところ５−（４−ヒドロキシベンジル
）ヒダントインの収率は９８％であった。Example 2 In a flask equipped with a stirrer, a thermometer, a condenser, and a hydrogen inlet tube, 100 g of 5-(4-hydroxybenzylidene)hydantoin and 2.0 g of 5% palladium-carbon (palladium 15-(4-hydroxybenzylidene)hydantoin.0 .1% by weight) and 450g of an 8% by weight aqueous sodium hydroxide solution were charged, and a hydrogenation reaction was carried out at 60°C and normal pressure. Hydrogen absorption ends in 3 hours, and the hydrogen absorption peak is 10
It was 0%. After filtering off the catalyst, the reaction solution was analyzed by liquid chromatography, and the yield of 5-(4-hydroxybenzyl)hydantoin was 98%.
実施例３
実施例２と同じ装置のフラスコに５〜（４−ヒドロキシ
ベンジリデン）ヒダントイン５０ｇ、５％パラジウム−
炭素１．０ｇ（パラジウム１５−（４−ヒドロキシベン
ジリデン）ヒダントイン・０．２重量％）及び水４５０
ｇを仕込み、８０℃、常圧で水素化反応を行った。水素
の吸収は１．５時間で終了し、水素吸収率は１０２％で
あった。Example 3 In a flask using the same equipment as in Example 2, 50 g of 5-(4-hydroxybenzylidene)hydantoin and 5% palladium-
Carbon 1.0g (palladium 15-(4-hydroxybenzylidene)hydantoin, 0.2% by weight) and water 450g
A hydrogenation reaction was carried out at 80° C. and normal pressure. Hydrogen absorption was completed in 1.5 hours, and the hydrogen absorption rate was 102%.
冷却後、４５重量％水酸化ナトリウム水溶液５０ｇを加
え析出している結晶を溶解し、触媒を濾別した後、反応
液を液体クロマトグラフィーで分析したところ５−（４
−ヒドロキシベンジル）ヒダントインの収率は９４％で
あった。After cooling, 50 g of a 45% by weight aqueous sodium hydroxide solution was added to dissolve the precipitated crystals, and the catalyst was filtered off. The reaction solution was analyzed by liquid chromatography to find that 5-(4
The yield of -hydroxybenzyl)hydantoin was 94%.
触媒を濾別した反応液を塩酸にて中和し析出した結晶を
濾別、水洗乾燥し、純度９９．５％の５−（４−ヒドロ
キシベンジル）ヒダントイン４７．０ｇ（収率９３％）
を得た。The reaction solution after filtering off the catalyst was neutralized with hydrochloric acid, and the precipitated crystals were separated by filtration, washed with water, and dried to obtain 47.0 g of 5-(4-hydroxybenzyl)hydantoin with a purity of 99.5% (yield: 93%).
I got it.
実施例４
実施例２と同じ装置のフラスコに５−（４−ヒドロキシ
ベンジリデン）ヒダントイン５０ｇ、５％パラジウム−
炭素１．５ｇ（パラジウム／５−（４−ヒドロキシベン
ジリデン）ヒダントイン・０．１５重１％）及び２０重
量％ｎ−ブチルアミン水溶液４５０ｇを仕込み、６０℃
、常圧で水素化反応を行った。水素の吸収は２時間で終
了し、水素吸収率は１００％であった。触媒を濾別後、
反応液を液体クロマトグラフィーで分析したところ５−
（４−ヒドロキシベンジル）ヒダントインの収率は９４
％であった。Example 4 In a flask with the same equipment as in Example 2, 50 g of 5-(4-hydroxybenzylidene)hydantoin and 5% palladium-
1.5 g of carbon (palladium/5-(4-hydroxybenzylidene)hydantoin, 0.15% by weight) and 450 g of a 20% by weight n-butylamine aqueous solution were charged and heated at 60°C.
, the hydrogenation reaction was carried out at normal pressure. Hydrogen absorption was completed in 2 hours, and the hydrogen absorption rate was 100%. After filtering out the catalyst,
When the reaction solution was analyzed by liquid chromatography, 5-
The yield of (4-hydroxybenzyl)hydantoin is 94
%Met.
実施例５
実施例２と同じ装置のフラスコに５−（４−ヒドロキシ
ベンジリデン）ヒダントイン５０ｇ、５％パラジウム−
炭素２．５ｇ（パラジウム１５− （４−ヒドロキシベ
ンジリデン）ヒダントイン＝０．２５重景％）及び４重
量％水酸化ナトリウム水溶液４５０ｇを仕込み、６０℃
、常圧で水素化反応を行つた。水素の吸収は２時間で終
了し、水素吸収率は１００％であった。Example 5 In a flask using the same equipment as in Example 2, 50 g of 5-(4-hydroxybenzylidene)hydantoin and 5% palladium-
2.5 g of carbon (palladium 15-(4-hydroxybenzylidene)hydantoin = 0.25% by weight) and 450 g of a 4% by weight aqueous sodium hydroxide solution were charged and heated at 60°C.
, the hydrogenation reaction was carried out at normal pressure. Hydrogen absorption was completed in 2 hours, and the hydrogen absorption rate was 100%.
その後触媒を濾別した。この濾別した触媒を用いて上述
と同様の操作を１０回繰り返したところ、水素の吸収時
間及び水素吸収率は１０回の反応を通してほとんど変わ
りなく、５−（４−ヒドロキシベンジル）ヒダントイン
の平均収率は９７％であった。Thereafter, the catalyst was filtered off. When the same operation as described above was repeated 10 times using this filtered catalyst, the hydrogen absorption time and hydrogen absorption rate remained almost unchanged throughout the 10 reactions, and the average yield of 5-(4-hydroxybenzyl)hydantoin was found to be almost constant throughout the 10 reactions. The rate was 97%.
比較例１
実施例と同じ装置のＩ！ガラス製耐圧容器に５−（４−
ヒドロキシベンジリデン）ヒダントイン５０ｇ、５％パ
ラジウム−炭素２０．０ｇ（パラジウム１５−（４−ヒ
ドロキシベンジリデン）ヒダントイン−２，０重量％）
及び４重量％水酸化ナトリウム水溶液４５０ｇを仕込み
、２５℃、１０Ｋｇ１０ＪＧで水素化反応を行った。Comparative Example 1 I! of the same device as in Example. 5-(4-
50 g of hydroxybenzylidene) hydantoin, 20.0 g of 5% palladium on carbon (palladium 15-(4-hydroxybenzylidene) hydantoin - 2.0% by weight)
and 450 g of a 4% by weight aqueous sodium hydroxide solution, and a hydrogenation reaction was carried out at 25° C. and 10 kg/10 JG.
１２時間反応後の水素吸収率は９５％であった。触媒を
濾別後、反応液を液体クロマトグラフィーで分析したと
ころ５−（４−ヒドロキシベンジル）ヒダントインの収
率は９３％、未反応５− （４−ヒドロキシベンジリデ
ン）ヒダントインは６％残存していた。The hydrogen absorption rate after 12 hours of reaction was 95%. After filtering off the catalyst, the reaction solution was analyzed by liquid chromatography, and the yield of 5-(4-hydroxybenzyl)hydantoin was 93%, with 6% of unreacted 5-(4-hydroxybenzylidene)hydantoin remaining. .
反応液を塩酸にて中和し、析出した結晶を濾別後水洗乾
燥し、純度９４．５％の５−（４−ヒドロキシベンジル
）ヒダントイン結晶を４９．５ ｇ得たが、原料の５−
（４−ヒドロキシベンジリデン）ヒダントインが５％含
まれていた。The reaction solution was neutralized with hydrochloric acid, and the precipitated crystals were separated by filtration, washed with water, and dried to obtain 49.5 g of 5-(4-hydroxybenzyl)hydantoin crystals with a purity of 94.5%.
It contained 5% (4-hydroxybenzylidene)hydantoin.
比較例２
実施例１と同じ装置の１２ガラス製耐圧容器に５−（４
−ヒドロキシベンジリデン）ヒダントイン５０ｇ、５％
パラジウム−炭素２０．０ｇ（パラジウム１５− （４
−ヒドロキシベンジリデン）ヒダントイン・０．２重量
％）及び４重量％水酸化ナトリウム水溶液４５０ｇを仕
込み、１１０℃、１０Ｋｇ／ａＪＧで水素化反応を行っ
た。Comparative Example 2 5-(4
-hydroxybenzylidene) hydantoin 50g, 5%
Palladium-carbon 20.0g (palladium 15-(4
-hydroxybenzylidene)hydantoin (0.2% by weight) and 450 g of a 4% by weight aqueous sodium hydroxide solution were charged, and a hydrogenation reaction was carried out at 110°C and 10 kg/aJG.
２時間反応後の水素吸収率は２５％であった。触媒を濾
別後、反応液を液体クロマトグラフィーで分析したとこ
ろ５−（４−ヒドロキシベンジル）ヒダントインの収率
は２７％であり、原料は消失していた。The hydrogen absorption rate after 2 hours of reaction was 25%. After filtering off the catalyst, the reaction solution was analyzed by liquid chromatography, and the yield of 5-(4-hydroxybenzyl)hydantoin was 27%, indicating that the raw material had disappeared.
実施例６〜１０
実施例１と同じ装置のＩＥガラス製耐圧容器に５−了り
−リデンヒダントイン５０ｇ、５％パラジウム−炭素２
０．０ｇ（パラジウム１５−アリーリデンヒダントイン
・０．２重量％）及び第１表に示す溶媒４５０ｇを仕込
み、４０℃、５Ｋｇ／ｄＧで水素化反応を行った。Examples 6 to 10 In an IE glass pressure-resistant container of the same apparatus as in Example 1, 50 g of 5-yellow-redenhydantoin and 5% palladium-carbon 2 were added.
0.0 g (palladium 15-arylidenehydantoin, 0.2% by weight) and 450 g of the solvent shown in Table 1 were charged, and a hydrogenation reaction was carried out at 40° C. and 5 kg/dG.
結果は第１表のとおりであった。The results are shown in Table 1.
（発明の効果）
本発明の方法によると、従来法に比べて著しく触媒量を
低減でき、触媒コストの低減及び触媒濾過機のコンパク
ト化が可能となり工業的に有利にヒダントイン類を製造
することができる。(Effects of the Invention) According to the method of the present invention, the amount of catalyst can be significantly reduced compared to the conventional method, the catalyst cost can be reduced, and the catalyst filter can be made more compact, making it possible to produce hydantoins industrially advantageously. can.
特許出願人 三井東圧化学株式会社 手続補正書（自発） 昭和６１年 ９月２５日Patent applicant: Mitsui Toatsu Chemical Co., Ltd. Procedural amendment (voluntary) September 25, 1986
Claims (1)
素数１〜６のアルコキシ基または炭素数１〜６のアルキ
ル基を示し、お互いに同一でも異なってもよい）で表さ
れる５−アリーリデンヒダントインをパラジウム−炭素
触媒の存在下、３０〜１００℃の温度で水素により還元
することを特徴とする一般式（II） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿１およびＲ＿２は一般式（ I ）の場合と
同じ意味である）で表されるヒダントイン類の製造方[Claims] 1) General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 and R_2 are a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a carbon 5-arylidenehydantoin (representing an alkyl group of numbers 1 to 6, which may be the same or different) is reduced with hydrogen at a temperature of 30 to 100 ° C. in the presence of a palladium-carbon catalyst. Characteristic general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) Production of hydantoins represented by (in the formula, R_1 and R_2 have the same meanings as in the general formula (I)) direction
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61162007A JPS6317864A (en) | 1986-07-11 | 1986-07-11 | Production of hydantoins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61162007A JPS6317864A (en) | 1986-07-11 | 1986-07-11 | Production of hydantoins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6317864A true JPS6317864A (en) | 1988-01-25 |
Family
ID=15746271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61162007A Pending JPS6317864A (en) | 1986-07-11 | 1986-07-11 | Production of hydantoins |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6317864A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012012319A (en) * | 2010-06-30 | 2012-01-19 | Sekisui Medical Co Ltd | Method for producing benzyl hydantoin compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54160373A (en) * | 1978-05-23 | 1979-12-19 | Lilly Industries Ltd | Arylhydantoin |
-
1986
- 1986-07-11 JP JP61162007A patent/JPS6317864A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54160373A (en) * | 1978-05-23 | 1979-12-19 | Lilly Industries Ltd | Arylhydantoin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012012319A (en) * | 2010-06-30 | 2012-01-19 | Sekisui Medical Co Ltd | Method for producing benzyl hydantoin compound |
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