JPH07110826B2 - Method for producing 2-methyl-resorcinol - Google Patents
Method for producing 2-methyl-resorcinolInfo
- Publication number
- JPH07110826B2 JPH07110826B2 JP61274871A JP27487186A JPH07110826B2 JP H07110826 B2 JPH07110826 B2 JP H07110826B2 JP 61274871 A JP61274871 A JP 61274871A JP 27487186 A JP27487186 A JP 27487186A JP H07110826 B2 JPH07110826 B2 JP H07110826B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- methylresorcinol
- acid
- catalyst
- present
- 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 - Lifetime
Links
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000011964 heteropoly acid Substances 0.000 claims description 10
- ZJVQGQWVXIMCMD-UHFFFAOYSA-N 4,6-ditert-butyl-2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C(C(C)(C)C)=CC(C(C)(C)C)=C1O ZJVQGQWVXIMCMD-UHFFFAOYSA-N 0.000 claims description 9
- 230000006210 debutylation Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZZZRZBIPCKQDQR-UHFFFAOYSA-N 2,4-ditert-butyl-6-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O ZZZRZBIPCKQDQR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MHBVEZRDCLAHPL-UHFFFAOYSA-K bis[(3-hydroxy-2-methylbenzoyl)oxy]alumanyl 3-hydroxy-2-methylbenzoate Chemical compound [Al+3].CC1=C(O)C=CC=C1C([O-])=O.CC1=C(O)C=CC=C1C([O-])=O.CC1=C(O)C=CC=C1C([O-])=O MHBVEZRDCLAHPL-UHFFFAOYSA-K 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
Description
本発明は、4,6−ジ−ターシャリブチル−２−メチルレ
ゾルシノールを脱ブチル反応させることにより２−メチ
ルレゾルシノールを製造する方法に関するものである。 ２−メチルレゾルシノールは、顔料、染料、毛髪染剤、
合成樹脂、医薬等の中間体として有用なものである。The present invention relates to a method for producing 2-methylresorcinol by subjecting 4,6-di-tert-butyl-2-methylresorcinol to a debutyl reaction. 2-methylresorcinol is a pigment, dye, hair dye,
It is useful as an intermediate for synthetic resins, medicines and the like.
4,6−ジ−ターシャリブチル−２−メチルレゾルシノー
ルの脱ブチル化反応により、２−メチルレゾルシノール
を製造する方法は、よく知られており、一般に、その時
に使用される触媒として、硫酸、アルミニウムフェノレ
ート、アルミニウムクレゾレート等のほか珪藻土、白
土、シリカアルミナ、強酸性イオン交換樹脂等が公知で
ある。 しかし、これらの触媒はたとえば硫酸の場合、脱ブチル
化反応を起こすと共に、自身が反応してスルホン酸類が
副生し、収率の低下をまねくだけでなく、得られた２−
メチルレゾルシノールを蒸留により取り出す前には、中
和処理が必要であるが、この時に発生する無機塩は蒸留
操作を円滑に進める上で、しばしば障害となっている。 又、スルホン酸類と生成したイソブチレンが反応した物
質は、蒸留操作時悪影響を及ぼすので、中和処理時に無
害化させねばならないが、そのために高温過酷な処理を
必要とする。 本発明者らは、上記実情に鑑み、鋭意研究を重ねた結
果、触媒としてヘテロポリ酸を使用することにより、高
収率でかつ工業的に有利に目的物が得られる事を見出
し、本発明を完成するに至った。The method for producing 2-methylresorcinol by the debutylation reaction of 4,6-di-tert-butyl-2-methylresorcinol is well known, and generally, as a catalyst used at that time, sulfuric acid, aluminum In addition to phenolate, aluminum cresolate, etc., diatomaceous earth, clay, silica-alumina, strongly acidic ion exchange resins, etc. are known. However, in the case of sulfuric acid, for example, these catalysts not only cause a debutylation reaction, but also react with themselves to produce sulfonic acids as a byproduct, which not only leads to a decrease in yield, but also the obtained 2-
Neutralization treatment is required before removing methylresorcinol by distillation, but the inorganic salt generated at this time is often an obstacle to the smooth progress of the distillation operation. Further, the substance obtained by reacting the sulfonic acids with the generated isobutylene has a bad influence during the distillation operation, and therefore must be rendered harmless during the neutralization treatment, which requires severe treatment at high temperature. In view of the above circumstances, the present inventors have conducted intensive studies, and as a result, by using a heteropolyacid as a catalyst, they found that the desired product can be industrially advantageously obtained in high yield, and the present invention It came to completion.
本発明の目的は、本発明に従って、4,6−ジーターシャ
リブチル−２−メチルレゾルシノールをヘテロポリ酸の
存在下、脱ブチル化反応させることにより達成される。 以下、本発明を詳細に説明する。 〈触媒〉 本発明は、触媒としてヘテロポリ酸を用いることを必須
の要件とするものである。本発明にいうヘテロポリ酸と
は、無機酸と結合してできるポリ酸のうち、２種以上の
金属によって生成される酸をいい、一般的には１種の金
属（またはヘテロ原子）を中心として、それに酸素等を
介して他の金属（ポリ原子）が配位して形成されたもの
の総称である。ここで、ヘテロ原子としては、ホウ素、
アルミニウム、ケイ素、リン、チタン、ゲルマニウム、
ヒ素、ジルコニウム、スズ、テルルなどを例示すること
ができる。また、ポリ原子としてはモリブデン、タング
ステン、バナジウム又はニオブ等を例示することができ
る。 具体的には、モリブドリン酸、モリブドケイ酸、モリブ
ドヒ酸、モリブドテルル酸、モリブドアルミン酸、タン
グストケイ酸、タングストリン酸、タングストホウ酸、
タングストチタン酸、タングストスズ酸等であり、これ
らのなかでもモリブドリン酸、モリブドケイ酸、タング
ストリン酸、タングストケイ酸等が好ましく用いられ
る。なお、これらのヘテロポリ酸は、通常水和物の形で
用いられる。 触媒の使用量は、4,6−ジターシャリブチル−２−メチ
ルレゾルシノールに対して0.01〜10重量％、好ましくは
0.1〜５重量％である。 〈反応条件〉 本発明における反応温度は、140〜300℃、好ましくは16
0〜250℃である。 反応温度は使用する触媒量と組合せて工業的に有利な反
応時間となる様に決めることができる。 反応時間は通常0.5〜10時間で充分である。 本発明の脱ブチル反応は、無溶媒でも可能であるが、溶
媒存在下でも可能である。使用される溶媒は、反応系で
レゾルシノール、触媒及び生成物に対して化学的に不活
性でなければならない。この様な性質を有する適当な溶
媒としては、ベンゼン、トルエン、キシレン、ニトロベ
ンゼン等の芳香族化合物が挙げられる。 これらの中で、ニトロベンゼンが特に好ましい溶媒とし
て使用される。 溶媒の使用量は、4,6−ジーターシャリブチル−２−メ
チルフェノールに対して0.2〜10重量倍、好ましくは0.5
〜1.0重量倍が適量である。 本発明の反応様式は、常圧、加圧もしくは減圧の回分式
または連続式のいずれでも可能であることは言うまでも
ない。本発明の反応は、窒素、ヘリウム、アルゴン等の
不活性気体の雰囲気下においても実施できる。 〈反応後の処理〉 反応後の処理は、析出する触媒を分離することにより、
再使用可能である。 分離する手段としては、濾過あるいは遠心分離あるいは
デカンターなど通常の分離手段で充分に目的を達するこ
とができる。 あるいは水酸化ナトリウム、炭酸ナトリウムなどのアル
カリで中和することにより触媒を無害化できる。これに
よって硫酸触媒使用時の様な、スルホン酸類の副生がな
いため、中和処理も高温にする必要がなく、緩和な条件
で充分である。 あるいは更に、水洗、分液によっても系内に存在するヘ
テロポリ酸を除くこともできる。 触媒除去あるいは無害化後の反応物は、触媒留去後通常
の蒸留操作を実施することにより、高収率、高純度の２
−メチルレゾルシノールを得ることができる。The object of the invention is achieved according to the invention by the debutylation reaction of 4,6-ditert-butyl-2-methylresorcinol in the presence of a heteropolyacid. Hereinafter, the present invention will be described in detail. <Catalyst> The present invention makes it essential to use a heteropolyacid as a catalyst. The heteropolyacid referred to in the present invention means an acid produced by two or more kinds of metals among polyacids formed by combining with an inorganic acid, and generally one kind of metal (or heteroatom) as a center. , Is a general term for those formed by coordinating another metal (poly atom) through oxygen or the like. Here, as the hetero atom, boron,
Aluminum, silicon, phosphorus, titanium, germanium,
Examples include arsenic, zirconium, tin, tellurium and the like. Examples of the poly atom include molybdenum, tungsten, vanadium, niobium, and the like. Specifically, molybdophosphoric acid, molybdosilicic acid, molybdoarsenic acid, molybdoteruric acid, molybdoaluminic acid, tungstosilicic acid, tungstophosphoric acid, tungstoboric acid,
Examples thereof include tungstotitanic acid and tungstostanic acid, and of these, molybdophosphoric acid, molybdosilicic acid, tungstophosphoric acid, tungstosilicic acid and the like are preferably used. Incidentally, these heteropolyacids are usually used in the form of hydrates. The amount of the catalyst used is 0.01 to 10% by weight with respect to 4,6-ditertiarybutyl-2-methylresorcinol, preferably
It is 0.1 to 5% by weight. <Reaction conditions> The reaction temperature in the present invention is 140 to 300 ° C, preferably 16
It is 0 to 250 ° C. The reaction temperature can be determined in combination with the amount of the catalyst used so that the reaction time is industrially advantageous. A reaction time of 0.5 to 10 hours is usually sufficient. The debutylation reaction of the present invention can be performed without a solvent, but can be performed in the presence of a solvent. The solvent used must be chemically inert to the resorcinol, catalyst and product in the reaction system. Suitable solvents having such properties include aromatic compounds such as benzene, toluene, xylene and nitrobenzene. Of these, nitrobenzene is used as a particularly preferred solvent. The amount of the solvent used is 0.2 to 10 times by weight, preferably 0.5 to 4,6-ditert-butyl-2-methylphenol.
An appropriate amount is ~ 1.0 times by weight. It goes without saying that the reaction mode of the present invention can be either a normal pressure, a pressure type or a reduced pressure batch type or a continuous type. The reaction of the present invention can also be carried out under an atmosphere of an inert gas such as nitrogen, helium or argon. <Treatment after the reaction> The treatment after the reaction is performed by separating the precipitated catalyst,
It can be reused. As a means for separation, a usual separation means such as filtration, centrifugation or decanter can sufficiently achieve the purpose. Alternatively, the catalyst can be rendered harmless by neutralizing with an alkali such as sodium hydroxide or sodium carbonate. As a result, since there is no by-product of sulfonic acids as in the case of using a sulfuric acid catalyst, it is not necessary to heat the neutralization treatment at high temperature, and mild conditions are sufficient. Alternatively, the heteropolyacid present in the system can be removed by washing with water and liquid separation. The reaction product after removal of the catalyst or detoxification is subjected to a normal distillation operation after removal of the catalyst to obtain a high yield, high purity 2
-Methylresorcinol can be obtained.
本発明方法で用いるヘテロポリ酸によって副反応が極め
て少なく、また反応終了後、析出するヘテロポリ酸を系
内から取り出すことによって、反応に再使用することも
でき、ヘテロポリ酸のコストを低くすることができる。 又、触媒として硫酸を使用した時の様なスルホン化物等
の不純物がなく、極めて高い収支で反応を実施すること
ができる。 〈実施例〉 以下、本発明を実施例により更に詳細に説明するが、本
発明はその要旨を越えない限り以下の実施例に限定され
るものではない。 尚、実施例中、部及び％はそれぞれ重量部及び重量％を
意味する。 実施例１ 4,6−ジ−ターシャリブチル−２−メチルレゾルシノー
ル50部（純度98％）とタングストケイ酸0.1部をフラス
コに入れ、窒素雰囲気下200℃まで昇温した。同温度に
て1.5時間保温した。留出するイソブチレンガスは深冷
・トラップに導いて回収した。 反応混合物27.5部が得られた。 ガスクロマトグラフィーにより組成分析したところ、２
−メチルレゾルシノール含量88.9％であった。これは4,
6−ジ−ターシャリブチル−２−メチルレゾルシノール
に対して95％の収率であった。 実施例２ 4,6−ジーターシャリブチル−２−メチルレゾルシノー
ル100部（純度98％）とニトロベンゼン80部をフラスコ
に仕込み、タングストリン酸0.1部を加えて、210℃まで
昇温した。同温度にて２時間保温した。100℃まで冷却
後、ソーダ灰にて中和し、濾過後、濾液をロータリーエ
バポレーターで処理して53.1部の固形物を得た。この固
形物をガスクロマトグラフィーにより分析したところ、
２−メチルレゾルシノール含量93.5％であった。これは
4,6−ジ−ターシャリブチル−２−メチルレゾルシノー
ルに対して96.5％の収率であった。 比較例 実施例１でタングストケイ酸0.1部の代わりに98％硫酸
0.8部を使用し、以下同様の条件で反応実施した。 反応混合物の重量は30.2部であり、ガスクロマトグラフ
ィー分析による組成は２−メチルレゾルシノール含量6
8.2％であった。これは4,6−ジ−ターシャリブチル−２
−メチルレゾルシノールに対して80％の収率である。 その他の成分として原料が20.2％、中間生成物が5.4
％、不明6.2％であった。By the heteropolyacid used in the method of the present invention, side reactions are extremely small, and after completion of the reaction, the precipitated heteropolyacid can be reused in the reaction by removing it from the system, and the cost of the heteropolyacid can be reduced. . In addition, the reaction can be carried out with an extremely high balance without impurities such as a sulfonated product as in the case of using sulfuric acid as a catalyst. <Examples> Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. In the examples, parts and% mean parts by weight and% by weight, respectively. Example 1 50 parts of 4,6-di-tert-butyl-2-methylresorcinol (purity 98%) and 0.1 part of tungstosilicic acid were placed in a flask and heated to 200 ° C. under a nitrogen atmosphere. It was kept at the same temperature for 1.5 hours. Distilled isobutylene gas was deep-cooled and led to a trap for recovery. 27.5 parts of reaction mixture were obtained. Composition analysis by gas chromatography showed 2
-Methylresorcinol content was 88.9%. This is 4,
The yield was 95% based on 6-di-tert-butyl-2-methylresorcinol. Example 2 100 parts of 4,6-ditert-butyl-2-methylresorcinol (purity 98%) and 80 parts of nitrobenzene were charged into a flask, 0.1 part of tungstophosphoric acid was added, and the temperature was raised to 210 ° C. The temperature was kept at the same temperature for 2 hours. After cooling to 100 ° C., the mixture was neutralized with soda ash, filtered, and the filtrate was treated with a rotary evaporator to obtain 53.1 parts of solid matter. When this solid was analyzed by gas chromatography,
The content of 2-methylresorcinol was 93.5%. this is
The yield was 96.5% based on 4,6-di-tert-butyl-2-methylresorcinol. Comparative Example In Example 1, 98% sulfuric acid was used instead of 0.1 part of tungstosilicic acid.
Using 0.8 parts, the reaction was carried out under the same conditions. The weight of the reaction mixture was 30.2 parts, and the composition by gas chromatography analysis was 2-methylresorcinol content 6
It was 8.2%. This is 4,6-di-tert-butyl-2
80% yield based on methylresorcinol. Other components are 20.2% of raw materials and 5.4 of intermediate products.
%, Unknown 6.2%.
Claims (3)
レゾルシノールをヘテロポリ酸の存在下、脱ブチル化反
応させることを特徴とする２−メチル−レゾルシノール
の製造法。1. A method for producing 2-methyl-resorcinol, which comprises subjecting 4,6-di-tert-butyl-2-methylresorcinol to a debutylation reaction in the presence of a heteropolyacid.
シャリブチル−２−メチルレゾルシノールに対して0.01
〜10重量％である特許請求の範囲第１項に記載の方法。2. The amount of heteropolyacid used is 0.01 with respect to 4,6-di-tertiarybutyl-2-methylresorcinol.
The method according to claim 1, wherein the method is -10% by weight.
の範囲第１項又は第２項に記載の方法。3. The method according to claim 1 or 2, wherein the reaction temperature is 140 ° C to 300 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61274871A JPH07110826B2 (en) | 1986-11-18 | 1986-11-18 | Method for producing 2-methyl-resorcinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61274871A JPH07110826B2 (en) | 1986-11-18 | 1986-11-18 | Method for producing 2-methyl-resorcinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63130546A JPS63130546A (en) | 1988-06-02 |
| JPH07110826B2 true JPH07110826B2 (en) | 1995-11-29 |
Family
ID=17547721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61274871A Expired - Lifetime JPH07110826B2 (en) | 1986-11-18 | 1986-11-18 | Method for producing 2-methyl-resorcinol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07110826B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0558931A (en) * | 1991-08-30 | 1993-03-09 | Sumitomo Chem Co Ltd | Production of 2-methylresorsinol and 2-methyl-1,3-cyclohexanedione |
-
1986
- 1986-11-18 JP JP61274871A patent/JPH07110826B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63130546A (en) | 1988-06-02 |
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