JPH0372054B2 - - Google Patents
Info
- Publication number
- JPH0372054B2 JPH0372054B2 JP10646283A JP10646283A JPH0372054B2 JP H0372054 B2 JPH0372054 B2 JP H0372054B2 JP 10646283 A JP10646283 A JP 10646283A JP 10646283 A JP10646283 A JP 10646283A JP H0372054 B2 JPH0372054 B2 JP H0372054B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- carbon atoms
- hydroxyphenoxy
- alkyl group
- 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
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LSMSSYSRCUNIFX-ONEGZZNKSA-N 1-methyl-4-[(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=C(C)C=C1 LSMSSYSRCUNIFX-ONEGZZNKSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- -1 heterocyclic ether phenoxy fatty acid Chemical class 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- AQIHDXGKQHFBNW-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)propanoic acid Chemical class OC(=O)C(C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004821 distillation Methods 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
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLHUBROMZOAQMV-UHFFFAOYSA-N 1,4-benzosemiquinone Chemical group [O]C1=CC=C(O)C=C1 XLHUBROMZOAQMV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- KATNUXHENWPMQJ-UHFFFAOYSA-N butyl 2-chloropropanoate Chemical compound CCCCOC(=O)C(C)Cl KATNUXHENWPMQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明は２−（４−ヒドロキシフエノキシ）ア
ルカン酸エステル類の製造法に関する。さらに詳
しくは、本発明は、式：
で表される化合物と、一般式：
XCHR1COOR2
（式中、R1は水素原子またはメチル基を、R2
は炭素数１〜５のアルキル基を、Ｘはハロゲン原
子を示す）
で表される化合物とを反応させ、一般式〔１〕：
（式中、R1は水素原子またはメチル基を、R2
は炭素数１〜５のアルキル基を示す）で表される
化合物を生成させ、ついで該化合物と過酸化水素
水とを鉱酸触媒下で反応させることを特徴とする
一般式〔２〕：
（式中、R1は水素原子またはメチル基を、R2
は炭素数１〜５のアルキル基を示す）で表される
２−（４−ヒドロキシフエノキシ）アルカン酸エ
ステル類の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-(4-hydroxyphenoxy)alkanoic acid esters. More specifically, the present invention provides the formula: A compound represented by the general formula: XCHR 1 COOR 2 (wherein, R 1 is a hydrogen atom or a methyl group, R 2
is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom) to react with a compound represented by the general formula [1]: (In the formula, R 1 is a hydrogen atom or a methyl group, R 2
represents an alkyl group having 1 to 5 carbon atoms), and then the compound is reacted with aqueous hydrogen peroxide under a mineral acid catalyst [2]: (In the formula, R 1 is a hydrogen atom or a methyl group, R 2
represents an alkyl group having 1 to 5 carbon atoms).
２−（４−ヒドロキシフエノキシ）アルカン酸
エステル類は特開昭56−16475号公報、特開昭54
−22371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
環エーテル系フエ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−ヒドロキシフエノキシ）
アルカン酸エステル類の製造法としては、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。 2-(4-hydroxyphenoxy)alkanoic acid esters are disclosed in JP-A-56-16475 and JP-A-54.
It is useful as an intermediate for compounds disclosed in JP-A-22371, 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-hydroxyphenoxy)
As a method for producing alkanoic acid esters, for example, there is a method shown by the following reaction formula disclosed in Japanese Patent Application Laid-Open No. 56-59718.
また、国際出願公開82／00639号公報に開示さ
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 International Application Publication No. 82/00639.
しかし、特開昭56−59718号公報に開示されて
いる方法は、ハイドロキノンの２個の水酸基が等
価であるので多量の２置換体が副生し、かつ未反
応ハイドロキノンが残存するので２−（４−ヒド
ロキシフエノキシ）アルカン酸を純度、収率よく
得られない欠点を有している。またこの反応条件
下では２−（４−ヒドロキシフエノキシ）プロピ
オン酸エステル類は容易に加水分解するので２−
（４−ヒドロキシフキシ）プロピオン酸を単離す
ることなくエステル化出来ない。また、国際出願
公開82／00639号公報に開示されている方法では、
過硫酸エステルを合成する工程の生成率が低く工
業的には好ましいとはいえない。 However, in the method disclosed in JP-A-56-59718, since the two hydroxyl groups of hydroquinone are equivalent, a large amount of disubstituted product is produced as a by-product, and unreacted hydroquinone remains, so 2-( It has the disadvantage that 4-hydroxyphenoxy)alkanoic acid cannot be obtained in high purity and yield. Furthermore, under these reaction conditions, 2-(4-hydroxyphenoxy)propionic acid esters are easily hydrolyzed, so 2-(4-hydroxyphenoxy)propionate is easily hydrolyzed.
(4-Hydroxyfoxy)propionic acid cannot be esterified without isolation. In addition, in the method disclosed in International Application Publication No. 82/00639,
The production rate of the process for synthesizing persulfate ester is low and it cannot be said to be industrially preferable.
本発明者らは、これらの方法が工業的に有利で
はないので、２−（４−ヒドロキシフエノキシ）
アルカン酸エステル類の優れた製造法を鋭意研究
した結果、容易にかつ高収率で２−（４−ヒドロ
キシフエノキシ）アルカン酸エステル類を製造す
る方法を見出し本発明を完成した。 Since these methods are not industrially advantageous, the inventors proposed that 2-(4-hydroxyphenoxy)
As a result of intensive research into an excellent method for producing alkanoic acid esters, the present invention was completed by discovering a method for producing 2-(4-hydroxyphenoxy)alkanoic acid esters easily and in high yield.
本発明において、一般式〔１〕で表される化合
物である２−（４−プロペニルフエノキシ）アル
カン酸エステル類の合成は、下記反応式により行
い得る。 In the present invention, 2-(4-propenylphenoxy)alkanoic acid esters, which are compounds represented by general formula [1], can be synthesized according to the following reaction formula.
（反応式中、R1は水素原子またはメチル基を、
R2は炭素数１〜５のアルキル基を、Ｘはハロゲ
ン原子を示す。）
原料の４−プロペニルフエノールは、特開昭50
−13341号公報に開示されている方法により製造
し得る。 (In the reaction formula, R 1 is a hydrogen atom or a methyl group,
R 2 represents an alkyl group having 1 to 5 carbon atoms, and X represents a halogen atom. ) The raw material 4-propenylphenol was published in Japanese Patent Application Publication No. 1983
It can be produced by the method disclosed in Japanese Patent No.-13341.
α−ハロゲノアルカン酸エステルのＸとしては
塩素原子、臭素原子が望ましい。塩基としては炭
酸ナトリウム、炭酸カリウム、炭酸水素ナトリウ
ム、炭酸水素カリウム等の炭酸塩を用いるが、一
種または二種以上混合して用いてもよい。塩基の
使用量としては４−プロペニルフエノールに対し
1.0〜10倍当量がよく、好ましくは1.2〜2.0倍当量
がよい。溶媒としては、ジメチルホルムアミド、
ジメチルスルホキシド、Ｎ，Ｎ−ジメチルイミダ
ゾリジノン、Ｎ−メチルピロリドン等の極性溶媒
を用いるが、ベンゼン、トルエン等の芳香族炭化
水素溶媒に上記極性溶媒を99〜10％混合して用い
てもよい。溶媒量は４−プロペニルフエノールに
対して２〜10倍重量がよい。反応温度は50〜150
℃でよいが、高温では加水分解が若干起こるので
好ましくは50〜100℃がよい。また、反応条件に
よつては反応が遅い場合もあるが、そのときには
トリメチルベンジルアンモニウムクロライド等の
相間移動触媒を４−プロペニルフエノールに対し
て、0.01〜0.1倍重量を添加すればよい。ヨウ化
カリウムも同様の効果がある。 As X in the α-halogenoalkanoic acid ester, a chlorine atom or a bromine atom is preferable. As the base, carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are used, but they may be used alone or in combination of two or more. The amount of base used is based on 4-propenylphenol.
The amount is preferably 1.0 to 10 times, preferably 1.2 to 2.0 times. As a solvent, dimethylformamide,
A polar solvent such as dimethyl sulfoxide, N,N-dimethylimidazolidinone, or N-methylpyrrolidone is used, but a mixture of 99 to 10% of the above polar solvent with an aromatic hydrocarbon solvent such as benzene or toluene may also be used. . The amount of solvent is preferably 2 to 10 times the weight of 4-propenylphenol. Reaction temperature is 50-150
The temperature may be 50°C to 100°C, but since some hydrolysis occurs at high temperatures, the temperature is preferably 50 to 100°C. Further, depending on the reaction conditions, the reaction may be slow, but in that case, a phase transfer catalyst such as trimethylbenzylammonium chloride may be added in an amount of 0.01 to 0.1 times the weight of 4-propenylphenol. Potassium iodide has a similar effect.
目的化合物である２−（４−プロペニルフエノ
キシ）アルカン酸エステル類を単離するには、転
化率がよい場合は無機塩をロ別してそのまま減圧
蒸溜すればよく、未反応物が若干残存する場合に
は水に溶解しない溶媒、例えばトルエンと水を加
えて無機塩を除去後１〜２％水酸化ナトリウム水
溶液を適量加えて洗浄後、溶媒留去して減圧蒸溜
すればよい。 In order to isolate the target compound, 2-(4-propenylphenoxy)alkanoic acid ester, if the conversion rate is good, the inorganic salt can be filtered out and distilled under reduced pressure as it is, but some unreacted substances may remain. In such a case, a water-insoluble solvent such as toluene and water may be added to remove inorganic salts, and then an appropriate amount of 1 to 2% aqueous sodium hydroxide solution may be added for washing, and the solvent may be distilled off under reduced pressure.
また、一般式〔２〕で表される化合物の製造の
際に用いる酸触媒としては、硫酸、塩酸等の無機
酸が挙げられ、その使用量としては0.1〜2.0モル
好ましくは0.1〜0.3モル量がよい。また、使用す
る過酸化水素水の濃度は30〜60重量％がよく、そ
の使用量は一般式〔１〕の化合物に対して1.0〜
2.5倍モル好ましくは1.1〜1.5倍モルがよく、その
他の反応条件によつて増減する。反応は無溶媒で
もよいが、必要に応じて過酸化水素に不活性な溶
媒を使用してもよい。溶媒としては、過酸化水素
水を用いるので水に溶解性のよい溶媒、例えばメ
タノール、エタノール等のアルコール、アセトニ
トリル等が用いられるが、一般式〔１〕で表され
る化合物のエステル部分と同じアルキル基を有す
るアルコールを使用するのが最も好ましい。 In addition, examples of the acid catalyst used in the production of the compound represented by the general formula [2] include inorganic acids such as sulfuric acid and hydrochloric acid, and the amount used is 0.1 to 2.0 mol, preferably 0.1 to 0.3 mol. Good. In addition, the concentration of hydrogen peroxide solution to be used is preferably 30 to 60% by weight, and the amount used is 1.0 to 1.0 to 60% by weight relative to the compound of general formula [1].
It is preferably 1.1 to 1.5 times by mole, and may be increased or decreased depending on other reaction conditions. The reaction may be carried out without a solvent, but if necessary, a solvent inert to hydrogen peroxide may be used. Since hydrogen peroxide is used as a solvent, solvents with good water solubility, such as alcohols such as methanol and ethanol, acetonitrile, etc., are used. Most preferably, alcohols with groups are used.
反応温度は、使用する原料の種類、過酸化水素
のモル比等、その他の反応条件によつて異なるが
20〜70℃がよい。ただし、反応温度が高いと副反
応としてエステル部分の加水分解がおこるので、
反応時間を長くして温度条件を低く設定すること
が好ましい。例えば、一般式〔２〕の化合物で
R2がエチル基の場合、エタノール溶媒を用い、
硫酸触媒下50℃で反応を行うと10〜15％の２−
（４−ヒドロキシフエノキシ）プロピオン酸が生
成する。 The reaction temperature varies depending on the type of raw materials used, the molar ratio of hydrogen peroxide, and other reaction conditions.
20-70℃ is good. However, if the reaction temperature is high, hydrolysis of the ester moiety will occur as a side reaction.
It is preferable to lengthen the reaction time and set the temperature conditions low. For example, in the compound of general formula [2]
When R 2 is an ethyl group, use ethanol solvent,
When the reaction is carried out at 50℃ under sulfuric acid catalyst, 10-15% of 2-
(4-Hydroxyphenoxy)propionic acid is produced.
反応終了後は必要に応じて溶媒を減圧下留去し
てトルエン等の溶媒を加え２〜３回水洗を行い、
つづいて亜硫酸ナトリウムの水溶液で洗浄し、さ
らに炭酸水素ナトリウムで洗浄した後、減圧蒸溜
によつて２−（４−ヒドロキシフエノキシ）アル
カン酸エステル類を得る。 After the reaction is complete, if necessary, the solvent is distilled off under reduced pressure, a solvent such as toluene is added, and the mixture is washed with water 2 to 3 times.
Subsequently, after washing with an aqueous solution of sodium sulfite and further washing with sodium hydrogen carbonate, 2-(4-hydroxyphenoxy)alkanoic acid esters are obtained by distillation under reduced pressure.
以下実施例を挙げてさらに詳細に説明するが、
本発明はこれらによつて限定されるものではな
い。 The following will be explained in more detail with reference to examples.
The present invention is not limited thereto.
実施例 １
４−プロペニルフエノール13.4ｇ，α−ブロム
プロピオン酸エチル20ｇ、炭酸カリウム13・８
ｇ、ジメチルホルムアミド40ｇを混合して100℃
で３時間撹拌したのちジメチルホルムアミドを減
圧下留去し、室温に冷却した。水およびトルエン
を加え分液、水洗したのちトルエンを減圧留去
し、減圧蒸溜によつて２−（４−プロペニルフエ
ノキシ）プロピオン酸エチルを無色透明液として
18.7ｇ得た。Example 1 4-propenylphenol 13.4g, ethyl α-bromopropionate 20g, potassium carbonate 13.8
Mix 40 g of dimethylformamide and heat to 100℃.
After stirring for 3 hours, dimethylformamide was distilled off under reduced pressure, and the mixture was cooled to room temperature. After adding water and toluene and separating the liquid, washing with water, toluene was distilled off under reduced pressure, and ethyl 2-(4-propenylphenoxy)propionate was obtained as a colorless transparent liquid by distillation under reduced pressure.
I got 18.7g.
沸点：115℃／１mmHg。 Boiling point: 115℃/1mmHg.
NMR（CDC13）：δ
7.06（m.4H）5.1（d.2H）4.73（q.1H）
4.23（q.2H）2.1（s.3H）1.6（d.3H）
1.2（t.3H）
実施例 ２
４−プロペニルフエノール13.4ｇ、α−クロル
プロピオン酸−ｎ−ブチル18.0ｇ、炭酸カリウム
８ｇ、ジメチルホルムアミド50ｇを混合して100
℃で５時間反応後、実施例１と同様の後処理を行
い、減圧蒸溜によつて２−（４−プロペニルフエ
ノキシ）プロピオン酸−ｎ−ブチルを無色透明液
として18.0ｇ得た。 NMR (CDC1 3 ): δ 7.06 (m.4H) 5.1 (d.2H) 4.73 (q.1H) 4.23 (q.2H) 2.1 (s.3H) 1.6 (d.3H) 1.2 (t.3H) Implemented Example 2 Mix 13.4 g of 4-propenylphenol, 18.0 g of n-butyl α-chloropropionate, 8 g of potassium carbonate, and 50 g of dimethylformamide and make 100 g.
After reacting at °C for 5 hours, the same post-treatment as in Example 1 was carried out, and 18.0 g of n-butyl 2-(4-propenylphenoxy)propionate was obtained as a colorless transparent liquid by distillation under reduced pressure.
沸点：130℃／0.4mmHg。 Boiling point: 130℃/0.4mmHg.
実施例 ３
２−（４−プロペニルフエノキシ）プロピオン
酸エチル11.7ｇ、30％過酸化水素水10ｇ、98％硫
酸３ｇおよびエタノール60ｇを加えたのち、50℃
で１時間反応後、減圧下エタノールを留去してト
ルエンと水を加えて水洗を３回行い、炭酸ナトリ
ウム水溶液で洗浄、水洗した。トルエンを留去し
たのち、減圧蒸溜によつて２−（４−ヒドロキシ
フエノキシ）プロピオン酸エチルを無色透明液と
して7.5ｇ得た。Example 3 After adding 11.7 g of ethyl 2-(4-propenylphenoxy)propionate, 10 g of 30% hydrogen peroxide, 3 g of 98% sulfuric acid and 60 g of ethanol, the mixture was heated to 50°C.
After reacting for 1 hour, ethanol was distilled off under reduced pressure, toluene and water were added, and the mixture was washed three times with water, followed by washing with an aqueous sodium carbonate solution and water. After distilling off toluene, 7.5 g of ethyl 2-(4-hydroxyphenoxy)propionate was obtained as a colorless transparent liquid by distillation under reduced pressure.
沸点：130℃／1mmHg
また、洗液をすべて合わせて酸性とし、酢酸エチ
ルで抽出して0.9ｇの２−（４−ヒドロキシフエノ
キシ）プロピオン酸を得、高速液体クロマトグラ
フイーにより確認した。 Boiling point: 130° C./1 mmHg All the washing liquids were combined and made acidic, and extracted with ethyl acetate to obtain 0.9 g of 2-(4-hydroxyphenoxy)propionic acid, which was confirmed by high performance liquid chromatography.
高速液体クロマトグラフイーの条件
充填剤：Nucleoail5C18
カラム：内径4.6mm×長さ250mm
溶離液：アセトニトリル／水／酢酸＝50／
50／７
実施例 ４
２−（４−プロペニルフエノキシ）プロピオン
酸ブチル13.1ｇ、30％過酸化水素水10ｇおよび35
％塩酸３ｇ、エタノール60ｇを加えたのち、50℃
で１時間反応後、実施例３と同様の後処理を行
い、減圧蒸溜によつて２−（４−ヒドロキシフエ
ノキシ）プロピオン酸ブチルを無色透明液として
8.3ｇ得た。 High performance liquid chromatography conditions Packing material: Nucleoail5C18 Column: Internal diameter 4.6 mm x Length 250 mm Eluent: Acetonitrile/water/acetic acid = 50/
50/7 Example 4 13.1 g of butyl 2-(4-propenylphenoxy)propionate, 10 g of 30% hydrogen peroxide and 35
After adding 3 g of % hydrochloric acid and 60 g of ethanol, heat at 50℃.
After reacting for 1 hour at
Obtained 8.3g.
沸点：145℃／0.4mmHg Boiling point: 145℃/0.4mmHg
Claims (1)
は炭素数１〜５のアルキル基を、Ｘはハロゲン原
子を示す） で表わされる化合物とを反応させ、 一般式〔１〕： （式中、R1は水素原子またはメチル基を、R2
は炭素数１〜５のアルキル基を示す） で表される化合物を生成させ、ついで該化合物と
過酸化水素水とを鉱酸触媒下で反応させることを
特徴とする、 一般式〔２〕： （式中、R1は水素原子またはメチル基を、R2
は炭素数１〜５のアルキル基を示す） で表される２−（４−ヒドロキシフエノキシ）ア
ルカン酸エステル類の製造法。 ２ 一般式〔１〕： （式中、R1は水素原子またはメチル基を、R2
は炭素数１〜５のアルキル基を示す） で表される化合物と過酸化水素水とを鉱酸触媒下
で反応させることを特徴とする 一般式〔２〕： （式中、R1は水素原子またはメチル基を、R2
は炭素数１〜５のアルキル基を示す） で表される２−（４−ヒドロキシフエノキシ）ア
ルカン酸エステル類の製造法。[Claims] 1 Formula: A compound represented by the general formula: XCHR 1 COOR 2 (wherein R 1 is a hydrogen atom or a methyl group, R 2
is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom) to react with a compound represented by the general formula [1]: (In the formula, R 1 is a hydrogen atom or a methyl group, R 2
represents an alkyl group having 1 to 5 carbon atoms), and then the compound and hydrogen peroxide are reacted under a mineral acid catalyst, General formula [2]: (In the formula, R 1 is a hydrogen atom or a methyl group, R 2
represents an alkyl group having 1 to 5 carbon atoms) A method for producing a 2-(4-hydroxyphenoxy)alkanoic acid ester represented by 2 General formula [1]: (In the formula, R 1 is a hydrogen atom or a methyl group, R 2
represents an alkyl group having 1 to 5 carbon atoms) General formula [2] characterized by reacting a compound represented by the following with hydrogen peroxide solution under a mineral acid catalyst: (In the formula, R 1 is a hydrogen atom or a methyl group, R 2
represents an alkyl group having 1 to 5 carbon atoms) A method for producing a 2-(4-hydroxyphenoxy)alkanoic acid ester represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10646283A JPS59231044A (en) | 1983-06-14 | 1983-06-14 | Production of hydroxyphenoxyalkanoic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10646283A JPS59231044A (en) | 1983-06-14 | 1983-06-14 | Production of hydroxyphenoxyalkanoic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59231044A JPS59231044A (en) | 1984-12-25 |
| JPH0372054B2 true JPH0372054B2 (en) | 1991-11-15 |
Family
ID=14434237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10646283A Granted JPS59231044A (en) | 1983-06-14 | 1983-06-14 | Production of hydroxyphenoxyalkanoic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59231044A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651140A (en) * | 2018-12-12 | 2019-04-19 | 江苏中旗科技股份有限公司 | A kind of synthetic method of cyhalofop-butyl active compound |
-
1983
- 1983-06-14 JP JP10646283A patent/JPS59231044A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59231044A (en) | 1984-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1257874A (en) | Process for preparing opticaly active 2-(4-hydroxy- phenoxy)propionic acid compounds | |
| CS198298B2 (en) | Method of producing substituted benzylesters of vinyl cyclopropane carboxylic acids | |
| JPH03372B2 (en) | ||
| JPH032134B2 (en) | ||
| CN107428648B (en) | Process for the preparation of compounds such as 3-arylbutyraldehyde useful for the synthesis of medetomidine | |
| US4537984A (en) | Process for producing 2-(4-hydroxyphenoxy) propionate derivatives | |
| JPH0372054B2 (en) | ||
| JPH11501314A (en) | Method for preparing esters of stilbene dicarboxylic acid | |
| JP3677786B2 (en) | Method for producing aryloxypropionic acid | |
| JP3823385B2 (en) | Process for producing 2,4,5-trifluoro-3-iodobenzoic acid and esters thereof | |
| JP3777407B2 (en) | Method for producing carboxylic acid derivative | |
| JP3944876B2 (en) | Method for producing citrate esters | |
| US4681941A (en) | Method of preparing esters of aryloxyphenoxy propanoic acid | |
| JP2743198B2 (en) | Cyclopentanes | |
| BG60580B1 (en) | Method for the preparation of 2,2-dimethyl-5-(2,5-dimethylphenoxy)-pentanoic acid, intermediate compounds for its preparation and method for the preparation of the intermediate compounds | |
| JP2903233B2 (en) | Method for producing high-purity dimethyl diphenyldicarboxylate | |
| JPS6216446A (en) | Production of optically active 2-(4-hydroxyphenoxy) propionic acid | |
| JPH0124782B2 (en) | ||
| EP0306936A2 (en) | Process for producing aminooxyacetic acid salts | |
| JP2861122B2 (en) | Method for producing pyrazolecarboxylic acid esters | |
| JPH0365336B2 (en) | ||
| JPH0321537B2 (en) | ||
| US6180801B1 (en) | Method for manufacturing 3-isochromanone | |
| JPH07247267A (en) | Production of phenyl ethers | |
| JPH0544448B2 (en) |