JPH04103550A - Production of dialkyl hydroquinone - Google Patents
Production of dialkyl hydroquinoneInfo
- Publication number
- JPH04103550A JPH04103550A JP2222214A JP22221490A JPH04103550A JP H04103550 A JPH04103550 A JP H04103550A JP 2222214 A JP2222214 A JP 2222214A JP 22221490 A JP22221490 A JP 22221490A JP H04103550 A JPH04103550 A JP H04103550A
- Authority
- JP
- Japan
- Prior art keywords
- hydroquinone
- olefin
- sulfonic acid
- strongly acidic
- yield
- 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims description 13
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 abstract description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 229940069096 dodecene Drugs 0.000 description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- -1 ■-dodecene Chemical compound 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- ADOQBZAVKYCFOI-HWKANZROSA-N (E)-2-dodecene Chemical compound CCCCCCCCC\C=C\C ADOQBZAVKYCFOI-HWKANZROSA-N 0.000 description 1
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical compound CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- OOKDYUQHMDBHMB-UHFFFAOYSA-N 3,6-dichloro-2-methoxybenzoic acid;2-(2,4-dichlorophenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CNC.COC1=C(Cl)C=CC(Cl)=C1C(O)=O.OC(=O)COC1=CC=C(Cl)C=C1Cl OOKDYUQHMDBHMB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- OBDUMNZXAIUUTH-UHFFFAOYSA-N trans-2-tetradecene Natural products CCCCCCCCCCCC=CC OBDUMNZXAIUUTH-UHFFFAOYSA-N 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はハイドロキノンとオレフィンとを反応させて、
高収率でジアルキルハイドロキノンを得る製造方法に関
する。[Detailed Description of the Invention] [Industrial Application Field] The present invention involves reacting hydroquinone with an olefin,
The present invention relates to a production method for obtaining dialkylhydroquinone in high yield.
従来ハイドロキノンとオレフィンとからジアルキルハイ
ドロキノンを製造する方法としては、塩化アルミニウム
、硫酸、弗化水素、三弗化硼素等を触媒として用いる方
法が知られている。Conventionally, as a method for producing dialkylhydroquinone from hydroquinone and an olefin, a method using aluminum chloride, sulfuric acid, hydrogen fluoride, boron trifluoride, etc. as a catalyst is known.
しかし、これらの触媒は、いずれも腐蝕性を有するので
、反応後にアルカリ洗浄等の複雑な後処理を必要とする
。又、オレフィンとしてａ−オレフィンを用いてジアル
キルハイドロキノンを製造する際には、これら上述の触
媒では十分な収率を得ることができない。However, all of these catalysts are corrosive and require complicated post-treatments such as alkaline cleaning after the reaction. Furthermore, when producing dialkylhydroquinone using an a-olefin as the olefin, a sufficient yield cannot be obtained with these above-mentioned catalysts.
一方、これらの欠点を改良するものとして、特公昭４６
−４２８９０号には、酸活性モンモリロナイト触媒によ
るジアルキルハイドロキノンの製造方法が開示されてい
る。On the other hand, as a way to improve these shortcomings,
No. 42,890 discloses a method for producing dialkylhydroquinone using an acid-activated montmorillonite catalyst.
しかしながら、この触媒を用いた場合には、より高い反
応温度が必要てあり、通常１６０°Ｃ以上の反応温度を
必要とし、工業的生産の場合には加熱を直火等で行わね
ばならず、特殊な装置が必要であった。However, when this catalyst is used, a higher reaction temperature is required, usually a reaction temperature of 160°C or higher, and in the case of industrial production, heating must be done with an open flame etc. Special equipment was required.
従って本発明の目的は、ハイドロキノンとオレフィンと
を反応させてジアルキルハイドロキノンを製造するに際
し、簡便かつ高収率で、しかも工業的に生産する場合に
も特殊な装置を必要としないジアルキルハイドロキノン
の製造方法を提供することにある。Therefore, an object of the present invention is to produce a dialkylhydroquinone by reacting hydroquinone with an olefin, which is simple and has a high yield, and which does not require any special equipment even in the case of industrial production. Our goal is to provide the following.
上記目的は、ハイドロキノンと炭素数６〜３０のオレフ
ィンとを反応させてジアルキルハイドロキノンを製造す
るに際し、強酸性ポリスチレン系スルホン酸型カチオン
樹脂を用いることを特徴とするジアルキルハイドロキノ
ンの製造方法によって達成される。The above object is achieved by a method for producing dialkyl hydroquinone, which is characterized in that a strongly acidic polystyrene-based sulfonic acid type cationic resin is used when producing dialkyl hydroquinone by reacting hydroquinone with an olefin having 6 to 30 carbon atoms. .
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で用いられる炭素数６〜３０のオレフィンとは、
炭素数６〜３０の炭素−炭素二重結合を有する化合物で
あり、例えばｌ−ヘキセン、２−メチル−１ペンテン、
２−メチル−２−ペンテン、ｌ−オクテン、ジイソブチ
レン、ｌ−デセン、■−ドデセン、２−ドデセン、１−
テトラデセン、２−テトラデセン、■−ヘキサデセン、
１−エイコセン、ａ−ピネン、カン７エン、リモネン、
スチレン等が挙げられる。The olefin having 6 to 30 carbon atoms used in the present invention is
A compound having a carbon-carbon double bond having 6 to 30 carbon atoms, such as l-hexene, 2-methyl-1 pentene,
2-methyl-2-pentene, l-octene, diisobutylene, l-decene, ■-dodecene, 2-dodecene, 1-
Tetradecene, 2-tetradecene, ■-hexadecene,
1-eicosene, a-pinene, can-7ene, limonene,
Examples include styrene.
これらのオレフィンの内ａ−オレフィンが好ましい。好
ましい理由としては、従来知られている塩化アルミニウ
ム、硫酸、弗化水素、三弗化硼素等の触媒を用いた場合
と比べて、本発明による強酸性ポリスチレン系スルホン
酸型カチオン樹脂を用いた場合、より高収率でジアルキ
ルハイドロキノンが得られ、本発明の効果がより一層顕
著に現れるからである。Among these olefins, a-olefins are preferred. The reason why it is preferable is that when using the strongly acidic polystyrene-based sulfonic acid type cationic resin according to the present invention, compared to using conventionally known catalysts such as aluminum chloride, sulfuric acid, hydrogen fluoride, boron trifluoride, etc. This is because dialkylhydroquinone can be obtained in a higher yield, and the effects of the present invention are even more pronounced.
ａ−オレフィンはエチレンの重合によって便宜に誘導さ
れ、従って主として偶数個の炭素原子を含むオレフィン
であり、例えば１−ヘキセン、ｌ−オクテン、ｌ−ドデ
セン、ｌ−テトラデセン、ｌ−へキサデセン、１−エイ
コセン等を挙げることができる。α-olefins are conveniently derived by the polymerization of ethylene and are therefore primarily olefins containing an even number of carbon atoms, such as 1-hexene, 1-octene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Examples include eicosene and the like.
又、σ−オレフィンは混合物であってもよく、例えば混
合Ｃ１□〜ＣＩ、ａ−オレフィン、混合Ｃ１□〜Ｃ□６
ａ−オレフィン、混合ＣＩａ〜Ｃ１，α−オレフィン、
混合ＣＩ６〜Ｃ３゜σ−オレフィン等を挙げることがで
きる。Moreover, the σ-olefin may be a mixture, for example, mixed C1□ to CI, a-olefin, mixed C1□ to C□6
a-olefin, mixed CIa to C1, α-olefin,
Mixed CI6-C3°σ-olefins and the like can be mentioned.
本発明で用いるオレフィンとハイドロキノンの割合は、
種々変動させることが可能であるが、好マシくはハイド
ロキノン１モルに対してオレフィン２〜３モルである。The ratio of olefin and hydroquinone used in the present invention is
Although it is possible to vary the amount, it is preferably 2 to 3 moles of olefin per 1 mole of hydroquinone.
本発明で用いられる強酸性ポリスチレン系スルホン酸型
カチオン樹脂は、強酸性のポリスチレン系スルホン酸型
カチオン樹脂なら何でもよく特に限定されない。The strongly acidic polystyrene-based sulfonic acid type cationic resin used in the present invention is not particularly limited and may be any strongly acidic polystyrene-based sulfonic acid type cationic resin.
上記強酸性ポリスチレン系スルホン酸型カチオン樹脂は
好ましくは水分５％（ｗ／Ｗ）以下のものであり、これ
らの例としては、アンバーリスト１５、アンバーリスト
１６、アンバーリスト１８、アンバーリスト３０（いず
れも東京有機化学社製）、ダイヤイオンＲＣＰ−１４５
ＨＤ （三菱化成社製）、バイエルに２４４１１バイエ
ルに−２６４１、バイエルに−１４８１（いずれもバイ
エル社製）等の市販の強酸性ポリスチレン系スルホン酸
型カチオン樹脂等を挙げることができる。The above-mentioned strongly acidic polystyrene-based sulfonic acid type cationic resin preferably has a moisture content of 5% (w/w) or less, and examples thereof include Amberlyst 15, Amberlyst 16, Amberlyst 18, and Amberlyst 30 (all (manufactured by Tokyo Organic Chemical Co., Ltd.), Diaion RCP-145
Examples include commercially available strongly acidic polystyrene-based sulfonic acid type cationic resins such as HD (manufactured by Mitsubishi Kasei), Bayer 24411, Bayer 2641, and Bayer 1481 (all manufactured by Bayer).
強酸性ポリスチレン系スルホン酸型カチオン樹脂の粒子
径が０．２ｍｍ以下であると、より高収率で目的とする
ジアルキルハイドロキノンが得られるので特に好ましい
。この理由は明確には判らないが、恐らく粒子径が小さ
くなる事によって表面積が増大し、そのため用いられる
オレフィンを効率よく活性化するためではないかと考え
られる。It is particularly preferable that the particle size of the strongly acidic polystyrene-based sulfonic acid type cationic resin is 0.2 mm or less, since the desired dialkylhydroquinone can be obtained in a higher yield. Although the reason for this is not clearly known, it is thought that the surface area increases as the particle size decreases, and as a result, the olefin used is efficiently activated.
本発明で用いられる強酸性ポリスチレン系スルホン酸型
カチオン樹脂とハイドロキノンとの割合は種々変動させ
ることが可能であるが、好ましくはハイドロキノン１重
量部に対して強酸性ポリスチレン系スルホン酸型カチオ
ン樹脂０．０５〜０．５重量部の割合で用いられる。The ratio of the strongly acidic polystyrene-based sulfonic acid-type cationic resin and hydroquinone used in the present invention can be varied, but preferably 0.00% of the strongly acidic polystyrene-based sulfonic acid-type cationic resin to 1 part by weight of hydroquinone. It is used in a proportion of 0.05 to 0.5 parts by weight.
反応温度は６０〜１６０°Ｃが好ましく、特に９０〜１
４０℃が好ましい。反応に要する時間は特に限定されな
いが、好ましくは３０分〜４０時間、より好ましくは１
時間〜１５時間である。The reaction temperature is preferably 60 to 160°C, especially 90 to 1
40°C is preferred. The time required for the reaction is not particularly limited, but is preferably 30 minutes to 40 hours, more preferably 1 hour.
hours to 15 hours.
本発明の製造方法において溶媒は用いても用いなくても
よいが、溶媒を用いない方が好ましい。Although a solvent may or may not be used in the production method of the present invention, it is preferable not to use a solvent.
本発明の製造方法において、オレフィンの酸化等の副反
応を抑える目的で窒素及びアルゴンガス等の不活性ガス
下で反応を行ってもよい。In the production method of the present invention, the reaction may be carried out under an inert gas such as nitrogen or argon gas in order to suppress side reactions such as olefin oxidation.
上記記載の如き本発明の方法によれば、ジアルキルハイ
ドロキノンが高収率で得られる。According to the method of the present invention as described above, dialkylhydroquinone can be obtained in high yield.
次に本発明で製造されるジアルキルハイドロキノンの代
表的具体例を示すが、本発明はこれらに限定されない。Next, typical examples of dialkylhydroquinone produced in the present invention will be shown, but the present invention is not limited thereto.
Ｑ−１
Ｈ
Ｑ
Ｑ−５
Ｈ
Ｈ
Ｈ
Ｑ−２
Ｕｔ
Ｑ）Ｉ
）（Ｑ
（ＪＨ
（’ＩＨ
Ｑ−３
○ｈ
Ｈ
Ｑ−７
（Ｊｔｌ
Ｈ
Ｑ−８
Ｈ
Ｑ−１３
Ｈ
Ｑ−９
Ｊｆｌ
ＨＱ −１４
（Ｊ）ｌ
ＨＱ −１０
ＨＱ −１１
ＨＱ −１２
混合ＣＩ２〜ＣＩ４ ｅｌ−オレフィンとハイドロキノ
ンとの反応生成物
混合Ｃ１２〜Ｃ１６α−オレフィンと
ハイドロキノンとの反応生成物
混合Ｃ１６〜Ｃ１，α−オレフィンと
・・ノＶロキノンとの反応生成物
ＨＱ −１５
Ｈ
υＨ
〔実施例〕
以下に本発明の具体的実施例を記載するが、本発明はこ
れらによって限定されるものではない。Q-1 H Q Q-5 H H H Q-2 Ut Q)I ) (Q (JH ('IH Q-3 ○h H Q-7 (Jtl H Q-8 H Q-13 H Q-9 Jfl HQ-14 (J)l HQ-10 HQ-11 HQ-12 Mixture CI2-CI4 Reaction product mixture of el-olefin and hydroquinone C12-C16α- Reaction product mixture of olefin and hydroquinone C16-C1,α- Reaction product of olefin and . . . V quinone HQ -15 H υH [Examples] Specific examples of the present invention are described below, but the present invention is not limited thereto.
例示化合物ＨＱ−４の合成
ハイドロキノン１３．８ｇ、 ｌ−ドデセン４８．８ｇ
及び表１に示す触媒４．５０ｇを混合し、窒素気流下１
２５°Ｃにて８時間反応させた。反応終了後、ガスクロ
マトグラフィーを用いて反応混合物を分析し、目的とす
る例示化合物ＨＱ−４の反応収率を求めた。Synthesis of Exemplary Compound HQ-4 Hydroquinone 13.8g, l-dodecene 48.8g
and 4.50 g of the catalyst shown in Table 1 were mixed and heated under a nitrogen stream for 1 hour.
The reaction was carried out at 25°C for 8 hours. After the reaction was completed, the reaction mixture was analyzed using gas chromatography to determine the reaction yield of the target exemplary compound HQ-4.
結果を併せて表−１に示す。The results are also shown in Table-1.
又、強酸性ポリスチレン系スルホン酸型カチオン樹脂に
ついては、その粒子径も併せて表−１に示した。Table 1 also shows the particle size of the strongly acidic polystyrene sulfonic acid type cationic resin.
表−１より明らかなように強酸性ポリスチレン系スルホ
ン酸型カチオン樹脂を用し゛た本発明は、高い反応収率
が得られる。更に粒子径が０ 、２ｍｍ以下であるバイ
エルト１４８１を用いた場合、更に高い反応収率で目的
とする例示化合物ＨＱ−４が得られる。As is clear from Table 1, the present invention using a strongly acidic polystyrene-based sulfonic acid type cationic resin can provide a high reaction yield. Furthermore, when Beiert 1481 having a particle size of 0.2 mm or less is used, the target exemplary compound HQ-4 can be obtained with an even higher reaction yield.
更に、触媒としてバイエルに−１４８１を用いたものに
ついては、以下のような手順で目的とする例示化合物Ｈ
Ｑ−４の単離・精製を行った。Furthermore, for those using Bayer -1481 as a catalyst, the desired exemplary compound H can be prepared using the following procedure.
Q-4 was isolated and purified.
反応液にトルエン７５ｍＱを加え、不溶物を濾別し、約
６０°Ｃの温水で３回洗浄した。溶媒及び過剰のｌ−ド
デセンを減圧溜去した後、減圧蒸溜によって目的とする
例示化合物ＨＱ−４を精製した。75 mQ of toluene was added to the reaction solution, and insoluble materials were filtered off and washed three times with warm water at about 60°C. After distilling off the solvent and excess 1-dodecene under reduced pressure, the target exemplary compound HQ-4 was purified by distillation under reduced pressure.
収量４７．５ｇ（収率８５％）（２１５−２５５°Ｃ／
０．９ｍｍＨｇ）構造はＮＭＲ，ＩＲ，Ｍａｓｓによ
り確認した。Yield 47.5g (yield 85%) (215-255°C/
0.9mmHg) structure was confirmed by NMR, IR, and Mass.
（比較参考例）
ハイドロキノン５５．１ｇ、 ｌ−ドデセン１９５ｇ及
び酸活性モンモリロナイト１８．２ｇを混合し、２２０
′ＣＩこて８時間反応させた。反応終了後、トルエン３
００ｍｆｆを加え、不溶物を濾別し、約６０°Ｃの温水
で３回洗浄し！；。溶媒及び過剰の１−ドデセンを減圧
溜去した後、減圧蒸溜Ｉ：よって目的とする例示化合物
ＨＱ−４を得た。(Comparative reference example) 55.1 g of hydroquinone, 195 g of l-dodecene and 18.2 g of acid-activated montmorillonite were mixed,
'CI trowel reaction was carried out for 8 hours. After the reaction is complete, toluene 3
Add 00mff, filter out insoluble matter, and wash 3 times with warm water at about 60°C! ;. After the solvent and excess 1-dodecene were distilled off under reduced pressure, the desired exemplary compound HQ-4 was obtained.
収量１０６ｇ（収率４８％８２４５〜２５８℃／ １．
６ｍｍＨｇ）構造はＮＭＲ，ＩＲ，Ｍａｓｓにより確認
した。Yield 106g (Yield 48% 8245-258℃/1.
6mmHg) structure was confirmed by NMR, IR, and Mass.
上述のように、酸活性モンモリロナイト触媒の場合には
２２０℃という高い反応温度が必要であり、収率的にも
十分でないことが判る。As mentioned above, in the case of an acid-activated montmorillonite catalyst, a high reaction temperature of 220° C. is required, and it is understood that the yield is not sufficient.
実施例２
例示化合物ＨＱ −１０の合成
ハイドロキノンｌｌｏｇ、バイエルト１４８１３６．３
ｇ及び混合ＣＩ□〜ＣＩ４σ−オレフィン（三菱化成ダ
イヤレン１２４ ； Ｃ１２Ｈ２４５８，２重量％、Ｃ
，、Ｈ２゜４１６重量％） ４１６ｇを混合し、窒素気
流下１２５°Ｃにて８時間反応させた。反応終了後、ト
ルエン６００１を加え、不溶物を濾別し、約６０℃の温
水で３回洗浄しｔ：。溶媒及び過剰のσ−オレフィンを
減圧溜去した後、減圧蒸溜によって目的とする例示化合
物ＨＱ −１０を得た。Example 2 Synthesis of Exemplary Compound HQ-10 Hydroquinone llog, Bayert 148136.3
g and mixed CI□ to CI4σ-olefin (Mitsubishi Kasei Dialene 124; C12H2458, 2% by weight, C
,,H2゜416% by weight) were mixed and reacted for 8 hours at 125°C under a nitrogen stream. After the reaction was completed, toluene 6001 was added, and insoluble materials were filtered off and washed three times with warm water at about 60°C. After the solvent and excess σ-olefin were distilled off under reduced pressure, the target exemplary compound HQ-10 was obtained by distillation under reduced pressure.
収量４１８ｇ（収率８７％８２４２〜２７５℃／ ｌ
、ＯｍｍＨｇ）構造はＮＭＲＳＩＲ及びＭａｓｓにより
確認しＩ：。Yield 418g (Yield 87% 8242-275℃/l
, OmmHg) structure was confirmed by NMRSIR and Mass I:.
実施例３
例示化合物ＨＱ −１３の合成
ハイドロキノンｌｌｏｇ、バイエルに−１４８１３６，
３ｇ及びジイソブチレン２５２ｇを混合し、窒素気流下
１２５°Ｃにて６時間反応させた。反応終了後、トルエ
ン６００ｍ１２を加え、不溶物を濾別し、約６０℃の温
水で３回洗浄した。溶媒及び過剰のオレフィンを減圧溜
去し、残渣をメタノール−水で再結晶して目的とする例
示化合物ＨＱ −１３を得た。Example 3 Synthesis of Exemplary Compound HQ-13 Hydroquinone log, Bayer-148136,
3 g and 252 g of diisobutylene were mixed and reacted for 6 hours at 125°C under a nitrogen stream. After the reaction was completed, 600 ml of toluene was added, and insoluble matter was filtered off and washed three times with warm water at about 60°C. The solvent and excess olefin were distilled off under reduced pressure, and the residue was recrystallized from methanol-water to obtain the target exemplary compound HQ-13.
収量２７１ｇ（収率８１％）融点１３０〜１３４°Ｃ構
造はＮＭＲ，ＩＲ及びＭａｓｓにより確認した。Yield: 271 g (yield: 81%) Melting point: 130-134°C The structure was confirmed by NMR, IR and Mass.
（比較参考例）
燐酸・硫酸触媒による例示化合物ＨＱ −１３の合成ハ
イドロキノンｌｌｏｇ、ジイソブチレン２５２ｇ及び酢
酸１８０ｍＲを混合し、そこに酢酸３Ｑｍ（１，８９％
燐酸２００１Ω及び９８％硫酸７５ｍ＋２の混液を滴下
し、３５℃にて６時間反応させた。反応終了後、反応液
を冷却し、析出しＩ：結晶を濾集する。この結晶をメタ
ノール−水で再結晶すること！こより目的とする例示化
合物ＨＱ −１３を得ｊ；。(Comparative Reference Example) Synthesis of Exemplified Compound HQ-13 Using Phosphoric Acid/Sulfuric Acid Catalyst 1 log of hydroquinone, 252 g of diisobutylene, and 180 mR of acetic acid were mixed, and 3Qm of acetic acid (1,89%
A mixed solution of 2001Ω of phosphoric acid and 75m+2 of 98% sulfuric acid was added dropwise, and the mixture was reacted at 35° C. for 6 hours. After the reaction is completed, the reaction solution is cooled, and precipitation I: crystals are collected by filtration. Recrystallize this crystal with methanol-water! From this, the desired exemplary compound HQ-13 was obtained.
収量１３４ｇ（収率４０％）融点１２９〜１３５℃構造
はＮＭＲＸＩＲ及びＭａｓｓにより確認した。Yield: 134 g (yield: 40%) Melting point: 129-135°C Structure was confirmed by NMRXIR and Mass.
上述のように、燐酸・硫酸触媒の場合には収率が十分と
は言えず、又、燐酸・硫酸の中和等の後処理が必要であ
る。As mentioned above, in the case of a phosphoric acid/sulfuric acid catalyst, the yield is not sufficient, and post-treatment such as neutralization of the phosphoric acid/sulfuric acid is required.
以上のように、本発明によれば簡便がっ高収率でジアル
キルハイドロキノンを製造することができる。As described above, according to the present invention, dialkylhydroquinone can be produced simply and with high yield.
Claims (2)
を反応させてジアルキルハイドロキノンを製造するに際
し、強酸性ポリスチレン系スルホン酸型カチオン樹脂を
用いることを特徴とするジアルキルハイドロキノンの製
造方法。(1) A method for producing dialkyl hydroquinone, which comprises using a strongly acidic polystyrene-based sulfonic acid type cationic resin when producing dialkyl hydroquinone by reacting hydroquinone with an olefin having 6 to 30 carbon atoms.
て、前記強酸性ポリスチレン系スルホン酸型カチオン樹
脂は粒子径が０．２ｍｍ以下の粒子であることを特徴と
する請求項１記載のジアルキルハイドロキノンの製造方
法。(2) The method for producing dialkyl hydroquinone according to claim 1, wherein the strongly acidic polystyrene-based sulfonic acid type cationic resin is a particle having a particle size of 0.2 mm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2222214A JPH04103550A (en) | 1990-08-23 | 1990-08-23 | Production of dialkyl hydroquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2222214A JPH04103550A (en) | 1990-08-23 | 1990-08-23 | Production of dialkyl hydroquinone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04103550A true JPH04103550A (en) | 1992-04-06 |
Family
ID=16778922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2222214A Pending JPH04103550A (en) | 1990-08-23 | 1990-08-23 | Production of dialkyl hydroquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04103550A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255538B1 (en) | 2000-01-05 | 2001-07-03 | Eastman Chemical Company | Process for the C-alkylation of aromatic hydroxyl compounds |
| CN115124407A (en) * | 2022-09-02 | 2022-09-30 | 西陇科学股份有限公司 | Preparation method of 2, 5-ditert octyl hydroquinone |
-
1990
- 1990-08-23 JP JP2222214A patent/JPH04103550A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255538B1 (en) | 2000-01-05 | 2001-07-03 | Eastman Chemical Company | Process for the C-alkylation of aromatic hydroxyl compounds |
| CN115124407A (en) * | 2022-09-02 | 2022-09-30 | 西陇科学股份有限公司 | Preparation method of 2, 5-ditert octyl hydroquinone |
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