JPH0335308B2 - - Google Patents
Info
- Publication number
- JPH0335308B2 JPH0335308B2 JP18398785A JP18398785A JPH0335308B2 JP H0335308 B2 JPH0335308 B2 JP H0335308B2 JP 18398785 A JP18398785 A JP 18398785A JP 18398785 A JP18398785 A JP 18398785A JP H0335308 B2 JPH0335308 B2 JP H0335308B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxybiphenyl
- carbon dioxide
- reaction
- pressure
- carboxylic acid
- 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 62
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000001569 carbon dioxide Substances 0.000 claims description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 31
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 159000000000 sodium salts Chemical class 0.000 claims description 16
- ZJWUEJOPKFYFQD-UHFFFAOYSA-N 2-hydroxy-3-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1O ZJWUEJOPKFYFQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LPADJMFUBXMZNL-UHFFFAOYSA-N 4-hydroxy-3-phenylbenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(C=2C=CC=CC=2)=C1 LPADJMFUBXMZNL-UHFFFAOYSA-N 0.000 description 3
- RKONDDJCEQGOBP-UHFFFAOYSA-N 4-hydroxy-5-phenylbenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(O)C(C=2C=CC=CC=2)=C1 RKONDDJCEQGOBP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-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
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- -1 2-hydroxyphenyl Chemical group 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KSQXVLVXUFHGJQ-UHFFFAOYSA-M Sodium ortho-phenylphenate Chemical compound [Na+].[O-]C1=CC=CC=C1C1=CC=CC=C1 KSQXVLVXUFHGJQ-UHFFFAOYSA-M 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
産業上の利用分野
本発明は式（）で表わされる２−ヒドロキシ
フエニル−３−カルボン酸の製造方法に関する。
２−ヒドロキシビフエニル−３−カルボン酸は、
近年感圧、感熱紙用顕色剤として着目されている
化合物である（特開昭50−20807号公報）。
従来の技術
従来、２−ヒドロキシビフエニル−３−カルボ
ン酸の工業的製造方法として次の方法が報告され
ている。
(1) ２−ヒドロキシビフエニルを過剰の炭酸カリ
ウムとともに、炭酸ガス圧力下160〜180℃に加
熱する方法［J.Gen.Chem.（U.S.S.R）、８、424
（1938）］。
(2) ２−ヒドロキシフエニルのナトリリウム塩を
炭酸ガス加圧下100〜220℃に加熱する方法（ド
イツ国特許61125号）。
前記の従来の方法は工業的観点から次のような
問題点を含んでいる。すなわち方法(1)では過剰量
の炭酸カリウムが必要であり、かつ約60気圧の高
圧炭酸ガス下で反応を行なうため、原料面や設備
面でコスト高となる。
一方、方法(2)を提唱した前記ドイツ国特許に
は、目的とする２−ヒドロキシビフエニル−３−
カルボン酸を選択的かつ経済的に与える反応条件
等が特定されていない。例えば本発明者等の検討
に依れば、前記ドイツ国特許に示された反応条件
範囲には２−ヒドロキシビフエニル−５−カルボ
ン酸（）や２−ヒドロキシビフエニル−３−、
５−ジカルボン酸（）が副生し、目的とする２
−ヒドロキシビフエニル−３−カルボン酸の収率
が低下する場合もあることが明らかとなつた。
発明が解決しようとする問題点
本発明者らは、前述のような従来法の問題点を
解決すべく鋭意検討を行ない、２−ヒドロキシビ
フエニル（）から相当するナトリウム塩（）
を生成させ、これと炭酸ガスとを反応させて２−
ヒドロキシビフエニル−３−カルボン酸（）を
製造する方法を用い、選択的かつ経済的に目的物
を得ることができる製造方法を完成させたもので
ある。
問題点を解決するための手段
本発明では、まず２−ヒドロキシビフエニルと
水酸化ナトリウムとをメタノールやエタノールの
如き低級アルコール類を溶媒に用いて反応させ、
しかる後に溶媒および生成した水を加熱留去して
２−ヒドロキシビフエニルのナトリウム塩を分離
する。溶媒の低級アルコール類としてはメタノー
ルが安価な点で好ましく使用できる。このような
場合、水を溶媒に用いるのが一般的な方法である
が、以下に示すように低級アルコールを溶媒に用
いる利点をいくつか見いだした。
すなわち２−ヒドロキシビフエニルのナトリウ
ム塩は吸湿性であるが、水を含有すると、これと
炭酸ガスとの反応において目的の２−ヒドロキシ
ビフエニル−３−カルボン酸の収率が著しく低下
する。このため水は完全に留去しておくことが必
要である。しかし水を溶媒に用いた場合、水の蒸
発潜熱が大きいため、その加熱留去には多大なエ
ネルギーを消費する。また、水を完全に除去する
ために最終的に130〜160℃で真空乾燥を行なう必
要があるが、この際残存する水と２−ヒドロキシ
ビフエニルのナトリウム塩とが可逆的に反応して
２−ヒドロキシビフエニルが一部生成し、これに
留出するため２−ヒドロキシビフエニルのナトリ
ウム塩の収率が低下する。
これに対して低級アルコール類、とりわけメタ
ノールを溶媒に用いた場合には、蒸発潜熱が小さ
いため溶媒留去が容易であり、かつ上述の如き真
空乾燥の際の２−ヒドロキシビフエニルの生成留
出は殆んど観測されない。
２−ヒドロキシビフエニルのナトリウム塩製造
の際に用いる溶媒は、経済的観点からその使用量
を必要最小限に抑えるため、加熱して用いること
が望ましい。すなわち水酸化ナトリウムの低級ア
ルコール溶液を加熱還流させながら撹拌し、これ
にほぼ等モル量の２−ヒドロキシビフエニルを加
える。この場合２−ヒドロキシビフエニル、水酸
化ナトリウムのいずれかを過剰量用いても以下の
反応は支障なく進行する。しかし過剰分は反応に
関与せず最終的に回収する必要があるので、経済
的観点からは両者は等モル量付近の量比で用いる
のが好ましい。
２−ヒドロキシビフエニルと水酸化ナトリウム
とは前記の条件ですみやかに反応し、２−ヒドロ
キシビフエニルのナトリウム塩が生じる。これは
この溶媒系でほぼ飽和している。この溶液を常圧
あるいは減圧で濃縮し、最終的に120〜140℃で真
空乾燥を行ない、２−ヒドロキシビフエニルのナ
トリウム塩を無色固体として得る。ついで２−ヒ
ドロキシビフエニルのナトリウム塩をボールミル
等で20メツシユ以下、好ましくは100メツシユ以
下に粉砕して炭酸ガスとの反応に供する。
炭酸ガスとの反応は、反応温度と炭酸ガスの圧
力に大きく依存する。反応温度が140℃未満もし
くは炭酸ガス圧力が７Kg／cm2・Ｇ未満の場合に
は、反応転化率が低く、原料の２−ヒドロキシビ
フエニルを大量に回収する必要が生ずることにな
り経済的でない。一方反応温度が高温になると２
−ヒドロキシビフエニル−３，５−ジカルボン酸
の副生が次第に多くなる。これは目的とする２−
ヒドロキシビフエニル−３−カルボン酸がさらに
炭酸ガスと反応するためであり、190℃を越える
とこの副反応により２−ヒドロキシビフエニル−
３−カルボン酸の生成収率は低下する。
また反応温度が190℃以下の場合であつても、
160℃〜190℃の範囲では炭酸ガスが高圧になると
２−ヒドロキシビフエニル−３，５−ジカルボン
酸の副生が多くなる。これは反応温度が高いほど
顕著である。副生成物２−ヒドロキシビフエニル
−３，５−ジカルボン酸は各種の溶媒に難溶であ
り、かつ不揮発性なので、再結晶や蒸留等の通常
の分離、精製方法では除去することが困難である
したがつて２−ヒドロキシビフエニル−３，５−
ジカルボン酸が殆んど副生しない反応条件で反応
を遂行することが望ましく、この観点から反応温
度160℃〜190℃の範囲では、炭酸ガス圧力は次式
Ｐ＝（220−Ｔ）／1.5
［式中、Ｔは反応温度（℃）である］
で表わされるＰの値（Kg／cm2・Ｇ）以下が好まし
い。一方反応温度が160℃以下の場合には、炭酸
ガス圧力が高い場合にも２−ヒドロキシビフエニ
ル−３，５−ジカルボン酸の副生はさぼど顕著で
はない。また炭酸ガス圧力が高い方が目的とする
２−ヒドロキシビフエニル−３−カルボン酸の生
成収率は高い。しかし炭酸ガス圧力をあまり高く
しても２−ヒドロキシビフエニル−３−カルボン
酸の生成収率はさほど改善されず、40Kg／cm2超で
は生成収率は実質的に殆んど向上しない。したが
つて40Kg／cm2を超える炭酸ガス圧力下で反応を行
なうことは経済的観点からは好ましくない。
以上述べたように２−ヒドロキシビフエニルの
ナトリウム塩と炭酸ガスとの反応は、反応温度と
炭酸ガス圧力とに大きく依存し、これらは相互に
関連する。選択的かつ経済的に目的とする２−ヒ
ドロキシビフエニル−３−カルボン酸を得る反応
温度と炭酸ガス圧力は、反応温度が140〜190℃、
炭酸ガス圧力が７〜40Kg／cm2・Ｇの範囲で、かつ
炭酸ガス圧力の上限Ｐ（Kg／cm2・Ｇ）は次式
Ｐ＝（220−Ｔ）／1.5
［式中、Ｔは反応温度（℃）である］
の値を越えない範囲である。
２−ヒドロキシビフエニルのナトリウム塩を前
記の反応温度、炭酸ガス圧力下で撹拌することに
より反応を完施することができ、反応時間は通常
30分〜６時間の範囲である。
反応終了後、反応混合物を水に溶かし、塩酸あ
るいは硫酸等の鉱酸を加えて酸析させ、必要に応
じて溶剤洗浄あるいは再結晶等の精製操作を行な
い、２−ヒドロキシビフエニル−３−カルボン酸
を単離することができる。
以下実施例および比較例により本発明の内容を
さらに詳細に説明する。
実施例 １
環流冷却器のついた１ナス型フラスコ中で、
水酸化ナトリウム40ｇをメタノール200mlに加熱
溶解させた。これに２−ヒドロキシビフエニル
170ｇを加え、加熱環流して均一な溶液を得た。
この溶液を減圧濃縮し、析出した結晶をさらに
130℃／５〜10Torrで２時間真空乾燥して２−ヒ
ドロキシビフエニルのナトリウム塩（無色固体）
190ｇを得た。この間、２−ヒドロキシビフエニ
ルの留出は殆んど見られなかつた。
得られた２−ヒドロキシビフエニルのナトリウ
ム塩をボールミルで20メツシユ以下に粉砕した。
これを25ｇ採取し、内容積200mlの撹拌機付きオ
ートクレーブに入れ、オートクレーブ内を炭酸ガ
スで置換後、炭酸ガスを圧力10Kg／cm2に導入設定
し、170℃で４時間加熱撹拌した。反応が進行す
るにしたがい炭酸ガスが消費され圧力が低下する
が、外部から炭酸ガスを補い、常に圧力が10Kg／
cm2に保つようにした。反応混合物を温水200mlに
溶かし、希塩酸を加えてPH７〜８に調整し、ジク
ロロメタン洗浄を施した。尚、このジクロロメタ
ン洗浄液を減圧濃縮して、２−ヒドロキシビフエ
ニル11.7ｇを回収した。
水層に濃塩酸を加えてPH１以下とし、析出した
結晶を濾取し、真空乾燥して無色固体11.8ｇを得
た。このものは、その一部をジアゾメタンにより
メチル化したのちガスクロマトグラフイーで分析
したところ、２−ヒドロキシビフエニル−３−カ
ルボン酸、２−ヒドロキシビフエニル−５−カル
ボン酸酸、２−ヒドロキシビフエニル−３，５−
ジカルボン酸の混合物であり、その混合比は94：
３：３（モル比）であることを判明した。
従つて、それぞれ収率は35.5％、1.3％、1.2％
と算出された。結果は、他の実施例並びに比較例
の結果を合せて表１に示した。
前記無色固体11.4ｇを採取し、水−メタノール
から再結晶させて２−ヒドロキシビフエニル−３
−カルボン酸8.1ｇを純品として得た。このもの
はmp.188〜189℃であつた。
比較例 １
実施例においてメタノール200mlの代りに水200
mlを用いて同様な操作を行ない、２−ヒドロキシ
ビフエニルのナトリウム塩175ｇを得た。この場
合真空乾燥の際、２−ヒドロキシビフエニル10.5
ｇが留出した。
実施例２〜５および比較例２〜６
実施例１における反応温度と炭酸ガス圧力を変
化させて同様の反応を行なつた。反応混合物を温
水200mlに溶かし、濃塩酸を加えてPH１以下とし
たのち酢酸エチル200mlで抽出した。抽出液の一
部をジアゾメタン処理したのちガスクロマトグラ
フイーで定量分析を行ない表１の結果を得た。
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing 2-hydroxyphenyl-3-carboxylic acid represented by formula ().
2-hydroxybiphenyl-3-carboxylic acid is
It is a compound that has recently attracted attention as a color developer for pressure-sensitive and thermal paper (Japanese Patent Application Laid-open No. 20807/1983). Prior Art Conventionally, the following method has been reported as an industrial method for producing 2-hydroxybiphenyl-3-carboxylic acid. (1) A method of heating 2-hydroxybiphenyl with excess potassium carbonate to 160-180°C under carbon dioxide pressure [J.Gen.Chem. (USSR), 8 , 424
(1938)]. (2) A method of heating the sodium salt of 2-hydroxyphenyl to 100 to 220°C under pressure of carbon dioxide gas (German Patent No. 61125). The conventional method described above has the following problems from an industrial standpoint. That is, method (1) requires an excessive amount of potassium carbonate and the reaction is carried out under high-pressure carbon dioxide gas of about 60 atmospheres, resulting in high costs in terms of raw materials and equipment. On the other hand, the above-mentioned German patent proposing method (2) states that the target 2-hydroxybiphenyl-3-
Reaction conditions that provide carboxylic acid selectively and economically have not been specified. For example, according to the studies of the present inventors, the reaction condition range shown in the German patent includes 2-hydroxybiphenyl-5-carboxylic acid (), 2-hydroxybiphenyl-3-,
5-dicarboxylic acid () is produced as a by-product, and the desired 2
It has become clear that the yield of -hydroxybiphenyl-3-carboxylic acid may decrease in some cases. Problems to be Solved by the Invention The present inventors have conducted intensive studies to solve the problems of the conventional method as described above, and have found that the sodium salt () corresponding to 2-hydroxybiphenyl () is
is produced and reacted with carbon dioxide gas to produce 2-
Using a method for producing hydroxybiphenyl-3-carboxylic acid (), we have completed a production method that can selectively and economically obtain the desired product. Means for Solving the Problems In the present invention, first, 2-hydroxybiphenyl and sodium hydroxide are reacted using a lower alcohol such as methanol or ethanol as a solvent.
Thereafter, the solvent and the water produced are distilled off under heating to separate the sodium salt of 2-hydroxybiphenyl. As the lower alcohol solvent, methanol is preferably used since it is inexpensive. In such cases, the common method is to use water as a solvent, but we have found some advantages in using lower alcohols as a solvent, as shown below. That is, the sodium salt of 2-hydroxybiphenyl is hygroscopic, but if it contains water, the yield of the target 2-hydroxybiphenyl-3-carboxylic acid in the reaction of this salt with carbon dioxide gas is significantly reduced. For this reason, it is necessary to completely distill off water. However, when water is used as a solvent, the latent heat of vaporization of water is large, so a large amount of energy is consumed for heating and distilling it off. In addition, in order to completely remove water, it is necessary to finally perform vacuum drying at 130 to 160°C, but at this time, the remaining water and the sodium salt of 2-hydroxybiphenyl react reversibly, resulting in 2-hydroxybiphenyl. -Hydroxybiphenyl is partially produced and distilled from it, resulting in a decrease in the yield of the sodium salt of 2-hydroxybiphenyl. On the other hand, when lower alcohols, especially methanol, are used as a solvent, the latent heat of vaporization is small, so the solvent can be easily distilled off, and 2-hydroxybiphenyl can be produced during vacuum drying as described above. is almost never observed. The solvent used in the production of the sodium salt of 2-hydroxybiphenyl is desirably heated before use in order to minimize the amount used from an economic standpoint. That is, a lower alcohol solution of sodium hydroxide is stirred while being heated to reflux, and approximately equimolar amount of 2-hydroxybiphenyl is added thereto. In this case, even if an excess amount of either 2-hydroxybiphenyl or sodium hydroxide is used, the following reaction will proceed without any problem. However, since the excess does not take part in the reaction and must be recovered in the end, from an economical point of view, it is preferable to use the two in an equimolar ratio. 2-Hydroxybiphenyl and sodium hydroxide react quickly under the above conditions to produce the sodium salt of 2-hydroxybiphenyl. It is nearly saturated in this solvent system. This solution is concentrated under normal pressure or reduced pressure and finally vacuum dried at 120-140°C to obtain the sodium salt of 2-hydroxybiphenyl as a colorless solid. Next, the sodium salt of 2-hydroxybiphenyl is ground into 20 meshes or less, preferably 100 meshes or less, using a ball mill or the like, and subjected to reaction with carbon dioxide gas. The reaction with carbon dioxide largely depends on the reaction temperature and the pressure of carbon dioxide. If the reaction temperature is less than 140°C or the carbon dioxide pressure is less than 7 kg/cm 2 G, the reaction conversion rate will be low and it will be necessary to recover a large amount of 2-hydroxybiphenyl as a raw material, which is not economical. . On the other hand, when the reaction temperature becomes high, 2
The by-product of -hydroxybiphenyl-3,5-dicarboxylic acid gradually increases. This is aimed at 2-
This is because hydroxybiphenyl-3-carboxylic acid further reacts with carbon dioxide gas, and when the temperature exceeds 190°C, this side reaction causes 2-hydroxybiphenyl-3-carboxylic acid to react with carbon dioxide gas.
The production yield of 3-carboxylic acid decreases. Also, even if the reaction temperature is below 190℃,
In the range of 160° C. to 190° C., when carbon dioxide gas becomes high pressure, the by-product of 2-hydroxybiphenyl-3,5-dicarboxylic acid increases. This becomes more noticeable as the reaction temperature increases. The by-product 2-hydroxybiphenyl-3,5-dicarboxylic acid is sparingly soluble in various solvents and is nonvolatile, so it is difficult to remove by normal separation and purification methods such as recrystallization and distillation. Therefore, 2-hydroxybiphenyl-3,5-
It is desirable to carry out the reaction under reaction conditions in which almost no dicarboxylic acid is produced as a by-product, and from this point of view, at a reaction temperature in the range of 160°C to 190°C, the carbon dioxide pressure is determined by the following formula: P = (220 - T) / 1.5 [ In the formula, T is the reaction temperature (° C.)] The value of P (Kg/cm 2 ·G) or less is preferable. On the other hand, when the reaction temperature is 160 DEG C. or lower, the by-product of 2-hydroxybiphenyl-3,5-dicarboxylic acid is not noticeable even when the carbon dioxide gas pressure is high. Furthermore, the higher the carbon dioxide gas pressure, the higher the production yield of the target 2-hydroxybiphenyl-3-carboxylic acid. However, even if the carbon dioxide gas pressure is increased too much, the production yield of 2-hydroxybiphenyl-3-carboxylic acid is not significantly improved, and when it exceeds 40 Kg/cm 2 , the production yield is hardly improved substantially. Therefore, it is not preferable from an economic point of view to carry out the reaction under a carbon dioxide gas pressure exceeding 40 kg/cm 2 . As described above, the reaction between the sodium salt of 2-hydroxybiphenyl and carbon dioxide gas largely depends on the reaction temperature and carbon dioxide pressure, and these are interrelated. The reaction temperature and carbon dioxide gas pressure to selectively and economically obtain the desired 2-hydroxybiphenyl-3-carboxylic acid are as follows:
When the carbon dioxide pressure is in the range of 7 to 40 Kg/cm 2・G, the upper limit P (Kg/cm 2・G) of the carbon dioxide gas pressure is calculated by the following formula P = (220 - T) / 1.5 [where T is the reaction Temperature (°C)] within a range that does not exceed the value. The reaction can be completed by stirring the sodium salt of 2-hydroxybiphenyl at the above reaction temperature and under carbon dioxide pressure, and the reaction time is usually
It ranges from 30 minutes to 6 hours. After the reaction is complete, the reaction mixture is dissolved in water, and a mineral acid such as hydrochloric acid or sulfuric acid is added for acid precipitation. If necessary, purification operations such as solvent washing or recrystallization are performed to obtain 2-hydroxybiphenyl-3-carboxylic acid. The acid can be isolated. The content of the present invention will be explained in more detail below using Examples and Comparative Examples. Example 1 In a single eggplant flask equipped with a reflux condenser,
40 g of sodium hydroxide was heated and dissolved in 200 ml of methanol. In this, 2-hydroxybiphenyl
170 g was added and heated under reflux to obtain a homogeneous solution.
This solution was concentrated under reduced pressure, and the precipitated crystals were further removed.
Vacuum dry at 130℃/5-10 Torr for 2 hours to obtain 2-hydroxybiphenyl sodium salt (colorless solid).
Obtained 190g. During this period, almost no 2-hydroxybiphenyl was observed to be distilled out. The obtained sodium salt of 2-hydroxybiphenyl was ground into 20 meshes or less using a ball mill.
25 g of this was collected and placed in an autoclave with an internal volume of 200 ml equipped with a stirrer. After purging the inside of the autoclave with carbon dioxide gas, carbon dioxide gas was introduced at a pressure of 10 kg/cm 2 and heated and stirred at 170° C. for 4 hours. As the reaction progresses, carbon dioxide gas is consumed and the pressure decreases, but carbon dioxide gas is supplemented from the outside and the pressure is constantly maintained at 10 kg/kg.
I tried to keep it at cm2 . The reaction mixture was dissolved in 200 ml of warm water, diluted hydrochloric acid was added to adjust the pH to 7-8, and the solution was washed with dichloromethane. The dichloromethane washing solution was concentrated under reduced pressure to recover 11.7 g of 2-hydroxybiphenyl. Concentrated hydrochloric acid was added to the aqueous layer to adjust the pH to below 1, and the precipitated crystals were collected by filtration and vacuum dried to obtain 11.8 g of a colorless solid. A part of this product was methylated with diazomethane and then analyzed by gas chromatography, and the results showed that it was 2-hydroxybiphenyl-3-carboxylic acid, 2-hydroxybiphenyl-5-carboxylic acid, and 2-hydroxybiphenyl-5-carboxylic acid. -3,5-
It is a mixture of dicarboxylic acids, and its mixing ratio is 94:
It was found that the molar ratio was 3:3. Therefore, the yields are 35.5%, 1.3%, and 1.2%, respectively.
It was calculated that The results are shown in Table 1 together with the results of other Examples and Comparative Examples. 11.4 g of the colorless solid was collected and recrystallized from water-methanol to give 2-hydroxybiphenyl-3.
- 8.1 g of carboxylic acid were obtained as pure product. This product had a mp. of 188-189°C. Comparative Example 1 In Example, 200ml of water was used instead of 200ml of methanol.
ml was used to obtain 175 g of sodium salt of 2-hydroxybiphenyl. In this case, during vacuum drying, 2-hydroxybiphenyl 10.5
g was distilled out. Examples 2 to 5 and Comparative Examples 2 to 6 The same reactions as in Example 1 were carried out by changing the reaction temperature and carbon dioxide pressure. The reaction mixture was dissolved in 200 ml of warm water, the pH was adjusted to below 1 by adding concentrated hydrochloric acid, and the mixture was extracted with 200 ml of ethyl acetate. After a portion of the extract was treated with diazomethane, quantitative analysis was performed using gas chromatography, and the results shown in Table 1 were obtained.
【表】
発明の効果
本発明により感熱紙顕色剤等の用途が見込まれ
る２−ヒドロキシビフエニル−３−カルボン酸を
選択的かつ経済的に製造し、当該業界に供給する
ことが可能となつた。[Table] Effects of the Invention The present invention has made it possible to selectively and economically produce 2-hydroxybiphenyl-3-carboxylic acid, which is expected to be used as a color developer for thermal paper, and supply it to the relevant industry. Ta.
Claims (1)
ムを低級アルコール溶媒中で反応させ、生成する
２−ヒドロキシビフエニルのナトリウム塩を分離
し、前記の２−ヒドロキシビフエニルのナトリウ
ム塩を炭酸ガス加圧下、加熱反応させるにあた
り、反応温度が140〜190℃、炭酸ガス圧力が７〜
40Kg／cm2・Ｇの範囲で、かつ炭酸ガス圧力の上限
Ｐ（Kg／cm2・Ｇ）が次式 Ｐ＝（220−Ｔ）／1.5 〔式中、Ｔは反応温度（℃）である〕 の値を越えない範囲で反応を行なうことを特徴と
する２−ヒドロキシビフエニル−３−カルボン酸
の製造方法。[Claims] 1. 2-hydroxybiphenyl and sodium hydroxide are reacted in a lower alcohol solvent, the resulting sodium salt of 2-hydroxybiphenyl is separated, and the sodium salt of 2-hydroxybiphenyl is separated. When conducting a heating reaction under pressure of carbon dioxide, the reaction temperature is 140-190℃ and the pressure of carbon dioxide is 7-7.
In the range of 40Kg/cm 2・G, and the upper limit P (Kg/cm 2・G) of carbon dioxide gas pressure is the following formula: P=(220−T)/1.5 [where T is the reaction temperature (℃) ] A method for producing 2-hydroxybiphenyl-3-carboxylic acid, characterized in that the reaction is carried out within a range not exceeding the value of .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18398785A JPS6245559A (en) | 1985-08-23 | 1985-08-23 | Production of 2-hydroxybiphenyl-3-carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18398785A JPS6245559A (en) | 1985-08-23 | 1985-08-23 | Production of 2-hydroxybiphenyl-3-carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6245559A JPS6245559A (en) | 1987-02-27 |
| JPH0335308B2 true JPH0335308B2 (en) | 1991-05-27 |
Family
ID=16145331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18398785A Granted JPS6245559A (en) | 1985-08-23 | 1985-08-23 | Production of 2-hydroxybiphenyl-3-carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6245559A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112720130A (en) * | 2020-12-29 | 2021-04-30 | 叶霖 | Computer housing burr grinding device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0467699U (en) * | 1990-10-22 | 1992-06-16 |
-
1985
- 1985-08-23 JP JP18398785A patent/JPS6245559A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112720130A (en) * | 2020-12-29 | 2021-04-30 | 叶霖 | Computer housing burr grinding device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6245559A (en) | 1987-02-27 |
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