JPH01258640A - Production of hydroxybenzoic acid - Google Patents
Production of hydroxybenzoic acidInfo
- Publication number
- JPH01258640A JPH01258640A JP8403588A JP8403588A JPH01258640A JP H01258640 A JPH01258640 A JP H01258640A JP 8403588 A JP8403588 A JP 8403588A JP 8403588 A JP8403588 A JP 8403588A JP H01258640 A JPH01258640 A JP H01258640A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- solvent
- alkali metal
- metal salt
- monocyclic aromatic
- 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
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 alkali metal salt Chemical class 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 239000003755 preservative agent Substances 0.000 abstract description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000002335 preservative effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AFZZYIJIWUTJFO-UHFFFAOYSA-N 1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 2
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 description 2
- QUBBAXISAHIDNM-UHFFFAOYSA-N 1-ethyl-2,3-dimethylbenzene Chemical compound CCC1=CC=CC(C)=C1C QUBBAXISAHIDNM-UHFFFAOYSA-N 0.000 description 2
- MEMBJMDZWKVOTB-UHFFFAOYSA-N 1-ethyl-2,4-dimethylbenzene Chemical compound CCC1=CC=C(C)C=C1C MEMBJMDZWKVOTB-UHFFFAOYSA-N 0.000 description 2
- JRLPEMVDPFPYPJ-UHFFFAOYSA-N 1-ethyl-4-methylbenzene Chemical compound CCC1=CC=C(C)C=C1 JRLPEMVDPFPYPJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006085 Schmidt reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 description 1
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 1
- CRRKRCWWYGGNIW-UHFFFAOYSA-N 1-methyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C)=C1.CC(C)C1=CC=CC(C)=C1 CRRKRCWWYGGNIW-UHFFFAOYSA-N 0.000 description 1
- CHIKRULMSSADAF-UHFFFAOYSA-N 2-ethyl-1,3-dimethylbenzene Chemical compound CCC1=C(C)C=CC=C1C CHIKRULMSSADAF-UHFFFAOYSA-N 0.000 description 1
- AXIUBBVSOWPLDA-UHFFFAOYSA-N 2-ethyl-p-xylene Chemical compound CCC1=CC(C)=CC=C1C AXIUBBVSOWPLDA-UHFFFAOYSA-N 0.000 description 1
- SBUYFICWQNHBCM-UHFFFAOYSA-N 4-Ethyl-o-xylene Chemical compound CCC1=CC=C(C)C(C)=C1 SBUYFICWQNHBCM-UHFFFAOYSA-N 0.000 description 1
- 150000005168 4-hydroxybenzoic acids Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100145155 Escherichia phage lambda cIII gene Proteins 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はヒドロキシ安息香酸の製造方法に関し、詳しく
はヒドロキシ安息香酸の収率が高く、副生ずるタール分
の除去や溶媒を含む系の移送などが容易な反応溶媒を用
いたヒドロキシ安息香酸の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing hydroxybenzoic acid, and more specifically, a method for producing hydroxybenzoic acid with a high yield, removal of by-product tar content, transfer of a system containing a solvent, etc. The present invention relates to a method for producing hydroxybenzoic acid using a reaction solvent that is easy to use.
〔従来の技術および発明が解決しようとする課題〕ヒド
ロキシ安息香酸、中でもｐ−ヒドロキシ安息香酸は防腐
剤、防黴剤、医薬、染料などの原料としてきわめて有用
な化合物である。近年は農薬。[Prior Art and Problems to be Solved by the Invention] Hydroxybenzoic acid, especially p-hydroxybenzoic acid, is an extremely useful compound as a raw material for preservatives, fungicides, medicines, dyes, and the like. In recent years, pesticides.
感熱記録紙用顕色剤、高分子化合物等の原料としての用
途も開発され、その重要性が増大している。Its use as a color developer for thermal recording paper, a raw material for polymeric compounds, etc. has also been developed, and its importance is increasing.
このｐ−ヒドロキシ安息香酸の製造方法として、従来よ
りコルベ・シュミット反応を用いる方法が知られており
、例えばフェノールの存在下、カリウムフェノラートと
二酸化炭素とをジフェニルなどの多環式芳香族炭化水素
溶媒中で反応させる方法が知られている（特開昭６１−
１１５０５３号公報）。As a method for producing this p-hydroxybenzoic acid, a method using the Kolbe-Schmidt reaction has been known. For example, in the presence of phenol, potassium phenolate and carbon dioxide are mixed with polycyclic aromatic hydrocarbons such as diphenyl A method of reacting in a solvent is known (Japanese Patent Application Laid-open No. 1983-
115053).
しかしながら、多環式芳香族炭化水素を反応溶媒として
用いた場合は、反応において良好な結果を与えるものの
、高沸点であるために副生ずるタール分を溶媒から除去
する際の蒸留精製に多大なエネルギーを要し、経済的に
好ましくなかった。However, when polycyclic aromatic hydrocarbons are used as a reaction solvent, although good results are obtained in the reaction, due to their high boiling points, a large amount of energy is required for distillation and purification when removing by-product tar from the solvent. It was economically unfavorable.
また、これら多環式芳香族炭化水素の多くは常温で固体
であり、移送などの点において問題があった。Furthermore, many of these polycyclic aromatic hydrocarbons are solid at room temperature, which poses problems in transportation and the like.
本発明者らは上記の問題点を解決すべく、鋭意研究を重
ねた結果、この反応に用いる溶媒として特定の単環式芳
香族炭化水素を選択、使用することによりヒドロキシ安
息香酸が高収率で得られ、しかもその情調操作が容易で
ある上に、溶媒を含む系の移送も簡便に行なえることを
見出し、かかる知見に基いて本発明を完成するに至った
。In order to solve the above problems, the present inventors have conducted intensive research and found that by selecting and using a specific monocyclic aromatic hydrocarbon as the solvent used in this reaction, hydroxybenzoic acid can be produced in high yield. The inventors have found that the system can be easily manipulated, and the system containing the solvent can be easily transferred.Based on these findings, the present invention has been completed.
すなわち、本発明はフェノールの存在下、フェノールの
アルカリ金属塩と二酸化炭素とを一般式ｎは１〜４の整
数を示し、ｎが２以上のときＲは互いに同一であっても
異なるものであってもよい。）で表わされる単環式芳香
族炭化水素溶媒中で反応させることを特徴とするヒドロ
キシ安息香酸の製造方法を提供するものである。That is, in the present invention, in the presence of phenol, an alkali metal salt of phenol and carbon dioxide are combined in the general formula n represents an integer of 1 to 4, and when n is 2 or more, R may be the same or different. You can. ) The present invention provides a method for producing hydroxybenzoic acid, which is characterized in that the reaction is carried out in a monocyclic aromatic hydrocarbon solvent represented by:
本発明は基本的にはコルベ・シュミット反応を用いるも
のであり、この反応はフェノールに水酸化カリウム、水
酸化ナトリウムなどを反応させてフェノールのアルカリ
金属塩を得、これにフェノールの存在下で二酸化炭素を
作用させてヒドロキシ安息香酸のアルカリ金属塩を生成
せしめ、さらにこれに塩酸などの鉱酸を作用させてヒド
ロキシ安息香酸を得るものである。この場合、フェノー
ルと反応させるアルカリがカリウム塩の場合はｐ−ヒド
ロキシ安息香酸、ナトリウム塩の場合はサリチル酸が主
として生成する。さらに、カリウム塩を用いる場合でも
、フェノールの添加量や反応温度等を調節することによ
ってサリチル酸の生成量を増やすことができる。The present invention basically uses the Kolbe-Schmidt reaction, which involves reacting phenol with potassium hydroxide, sodium hydroxide, etc. to obtain an alkali metal salt of phenol, which is then reacted with dioxide in the presence of phenol. Hydroxybenzoic acid is obtained by reacting with carbon to produce an alkali metal salt of hydroxybenzoic acid, and further reacting with a mineral acid such as hydrochloric acid. In this case, when the alkali to be reacted with phenol is a potassium salt, p-hydroxybenzoic acid is mainly produced, and when the alkali is a sodium salt, salicylic acid is mainly produced. Furthermore, even when a potassium salt is used, the amount of salicylic acid produced can be increased by adjusting the amount of phenol added, the reaction temperature, etc.
本発明ではフェノールのアルカリ金属塩と二酸化炭素を
反応させるにあたり、一般式
ｎは１〜４の整数を示し、ｎが２以上のときＲは互いに
同一であっても異なるものであってもよい。）で表わさ
れる単環式芳香族炭化水素を溶媒として使用する。In the present invention, when reacting an alkali metal salt of phenol with carbon dioxide, the general formula n represents an integer of 1 to 4, and when n is 2 or more, R may be the same or different. ) is used as a solvent.
上記一般式で表われる単環式芳香族炭化水素としては各
種のものがあるが、特に炭素数９（Ｃ９）および炭素数
１０（ＣＩ。）の単環式芳香族炭化水素の中から選択し
、単独でもしくは２種以上を組合せて用いることが好ま
しい。これら炭化水素の具体例として１，２．３−）ジ
メチルベンゼン、１０２．４−）リメチルベンゼン、１
．３．５−トリメチルベンゼン（メシチレン）、ｌ−エ
チル−２−メチルベンゼン、■−エチルー３−メチルベ
ンゼン、１−エチル−４−メチルベンゼン、１ｓｏ−プ
ロピルベンゼン（クメン）、ｎ−プロピルベンゼン、１
．２．３．４−テトラメチルベンゼン、１．２，３゜５
−テトラメチルベンゼン（インデュレン）、１−エチル
−２，３−ジメチルベンゼン、１−エチル−２，４−ジ
メチルベンゼン、１−エチル−２，５−ジメチルベンゼ
ン、１−エチル−３，４−ジメチルベンゼン、１−エチ
ル−３，５−ジメチルベンゼン、１−エチル−２，６−
ジメチルベンゼン、ｌ−メチル−２−プロピルベンゼン
、ｌ−メチル−３−プロピルベンゼン、１−メチル−４
−ブロヒ、ルヘンゼン、１−メチル−２−イソプロピル
ベンゼン（０−シメン）、１−メチル−３−イソプロピ
ルベンゼン（ｍ−シメン）、１−メチル−４＝イソプロ
ピルベンゼン（ｐ−シメン）、１．２−ジエチルベンゼ
ン、１，３−ジエチルベンゼン、１．４−ジエチルベン
ゼン、ｎ−ブチルベンゼン、イソブチルベンゼン、５ｅ
ｅ−ブチルベンゼン、ｔｅｒｔ−ブチルベンゼンなどが
挙げられる。There are various types of monocyclic aromatic hydrocarbons represented by the above general formula, but in particular, monocyclic aromatic hydrocarbons with 9 carbon atoms (C9) and 10 carbon atoms (CI.) are selected. It is preferable to use them alone or in combination of two or more. Specific examples of these hydrocarbons include 1,2.3-)dimethylbenzene, 102.4-)limethylbenzene, 1
．． 3.5-trimethylbenzene (mesitylene), l-ethyl-2-methylbenzene, ■-ethyl-3-methylbenzene, 1-ethyl-4-methylbenzene, 1so-propylbenzene (cumene), n-propylbenzene, 1
．． 2.3.4-tetramethylbenzene, 1.2,3°5
-Tetramethylbenzene (indulene), 1-ethyl-2,3-dimethylbenzene, 1-ethyl-2,4-dimethylbenzene, 1-ethyl-2,5-dimethylbenzene, 1-ethyl-3,4-dimethyl Benzene, 1-ethyl-3,5-dimethylbenzene, 1-ethyl-2,6-
Dimethylbenzene, l-methyl-2-propylbenzene, l-methyl-3-propylbenzene, 1-methyl-4
- Brohy, Luhenzen, 1-methyl-2-isopropylbenzene (0-cymene), 1-methyl-3-isopropylbenzene (m-cymene), 1-methyl-4=isopropylbenzene (p-cymene), 1.2 -diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, n-butylbenzene, isobutylbenzene, 5e
Examples include e-butylbenzene and tert-butylbenzene.
次に、反応条件については、フェノールのアルカリ金属
塩１モルに対してフェノールを０．０５〜ｌＯモル、好
ましくは０．１〜５モル存在させ、二酸化炭素を０．１
〜１００モル、好ましくは０．５〜５０モルの割合で加
えて反応させる。なお、上記溶媒の使用量はフェノール
のアルカリ金属塩１モ）Ｌｔニ対しｌＯ〜１００００１
Ｉｉ、好ましくはｉｏ。Next, regarding the reaction conditions, 0.05 to 10 mol of phenol, preferably 0.1 to 5 mol, is present per 1 mol of the alkali metal salt of phenol, and 0.1 mol of carbon dioxide is present.
It is added and reacted in a proportion of ~100 mol, preferably 0.5-50 mol. The amount of the above solvent used is 1O to 100,001 for 1 mo) Lt of the alkali metal salt of phenol.
Ii, preferably io.
〜５０００Ｉ１１が適当である。また、反応は１５０℃
以上の温度で行なわれ、１７０〜３００ ’Ｃが好適で
あり、反応時間は０．０１〜５０時間、好ましくは０．
１〜５時間である。反応は常圧で行なえばよいが、必要
に応じ１００ｋｇ／ｃＩＩＩ程度まで加圧して行なうこ
ともできる。~5000I11 is suitable. In addition, the reaction was conducted at 150°C.
The reaction temperature is preferably 170 to 300'C, and the reaction time is 0.01 to 50 hours, preferably 0.01 to 50 hours.
1 to 5 hours. The reaction may be carried out at normal pressure, but it can also be carried out under pressure up to about 100 kg/cIII if necessary.
フェノールのアルカリ金属塩と二酸化炭素との反応混合
物にはヒドロキシ安息香酸のアルカリ金属塩のほか未反
応のフェノールのアルカリ金属塩。The reaction mixture of the alkali metal salt of phenol and carbon dioxide contains the alkali metal salt of hydroxybenzoic acid and unreacted alkali metal salt of phenol.
フェノールや溶媒などが含まれている。そこで、この反
応混合物に水を加え、水溶性成分を水相に移行させ、溶
媒相から分離する。この場合に添加する水の量は、反応
混合物の０．１〜１０倍量、好ましくは０．３〜５倍量
が適当である。Contains phenol and solvents. Water is then added to the reaction mixture, and the water-soluble components are transferred to the aqueous phase and separated from the solvent phase. In this case, the appropriate amount of water to be added is 0.1 to 10 times the amount of the reaction mixture, preferably 0.3 to 5 times the amount of the reaction mixture.
得られた水相に抽剤としてベンゼン、トルエン。Add benzene and toluene to the resulting aqueous phase as extractants.
キシレンなどの溶媒を加えてフェノールを抽出除去した
のち、常法により鉱酸を加え、ヒドロキシ安息香酸を析
出させる。この際に用いる鉱酸としては塩酸、硫酸、硝
酸などがあるが、塩酸が好ましい。鉱酸の使用量は水相
１００重量部あたり鉱酸０．１〜５００重量部が適当で
あり、通常は濃度１〜８０重量％の水溶液として加える
。After adding a solvent such as xylene to extract and remove phenol, mineral acid is added in a conventional manner to precipitate hydroxybenzoic acid. Mineral acids used in this case include hydrochloric acid, sulfuric acid, and nitric acid, with hydrochloric acid being preferred. The appropriate amount of mineral acid to be used is 0.1 to 500 parts by weight per 100 parts by weight of the aqueous phase, and it is usually added as an aqueous solution with a concentration of 1 to 80% by weight.
上記酸析処理により析出したヒドロキシ安息香酸を濾過
、遠心分離などの手段により分離、回収する。一方、水
相中に含まれるアルカリ金属を電解処理、逆浸透膜処理
などにより回収して再使用したり、溶媒相中のフェノー
ルもアルカリ洗浄などによりフェノールのアルカリ金属
塩として回収し、再使用する。The hydroxybenzoic acid precipitated by the acid precipitation treatment is separated and recovered by means such as filtration and centrifugation. On the other hand, the alkali metals contained in the aqueous phase can be recovered and reused through electrolytic treatment, reverse osmosis membrane treatment, etc., and the phenol in the solvent phase can also be recovered and reused as alkali metal salts of phenol through alkali washing, etc. .
次に、本発明を実施例により詳しく説明する。 Next, the present invention will be explained in detail with reference to examples.
実施例１−１０
２５０ｄのオートクレーブに予め合成、脱水したフェノ
ールのアルカリ金属塩、フェノールおよび溶媒の各所定
量を加えたのち、窒素置換した。Example 1-10 Predetermined amounts of an alkali metal salt of phenol, phenol, and a solvent previously synthesized and dehydrated were added to a 250 d autoclave, and then the autoclave was purged with nitrogen.
次いで、攪拌しつつ所定の温度まで昇温した後、二酸化
炭素を所定圧力まで導入した。内圧を保ったまま所定の
時間反応させた後、急冷し、水を加えて反応を停止した
。Next, the temperature was raised to a predetermined temperature while stirring, and then carbon dioxide was introduced to a predetermined pressure. After reacting for a predetermined time while maintaining the internal pressure, it was rapidly cooled and water was added to stop the reaction.
反応停止後、オートクレーブから内容物を抜き出し、水
相と溶媒相に分離した。次いで、水相に塩酸を加えたの
ち希釈し、また溶媒相はそのまま希釈し、それぞれにつ
いて高速液体クロマトグラフィーにより分析、定量を行
なった。結果を第１表に示す。After the reaction was stopped, the contents were extracted from the autoclave and separated into an aqueous phase and a solvent phase. Next, hydrochloric acid was added to the aqueous phase and then diluted, and the solvent phase was diluted as it was, and each was analyzed and quantitatively determined by high performance liquid chromatography. The results are shown in Table 1.
＊１「イブゾール１５０Ｊ ：出光石油化学■製、Ｃ１
０アルキルベンゼン
＊２「イブゾール１００Ｊ ：出光石油化学■製、Ｃ，
アルキルベンゼン
〔発明の効果〕
本発明では、ヒドロキシ安息香酸の製造にあたり、溶媒
として特定の単環式芳香族炭化水素を使用するため、目
的物を高収率で得られる上に、副生ずるタール分の除去
を容易に行なうことができる。そのため、該タール分除
去に要するエネルギーを従来法よりも軽減できる。また
、本発明に用いる溶媒は常温で液体であり、移送上のト
ラブルも生じない。*1 “Ibusol 150J: Manufactured by Idemitsu Petrochemical ■, C1
0 alkylbenzene*2 Ibusol 100J: manufactured by Idemitsu Petrochemical ■, C,
Alkylbenzene [Effects of the Invention] In the present invention, a specific monocyclic aromatic hydrocarbon is used as a solvent in the production of hydroxybenzoic acid. Removal can be carried out easily. Therefore, the energy required for removing the tar component can be reduced compared to the conventional method. Furthermore, the solvent used in the present invention is liquid at room temperature, and does not cause any trouble during transportation.
Claims (2)
塩と二酸化炭素とを一般式 ▲数式、化学式、表等があります▼（ここで、Ｒは低級
アルキル基、 ｎは１〜４の整数を示し、ｎが２以上のときＲは互いに
同一であっても異なるものであってもよい。）で表わさ
れる単環式芳香族炭化水素溶媒中で反応させることを特
徴とするヒドロキシ安息香酸の製造方法。(1) In the presence of phenol, the alkali metal salt of phenol and carbon dioxide are combined into a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R is a lower alkyl group, n is an integer from 1 to 4, (When n is 2 or more, R may be the same or different.) A method for producing hydroxybenzoic acid, which comprises reacting in a monocyclic aromatic hydrocarbon solvent.
＿１＿０のものである請求項１記載の製造方法。(2) Monocyclic aromatic hydrocarbon is C_9 and/or C
The manufacturing method according to claim 1, wherein the manufacturing method is _1_0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8403588A JPH01258640A (en) | 1988-04-07 | 1988-04-07 | Production of hydroxybenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8403588A JPH01258640A (en) | 1988-04-07 | 1988-04-07 | Production of hydroxybenzoic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01258640A true JPH01258640A (en) | 1989-10-16 |
Family
ID=13819269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8403588A Pending JPH01258640A (en) | 1988-04-07 | 1988-04-07 | Production of hydroxybenzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01258640A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393332A (en) * | 1991-12-27 | 1995-02-28 | Sanko Kaihatsu Kagaku Kenkyusho | Color developer for pressure-sensitive recording sheets |
-
1988
- 1988-04-07 JP JP8403588A patent/JPH01258640A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393332A (en) * | 1991-12-27 | 1995-02-28 | Sanko Kaihatsu Kagaku Kenkyusho | Color developer for pressure-sensitive recording sheets |
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