JPS6379879A - Production of hydantoins - Google Patents
Production of hydantoinsInfo
- Publication number
- JPS6379879A JPS6379879A JP61222117A JP22211786A JPS6379879A JP S6379879 A JPS6379879 A JP S6379879A JP 61222117 A JP61222117 A JP 61222117A JP 22211786 A JP22211786 A JP 22211786A JP S6379879 A JPS6379879 A JP S6379879A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- hydantoins
- hydantoin
- noble metal
- raw material
- 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.)
- Granted
Links
- 150000001469 hydantoins Chemical class 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 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
- 238000007429 general method Methods 0.000 claims 1
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 13
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 abstract description 12
- 229940091173 hydantoin Drugs 0.000 abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000007796 conventional method Methods 0.000 abstract description 6
- 229940100595 phenylacetaldehyde Drugs 0.000 abstract description 6
- IDNMGSROWDHHRA-UHFFFAOYSA-N 5-[hydroxy(phenyl)methyl]imidazolidine-2,4-dione Chemical compound C=1C=CC=CC=1C(O)C1NC(=O)NC1=O IDNMGSROWDHHRA-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- 235000008206 alpha-amino acids Nutrition 0.000 abstract description 4
- -1 leucine Chemical class 0.000 abstract description 4
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 abstract description 2
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 abstract 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 abstract 1
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 4
- DBOMTIHROGSFTI-UHFFFAOYSA-N 5-benzylimidazolidine-2,4-dione Chemical compound O=C1NC(=O)NC1CC1=CC=CC=C1 DBOMTIHROGSFTI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UDTSPKADQGPZFS-VURMDHGXSA-N (5z)-5-benzylideneimidazolidine-2,4-dione Chemical compound N1C(=O)NC(=O)\C1=C\C1=CC=CC=C1 UDTSPKADQGPZFS-VURMDHGXSA-N 0.000 description 2
- GLLIXWMNULCIKR-UHFFFAOYSA-N (R)-5-(4-hydroxybenzyl)hydantoin Natural products C1=CC(O)=CC=C1CC1C(=O)NC(=O)N1 GLLIXWMNULCIKR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 2
- 150000001371 alpha-amino acids Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 2
- VJUNTPRQTFDQMF-UHFFFAOYSA-N 1-benzylimidazolidine-2,4-dione Chemical compound O=C1NC(=O)CN1CC1=CC=CC=C1 VJUNTPRQTFDQMF-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- FYWDUQCSMYWUHV-UHFFFAOYSA-N 3-chloro-5-hydroxypentan-2-one Chemical compound CC(=O)C(Cl)CCO FYWDUQCSMYWUHV-UHFFFAOYSA-N 0.000 description 1
- GSTYGEGWJKJKQF-UHFFFAOYSA-N 5-(1,3-benzodioxol-5-ylmethylidene)imidazolidine-2,4-dione Chemical compound N1C(=O)NC(=O)C1=CC1=CC=C(OCO2)C2=C1 GSTYGEGWJKJKQF-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
- WVUAXUSTFAIYET-UHFFFAOYSA-N 5-[1,3-benzodioxol-5-yl(hydroxy)methyl]imidazolidine-2,4-dione Chemical compound C=1C=C2OCOC2=CC=1C(O)C1NC(=O)NC1=O WVUAXUSTFAIYET-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 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、フェニルアラニン、チロシ
ン、ＤＯＰＡ等のα−アミノ酸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 such as phenylalanine, tyrosine, and DOPA.
（従来の技術）
一般式、（■）で示されるヒダントイン類の合成法には
、以下の方法がある。(Prior Art) There are the following methods for synthesizing hydantoins represented by the general formula (■).
■ フェニルアセトアルデヒド類から合成する方法。■ Method of synthesis from phenylacetaldehyde.
フェニルアセトアルデヒド類とシアン化゛ノーダと炭酸
アンモニウムとからヒダントイン類を合成する。Hydantoins are synthesized from phenylacetaldehyde, cyanide, and ammonium carbonate.
その場合フェニルアセトアルデヒドとシアン化ソーダの
代わりにフェニルアセトアルデヒドと青酸とからのシア
ンヒドリンを用いることも可能である。In that case, instead of phenylacetaldehyde and sodium cyanide, it is also possible to use cyanohydrin made from phenylacetaldehyde and hydrocyanic acid.
■ ヒダントインとヘンズアルデヒド類とからアリーリ
チンヒダントイン類を合成し、次に水素添加してベンジ
ルヒダントイン類とする方法。■ A method of synthesizing aryritin hydantoins from hydantoin and henzaldehydes, and then hydrogenating them to produce benzylhydantoins.
この場合、グリコロニトリルまたはグリシノニトリルか
ら合成されるヒダントインとベンズアルデヒド類とから
アリーリチンヒダントイン類を得、その後、水素添加し
て目的とするヒダントイン類を得る。In this case, aryritin hydantoins are obtained from hydantoin synthesized from glycolonitrile or glycinonitrile and benzaldehydes, and then hydrogenated to obtain the desired hydantoins.
■ α−アミノ酸から合成する方法。■ Method of synthesis from α-amino acids.
α−アミノ酸とシアン酸カリウムとから合成されるヒダ
ントイン酸を酸処理してヒダントイン類を得、る。Hydantoin is obtained by acid treatment of hydantoic acid synthesized from α-amino acid and potassium cyanate.
（発明が解決しようとする問題点）
上記従来技術のうち、■の方法は原料とするフェニルア
セトアルデヒド類の人手が困難な場合がおおく、更に毒
性の強いシアン化合物を必要とするなど、必ずしも工業
的に十分満足される製造法とはいい難い、また、■の方
法は、中間体のアリーリチンヒダントイン類を合成する
段階において、多量のアルカリ存在下、無水の条件また
はモノエタノールアミン等の触媒存在下などの条件の特
殊化による煩雑な工程が増加して好ましくない。(Problems to be Solved by the Invention) Among the above conventional techniques, method (2) is not necessarily industrially viable, as it is often difficult to handle the raw material phenylacetaldehyde, and it also requires a highly toxic cyanide compound. It cannot be said that this is a production method that is fully satisfactory.In addition, method (2) requires the synthesis of the intermediate aryritine hydantoins in the presence of a large amount of alkali, anhydrous conditions, or the presence of a catalyst such as monoethanolamine. This is undesirable because it increases the number of complicated steps due to specialization of conditions such as the following.
■の方法は目的化合物を原料としており特別の場合以外
、工業的に価値がない。Method (2) uses the target compound as a raw material and has no industrial value except in special cases.
このような従来技術でヒダントイン類を高収率でかつ安
価に製造することは不可能であった。It has been impossible to produce hydantoins in high yield and at low cost using such conventional techniques.
（問題点を解決するための手段及び作用）本発明者らは
、前記公知技術の有する種々の問題点を解決するため鋭
意検討を行った結果、前記■の方法における中間体のア
リーリチンヒダントイン類を合成する段階において、副
生成物として考えられている５−（フェニルヒドロキシ
ルメチル）ヒダントイン類を接触水素還元しても目的の
化合物が得られることを見出し、本発明を完成するに至
った。(Means and effects for solving the problems) As a result of intensive studies to solve the various problems of the above-mentioned known techniques, the present inventors found that aryritinhydantoins, which are intermediates in the method (2) above, At the stage of synthesizing 5-(phenylhydroxylmethyl)hydantoins, which are considered as by-products, the inventors discovered that the desired compound could be obtained by catalytic hydrogen reduction, and the present invention was completed.
即ち、本発明は、一般式（［）
（式中、Ｒ，及びＲ２は水素原子、水酸基、炭素数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いでもよい）で表される
５−（フェニルヒドロキンルメチル）ヒダントイン類を
、貴金属触媒の存在下で接触水素還元することを特徴と
する一般式（（式中、Ｒ，及びＲ□は一般式（［）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 is based on the general formula ([) (wherein R and R2 are a hydrogen atom, a hydroxyl group, and a carbon number of 1 to
6 alkoxy group or an alkyl group having 1 to 6 carbon atoms, which may be the same or different from each other), is subjected to catalytic hydrogen reduction in the presence of a noble metal catalyst. This is a method for producing hydantoins represented by the general formula (wherein R and R□ have the same meanings as in the general formula ([)).
一般式（ＩＩ）で示される目的とする化合物は、具体的
には、フェニルアラニンの前駆体であるベンジルヒダン
トイン、またはＰ−ヒドロキシフェニルアラニンの前駆
体であるＰ−ヒドロキシヘンシルヒダントイン、ＤＯＰ
Ａの前駆体である３、４−ジヒドロキシヘンシルヒダン
トイン等である。Specifically, the target compound represented by general formula (II) is benzylhydantoin, which is a precursor of phenylalanine, or P-hydroxyhensylhydantoin, which is a precursor of P-hydroxyphenylalanine, DOP
3,4-dihydroxyhensylhydantoin, which is a precursor of A, and the like.
各々に相当する出発物質としての５−（フェニルヒドロ
キシルメチルン ヒダントイン類は、水またはアルコー
ル媒体中、アルカリの存在下でフェニルアセトアルデヒ
ド類とヒダントインとを反応させることにより容易に得
られる。The corresponding 5-(phenylhydroxylmethyl) hydantoins as starting materials can be easily obtained by reacting phenylacetaldehydes and hydantoins in the presence of an alkali in water or an alcoholic medium.
この反応で用いられるアルコールは、エチルアルコール
、イソプロピルアルコール等が好ましい、又、アルカリ
としては、ＮａＱＨＳＫＯＮ、第三級アミン類等が好ま
しい。The alcohol used in this reaction is preferably ethyl alcohol, isopropyl alcohol, etc., and the alkali is preferably NaQHSKON, tertiary amines, etc.
この反応の条件として、５０〜１００℃、好まくしは６
０〜９０℃の温度範囲が良い、圧力は常圧でも良い。The conditions for this reaction are 50 to 100°C, preferably 6
The temperature range is preferably from 0 to 90°C, and the pressure may be normal pressure.
本発明の方法では、水、アルカリ性水？８液、アルコー
ルまたは上記反応媒体と同じ媒体を用い、一般式（［）
で示される化合物を貴金属の存在下で接触水素還元する
。In the method of the present invention, water, alkaline water? Using liquid 8, alcohol or the same medium as the above reaction medium, the general formula ([)
The compound represented by is subjected to catalytic hydrogen reduction in the presence of a noble metal.
本発明で用いられるアルコールは、メチルアルコール、
エチルアルコール、イソプルピルアルコール等が好まし
い、アルカリはＮａＯＨ２にＯＨ、アミン、ＮＨ３等を
溶解手段として用いるのが良い。The alcohol used in the present invention includes methyl alcohol,
Ethyl alcohol, isopropyl alcohol, etc. are preferable, and as the alkali, it is preferable to use OH, amine, NH3, etc. in NaOH2 as a dissolving means.
本発明による方法では、貴金属触媒として既知の触媒を
使用することができる。更に詳しくは、周期律表の第８
亜属の元素（Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ）を
挙げることができ、なかでもバラジュウム（Ｐｄ）が特
に好ましい、貴金属触媒は、通常、既知の担体材料、例
えば、ＳｉＯいカーボン、酸化アルミニウム等に担持さ
れる。上記貴金属触媒の担持率は０．５〜ＩＯ重量％が
適当である。また該触媒は原料ヒダントイン類に対して
１〜３０重世％程度使用される。In the process according to the invention, known catalysts can be used as noble metal catalysts. For more details, see the 8th column of the periodic table.
Precious metal catalysts, of which mention may be made of the subgenus of elements (Ru, Rh, Pd, Os, Ir, Pt), of which baradium (Pd) is particularly preferred, are usually carried out on known support materials, such as SiO, carbon, etc. Supported on aluminum oxide, etc. The supporting ratio of the noble metal catalyst is suitably 0.5 to IO weight %. Further, the catalyst is used in an amount of about 1 to 30 weight percent based on the raw material hydantoin.
次に反応圧力は常圧で充分であるが、約１０Ｋｇ／ａｊ
Ｇまでの水素加圧でも反応を行うことができる。もっと
高い圧力は一般に何の利益ももたらさない。Next, the reaction pressure is sufficient at normal pressure, but about 10 kg/aj
The reaction can also be carried out under hydrogen pressure up to G. Higher pressures generally do not provide any benefit.
反応温度は、反応圧力や使用する媒体としてのアルカリ
の種類によって多少異なるが、通常、３０〜１００℃の
範囲、好ましくは５０〜８０℃の範囲である０反応時間
は１〜５時間時間色要である。The reaction temperature varies somewhat depending on the reaction pressure and the type of alkali used as a medium, but is usually in the range of 30 to 100°C, preferably in the range of 50 to 80°C.The reaction time is 1 to 5 hours. It is.
このようにして接触水素還元が終了した後は、常法にし
たがって触媒成分を除去したのち、反応ろ液のｐＨを７
〜８に調整して、ヒダントイン類の分解を避けるためｌ
ｏＯ’ｃ以下、好ましくは８０℃以下の温度で濃縮し、
常法により冷却して結晶としてとりだす、これを常法に
より乾燥して製品を得る。After the catalytic hydrogen reduction is completed in this way, the catalyst component is removed according to a conventional method, and the pH of the reaction filtrate is adjusted to 7.
~8 to avoid decomposition of hydantoins.
Concentrate at a temperature below oO'c, preferably below 80°C,
Cool it by a conventional method and take it out as a crystal, and dry it by a conventional method to obtain a product.
必要であれば活性炭処理、再結晶等の任意の精製が実施
可能である。If necessary, optional purification such as activated carbon treatment and recrystallization can be carried out.
（実施例）
以下、実施例を挙げて、本発明の方法を更に詳しく説明
するが、本発明はこれに限定されるものではない。(Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例１
撹はん機並びに温度計を備えた１ｏｏｏｃｃのオートク
レーブに５−（フェニルヒドロキシルメチル）ヒダント
イン１００．０ｇ 、 ４．０％ＮａＯＨ４５０，Ｏ
ｇ。Example 1 100.0 g of 5-(phenylhydroxylmethyl)hydantoin, 4.0% NaOH450,0 was placed in a 100cc autoclave equipped with a stirrer and a thermometer.
g.
５％Ｐｄ／Ｃ３，Ｏｇを充填して、窒素置換後、水素を
供給しながら昇温し、６０℃で水素の吸収が停止するま
で反応させた。その時の圧力は９にｇ／ｃｔＪＧであっ
た０反応終了後、冷却し反応生成液から触媒をろ別して
、ろ液を液体クロマトグラフィーで分析した。その結果
、５−ベンジルヒダントインが原料の５−（フェニルヒ
ドロキシルメチル）ヒダントインに対して９５％の収率
でえられた。After filling with 5% Pd/C3, Og and purging with nitrogen, the temperature was raised while supplying hydrogen, and the reaction was carried out at 60° C. until hydrogen absorption stopped. The pressure at that time was 9 g/ctJG. After the reaction was completed, it was cooled, the catalyst was filtered off from the reaction product solution, and the filtrate was analyzed by liquid chromatography. As a result, 5-benzylhydantoin was obtained in a yield of 95% based on the raw material 5-(phenylhydroxylmethyl)hydantoin.
実施例２
実施例１と同じオートクレーブに５−（）山ニルヒドロ
キシルメチル）ヒダントイン５０ｇ、メタノール３００
ｇ、５％Ｐｄ／ｃ １．５ｇを充填する以外は、実施例
Ｉと同じ操作をおこなった。Example 2 In the same autoclave as in Example 1, 50 g of 5-(hypernylhydroxylmethyl)hydantoin and 300 g of methanol were placed in the same autoclave as in Example 1.
The same operation as in Example I was performed except that 1.5 g of 5% Pd/c was charged.
その結果、５−ヘンシルヒダントインの収率ハ９０．５
％であった。As a result, the yield of 5-hensylhydantoin was 90.5
%Met.
実施例３
触媒として５％Ｒｕ／Ｓｉｎｇを用いる以外は、実施例
２と同じ条件で接触水素還元をおこなった。Example 3 Catalytic hydrogen reduction was carried out under the same conditions as in Example 2, except that 5% Ru/Sing was used as a catalyst.
その結果、５−ベンジルヒダントインの収率は９２．４
％であった。As a result, the yield of 5-benzylhydantoin was 92.4
%Met.
実施例４
原料としてベンズアルデヒドとヒダントインとから得ら
れるベンジリデンヒダントインと５−（フェニルヒドロ
キシルメチル）ヒダントインとの組成比がｌ：ｌである
混合物を、実施例２と同じ方法で接触水素還元した。Example 4 A mixture of benzylidenehydantoin and 5-(phenylhydroxylmethyl)hydantoin in a composition ratio of 1:1 obtained from benzaldehyde and hydantoin as raw materials was subjected to catalytic hydrogen reduction in the same manner as in Example 2.
その結果、ベンジリデンヒダントインと５−（フェニル
ヒドロキシルメチル）ヒダントインに対して５−ベンジ
ルヒダントインが収率９１．５％でえられた。As a result, 5-benzylhydantoin was obtained in a yield of 91.5% based on benzylidenehydantoin and 5-(phenylhydroxylmethyl)hydantoin.
実施例５
原料として５−（Ｐ−ヒドロキシフェニルヒドロキシル
メチル〉ヒダントイン１００ｇを用い１０％アンモニア
メタノール溶液４５０ｇの中で５％Ｐｄ／Ｃ１，５ｇを
触媒として接触水素還元した。Example 5 Using 100 g of 5-(P-hydroxyphenylhydroxylmethyl)hydantoin as a raw material, catalytic hydrogen reduction was carried out in 450 g of a 10% ammonia methanol solution using 1.5 g of 5% Pd/C as a catalyst.
その結果、５−（Ｐ−ヒドロキシベンジル）ヒダントイ
ンが収率８７．６％でえられた。As a result, 5-(P-hydroxybenzyl)hydantoin was obtained with a yield of 87.6%.
実施例６
原料としてＰ−ヒドロキシヘンズアルデヒドとヒダント
インとを縮合してえられる５−（Ｐ−ヒドロキシフェニ
ルヒドロキシルメチル）ヒダントインとＰ−ヒドロキシ
ベンジリデンヒダントインとの組成比がｌ；２である混
合物を実施例４と同じ方法で接触水素還元した。Example 6 A mixture having a composition ratio of 1:2 of 5-(P-hydroxyphenylhydroxylmethyl)hydantoin and P-hydroxybenzylidenehydantoin obtained by condensing P-hydroxyhenzaldehyde and hydantoin as raw materials was used as an example. Catalytic hydrogen reduction was performed in the same manner as in 4.
その結果、５−（Ｐ−ヒドロキシベンジル）ヒダントイ
ンが９１．８％の収率でえられた。As a result, 5-(P-hydroxybenzyl)hydantoin was obtained with a yield of 91.8%.
実施ｆＮ７
原料としてバニリンとヒダントインとを縮合してえられ
る５−（３−ヒドロキシ−４−メトキシフェニルヒドロ
キシルメチル）ヒダントインと３−ヒドロキシ−４−メ
トキシベンジリデンヒダントインとの組成比が１；２で
ある混合物１００ｇを、メタノール４００ｇに溶解し、
それに触媒として５％ｐｄ／ｃ １．５ｇを添加して６
０℃で接触水素還元を実施した。Implementation fN7 A mixture in which the composition ratio of 5-(3-hydroxy-4-methoxyphenylhydroxylmethyl)hydantoin and 3-hydroxy-4-methoxybenzylidenehydantoin is 1:2, which is obtained by condensing vanillin and hydantoin as raw materials. Dissolve 100g in 400g of methanol,
Add 1.5g of 5% pd/c as a catalyst to 6
Catalytic hydrogen reduction was performed at 0°C.
その結果、３−ヒドロキシ−４−メトキシヘンシルヒダ
ントインが９１．６％の収率で得られた。As a result, 3-hydroxy-4-methoxyhensylhydantoin was obtained with a yield of 91.6%.
実施例８
原料として３．４−メチレンジオキシヘンズアルデヒド
とヒダントインとを縮合してえられる５−（３，４−メ
チレンジオキシフェニルヒドロキシルメチル）ヒダント
インと３．４−メチレンジオキシベンジリデンヒダント
インとの組成比がｌ：５である混合物１００ｇを、メタ
ノール４００ｇに溶解し、それに触媒として５％Ｐｄ／
Ｃ１，５ｇを添加して６０℃°で接触水素還元を実施し
た。Example 8 5-(3,4-methylenedioxyphenylhydroxylmethyl)hydantoin obtained by condensing 3,4-methylenedioxyhenzaldehyde and hydantoin as raw materials and 3,4-methylenedioxybenzylidenehydantoin 100 g of a mixture with a composition ratio of 1:5 was dissolved in 400 g of methanol, and 5% Pd/
Catalytic hydrogen reduction was carried out at 60° C. by adding 1.5 g of C.
その結果、３．４−メチレンジオキンヘンシルヒダント
インが９０，８％の収率でえられた。As a result, 3,4-methylenedioquinhensylhydantoin was obtained with a yield of 90.8%.
（発明の効果）
本発明のヒダントイン類の製造方法は、アリーリチンヒ
ダントイン類を合成する段階において副生成物として考
えられていた５−（フェニルヒドロキシルメチル）ヒダ
ントイン類を除去する必要もなく、混合物のまま接触水
素還元することにより、目的とするヒダントイン類をｆ
％ることができる工業的に存利な方法である。(Effects of the Invention) The method for producing hydantoins of the present invention eliminates the need to remove 5-(phenylhydroxylmethyl)hydantoins, which were considered as by-products in the step of synthesizing aryritin hydantoins, and By catalytic hydrogen reduction, the desired hydantoins are
It is an industrially viable method that can reduce
Claims (1)
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いてもよい）で表さ
れる５−（フェニルヒドロキシルメチル）ヒダントイン
類を、貴金属触媒の存在下で接触水素還元することを特
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及び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法。[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 number A general method characterized by catalytic hydrogen reduction of 5-(phenylhydroxylmethyl)hydantoins represented by (1 to 6 alkyl groups, which may be the same or different) in the presence of a noble metal catalyst. Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 and R_2 have the same meanings as in the general formula (I)) A method for producing hydantoins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61222117A JPH0791272B2 (en) | 1986-09-22 | 1986-09-22 | Method for producing hydantoins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61222117A JPH0791272B2 (en) | 1986-09-22 | 1986-09-22 | Method for producing hydantoins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6379879A true JPS6379879A (en) | 1988-04-09 |
| JPH0791272B2 JPH0791272B2 (en) | 1995-10-04 |
Family
ID=16777420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61222117A Expired - Fee Related JPH0791272B2 (en) | 1986-09-22 | 1986-09-22 | Method for producing hydantoins |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791272B2 (en) |
-
1986
- 1986-09-22 JP JP61222117A patent/JPH0791272B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791272B2 (en) | 1995-10-04 |
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