JPS6216446A - Production of optically active 2-(4-hydroxyphenoxy) propionic acid - Google Patents
Production of optically active 2-(4-hydroxyphenoxy) propionic acidInfo
- Publication number
- JPS6216446A JPS6216446A JP59225327A JP22532784A JPS6216446A JP S6216446 A JPS6216446 A JP S6216446A JP 59225327 A JP59225327 A JP 59225327A JP 22532784 A JP22532784 A JP 22532784A JP S6216446 A JPS6216446 A JP S6216446A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- hydroxyphenoxy
- alkali metal
- propionic acid
- alkali metallic
- 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.)
- Granted
Links
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】
〔産業上の利用分野〕
本発明は、光学活性２−（４−ヒドロキシフェノキシ）
プロピオン酸の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides optically active 2-(4-hydroxyphenoxy)
The present invention relates to a method for producing propionic acid.
２−（４−ヒドロキシフェノキシ）プロピオン酸は、特
開昭５６−１６４７５号公報（ま゛たは英国特許公開公
報ＧＢ２０４２５３９Ｂ） 、特開昭５４−２２３７１
号公報、特開昭５３−４０７６７号公報等に開示されて
いる優れた除草剤の中間体として有用な化合物である。2-(4-hydroxyphenoxy)propionic acid is disclosed in JP-A-56-16475 (or British Patent Publication GB2042539B) and JP-A-54-22371.
It is a compound useful as an intermediate for excellent herbicides disclosed in JP-A-53-40767 and the like.
さらに重要なことは、２−（４−ヒドロキシフェノキシ
）プロピオン酸を中間体とするこれらの除草剤はその構
造中に不斉炭素原子を有するので２種類の光学活性体が
存在することであり、その１種の４体が強力な除草活性
を有することが知られている（例えば、特開昭５６−５
５３７２号公報参照）。More importantly, these herbicides that use 2-(4-hydroxyphenoxy)propionic acid as an intermediate have an asymmetric carbon atom in their structure, so there are two types of optically active forms. It is known that four members of one species have strong herbicidal activity (for example, JP-A-56-5
(See Publication No. 5372).
従って９強力な除草活性を有する光学活性体のみを使用
して除草剤とすれば必要とする投与薬量がラセミ体のほ
ぼ半量となり、環境保護、省資源のみならず除草剤製造
、除草剤散布のコストが低減できる等有意義である。Therefore, if only optically active forms with strong herbicidal activity are used to make herbicides, the required dose will be approximately half that of the racemic form, which will not only contribute to environmental protection and resource conservation, but also to herbicide production and herbicide spraying. This is significant as it can reduce costs.
光学活性２−（４−ヒドロキシフェノキシ）プロピオン
酸製造の従来技術としては、特開昭５９−９５２３７号
公報に記載の方法（以下、従来法人という）。As a conventional technique for producing optically active 2-(4-hydroxyphenoxy)propionic acid, there is a method described in JP-A-59-95237 (hereinafter referred to as "conventional corporation").
すなわち、光学活性２−ハロプロピオン酸とハイドロキ
ノンとを水性アルカリ性溶液中で縮合させる方法がある
。また、光学活性２−（４−ヒドロキシフェノキシ）プ
ロピオン酸のエステル類を製造する従来技術としては、
***特許公開公報Ｇ、０゜ＤＥ３１５０２３３に記載の
方法（以下、従来法Ｂという）。That is, there is a method in which optically active 2-halopropionic acid and hydroquinone are condensed in an aqueous alkaline solution. In addition, as a conventional technology for producing esters of optically active 2-(4-hydroxyphenoxy)propionic acid,
The method described in West German Patent Publication G, 0°DE3150233 (hereinafter referred to as conventional method B).
すなわち、光学活性２−ハロプロピオン酸エステルとハ
イドロキノンとをＤＭＳＯ溶媒、水酸化カルシウム共存
下に縮合させる方法がある。That is, there is a method of condensing an optically active 2-halopropionic acid ester and hydroquinone in the presence of a DMSO solvent and calcium hydroxide.
従来法Ａに関する上記特許には、光学活性な２−（４−
ヒドロキシフェノキシ）プロピオン酸の製造法および物
性の具体的記述がほとんどないため、結果については不
明である。The above patent regarding Conventional Method A includes optically active 2-(4-
Since there is almost no specific description of the manufacturing method and physical properties of hydroxyphenoxy)propionic acid, the results are unknown.
従来法Ｂでは９例えば、光学活性な２−クロルプロピオ
ン酸ｎ−ブチルのような高価な光学活性資材を使用する
にもかかわらず２反応中におこる部分的なラセミ化を回
避することが困難なので光学純度の高い２−（４−ヒド
ロキシフェノキシ）プロピオン酸アルキルエステルを得
ることができない（Ｇ、Ｏ，ＤＥ３１５０２３３の実施
例３には光学活性２−（４−ヒドロキシフェノキシ）プ
ロピオン１Ｉｎ−ブチルの製造例があり、 〔α） ”
＋１１．８°といし
う旋光度の記載があるが５本発明者が製造した光学活性
２−（４−ヒドロキシフェノキシ）プロピオン酸ｎ−ブ
チルの値、〔α） ”＋５７．６°（ｎｅａ ｔ）り
と比較して、明らかにラセミ化をおこしていることがわ
かる。Conventional Method B9 For example, it is difficult to avoid partial racemization that occurs during the reaction despite using an expensive optically active material such as optically active n-butyl 2-chloropropionate. 2-(4-hydroxyphenoxy)propionic acid alkyl ester with high optical purity cannot be obtained (G,O, Example 3 of DE3150233 includes an example of the production of optically active 2-(4-hydroxyphenoxy)propion 1In-butyl There is [α)”
There is a description of the optical rotation of +11.8°, but the value of the optically active n-butyl 2-(4-hydroxyphenoxy)propionate produced by the present inventor, [α) ” +57.6° (neat ), it can be seen that racemization has clearly occurred.
さらに、従来法Ａ、Ｂに共通する問題点として。Furthermore, as a problem common to conventional methods A and B.
ハイドロキノンの２個の水酸基が両方ともにアルキル化
された化合物が多量副生するために収率が低くなり、高
価な光学活性資材を必要以上に使用しなければならない
問題点がある。Since a large amount of a compound in which both of the two hydroxyl groups of hydroquinone are alkylated is produced as a by-product, the yield is low, and there are problems in that expensive optically active materials must be used more than necessary.
つまり８技術的に求められることは、ひとつは光学純度
の高い２−（４−ヒドロキシフェノキシ）プロピオン酸
を製造すること、さらに、ハイドロキノンのモノ置換体
を選択率よく得ることである。In other words, what is technically required is to produce 2-(4-hydroxyphenoxy)propionic acid with high optical purity, and to obtain monosubstituted hydroquinone with high selectivity.
このふたつの問題を解決しないと工業的製造方法として
利用できない。Unless these two problems are resolved, this method cannot be used as an industrial manufacturing method.
Ｃ問題点を解決するための手段および発明の態様〕本発
明者は光学活性２−（４−ヒドロキシフェノキシ）プロ
ピオン酸の工業的製造方法を鋭意研究した結果、以下に
示す方法により光学純度の高い２−（４−ヒドロキシフ
ェノキシ）プロピオン酸を高い選択率で特殊な装置を用
いることなく簡単に得る方法を確立した。Means for Solving Problem C and Aspects of the Invention] As a result of intensive research into an industrial method for producing optically active 2-(4-hydroxyphenoxy)propionic acid, the present inventors obtained a method for producing optically active 2-(4-hydroxyphenoxy)propionic acid with high optical purity by the method shown below. We have established a method for easily obtaining 2-(4-hydroxyphenoxy)propionic acid with high selectivity without using any special equipment.
具体的には、光学活性α−ハロプロピオン酸アルカリ金
属塩をメタノールまたはエタノールに溶解してアルカリ
金属水酸化物またはアルカリ金属アルコキシドの存在下
ハイドロキノンまたはハイドロキノンのアルカリ金属塩
とを反応させることである。Specifically, the optically active α-halopropionic acid alkali metal salt is dissolved in methanol or ethanol and reacted with hydroquinone or an alkali metal salt of hydroquinone in the presence of an alkali metal hydroxide or an alkali metal alkoxide.
光学活性α−ハロプロピオン酸アルカリ金属塩はそのエ
ステル類から製造可能でありアルカリ金属水溶液中にエ
ステル類を加え加水分解し水を留去して単離することに
より光学純度を損うことなく光学活性α−ハロプロピオ
ン酸アルカリ金属塩を得ることができる。これをメタノ
ールまたはエタノール溶液として反応に用いる。水溶液
のまま反応すると選択率が極端に低下しハイドロキノン
のジ置換体が多量生成し高価な原料である光学活性α−
ハロプロピオン酸アルカリ金属塩を無駄に使用すること
になる。Optically active α-halopropionic acid alkali metal salts can be produced from their esters, and by adding the esters to an aqueous alkali metal solution, hydrolyzing the salts, and isolating the salts by distilling off water, optically active α-halopropionic acid alkali metal salts can be produced without loss of optical purity. Active α-halopropionic acid alkali metal salts can be obtained. This is used in the reaction as a methanol or ethanol solution. If the reaction is carried out in an aqueous solution, the selectivity will be extremely reduced and a large amount of disubstituted hydroquinone will be produced, resulting in the production of an expensive raw material, optically active α-
This results in wasteful use of the halopropionate alkali metal salt.
一般式（１）のＸとしては塩素原子、臭素原子が使用し
得る。経済性を考慮して塩素原子が最も好ましい。また
、エステル類を用いアルカリ金属塩“を製造する場合、
エステル部は低級アルキル基が使用されるが炭素数が少
ないほど光学純度はよい。As X in general formula (1), a chlorine atom or a bromine atom can be used. In consideration of economic efficiency, chlorine atoms are most preferred. In addition, when producing alkali metal salts using esters,
A lower alkyl group is used for the ester moiety, and the smaller the number of carbon atoms, the better the optical purity.
反応温度は０〜１００℃が好ましいが、光学純度および
選択率を考慮して３０〜７０℃が最も好ましい。The reaction temperature is preferably 0 to 100°C, but most preferably 30 to 70°C in consideration of optical purity and selectivity.
また５反応初期は低温で反応させ（たとえば３０〜４０
℃）、その後加温（たとえば６０〜７０℃）することに
よって光学純度および選択率を高めるとともに反応時間
を短縮し得る。In addition, in the initial stage of the 5 reaction, the reaction is carried out at a low temperature (for example, 30 to 40
C) and then heating (eg, 60 to 70 C), the optical purity and selectivity can be increased and the reaction time can be shortened.
縮合に用いるアルカリ金属水酸化物としては。As an alkali metal hydroxide used for condensation.
水酸化リチウム、水酸化ナトリウム、水酸化カリウム等
が挙げられ、アルカリ金属アルコキシドとしてはナトリ
ウムメチラート、ナトリウムエチラート等が挙げられる
が、経済性１選択率の面より水酸化ナトリウムが最も好
ましい。塩基の量としては、ハイドロキノンの２〜１０
倍モルが使用されるが、２〜４倍モルが最も好ましい。Examples of the alkali metal alkoxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc., and examples of the alkali metal alkoxide include sodium methylate, sodium ethylate, and sodium hydroxide is most preferred from the viewpoint of economic efficiency and selectivity. The amount of base is 2 to 10 of hydroquinone.
Although twice the molar amount is used, 2 to 4 times the molar amount is most preferred.
得られた光学活性２−（４−ヒドロキシフェノキシ）プ
ロピオン酸は、ベンゼン等の芳香族炭化水素系あるいは
ｎ−ブチルエーテル等のエーテル系溶媒中において酸触
媒、具体的には塩酸、硫酸。The obtained optically active 2-(4-hydroxyphenoxy)propionic acid is treated with an acid catalyst, specifically hydrochloric acid or sulfuric acid, in an aromatic hydrocarbon solvent such as benzene or an ether solvent such as n-butyl ether.
ｐ−）ルエンスルホン酸等の存在下、目的にあったアル
コール類（例えばメタノール、エタノール。p-) In the presence of luenesulfonic acid, etc., an alcohol suitable for the purpose (e.g. methanol, ethanol).
ｎ−ブタノール等）と共沸脱水しながらエステル形成縮
合反応させることによって目的とするアルキルエステル
に変換することができる。エステル化反応中、ラセミ化
はほとんど起こらず、立体構造は保持される。ここで使
用するアルコール類はメタノール、エタノール、ｎ−ブ
タノール等の低級アルキルアルコールが実用的であるが
、これらに限定されるものではない。例えばアルコキシ
アルコール、シクロアルキルアルコール、アルケニルア
ルコール等であっても反応は進行する。The desired alkyl ester can be converted by carrying out an ester-forming condensation reaction with n-butanol, etc.) while undergoing azeotropic dehydration. During the esterification reaction, racemization hardly occurs and the steric structure is maintained. Practical alcohols used here include lower alkyl alcohols such as methanol, ethanol, and n-butanol, but are not limited to these. For example, the reaction proceeds even with alkoxy alcohol, cycloalkyl alcohol, alkenyl alcohol, etc.
光学活性クロルプロピオン酸エステルまたは光学活性ク
ロルプロピオン酸アルカリ金属塩とハイドロキノンまた
はそのアルカリ金属塩とを反応させて、高い選択率で光
学純度のよい光学活性２−（４−ヒドロキシフェノキシ
）プロピオン酸あるいはそのエステル類を製造する方法
を開発したことにより、優れた除草剤の有効成分である
２−（４−ヘテロアルキルオキシフェノキシ）プロピオ
ン酸アルキルエステルを工業的に有利に製造することが
可能となった。An optically active chloropropionic acid ester or an optically active alkali metal salt of chloropropionic acid is reacted with hydroquinone or an alkali metal salt thereof to produce optically active 2-(4-hydroxyphenoxy)propionic acid or its alkali metal salt with high selectivity and good optical purity. By developing a method for producing esters, it has become possible to industrially and advantageously produce alkyl 2-(4-heteroalkyloxyphenoxy)propionic acid, which is an effective ingredient of an excellent herbicide.
以下、実施例および参考例を挙げて本発明をさらに詳し
く説明するが９本発明はこれらによって限定されるもの
ではない。The present invention will be explained in more detail below with reference to Examples and Reference Examples, but the present invention is not limited thereto.
案施侃工
ｌ−α−クロルプロピオン酸メチル８５．８ｇを水酸化
ナトリウム２８ｇ と水１５０ｇよりなる水溶液の中へ
２０〜４０℃で滴下した。滴下後、減圧下で水を留去し
て白色固体を得た。これをエタノール３００ｇに溶解し
ｌ−α−クロルプロピオン酸ナトリウムのエタノール溶
液を得た。85.8 g of methyl l-α-chloropropionate was added dropwise at 20 to 40°C into an aqueous solution consisting of 28 g of sodium hydroxide and 150 g of water. After the dropwise addition, water was distilled off under reduced pressure to obtain a white solid. This was dissolved in 300 g of ethanol to obtain an ethanol solution of sodium l-α-chloropropionate.
ハイドロキノン１１０ｇと水酸化ナトリウム１００ｇを
４０℃で１時間攪拌後、ｌ−α−クロルプロピオン酸ナ
トリウムのエタノール溶液を加え６０℃に加熱した。２
時間反応したあと塩化水素ガス１００ｇを吹き込み生成
した塩化ナトリウムを濾別し、濾液にベンゼン３００ｇ
を加え共沸脱水してエチルエステル化を行った。溶媒留
去後、水洗を行いハイドロキノンを除いたあと熱温を行
いｄ−２−（４−ヒドロキシフェノキシ）プロピオン酸
エチル１３０ｇを得た。光学純度は液体クロマトグラフ
ィーで測定した結果９３％ｅ、ｅ、であった。ジ置換体
は６．５ｇであった。After stirring 110 g of hydroquinone and 100 g of sodium hydroxide at 40°C for 1 hour, an ethanol solution of sodium l-α-chloropropionate was added and heated to 60°C. 2
After reacting for an hour, 100g of hydrogen chloride gas was blown in, the generated sodium chloride was filtered off, and the filtrate contained 300g of benzene.
was added and azeotropically dehydrated to perform ethyl esterification. After distilling off the solvent, the residue was washed with water to remove hydroquinone, and heated to give 130 g of ethyl d-2-(4-hydroxyphenoxy)propionate. The optical purity was 93%e, as measured by liquid chromatography. The amount of di-substituted product was 6.5 g.
去Ｊｕ１影
実施例１のエタノール溶媒をメタノールにかえて反応し
た。熱温後ｄ−２−（４−ヒドロキシフェノキシ）プロ
ピオン酸メチル１１０ｇを得た。光学純度は液体クロマ
トグラフィーで測定した結果。The reaction was carried out by replacing the ethanol solvent in Example 1 with methanol. After heating, 110 g of methyl d-2-(4-hydroxyphenoxy)propionate was obtained. Optical purity is the result measured by liquid chromatography.
９３％ｅ、ｅ、であった。ジ置換体は１０ｇであった。It was 93% e,e. The amount of di-substituted product was 10 g.
裏旌斑主
実施例１のｌ−α−クロルプロピオン酸メチル８５．８
ｇヲｊ！−α−クロルプロピオン酸エチル９５．６ｇに
かえて反応した。熱温後ｄ−２−（４−ヒドロキシフェ
ノキシ）プロピオン酸エチル１３１ｇを得た。光学純度
は液体クロマトグラフィーで測定した結果、９０％ｅ、
ｅ、であった。ジ置換体は６ｇであった。Methyl l-α-chloropropionate of Main Example 1 85.8
gwoj! -95.6 g of ethyl α-chloropropionate was used instead for the reaction. After heating, 131 g of ethyl d-2-(4-hydroxyphenoxy)propionate was obtained. The optical purity was determined by liquid chromatography and was 90% e.
It was e. The amount of di-substituted product was 6 g.
参１１１１
２．６−シクロロキノキザリン３．９８ｇ、 ｄ −２
−（４−ヒドロキシフェノキシ）プロピオン酸エチル（
〔α）ｏ＋４２．５°（Ｃ＝１．１４．クロロホルム）
、光学純度９３％ｅ、ｅ、） ４．３３ｇ＋炭酸カリウ
ム゛２．７６ｇアセトニトリル１９．９ｇを混合した。Reference 1111 2.6-cycloquinoxaline 3.98g, d-2
-(4-hydroxyphenoxy)ethyl propionate (
[α) o+42.5° (C=1.14.chloroform)
, optical purity 93% e, e, ) 4.33 g + potassium carbonate (2.76 g) and acetonitrile (19.9 g) were mixed.
それを攪拌しながら６時間還流させたのち減圧下に溶媒
留去した。残渣にトルエン１００ｍ１および水５０ｍ
ｌを加えて抽出した。トルエン層をとり、水５０ｍ１で
２回洗浄後溶媒留去して淡黄色固体７．５５ｇを得た。After stirring and refluxing for 6 hours, the solvent was distilled off under reduced pressure. To the residue, add 100ml of toluene and 50ml of water.
1 was added for extraction. The toluene layer was taken, washed twice with 50 ml of water, and the solvent was distilled off to obtain 7.55 g of a pale yellow solid.
これをエタノール１１．９ｇより再結晶してｄ−２−（
４−（６−クロル−２−キノキザリルオキシ）フェノキ
シ〕プロピオン酸エチル６．４５ｇを無色結晶として得
た。収率８７％。シフト試薬を用いたＮＭＲ分析による
光学純度は９３％ｅ、ｅ、であった。This was recrystallized from 11.9 g of ethanol and d-2-(
6.45 g of ethyl 4-(6-chloro-2-quinoxalyloxy)phenoxypropionate was obtained as colorless crystals. Yield 87%. The optical purity by NMR analysis using a shift reagent was 93%e,e.
Claims (3)
またはアルカリ金属原子を示す。）で表される光学活性
化合物とハイドロキノンまたはハンドロキノンのアルカ
リ金属塩とを、アルカリ金属水酸化物またはアルカリ金
属アルコキシドの存在下、メタノールまたはエタノール
中で反応させることを特徴とする光学活性２−（４−ヒ
ドロキシフェノキシ）プロピオン酸の製造方法。(1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, X represents a chlorine atom or a bromine atom, and M represents a hydrogen or alkali metal atom.) Represented by Optically active 2-(4-hydroxyphenoxy) characterized by reacting an optically active compound and an alkali metal salt of hydroquinone or handoquinone in methanol or ethanol in the presence of an alkali metal hydroxide or alkali metal alkoxide. Method for producing propionic acid.
範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein X in the general formula [I] is a chlorine atom.
リウム原子である特許請求の範囲第１項記載の製造方法
。(3) The manufacturing method according to claim 1, wherein X in the general formula [I] is a chlorine atom and M is a sodium atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59225327A JPH0610153B2 (en) | 1984-10-26 | 1984-10-26 | Process for producing optically active 2- (4-hydroxyphenoxy) propionic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59225327A JPH0610153B2 (en) | 1984-10-26 | 1984-10-26 | Process for producing optically active 2- (4-hydroxyphenoxy) propionic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6216446A true JPS6216446A (en) | 1987-01-24 |
| JPH0610153B2 JPH0610153B2 (en) | 1994-02-09 |
Family
ID=16827612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59225327A Expired - Lifetime JPH0610153B2 (en) | 1984-10-26 | 1984-10-26 | Process for producing optically active 2- (4-hydroxyphenoxy) propionic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610153B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH045255A (en) * | 1990-04-24 | 1992-01-09 | Sankyo Kagaku Kk | Production of phenoxyalkanecarboxylic acid derivative |
| CN105753656A (en) * | 2016-04-26 | 2016-07-13 | 张家港市三联化工科技有限公司 | Synthesizing method for (R)-(+)-2-(4-hydroxy phenoxy) methyl propionate |
| CN112694403A (en) * | 2020-12-30 | 2021-04-23 | 锦州三丰科技有限公司 | Method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5419925A (en) * | 1977-07-11 | 1979-02-15 | Ici Ltd | Process for preparing monoalkyldihydroxybenzene |
-
1984
- 1984-10-26 JP JP59225327A patent/JPH0610153B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5419925A (en) * | 1977-07-11 | 1979-02-15 | Ici Ltd | Process for preparing monoalkyldihydroxybenzene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH045255A (en) * | 1990-04-24 | 1992-01-09 | Sankyo Kagaku Kk | Production of phenoxyalkanecarboxylic acid derivative |
| CN105753656A (en) * | 2016-04-26 | 2016-07-13 | 张家港市三联化工科技有限公司 | Synthesizing method for (R)-(+)-2-(4-hydroxy phenoxy) methyl propionate |
| CN112694403A (en) * | 2020-12-30 | 2021-04-23 | 锦州三丰科技有限公司 | Method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0610153B2 (en) | 1994-02-09 |
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Legal Events
| Date | Code | Title | Description |
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| EXPY | Cancellation because of completion of term |