JPS6345664B2 - - Google Patents
Info
- Publication number
- JPS6345664B2 JPS6345664B2 JP7803083A JP7803083A JPS6345664B2 JP S6345664 B2 JPS6345664 B2 JP S6345664B2 JP 7803083 A JP7803083 A JP 7803083A JP 7803083 A JP7803083 A JP 7803083A JP S6345664 B2 JPS6345664 B2 JP S6345664B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- mol
- nitrobenzoylglutamic
- aminobenzoylglutamic
- magnesium
- 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
- 239000002253 acid Substances 0.000 claims description 14
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002681 magnesium compounds Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- BCHONLIBKIBVRS-VIFPVBQESA-N (2s)-2-[amino(benzoyl)amino]pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)N(N)C(=O)C1=CC=CC=C1 BCHONLIBKIBVRS-VIFPVBQESA-N 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- GADGMZDHLQLZRI-VIFPVBQESA-N N-(4-aminobenzoyl)-L-glutamic acid Chemical compound NC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 GADGMZDHLQLZRI-VIFPVBQESA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 235000013923 monosodium glutamate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229940073490 sodium glutamate Drugs 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 1
- 238000003436 Schotten-Baumann reaction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229960000304 folic acid Drugs 0.000 description 1
- 235000019152 folic acid Nutrition 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Peptides Or Proteins (AREA)
Description
【発明の詳細な説明】
本発明はＰ−アミノベンゾイルグルタミン酸の
新規な製造法に代わり、その目的とするところは
該化合物を高収率かつ工業的に有利に得んとする
ことにある。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel method for producing P-aminobenzoylglutamic acid, and its purpose is to obtain the compound in high yield and industrially advantageously.
Ｐ−アミノベンゾイルグルタミン酸は葉酸等医
薬の原料として、利用される有用な物質である。 P-aminobenzoylglutamic acid is a useful substance used as a raw material for pharmaceuticals such as folic acid.
従来、Ｐ−アミノベンゾイルグルタミン酸の製
造法としてはＰ−ニトロベンゾイルグルタミン酸
の還元が知られており、アンモニア水一硫化アン
モニウムによる方法（薬学雑誌69457〜458
（1949））や接触水添による方法（J.Am.Chem.
Soc.794391〜4394（1957））などがある。 Conventionally, the reduction of P-nitrobenzoylglutamic acid has been known as a method for producing P-aminobenzoylglutamic acid, and the method using ammonium monosulfide in aqueous ammonia (Pharmacy Journal 69 457-458
(1949)) and catalytic hydrogenation method (J.Am.Chem.
Soc. 79 4391-4394 (1957)).
しかし乍ら、本発明者の実験によれば前者につ
いては原料であるＰ−ニトロベンゾイルグルタミ
ン酸の素性により再現性に乏しく、また、後者に
ついては収率が75％と低く触媒回収も困難を要す
る欠点があり、工業的製法としては必らずしも充
分な結果が得られなかつた。 However, according to the inventor's experiments, the former has poor reproducibility due to the nature of the raw material P-nitrobenzoylglutamic acid, and the latter has the disadvantage that the yield is as low as 75% and catalyst recovery is difficult. However, as an industrial production method, satisfactory results were not always obtained.
本発明者は、上記欠点のないＰ−アミノベンゾ
イルグルタミン酸を得る方法について鋭意研究を
重ねた結果、本発明を完成するに至つた。すなわ
ち、本発明はＰ−ニトロベンゾイルグルタミン酸
からＰ−アミノベンゾイルグルタミン酸を合成す
るに際し、水及びマグネシウム化合物の共在下、
Ｐ−ニトロベンゾイルグルタミン酸を可溶性塩の
形で、水硫化ソーダと反応させることを特徴とす
るＰ−アミノベンゾイルグルタミン酸の製造法で
ある。 The present inventor has completed the present invention as a result of extensive research into a method for obtaining P-aminobenzoylglutamic acid that does not have the above-mentioned drawbacks. That is, in the present invention, when synthesizing P-aminobenzoylglutamic acid from P-nitrobenzoylglutamic acid, in the coexistence of water and a magnesium compound,
This is a method for producing P-aminobenzoylglutamic acid, which is characterized by reacting P-nitrobenzoylglutamic acid in the form of a soluble salt with sodium hydrogen sulfide.
本発明に従うＰ−ニトロベンゾイルグルタミン
酸からＰ−アミノベンゾイルグルタミン酸を得る
場合、反応式は次の如く考えられる。 When P-aminobenzoylglutamic acid is obtained from P-nitrobenzoylglutamic acid according to the present invention, the reaction formula can be considered as follows.
本発明において、使用するＰ−ニトロベンゾイ
ルグルタミン酸は、いかなる方法で合成されても
よいが、例えば、グルタミン酸ソーダとＰ−ニト
ロ安息香酸塩化物とのシヨツテン・バウマン反応
によつて容易に収率よく製造することができる。
（薬学雑誌69457〜458（1949））また、出発原料と
しては純品、粗製品どちらも使用でき、通常10〜
40％水溶液で適用される。 In the present invention, P-nitrobenzoylglutamic acid used may be synthesized by any method, but for example, it can be easily produced with good yield by the Schotten-Baumann reaction between sodium glutamate and P-nitrobenzoic acid chloride. can do.
(Pharmaceutical Journal 69 457-458 (1949)) Both pure and crude products can be used as starting materials, and usually 10 to
Applied in a 40% aqueous solution.
本発明において、使用するマグネシウム化合物
は例えば、酸化マグネシウム、水酸化マグネシウ
ム等の塩基性物や、塩化マグネシウム、硫酸マグ
ネシウム、硝酸マグネシウム等の中性物が挙げら
れる。前者らは原料水溶液に可溶であり、直接原
料を可溶性塩となし得るが、後者らは不溶であ
り、この場合さらに約等モルの苛性ソーダを加え
ることで、可溶性塩となす必要がある。 In the present invention, examples of the magnesium compound used include basic compounds such as magnesium oxide and magnesium hydroxide, and neutral compounds such as magnesium chloride, magnesium sulfate, and magnesium nitrate. The former are soluble in the raw material aqueous solution and can be made directly into soluble salts, but the latter are insoluble, and in this case it is necessary to further add approximately equimolar amount of caustic soda to make them into soluble salts.
これ等の中、特に酸化マグネシウムが好適であ
る。その使用量はＰ−ニトロベンゾイルグルタミ
ン酸に対し約0.9〜1.2モル倍が好適である。な
お、これらマグネシウム化合物の代わりに苛性ソ
ーダ（単独）を用いるとＰ−アミノベンゾイルグ
ルタミン酸がＰ−ニトロベンゾイルグルタミン酸
の素性により得られないことがあり、不適当であ
る。 Among these, magnesium oxide is particularly suitable. The amount used is preferably about 0.9 to 1.2 moles relative to P-nitrobenzoylglutamic acid. Note that if caustic soda (alone) is used instead of these magnesium compounds, P-aminobenzoylglutamic acid may not be obtained due to the nature of P-nitrobenzoylglutamic acid, which is inappropriate.
水硫化ソーダは20〜30％水溶液が好ましいが固
体でもかまわない。 Sodium hydrosulfide is preferably a 20 to 30% aqueous solution, but may be solid.
その使用量は、Ｐ−ニトロベンゾイルグルタミ
ン酸に対し約2.0〜3.0モル倍が好適である。水硫
化ソーダの滴下は撹拌下で、適当な反応温度を保
ちながら行われるが、滴下速度は除熱に見合つて
適当に決定されるべきで限定されない。 The amount used is preferably about 2.0 to 3.0 times the mole of P-nitrobenzoylglutamic acid. The dropping of sodium hydrogen sulfide is carried out under stirring while maintaining a suitable reaction temperature, but the dropping rate should be appropriately determined in accordance with the heat removal and is not limited.
反応（熟成）は撹拌下で約40〜100℃の温度を
保ちつつ行われ、通常約２〜４時間の反応時間が
適当である。 The reaction (ripening) is carried out under stirring while maintaining a temperature of about 40 to 100°C, and a reaction time of about 2 to 4 hours is usually appropriate.
上記反応により生成したＰ−アミノベンゾイル
グルタミン酸は反応粗液を酸性化、別、洗浄、
乾燥等の公知の手段により分離取得できる。 The P-aminobenzoylglutamic acid produced by the above reaction is obtained by acidifying the reaction crude solution, separating it, washing it, and
It can be separated and obtained by known means such as drying.
本発明の方法に依れば、従来低収率で、しかも
再現性の乏しかつたＰ−アミノベンゾイルグルタ
ミン酸を高収率で再現性よく得ることができ、そ
の工業的有用性は極めて大である。 According to the method of the present invention, P-aminobenzoylglutamic acid, which conventionally had a low yield and poor reproducibility, can be obtained in a high yield and with good reproducibility, and its industrial usefulness is extremely large. .
以下、本発明の方法を実施例及び比較例により
さらに詳しく説明する。 Hereinafter, the method of the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例 １
Ｐ−ニトロベンゾイルグルタミン酸44.4ｇ
（0.15モル）を水110ｇの中に加え、さらに撹拌下
酸化マグネシウム6.05ｇ（0.15モル）を加え溶解
した。これに30％水硫化ソーダ水溶液56.1ｇ
（0.30モル）を約30分間かけて滴下した。滴下後
60℃で４時間維持した。Example 1 P-nitrobenzoylglutamic acid 44.4g
(0.15 mol) was added to 110 g of water, and while stirring, 6.05 g (0.15 mol) of magnesium oxide was added and dissolved. Add to this 56.1g of 30% sodium hydrogen sulfide aqueous solution.
(0.30 mol) was added dropwise over about 30 minutes. After dripping
It was maintained at 60°C for 4 hours.
反応終了後、PH４になるまで34％HCl水溶液を
加え析出したイオウ分を別し、その液に34％
HCl水溶液を加えることによりPH３にし、結晶と
して析出させ、過しさらに乾燥することにより
目的物を34.8ｇ得た。（収率82.7％）
実施例 ２
Ｐ−ニトロベンゾイルグルタミン酸44.4ｇ
（0.15モル）を水110ｇの中に加え、さらに撹拌下
酸化マグネシウム14.3ｇ（0.15モル）を加え、さ
らに25％苛性ソーダ水溶液を44.8ｇ（0.28モル）
を加え溶解した。 After the reaction is complete, add 34% HCl aqueous solution until the pH is 4, separate the precipitated sulfur, and add 34% HCl to the solution.
The pH was adjusted to 3 by adding an aqueous HCl solution, and 34.8 g of the desired product was obtained by precipitating crystals, filtering, and drying. (Yield 82.7%) Example 2 P-nitrobenzoylglutamic acid 44.4g
(0.15 mol) into 110 g of water, then 14.3 g (0.15 mol) of magnesium oxide with stirring, and 44.8 g (0.28 mol) of 25% caustic soda aqueous solution.
was added and dissolved.
これに30％水硫化ソーダ水溶液56.1ｇ（0.30モ
ル）を約30分間かけて滴下した。滴下後60℃で４
時間維持した。 To this, 56.1 g (0.30 mol) of a 30% aqueous sodium hydrogen sulfide solution was added dropwise over about 30 minutes. 4 at 60℃ after dropping
Time was maintained.
以後の操作を実施例１に準じて行い、目的物を
31.1ｇ得た。（収率73.5％）
比較例 １
Ｐ−ニトロベンゾイルグルタミン酸44.4ｇ
（0.15モル）を水110ｇの中に加え、さらに撹拌下
25％苛性ソーダ水溶液を42.0ｇ（0.26モル）加え
溶解した。 The subsequent operations were performed according to Example 1, and the target object was obtained.
Obtained 31.1g. (Yield 73.5%) Comparative Example 1 P-nitrobenzoylglutamic acid 44.4g
(0.15 mol) into 110 g of water and further stirred.
42.0 g (0.26 mol) of 25% aqueous caustic soda solution was added and dissolved.
以後の操作を実施例１に準じて行つたが、結晶
物は得られなかつた。 The subsequent operations were carried out according to Example 1, but no crystalline product was obtained.
実施例 ３
グルタミン酸ソーダ28.0ｇ（0.15モル）を水
180ｇに溶かし、酸化マグネシウム8.3ｇ（0.20モ
ル）を加え、撹拌下Ｐ−ニトロ安息香酸クロライ
ド27.8ｇ（0.15モル）を含むトルエン溶液77ｇを
約30分間滴下し、温度を40℃に保ち、４時間熟成
した。熟成後、微量の不溶物を別し、更にトル
エン層を分液し、Ｐ−ニトロベンゾイルグルタミ
ン酸塩の約19.0％水溶液241ｇを得た。Example 3 Add 28.0 g (0.15 mol) of sodium glutamate to water.
180 g, add 8.3 g (0.20 mol) of magnesium oxide, and dropwise add 77 g of a toluene solution containing 27.8 g (0.15 mol) of P-nitrobenzoyl chloride under stirring for about 30 minutes, maintain the temperature at 40°C for 4 hours. Aged. After aging, a trace amount of insoluble matter was separated and the toluene layer was further separated to obtain 241 g of an approximately 19.0% aqueous solution of P-nitrobenzoylglutamate.
引続き上記マグネシウム化合物を含んだＰ−ニ
トロベンゾイルグルタミン酸塩の水溶液に、30％
水硫化ソーダ58.0ｇ（0.30モル）を約30分間かけ
て滴下した。滴下後60℃で４時間維持した。 Subsequently, add 30% to an aqueous solution of P-nitrobenzoylglutamate containing the above magnesium compound
58.0 g (0.30 mol) of sodium hydrogen sulfide was added dropwise over about 30 minutes. After dropping, the temperature was maintained at 60°C for 4 hours.
以後の操作を実施例１に準じて行い、目的物を
32.3ｇ得た。（収率77.0％） The subsequent operations were performed according to Example 1, and the target object was obtained.
Obtained 32.3g. (yield 77.0%)
Claims (1)
アミノベンゾイルグルタミン酸を合成するに際
し、水及びマグネシウム化合物の共存下、Ｐ−ニ
トロベンゾイルグルタミン酸を可溶性塩の形で、
水硫化ソーダと反応させることを特徴とするＰ−
アミノベンゾイルグルタミン酸の製造法。1 P-nitrobenzoylglutamic acid to P-
When synthesizing aminobenzoylglutamic acid, in the presence of water and a magnesium compound, P-nitrobenzoylglutamic acid in the form of a soluble salt,
P- characterized by reacting with sodium hydrogen sulfide
Method for producing aminobenzoylglutamic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7803083A JPS59204158A (en) | 1983-05-02 | 1983-05-02 | Production of p-aminobenzoylglutamic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7803083A JPS59204158A (en) | 1983-05-02 | 1983-05-02 | Production of p-aminobenzoylglutamic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59204158A JPS59204158A (en) | 1984-11-19 |
| JPS6345664B2 true JPS6345664B2 (en) | 1988-09-12 |
Family
ID=13650408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7803083A Granted JPS59204158A (en) | 1983-05-02 | 1983-05-02 | Production of p-aminobenzoylglutamic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59204158A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63115369U (en) * | 1987-01-20 | 1988-07-25 |
-
1983
- 1983-05-02 JP JP7803083A patent/JPS59204158A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63115369U (en) * | 1987-01-20 | 1988-07-25 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59204158A (en) | 1984-11-19 |
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