JPH0413644A - Production of cyclohexanediones - Google Patents
Production of cyclohexanedionesInfo
- Publication number
- JPH0413644A JPH0413644A JP2117862A JP11786290A JPH0413644A JP H0413644 A JPH0413644 A JP H0413644A JP 2117862 A JP2117862 A JP 2117862A JP 11786290 A JP11786290 A JP 11786290A JP H0413644 A JPH0413644 A JP H0413644A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- pressure
- cyclohexanediones
- solvent
- dihydric phenols
- 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
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical class O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 150000002989 phenols Chemical class 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- -1 aliphatic secondary Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 239000010948 rhodium Substances 0.000 claims abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960001755 resorcinol Drugs 0.000 abstract description 10
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SKERYXCINSLNTC-UHFFFAOYSA-N 3-(dibutylamino)cyclohex-2-en-1-one Chemical compound CCCCN(CCCC)C1=CC(=O)CCC1 SKERYXCINSLNTC-UHFFFAOYSA-N 0.000 description 2
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 description 2
- HFLGBNBLMBSXEM-UHFFFAOYSA-N 4-Ethyl-1,2-benzenediol Chemical compound CCC1=CC=C(O)C(O)=C1 HFLGBNBLMBSXEM-UHFFFAOYSA-N 0.000 description 2
- FNYDIAAMUCQQDE-UHFFFAOYSA-N 4-methylbenzene-1,3-diol Chemical compound CC1=CC=C(O)C=C1O FNYDIAAMUCQQDE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LAVPWYRENKSWJM-UHFFFAOYSA-N 4-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=C(O)C(O)=C1 LAVPWYRENKSWJM-UHFFFAOYSA-N 0.000 description 1
- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 description 1
- WYVMDJWLFVQZAL-UHFFFAOYSA-N 4-propan-2-ylbenzene-1,2-diol Chemical compound CC(C)C1=CC=C(O)C(O)=C1 WYVMDJWLFVQZAL-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- JBYQSYLXSFHOMT-UHFFFAOYSA-N 5-butan-2-ylbenzene-1,3-diol Chemical compound CCC(C)C1=CC(O)=CC(O)=C1 JBYQSYLXSFHOMT-UHFFFAOYSA-N 0.000 description 1
- JOZMGUQZTOWLAS-UHFFFAOYSA-N 5-butylbenzene-1,3-diol Chemical compound CCCCC1=CC(O)=CC(O)=C1 JOZMGUQZTOWLAS-UHFFFAOYSA-N 0.000 description 1
- MSFGJICDOLGZQK-UHFFFAOYSA-N 5-ethylbenzene-1,3-diol Chemical compound CCC1=CC(O)=CC(O)=C1 MSFGJICDOLGZQK-UHFFFAOYSA-N 0.000 description 1
- RKCBNCOFPKXLIQ-UHFFFAOYSA-N 5-propan-2-ylbenzene-1,3-diol Chemical compound CC(C)C1=CC(O)=CC(O)=C1 RKCBNCOFPKXLIQ-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- MWBPRDONLNQCFV-UHFFFAOYSA-N Tri-allate Chemical group CC(C)N(C(C)C)C(=O)SCC(Cl)=C(Cl)Cl MWBPRDONLNQCFV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- CYQYCASVINMDFD-UHFFFAOYSA-N n,n-ditert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)N(C(C)(C)C)C(C)(C)C CYQYCASVINMDFD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater 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
- 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】
皮呈上■剋里立団
本発明は、シクロヘキサンジオン類の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing cyclohexanediones.
ｌ米■肢歪
医薬、農薬、感熱感圧性染料の製造原料として有用な１
．３−シクロヘキサンジオンは、例えば、ラネーニッケ
ル触媒の存在下に、レゾルシンのモノナトリウム塩を高
圧の水素を用いて水添することによって得ることができ
ることが知られている（Ｏｒｇ、 ５ｙｎｔｈｅｓｉｓ
、 Ｃｏｌ、 Ｖｏｌ、 ３． ｐ、２７８） ＊
しかし、この方法によれば、上記したように、高圧の水
素下に反応を行なうことが必要であるほか、反応終了後
、中和反応を必要とし、その結果、生成物と等モルのナ
トリウム塩を含む廃水を生じるので、工業的に実施する
には、反応装置及び廃水処理の点から、不利である。1 Useful as a raw material for manufacturing limb strain medicines, agricultural chemicals, and heat- and pressure-sensitive dyes
．． It is known that 3-cyclohexanedione can be obtained, for example, by hydrogenating the monosodium salt of resorcinol using high pressure hydrogen in the presence of a Raney nickel catalyst (Org, 5ynthesis
, Col, Vol, 3. p, 278) *
However, according to this method, as mentioned above, it is necessary to carry out the reaction under high pressure hydrogen, and after the reaction is completed, a neutralization reaction is required, and as a result, the sodium salt is equimolar to the product. Since this produces wastewater containing
曇 を′するための
本発明は、従来のシクロヘキサンジオン類、特に、１．
３−シクロヘキサンジオンの製造における上記した問題
を解決するためになされたものであって、脂肪族アミン
の共存下に、二価フェノール類を接触水素化することに
よって、低圧の水素下でシクロヘキサンジオン類を得る
ことができることを見出して、本発明に至ったものであ
る。The present invention for removing haze uses conventional cyclohexanediones, particularly 1.
This was done in order to solve the above-mentioned problems in the production of 3-cyclohexanediones, and by catalytic hydrogenation of dihydric phenols in the coexistence of aliphatic amines, cyclohexanediones can be produced under low pressure of hydrogen. The present invention was developed based on the discovery that the following can be obtained.
”するための
本発明によるシクロヘキサンジオン類の製造方法は、二
価フェノール類に溶剤中、第■族金属からなる触媒及び
脂肪族第２級アミン又は第３級アミンの存在下に水素を
反応させることを特徴とする。The method for producing cyclohexanediones according to the present invention involves reacting dihydric phenols with hydrogen in a solvent in the presence of a catalyst consisting of a Group Ⅰ metal and an aliphatic secondary amine or tertiary amine. It is characterized by
本発明において、二価フェノール類としては、例えば、
ハイドロキノン、レゾルシン、カテコール等の無置換二
価フェノール類、２−メチルハイドロキノン、４−メチ
ルレゾルシン、５−メチルレゾルシン、５−エチルレゾ
ルシン、５−イソプロピルレゾルシン、５−ｎ−ブチル
レゾルシン、５−ｓｅｃ−ブチルレゾルシン、５−ｔｅ
ｒｔ−ブチルレゾルシン、３−メチルカテコール、４−
メチルカテコール、４−エチルカテコール、４−イソプ
ロピルカテコール、４−ｎ−ブチルカテコール、４−ｓ
ｅｃ−ブチルカテコール、４−ｔｅｒｔ−ブチルカテコ
ール等のアルキル置換二価フェノール等類が用いられる
。これらのなかでは、無置換二価フェノール類が好まし
く、特に、レゾルシンが好ましく用いられる。In the present invention, examples of dihydric phenols include:
Unsubstituted dihydric phenols such as hydroquinone, resorcinol, and catechol, 2-methylhydroquinone, 4-methylresorcinol, 5-methylresorcinol, 5-ethylresorcinol, 5-isopropylresorcinol, 5-n-butylresorcinol, 5-sec- Butyl resorcinol, 5-te
rt-butylresorcin, 3-methylcatechol, 4-
Methylcatechol, 4-ethylcatechol, 4-isopropylcatechol, 4-n-butylcatechol, 4-s
Alkyl-substituted dihydric phenols such as ec-butylcatechol and 4-tert-butylcatechol are used. Among these, unsubstituted dihydric phenols are preferred, and resorcinol is particularly preferably used.
脂肪族第２級アミン又は第３級アミンは、好ましくは、
一般式
％式％
（式中、Ｒ１は水素又は炭素数１〜５のアルキル基を示
し、Ｒ２及びＲ３はそれぞれ独立に炭素数１〜５のアル
キル基を示す。）
で表わされる。The aliphatic secondary amine or tertiary amine is preferably
It is represented by the general formula % formula % (wherein R1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R2 and R3 each independently represent an alkyl group having 1 to 5 carbon atoms).
従って、好ましい第２級アミンとして、例えば、ジメチ
ルアミン、ジエチルアミン、ジ−ｎ−プロピルアミン、
ジイソプロピルアミン、ジ−ｎ−ブチルアミン、ジー５
ｅｃ−ブチルアミン、ジーｔｅｒ ｔ−ブチルアミン、
シアミルアミン等を挙げることができ、また、第３級ア
ミンとしては、例えば、トリメチルアミン、トリエチル
アミン、トリーｎ−プロピルアミン、トリイソプロピル
アミン、トリーｎ−ブチルアミン、トリー５ｅｃ−ブチ
ルアミン、トリーｔｅｒｔ−ブチルアミン、トリアミル
アミン等を挙げることができる。Therefore, preferred secondary amines include dimethylamine, diethylamine, di-n-propylamine,
Diisopropylamine, di-n-butylamine, di-5
ec-butylamine, tert-butylamine,
Examples of tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-5ec-butylamine, tri-tert-butylamine, and triamyl. Examples include amines and the like.
このような脂肪族アミンは、二価フェノール類に対して
、モル比にて０．５〜１．５の範囲で用いられる。Such aliphatic amines are used in a molar ratio of 0.5 to 1.5 with respect to dihydric phenols.
本発明においては、反応は、溶剤の存在下に、周期律表
第■族金属からなる触媒を用いて、行なわれる。触媒と
しては、特に、パラジウム、白金、ルテニウム又はロジ
ウムが好ましく用いられる。In the present invention, the reaction is carried out in the presence of a solvent using a catalyst consisting of a metal from Group 1 of the periodic table. As the catalyst, palladium, platinum, ruthenium or rhodium is particularly preferably used.
なかでも、前二者が好ましい、触媒の使用量は、二価フ
ェノール類に対して、モル比にて０．００１〜０．１の
範囲が好適である。Among them, the former two are preferred, and the amount of catalyst used is preferably in the range of 0.001 to 0.1 in terms of molar ratio to the dihydric phenols.
溶剤としては、例えば、ベンゼン、トルエン、キシレン
のような芳香族炭化水素、メタノール、エタノール、イ
ソプロパツール等のような脂肪族低級アルコール、これ
らの水溶液又は水等が用いられるが、特に、目的とする
シクロヘキサンジオン類を高選択率にて得ることができ
る水が好ましく用いられる。溶剤は、好ましくは、二価
フェノール類に対して、重量比にて１以上の範囲、通常
、１〜３の範囲で用いられる。二価フェノール類に対し
て、溶剤量が重量比で１よりも小さいときは、反応成績
が著しく低下する。Examples of solvents used include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic lower alcohols such as methanol, ethanol, and isopropanol, and aqueous solutions or water of these. Preferably, water is used since it can obtain cyclohexanediones with high selectivity. The solvent is preferably used in a weight ratio of 1 or more, usually 1 to 3, relative to the dihydric phenol. When the weight ratio of the solvent to the dihydric phenol is less than 1, the reaction results are significantly reduced.
反応は、常圧乃至２０ｋｇ／ｃ′ｌｌ１Ｇの水素圧下に
、通常、０．５〜５時間、好ましくは、０．５〜２時間
にわたって行なわれる。水素は、反応系に一括して封入
してもよく、或いは連続して又は断続的に反応系に加え
てもよい。反応温度は、常温から１４０°Ｃ１好ましく
は５０〜１１０℃の範囲である。The reaction is carried out under a hydrogen pressure of from normal pressure to 20 kg/c'll1G for usually 0.5 to 5 hours, preferably 0.5 to 2 hours. Hydrogen may be enclosed in the reaction system all at once, or may be added to the reaction system continuously or intermittently. The reaction temperature ranges from room temperature to 140°C, preferably from 50 to 110°C.
このようにして生成するシクロヘキサンジオン類は、反
応液にベンゼン、トルエン、キシレン等の芳香族炭化水
素を加えた後、水で抽出し、更に、再結晶を行なうこと
によって、容易に分離精製することができる。The cyclohexanediones produced in this way can be easily separated and purified by adding aromatic hydrocarbons such as benzene, toluene, xylene, etc. to the reaction solution, extracting with water, and further recrystallizing. I can do it.
本発明の方法によれば、用いる脂肪族アミンに対応して
、目的とするシクロヘキサンジオン類と共に、Ｎ、Ｎ−
ジアルキルアミノ−１−シクロヘキセノンが生成する。According to the method of the present invention, N, N-
Dialkylamino-1-cyclohexenone is produced.
このＮ、Ｎ−ジアルキルアミノ−１−シクロヘキセノン
は、例えば、Ｎ、Ｎ−ジアルキルアミノフェノール類の
製造のための前駆体として有用である。従って、本発明
の方法は、二価フェノール類からかかるＮ、Ｎ−ジアル
キルアミノ−１−シクロヘキセノンの製造方法としても
有用である。This N,N-dialkylamino-1-cyclohexenone is useful, for example, as a precursor for the production of N,N-dialkylaminophenols. Therefore, the method of the present invention is also useful as a method for producing N,N-dialkylamino-1-cyclohexenone from dihydric phenols.
光里■四釆
以上のように、本発明の方法によれば、二価フェノール
類を触媒の存在下に水素化して、対応するシクロヘキサ
ンジオン類を製造するに際して、第２級又は第３級アミ
ンを共存させることによって、低圧の水素下にシクロヘ
キサンジオンを高選択率及び高収率にて得ることができ
る。As described above, according to the method of the present invention, when dihydric phenols are hydrogenated in the presence of a catalyst to produce corresponding cyclohexanediones, secondary or tertiary amines are not added. By allowing them to coexist, cyclohexanedione can be obtained with high selectivity and high yield under low pressure hydrogen.
１施■
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLE 1 The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
１００ｍｌ容量耐圧オートクレーブにレゾルシン５．５
０ｇ（５０ミリモル）、ジ−ｎ−ブチルアミン９．６９
ｇ（７５ミリモル）、５％パラジウム／炭素（日本エン
ゲルハルト−製にタイプ）１．０６４ｇ（０，５ミリモ
ル）及び水１１．０ｇ（水に対する重量比２．０）を仕
込み、水素圧１５ｋｇ／ｃ７Ｇの下に１００°Ｃの油浴
に浸し、１．５時間反応させた。Example 1 Resorcinol 5.5 in a 100ml capacity pressure autoclave
0 g (50 mmol), di-n-butylamine 9.69
(75 mmol), 1.064 g (0.5 mmol) of 5% palladium/carbon (type manufactured by Nippon Engelhardt) and 11.0 g of water (weight ratio to water 2.0), hydrogen pressure 15 kg/ It was immersed in a 100°C oil bath under c7G and allowed to react for 1.5 hours.
反応終了後、反応液にメタノール２０＋１を加え、触媒
を濾別した後、ガスクロマトグラフィーにて分析した結
果、１，３−シクロヘキサンジオンの生成量は４．３９
ｇ（レゾルシン基準７８．３モル％）、Ｎ、Ｎ−ジブチ
ルアミノ−１−シクロヘキセン−３オンの生成量は０．
７６ｇ（レゾルシン基準６．８モル％）、未反応レゾル
シン量は０．０２ｇ（レゾルシン転化率９９．６％）で
あった。選択率は７８゜６％であった。After the reaction was completed, 20+1 methanol was added to the reaction solution, the catalyst was filtered off, and as a result of gas chromatography analysis, the amount of 1,3-cyclohexanedione produced was 4.39.
g (78.3 mol% based on resorcinol), the amount of N,N-dibutylamino-1-cyclohexen-3one produced was 0.
The amount of unreacted resorcin was 0.02 g (resorcin conversion rate 99.6%). The selectivity was 78.6%.
上記メタノール溶液を濃縮した後、トルエン１００ｍ１
を加えて、水２５ｍ１で４回、抽出を行なった。抽出し
た水相を脱水濃縮して、黄色結晶を得、これを更にトル
エン５０１から再結晶して、純度９６．１％の１，３−
シクロヘキサンジオン３．８５ ｇを淡黄色結晶として
得た。After concentrating the above methanol solution, 100ml of toluene
was added and extracted four times with 25 ml of water. The extracted aqueous phase was dehydrated and concentrated to obtain yellow crystals, which were further recrystallized from toluene 501 to obtain 1,3-
3.85 g of cyclohexanedione was obtained as pale yellow crystals.
一方、トルエン相を脱溶側し、蒸留して、純度９７％の
Ｎ、Ｎ−ジブチルアミノ−１−シクロヘキセン−３−オ
ン０．６７ ｇを得た。On the other hand, the toluene phase was removed and distilled to obtain 0.67 g of N,N-dibutylamino-1-cyclohexen-3-one with a purity of 97%.
実施例２〜６及び比較例１〜２
実施例１と同様にして、第１表に示す反応条件にて、レ
ゾルシンについて反応を行なった。但し、すべての実施
例及び比較例において、触媒として、レゾルシンに対す
るモル比０．０１の量で５％パラジウム／炭素を用いて
、反応を１００°Ｃで１時間行なった。結果を第１表に
示す。Examples 2 to 6 and Comparative Examples 1 to 2 In the same manner as in Example 1, resorcinol was reacted under the reaction conditions shown in Table 1. However, in all Examples and Comparative Examples, 5% palladium/carbon was used as a catalyst in an amount of 0.01 molar ratio to resorcinol, and the reaction was carried out at 100° C. for 1 hour. The results are shown in Table 1.
特許出願人 三井石油化学工業株式会社代理人 弁理士
牧 野 逸 部Patent applicant Mitsui Petrochemical Industries Co., Ltd. Agent Patent attorney Itsube Makino
Claims (4)
る触媒及び脂肪族第２級アミン又は第３級アミンの存在
下に水素を反応させることを特徴とするシクロヘキサン
ジオン類の製造方法。(1) A method for producing cyclohexanediones, which comprises reacting dihydric phenols with hydrogen in a solvent in the presence of a catalyst made of a Group VIII metal and an aliphatic secondary amine or tertiary amine.
する請求項第１項記載の方法。(2) The method according to claim 1, wherein the dihydric phenol is resorcinol.
ムであることを特徴とする請求項第１項記載の方法。(3) The method according to claim 1, wherein the catalyst is palladium, platinum, ruthenium or rhodium.
の方法。(4) The method according to claim 1, wherein the solvent is water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2117862A JPH0413644A (en) | 1990-05-07 | 1990-05-07 | Production of cyclohexanediones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2117862A JPH0413644A (en) | 1990-05-07 | 1990-05-07 | Production of cyclohexanediones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0413644A true JPH0413644A (en) | 1992-01-17 |
Family
ID=14722136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2117862A Pending JPH0413644A (en) | 1990-05-07 | 1990-05-07 | Production of cyclohexanediones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0413644A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014163080A1 (en) * | 2013-04-05 | 2014-10-09 | 三井化学株式会社 | Method for producing cyclohexanone compound |
-
1990
- 1990-05-07 JP JP2117862A patent/JPH0413644A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014163080A1 (en) * | 2013-04-05 | 2014-10-09 | 三井化学株式会社 | Method for producing cyclohexanone compound |
| US9481625B2 (en) | 2013-04-05 | 2016-11-01 | Mitsui Chemicals, Inc. | Process for producing cyclohexanone compound |
| JPWO2014163080A1 (en) * | 2013-04-05 | 2017-02-16 | 三井化学株式会社 | Method for producing cyclohexanone compound |
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