JPH02101048A - Production of salicylic acid derivative - Google Patents
Production of salicylic acid derivativeInfo
- Publication number
- JPH02101048A JPH02101048A JP63253358A JP25335888A JPH02101048A JP H02101048 A JPH02101048 A JP H02101048A JP 63253358 A JP63253358 A JP 63253358A JP 25335888 A JP25335888 A JP 25335888A JP H02101048 A JPH02101048 A JP H02101048A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- salicylic acid
- compound shown
- acid derivative
- 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 5
- 150000003872 salicylic acid derivatives Chemical class 0.000 title claims description 4
- -1 hydroxyethoxy-substituted salicylic acid Chemical class 0.000 claims abstract description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 5
- UIAFKZKHHVMJGS-UHFFFAOYSA-N beta-resorcylic acid Natural products OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 150000004820 halides Chemical class 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の分野）
本発明は、サリチル酸誘導体の製造方法に関し、特に感
光紙、感圧紙、感熱紙等の記録材料用の顕色剤又は医薬
、農薬、酸化防止剤等の中間体に有用なヒドロキシエト
キシ置換サリチル酸誘導体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a method for producing salicylic acid derivatives, and in particular to color developers for recording materials such as photosensitive paper, pressure-sensitive paper, thermal paper, etc., or pharmaceuticals, agricultural chemicals, antioxidants, etc. The present invention relates to a method for producing hydroxyethoxy-substituted salicylic acid derivatives useful as intermediates.
（従来技術）
発色反応を利用した記録材料として感圧紙、感熱紙、感
光感圧紙、定着型感熱紙、通電感熱紙などの記録材料、
表示材料が開発されてきた。(Prior art) Recording materials that utilize color reactions include pressure-sensitive paper, thermal paper, light-sensitive pressure-sensitive paper, fixing type thermal paper, and electrically conductive thermal paper.
Display materials have been developed.
本発明者は既にビニル基又はビニリチン基を有する発色
剤が重合することを見い出し、それらがカブリの減少、
感度の上昇などの軽重しい特性を発揮することを確認し
ている。The present inventor has already discovered that color formers having a vinyl group or a vinylitin group can be polymerized, and they have been found to reduce fog,
It has been confirmed that it exhibits light and heavy characteristics such as increased sensitivity.
一方、ビニル基又は、ビニリデン基を有する顕色剤の高
分子化についても本発明者らにより試みられている。ま
た、従来よシ発色剤と顕色剤を使用する記録材料の顕色
剤にサリチル酸誘導体の金属塩を用いることは知られて
いる。これ１で顕色剤の高分子化に供していた顕色剤モ
ノマーは、サリチル酸のカルボキシル基にビニル基の様
な重合基を導入しているため金属塩とすることができな
かった。On the other hand, the present inventors have also attempted to polymerize a color developer having a vinyl group or a vinylidene group. Furthermore, it is known to use a metal salt of a salicylic acid derivative as a color developer for recording materials that conventionally use a color former and a color developer. The color developer monomer that was used to polymerize the color developer in Example 1 could not be converted into a metal salt because a polymerizable group such as a vinyl group was introduced into the carboxyl group of salicylic acid.
（発明の目的）
従って本発明の目的は、４−ヒドロキシサリチル酸エス
テルを出発原料に≠位に重合基を導入するなど等に有用
な前駆体であるヒドロキシエトキシ置換サリチル酸誘導
体を提供するものである。(Object of the Invention) Therefore, the object of the present invention is to provide a hydroxyethoxy-substituted salicylic acid derivative which is a useful precursor for introducing a polymerizable group into the ≠ position using 4-hydroxysalicylic acid ester as a starting material.
（発明の構成）
本発明は、４−ヒドロキシサリチル酸エステルにエチレ
ンカーボネート又はエチレンオキシドを反応きせること
を特徴とするヒドロキシエトキシ置換サリチル酸誘導体
の製造方法である。(Structure of the Invention) The present invention is a method for producing a hydroxyethoxy-substituted salicylic acid derivative, which is characterized by reacting 4-hydroxysalicylic acid ester with ethylene carbonate or ethylene oxide.
本発明による化合物は、≠−ヒドロキシサリチル酸ニス
ｆルに、例えば≠級アンモニウム塩等ノ触媒を用い、エ
チレンカーボネート又はエチレンオキシドを反応させる
ことによって合成される。The compound according to the invention is synthesized by reacting ≠-hydroxysalicylic acid varnish with ethylene carbonate or ethylene oxide using a catalyst such as a ≠-grade ammonium salt.
（Ｉ）
（Ｕ）
上式中Ｒは、メチル基、エチル基など低級アルキル基で
あり、（■）としては、＼７ も使用できる。触媒には
、上述の他に水素化リチウム、炭酸ナトリウム、水酸化
カリウム、トリエチルアミン等も使用できる。(I) (U) In the above formula, R is a lower alkyl group such as a methyl group or an ethyl group, and \7 can also be used as (■). In addition to the above-mentioned catalysts, lithium hydride, sodium carbonate, potassium hydroxide, triethylamine, etc. can also be used.
本発明の方法では、温和な条件下、簡便な操作で確実に
エーテル化反応を行うことができ、収率よく同的物を得
ることができる。In the method of the present invention, the etherification reaction can be reliably carried out under mild conditions with simple operations, and the same product can be obtained in good yield.
反応は、例えばテトラエチルアンモニウムヨーグイド、
ブロマイドの如き≠級アンモニウム塩を触媒に用い無溶
媒にて攪拌することにより行われる。反応湛匿は１００
〜／ｊｔＯ’Ｃが好ましい。The reaction is carried out, for example, with tetraethylammonium iodine,
This is carried out by using a ≠ grade ammonium salt such as bromide as a catalyst and stirring without a solvent. The reaction rate is 100
~/jtO'C is preferred.
反応時間は、０．！−４’時間である。The reaction time was 0. ! -4' hours.
こうして合成された化合物は反応溶液を水にあけ酢酸エ
チルなどで抽出し、水洗後常法に従って溶媒を留去して
単離することができる。化合物が固体の場合にはさらに
適当な溶媒を用いて再結晶することにより精製すること
ができる。The compound thus synthesized can be isolated by pouring the reaction solution into water, extracting with ethyl acetate, etc., washing with water, and then distilling off the solvent according to a conventional method. When the compound is solid, it can be further purified by recrystallization using an appropriate solvent.
また、この化合物は酸又はアルカリによる加水分ＭＫよ
り≠−ヒドロキシエトキシサリチル酸（Ｆ／）に容易に
誘導できる。Further, this compound can be easily converted into ≠-hydroxyethoxysalicylic acid (F/) by hydrolyzing MK with acid or alkali.
（ＩＶ）は、例えば、特願昭２−一２ｊり１０りに示さ
れる方法によυ、サリチル醸酵導体亜鉛塩に導く事もで
きる。さらにｌ’）はビニル基を有する酸ハライド、エ
ステル、ハロゲン化物又はインシアネートなどの活性基
を持つ化合物を反応させることにより、重合性モノマー
としても利用できる。(IV) can also be converted into a salicylic fermentation conductor zinc salt, for example, by the method shown in Japanese Patent Application No. 2-12J. Furthermore, l') can be used as a polymerizable monomer by reacting with a compound having an active group such as an acid halide, ester, halide or incyanate having a vinyl group.
以下に実施例を挙げ本発明をさらに説明する。The present invention will be further explained with reference to Examples below.
（実施例）
４−ヒドロキシサリチル酸のメチルエステルｊ０２、エ
チレンカーボネート２６ｔ１エト２エテルアンモニウム
ヨーダイト≠ｆｆＩμ０ ’（’ニ４４時間攪拌した。(Example) Methyl ester of 4-hydroxysalicylic acid j02, ethylene carbonate 26t1 ethyethelammonium iodite≠ffIμ0' (stirred for 44 hours.
次いで反応物を水に注ぎ、析出した結晶を戸数した。水
洗後メタノールで再結晶し、目的とするグーヒドロキシ
エトキシサリチル酸メチルエステルグ！１（収率７／％
）を得た。Next, the reaction product was poured into water, and the precipitated crystals were counted. After washing with water, recrystallize with methanol to obtain the desired hydroxyethoxysalicylic acid methyl ester! 1 (yield 7/%
) was obtained.
融点ｒｐ、ｚ−ざｊ、ｊ”Ｃ
（参考例）
グーヒドロキシエトキシサリチル酸メチルエステル２０
ｆを、３当量のアルカリ水浴液に加え、３０分攪拌して
ｉ＠ｗＩさせこれに塩酸を添加して、系ＯｐＨを酸性に
し結晶を析出させた。これを炉ｊ−一Melting point rp, z-zaj, j”C (Reference example) Hydroxyethoxysalicylic acid methyl ester 20
f was added to 3 equivalents of alkaline water bath solution and stirred for 30 minutes to form i@wI, to which hydrochloric acid was added to acidify the system OpH and precipitate crystals. Heat this to furnace j-1
Claims (1)
ート又は、エチレンオキシドを反応させることを特徴と
するサリチル酸誘導体の製造方法。A method for producing a salicylic acid derivative, which comprises reacting 4-hydroxysalicylic acid ester with ethylene carbonate or ethylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63253358A JPH02101048A (en) | 1988-10-07 | 1988-10-07 | Production of salicylic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63253358A JPH02101048A (en) | 1988-10-07 | 1988-10-07 | Production of salicylic acid derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02101048A true JPH02101048A (en) | 1990-04-12 |
Family
ID=17250229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63253358A Pending JPH02101048A (en) | 1988-10-07 | 1988-10-07 | Production of salicylic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02101048A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0699673A1 (en) * | 1994-08-31 | 1996-03-06 | Eli Lilly And Company | Process for preparing benzoic acid derivative intermediates and benzothiophene pharmaceutical agents |
-
1988
- 1988-10-07 JP JP63253358A patent/JPH02101048A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0699673A1 (en) * | 1994-08-31 | 1996-03-06 | Eli Lilly And Company | Process for preparing benzoic acid derivative intermediates and benzothiophene pharmaceutical agents |
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