JPH0555495B2 - - Google Patents
Info
- Publication number
- JPH0555495B2 JPH0555495B2 JP20175887A JP20175887A JPH0555495B2 JP H0555495 B2 JPH0555495 B2 JP H0555495B2 JP 20175887 A JP20175887 A JP 20175887A JP 20175887 A JP20175887 A JP 20175887A JP H0555495 B2 JPH0555495 B2 JP H0555495B2
- Authority
- JP
- Japan
- Prior art keywords
- dihydroxy
- naphthoic acid
- reaction
- acid
- producing
- 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 - Lifetime
Links
- VOJUXHHACRXLTD-UHFFFAOYSA-N 1,4-dihydoxynaphthalene-2-carboxylic acid Natural products C1=CC=CC2=C(O)C(C(=O)O)=CC(O)=C21 VOJUXHHACRXLTD-UHFFFAOYSA-N 0.000 claims description 38
- -1 1,4-dihydroxy-2-naphthoic acid aryl ester Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000539 dimer Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007860 aryl ester derivatives Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XDUXGEPGVNWEBQ-UHFFFAOYSA-N phenyl 1,4-dihydroxynaphthalene-2-carboxylate Chemical compound OC=1C2=CC=CC=C2C(O)=CC=1C(=O)OC1=CC=CC=C1 XDUXGEPGVNWEBQ-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- USZZLTVYRPLBMB-UHFFFAOYSA-N 1,3-dihydroxynaphthalene-2-carboxylic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=C(O)C=C21 USZZLTVYRPLBMB-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 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
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RDOFXDKHPHWUQW-UHFFFAOYSA-N methyl 4-methoxynaphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OC)=CC(OC)=C21 RDOFXDKHPHWUQW-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
＜産業上の利用分野＞
本発明は、下記一般式［］で示される１，４
−ジヒドロキシ−２−ナフトエ酸アリールエステ
ルの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to 1,4 represented by the following general formula []
The present invention relates to a method for producing a dihydroxy-2-naphthoic acid aryl ester.
詳しく述べると、本発明は１，４−ジヒドロキ
シ−２−ナフトエ酸とトリアリール亜リン酸エス
テルとから１，４−ジヒドロキシ−２−ナフトエ
酸アリールエステルを製造する際、１，４−ジヒ
ドロキシ−２−ナフトエ酸１モルに対してトリア
リール亜リン酸エステルを0.9〜３モルの範囲の
比で用いて反応せしめると共に当該反応中に副生
する下記一般式［］で示される２量体をアルカ
リ性水溶液で加水分解して、１，４−ジヒドロキ
シ−２−ナフトエ酸とし、これを原料として再使
用することで効率よく１，４−ジヒドロキシ−２
−ナフトエ酸アリールエステルを製造する方法に
関するものである。 Specifically, the present invention provides 1,4-dihydroxy-2-naphthoic acid aryl ester when producing 1,4-dihydroxy-2-naphthoic acid aryl ester from 1,4-dihydroxy-2-naphthoic acid and triaryl phosphite. - A reaction is carried out using triaryl phosphite in a ratio of 0.9 to 3 moles per mole of naphthoic acid, and a dimer represented by the following general formula [], which is produced as a by-product during the reaction, is dissolved in an alkaline aqueous solution. 1,4-dihydroxy-2-naphthoic acid, which can be reused as a raw material to efficiently produce 1,4-dihydroxy-2-naphthoic acid.
- A method for producing a naphthoic acid aryl ester.
本発明が目的とする１，４−ジヒドロキシ−２
−ナフトエ酸アリールエステルは、染料、顔料中
間体及び感光材料として有用な化合物である。し
かしながら、工業的に有利な製造方法は未だ開発
されていない。 1,4-dihydroxy-2 which is the object of the present invention
-Naphthoic acid aryl esters are compounds useful as dyes, pigment intermediates, and photosensitive materials. However, an industrially advantageous manufacturing method has not yet been developed.
［］
［］
（式中Ｒは水素、ハロゲン原子又は炭素数１〜
10のアルキル基を示す）
＜従来技術＞
多環式カルボン酸エステル類の製造方法として
は、多環式カルボン酸とアルコール類を酸触媒の
存在下で脱水する方法が一般に良く知られてお
り、例えば米国特許第2415884号明細書では、１，
４−ジヒドロキシ−２−ナフトエ酸をメタノール
溶媒中、塩化水素ガスを用いて１−ヒドロキシ−
４−メトキシ−２−ナフトエ酸メチルエステルを
合成している。 [] [] (In the formula, R is hydrogen, a halogen atom, or a carbon number of 1 to
10) <Prior art> As a method for producing polycyclic carboxylic acid esters, a method in which polycyclic carboxylic acids and alcohols are dehydrated in the presence of an acid catalyst is generally well known. For example, in US Pat. No. 2,415,884, 1,
4-Dihydroxy-2-naphthoic acid was diluted with 1-hydroxy-2-naphthoic acid using hydrogen chloride gas in methanol solvent.
Synthesizing 4-methoxy-2-naphthoic acid methyl ester.
又、当該カルボン酸とフエノール類とからのエ
ステル類の合成法としては米国特許第3839044号
明細書で１，４−ジヒドロキシ−２−ナフトエ酸
と４位水酸基をヘテロ環で保護したフエノールと
三塩化リンでフエニルエステルとする方法が知ら
れている。 Furthermore, as a method for synthesizing esters from the carboxylic acid and phenols, US Pat. A method of converting phenyl ester with phosphorus is known.
さらに、特開昭53−28139号公報ではアリール
オキシカルボン酸と、三塩化リン１モルに対し２
モルのフエノールを反応させて得られるアリール
亜リン酸エステルとを反応させアリールオキシカ
ルボン酸アリールエステルを製造しているが、こ
れはアリールオキシカルボン酸の水酸基が１個の
アリール基の場合であり、この場合ほぼ定量的に
アリールエステルが生成する。しかしながら、本
発明が目的とする１，４−ジヒドロキシ−２−ナ
フトエ酸フエニルエステルについての反応例は無
い。 Furthermore, in Japanese Patent Application Laid-open No. 53-28139, aryloxycarboxylic acid and
Aryloxycarboxylic acid aryl ester is produced by reacting with an aryl phosphite obtained by reacting moles of phenol, but this is a case where the aryloxycarboxylic acid has one hydroxyl group, In this case, aryl esters are produced almost quantitatively. However, there is no reaction example regarding 1,4-dihydroxy-2-naphthoic acid phenyl ester, which is the object of the present invention.
＜問題点を解決する為の手段＞
このような状況に鑑み、本発明者らは１，４−
ジヒドロキシ−２−ナフトエ酸のアリールエステ
ル化反応について検討したところ、１，４−ジヒ
ドロキシ−２−ナフトエ酸と反応剤としてのトリ
アリール亜リン酸エステルを用い、１，４−ジヒ
ドロキシ−２−ナフトエ酸アリールエステルを製
造する方法において、１，４−ジヒドロキシ−２
−ナフトエ酸１モルに対しトリアリール亜リン酸
エステル0.8モ倍以上、好ましくは0.9〜３モル倍
を用い、反応温度90〜150℃の範囲で反応するこ
とを特徴とする１，４−ジヒドロキシ−２−ナフ
トエ酸アリールエステルを製造方法を見い出し
た。<Means for solving the problems> In view of this situation, the present inventors have taken steps 1, 4-
When we investigated the aryl esterification reaction of dihydroxy-2-naphthoic acid, we found that 1,4-dihydroxy-2-naphthoic acid was produced using 1,4-dihydroxy-2-naphthoic acid and triaryl phosphite as a reactant. In the method for producing an aryl ester, 1,4-dihydroxy-2
- 1,4-dihydroxy- characterized in that the reaction is carried out using 0.8 mole or more, preferably 0.9 to 3 mole times, of triaryl phosphite per 1 mole of naphthoic acid at a reaction temperature in the range of 90 to 150°C. We have discovered a method for producing 2-naphthoic acid aryl ester.
しかしながら、上記製造条件においてはメタノ
ール水溶性の副反応生成物が５〜50モル％副生
し、目的物の収率を著しく悪くしていることが判
明した。本発明者等は該副反応生成物について構
造解析を行なつたところ、一般式［］で示され
る１，４−ジヒドロキシ−２−ナフトエ酸アリー
ルエステルの４位ヒドロキシ基と原料の１，４−
ジヒドロキシ−２−ナフトエ酸が脱水縮合したと
考えられる２量体であることが判明した。又、こ
の該２量体がアルカリ性水溶液で容易に加水分解
して原料の１，４−ジヒドロキシ−２−ナフトエ
酸を生成することを見い出し本発明を完成した。 However, it was found that under the above production conditions, 5 to 50 mol% of methanol water-soluble side reaction products were produced, significantly reducing the yield of the target product. The present inventors conducted a structural analysis of the side reaction product and found that the 4-hydroxy group of the 1,4-dihydroxy-2-naphthoic acid aryl ester represented by the general formula [] and the 1,4-
It was found that it is a dimer that is thought to be a product of dehydration condensation of dihydroxy-2-naphthoic acid. They also found that this dimer was easily hydrolyzed in an alkaline aqueous solution to produce 1,4-dihydroxy-2-naphthoic acid as a raw material, and completed the present invention.
次に本発明の実施大要を述べる。 Next, a summary of the implementation of the present invention will be described.
副生する２量体（式［］で示される化合物）
１モルを水性スラリーとし、４〜６モルのアルカ
リ性物質を窒素などの不活性ガス気流下20〜80
℃、好ましくは40〜70℃で滴下し、加水分解を行
ない、冷却後使用したアルカリ性物質に対し当量
の酸を加え中和することにより１，４−ジヒドロ
キシ−２−ナフトエ酸を析出させ、過、水洗、
乾燥して高純度の１，４−ジヒドロキシ−２−ナ
フトエ酸を高収率で回収することが出来る。 By-produced dimer (compound represented by formula [])
1 mol is made into an aqueous slurry, and 4 to 6 mol of an alkaline substance is mixed with 20 to 80 mol of an aqueous slurry under a stream of inert gas such as nitrogen.
℃, preferably 40 to 70℃, hydrolysis is carried out, and after cooling, an equivalent amount of acid is added to the used alkaline substance to neutralize it to precipitate 1,4-dihydroxy-2-naphthoic acid. , washing with water,
By drying, highly pure 1,4-dihydroxy-2-naphthoic acid can be recovered in high yield.
本発明で用いるアルカリ性物質としては、例え
ば水酸化ナトリウム、炭酸ナトリウム、水酸化カ
リウム、水酸化アンモニウム等が挙げられる。
又、酸としては例えば硫酸、塩酸、リン酸、酢酸
等が例示される。このようにして回収した１，４
−ジヒドロキシ−２−ナフトエ酸を原料として再
使用することにより高収率、高品質の１，４−ジ
ヒドロキシ−２−ナフトエ酸アリールエステルを
効率的に製造することが出来る。又、加水分解反
応は水性スラリーと有機溶媒の存在下で実施する
ことが出来る。有機溶媒としては加水分解生成物
の１，４−ジヒドロキシ−２−ナフトエ酸が可溶
性の溶媒たとえば、トルエン、ベンゼンなどの芳
香族炭化水素、モノクロルベンゼン、ジクロルベ
ンゼン、クロロトルエンなどのハロゲン化炭化水
素、メチル−ｎ−プロピルケトン、メチル−ｎ−
ブチルケトン、メチルイソブチルケトン、メチル
アミルケトン、ジイソブチルケトンなどのケトン
類などから選択され、この有機溶媒の使用で高純
度の１，４−ジヒドロキシ−２−ナフトエ酸が回
収される。 Examples of the alkaline substance used in the present invention include sodium hydroxide, sodium carbonate, potassium hydroxide, and ammonium hydroxide.
Examples of acids include sulfuric acid, hydrochloric acid, phosphoric acid, and acetic acid. 1,4 recovered in this way
By reusing -dihydroxy-2-naphthoic acid as a raw material, it is possible to efficiently produce high-yield, high-quality 1,4-dihydroxy-2-naphthoic acid aryl ester. Alternatively, the hydrolysis reaction can be carried out in the presence of an aqueous slurry and an organic solvent. Examples of organic solvents include solvents in which the hydrolysis product 1,4-dihydroxy-2-naphthoic acid is soluble, such as aromatic hydrocarbons such as toluene and benzene, and halogenated hydrocarbons such as monochlorobenzene, dichlorobenzene, and chlorotoluene. , methyl-n-propyl ketone, methyl-n-
The organic solvent is selected from ketones such as butyl ketone, methyl isobutyl ketone, methyl amyl ketone, and diisobutyl ketone, and highly purified 1,4-dihydroxy-2-naphthoic acid is recovered by using this organic solvent.
以下実施例及び合成例により本発明をさらに詳
細に説明する。 The present invention will be explained in more detail with reference to Examples and Synthesis Examples below.
合成例
攪拌機付き容量１の反応器に、トリフエニル
ホスフアイト（以下TPPと称す）182ｇと１，４
−ジヒドロキシ−２−ナフトエ酸（以下DTNと
称す）120ｇを仕込み、110℃に加温し10時間の反
応を行なつた。内容物は褐色澄明の液状となり反
応は完結した。Synthesis example: In a reactor with a capacity of 1 and equipped with a stirrer, 182 g of triphenyl phosphite (hereinafter referred to as TPP) and 1,4
120 g of -dihydroxy-2-naphthoic acid (hereinafter referred to as DTN) was charged, heated to 110°C, and reacted for 10 hours. The contents became a clear brown liquid and the reaction was completed.
この間液体クロマトグラフによる未反応DHN
分析をし反応終点を判定した。 During this time, unreacted DHN was detected by liquid chromatography.
Analysis was performed to determine the end point of the reaction.
ついで内容物を50℃に冷却後600c.c.の純水を滴
下し、５時間放冷後析出物を別し、さらに水洗
乾燥して粗製生成物155.5ｇを得た。 After cooling the contents to 50° C., 600 c.c. of pure water was added dropwise to the contents, and after standing to cool for 5 hours, the precipitate was separated, washed with water and dried to obtain 155.5 g of a crude product.
次にえられた粗製生成物にメタノール1500c.c.を
加え、常温攪拌下１時間で抽出処理し、過・乾
燥して白色の２量体粉末43.8ｇを回収した。又抽
出液のメタノール溶液を350c.c.まで濃縮し、この
濃縮液に200c.c.の水を滴下し、析出した結晶を
過、乾燥して１，４−ジヒドロキシ−２−ナフト
エ酸フエニルエステルの結晶（M.P.152.5℃）
108.5ｇを得た。 Next, 1500 c.c. of methanol was added to the obtained crude product, and the mixture was extracted for 1 hour with stirring at room temperature, and then overdried to recover 43.8 g of white dimer powder. Also, the methanol solution of the extract was concentrated to 350 c.c., 200 c.c. of water was added dropwise to this concentrated liquid, and the precipitated crystals were filtered and dried to obtain phenyl 1,4-dihydroxy-2-naphthoate. Ester crystal (MP152.5℃)
108.5g was obtained.
実施例 １
合成例で回収した２量体43.8ｇを攪拌機、窒素
導入管付き反応器に仕込み300c.c.の脱気水に懸濁
させ、窒素気流下で48％水酸化ナトリウム水溶液
47.0を40〜70℃に保ちながら１時間で滴下した。
さらに２時間保ち加水分解反応を完結した。Example 1 43.8 g of the dimer recovered in the synthesis example was placed in a reactor equipped with a stirrer and a nitrogen inlet tube, suspended in 300 c.c. of degassed water, and added to a 48% aqueous sodium hydroxide solution under a nitrogen stream.
47.0 was added dropwise over 1 hour while maintaining the temperature between 40 and 70°C.
The mixture was kept for an additional 2 hours to complete the hydrolysis reaction.
次に、反応液を30℃に冷却した後、濃硫酸の
28.0ｇを反応液が40℃をこえないようにに滴下し
析出物を過した。析出物をさらに水洗・乾燥し
33.8ｇの淡褐色粉末状の１，４−ジヒドロキシ−
２−ナフトエ酸を得た。純度は98.7％（M.P.187
℃）で、収率は86.6モル％であつた。 Next, after cooling the reaction solution to 30℃, add concentrated sulfuric acid to
28.0 g of the reaction solution was added dropwise to prevent the temperature of the reaction solution from exceeding 40°C, and the precipitate was filtered out. Further wash the precipitate with water and dry it.
33.8g light brown powder of 1,4-dihydroxy-
2-naphthoic acid was obtained. Purity is 98.7% (MP187
℃), the yield was 86.6 mol%.
実施例 ２
合成例と同様に回収した２量体43.8ｇを実施例
１と同様の反応器に仕込み、300c.c.の脱気水と300
c.c.のメチルイソブチルケトンの混合液に懸濁さ
せ、窒素気流下で48％水酸化ナトリウム水溶液
47.0を40〜70℃に保ちながら１時間で滴下し、さ
らに２時間保ち加水分解反応を完結した。Example 2 43.8 g of the dimer recovered in the same manner as in the synthesis example was charged into the same reactor as in Example 1, and 300 c.c. of degassed water and 300 c.c.
Suspend in a mixture of cc of methyl isobutyl ketone and add 48% aqueous sodium hydroxide solution under nitrogen stream.
47.0 was added dropwise over 1 hour while maintaining the temperature at 40 to 70°C, and the hydrolysis reaction was completed for an additional 2 hours.
次に反応液を30℃に冷却し濃硫酸の28.0ｇを反
応液が40℃以下となるように滴下し、ついで水層
を分液除去した。回収したメチルイソブチルケト
ン層は水洗した後、濃縮し析出物を100c.c.のオル
ソキシレンを加えて取り出し、過・乾燥し、淡
褐色結晶状の１，４−ジヒドロキシ−２−ナフト
エ酸32.4ｇを得た。純度は99.2％（M.P.187.5℃）、
収率は83.4モル％であつた。 Next, the reaction solution was cooled to 30° C., 28.0 g of concentrated sulfuric acid was added dropwise so that the temperature of the reaction solution was 40° C. or lower, and then the aqueous layer was separated and removed. The collected methyl isobutyl ketone layer was washed with water, concentrated, and the precipitate was taken out by adding 100 c.c. of ortho-xylene, filtered and dried to obtain 32.4 g of light brown crystalline 1,4-dihydroxy-2-naphthoic acid. I got it. Purity is 99.2% (MP187.5℃),
The yield was 83.4 mol%.
実施例 ３
合成例から回収した２量体の４回分を実施例１
と同様の方法でアルカリ加水分解反応し回収した
１，４−ジヒドロキシ−２−ナフトエ酸120ｇを
用い、合成例と同様に行ない１，４−ジヒドロキ
シ−２−ナフトエ酸フエニルエステルの結晶
（M.P.152.0）106.5ｇを得た。収率は88.8重量％で
あつた。Example 3 Four doses of the dimer recovered from the synthesis example were used in Example 1.
Crystals of 1,4-dihydroxy-2-naphthoic acid phenyl ester (MP152. 0) 106.5g was obtained. The yield was 88.8% by weight.
比較例 １
DHN120ｇに対し、TPP121.3ｇ（TPP／
DHN＝0.67モル比）を仕込んだ以外は合成例と
同様に行ない、１，４−ジヒドロキシ−２−ナフ
トエ酸フエニルエステルの結晶87.0ｇ（m.
P.151.8℃）を得た。収率は対DHN52.8重量％で
あつた。Comparative example 1 DHN120g, TPP121.3g (TPP/
87.0 g (m.
P.151.8℃) was obtained. The yield was 52.8% by weight based on DHN.
Claims (1)
リアリール亜リン酸エステルとから下記一般式
［］で示される１，４−ジヒドロキシ−２−ナ
フトエ酸アリールエステルを製造するに際し、
１，４−ジヒドロキシ−２−ナフトエ酸１モルに
対してトリアリール亜リン酸エステルを0.9〜３
モルの範囲の比で用いて反応せしめると共に当該
反応中に副生する下記一般式［］で示される２
量体をアルカリ性水溶液中で加水分解しえられる
１，４−ジヒドロキシ−２−ナフトエ酸を原料と
して再使用することを特徴とする１，４−ジヒド
ロキシ−２−ナフトエ酸アリールエステルの製造
方法。 ［］ ［］ （式中Ｒは水素、ハロゲン原子又は炭素数１〜
10のアルキル基を示す）[Claims] 1. In producing 1,4-dihydroxy-2-naphthoic acid aryl ester represented by the following general formula [] from 1,4-dihydroxy-2-naphthoic acid and triaryl phosphite ester. ,
0.9 to 3 triaryl phosphites per mole of 1,4-dihydroxy-2-naphthoic acid
2 represented by the following general formula [ ] which is used in a molar ratio to react and is produced as a by-product during the reaction.
1. A method for producing 1,4-dihydroxy-2-naphthoic acid aryl ester, which comprises reusing 1,4-dihydroxy-2-naphthoic acid, which can be hydrolyzed in an alkaline aqueous solution, as a raw material. [] [] (In the formula, R is hydrogen, a halogen atom, or a carbon number of 1 to
10 alkyl groups)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20175887A JPS6445342A (en) | 1987-08-14 | 1987-08-14 | Production of 1,4-dihydroxy-2-naphthoic acid aryl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20175887A JPS6445342A (en) | 1987-08-14 | 1987-08-14 | Production of 1,4-dihydroxy-2-naphthoic acid aryl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6445342A JPS6445342A (en) | 1989-02-17 |
| JPH0555495B2 true JPH0555495B2 (en) | 1993-08-17 |
Family
ID=16446451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20175887A Granted JPS6445342A (en) | 1987-08-14 | 1987-08-14 | Production of 1,4-dihydroxy-2-naphthoic acid aryl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6445342A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387043C (en) | 2003-01-28 | 2008-05-07 | 汤姆森特许公司 | Robust mode staggercasting |
-
1987
- 1987-08-14 JP JP20175887A patent/JPS6445342A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6445342A (en) | 1989-02-17 |
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