JPH0543531A - Production of p-hydroxybenzamide - Google Patents
Production of p-hydroxybenzamideInfo
- Publication number
- JPH0543531A JPH0543531A JP22365591A JP22365591A JPH0543531A JP H0543531 A JPH0543531 A JP H0543531A JP 22365591 A JP22365591 A JP 22365591A JP 22365591 A JP22365591 A JP 22365591A JP H0543531 A JPH0543531 A JP H0543531A
- Authority
- JP
- Japan
- Prior art keywords
- hba
- parahydroxybenzamide
- acid
- reaction
- urea
- 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
- QXSAKPUBHTZHKW-UHFFFAOYSA-N 4-hydroxybenzamide Chemical compound NC(=O)C1=CC=C(O)C=C1 QXSAKPUBHTZHKW-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 13
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract 1
- -1 acid amide compound Chemical class 0.000 description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 description 1
- OOHIGOIEQKKEPK-UHFFFAOYSA-N HBA Chemical compound CC(O)CC(N)=O OOHIGOIEQKKEPK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はパラヒドロキシベンズア
ミドの製造方法に関し、特にパラヒドロキシ安息香酸を
原料とするパラヒドロキシベンズアミドの製造方法に関
するものである。FIELD OF THE INVENTION The present invention relates to a method for producing parahydroxybenzamide, and more particularly to a method for producing parahydroxybenzamide using parahydroxybenzoic acid as a raw material.
【０００２】パラヒドロキシベンズアミドは漂白剤組成
物、写真薬、医薬品等の中間体として用い得る化合物で
ある。Parahydroxybenzamide is a compound which can be used as an intermediate for bleaching compositions, photographic agents, pharmaceuticals and the like.
【０００３】[0003]
【従来の技術】カルボン酸化合物より酸アミド化合物を
合成する一般的な方法としては、 （１）カルボン酸化合物にアミン又はアンモニアを反応
させた後、 1分子の水を脱水して酸アミド化合物とす
る。 （２）カルボン酸化合物に尿素を反応させて酸アミド化
合物とする。 （３）カルボン酸化合物を酸ハロゲン化物とした後、ア
ンモニアを反応させて酸アミド化合物とする。 などが知られている。2. Description of the Related Art As a general method for synthesizing an acid amide compound from a carboxylic acid compound, (1) reacting a carboxylic acid compound with amine or ammonia, and dehydrating one molecule of water to form an acid amide compound. To do. (2) Urea is reacted with a carboxylic acid compound to give an acid amide compound. (3) After converting the carboxylic acid compound into an acid halide, it is reacted with ammonia to form an acid amide compound. Are known.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
（１）又は（２）の方法は、カルボン酸として安息香酸
に適用した場合には高収率でベンズアミドが合成される
が、水酸基を有するパラヒドロキシ安息香酸（以下ＨＢ
Ａと略記する。）に適用してパラヒドロキシベンズアミ
ドを製造する場合、ＨＢＡの脱炭酸反応が起こり、収率
が極度に低下する。また、上記（３）方法も分子内に水
酸基を有しないカルボン酸の場合には容易にアミド化合
物が得られるが、分子内に水酸基を有するカルボン酸の
場合には、予め水酸基をアセチル化などで保護しておく
必要があり、工程が複雑となり、工業的には不利であ
る。However, according to the above method (1) or (2), when benzamide is applied as a carboxylic acid, benzamide is synthesized in a high yield, but a paraffin having a hydroxyl group is used. Hydroxybenzoic acid (hereinafter HB
Abbreviated as A. In the case of producing para-hydroxybenzamide by applying the above method to H.), decarboxylation reaction of HBA occurs and the yield is extremely reduced. Further, in the above method (3), an amide compound can be easily obtained in the case of a carboxylic acid having no hydroxyl group in the molecule, but in the case of a carboxylic acid having a hydroxyl group in the molecule, the hydroxyl group can be previously acetylated or the like. It needs to be protected, which complicates the process and is industrially disadvantageous.
【０００５】リン酸の存在下でＨＢＡと尿素を反応させ
てパラヒドロキシベンズアミドを製造する方法が、エジ
プシャン・ジャーナル・オブ・ファーマシューティカル
・サイエンス 13, No.2, p 231〜235 (1972)に記載され
ている。しかしこの方法によっても、依然として大半の
ＨＢＡの脱炭酸が生じ、パラヒドロキシベンズアミドの
収率は25％（ＨＢＡ基準) にすぎなかった。A method for producing parahydroxybenzamide by reacting HBA with urea in the presence of phosphoric acid is disclosed in Egyptian Journal of Pharmaceutical Science 13 , No. 2, p 231-235 (1972). Have been described. However, even with this method, most of HBA was decarboxylated, and the yield of parahydroxybenzamide was only 25% (based on HBA).
【０００６】このような状況で、工業的に容易な方法に
てパラヒドロキシベンズアミドを好収率で製造すること
が課題とされていた。Under such circumstances, it has been a subject to produce parahydroxybenzamide in a good yield by an industrially easy method.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意研究を進めた結果、ＨＢＡと尿素
との反応にスルファミン酸を共存させることにより、脱
炭酸反応を抑制し得ることを見出した。Means for Solving the Problems As a result of intensive research to solve the above-mentioned problems, the present inventors suppress the decarboxylation reaction by allowing sulfamic acid to coexist in the reaction between HBA and urea. Found to get.
【０００８】すなわち本発明は、ＨＢＡと尿素及びスル
ファミン酸を加熱・反応させることにより、好収率にて
パラヒドロキシベンズアミドを製造する技術を提供する
ものである。That is, the present invention provides a technique for producing parahydroxybenzamide in good yield by heating and reacting HBA with urea and sulfamic acid.
【０００９】[0009]
【発明の具体的説明】本発明におけるＨＢＡと尿素及び
スルファミン酸の反応は有機溶媒の存在下で行なわれ
る。使用できる有機溶媒は、本反応に対して不活性で、
且つその沸点が160℃以上のものであればいかなる溶媒
でも使用でき、例えば、ジフェニルエーテル、ジフェニ
ルメタン、ジフェニルエタン、ニトロベンゼン、ジクロ
ルベンゼン、ジエチルベンゼンなどを挙げることができ
る。溶媒のの使用量は特に制限はないが、通常ＨＢＡに
対して 3〜5 倍が好ましい。DETAILED DESCRIPTION OF THE INVENTION The reaction of HBA with urea and sulfamic acid in the present invention is carried out in the presence of an organic solvent. The organic solvent that can be used is inert to this reaction,
Any solvent having a boiling point of 160 ° C. or higher can be used, and examples thereof include diphenyl ether, diphenylmethane, diphenylethane, nitrobenzene, dichlorobenzene and diethylbenzene. The amount of the solvent used is not particularly limited, but is usually 3 to 5 times that of HBA.
【００１０】反応温度は通常 150℃以上、好ましくは 1
80〜230 ℃である。反応時間は特に制限されず、原料の
ＨＢＡが消失した時点を終点とすることができる。The reaction temperature is usually 150 ° C. or higher, preferably 1
80-230 ℃. The reaction time is not particularly limited, and the time point when the HBA of the raw material disappears can be the end point.
【００１１】反応に用いるＨＢＡ、尿素及びスルファミ
ン酸の使用割合は、ＨＢＡ 1モルに対して尿素 1.5〜5
モル、好ましくは 2〜3 モルであり、スルファミン酸は
0.8〜1.5 モル、好ましくは 1.0〜1.2 モルである。The proportion of HBA, urea and sulfamic acid used in the reaction is 1.5 to 5 urea per mole of HBA.
Mol, preferably 2-3 mol, and sulfamic acid is
The amount is 0.8 to 1.5 mol, preferably 1.0 to 1.2 mol.
【００１２】尿素が 1.5モル未満の場合はパラヒドロキ
シベンズアミドの収率が低下し、 5モルを超えて使用し
ても収量の増加には効果がない。When the amount of urea is less than 1.5 mol, the yield of parahydroxybenzamide is reduced, and when it is used in excess of 5 mol, there is no effect in increasing the yield.
【００１３】一方、スルファミン酸が 0.8モル未満の場
合はＨＢＡの脱炭酸が生じ、 1.5モルを超えて使用した
場合には副生物の生成により、急激にパラヒドロキシベ
ンズアミドの収率が低下する。On the other hand, when the sulfamic acid content is less than 0.8 mol, decarboxylation of HBA occurs, and when it is used in excess of 1.5 mol, the yield of parahydroxybenzamide is drastically reduced due to the formation of by-products.
【００１４】反応終了後は反応液を 100〜150 ℃まで冷
却し、濾過により反応液に含まれる不溶物を取り除く。
この場合、パラヒドロキシベンズアミドは有機溶媒相に
溶解している。この有機溶媒相からパラヒドロキシベン
ズアミドを水酸化ナトリウム水溶液により抽出し、次い
で硫酸などの鉱酸で中和した後、冷却してパラヒドロキ
シベンズアミドの結晶を得ることができる。After completion of the reaction, the reaction solution is cooled to 100 to 150 ° C. and the insoluble matter contained in the reaction solution is removed by filtration.
In this case, the parahydroxybenzamide is dissolved in the organic solvent phase. Parahydroxybenzamide can be extracted from this organic solvent phase with an aqueous sodium hydroxide solution, neutralized with a mineral acid such as sulfuric acid, and then cooled to obtain crystals of parahydroxybenzamide.
【００１５】[0015]
【作用】本発明に使用するスルファミン酸の作用につい
ては、必ずしも明確ではないが、本発明に規定する範囲
を超えて使用した場合、目的物のパラヒドロキシベンズ
アミドの脱水物であるp-シアノフェノールが生成し、ま
た、使用量が少ないときにはＨＢＡの脱炭酸によるフェ
ノールの生成が見られることから、スルファミン酸は脱
炭酸を抑制すると同時に脱水剤として作用しているもの
と思われる。The action of sulfamic acid used in the present invention is not always clear, but when it is used beyond the range specified in the present invention, p-cyanophenol, which is a dehydration product of parahydroxybenzamide, which is a target, is Since it is produced, and when the amount used is small, phenol is produced by decarboxylation of HBA, it is considered that sulfamic acid acts as a dehydrating agent while suppressing decarboxylation.
【００１６】[0016]
【実施例】以下に実施例により本発明を具体的に説明す
る。EXAMPLES The present invention will be described in detail below with reference to examples.
【００１７】実施例１ コンデンサー、温度計及び攪拌機を備えた 200ml容四ツ
口フラスコに、ＨＢＡ27.6g、尿素 24.0g、スルファミ
ン酸 19.4g及びジフェニルエーテル138.0gを仕込み、 2
30℃で 2時間攪拌して反応させた。Example 1 A 200 ml four-necked flask equipped with a condenser, a thermometer and a stirrer was charged with 27.6 g of HBA, 24.0 g of urea, 19.4 g of sulfamic acid and 138.0 g of diphenyl ether, and 2
The mixture was reacted at 30 ° C. for 2 hours with stirring.
【００１８】反応終了後、反応液を 130℃まで冷却して
濾過し、有機溶媒相と不溶物とに分離した。不溶物はさ
らに 100℃に加熱されたジフェニルエーテル100gにて洗
浄し、洗液は有機溶媒相と合せた。After the reaction was completed, the reaction solution was cooled to 130 ° C. and filtered to separate an organic solvent phase and an insoluble matter. The insoluble matter was further washed with 100 g of diphenyl ether heated to 100 ° C., and the washing liquid was combined with the organic solvent phase.
【００１９】この液をガスクロマトグラフィーで分析し
た結果、パラヒドロキシベンズアミド 21.0gが含まれて
いた。これはＨＢＡ基準で76.6％の収率に相当する。As a result of analyzing this liquid by gas chromatography, 21.0 g of parahydroxybenzamide was contained. This corresponds to a yield of 76.6% based on HBA.
【００２０】実施例２ ＨＢＡ 27.6g、尿素 60.1g、スルファミン酸 19.4g及び
ニトロベンゼン110.4gを実施例１と同様のフラスコに仕
込み、 180℃で 6時間攪拌して反応させた。Example 2 27.6 g of HBA, 60.1 g of urea, 19.4 g of sulfamic acid and 110.4 g of nitrobenzene were charged in the same flask as in Example 1 and reacted at 180 ° C. for 6 hours with stirring.
【００２１】反応後、ジフェニルエーテル100gの代わり
に、ニトロベンゼン100gを用いた以外は、実施例１と同
様の操作をした。この液をガスクロマトグラフィーで分
析した結果、パラヒドロキシベンズアミド 22.5gが含ま
れていた。これはＨＢＡ基準で82.1％の収率に相当す
る。After the reaction, the same operation as in Example 1 was carried out except that 100 g of nitrobenzene was used instead of 100 g of diphenyl ether. As a result of analyzing this liquid by gas chromatography, 22.5 g of parahydroxybenzamide was contained. This corresponds to a yield of 82.1% based on HBA.
【００２２】[0022]
【発明の効果】本発明は、ＨＢＡと尿素及びスルファミ
ン酸とを反応させることによりＨＢＡの脱炭酸反応が抑
制されて、パラヒドロキシベンズアミドが好収率で得ら
れ、パラヒドロキシベンズアミドの工業的製造方法とし
てその産業的意義は極めて大きい。INDUSTRIAL APPLICABILITY According to the present invention, by reacting HBA with urea and sulfamic acid, the decarboxylation reaction of HBA is suppressed and parahydroxybenzamide is obtained in good yield. As a result, its industrial significance is extremely large.
Claims (1)
ファミン酸と加熱・反応させることを特徴とするパラヒ
ドロキシベンズアミドの製造方法。1. A process for producing parahydroxybenzamide, which comprises heating and reacting parahydroxybenzoic acid with urea and sulfamic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22365591A JPH0543531A (en) | 1991-08-09 | 1991-08-09 | Production of p-hydroxybenzamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22365591A JPH0543531A (en) | 1991-08-09 | 1991-08-09 | Production of p-hydroxybenzamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0543531A true JPH0543531A (en) | 1993-02-23 |
Family
ID=16801588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22365591A Pending JPH0543531A (en) | 1991-08-09 | 1991-08-09 | Production of p-hydroxybenzamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0543531A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2017221908A1 (en) * | 2016-06-22 | 2019-04-11 | 三菱瓦斯化学株式会社 | Method for producing aromatic nitrile compound and method for producing carbonate ester |
-
1991
- 1991-08-09 JP JP22365591A patent/JPH0543531A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2017221908A1 (en) * | 2016-06-22 | 2019-04-11 | 三菱瓦斯化学株式会社 | Method for producing aromatic nitrile compound and method for producing carbonate ester |
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