JPH0267245A - Production of 4-(alkylphenoxy)butyric acid - Google Patents
Production of 4-(alkylphenoxy)butyric acidInfo
- Publication number
- JPH0267245A JPH0267245A JP21942088A JP21942088A JPH0267245A JP H0267245 A JPH0267245 A JP H0267245A JP 21942088 A JP21942088 A JP 21942088A JP 21942088 A JP21942088 A JP 21942088A JP H0267245 A JPH0267245 A JP H0267245A
- Authority
- JP
- Japan
- Prior art keywords
- alkylphenol
- butyrolactone
- alkali metal
- butyric acid
- alkylphenoxy
- 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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 54
- -1 alkali metal salt Chemical class 0.000 claims abstract description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 10
- YKYVPFIBWVQZCE-UHFFFAOYSA-N 4-phenoxybutanoic acid Chemical class OC(=O)CCCOC1=CC=CC=C1 YKYVPFIBWVQZCE-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WMVJWKURWRGJCI-UHFFFAOYSA-N 2,4-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=C(O)C(C(C)(C)CC)=C1 WMVJWKURWRGJCI-UHFFFAOYSA-N 0.000 description 4
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical group CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BRIRGRNYHFFFHD-UHFFFAOYSA-N 2,3-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=CC(O)=C1C(C)(C)CC BRIRGRNYHFFFHD-UHFFFAOYSA-N 0.000 description 1
- BGRKGHSKCFAPCL-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=CC=C1O BGRKGHSKCFAPCL-UHFFFAOYSA-N 0.000 description 1
- TVSPPYGAFOVROT-UHFFFAOYSA-N 2-phenoxybutanoic acid Chemical class CCC(C(O)=O)OC1=CC=CC=C1 TVSPPYGAFOVROT-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- RBLLZFKXJIFDCL-UHFFFAOYSA-N 3-(aminomethyl)-n-propan-2-ylbenzenesulfonamide Chemical compound CC(C)NS(=O)(=O)C1=CC=CC(CN)=C1 RBLLZFKXJIFDCL-UHFFFAOYSA-N 0.000 description 1
- LZSDVFDKDUZVFK-UHFFFAOYSA-N 4-[2,4-bis(2-methylbutan-2-yl)phenoxy]butanoic acid Chemical compound CCC(C)(C)C1=CC=C(OCCCC(O)=O)C(C(C)(C)CC)=C1 LZSDVFDKDUZVFK-UHFFFAOYSA-N 0.000 description 1
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は４−（アルキルフェノキシ）醋酸の製造方法に
関し、特にγ−ブチロラクトンとアルキルフェノールの
アルカリ金属塩とを反応さて４−フェノキシ酪酸類を製
造する方法に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing 4-(alkylphenoxy)acetic acid, and in particular to a method for producing 4-phenoxybutyric acids by reacting γ-butyrolactone and an alkali metal salt of alkylphenol. It's about how to do it.
４−（アルキルフェノキシ）酪酸は写真薬等の原料とな
る有用な物質であり、本発明の方法によれば、簡便かつ
経済的に４−（アルキルフェノキシ）酪酸を製造するこ
とができる。4-(Alkylphenoxy)butyric acid is a useful substance that is a raw material for photographic drugs and the like, and according to the method of the present invention, 4-(alkylphenoxy)butyric acid can be produced simply and economically.
［従来の技術］
γ−ブチロラクトンとフェノール類とを反応させること
により、４−フェノキシ酪酸類を製造する方法は古くか
ら知られている。[Prior Art] A method for producing 4-phenoxybutyric acids by reacting γ-butyrolactone and phenols has been known for a long time.
例えば、フェノール類のナトリウム塩を調製した後、溶
媒等を回収してフェノール類のナトリウム塩を単離し、
無溶媒の条件下でγ−ブチロラクトンと反応させ、４−
フェノキシ酪酸類を製造する方法（レビスタ・デ・キミ
エ（Ｒｅｖ、Ｃｈｅｍ、１．１９６９゜２０、１＋ 、
ツーラル・オブシェケイ・キミイ１２ｈｕｒ、 ０ｂｓ
ｈｃｈｅｉ Ｋｈｉｓ、１１９５９．２９．３７４４、
ドイツ特許筒１．０４２．６００明細書等）がある、こ
れらの方法では、フェノール類のナトリウム塩を合成す
る際に生成するアルコールや水を完全に除去するのが困
難なため、γ−ブチロラクトンの加水分解等の副反応が
起こり、４−フェノキシ酪酸の収率が低いという欠点が
あった。For example, after preparing the sodium salt of phenols, the solvent etc. are recovered and the sodium salt of phenols is isolated.
By reacting with γ-butyrolactone under solvent-free conditions, 4-
Method for producing phenoxybutyric acids (Revista de Quimier (Rev, Chem, 1.1969°20, 1+,
Toural obshekei Kimii 12 hr, 0bs
hchei Khis, 11959.29.3744,
With these methods, it is difficult to completely remove alcohol and water produced when synthesizing sodium salts of phenols, so it is difficult to completely remove γ-butyrolactone. There were disadvantages in that side reactions such as hydrolysis occurred and the yield of 4-phenoxybutyric acid was low.
英国特許筒７９４．１５６号明細書には、フェノールと
水酸化ナトリウム水溶液からフェノールのナトリウム塩
を合成する際に、クロロベンゼン等の溶媒を用いて水を
共沸によって除去した後、γ−ブチロラクトンと反応さ
せて４−フェノキシ醋酸を製造する方法が開示されてい
る。British Patent No. 794.156 describes that when synthesizing the sodium salt of phenol from an aqueous solution of phenol and sodium hydroxide, water is removed azeotropically using a solvent such as chlorobenzene, and then the reaction is performed with γ-butyrolactone. A method for producing 4-phenoxyacetic acid is disclosed.
［発明が解決しようとする課題］
本発明者らが、前述の英国特許明細書記載の方法を、２
．４−ジー第三アミルフェノールのようなアルキルフェ
ノール類に応用したところ、アルキルフェノールのナト
リウム塩を合成する際に反応混合物から水を全量回収す
ることは、事実上不可能であり、長時間加熱還流しても
水が相等量反応混合物中に残存するため、４−（アルキ
ルフェノキシ）酪酸の収率が低かった。[Problem to be solved by the invention] The present inventors have applied the method described in the above-mentioned British patent specification to two
．． When applied to alkylphenols such as 4-di-tertiary amylphenol, it is virtually impossible to recover the entire amount of water from the reaction mixture when synthesizing the sodium salt of alkylphenol, and it is difficult to recover the entire amount of water from the reaction mixture by heating under reflux for a long time. However, the yield of 4-(alkylphenoxy)butyric acid was low because an equal amount of water remained in the reaction mixture.
さらに、生成物である４−（アルキルフェノキシ）酪酸
は、一般に晶析により単離されるが、クロロベンゼン等
の芳香族炭化水素に対する溶解度が大きく、シかも温度
による溶解度の変化が小さいため、これらの溶媒から晶
析により単離した場合の回収率が低い、また、芳香族炭
化水素で晶析した場合には、得られた４−（アルキルフ
ェノキシ）酪酸は黄色に着色しており、同じ溶媒での晶
析を繰り返しても色は抜けず、写真薬等の原料として用
いるには更に活性炭等で脱色する必要がある。Furthermore, the product 4-(alkylphenoxy)butyric acid is generally isolated by crystallization, but it has a high solubility in aromatic hydrocarbons such as chlorobenzene, and its solubility changes little with temperature, so it cannot be used in these solvents. The recovery rate is low when isolated by crystallization from aromatic hydrocarbons, and the obtained 4-(alkylphenoxy)butyric acid is yellow colored when crystallized from aromatic hydrocarbons. Even after repeated crystallization, the color does not disappear, and in order to use it as a raw material for photographic drugs, it is necessary to further decolorize it with activated carbon or the like.
［課題を解決するための手段］
本発明者等は、かかる不利益を克服するため、鋭意検討
を行ない、アルキルフェノールのアルカリ金属塩は、原
料のアルキルフェノールに対する溶解度が大きいため、
過剰のアルキルフェノールの存在下でアルカリ金属塩を
合成すると、反応混合物が低粘度化するために水の回収
が容易となり、実質的に無水のアルキルフェノール類の
アルカリ金属塩を合成することができることを見出し、
本発明を完成した。[Means for Solving the Problems] In order to overcome such disadvantages, the present inventors have conducted extensive studies, and found that alkali metal salts of alkylphenols have a high solubility in the raw material alkylphenol.
We have discovered that when an alkali metal salt is synthesized in the presence of an excess of alkylphenol, the viscosity of the reaction mixture becomes low, making it easy to recover water, and it is possible to synthesize an alkali metal salt of a substantially anhydrous alkylphenol.
The invention has been completed.
即ち１本発明は、アルキルフェノールのアルカリ金属塩
にγ−ブチロラクトンを反応させて４−フェノキシ酪酸
類を製造する方法において、過剰量のアルキルフェノー
ルの存在下に、実質的に無水の状態でγ−ブチロラクト
ンを反応させることを特徴とする４−（アルキルフェノ
キシ）酪酸の製造方法である。That is, 1 the present invention provides a method for producing 4-phenoxybutyric acids by reacting γ-butyrolactone with an alkali metal salt of alkylphenol, in which γ-butyrolactone is reacted in a substantially anhydrous state in the presence of an excess amount of alkylphenol. This is a method for producing 4-(alkylphenoxy)butyric acid, which is characterized by carrying out a reaction.
本発明の方法を用いれば、γ−ブチロラクトンが加水分
解等の副反応を受けることなく、目的とする４−（アル
キルフェノキシ）酪酸を合成することができる。By using the method of the present invention, the desired 4-(alkylphenoxy)butyric acid can be synthesized without γ-butyrolactone undergoing side reactions such as hydrolysis.
本発明の方法で用いられるアルキルフェノールのアルカ
リ金属塩は、アルキルフェノールにアルカリ金属やその
アルコキシドを加えて合成することもできるが、一般に
、アルキルフェノールにアルカリ金属の水酸化物を加え
て減圧下で加熱脱水し、アルキルフェノールアルカリ金
属塩のアルキルフェノール溶液として調製される０反応
で生成する水は理論量の９８％以上を回収除去して、実
質上無水の状態とする。The alkali metal salt of an alkylphenol used in the method of the present invention can be synthesized by adding an alkali metal or its alkoxide to an alkylphenol, but generally, an alkali metal hydroxide is added to an alkylphenol and then heated and dehydrated under reduced pressure. , 98% or more of the theoretical amount of water produced in the 0 reaction prepared as an alkylphenol solution of an alkylphenol alkali metal salt is recovered and removed, resulting in a substantially anhydrous state.
アルキルフェノールアルカリ金属塩のアルキルフェノー
ル溶液の調製に用いられるアルキルフェノールとしては
、例えば、２−第三ブチルフェノール、２−第三アミル
フェノール等の２−アルキルフェノール類や、４−第三
ブチルフェノール、４−第三アミルフェノール等の４−
アルキルフェノール類、２．４−ジー第三ブチルフェノ
ール、２−メチル−４−第三ブチルフェノール、２．４
−ジー第三アミルフェノールなどの２．４−ジアルキル
フェノール類、２．６−ジ−メチルフェノールなどの２
．６−ジ−アルキルフェノール類及び２．６−ジー第三
ブチル−４−メチルフェノールなどのトリアルキルフェ
ノール類がある。これらは単独で使用される。Examples of alkylphenols used in preparing an alkylphenol solution of alkylphenol alkali metal salts include 2-alkylphenols such as 2-tert-butylphenol and 2-tert-amylphenol, 4-tert-butylphenol, and 4-tert-amylphenol. etc. 4-
Alkylphenols, 2.4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 2.4
-2,4-dialkylphenols such as di-tertiary amylphenol, 2,4-dialkylphenols such as 2,6-di-methylphenol, etc.
．． There are trialkylphenols such as 6-di-alkylphenols and 2,6-di-tert-butyl-4-methylphenol. These are used alone.
反応に使用されるアルカリ金属の水酸化物としては、水
酸化リチウム、水酸化ナトリウム、水酸化カリウムなど
がある。これらは固体でも、任意の濃度の水溶液でもど
ちらでも使用することができる。Examples of the alkali metal hydroxide used in the reaction include lithium hydroxide, sodium hydroxide, and potassium hydroxide. These can be used either as a solid or as an aqueous solution of any concentration.
反応に使用するアルカリ金属水酸化物の量は、アルキル
フェノール１モルに対し０．１１〜０．８０モル、好ま
しくは０．２５〜０．６０モルで、これより少ないと生
産性が著しく低下し、また、これより多いと高融点のア
ルキルフェノールアルカリ金属塩の割合が高くなって高
粘度となり、水の回収が著しく困難となって、実質的に
無水の状態にすることができず、４−（アルキルフェノ
キシ）酪酸の収率が著しく低下し好ましくない。The amount of alkali metal hydroxide used in the reaction is 0.11 to 0.80 mol, preferably 0.25 to 0.60 mol, per 1 mol of alkylphenol; if it is less than this, productivity will drop significantly; In addition, if the amount exceeds this range, the proportion of the alkylphenol alkali metal salt with a high melting point will increase, resulting in high viscosity, making it extremely difficult to recover water, making it impossible to achieve a substantially anhydrous state, and 4-(alkyl The yield of phenoxy)butyric acid decreases significantly, which is undesirable.
アルキルフェノールのアルカリ金属塩を調製する際の温
度は、４０〜２００℃、好ましくは６０〜１５０℃で、
反応温度が４０℃以下だと脱水効果が著しく低下し長時
間を要するため実用的でない、また、２００℃以上の温
度で反応を行なうと、著しく着色するため好ましくない
。The temperature when preparing the alkali metal salt of alkylphenol is 40 to 200°C, preferably 60 to 150°C,
If the reaction temperature is below 40°C, the dehydration effect will be significantly reduced and a long time will be required, making it impractical, and if the reaction is carried out at a temperature above 200°C, it will be undesirable because it will cause significant coloration.
また、この際の圧力は５００ｍｓＨｇ以下、好ましくは
１００■■Ｈｇ以下、特に好ましくは３０ｍ■Ｈｇ以下
で、これより高い圧力では脱水の効率は著しく低下し実
用的でない、脱水操作は回収され得る水の理論量の９８
％以上が回収されるまで続ける。ここでいう回収され得
る水の理論量とは、水酸化アルカリ金属水溶液中に含ま
れる水の量と、アルキルフェノールと水酸化アルカリ金
属との反応によって生成する水の量との和で１次式で示
される。In addition, the pressure at this time is 500 msHg or less, preferably 100 mHg or less, particularly preferably 30 mHg or less; if the pressure is higher than this, the efficiency of dewatering will decrease significantly and it is not practical. 98 of the theoretical quantity of
Continue until % or more is recovered. The theoretical amount of water that can be recovered here is the sum of the amount of water contained in the aqueous alkali metal hydroxide solution and the amount of water produced by the reaction between the alkylphenol and the alkali metal hydroxide, expressed by a linear equation. shown.
水の回収理論量＝
ＭＯＩＩ水ｆｆｉ液ＪＩ Ｘ （１−１１０Ｈｉ１度＋
％ｌ／１００１＋１８ＸＭＯ）１モル数
ここでＭはアルカリ金属を表わす。Theoretical amount of water recovered = MOII water ffi liquid JI X (1-110Hi1 degree +
%l/1001+18XMO) 1 mole where M represents an alkali metal.
なお、溶媒としてアルキルフェノールのアルカリ金属塩
と異なったアルキルフェノール類を使用すると、アルキ
ルフェノールのアルカリ金属塩の不均化反応により、生
成する４−（アルキルフェノキシ）酪酸は混合物となる
ため好ましくない。Note that if an alkylphenol different from the alkali metal salt of alkylphenol is used as a solvent, the 4-(alkylphenoxy)butyric acid produced will be a mixture due to the disproportionation reaction of the alkali metal salt of alkylphenol, which is not preferable.
本発明の方法は、前記のようにして調製された実質的に
無水のアルキルフェノールアルカリ金属塩のアルキルフ
ェノール溶液に、γ−ブチロラクトンを加えた後、加熱
撹拌し開環付加反応を行なう。In the method of the present invention, γ-butyrolactone is added to the alkylphenol solution of the substantially anhydrous alkylphenol alkali metal salt prepared as described above, followed by heating and stirring to perform a ring-opening addition reaction.
反応は実質的に無水の条件下で行なわれる。ここで、実
質的に無水の条件とは１反応系中の水の量が、用いられ
るγ−ブチロラクトン全量に対して５モル％以下、好ま
しくは３モル％以下とすることである。水の残存量が多
いと、γ−ブチロラクトンの加水分解による損失量が多
くなり本発明の効果が得られない。The reaction is conducted under substantially anhydrous conditions. Here, the substantially anhydrous condition means that the amount of water in one reaction system is 5 mol % or less, preferably 3 mol % or less, based on the total amount of γ-butyrolactone used. If the remaining amount of water is large, the amount of loss due to hydrolysis of γ-butyrolactone will be large, making it impossible to obtain the effects of the present invention.
γ−ブチロラクトンの使用量は、好ましくはアルキルフ
ェノールアルカリ金属塩１モルに対し０．８〜１．０モ
ルで、これ以下だと生産性が低下するため好ましくなく
、１．０モル以上だとγ−ブチロラクトンからの収率が
低下し好ましくない。The amount of γ-butyrolactone to be used is preferably 0.8 to 1.0 mol per 1 mol of the alkylphenol alkali metal salt; if it is less than this, productivity will decrease, which is undesirable, and if it is more than 1.0 mol, γ- This is not preferable because the yield from butyrolactone decreases.
γ−ブチロラクトンは全量を一度に、又は数回に分割し
て加えてもよいが、通常は所定の時間内で連続的に導入
される。導入終了までの時間は、好ましくは０．０５〜
４．０時間、特に好ましくは０．２〜２．０時間で、こ
れより長時間をかけて導入しても反応結果は変りなく、
工程時間が長くなり効率的でない、また、これより短時
間だと反応熱等の除去が困難となり、温度が急激に上昇
する可能性があり危険である。Although γ-butyrolactone may be added in its entirety at once or in several portions, it is usually introduced continuously within a predetermined period of time. The time until the end of the introduction is preferably 0.05~
The reaction time is 4.0 hours, particularly preferably 0.2 to 2.0 hours, and even if the reaction is introduced over a longer period of time, the reaction results will not change.
The process time is long, which is not efficient, and if the process is shorter than this, it becomes difficult to remove the reaction heat, etc., and the temperature may rise rapidly, which is dangerous.
縮合反応の温度は６０〜２５０℃、好ましくは１００〜
１８０℃で、反応温度が６０℃以下だと反応速度が著し
く低下し、反応終了まで長時間を要するので実際的でな
い、また、２５０℃以上の温度では生成物が著しく着色
するため好ましくない。The temperature of the condensation reaction is 60-250°C, preferably 100-250°C.
If the reaction temperature is 180°C and below 60°C, the reaction rate will drop significantly and it will take a long time to complete the reaction, which is impractical, and if the reaction temperature is above 250°C, the product will be markedly colored, which is not preferable.
［実施例〕
以下に実施例と比較例を示し１本発明の詳細な説明する
。[Example] Below, examples and comparative examples will be shown to provide a detailed explanation of the present invention.
実施例
２００ｎ＋ｊ三ツロフラスコに２．４−ジー第三アミル
フェノールロア、２ｇ ＋０．５モル） 、４７．５％
水酸化ナトリウム水溶液２０．２ｇ ＋０．２４モル）
を加え、 １６０℃、１７ｗｎＨｇで２時間、氷冷した
受器に水を回収しながらナトリウムフェノラートを調製
した。この際、回収された水の量は１４．８ｇで回収理
論量（１４，９ｇ＋の９９３％に相当する。Example 200n+j 2.4-di-tertiary amylphenol loa, 2g + 0.5 mole), 47.5% in a three tube flask
Sodium hydroxide aqueous solution 20.2g +0.24mol)
Sodium phenolate was prepared by adding water at 160° C. and 17 wnHg for 2 hours while collecting water in an ice-cooled receiver. At this time, the amount of water collected was 14.8 g, which corresponds to 993% of the theoretical amount of water collected (14.9 g+).
脱水された反応系に窒素ガスを導入して常圧とし、γ−
ブチロラクトン１７．２ｇ １０．２−ｔ−ル）を３０
分間かけて連続的に添加し、 １６０℃で３時間攪拌し
た。Nitrogen gas is introduced into the dehydrated reaction system to bring it to normal pressure, and γ-
Butyrolactone 17.2g 10.2-t-l) 30
The mixture was added continuously over a period of minutes and stirred at 160°C for 3 hours.
反応混合物を６０℃まで冷却し、蒸留水５０ｎ＋１と濃
硫ａ １２．８ｇｌ０．１２Ｂ −１−ル）を加エテ中
和した後、水相を分離し、さらに蒸留水５０１で２回水
洗を行ない、淡黄色のオイル１３６．７ｇを（得た。こ
のオイルを高速液体クロマトグラフで分析したところ、
原料の２．４−ジー第三アミルフェノールが７０．３ｇ
、生成物である４−（２，４−ジー第三アミルフェノキ
シ）酪酸６４．１ｇが含まれていた。これはγ−ブチロ
ラクトンからの収率で１００％に相当する。The reaction mixture was cooled to 60°C and neutralized by adding 50n+1 distilled water and 12.8gl of concentrated sulfur (0.12B-1-l), then the aqueous phase was separated and further washed twice with 501g of distilled water. , 136.7 g of light yellow oil was obtained. When this oil was analyzed by high performance liquid chromatography,
70.3g of 2.4-di-tertiary amylphenol as raw material
, 64.1 g of the product 4-(2,4-di-tertiary amylphenoxy)butyric acid was contained. This corresponds to a yield of 100% from γ-butyrolactone.
反応混合物オイルを減圧蒸留して未反応の２．４−ジー
第三アミルフェノール６４．５ｇを回収分離した後、ｎ
−へブタン１３０ｇを加えて加熱し、ついで室温まで冷
却して析出した結晶を濾別し、ｎ−へブタン６０ｇでリ
ンスした後、６０℃で３時間乾燥し、白色微結晶状の４
１２．４−ジー第三アミルフェノキシ）酪酸５８． ｌ
１１ｇを得た。γ−ブチロラクトンからの単離収率は９
１．８％で、高速液体クロマトグラフ分析による純度は
９９．３％（ＵＶ ２ｇ０Ｏｍにおける面積パーセント
）で、未反応の２．４−ジー第三アミルフェノールは全
く含まれていなかった。After distilling the reaction mixture oil under reduced pressure to recover and separate 64.5 g of unreacted 2,4-di-tertiary amylphenol, n
- Add 130 g of hebutane and heat, then cool to room temperature, filter out the precipitated crystals, rinse with 60 g of n-hebutane, dry at 60°C for 3 hours, and form white microcrystalline 4
12.4-di-tertiary amylphenoxy)butyric acid58. l
11 g was obtained. The isolated yield from γ-butyrolactone is 9
1.8%, and the purity by high performance liquid chromatography analysis was 99.3% (area percent at UV 2g0Om), containing no unreacted 2,4-di-tertiary amylphenol.
比較例
３００ｍ１なす型フラスコに、２．４−ジー第三アミル
フェノール５８．６ｇ１Ｏ，２５モル） 、４７．５％
水酸化ナトリウム水溶液２１．１ｇ１Ｏ，２５モル）及
びクロロベンゼン１５０１を加え、加熱還流しながら水
の回収を４時間行なった。これによって回収された水の
量は１４、０ｇで、回収理論量の８９．７％に相当する
。更に加熱還流を２時間続けたが、これ以上水は回収さ
れなかった。Comparative Example In a 300 ml eggplant flask, 58.6 g of 2,4-di-tertiary amylphenol (1O, 25 mol), 47.5%
21.1 g of an aqueous sodium hydroxide solution (25 mol) and 1501 chlorobenzene were added, and water was recovered for 4 hours while heating under reflux. The amount of water thus recovered was 14.0 g, corresponding to 89.7% of the theoretical amount recovered. Heating under reflux was continued for an additional 2 hours, but no more water was recovered.
反応混合物を１２０℃まで冷却し、γ−ブチロラクトン
２１．５ｇ１０．２５モル）を３０分間かけて連続的に
添加し、加熱還流下３時間撹拌した。The reaction mixture was cooled to 120° C., 21.5 g (10.25 mol) of γ-butyrolactone was added continuously over 30 minutes, and the mixture was stirred under heating under reflux for 3 hours.
反応混合物を６０℃まで冷却し、蒸留水１００層１と濃
硫酸１３．８ｇ（０，１３８モル）を加えて中和した後
、水相を分離し、更に蒸留水１００ｍ１で洗浄した。The reaction mixture was cooled to 60° C., neutralized by adding 100 layers of distilled water and 13.8 g (0,138 mol) of concentrated sulfuric acid, and then the aqueous phase was separated and further washed with 100 ml of distilled water.
溶媒のクロロベンゼンを減圧蒸留で回収し、淡褐色の固
体７５．４ｇを得た。このものを高速液体クロマトグラ
フで組成を分析したところ、未反応の２．４−ジー第三
アミルフェノール１７．５ｇと、目的とする４−１２，
４−ジー第三アミルフェノキシ）酪酸５０、３ｇを含ん
でいた。これはγ−ブチロラクトンからの収率で６２．
８％に相当する。The solvent chlorobenzene was recovered by vacuum distillation to obtain 75.4 g of a light brown solid. When this product was analyzed for composition using high performance liquid chromatography, it was found that 17.5 g of unreacted 2,4-di-tertiary amylphenol and the desired 4-12,
It contained 50.3 g of 4-di-tertiary amylphenoxy)butyric acid. This is the yield from γ-butyrolactone of 62.
This corresponds to 8%.
粗生成物にｎ−へブタン１０５ｇを加えて加熱溶解し、
室温まで冷却して析出した結晶を濾別した。Add 105g of n-hebutane to the crude product and dissolve by heating.
After cooling to room temperature, the precipitated crystals were filtered off.
得られた結晶をｎ−へブタン１００ｇで洗浄し、６０℃
で３時間乾燥し、淡黄色微結晶状の４−１２．４−ジー
第三アミルフェノキシ）酪酸４６．６ｇを得た。γ−ブ
チロラクトンからの単離収率は５８，１％で、高速液体
クロマトグラフ分析による純度は９６．５％（ＵｖＺ８
０ｎｍにおける面積％）で、未反応の２．４−ジー第三
アミルフェノールを３．３％含んでいた。The obtained crystals were washed with 100 g of n-hebutane and heated at 60°C.
The mixture was dried for 3 hours to obtain 46.6 g of pale yellow microcrystalline 4-12.4-di-tertiary amylphenoxy)butyric acid. The isolated yield from γ-butyrolactone was 58.1%, and the purity by high performance liquid chromatography analysis was 96.5% (UvZ8
It contained 3.3% of unreacted 2.4-di-tertiary amylphenol (area % at 0 nm).
［発明の効果］
本発明の方法により、γ−ブチロラクトンの加水分解等
の副反応を抑え、高収率で簡便、かつ、経済的に４−（
アルキルフェノキシ）酪酸を製造することができる。[Effects of the Invention] The method of the present invention suppresses side reactions such as hydrolysis of γ-butyrolactone, and easily and economically produces 4-(
Alkylphenoxy)butyric acid can be produced.
Claims (2)
ロラクトンを反応させて４−フェノキシ酪酸類を製造す
る方法において、過剰量のアルキルフェノールの存在下
に、実質的に無水の状態でγ−ブチロラクトンを反応さ
せることを特徴とする４−（アルキルフェノキシ）酪酸
の製造方法。(1) In the method of producing 4-phenoxybutyric acids by reacting γ-butyrolactone with an alkali metal salt of alkylphenol, γ-butyrolactone is reacted in a substantially anhydrous state in the presence of an excess amount of alkylphenol. A method for producing 4-(alkylphenoxy)butyric acid, characterized by:
ロラクトンを反応させて４−フェノキシ酪酸類を製造す
る方法において、アルキルフェノール１モルに対してア
ルカリ金属水酸化物を０．１１〜０．８０モル加え、減
圧下に実質的に無水状態になるまで水分を除去した後、
γ−ブチロラクトンを反応させることを特徴とする４−
（アルキルフェノキシ）酪酸の製造方法。(2) In a method for producing 4-phenoxybutyric acids by reacting an alkali metal salt of alkylphenol with γ-butyrolactone, 0.11 to 0.80 mol of alkali metal hydroxide is added to 1 mol of alkylphenol, and the pressure is reduced. After removing moisture until the bottom is virtually anhydrous,
4- characterized by reacting γ-butyrolactone
A method for producing (alkylphenoxy)butyric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21942088A JPH0267245A (en) | 1988-09-01 | 1988-09-01 | Production of 4-(alkylphenoxy)butyric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21942088A JPH0267245A (en) | 1988-09-01 | 1988-09-01 | Production of 4-(alkylphenoxy)butyric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0267245A true JPH0267245A (en) | 1990-03-07 |
Family
ID=16735113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21942088A Pending JPH0267245A (en) | 1988-09-01 | 1988-09-01 | Production of 4-(alkylphenoxy)butyric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0267245A (en) |
-
1988
- 1988-09-01 JP JP21942088A patent/JPH0267245A/en active Pending
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