JPH03200741A - Production of hydroxynaphthalenecarboxylic acids - Google Patents
Production of hydroxynaphthalenecarboxylic acidsInfo
- Publication number
- JPH03200741A JPH03200741A JP33820289A JP33820289A JPH03200741A JP H03200741 A JPH03200741 A JP H03200741A JP 33820289 A JP33820289 A JP 33820289A JP 33820289 A JP33820289 A JP 33820289A JP H03200741 A JPH03200741 A JP H03200741A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxynaphthalene
- carboxylic acid
- naphthol
- salt
- carbon dioxide
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical class C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 title description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 229950011260 betanaphthol Drugs 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims abstract description 5
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- -1 alkali metal salt Chemical class 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 159000000000 sodium salts Chemical class 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- AJXVJQAPXVDFBT-UHFFFAOYSA-M sodium;naphthalen-2-olate Chemical group [Na+].C1=CC=CC2=CC([O-])=CC=C21 AJXVJQAPXVDFBT-UHFFFAOYSA-M 0.000 description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PPDZLUVUQQGIOJ-UHFFFAOYSA-N 1-dihexylphosphorylhexane Chemical compound CCCCCCP(=O)(CCCCCC)CCCCCC PPDZLUVUQQGIOJ-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- NIOAVQYSSKOCQP-UHFFFAOYSA-N 4-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC(O)=C21 NIOAVQYSSKOCQP-UHFFFAOYSA-N 0.000 description 1
- 241001532207 Dasylirion Species 0.000 description 1
- 235000008763 Dasylirion wheeleri Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 150000001218 Thorium Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZENVDAOWLCNJHY-UHFFFAOYSA-N carbonic acid;naphthalene Chemical compound OC(O)=O.C1=CC=CC2=CC=CC=C21 ZENVDAOWLCNJHY-UHFFFAOYSA-N 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ナフタレンヒドロキシカルボン酸の製造法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing naphthalene hydroxycarboxylic acid.
従来、ナフトール類の二酸化炭素によるカルボキシル化
方法としては、２−ナフトールのナトリウム塩の無水物
の固体と二酸化炭素を１３０℃で反応させることにより
２−ヒドロキシナフタレン−１−カルボン酸く以下、２
．１−１１Ｎ＾と略記する〉が得られ２３０〜２４０℃
で反応させることにより２．ヒドロキシナフタレン−３
−カルボン酸（以下、２．３−１１ＮＡと略記する）が
得られる。また、カリウム塩の無水物の固体と二酸化炭
素を２００℃で反応させることにより２−ヒドロキシナ
フタレン−６−カルボン酸（以下、２．６−１１Ｎ＾と
略記する）が６０χの選択率で得られる。このことは、
堀口 博「実験有機合成論」上巻５４３頁に記載されて
いる。また、非プロトン性極性溶媒として、ジメチルス
ルホキシド、ジメチルフォルムアミド、ピリジン、ジオ
キサン、ニトロベンゼンを用いる方法（日本化学会誌、
１９８９（７） １１６４頁）が山口等により検討され
ている、彼らは、無水のカリウム塩を用い８０℃で２．
１−１１Ｎ＾を収率４６〜７７！で得ている。Conventionally, as a method for carboxylating naphthols with carbon dioxide, 2-hydroxynaphthalene-1-carboxylic acid, 2-hydroxynaphthalene-1-carboxylic acid, etc.
．． 1-11N^ was obtained at 230-240°C.
By reacting with 2. Hydroxynaphthalene-3
-carboxylic acid (hereinafter abbreviated as 2.3-11NA) is obtained. In addition, 2-hydroxynaphthalene-6-carboxylic acid (hereinafter abbreviated as 2.6-11N^) can be obtained with a selectivity of 60χ by reacting a solid potassium salt anhydride with carbon dioxide at 200°C. . This means that
It is described in Hiroshi Horiguchi's "Experimental Organic Synthesis" Volume 1, page 543. In addition, a method using dimethyl sulfoxide, dimethyl formamide, pyridine, dioxane, or nitrobenzene as an aprotic polar solvent (Journal of the Chemical Society of Japan,
1989 (7) p. 1164) was reviewed by Yamaguchi et al., who used anhydrous potassium salt at 80°C for 2.
Yield 46-77 for 1-11N^! I am getting it from
しかし、上述した従来の方法では、無水のカリラム塩の
固体との反応では反応温度が高く、且つ反応が１５時間
以上かかるという問題があり、また、極１生溶媒を用い
る反応では有用性の高い２．３−１１ＮＡまたは２．６
−１１ＮＡの選択性は１０２以下である。However, in the conventional method described above, there are problems in that the reaction temperature is high and the reaction takes more than 15 hours when reacting anhydrous kalirum salt with a solid. 2.3-11NA or 2.6
-11NA has a selectivity of 102 or less.
ｃ問題点を解決するための手段〕
本発明は、前記課題を解決するため鋭意明文を行った結
果、有機フメスフィンオキン１′溶媒中で２−ナフト−
ルのナトリウム塩またはカリ１シム塩を二酸化炭素と反
応さ・吐るごとに上り２，３１１Ｎ＾及び２、Ｇ−１１
Ｎ八を、より温和な条件で高選択率で得られることを見
出し、本発明を完成さｌたものである。ずなわら、本発
明は、下記−・船人（１）で表される４１機フォスフィ
ンオ二トシドの一神またも、Ｌ二捕以上の７１Ｌ合物を
溶媒として、２−ナフト−ルのアルカリ金属塩と二酸化
炭素との反応を行うことを１、！酸とする２−ヒドロキ
シナフタレン−３−カルボン酸及び２−ヒドロキシナフ
タレン−６−カルボン酸の製造法である。Means for Solving Problems c] As a result of extensive efforts to solve the above-mentioned problems, the present invention has been achieved by producing 2-naphtho-2-naphtho-
2,311 N^ and 2, G-11 of sodium salt or potassium salt reacts with carbon dioxide.
The present invention was completed by discovering that N8 can be obtained with high selectivity under milder conditions. In addition, the present invention is directed to the use of an alkali of 2-naphthol using a 71L compound having two or more L compounds as a solvent. 1, to perform a reaction between a metal salt and carbon dioxide! This is a method for producing 2-hydroxynaphthalene-3-carboxylic acid and 2-hydroxynaphthalene-6-carboxylic acid as acids.
（Ｒ，、Ｒ１，及びＲ１は炭素数４〜８のアル・１−ル
丞、またはフェニル基を示す）。(R, , R1, and R1 each represent an alkyl group having 4 to 8 carbon atoms or a phenyl group).
本発明に用いる有機フォスフインオキシ１′と【上（Ｒ
０Ｒ５及びＲ１は炭素数４〜Ｂのアルキル凸、またはフ
ェニル基を示し、互いに同一・でも異なっていてもよい
）で表される。Organic phosphineoxy 1' used in the present invention and [upper (R
0R5 and R1 represent a convex alkyl group having 4 to B carbon atoms or a phenyl group, and may be the same or different from each other.
具体的には、トリー〇−プチルフＡスフィンオートシト
、トリセカンダリ−ブチルフォスフインオキシド、トリ
ーｎ−ヘキシルフォスフインオキシド、トリーｎ−オク
チルフォスフインオキシド、トリフェニルフォスフイン
オキシド等が挙げられる。Specific examples include tri0-butylphosphine oxide, tri-butylphosphine oxide, tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide, triphenylphosphine oxide, and the like.
好ましくは、−船人（１）において、Ｒ，、）？、、及
びＲ，が互いに同一である炭素数４〜８のトリアルキル
フォスフインオキシド、あるいはトリフェニルフォスフ
インオキシドである。Preferably, in -Sailor (1), R,, )? , , and R are the same as each other, a trialkylphosphine oxide having 4 to 8 carbon atoms, or a triphenylphosphine oxide.
これら有機フォスフインオキシドは反応に際し、溶媒と
して単独であるいは二種以上の混合物とし°Ｃ用いるこ
とが出来る。These organic phosphine oxides can be used as a solvent alone or in a mixture of two or more at °C during the reaction.
また、２−ナフトールのアルカリ金属塩は、アルカリ金
属塩がカリウムであっても、ナトリウムであっ°ζも高
い選択率で２．３−１１ＮＡ 、 ２．（ｉ−１１Ｎ＾
を与える。In addition, even if the alkali metal salt of 2-naphthol is potassium or sodium, it has a high selectivity of 2.3-11NA. (i-11N^
give.
使用する２−ナフトールのアルカリ金属塩は種々の方法
で得ることができる０例えば、２−ナフトールに当量の
水酸化アルカリ金属水溶液を加え、蒸発乾固した後、真
空下に実質的に無水物を生成する方法、更に好ましくは
、有８１溶媒に２−ナフＩ−−ルを溶解し、水酸化アル
カリ金属水溶液により中和した後、有機溶媒を留去する
ことにより適切な−）°トリウム塩が得られる。The alkali metal salt of 2-naphthol used can be obtained in various ways.For example, an equivalent amount of aqueous alkali metal hydroxide solution is added to 2-naphthol, evaporated to dryness, and then the substantially anhydrous salt is prepared under vacuum. More preferably, a suitable -)° thorium salt is produced by dissolving 2-naph I-- in a solvent, neutralizing it with an aqueous alkali metal hydroxide solution, and then distilling off the organic solvent. can get.
２〜ナフトールのアルカリ金属塩は前記有機フォスフイ
ンオキシドに高濃度で溶解するため、カル、１ξキンル
化が迅速に進むものと考えられる。Since the alkali metal salt of 2 to naphthol is dissolved in the organic phosphine oxide at a high concentration, it is thought that the quinlation of cal and 1ξ proceeds rapidly.
好ましい反応温度は、１００〜２２０°Ｃである。反応
温度が１００°Ｃより低いと、アルカリ金属塩の転化率
が低下し、２２０’Ｃを越えると不純物の副４Ｉが署し
くなる。The preferred reaction temperature is 100-220°C. When the reaction temperature is lower than 100°C, the conversion rate of the alkali metal salt decreases, and when it exceeds 220°C, the impurity sub-4I becomes significant.
反応時間は特に阻止されないが、一般に反１．６１−ｒ
間を延ばずことによっ゛（転化率を、；ｆｉめることが
できる０反応時間は、原料、溶媒の種類、反応温度によ
り変わるが、例えば、反応温度＋５０ ’Ｃ′ｒ：４：
１１２時間以内に反応は完結する。The reaction time is not particularly limited, but generally anti-1.61-r
The conversion rate can be reduced by not prolonging the reaction time. The reaction time varies depending on the raw materials, the type of solvent, and the reaction temperature, but for example, reaction temperature + 50'C'r: 4:
The reaction is complete within 112 hours.
二酸化炭素の量は本反応が起こるのに必要な化学量論量
以上供給すれば良い。The amount of carbon dioxide may be supplied in a stoichiometric amount or more necessary for this reaction to occur.
反応方法としては、原料のアルカリ金属塩を反応溶媒に
溶解して二酸化炭素を化学Ｍ論量吸収させてから昇温し
てカルボキシル化反応を生起させても良いし、原料溶液
を所定の反応温度に加熱した状態で二酸化炭素を吹き込
みながら反応を行っても良い。As a reaction method, the alkali metal salt of the raw material may be dissolved in a reaction solvent to absorb a stoichiometric amount of carbon dioxide, and then the temperature may be raised to cause the carboxylation reaction, or the raw material solution may be heated to a predetermined reaction temperature. The reaction may be carried out while blowing carbon dioxide in a heated state.
反応は減圧下、常圧下、加圧下いずれでも実施でき、例
えば、二酸化炭素の加圧下で行う場合には、反応時間を
短縮することができる。この場合の二酸化炭素圧力は１
〜２０ｋｇ／ｃｄゲージ程度で充分である。叉、本反応
は、回分てもｉ！ｌ！続でも行うことができる。The reaction can be carried out under reduced pressure, normal pressure, or increased pressure. For example, when carried out under increased pressure of carbon dioxide, the reaction time can be shortened. In this case, the carbon dioxide pressure is 1
~20 kg/cd gauge is sufficient. For this reaction, even if it's a batch, it's i! l! It can also be done continuously.
〔実施例）
以下、本発明を実施例により更に具体的に説明する、な
お、原料および生成物は液体クロマトグラフ（充填剤ニ
ジリカゲル−〇４、溶離液ニアセトニトリル−水）によ
り分析した。[Example] Hereinafter, the present invention will be described in more detail with reference to Examples. The raw materials and products were analyzed by liquid chromatography (filling material Nijirica gel-04, eluent Niacetonitrile-water).
実施例１
２−ナフトール２９．８ｇ（０，２０６＋ｗｏｌ）に水
酸化ナトリウム８．７ｇを加え脱水し、実質上無水の原
料固体を得た。このようにして得られた無水のす１・１
Ｊウム塩を原料とし、撹拌機、二酸化炭素吹き込み管、
還流冷却器を備えた３００ｄガラス製四っに１フラスコ
に入れ、溶媒として予めモレキュラシープで乾燥した無
水のトリブチルフォスフインオキシド（以下、ＴＩＩＰ
Ｏと略記する。 ） １８０ｇを加え、攪拌下７５°Ｃ
で溶解し、均一な液を得た０次いで常圧下７５°Ｃに保
った状態で二酸化炭素を吹き込み充分吸収さセた後、同
様に二酸化炭素を吹き込みながら反応器の内温を１８０
°Ｃまで昇温し、３時間反応を行った。内温を８０°Ｃ
まで冷却した後、反応マスに水２００ｉｄを加えよく振
盪し、静置して水層とＴＯＰＯ層とに分液後、それぞれ
を液体クロマトグラフにより分析した。Example 1 8.7 g of sodium hydroxide was added to 29.8 g (0,206+wol) of 2-naphthol and dehydrated to obtain a substantially anhydrous raw material solid. Anhydrous 1.1 obtained in this way
Jum salt is used as raw material, stirrer, carbon dioxide blowing pipe,
Anhydrous tributylphosphine oxide (hereinafter referred to as TIIP), which had been previously dried with molecular sheep, was added as a solvent to a 300D glass quarter flask equipped with a reflux condenser.
It is abbreviated as O. ) Add 180g and stir at 75°C.
After dissolving and obtaining a homogeneous liquid, carbon dioxide was blown into the reactor while maintaining the temperature at 75°C under normal pressure to ensure sufficient absorption.
The temperature was raised to °C and the reaction was carried out for 3 hours. Internal temperature 80°C
After cooling, 200 id of water was added to the reaction mass, shaken well, allowed to stand, and separated into an aqueous layer and a TOPO layer, each of which was analyzed by liquid chromatography.
２−ナフトール転化率２１％、２．３−１１ＮＡ選択率
４４％、２．［１−１１ＮＡ選沢率５０％を得た。その
他２．１−１１Ｎ八が少量見出された。2-naphthol conversion rate 21%, 2.3-11NA selectivity 44%, 2. [1-11NA selection rate of 50% was obtained. In addition, a small amount of 2.1-11N8 was found.
実施例２
原料塩を２−ナフトールナトリウム塩に代え°Ｃ実ｈＮ
例１と同Ｊ″Ｑな方法により得られた２−）・ソト−ル
カリウｌ、塩を用い、反応時間を１時間とした他は実施
例Ｉと同様に行った０分析の結果、２−ナフトール転化
率３３％、２．３１１ＮＡ選択率３４％、２．（ｉ Ｉ
ＩＮ八選へ率６３％であった。Example 2 Raw material salt was replaced with 2-naphthol sodium salt °C actual hN
As a result of 0 analysis carried out in the same manner as in Example I, except that 2-).sotol potassium l obtained by the same method as in Example 1 and salt was used and the reaction time was 1 hour, 2- Naphthol conversion rate 33%, 2.311NA selectivity 34%, 2.(i I
The rate of passing the IN8 selection was 63%.
実施例３
溶媒をＴＩＩＩＩＯに代えトリオクチルツメスフィンオ
キシド（以下、ＴＯＰＯと略記する。）を用い、反ＪＩ
Ｌ＞時間を６時間とした他は実施例１と同様に１１った
。Example 3 Using trioctyltumesphine oxide (hereinafter abbreviated as TOPO) in place of TIIIO as a solvent,
Example 11 was carried out in the same manner as in Example 1 except that L>time was set to 6 hours.
分ＪＪＦ ｃ７） 結果、２− す７１・−ル転化率１
４％、２．３−１１ＮＡ選沢率６２％、２．６−１１Ｎ
Ａ選択率２９％であった。min JJF c7) Result, 2-su71·-le conversion rate 1
4%, 2.3-11NA selection rate 62%, 2.6-11N
The A selection rate was 29%.
実施例４
反応温度を１５０°Ｃに変えた他は実施例１と同様に行
った０分析の結果、２−ナフトール転化率１３％、２．
３−１１ＮＡ選択率３８％、２．（ｉ−１１ＮＡ ！ベ
キ２５％であった。その（１１１２，１−１１Ｎ八が少
量見出された。Example 4 A zero analysis conducted in the same manner as in Example 1 except that the reaction temperature was changed to 150°C revealed that the 2-naphthol conversion rate was 13%, 2.
3-11NA selectivity 38%, 2. (i-11NA! power was 25%. A small amount of (1112, 1-11N8) was found.
実施例５
実施例１で得られた無水のすトリウＪ、Ｊムと乾燥した
Ｔｌ１ｌ’０１８０ｇを内容積３００ｒＩｒｆｆｉの５
Ｏ５−３１（ｉＬ製のオートクレーブに入れ、１８０℃
に加熱した後、二酸化炭素を吹き込み、全圧をｌｏｋｇ
／ｅＩｉゲージに保らながら３時間反応を行った。内温
を８０°Ｃまで冷却した後、反応マスに水２００ｓｆｆ
ｉを加え振盪した後静置して、水層とＴＯＰＯ層とに分
離した。 ＴＩＩＰＯＷＪには未反応の２−ナフトール
、２−ナフトールナトリウム塩及び少量の２．３−１１
Ｎ＾ナトリウム塩、２．６−１１Ｎ＾ナトリウム塩が含
まれていた。水層には各種のＩＩＮ＾すトリウム塩が抽
出された０分析の結果、２−ナフトール転化率３７％、
２．３−１１ＮＡ選択率４３％、２．（ｉ−１１ＮＡ選
択率４８％であった。Example 5 180 g of the anhydrous Sutriu J, Jmu and dried Tl1l' obtained in Example 1 were placed in a
O5-31 (Put in iL autoclave, 180℃
After heating to , blow in carbon dioxide and reduce the total pressure to
The reaction was carried out for 3 hours while maintaining the /eIi gauge. After cooling the internal temperature to 80°C, add 200sff of water to the reaction mass.
After adding i and shaking, the mixture was allowed to stand to separate into an aqueous layer and a TOPO layer. TIIPOWJ contains unreacted 2-naphthol, 2-naphthol sodium salt and a small amount of 2.3-11.
It contained N^sodium salt, 2.6-11N^sodium salt. Various IIN^thorium salts were extracted from the aqueous layer.As a result of analysis, the conversion rate of 2-naphthol was 37%,
2.3-11NA selectivity 43%, 2. (The i-11NA selectivity was 48%.
実施例６
溶媒をＴ １１１１０に代え１リフエニルフＡ・スフィ
ンオ・トシド（以下Ｔ １１１１０と略記する。）を用
い、反１５時間を８特問とした他は実施例１と同様に行
った。Example 6 The same procedure as in Example 1 was carried out, except that the solvent was replaced with T 11110 and 1 rifenylph A. sphinotoside (hereinafter abbreviated as T 11110) was used, and 8 special questions were used for 15 hours.
分析の結果、２−ナフトール転化率９％、２．３−１１
ＮＡ選択率５９％、２．６−１１ＮＡ選沢率２７％であ
った。As a result of analysis, 2-naphthol conversion rate was 9%, 2.3-11
The NA selection rate was 59%, and the 2.6-11NA selection rate was 27%.
本発明の方法によれば、染料中間体あるい（よ全芳香族
系ポリエステル系原料として有用なヒドロキシナフタレ
ンカルボン酸は、有機フォスフインオキシド溶媒中で反
応を行うことにより、原料に用いる２−ナフトールのア
ルカリ金属塩がす１リウム塩でもカリウム塩と同様に高
選択率で得ることができ、経済的に有利であり産業に利
するところ極めて大である。According to the method of the present invention, hydroxynaphthalenecarboxylic acid, which is useful as a dye intermediate or a fully aromatic polyester raw material, can be obtained by reacting it in an organic phosphine oxide solvent. The monolium salt of the alkali metal salt can be obtained with high selectivity in the same way as the potassium salt, which is economically advantageous and extremely beneficial to industry.
Claims (1)
の一種または二種以上の混合物を溶媒として、２−ナフ
トールのアルカリ金属塩と二酸化炭素との反応を行うこ
とを特徴とする２−ヒドロキシナフタレン−３−カルボ
ン酸及び２−ヒドロキシナフタレン−６−カルボン酸の
製造法。 一般式▲数式、化学式、表等があります▼（１） （Ｒ＿１、Ｒ＿２、及びＲ＿３は炭素数４〜８のアルキ
ル基、またはフェニル基を示す）。[Claims] The method is characterized by carrying out a reaction between an alkali metal salt of 2-naphthol and carbon dioxide using one or a mixture of two or more organic phosphine oxides represented by the following general formula (1) as a solvent. A method for producing 2-hydroxynaphthalene-3-carboxylic acid and 2-hydroxynaphthalene-6-carboxylic acid. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (R_1, R_2, and R_3 represent an alkyl group having 4 to 8 carbon atoms or a phenyl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33820289A JPH03200741A (en) | 1989-12-28 | 1989-12-28 | Production of hydroxynaphthalenecarboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33820289A JPH03200741A (en) | 1989-12-28 | 1989-12-28 | Production of hydroxynaphthalenecarboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03200741A true JPH03200741A (en) | 1991-09-02 |
Family
ID=18315890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33820289A Pending JPH03200741A (en) | 1989-12-28 | 1989-12-28 | Production of hydroxynaphthalenecarboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03200741A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007269717A (en) * | 2006-03-31 | 2007-10-18 | Ueno Technology:Kk | Method for producing 2-hydroxynaphthalene-3,6-dicarboxylic acid |
-
1989
- 1989-12-28 JP JP33820289A patent/JPH03200741A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007269717A (en) * | 2006-03-31 | 2007-10-18 | Ueno Technology:Kk | Method for producing 2-hydroxynaphthalene-3,6-dicarboxylic acid |
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