JPS6115872B2 - - Google Patents
Info
- Publication number
- JPS6115872B2 JPS6115872B2 JP53044816A JP4481678A JPS6115872B2 JP S6115872 B2 JPS6115872 B2 JP S6115872B2 JP 53044816 A JP53044816 A JP 53044816A JP 4481678 A JP4481678 A JP 4481678A JP S6115872 B2 JPS6115872 B2 JP S6115872B2
- Authority
- JP
- Japan
- Prior art keywords
- hydantoin
- acid
- reaction
- glycinonitrile
- temperature
- 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
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 23
- 229940091173 hydantoin Drugs 0.000 claims description 23
- -1 Glycinonitrile inorganic acid salt Chemical class 0.000 claims description 20
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 2
- JYQQWQJCEUMXQZ-UHFFFAOYSA-N methyl cyanate Chemical compound COC#N JYQQWQJCEUMXQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 239000013078 crystal Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001913 cyanates Chemical class 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- NFODSNOCEFVBRY-UHFFFAOYSA-N 2-(carbamoylamino)acetamide Chemical compound NC(=O)CNC(N)=O NFODSNOCEFVBRY-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XFKYKTBPRBZDFG-UHFFFAOYSA-N 2-aminoacetonitrile;hydrochloride Chemical compound Cl.NCC#N XFKYKTBPRBZDFG-UHFFFAOYSA-N 0.000 description 2
- FYWDUQCSMYWUHV-UHFFFAOYSA-N 3-chloro-5-hydroxypentan-2-one Chemical compound CC(=O)C(Cl)CCO FYWDUQCSMYWUHV-UHFFFAOYSA-N 0.000 description 2
- 238000006150 Bucherer-Bergs reaction Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008361 aminoacetonitriles Chemical class 0.000 description 2
- 125000005219 aminonitrile group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 150000001469 hydantoins Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- UEKDRLRXXAOOFP-UHFFFAOYSA-N imidazolidine-2,4-dione Chemical class O=C1CNC(=O)N1.O=C1CNC(=O)N1 UEKDRLRXXAOOFP-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はグリシノニトリル無機酸塩とシアン酸
のアルカリ金属塩からヒダントインを製造する方
法に関するものである。
従来、ヒダントインの製造法として種々の方法
が提案されており、たとえばグリオキザールと尿
素を下記〔〕または〔〕式にしたがい反応さ
せてヒダントインを製造する方法が知られてい
る。
この方法によれば比較的好収率でヒダントイン
が得られるが、原料グリオキザールが高価なため
経済的な方法ではなく、また製造過程で多量の無
機酸を使用するのでその除去に手間がかかる。
一方、経済的な製造法としてホルムアルデヒド
とシアン化物を下記〔〕式にしたがい反応させ
る、いわゆるBucherer−Bergs法がある。
しかしこの方法は目的生成物の選択率が低いの
でこれを向上させる方法として反応生成物を無機
酸で処理する方法(特公昭39−24807号公報)、反
応系に第3アミンを添加する方法(特開昭48−
92371号公報)などが提案されているが、いずれ
の方法も〔〕および〔〕の反応にくらべると
副反応が多く、また目的生成物が着色し易いので
精製を必要とする。
更にヒダントインの他の製造法として下記
〔〕式に示すようなグリシンと尿素を反応させ
る方法も提案されている。
しかしこの方法は熔融反応であるため工業的に
は問題が多い。
また、下記〔〕式に示すようにグリシンエス
テルとシアン酸塩を反応させる方法もある。
この方法によれば比較的純度の高い目的生成物
が高収率で得られるが、原料グリシンエステルが
高価なため経済的な方法とは云えない。
ところで、従来、各種アミノニトリル類(また
はその誘導体)とシアン酸塩を反応させて、置換
ヒダントインを製造する方法が知られており、た
とえば以下に示すような合成法が試みられてい
る。
収率62%〔J.A.C.S、44、1746、(1922)〕
収率71%〔J.A.C.S、58、474(1936)〕
収率73%〔J.A.C.S、70、900、(1948)〕
(ニ) KCN、KOCNおよびアルデヒドとアンモニ
アとの付加化合物とを混合して得られる溶液と
稀硫酸とを徐々に反応させる。
〔Ann、169、125、(1873)〕
本発明は本質的にこの反応を利用してグリシノ
ニトリル塩とシアン酸塩から無置換ヒダントイン
(ヒダントイン)を製造しようとするものである
が、かかる方法でヒダントインを製造しようと云
う試みは未だ報告されていない。これは恐らくア
ミノニトリルのなかでもグリシノニトリルは特に
不安定な化合物であつて重合等を起し易いため、
これを用いた場合は副反応が起り易いことおよび
よく知られているようにヒダントインは置換ヒダ
ントインにくらべて加水分解を起し易いこと等の
理由により、かかる方法でヒダントインを製造し
ても高収率で目的物が得られないと考えられるか
らであると推定される。
しかるに本発明者らはグリシノニトリルの塩酸
塩、硫酸塩等とシアン酸のアルカリ金属塩をまず
水性媒体中で反応させ、次いで得られた反応混合
物を硫酸、塩酸等で加熱処理することにより、意
外にも高収率、高選択率でヒダントインが得られ
ることおよびこの方法にしたがえば従来法よりも
種々有利にヒダントインを製造することができる
こと等を見出し、本発明をなすに到つた。
すなわち、本発明は一般式
The present invention relates to a method for producing hydantoin from an inorganic acid salt of glycinonitrile and an alkali metal salt of cyanic acid. Conventionally, various methods for producing hydantoin have been proposed. For example, a method for producing hydantoin by reacting glyoxal and urea according to the following formula [] or [] is known. According to this method, hydantoin can be obtained in a relatively good yield, but it is not an economical method because the raw material glyoxal is expensive, and since a large amount of inorganic acid is used in the production process, its removal is time-consuming. On the other hand, as an economical production method, there is the so-called Bucherer-Bergs method in which formaldehyde and cyanide are reacted according to the following formula. However, this method has a low selectivity for the target product, so methods to improve this include treating the reaction product with an inorganic acid (Japanese Patent Publication No. 39-24807), adding a tertiary amine to the reaction system ( Japanese Patent Application Publication 1973-
92371) have been proposed, but both methods involve more side reactions than the reactions [ ] and [ ] and require purification because the desired product is likely to be colored. Furthermore, as another method for producing hydantoin, a method has been proposed in which glycine and urea are reacted as shown in the following formula []. However, since this method involves a melt reaction, there are many problems from an industrial perspective. There is also a method in which glycine ester and cyanate are reacted as shown in the following formula []. According to this method, a target product of relatively high purity can be obtained in high yield, but the raw material glycine ester is expensive, so it cannot be called an economical method. By the way, methods for producing substituted hydantoins by reacting various aminonitriles (or derivatives thereof) with cyanates have been known, and for example, the following synthetic methods have been attempted. Yield 62% [JACS, 44 , 1746, (1922)] Yield 71% [JACS, 58 , 474 (1936)] Yield 73% [JACS, 70 , 900, (1948)] (d) A solution obtained by mixing KCN, KOCN, and an addition compound of aldehyde and ammonia is gradually reacted with dilute sulfuric acid. [Ann, 169 , 125, (1873)] The present invention essentially utilizes this reaction to produce unsubstituted hydantoin (hydantoin) from glycinonitrile salt and cyanate; No attempt to produce hydantoin has yet been reported. This is probably because glycinonitrile is a particularly unstable compound among aminonitrile and is prone to polymerization.
When using this method, side reactions are likely to occur, and as is well known, hydantoin is more easily hydrolyzed than substituted hydantoins, so even if hydantoin is produced using this method, the yield is high. It is presumed that this is because it is thought that the target product cannot be obtained at this rate. However, the present inventors first reacted glycinonitrile hydrochloride, sulfate, etc. with an alkali metal salt of cyanic acid in an aqueous medium, and then heat-treated the resulting reaction mixture with sulfuric acid, hydrochloric acid, etc. The present inventors have surprisingly discovered that hydantoin can be obtained in high yield and high selectivity, and that hydantoin can be produced using this method in a variety of ways more advantageously than conventional methods, leading to the present invention. That is, the present invention is based on the general formula
【式】(式中、ZはHClまたはH2SO4
をあらわす)で示されるグリシノニトリル無機酸
塩と一般式MeOCN(式中、MeはNaまたはKを
あらわす)で示されるシアン酸のアルカリ金属塩
を水性媒体中で温度0〜20℃の範囲で反応させ、
次いで得られた反応混合物に硫酸または塩酸を添
加して温度70〜110℃の範囲で加熱処理すること
を特徴とするヒダントインの製造法を要旨とする
ものである。
本発明の利点を列挙すればたとえば次のごとく
である。
(1) 原料グリシノニトリル無機酸塩は青酸、ホル
マリンおよびアンモニアより容易に合成される
物質で、通常、高価なものではないため本発明
によれば従来よりも経済的に有利にヒダントイ
ンを製造することができる。
(2) 反応の選択率が高く、80%以上の収率でヒダ
ントインが得られる。
(3) 特にBucherer−Bergs法にくらべると、ヒダ
ントイン化不能の副反応が少なく、かつ生成物
の精製が容易で、製品の着色が著しく少ない。
本発明について説明すると、原料として用いる
グリシノニトリル無機酸塩は、グリシノニトリル
を硫酸または塩酸により中和することにより容易
に得られる。
またもう一方の原料であるシアン酸のアルカリ
金属塩は工業的に製造されていて入手は容易であ
る。
グリシノニトリル無機酸塩とシアン酸のアルカ
リ金属塩の使用割合は通常等モルかまたはシアン
酸塩を僅か過剰に用いる。
本発明においてはグリシノニトリル無機酸塩と
シアン酸のアルカリ金属塩の反応に際し、媒体と
して通常水を用いるがその使用量はグリシノニト
リル無機酸塩1モルについて400〜1000mlとする
のが好ましい。
反応方法としては、グリシノニトリル無機酸塩
の水溶液中にシアン酸塩を少量ずつ添加して反応
させる方法がよい。
反応温度は通常0〜20℃、好ましくは、0〜10
℃である。20℃以上の温度で反応させると、副反
応が増加するので好ましくない。
シアン酸塩の添加は通常1時間以内で終了させ
るのが望ましい。
シアン酸塩の添加終了後、反応温度を保ちなが
ら反応混合物を1〜2時間熟成して反応を完結さ
せる。
本発明においてはグリシノニトリル無機酸塩と
シアン酸塩の反応により、先ずヒダントイン酸ニ
トリルが生成し、次いでこれが水和してヒダント
イン酸アマイドが生成するものと考えられる。こ
の反応の過程で無機塩が副生する。
反応終了後、反応混合物に硫酸または塩酸を加
えて加熱処理するが、この処理によりヒダントイ
ンが生成する。
この際用いる硫酸または塩酸の量は原料グリシ
ノニトリル無機酸塩1モルに対して1〜2モルで
あり、それぞれ濃硫酸または濃塩酸が用いられ
る。
加熱処理等の温度は通常70〜110℃であり、好
ましくは80〜100℃である。
硫酸または塩酸は反応混合物に徐々に加え、添
加時間は通常1時間以内とするのが、好ましい。
酸の添加後、処理温度を保ちながら処理物を1
〜4時間熟成してヒダントイン化を完結させる。
処理後、塩酸を用いた場合は処理液を減圧蒸溜
して塩化水素をできるだけ除去したのち、水を蒸
発させて乾固する。
次いで得られた残渣を副生無機塩は溶かさない
がヒダントインを溶かす有機溶媒で抽出する。
この際、用いられる有機溶媒の種類としてジグ
ライム、ジメチルホルムアミド、N・N−ジメチ
ルアセトアミド、N−メチルピロリドンなどが挙
げられる。
一方、硫酸が用いられた場合は、処理後、処理
物をアンモニア、炭酸ソーダ、重曹、苛性ソー
ダ、生石灰、消石灰、炭酸カルシウム等の塩基で
中和したのち水を蒸発させて乾固する。次いで得
られた残渣を塩酸処理の場合と同様の有機溶媒で
抽出する。
以上のようにして得られた抽出液は適宜の方法
により濃縮して目的物のヒダントインを取得す
る。
本発明は次のごとく実施するのが望ましい。
還流コンデンサー、撹拌機、温度計、滴下ロー
トを備えた反応器にグリシノニトリル無機酸塩を
仕込み、これに所定量の水を加えて溶解する。
次いで溶液を温度10℃以下に冷却してこのなか
にシアン酸塩の粉末を徐々に入れて反応させる。
反応は僅かの発熱反応で、次第に液は濁り、明
瞭に沈澱をみる。
シアン酸塩の添加終了後、反応温度を保ちなが
ら約1時間熟成して反応を完結させる。
次に、反応混合物を90℃の温度に加温し、この
なかに滴下ロートより所定量の硫酸または塩酸を
滴下して酸処理をする。
酸の滴下中は処理物の温度が90〜100℃を保つ
よう滴下量を調節する。
滴下終了後、上記温度を保ちながら処理物を2
〜4時間熟成する。
この酸処理に硫酸を用いた場合は、処理後、処
理物に炭酸ソーダを加えて処理物のPHを3〜5に
する。
中和後、処理物より減圧下に水を除去して乾固
させる。
次いで得られた残渣にジメチルホルムアミドを
加え、約80℃の温度で1〜2時間加熱撹拌して可
溶分を抽出する。
抽出物を熱時過して副生無機塩を分離する。
ジメチルホルムアミド溶液を減圧下に濃縮して
目的物のヒダントインを取得する。
このような方法により着色が少なく純度の高い
ヒダントインを得ることができる。
次に本発明を実施例により更に詳細に説明す
る。
実施例 1
還流コンデンサー、撹拌機、温度計、滴下ロー
トを付した内容500mlのセパラブルフラスコに工
業用グリシノニトリル硫酸塩26.25g(0.25モ
ル)および水150mlを入れて溶解させた。
次に、フラスコ内部を10℃以下の温度に冷却し
て工業用シアン酸ソーダ18.08g(純分90%以
上)の粉末を少量ずつ加えて反応させた。
僅かの発熱が認められ、溶液は漸次濁りを増
し、沈澱が生成した。
シアン酸ソーダの添加終了後、フラスコ内容物
を5〜10℃で1時間さらに室温で1時間熱成し
た。
次いでフラスコ内を90℃に加温し、31.85gの
濃硫酸(0.325モル)を滴下した。
明瞭な発熱反応が起るが、フラスコ内部は90〜
100℃を保つようにする。
滴下終了後、上記温度で約2時間熟成した。
次に、フラスコを室温迄冷却したのちフラスコ
内に炭酸ソーダ粉末を加え、内容物のPHを3〜5
にした。
中和後、フラスコ内より減圧下に水を留出させ
て乾固した。
次にフラスコ内にジメチルホルムアミド100ml
を加え、80℃で約1時間撹拌した後、過した。
液よりジメチルホルムアミドを減圧下に90ml
留出させたのち、常温で放置した。
析出結晶を分離し、少量のジメチルホルムアミ
ドで洗浄し、取得結晶を60℃で真空乾燥した。
取得結晶の量は20.94g(収率83.8%)で結晶
は微黄色を呈し、結晶中のヒダントイン酸または
ヒダントイン酸アミドの含有量はErlich試薬を用
いて比色分析したところ2%以下であつた。
なお、結晶分離母液および洗液より更に1.5g
のヒダントインが回収された。
実施例 2
実施例1で用いたのと同様の反応器に工業用グ
リシノニトリル塩酸塩23.13g(0.25モル)と水
80mlを仕込んで溶解させた。
次に、フラスコ内部を10℃以下に冷却し、フラ
スコ中にシアン酸カリ22.5g(純度95%以上)を
少量ずつ加えた。
シアン酸カリを添加するにつれフラスコ内は僅
かの発熱を示し、結晶が析出してくる。
シアン酸カリの添加終了後、フラスコ内容物を
5〜10℃で1時間さらに室温で1時間熟成した。
次にフラスコ内を90℃に加熱して33.85%の濃
硫酸(0.325モル)を滴下した。
濃硫酸の滴下中、フラスコ内部は90〜100℃を
保つようにする。
滴下終了後、上記温度で約2時間熟成した。
次に、フラスコ内より減圧下に塩化水素および
水を蒸発させて乾固した。
次いで、フラスコ内にジメチルホルムアミド
100mlを加え、80℃で約1時間撹拌した後、過
した。
液よりジメチルホルムアミドを減圧下に90ml
留出させたのち、常温で放置した。
析出結晶を分離し、少量のジメチルホルムアミ
ドで洗浄し、取得結晶を真空乾燥した。
取得結晶の量は21.75g(収率87%)で結晶は
微黄色を呈し、結晶中のヒダントイン酸またはヒ
ダントイン酸アミドの含有量はErlich試薬を用い
て比色分析したところ1%以下であつた。
なお、結晶分離母液および洗液より更に1.5g
のヒダントインが回収された。
より高純度のヒダントインを得ようとする場合
は、結晶を少量の塩酸(濃度10〜20%)で熱処理
したのち、塩化水素を減圧下に除去してから放冷
静置し、析出結晶を分離乾燥すると無色の結晶が
得られる。[Formula] (wherein, Z represents HCl or H 2 SO 4 ) glycinonitrile inorganic acid salt and general formula MeOCN (wherein, Me represents Na or K) alkali cyanate Reacting the metal salt in an aqueous medium at a temperature range of 0 to 20°C,
The gist of the present invention is a method for producing hydantoin, which is characterized in that sulfuric acid or hydrochloric acid is then added to the resulting reaction mixture and heat-treated at a temperature in the range of 70 to 110°C. For example, the advantages of the present invention are as follows. (1) The raw material glycinonitrile inorganic acid salt is a substance that can be easily synthesized from hydrocyanic acid, formalin, and ammonia, and is usually not expensive. According to the present invention, hydantoin can be produced more economically than before. be able to. (2) The reaction selectivity is high, and hydantoin can be obtained with a yield of 80% or more. (3) Especially compared to the Bucherer-Bergs method, there are fewer side reactions that cannot be converted into hydantoin, the product is easy to purify, and the product is significantly less colored. To explain the present invention, the glycinonitrile inorganic acid salt used as a raw material can be easily obtained by neutralizing glycinonitrile with sulfuric acid or hydrochloric acid. The other raw material, an alkali metal salt of cyanic acid, is manufactured industrially and is easily available. The proportions of the inorganic acid salt of glycinonitrile and the alkali metal salt of cyanic acid are usually equimolar, or the cyanate is used in slight excess. In the present invention, water is usually used as a medium in the reaction of the inorganic acid salt of glycinonitrile and the alkali metal salt of cyanic acid, and the amount used is preferably 400 to 1000 ml per mole of the inorganic acid salt of glycinonitrile. As a reaction method, it is preferable to add a cyanate salt little by little to an aqueous solution of an inorganic glycinonitrile salt and cause the reaction to occur. The reaction temperature is usually 0 to 20°C, preferably 0 to 10°C.
It is ℃. If the reaction is carried out at a temperature higher than 20°C, side reactions will increase, which is not preferable. It is generally desirable to complete the addition of cyanate within one hour. After the addition of the cyanate salt is completed, the reaction mixture is aged for 1 to 2 hours while maintaining the reaction temperature to complete the reaction. In the present invention, it is thought that hydantoic acid nitrile is first produced by the reaction between glycinonitrile inorganic acid salt and cyanate, and then this is hydrated to produce hydantoic acid amide. In the course of this reaction, inorganic salts are produced as by-products. After the reaction is completed, sulfuric acid or hydrochloric acid is added to the reaction mixture and heat treated, and hydantoin is produced by this treatment. The amount of sulfuric acid or hydrochloric acid used at this time is 1 to 2 mol per 1 mol of the raw material glycinonitrile inorganic acid salt, and concentrated sulfuric acid or concentrated hydrochloric acid is used, respectively. The temperature of the heat treatment etc. is usually 70 to 110°C, preferably 80 to 100°C. Sulfuric acid or hydrochloric acid is preferably added gradually to the reaction mixture, and the addition time is usually within 1 hour. After adding the acid, the treated material is heated to 1°C while maintaining the treatment temperature.
Aging for ~4 hours to complete hydantoinization. After the treatment, if hydrochloric acid is used, the treatment solution is distilled under reduced pressure to remove as much hydrogen chloride as possible, and then the water is evaporated to dryness. The resulting residue is then extracted with an organic solvent that does not dissolve the by-product inorganic salt but dissolves the hydantoin. At this time, examples of the organic solvent used include diglyme, dimethylformamide, N.N-dimethylacetamide, and N-methylpyrrolidone. On the other hand, when sulfuric acid is used, after the treatment, the treated product is neutralized with a base such as ammonia, soda carbonate, sodium bicarbonate, caustic soda, quicklime, slaked lime, calcium carbonate, etc., and then the water is evaporated to dryness. The resulting residue is then extracted with the same organic solvent as in the case of hydrochloric acid treatment. The extract obtained as described above is concentrated by an appropriate method to obtain the target hydantoin. The present invention is preferably implemented as follows. Glycinonitrile inorganic acid salt is charged into a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel, and a predetermined amount of water is added to dissolve it. Next, the solution is cooled to a temperature below 10°C, and cyanate powder is gradually added thereto for reaction. The reaction was slightly exothermic, and the liquid gradually became cloudy and a precipitate was clearly visible. After the addition of the cyanate salt is completed, the reaction is aged for about 1 hour while maintaining the reaction temperature to complete the reaction. Next, the reaction mixture is heated to a temperature of 90° C., and a predetermined amount of sulfuric acid or hydrochloric acid is added dropwise into the reaction mixture through a dropping funnel for acid treatment. While dropping the acid, adjust the dropping amount so that the temperature of the material to be treated remains between 90 and 100°C. After dropping, the treated material is heated for 2 hours while maintaining the above temperature.
Age for ~4 hours. When sulfuric acid is used for this acid treatment, sodium carbonate is added to the treated material after the treatment to adjust the pH of the treated material to 3 to 5. After neutralization, water is removed from the treated product under reduced pressure and the product is dried. Next, dimethylformamide is added to the obtained residue, and the mixture is heated and stirred at a temperature of about 80°C for 1 to 2 hours to extract the soluble content. The extract is heated to separate by-product inorganic salts. The dimethylformamide solution is concentrated under reduced pressure to obtain the target hydantoin. By such a method, hydantoin with little coloring and high purity can be obtained. Next, the present invention will be explained in more detail with reference to Examples. Example 1 In a 500 ml separable flask equipped with a reflux condenser, stirrer, thermometer, and dropping funnel, 26.25 g (0.25 mol) of industrial glycinonitrile sulfate and 150 ml of water were dissolved. Next, the inside of the flask was cooled to a temperature of 10° C. or less, and 18.08 g (purity: 90% or more) of industrial sodium cyanate powder was added little by little to cause a reaction. A slight exotherm was observed, the solution gradually became cloudy, and a precipitate formed. After the addition of the sodium cyanate was complete, the contents of the flask were heated at 5-10 DEG C. for 1 hour and at room temperature for 1 hour. Next, the inside of the flask was heated to 90°C, and 31.85 g of concentrated sulfuric acid (0.325 mol) was added dropwise. A clear exothermic reaction occurs, but the temperature inside the flask is 90~
Make sure to maintain the temperature at 100℃. After the dropwise addition was completed, the mixture was aged at the above temperature for about 2 hours. Next, after cooling the flask to room temperature, add soda carbonate powder into the flask to adjust the pH of the contents to 3-5.
I made it. After neutralization, water was distilled out from inside the flask under reduced pressure and dried. Next, add 100ml of dimethylformamide to the flask.
was added, stirred at 80°C for about 1 hour, and then filtered. Add 90ml of dimethylformamide from the liquid under reduced pressure.
After distillation, it was left at room temperature. The precipitated crystals were separated and washed with a small amount of dimethylformamide, and the obtained crystals were vacuum dried at 60°C. The amount of crystals obtained was 20.94 g (yield 83.8%), the crystals exhibited a slight yellow color, and the content of hydantoic acid or hydantoic acid amide in the crystals was determined to be less than 2% by colorimetric analysis using Erlich reagent. . In addition, an additional 1.5 g from the crystal separation mother liquor and washing solution
of hydantoin was recovered. Example 2 In a reactor similar to that used in Example 1, 23.13 g (0.25 mol) of industrial glycinonitrile hydrochloride and water were added.
80ml was charged and dissolved. Next, the inside of the flask was cooled to 10° C. or lower, and 22.5 g of potassium cyanate (purity of 95% or more) was added little by little into the flask. As potassium cyanate is added, a slight heat generation occurs inside the flask, and crystals begin to precipitate. After the addition of potassium cyanate was completed, the contents of the flask were aged at 5-10°C for 1 hour and at room temperature for 1 hour. Next, the inside of the flask was heated to 90°C, and 33.85% concentrated sulfuric acid (0.325 mol) was added dropwise. While dropping concentrated sulfuric acid, maintain the temperature inside the flask at 90-100°C. After the dropwise addition was completed, the mixture was aged at the above temperature for about 2 hours. Next, hydrogen chloride and water were evaporated from the inside of the flask under reduced pressure to dryness. Then add dimethylformamide to the flask.
After adding 100 ml and stirring at 80°C for about 1 hour, it was filtered. Add 90ml of dimethylformamide from the liquid under reduced pressure.
After distillation, it was left at room temperature. The precipitated crystals were separated, washed with a small amount of dimethylformamide, and the obtained crystals were vacuum-dried. The amount of crystals obtained was 21.75 g (yield 87%), the crystals exhibited a slight yellow color, and the content of hydantoic acid or hydantoic acid amide in the crystals was determined to be less than 1% by colorimetric analysis using Erlich reagent. . In addition, an additional 1.5 g from the crystal separation mother liquor and washing solution
of hydantoin was recovered. If you want to obtain hydantoin with higher purity, heat-treat the crystals with a small amount of hydrochloric acid (concentration 10-20%), remove hydrogen chloride under reduced pressure, leave to stand, and separate and dry the precipitated crystals. Colorless crystals are then obtained.
Claims (1)
されるグリシノニトリル無機酸塩と一般式
MeOCN(式中、MeはNaまたはKをあらわす)
で示されるシアン酸のアルカリ金属塩を水性媒体
中で温度0〜20℃の範囲で反応させ、次いで得ら
れた反応混合物に硫酸または塩酸を添加して温度
70〜110℃の範囲で加熱処理することを特徴とす
るヒダントインの製造法。[Claims] 1 Glycinonitrile inorganic acid salt represented by the general formula [formula] (wherein Z represents HCl or H 2 SO 4 ) and the general formula
MeOCN (In the formula, Me represents Na or K)
An alkali metal salt of cyanic acid represented by
A method for producing hydantoin, characterized by heat treatment in the range of 70 to 110°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4481678A JPS54138556A (en) | 1978-04-18 | 1978-04-18 | Preparation of hydantoin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4481678A JPS54138556A (en) | 1978-04-18 | 1978-04-18 | Preparation of hydantoin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS54138556A JPS54138556A (en) | 1979-10-27 |
JPS6115872B2 true JPS6115872B2 (en) | 1986-04-26 |
Family
ID=12701949
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4481678A Granted JPS54138556A (en) | 1978-04-18 | 1978-04-18 | Preparation of hydantoin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS54138556A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62146360U (en) * | 1986-03-07 | 1987-09-16 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6178769A (en) * | 1984-09-27 | 1986-04-22 | Showa Denko Kk | Production of hydantoin |
CN100427471C (en) * | 2002-12-31 | 2008-10-22 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Process for preparing hydantoin |
-
1978
- 1978-04-18 JP JP4481678A patent/JPS54138556A/en active Granted
Non-Patent Citations (2)
Title |
---|
JOURNAL FUER PRAKTISCHE CHEMIC=P233-240 * |
JOURNAL FUER PRAKTISCHECHEMIC * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62146360U (en) * | 1986-03-07 | 1987-09-16 |
Also Published As
Publication number | Publication date |
---|---|
JPS54138556A (en) | 1979-10-27 |
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