JPH0713035B2 - Process for producing β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid alkyl ester - Google Patents
Process for producing β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid alkyl esterInfo
- Publication number
- JPH0713035B2 JPH0713035B2 JP62114258A JP11425887A JPH0713035B2 JP H0713035 B2 JPH0713035 B2 JP H0713035B2 JP 62114258 A JP62114258 A JP 62114258A JP 11425887 A JP11425887 A JP 11425887A JP H0713035 B2 JPH0713035 B2 JP H0713035B2
- Authority
- JP
- Japan
- Prior art keywords
- butyl
- mol
- methylphenyl
- hydroxy
- propionic acid
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 15
- 239000003054 catalyst Substances 0.000 claims description 19
- -1 t-butyl-4-hydroxy-5-methylphenyl Chemical group 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 claims description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000006227 byproduct Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QWVNSESNLIQMSH-UHFFFAOYSA-M lithium 2-tert-butyl-6-methylphenolate Chemical compound C(C)(C)(C)C1=C([O-])C(=CC=C1)C.[Li+] QWVNSESNLIQMSH-UHFFFAOYSA-M 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- LSAZFRWHTISISY-UHFFFAOYSA-M potassium 2-tert-butyl-6-methylphenolate Chemical compound C(C)(C)(C)C1=C([O-])C(=CC=C1)C.[K+] LSAZFRWHTISISY-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はβ−（３−ｔ−ブチル−４−ヒドロキシ−５−
メチルフェニル）プロピオン酸アルキルエステルの改良
された製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to β- (3-t-butyl-4-hydroxy-5-
It relates to an improved process for the preparation of methylphenyl) propionic acid alkyl esters.
β−（3,5−ジアルキル−４−ヒドロキシフェニル）プ
ロピオン酸アルキルエステルは、それ自身酸化防止剤と
して有用であるばかりでなく、多価アルコールまたは多
価アミンと反応させて高分子量の酸化防止剤を製造する
中間体として有用であり、2,6−ジアルキルフェノール
とアクリル酸アルキルエステルとを反応させることによ
って得られることが知られている。The β- (3,5-dialkyl-4-hydroxyphenyl) propionic acid alkyl ester is not only useful as an antioxidant by itself, but is also a high molecular weight antioxidant when reacted with a polyhydric alcohol or a polyvalent amine. It is known to be useful as an intermediate for the production of ## STR7 ## and can be obtained by reacting a 2,6-dialkylphenol with an alkyl acrylate.
例えば、特公昭39−28324号公報には、塩基性触媒の存
在下で、2,6−ジアルキルフェノールとアクリル酸誘導
体との反応により得られることが記載されている。しか
し、この方法では収率が低く、その上、大量の反応溶媒
を必要とするため量産を目的とした場合には不利であ
り、さらに触媒を製造する際に用いる金属ナトリウム、
金属カリウムなどが取扱い上危険性が大きく好ましい方
法ではなかった。For example, JP-B-39-28324 describes that it can be obtained by reacting a 2,6-dialkylphenol with an acrylic acid derivative in the presence of a basic catalyst. However, in this method, the yield is low, and in addition, a large amount of reaction solvent is required, which is disadvantageous for the purpose of mass production. Further, sodium metal used in the production of the catalyst,
Metallic potassium is not a preferable method because it is dangerous in handling.
また、特公昭46−7933号公報には、ジメチルスルホキシ
ド中、塩基性触媒の存在下で同じ反応により約60〜87％
の収率で目的物が得られることが記載されている。該公
報記載の方法では、触媒として安価な水酸化カリウムな
どが使用できる利点はあるが、反応溶媒であるジメチル
スルホキシドは非常に高価であり、実用的な方法ではな
かった。この方法において、ジメチルスルホキシドに代
えて工業的に安価なトルエン、キシレン、メタノールな
どの一般的な溶媒と用いると、これらの塩基性触媒の存
在下ではほとんど反応は起こらないか、あるいは収率が
著しく低く、工業的な方法とはなり得ないものであっ
た。Further, JP-B-46-7933 discloses that about 60-87% by the same reaction in the presence of a basic catalyst in dimethyl sulfoxide.
It is described that the target product can be obtained in a yield of. The method described in the publication has an advantage that inexpensive potassium hydroxide or the like can be used as a catalyst, but dimethyl sulfoxide, which is a reaction solvent, is very expensive and is not a practical method. In this method, when dimethylsulfoxide is used in place of industrially inexpensive common solvents such as toluene, xylene, and methanol, almost no reaction occurs in the presence of these basic catalysts, or the yield is remarkably high. It was low and could not be an industrial method.
また、特開昭56−161350号公報には、原料フェノール化
合物１モルに対して、アルカリ金属水酸化物0.05〜0.5
モルをあらかじめ反応させ、次いでアクリル酸アルキル
エステルと反応させることにより、比較的高収率で目的
物が得られることが記載されている。しかしながら、こ
の方法では多量の塩基性触媒を使用するため、中和に要
する酸性物質の量が多く、多量の廃棄物が生成する欠点
があるばかりでなく、本発明者等の検討によれば、原料
として、２−ｔ−ブチル−６−メチルフェノールを用い
た場合には、下記の式（Ｉ）を有する副生物が比較的多
量生成する欠点があることが明らかとなった。Further, in JP-A-56-161350, an alkali metal hydroxide of 0.05 to 0.5 is used for 1 mol of a starting phenol compound.
It is described that a desired product can be obtained in a relatively high yield by reacting a mole in advance and then reacting with an acrylic acid alkyl ester. However, in this method, since a large amount of basic catalyst is used, the amount of acidic substance required for neutralization is large, and not only there is the drawback that a large amount of waste is generated, but according to the study by the present inventors, When 2-t-butyl-6-methylphenol was used as a raw material, it became clear that a by-product having the following formula (I) was produced in a relatively large amount.
上記式（Ｉ）で表される副生物は、多価アルコールまた
は多価アミンと反応させ、高分子量の酸化防止剤を製造
する際にポリマーを生成させるため、その含有量をβ−
（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニ
ル）プロピオン酸アルキルエステルに対し、0.2重量％
以下、好ましくは0.1重量％以下とすることが必要であ
る。ところが、特開昭56−161350号公報記載の方法では
真空蒸留の後においてすら上記式（Ｉ）で表される副生
物を約0.3重量％以上を含有しており、目的の純度の製
品を得るためには、煩雑でかつ収率を低下させる精密蒸
留、再結晶等の操作が必要であった。 The by-product represented by the above formula (I) is reacted with a polyhydric alcohol or a polyvalent amine to produce a polymer when producing a high molecular weight antioxidant, and therefore its content is β-.
0.2% by weight relative to (3-t-butyl-5-methyl-4-hydroxyphenyl) propionic acid alkyl ester
Hereafter, it is necessary to set it to preferably 0.1% by weight or less. However, in the method described in JP-A-56-161350, a by-product represented by the above formula (I) is contained in an amount of about 0.3% by weight or more even after vacuum distillation, and a product having a desired purity is obtained. For this purpose, operations such as precision distillation, recrystallization and the like, which are complicated and reduce the yield, were necessary.
また、前期の各公報記載の方法においては、いずれも2,
6−ジ−ｔ−ブチルフェノールを用いた実施例しか記載
されておらず、２−ｔ−ブチル−６−メチルフェノール
を用いた実施例は記載されておらず、上記問題点につい
ては全く認識されていない。In addition, in the method described in each publication in the first term,
Only the examples using 6-di-t-butylphenol are described, the examples using 2-t-butyl-6-methylphenol are not described, and the above problems are completely recognized. Absent.
本発明者等は、前述の欠点のないβ−（３−ｔ−ブチル
−４−ヒドロキシ−５−メチルフェニル）プロピオン酸
アルキルエステルの製法を検討した結果、触媒として、
２−ｔ−ブチル−６−メチルフェノール１モルに対し0.
05モル未満の少量のアルカリ金属−２−ｔ−ブチル−６
−メチルフェノキサイドを用いることにより、高純度の
目的物を高収率で製造し得ることを見出した。The present inventors have studied the production method of β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid alkyl ester which does not have the above-mentioned defects, and as a result, as a catalyst,
0.2 mol per mol of 2-t-butyl-6-methylphenol.
A small amount of alkali metal 2-t-butyl-6 less than 05 mol
It was found that by using -methylphenoxide, a high-purity target product can be produced in high yield.
即ち、本発明は２−ｔ−ブチル−６−メチルフェノール
とアクリル酸アルキルエステルとを反応させて、β−
（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニ
ル）プロピオン酸アルキルエステルを製造する際に、触
媒として、２−ｔ−ブチル−６−メチルフェノール１モ
ルに対して0.001モルないし0.05モル未満のアルカリ金
属−２−ｔ−ブチル−６−メチルフェノキサイドの存在
下に該反応を行わせることを特徴とするβ−（３−ｔ−
ブチル−４−ヒドロキシ−５−メチルフェニル）プロピ
オン酸アルキルエステルの製法を提供するものである。That is, the present invention reacts 2-t-butyl-6-methylphenol with an alkyl acrylate to give β-
When producing (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid alkyl ester, as a catalyst, 0.001 mol to less than 0.05 mol per mol of 2-t-butyl-6-methylphenol Β- (3-t-, characterized in that the reaction is carried out in the presence of the alkali metal 2-t-butyl-6-methylphenoxide.
A method for producing an alkyl ester of butyl-4-hydroxy-5-methylphenyl) propionic acid is provided.
本発明の方法により製造されるβ−（３−ｔ−ブチル−
４−ヒドロキシ−５−メチルフェニル）プロピオン酸ア
ルキルエステルは、前述の如く、劣化を受け易い物質、
例えば炭化水素油、潤滑油、その他ポリプロピレン、ポ
リエチレン、天然ゴム、合成ゴムなどの可塑性物質に対
する酸化防止剤として有用であるばかりでなく、種々の
誘導体の中間体として有用である。Β- (3-t-butyl-produced by the method of the present invention
As described above, 4-hydroxy-5-methylphenyl) propionic acid alkyl ester is a substance susceptible to deterioration,
For example, it is useful not only as an antioxidant for hydrocarbon oils, lubricating oils, and other plastic substances such as polypropylene, polyethylene, natural rubber and synthetic rubber, but also as an intermediate for various derivatives.
本発明で使用される触媒のアルカリ金属−２−ｔ−ブチ
ル−６−メチルフェノノキサイドとしては、カリウム、
ナトリウムまたはリチウム−２−ｔ−ブチル−６−メチ
ルフェノノキサイドがあげられる。As the alkali metal 2-t-butyl-6-methylphenoxide of the catalyst used in the present invention, potassium,
Sodium or lithium-2-t-butyl-6-methylphenoxide can be mentioned.
触媒の使用量は、用いられる原料フェノールに対し、0.
1モル％ないし５モル％未満、好ましくは、0.5モル％な
いし４モル％が使用される。触媒の使用量が0.1モル％
より少ないと反応の進行が著しく遅くなり、また、５モ
ル％以上使用すると前述の副生物の量が多くなるばかり
でなく、触媒の処理に多量の酸性物質を用いる必要があ
り、廃棄物が多くなる等の欠点が生じる。また、５モル
％以上の触媒を使用しても反応速度、収率等はこれ以上
改善されない。The amount of catalyst used was 0.
1 mol% to less than 5 mol%, preferably 0.5 mol% to 4 mol% are used. 0.1 mol% of catalyst used
If it is less, the reaction progresses significantly, and if it is used in an amount of 5 mol% or more, not only the amount of the by-product described above increases, but also a large amount of acidic substance needs to be used for the treatment of the catalyst, and a large amount of waste is generated However, there are some drawbacks. Further, even if 5 mol% or more of the catalyst is used, the reaction rate, yield, etc. are not further improved.
これらの触媒は、２−ｔ−ブチル−６−メチルフェノー
ルとアルカリ金属水酸化物とを直接に、又は脂肪属炭化
水素、脂環式炭化水素、芳香属炭化水素などの有機溶剤
中で加熱することにより容易に製造することができる。
また、２−ｔ−ブチル−６−メチルフェノールとアルカ
リ金属水酸化物とを、生成するアルカリ金属フェノキサ
イドの量が、２−ｔ−ブチル−６−メチルフェノール１
モルに対し0.001モルないし0.05モル未満となるような
割合で予め反応させ、これをそのまま次のアクリル酸ア
ルキルエステルとの反応に使用することもできる。These catalysts heat 2-t-butyl-6-methylphenol and an alkali metal hydroxide directly or in an organic solvent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon. Therefore, it can be easily manufactured.
In addition, the amount of alkali metal phenoxide that produces 2-t-butyl-6-methylphenol and alkali metal hydroxide is 2-t-butyl-6-methylphenol 1
It is also possible to pre-react at a ratio of 0.001 mol to less than 0.05 mol per mol, and use this as it is for the subsequent reaction with the alkyl acrylate ester.
また、触媒は実質的に無水であることが好ましく、触媒
の調製の際に生成した水は減圧及び／又は有機溶剤との
共沸蒸留により系内が実質的に無水状態になるまで除去
することが好ましい。Further, the catalyst is preferably substantially anhydrous, and the water produced during the preparation of the catalyst is removed by reduced pressure and / or azeotropic distillation with an organic solvent until the inside of the system becomes substantially anhydrous. Is preferred.
本発明に使用されるアクリル酸アルキルエステルとして
は、例えばメチル、エチル、プロピル、ブチル、ペンチ
ル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、
ウンデシル、ドデシル、トリデシル、テトラデシル、ペ
ンタデシル、ヘキサデシル、ヘプタデシル、オクタデシ
ル、ノナデシル、エイコシルエステル等が挙げられる。Examples of the alkyl acrylate used in the present invention include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl ester and the like can be mentioned.
２−ｔ−ブチル−６−メチルフェノールとアクリル酸ア
ルキルエステルの使用割合は、通常フェノール１モルに
対しアクリル酸エステル0.8〜２モルである。アクリル
酸アルキルエステルを２モル以上の大過剰に使用しても
効果は変わらず、反応終了時に除去すべきアクリル酸エ
ステルの量が増加するので好ましくない。また、アクリ
ル酸エステルの使用量を0.8モル以下とすると、フェノ
ールに対する反応率が低下し、反応終了時に除去すべき
フェノールの量が増加することとなる。The usage ratio of 2-t-butyl-6-methylphenol and alkyl acrylate is usually 0.8 to 2 mol of acrylic ester per mol of phenol. Even if the acrylic acid alkyl ester is used in a large excess of 2 mol or more, the effect does not change, and the amount of acrylic acid ester to be removed at the end of the reaction increases, which is not preferable. Further, if the amount of the acrylic ester used is 0.8 mol or less, the reaction rate with respect to phenol decreases, and the amount of phenol to be removed at the end of the reaction increases.
反応温度は室温から約200℃までの範囲から適宜選択さ
れるが、通常は70〜150℃の範囲で行うことが好まし
い。また、本反応は、常圧ないし自然発生圧力下で行わ
れるが、所望により、減圧下または加圧下で行うことも
できる。The reaction temperature is appropriately selected from the range of room temperature to about 200 ° C, but it is usually preferable to carry out in the range of 70 to 150 ° C. Further, this reaction is carried out under normal pressure or spontaneously generated pressure, but it may be carried out under reduced pressure or under pressure if desired.
反応は無溶媒でも充分に進行するので、特に溶媒を使用
する必要はないが、所望により溶媒の存在下で行うこと
もできる。溶媒としてはエーテル系、脂肪族ジアルキル
アミド系、芳香族並びに脂肪族ニトリル系、炭化水素
系、ジアルキルスルホキシド系、エステル系、ケトン
系、塩素化合物系等広範囲のものを使用し得る。溶媒の
使用量は単に溶質を溶かすに足る少量から、急激な反応
を抑制するに充分な量まで広範囲に変更することができ
る。Since the reaction proceeds sufficiently even without solvent, it is not necessary to use a solvent, but it can be carried out in the presence of a solvent if desired. As the solvent, a wide range of solvents such as ether type, aliphatic dialkylamide type, aromatic and aliphatic nitrile type, hydrocarbon type, dialkyl sulfoxide type, ester type, ketone type and chlorine compound type can be used. The amount of the solvent used can be varied over a wide range from a small amount sufficient to dissolve the solute to an amount sufficient to suppress a rapid reaction.
反応終了後触媒を除去して蒸溜すれば、再結晶等のそれ
以上の精製処理を行わずとも、目的化合物は略々純粋な
形で得られる。If the catalyst is removed and distilled after the reaction is completed, the target compound can be obtained in a substantially pure form without further purification treatment such as recrystallization.
以下に本発明を実施例によって説明するが、本発明はこ
れら実施例によって制限されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例−１ ２−ｔ−ブチル−６−メチルフェノール164g（１モ
ル）、カリウム−２−ｔ−ブチル−６−メチルフェノキ
サイド7.7g（0.035モル）を500mlフラスコに仕込み、撹
拌しながら120〜140℃で103.2g（1.2モル）のアクリル
酸メチルを滴下し、滴下終了後120〜140℃で更に５時間
撹拌した。冷却後、トルエン164gで希釈し、酢酸で中和
後水洗した。トルエン及び過剰のアクリル酸メチルを留
去し、粗生成物を得た。Example-1 2-t-butyl-6-methylphenol 164 g (1 mol) and potassium-2-t-butyl-6-methylphenoxide 7.7 g (0.035 mol) were charged into a 500 ml flask and stirred at 120-. At 140 ° C., 103.2 g (1.2 mol) of methyl acrylate was added dropwise, and after completion of the addition, the mixture was stirred at 120 to 140 ° C. for 5 hours. After cooling, it was diluted with 164 g of toluene, neutralized with acetic acid and washed with water. Toluene and excess methyl acrylate were distilled off to obtain a crude product.
粗生成物をガスクロマトグラフィーにより分析した結
果、前記式（Ｉ）で表される副生物の含有率は0.3％で
あった。As a result of analyzing the crude product by gas chromatography, the content of the by-product represented by the formula (I) was 0.3%.
この粗生成物を真空蒸留し、沸点164〜170℃/4mmHgの留
分として、230g（収率92％）のβ−（３−ｔ−ブチル−
４−ヒドロキシ−５−メチルフェニル）プロピオン酸メ
チルを得た。This crude product was subjected to vacuum distillation to obtain 230 g (yield 92%) of β- (3-t-butyl-) as a fraction having a boiling point of 164-170 ° C./4 mmHg.
Methyl 4-hydroxy-5-methylphenyl) propionate was obtained.
この精製物をガスクロマトグラフィーにより分析した結
果、前記式（Ｉ）で表される副生物の含有量は0.09％で
あった。As a result of analyzing this purified product by gas chromatography, the content of the by-product represented by the formula (I) was 0.09%.
実施例−２ ２−ｔ−ブチル−６−メチルフェノール164g（１モ
ル）、水酸化カリウム2.0g（0.035モル）及びトルエン5
0gを500mlフラスコに仕込み、還流下脱水し、略理論量
の生成水を除去した後トルエンを留去した。次いで、12
0〜140℃で103.2g（1.2モル）のアクリル酸メチルを滴
下し、滴下終了後同温度で更に５時間撹拌した。冷却
後、トルエン164gで希釈し、酢酸で中和後水洗した。ト
ルエン及び過剰のアクリル酸メチルを留去し、粗生成物
を得た。Example-2 2-t-butyl-6-methylphenol 164 g (1 mol), potassium hydroxide 2.0 g (0.035 mol) and toluene 5
0 g was placed in a 500 ml flask and dehydrated under reflux to remove an approximately theoretical amount of produced water and then distill off toluene. Then 12
103.2 g (1.2 mol) of methyl acrylate was added dropwise at 0 to 140 ° C, and after completion of the addition, the mixture was stirred at the same temperature for 5 hours. After cooling, it was diluted with 164 g of toluene, neutralized with acetic acid and washed with water. Toluene and excess methyl acrylate were distilled off to obtain a crude product.
粗生成物をガスクロマトグラフィーにより分析した結
果、前記式（Ｉ）で表される副生物の含有率は0.3％で
あった。As a result of analyzing the crude product by gas chromatography, the content of the by-product represented by the formula (I) was 0.3%.
この粗生成物を真空蒸留し、沸点164〜170℃/4mmHgの留
分として、227g（収率91％）のβ−（３−ｔ−ブチル−
４−ヒドロキシ−５−メチルフェニル）プロピオン酸メ
チルを得た。This crude product was subjected to vacuum distillation to obtain 227 g (yield 91%) of β- (3-t-butyl-) as a fraction having a boiling point of 164-170 ° C./4 mmHg.
Methyl 4-hydroxy-5-methylphenyl) propionate was obtained.
この精製物をガスクロマトグラフィーにより分析した結
果、前記式（Ｉ）で表される副生物の含有量は0.08％で
あった。As a result of analyzing this purified product by gas chromatography, the content of the by-product represented by the formula (I) was 0.08%.
比較例 水酸化カリウムを5.6g（0.1モル）と増量した他は実施
例−２と同様の操作を行い、粗生成物を得た。Comparative Example A crude product was obtained by performing the same operation as in Example-2 except that the amount of potassium hydroxide was increased to 5.6 g (0.1 mol).
粗生成物をガスクロマトグラフィーにより分析した結
果、前記式（Ｉ）で表される副生物の含有率は1.2％で
あった。As a result of analyzing the crude product by gas chromatography, the content of the by-product represented by the formula (I) was 1.2%.
この粗生成物を真空蒸留し、沸点164〜170℃/4mmHgの留
分として、224g（収率90％）のβ−（３−ｔ−ブチル−
４−ヒドロキシ−５−メチルフェニル）プロピオン酸メ
チルを得た。This crude product was subjected to vacuum distillation to obtain 224 g (yield 90%) of β- (3-t-butyl-) as a fraction having a boiling point of 164-170 ° C./4 mmHg.
Methyl 4-hydroxy-5-methylphenyl) propionate was obtained.
この精製物をガスクロマトグラフィーにより分析した結
果、前記式（Ｉ）で表される副生物の含有量は0.32％で
あった。As a result of analyzing this purified product by gas chromatography, the content of the by-product represented by the formula (I) was 0.32%.
本発明の方法によれば前記式（Ｉ）で表される副生物の
生成量は著しく少なく、減圧蒸留によるだけで充分満足
し得る約0.1％まで低減できるのに対し、従来の方法に
よる場合は前記式（Ｉ）で表される副生物の生成量が多
く、必要な0.2％以下まで副生物を減らすことができな
かった。According to the method of the present invention, the amount of the by-product represented by the formula (I) is extremely small, and it can be reduced to about 0.1% which is sufficiently satisfactory only by vacuum distillation. The amount of the by-product represented by the above formula (I) was large, and the by-product could not be reduced to the required 0.2% or less.
また、本発明の方法による目的物の収率は、従来の方法
による収率と同等以上であり、副生物の生成量が少ない
こと、触媒の中和に必要な酸性物質の量が少ないことを
併せ考えると、本発明の方法が従来の方法と比較して極
めて優れたものであることが明らかである。In addition, the yield of the target product by the method of the present invention is equal to or higher than the yield by the conventional method, the amount of by-products formed is small, and the amount of the acidic substance necessary for neutralizing the catalyst is small. Taken together, it is clear that the method of the present invention is extremely superior to the conventional methods.
Claims (1)
アクリル酸アルキルエステルとを反応させてβ−（３−
ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プ
ロピオン酸アルキルエステルを製造する際に、触媒とし
て、２−ｔ−ブチル−６−メチルフェノール１モルに対
して0.001モルないし0.05モル未満のアルカリ金属−２
−ｔ−ブチル−６−メチルフェノキサイドの存在下に該
反応を行わせることを特徴とする、β−（３−ｔ−ブチ
ル−４−ヒドロキシ−５−メチルフェニル）プロピオン
酸アルキルエステルの製法。1. 2-t-Butyl-6-methylphenol is reacted with alkyl acrylate to form β- (3-
When producing t-butyl-4-hydroxy-5-methylphenyl) propionic acid alkyl ester, as a catalyst, 0.001 mol to less than 0.05 mol of an alkali metal relative to 1 mol of 2-t-butyl-6-methylphenol is used. -2
A process for producing an alkyl ester of β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid, which comprises carrying out the reaction in the presence of -t-butyl-6-methylphenoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114258A JPH0713035B2 (en) | 1987-05-11 | 1987-05-11 | Process for producing β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid alkyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114258A JPH0713035B2 (en) | 1987-05-11 | 1987-05-11 | Process for producing β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid alkyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63277647A JPS63277647A (en) | 1988-11-15 |
| JPH0713035B2 true JPH0713035B2 (en) | 1995-02-15 |
Family
ID=14633282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62114258A Expired - Fee Related JPH0713035B2 (en) | 1987-05-11 | 1987-05-11 | Process for producing β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid alkyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713035B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02180851A (en) * | 1988-12-29 | 1990-07-13 | Yoshitomi Pharmaceut Ind Ltd | Production of alkyl beta-(3,5-dialkyl-4-hydroxyphenyl) propionate |
| JPH02180852A (en) * | 1989-01-06 | 1990-07-13 | Yoshitomi Pharmaceut Ind Ltd | Production of alkyl beta-(3,5-dialkyl-4-hydroxyphenyl) propionate |
-
1987
- 1987-05-11 JP JP62114258A patent/JPH0713035B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63277647A (en) | 1988-11-15 |
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