JPS60123443A - Production of 2-(4-hydroxyphenoxy)alkanoic acid - Google Patents
Production of 2-(4-hydroxyphenoxy)alkanoic acidInfo
- Publication number
- JPS60123443A JPS60123443A JP23078783A JP23078783A JPS60123443A JP S60123443 A JPS60123443 A JP S60123443A JP 23078783 A JP23078783 A JP 23078783A JP 23078783 A JP23078783 A JP 23078783A JP S60123443 A JPS60123443 A JP S60123443A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyphenoxy
- hydroquinone
- acid
- reaction
- formula
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- XLHUBROMZOAQMV-UHFFFAOYSA-N 1,4-benzosemiquinone Chemical group [O]C1=CC=C(O)C=C1 XLHUBROMZOAQMV-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 24
- 150000001875 compounds Chemical class 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 5
- AQIHDXGKQHFBNW-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-UHFFFAOYSA-N 0.000 abstract description 3
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004009 herbicide Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 125000001246 bromo group Chemical group Br* 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- -1 hydroxyphenoxy Chemical group 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ILYSHPJWNMPBPE-UHFFFAOYSA-N ethyl 2-(4-hydroxyphenoxy)propanoate Chemical compound CCOC(=O)C(C)OC1=CC=C(O)C=C1 ILYSHPJWNMPBPE-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 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
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 150000001218 Thorium Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 230000002363 herbicidal effect Effects 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
- 239000000314 lubricant Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は2−(4−ヒドロキシフェノキシ)アルカン酸
類の製造法に関する。さらに詳しくは。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-(4-hydroxyphenoxy)alkanoic acids. More details.
本発明は、ハイドロキノンまたはハイドロキノンの塩と
一般式(1)
%式%(1)
(式中、Xは塩素または臭素原子を、Rは水素または低
級アルキル基を示す。)
で表される化合物とを溶媒中においてアルカリ金属の水
酸化物を用いて反応させることを特徴とする2−(4−
ヒドロキシフェノキシ)アルカン酸の製造方法に関する
。The present invention relates to hydroquinone or a salt of hydroquinone, and a compound represented by the general formula (1) (wherein, X represents a chlorine or bromine atom, and R represents hydrogen or a lower alkyl group). 2-(4-
The present invention relates to a method for producing hydroxyphenoxy)alkanoic acid.
2−(4−ヒドロキシフェノキシ)アルカン酸エステル
類は特開昭56−16475号公報、特開昭54−.2
2371号公報、特開昭53−40767号公報等によ
り開示されている化合物の中間体として有用である。例
えば特開昭56−16475号公報に記載の複素環エー
テル系フェノキシ脂肪酸誘導体を有効成分とする優れた
効果のある除草剤の製造原料として有用である。2-(4-hydroxyphenoxy)alkanoic acid esters are disclosed in JP-A-56-16475 and JP-A-54-. 2
It is useful as an intermediate for compounds disclosed in JP-A-2371, JP-A-53-40767, and the like. For example, it is useful as a raw material for producing a highly effective herbicide containing a heterocyclic ether phenoxy fatty acid derivative as an active ingredient, as described in JP-A-56-16475.
2−(4−ヒドロキシフェノキシ)アルカン酸エステル
類の製造法としては1例えば特開昭56−59718号
公報に開示されている下記反応式で示される方法がある
。As a method for producing 2-(4-hydroxyphenoxy)alkanoic acid esters, there is, for example, a method shown in the following reaction formula disclosed in JP-A-56-59718.
また1国際出願公開82 / (1(l [i 39号
公報Gこ開示されている下記反応式で示される方法もあ
る。There is also a method shown by the following reaction formula disclosed in Publication No. 1 International Application Publication No. 82/(1).
さらに、ヨーロッパ特許82413号公報に開示されて
いる下記反応式で示される方法がある。Furthermore, there is a method shown in the following reaction formula disclosed in European Patent No. 82413.
(式中、Xは塩素または臭素原子を、Rは低級アルキル
基を示す。)
しかし、特開昭56−59718号公報の実施例に開示
されている2−(4−ヒドロキシフェノキシ)プロピオ
ン酸の融点は228〜230 ’cであるのに対し2本
発明者等が必要としている2−(4−ヒドロキシフェノ
キシ)プロピオン酸の融点は147〜15−0℃である
。(In the formula, X represents a chlorine or bromine atom, and R represents a lower alkyl group.) The melting point is 228-230'C, whereas the melting point of 2-(4-hydroxyphenoxy)propionic acid required by the present inventors is 147-15-0C.
また2国際出願公開82100639号公報に開示され
ている方法は、過硫酸エステルを合成する工程の生成率
が低く、かつ工程数が多いために工業的に好ましいとは
いえない。In addition, the method disclosed in International Application Publication No. 82100639 has a low production rate in the step of synthesizing persulfate ester and requires a large number of steps, so it is not industrially preferred.
さらに、ヨーロッパ特許82413号に開示されている
反応は選択性が不十分でありハイドロキノンの転化率を
50%以内にしないと二量体の生成が多くなる。よって
、工業的には多量のハイド1jキノンの回収1榮作のた
めコストが高くなる。また未反応のハイドl」キノンを
減らずため反応率を。Furthermore, the reaction disclosed in European Patent No. 82413 has insufficient selectivity, and unless the conversion of hydroquinone is kept within 50%, a large amount of dimer is produced. Therefore, industrially, a large amount of hydride 1j quinone must be recovered and produced, which increases the cost. In addition, the reaction rate is reduced because unreacted hydride quinone is not reduced.
(式中、kl、に2は反応速j襄を、1?は低級アルキ
ル基を示す。)
」二げると二量体の生成率が増加し収率が著しく低下す
る。(In the formula, 2 indicates the reaction rate, and 1 indicates a lower alkyl group.) If the reaction rate is increased, the production rate of dimers increases and the yield decreases significantly.
本発明’tFらは、これらの方法が工業的に自利ではな
いので、2−(4−ヒドロキシフェノキシ)アルカン酸
の優れゾこ製造方法を観念研究した結果。Since these methods are not industrially advantageous, the present invention'tF et al. conducted conceptual research into an excellent method for producing 2-(4-hydroxyphenoxy)alkanoic acid.
従来法の欠点を克服し、容易にかつ選択率よく2− (
4−ヒトI:Jキソフエノキシ))′ルカン酸を!11
1.!造する方法を見出し本発明を完成した。Overcoming the drawbacks of the conventional method, it is easy and highly selective for 2-(
4-Human I:Jxophenoxy))'Lucanoic acid! 11
1. ! The present invention was completed by discovering a method for manufacturing.
ずなわら1本発明は、α−りiJルブUピオン醇を溶媒
中2モル以上のアルカリ全屈水酸化物を用いることによ
り1選択率よ<2−(4−ヒト【Jキソフェノキシ)ア
ルカン酸を17る製造方法である。Zunawara 1 The present invention provides α-ri iJ lubricant with a selectivity of < 2-(4-human[J This is a method for producing 17 acids.
一般式(1):XCHRCOOR(1)において、Xは
塩素、臭素が使用されるが、経済的にば塩素が好ましい
。使用量は通常ハイドロキノンと等モル使用するが、特
に選択率を必要とする場合は70〜80%モル使用すれ
ばよい。In the general formula (1): The amount used is usually equimolar to that of hydroquinone, but if particularly high selectivity is required, it may be used in a molar amount of 70 to 80%.
溶媒としては、メタノール、エタノール、イソプロパツ
ール、エチレングリコール、セロソルダ類等のアルコー
ル類または水が使用される。使用量は各溶媒の種類2反
応温度によっても異なり限定されない。アルカリ金属の
水酸化物としては水酸化リチウム、水酸化すトリウJい
、水酸化カリウムが用いられるが、経済性を考慮すると
水酸化す1〜リウムが最も好ましい。その使用量は原料
、ずなわぢ、XCHIンC00II(式中、Rは水素ま
たは低級アルキル法を示す)の2倍モル以上を用いるが
選択率の面から2.8モル以上が好ましい。ただし、ハ
イドロキノンのすトリウム塩を用いる場合は当モルまた
はそれ以上でよい。ハイドロキノンのす1〜リウム塩は
す1−リウムメチラート、すトリウムエチラートを加え
て系内であらかじめつくってもよいし、ハイドロキノン
と当モル〜2倍゛ロルの水酸化アルカリを反応さ−l、
単ア1[シて使用してもよい。As the solvent, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and cellosolders, or water are used. The amount used varies depending on the type of each solvent and the reaction temperature and is not limited. As the alkali metal hydroxide, lithium hydroxide, sodium hydroxide, and potassium hydroxide are used, but mono-lithium hydroxide is most preferable in consideration of economical efficiency. The amount used is at least twice the mole of the raw material, Zunawaji, XCHIN C00II (in the formula, R represents hydrogen or a lower alkyl method), but from the viewpoint of selectivity, it is preferably 2.8 moles or more. However, when using the thorium salt of hydroquinone, the amount may be equivalent to the same molar amount or more. The sodium salt of hydroquinone may be prepared in advance in the system by adding sodium 1-lium methylate or sodium ethylate, or it can be prepared by reacting hydroquinone with an equivalent mole to twice the amount of alkali hydroxide. ,
Single A1 may be used.
反応温度は、使用する原料、アルカリ金属およびt8媒
の種類等によって異なるが0〜100℃が好ましい。反
応速度2選択性を考慮して50〜80℃が最も好ましい
。生成した酸は、はとんどの場合エステルとして使用さ
れるので、エステル化したものを蒸1ii71.て二足
体と分離して精製し得る。The reaction temperature varies depending on the raw materials used, the alkali metal, the type of T8 medium, etc., but is preferably 0 to 100°C. In consideration of reaction rate 2 selectivity, the temperature is most preferably 50 to 80°C. The produced acid is mostly used as an ester, so the esterified acid is steamed1ii71. The bipods can be separated and purified.
また9反応溶媒が目的とするエステルと同じアルキル基
を有する場合は塩化水素ガス濃硫酸またG」発煙硫酸に
より酸性とした後jJTI常の後処理を行い魚油してエ
ステルを得ることも可能である。In addition, if the reaction solvent has the same alkyl group as the desired ester, it is also possible to obtain the ester by acidifying it with hydrogen chloride gas, concentrated sulfuric acid, or fuming sulfuric acid, and then performing the usual post-treatment with fish oil to obtain the ester. .
純度のよい2−(4−ヒドロキシフェノキシ)プロピオ
ン酸を得るためには管!Iた2−(4−ヒドロキシフェ
ノキシ)ブ1」ピオン酸エチルを2倍モル以上の水酸化
ナトリウムを用いて加水分解を行い、さらに塩酸酸性と
して冷却しくJi出する固体を濾別、水溶媒で再結晶を
行えばよい。このようにして得られた白色固体の融点は
147〜l 50 ’Cであった。To obtain 2-(4-hydroxyphenoxy)propionic acid with good purity, tube! Hydrolyze ethyl 2-(4-hydroxyphenoxy)pionate using at least twice the molar amount of sodium hydroxide, acidify it with hydrochloric acid, cool and separate the resulting solid by filtration, and dilute with aqueous solvent. All you have to do is recrystallize. The melting point of the white solid thus obtained was 147-150'C.
以下実施例を挙げてさらに詳411+に説明するが。This will be explained in more detail below with reference to Examples.
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 is not limited to these.
災胤皿土
ハイドロキノン22g、エタノール120gおよびα−
クロルプロピオン酸21.7gを仕込み。Disaster 22g of hydroquinone, 120g of ethanol and α-
Prepare 21.7g of chloropropionic acid.
窒素置換した後水酸化すトリウム28gを加え。After purging with nitrogen, 28 g of sthorium hydroxide was added.
60℃で4時間攪拌した。水200gを加え、塩酸によ
りpHlとして酢酸エチル200gで2回抽出し酢酸エ
チルを留去した。得られた固体をジアゾメタンでメチル
化して下記組成物を得た。The mixture was stirred at 60°C for 4 hours. 200 g of water was added, the pH was adjusted to pH1 with hydrochloric acid, and the mixture was extracted twice with 200 g of ethyl acetate, and the ethyl acetate was distilled off. The obtained solid was methylated with diazomethane to obtain the following composition.
ハイドロキノンー−−−−−−−−−−−−13、6モ
ル%2−(4−ヒドロキシフェノキシ)
プロピオン酸メチルー−−−77、8モル%二■体−−
−−−−−−−−−−−−−−−−−−−−−−−−−
8、6モル%この組成物にエタノール100gと濃硫酸
1gを加え1時間還流した後、エタノールを留去し、水
100g、I−ルエン100gを加え不溶物を濾別。Hydroquinone---13, 6 mol% Methyl 2-(4-hydroxyphenoxy) propionate---77, 8 mol% diform---
−−−−−−−−−−−−−−−−−−−−−−−−−
8.6 mol% To this composition, 100 g of ethanol and 1 g of concentrated sulfuric acid were added and refluxed for 1 hour, then the ethanol was distilled off, 100 g of water and 100 g of I-toluene were added, and insoluble matter was filtered off.
分液、さらにl・ルエン層を2回水洗してトルエン留去
した。残渣を減圧薄溝して2−(4−ヒドロキシフェノ
キシ)プロピオン酸エチルを淡茶色液体として30.2
g得た。The liquid was separated, and the l.toluene layer was washed twice with water and toluene was distilled off. The residue was filtered under reduced pressure to obtain ethyl 2-(4-hydroxyphenoxy)propionate as a light brown liquid at 30.2
I got g.
沸点:135〜140°C/ l mm11g。Boiling point: 135-140°C/l mm11g.
」1糺ム
水88g、ハイドロキノンl1g、水酸化ナトリウム1
2g、およびα−りlコルプロピオン酸7゜6gを加え
窒素雰囲気下60℃で411M間反応全反応1つだ。反
応終了後塩酸を加えpHlとして酢酸エチル200gで
2回抽出し酢酸エチルを留去した。1 88g of water, 1g of hydroquinone, 1g of sodium hydroxide
2 g and 7.6 g of α-lyl colpropionic acid were added and the reaction between 411M and 7.6 g of α-lyl colpropionic acid was carried out at 60° C. under a nitrogen atmosphere.The total reaction was one. After the reaction was completed, hydrochloric acid was added to adjust the pH to l, and the mixture was extracted twice with 200 g of ethyl acetate, and the ethyl acetate was distilled off.
iqられた固体をジアゾメタンでメチル化して下記組成
物を得た。The iq solid was methylated with diazomethane to obtain the following composition.
ハイドロキノン−、−−−−−−−−−−−−36、1
モル%2−(4−ヒドロ革シフ、7゜ノキシ)プロピオ
ン酸メチルー−60,5モル%二量体−−−、−,−−
−−−−−−−−−一〜−4,、8モル%実施例1と同
様の後処理を行い、減圧薄溝して2− (4−ヒドロキ
ソフェノキシ)プロピオン酸エチルを淡褐色液体として
11.5g17た。Hydroquinone, ---------36, 1
Mol% 2-(4-Hydroxy)methyl propionate-60.5 Mol% dimer ---, --, --
---------1 to -4,8 mol% The same post-treatment as in Example 1 was carried out, and ethyl 2-(4-hydroxyphenoxy)propionate was converted into a light brown liquid by thin grooves under reduced pressure. It was 11.5g17.
沸点: l 35〜140’C/ 1mm1lH。Boiling point: l 35-140'C/1mm1lH.
爽施園主
窒素雰囲気下、ハイドロキノンlI[r、メチルセロソ
ルブ88g、水酸化す1へリウJ第12gおよびα−ク
ロルプロピオン酸7,6gを加え60°Cで4時間反応
を行った。反応終了後塩酸を加え、酢酸エチル200g
で2回抽出しi!it酸エチルを留去した。t47られ
た固体をジアゾメタンごメチル化し。Under a fresh nitrogen atmosphere, 88 g of hydroquinone lI[r, methyl cellosolve, 12 g of hydroxide, 12 g of hydroxide, and 7.6 g of α-chloropropionic acid were added, and the reaction was carried out at 60° C. for 4 hours. After the reaction is complete, add hydrochloric acid and add 200g of ethyl acetate.
Extract twice with i! Ethyl itate was distilled off. The obtained solid was methylated with diazomethane.
ガスクlコマトゲラフイー分析の結果、下記の組成を示
した。As a result of the gas chromatography analysis, the following composition was shown.
ハイドロキノンー−−−−−一一一−一−−−−・−1
9,2モル%2− (4−ヒドロキシフェノキシ)
プロピオン酸メチルーーーー−73、1モル%二■体−
−−−−−−−−−−−−−−−−−−−−−−−7、
7モル%実施例1と同様の後処理を行い、減圧薄溝して
2−(4−ヒドロキシフェノキシ)プ1」ピオン酸エチ
ルを淡褐色液体として14.3gf!7だ。Hydroquinone---111-1----1
9,2 mol% 2- (4-hydroxyphenoxy) methyl propionate --- 73, 1 mol% di-
−−−−−−−−−−−−−−−−−−−−−7,
7 mol% The same post-treatment as in Example 1 was carried out, and ethyl 2-(4-hydroxyphenoxy)p1'pionate was converted into a light brown liquid by vacuum thin grooves to yield 14.3 gf! It's 7.
沸点:135−140°C/ 1 mm11g0」韮(
窒素雰囲気下、ハイドレキ2フ11g、エタノール88
g、水酸化ナトリウム12[およびクロル酢酸9.5g
を加え60 ’Cで411.+J間反応を行った。Boiling point: 135-140°C / 1 mm 11 g 0'' (under nitrogen atmosphere, Hydreki 2F 11 g, ethanol 88
g, sodium hydroxide 12 [and chloroacetic acid 9.5 g
411 at 60'C. +J reaction was performed.
反Lw+終了後塩酸を加え、酢酸エチル200gで21
抽出し酢酸エチルを留去した。(jJられた固体をジア
ゾメタンでメチル化し、ガスクロマI・グラフィー分析
の結果、下記の組成を示した。After finishing the anti-Lw +, add hydrochloric acid and add 200 g of ethyl acetate to 21
The mixture was extracted and ethyl acetate was distilled off. (The resulting solid was methylated with diazomethane, and gas chroma I/graph analysis showed the following composition.
ハイトロキノン−−−−20,2モル%2−(4−ヒド
ロキシフェノキシ)
プロピオン酸メチルー−16,9モル%二量体−−−−
−−−−−−−一−−−2、9モルシ石遍1址デ
窒素雰囲気下、ハイドロキノンl1g、エタノール(1
8g、水酸化ナトリウノ、14gおよびα−ブl」ムプ
ロピオン酸15.3[を加え60℃で4時間反応を行っ
た。反応終了1々ルi酸を加え、酢酸エチル200gで
2回抽出し酢酸エチルを留去した。1!7られた固体を
ジアゾメタンでメチル化し、ガスクロマトグラフィー分
析の結果、下記の組成を示した。Hytroquinone---20.2 mol% 2-(4-hydroxyphenoxy) methyl propionate-16.9 mol% dimer---
----------1--2, 9 pieces of morsilicate under nitrogen atmosphere, 1 g of hydroquinone, 1 g of ethanol, 1 g of ethanol (1 g)
8g of sodium hydroxide, 14g of sodium hydroxide, and 15.3g of α-propionic acid were added, and the reaction was carried out at 60°C for 4 hours. Upon completion of the reaction, phosphoric acid was added, and the mixture was extracted twice with 200 g of ethyl acetate, and the ethyl acetate was distilled off. The obtained solid was methylated with diazomethane, and gas chromatography analysis showed the following composition.
ハイドロキノンー−−−−−−15、4モル%2−(4
−ヒドロキシフェノキシ)
プロピオン酸メチル−73,8モル%
二M体−−−−−−−−一−−10、8モル%特許出願
人 日産化学工業株式会社
手続補正書(自発)
昭和59年 3月30日
1 事件の表示
昭和58年特許願第230787’号
2 発明の名称
2−(4−ヒドロキシフェノキシ)アルカン酸の製造方
法
3 ?i正をする者
事件との関係 特許出願人
住所 101東京都千代田区神口1錦町3丁目7番地1
4 補正の対象
明細書の特許請求の範囲の欄および明細書の発明の詳細
な説明の欄
5 補正の内容
(1)別紙のとおり。Hydroquinone---15, 4 mol% 2-(4
-Hydroxyphenoxy) Methyl propionate - 73.8 mol% 2M form - 10, 8 mol% Patent applicant Nissan Chemical Industries, Ltd. Procedural amendment (voluntary) 1988 3 March 30th 1 Display of the case 1982 Patent Application No. 230787' 2 Title of the invention 2 Process for producing -(4-hydroxyphenoxy)alkanoic acid 3 ? Relationship with the I-correction case Patent applicant address 3-7-1 Nishikicho, 1 Kamiguchi, Chiyoda-ku, Tokyo 101
4 Claims column of the specification to be amended and Detailed explanation of the invention column 5 Contents of the amendment (1) As shown in the attached sheet.
(2)明細書第2頁、第9行目に記載されているr X
CHRCOOR(1)
(式中、Xは塩素または臭素原子を、Rは水素または低
級アルキル基を示す。)
を。(2) rX stated on page 2, line 9 of the specification
CHRCOOR (1) (wherein, X represents a chlorine or bromine atom, and R represents hydrogen or a lower alkyl group).
r XCHRI COOR2’(1)
(式中、Xは塩素または臭素原子を R1は水素原子ま
たは低級アルキル基を R2は水素またはアルカリ金属
原子を示す。)
に訂正する。r
(3)明細■第3頁、後半の反応式に記載されている’
に2320J
を。(3) Specifications■Described in the reaction formula in the second half of page 3'
2320J to.
’に2 S2013 J に訂正する。'ni 2 S2013 J Correct to.
(4)明細書第5頁、最後の行に記載されている「α−
クロルプロピオン@j
を。(4) “α-
Chlorpropion @j.
「前記一般式(1)で表される化合物とハイドロキノン
またはハイドロキノンの塩と 1に訂正する。``The compound represented by the general formula (1) and hydroquinone or a salt of hydroquinone'' is corrected to 1.
(5)明m書第6頁、第1行目に記載されている「2モ
ル以上の」
を削除する。(5) Delete "2 moles or more" written in the first line of page 6 of the Memorandum of Understanding.
(6)明細書第6頁、第4行目に記載されている’ X
CHRCOOR(1)J
を。(6) 'X stated on page 6, line 4 of the specification
CHRCOOR(1)J.
’ XCHR’ C0OR” [1)Jに訂正する。'XCHR' C0OR” [1) Correct to J.
(7)明細書第6頁、第81j目と第9行目のあいだに
。(7) Page 6 of the specification, between line 81j and line 9.
「また、一般式〔1〕でR2が水素の場合はまず系内で
アルカリ金属塩となっ°ζから反応している。 J
を加入する。"Also, when R2 is hydrogen in the general formula [1], it first becomes an alkali metal salt in the system and reacts from °ζ. Add J.
(8)明細書第6頁、第17行目に記載されているr
X CHRCOOH(式中、Rは水素または低級アルキ
ル基を示す) 」
を。(8) r stated on page 6, line 17 of the specification
X CHRCOOH (wherein R represents hydrogen or a lower alkyl group).
rXcHRI COOR2(式中、Xは塩素または臭素
原子を R1ば水素または低級アルキル基を R2は水
素またはアルカリ金属原子を示す。) J
に訂正する。rXcHRI COOR2 (wherein, X represents a chlorine or bromine atom, R1 represents hydrogen or a lower alkyl group, and R2 represents a hydrogen or alkali metal atom) J.
(9)明細書第10頁、第6行目に記載されている’?
、6J
’10. 8J
に訂正する。(9) '?' stated on page 10, line 6 of the specification?
, 6J '10. Corrected to 8J.
(10)明細書第12頁、第4行目のつぎに。(10) Next to the 4th line on page 12 of the specification.
「実施例6゜
窒素雰囲気下、ハイドロキノン11g、エタノール88
g、水酸化ナトリウム10gおよびα−クロルプロピオ
ン酸のナトリウム塩1’3.0gを加えて60℃で4時
間反応を行った。反応終了後塩酸を加え、酢酸エチル2
00gで2回抽出し酢酸エチルを留去した。得られた固
体をジアゾメタンでメチル化しガスクロマトグラフィー
の結果は下記の組成を示した。Example 6 Under nitrogen atmosphere, 11 g of hydroquinone, 88 g of ethanol
g, 10 g of sodium hydroxide, and 3.0 g of the sodium salt of α-chloropropionic acid 1' were added, and the reaction was carried out at 60° C. for 4 hours. After the reaction is complete, add hydrochloric acid and add ethyl acetate.
00g twice and ethyl acetate was distilled off. The obtained solid was methylated with diazomethane and gas chromatography showed the following composition.
ハイドロキノンー−−−一・・−・・・−−−−−−−
−14、5モ一ル%二量体・−−−−−−−−一一−−
−−−−−−−−・−・−一−−−−−−−−5,7モ
ル% 」を追加する。Hydroquinone--------
-14, 5 mol% dimer -------11--
−−−−−−−・−・−−−−−−−−−−5.7 mol %'' is added.
別紙
2、特許請求の範囲
(1)
ハイドロキノンまたはハイドロキノンの塩と一般式〔1
〕
XCHRI GOOR” (1)
(式中、Xは塩素または臭素原子を、lFは水素または
低級アルキル基を、!!(↓
−ア」り髪1」1尾朋j5聚示ず。)
で表される化合物とを溶媒中においてアルカリ金属の水
酸化物を用い°ζ反応さ田ることを特′徴とする2−(
4−ヒドロキシフェノキシ)アルカン酸の製造方法。Attachment 2, Claims (1) Hydroquinone or a salt of hydroquinone and the general formula [1
] XCHRI GOOR” (1) (wherein, 2-(
A method for producing 4-hydroxyphenoxy)alkanoic acid.
(2)
溶媒がメタノール、エタノール、メチルセロソルブ、エ
チルセロソルブまたは水の1種または2種以上である特
許請求の範囲第1項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the solvent is one or more of methanol, ethanol, methyl cellosolve, ethyl cellosolve, or water.
Claims (3)
(1) %式%(1) (式中、Xは塩素または臭素原子を、Rは水素または低
級アルキル基を示す。) で表される化合物とを溶媒中においてアルカリ金属の水
酸化物を用いて反)1ムさせることを特徴とする2−(
4−ヒドロキシフェノキシ)チルカン酸の製造方法。(1) Salt of hydroquinone or H-1-quinone and general formula (1) % formula % (1) (wherein, X represents chlorine or bromine atom, R represents hydrogen or lower alkyl group) 2-(
A method for producing 4-hydroxyphenoxy)chilucanoic acid.
エチルセロソルブまたは水の1種または2種以上である
特許請求の範囲第1項記載の製造方法。(2) l medium is methanol, ethanol, methyl cellosolve,
The manufacturing method according to claim 1, wherein one or more types of ethyl cellosolve or water are used.
造方法。(3) The manufacturing method according to claim 1, wherein the solvent is ethanol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23078783A JPS60123443A (en) | 1983-12-07 | 1983-12-07 | Production of 2-(4-hydroxyphenoxy)alkanoic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23078783A JPS60123443A (en) | 1983-12-07 | 1983-12-07 | Production of 2-(4-hydroxyphenoxy)alkanoic acid |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS60123443A true JPS60123443A (en) | 1985-07-02 |
Family
ID=16913259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23078783A Pending JPS60123443A (en) | 1983-12-07 | 1983-12-07 | Production of 2-(4-hydroxyphenoxy)alkanoic acid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60123443A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007507478A (en) * | 2003-09-30 | 2007-03-29 | シンジェンタ リミテッド | Method for producing optically pure 2- (4-hydroxyphenoxy) -propionic acid compound |
CN108314619A (en) * | 2017-12-12 | 2018-07-24 | 南京红太阳生物化学有限责任公司 | A kind of synthetic method of R- (+) -2- (4- hydroxyphenoxies) propionic acid |
-
1983
- 1983-12-07 JP JP23078783A patent/JPS60123443A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007507478A (en) * | 2003-09-30 | 2007-03-29 | シンジェンタ リミテッド | Method for producing optically pure 2- (4-hydroxyphenoxy) -propionic acid compound |
JP2011236244A (en) * | 2003-09-30 | 2011-11-24 | Syngenta Ltd | Method for manufacturing optically pure 2-(4-hydroxyphenoxy)-propionic acid compound |
CN108314619A (en) * | 2017-12-12 | 2018-07-24 | 南京红太阳生物化学有限责任公司 | A kind of synthetic method of R- (+) -2- (4- hydroxyphenoxies) propionic acid |
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