JPS629098B2 - - Google Patents
Info
- Publication number
- JPS629098B2 JPS629098B2 JP53051729A JP5172978A JPS629098B2 JP S629098 B2 JPS629098 B2 JP S629098B2 JP 53051729 A JP53051729 A JP 53051729A JP 5172978 A JP5172978 A JP 5172978A JP S629098 B2 JPS629098 B2 JP S629098B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- ring
- imidazolidinone
- alkali metal
- compound
- 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
Links
- 238000000034 method Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- -1 methylene compound Chemical class 0.000 claims description 15
- 150000002576 ketones Chemical class 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- JJNFHWKVZWAKEB-UHFFFAOYSA-N 1,3,4-trimethylimidazolidin-2-one Chemical compound CC1CN(C)C(=O)N1C JJNFHWKVZWAKEB-UHFFFAOYSA-N 0.000 claims description 2
- AZLXQBNSOMJQEJ-UHFFFAOYSA-N 1,3-di(propan-2-yl)imidazolidin-2-one Chemical compound CC(C)N1CCN(C(C)C)C1=O AZLXQBNSOMJQEJ-UHFFFAOYSA-N 0.000 claims description 2
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 229960005235 piperonyl butoxide Drugs 0.000 claims 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 239000012965 benzophenone Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 150000003983 crown ethers Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZSQCNVWYBBKUHS-UHFFFAOYSA-N (2,3-dimethylphenyl)-phenylmethanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1C ZSQCNVWYBBKUHS-UHFFFAOYSA-N 0.000 description 2
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical compound C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 description 2
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 description 2
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DBOLXXRVIFGDTI-UHFFFAOYSA-N 4-benzylpyridine Chemical compound C=1C=NC=CC=1CC1=CC=CC=C1 DBOLXXRVIFGDTI-UHFFFAOYSA-N 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
- 239000002841 Lewis acid Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QPOWUYJWCJRLEE-UHFFFAOYSA-N dipyridin-2-ylmethanone Chemical compound C=1C=CC=NC=1C(=O)C1=CC=CC=N1 QPOWUYJWCJRLEE-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 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
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Pyrane Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、アルカリ触媒の存在下において芳香
族メチレン化合物または複素環式メチレン化合物
（以下メチレン化合物と略称する）と酸素を反応
させて芳香族ケトンまたは複素環式ケトン（以下
ケトン誘導体と略称する）を製造する方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an aromatic ketone or a heterocyclic ketone ( The present invention relates to a method for producing a ketone derivative (hereinafter abbreviated as a ketone derivative).
ケトン誘導体は有機化合物合成中間体として工
業的に極めて有用な化合物であり、その安価な製
造方法の確立が望まれている。 Ketone derivatives are industrially extremely useful compounds as intermediates for the synthesis of organic compounds, and it is desired to establish an inexpensive method for producing them.
従来、ケトン誘導体を得るには、塩化アルミニ
ウム等のルイス酸存在下、カルボン酸クロリドと
芳香族化合物との反応による方法、芳香族メチレ
ン化合物を金属酸化物、あるいは含酸素雰囲気
下、金属触媒を用いて酸化する方法が一般的によ
く用いられる方法である。しかしながら金属を用
いる反応では金属を含む大量の排液が生成して、
処理に大きな労力を要すること、金属触媒を用い
る反応では特別な技術を必要とすることなどの欠
点がある。 Conventionally, ketone derivatives have been obtained by reacting a carboxylic acid chloride with an aromatic compound in the presence of a Lewis acid such as aluminum chloride, by reacting an aromatic methylene compound with a metal oxide, or by using a metal catalyst in an oxygen-containing atmosphere. A commonly used method is oxidation. However, in reactions using metals, a large amount of waste liquid containing metals is generated.
Disadvantages include that the treatment requires a lot of effort and that reactions using metal catalysts require special techniques.
また、含酸素雰囲気下、アルカリ触媒を用いた
極性溶媒中の反応でも目的物が得られている。溶
媒として、トリス（ジメチルアミノ）ホスフイン
オキシド（HMPA）を用いる方法（Compt.rend.
，268，419（1968））、ジフエニルスルホキシドを
用いる方法（Chem.Ind.，1316（1964））、ジメチ
ルホルムアミド（DMF）を用いる方法（J.Org.
Chem.28，410，（1963））などが知られている。
この他、４級アンモニウム塩（Tetrahedron
Lett.，2117（1977）），クラウンエーテル
（Synthesis，168（1976））を用いる方法もある。
しかしながらHMPAやクラウンエーテルは毒性
が高いこと、DMFは強アルカリに不安定である
こと、４級アンモニウム塩を用いる方法は反応時
間が長いことなどの欠点があり、工業的製法とし
ては不満足なものである。 The desired product has also been obtained by reaction in a polar solvent using an alkali catalyst under an oxygen-containing atmosphere. A method using tris(dimethylamino)phosphine oxide (HMPA) as a solvent (Compt.rend.
, 268 , 419 (1968)), a method using diphenyl sulfoxide (Chem.Ind., 1316 (1964)), a method using dimethylformamide (DMF) (J.Org.
Chem. 28 , 410, (1963)) are known.
In addition, quaternary ammonium salts (Tetrahedron
Lett., 2117 (1977)) and crown ether (Synthesis, 168 (1976)).
However, HMPA and crown ethers have drawbacks such as high toxicity, DMF is unstable in strong alkalis, and methods using quaternary ammonium salts require long reaction times, making them unsatisfactory as industrial production methods. be.
本発明者らは上記従来技術の問題点を解消し、
ケトン誘導体を工業的に高収率で得る方法につい
て種々研究し、本発明を完成するに至つた。 The present inventors solved the problems of the above-mentioned conventional technology,
The present invention has been completed through various studies on methods for industrially obtaining ketone derivatives in high yields.
すなわち、本発明は特定アルキル−２−イミダ
ゾリジノン化合物を溶媒として用い、アルカリ触
媒の存在下にメチレン化合物と酸素を反応させて
ケトン誘導体を得る方法を提供するものである。 That is, the present invention provides a method for obtaining a ketone derivative by reacting a methylene compound with oxygen in the presence of an alkali catalyst using a specific alkyl-2-imidazolidinone compound as a solvent.
本発明方法に従つて、メチレン化合物、アルカ
リ触媒および、アルキル−２−イミダゾリジノン
化合物の混合系中に、酸素または、空気を導入し
て０℃ないし220℃、好ましくは10℃ないし130℃
の温度で撹拌しながら反応させるとケトン誘導体
が高収率で得られる。反応終了後水を加えて触媒
を溶解し、無機酸もしくは有機酸で中和して溶媒
でケトン誘導体を抽出する。このようにして得ら
れた抽出液を蒸留すれば、ケトン誘導体が得られ
る。 According to the method of the present invention, oxygen or air is introduced into a mixed system of a methylene compound, an alkali catalyst, and an alkyl-2-imidazolidinone compound, and then 0°C to 220°C, preferably 10°C to 130°C.
The ketone derivative can be obtained in high yield by reacting with stirring at a temperature of . After the reaction is completed, water is added to dissolve the catalyst, neutralized with an inorganic or organic acid, and the ketone derivative is extracted with a solvent. If the extract thus obtained is distilled, a ketone derivative can be obtained.
本発明方法の出発物質として用いられるメチレ
ン化合物は、式（）ないし（）
［ただし式中、環Ａおよび環Ｂは、式（）の
場合はベンゼン環またはピリジン環より選ばれ、
式（）および式（）の場合はベンゼン環を表
し、環Ａおよび環Ｂは、互いに同一でも相異なつ
てもよい。］
で表わされる化合物である。これらのメチレン化
合物の代表的なものとしては、たとえば、ジフエ
ニルメタン、ジメチルジフエニルメタン、２−ベ
ンジルピリジン、４−ベンジルピリジン、フルオ
レン、９，10−ジヒドロアントラセンなどがあげ
られる。 The methylene compound used as a starting material for the method of the present invention has the formula () to () [In the formula, ring A and ring B are selected from a benzene ring or a pyridine ring in the case of formula (),
In the case of formula () and formula (), a benzene ring is represented, and ring A and ring B may be the same or different from each other. ] It is a compound represented by Representative examples of these methylene compounds include diphenylmethane, dimethyldiphenylmethane, 2-benzylpyridine, 4-benzylpyridine, fluorene, and 9,10-dihydroanthracene.
本発明方法で用いられるアルカリ触媒は、アル
カリ金属水酸化物およびアルカリ金属アルコキシ
ドから選択することができる。アルカリ金属水酸
化物としては、水酸化ナトリウムおよび水酸化カ
リウムがある。アルカリ金属アルコキシドとして
は、たとえばナトリウムメトキシド、ナトリウム
エトキシド、カリウム−ｔ−ブトキシド、および
カリウムフエノキシド等の、ナトリウム、カリウ
ムの脂肪族アルコキシド、および芳香族アルコキ
シドがあげられる。これらのアルカリ触媒は、原
料のメチレン化合物に対し0.1ないし10モル当
量、好ましくは0.1ないし３モル当量用いられ
る。 The alkali catalyst used in the process of the invention can be selected from alkali metal hydroxides and alkali metal alkoxides. Alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Alkali metal alkoxides include aliphatic and aromatic alkoxides of sodium and potassium, such as sodium methoxide, sodium ethoxide, potassium t-butoxide, and potassium phenoxide. These alkali catalysts are used in an amount of 0.1 to 10 molar equivalents, preferably 0.1 to 3 molar equivalents, based on the methylene compound as a raw material.
本発明方法によつて得られるケトン誘導体は、
式（）ないし（）に対応した式（′）ない
し（′）
〔ただし式中、環Ａおよび環Ｂは前記定義に同
じ〕
で示される化合物である。これらのケトン誘導体
の代表的なものとしては、たとえば、ベンゾフエ
ノン、ジメチルベンゾフエノン、フエニル−２−
ピリジルケトン、フルオレノン、およびアントラ
キノンなどがある。 The ketone derivative obtained by the method of the present invention is
Expression () or (′) corresponding to expression () or () [In the formula, ring A and ring B are the same as defined above.] This is a compound represented by the following formula. Representative examples of these ketone derivatives include benzophenone, dimethylbenzophenone, and phenyl-2-
These include pyridyl ketones, fluorenone, and anthraquinone.
本発明方法において溶媒として用いられるアル
キル−２−イミダゾリジノン化合物は一般式
（）で示されるものである。 The alkyl-2-imidazolidinone compound used as a solvent in the method of the present invention is represented by the general formula ().
〔式中R1およびR2は、それぞれ同一、もしく
は相異なる炭素数１ないし３のアルキル基であ
り、R3は水素原子またはメチル基である。〕
本発明方法において溶媒として用いられる好ま
しいアルキル−２−イミダゾリジノン化合物は、
たとえば１，３−ジメチル−２−イミダゾリジノ
ン、１，３−ジエチル−２−イミダゾリジノン、
１，３−ジイソプロピル−２−イミダゾリジノ
ン、および１，３，４−トリメチル−２−イミダ
ゾリジノンなどから選ばれた１種または２種以上
の混合物である。 [In the formula, R 1 and R 2 are the same or different alkyl groups having 1 to 3 carbon atoms, and R 3 is a hydrogen atom or a methyl group. ] Preferred alkyl-2-imidazolidinone compounds used as solvents in the method of the present invention are:
For example, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone,
It is one or a mixture of two or more selected from 1,3-diisopropyl-2-imidazolidinone, 1,3,4-trimethyl-2-imidazolidinone, and the like.
本発明方法と従来法を比較するとき、たとえば
ジフエニルスルホキシド中で、ジフエニルメタン
を酸素雰囲気下、３モル当量のカリウム−ｔ−ブ
トキシドを用いて、100℃で20時間反応させると
ベンゾフエノンが68％収率で得られるが、この反
応を本発明方法により溶媒として１，３−ジメチ
ル−２−イミダゾリジノン中で、0.3モル当量の
水酸化ナトリウム存在下、90〜100℃で15時間反
応させると、目的物であるベンゾフエノンを85％
の高収率で得ることができる。HMPAおよびク
ラウンエーテルを用いた場合も、高い収率で得ら
れるが、高毒性のため工業的に不適当である。ま
たDMFはアルカリに不安定で、本反応に用いる
と分解してジメチルアミンを生成するが、１，３
−ジアルキル−２−イミダゾリジノンは安定で分
解せず、反応後容易に回収することができる。 When comparing the method of the present invention with the conventional method, for example, when diphenylmethane is reacted in diphenyl sulfoxide with 3 molar equivalents of potassium t-butoxide in an oxygen atmosphere at 100°C for 20 hours, benzophenone is produced in a yield of 68%. However, when this reaction is carried out according to the method of the present invention in 1,3-dimethyl-2-imidazolidinone as a solvent in the presence of 0.3 molar equivalent of sodium hydroxide at 90 to 100°C for 15 hours, 85% of the target benzophenone
can be obtained in high yield. Although high yields can be obtained using HMPA and crown ether, they are unsuitable for industrial use due to their high toxicity. Furthermore, DMF is unstable in alkalis and decomposes when used in this reaction to produce dimethylamine.
-Dialkyl-2-imidazolidinone is stable, does not decompose, and can be easily recovered after the reaction.
本発明方法が上述のように優れている理由は必
ずしも明らかではないが、溶媒として用いられる
一般式（）のアルキル−２−イミダゾリジノン
化合物が極性非プロトン溶媒であつて、アルカリ
が活性化され出発物質であるメチレン化合物のメ
チレン基より水素原子を引き抜き、生成するアニ
オンが酸素と反応してカルボニル基に変化するも
のと考えられる。またアルキル−２−イミダゾリ
ジノン化合物は、アルカリや酸素に対し高い安定
性を有して反応を円滑に進めるものと考えられ
る。 The reason why the method of the present invention is so superior as described above is not necessarily clear, but the reason is that the alkyl-2-imidazolidinone compound of the general formula () used as a solvent is a polar aprotic solvent, and the alkali is not activated. It is thought that a hydrogen atom is extracted from the methylene group of the methylene compound that is the starting material, and the resulting anion reacts with oxygen and changes into a carbonyl group. Furthermore, it is believed that the alkyl-2-imidazolidinone compound has high stability against alkali and oxygen and facilitates the reaction.
以下実施例について本発明を詳細に説明する。 The present invention will be described in detail with reference to Examples below.
実施例 １
酸素ガスホルダーからフラスコの底部に至るガ
ス導入口、還流冷却器、滴下ロートおよび磁気撹
拌機を備えた100mlの三ツ口フラスコ中に水酸化
ナトリウム0.24ｇと1.3−ジメチル−２−イミダ
ゾリジノン20mlを入れ、酸素ガスでフラスコ中の
空気を置換した。室温で撹拌しながら滴下ロート
より、ジフエニルメタン3.36ｇを、５mlの１，３
−ジメチル−２−イミダゾリジノンに溶解した混
合液を５分間で滴下し、滴下終了後酸素ガスを送
入しながら油浴で90〜100℃に保つて15時間撹拌
を続けた。次いで70mlの冷水を反応液に加え、エ
ーテル70mlで生成化合物を抽出した。この抽出液
を無水硫酸ナトリウムで乾燥した後エーテルを留
去し、残留物をｎ−ヘキサンを用いて再結晶を行
つたところ、融点47〜48℃の純粋なベンゾフエノ
ンの結晶が30.9ｇ得られた。理論収率は85％であ
つた。生成物はNMR，IRおよび元素分析によ
り、ベンゾフエノンであることが確認された。Example 1 0.24 g of sodium hydroxide and 1,3-dimethyl-2-imidazolidinone in a 100 ml three-necked flask equipped with a gas inlet from the oxygen gas holder to the bottom of the flask, a reflux condenser, a dropping funnel and a magnetic stirrer. 20 ml was added, and the air in the flask was replaced with oxygen gas. While stirring at room temperature, add 3.36 g of diphenylmethane from the dropping funnel to 5 ml of 1,3
A mixed solution dissolved in -dimethyl-2-imidazolidinone was added dropwise over a period of 5 minutes, and after completion of the addition, stirring was continued for 15 hours at 90 to 100°C in an oil bath while supplying oxygen gas. Then, 70 ml of cold water was added to the reaction solution, and the product compound was extracted with 70 ml of ether. After drying this extract over anhydrous sodium sulfate, the ether was distilled off, and the residue was recrystallized using n-hexane to obtain 30.9 g of pure benzophenone crystals with a melting point of 47-48°C. . The theoretical yield was 85%. The product was confirmed to be benzophenone by NMR, IR and elemental analysis.
NMR（δ（CCl4）ppm）
；7.4〜8.0（ｍ、10H）
IR（cm-1、CCl4溶液）
；3060、1657、1599、700
元素分析（％）；Ｃ＝85.84、Ｈ＝5.47、
計算値Ｃ＝85.69、Ｈ＝5.53
実施例 ２
１，３−ジメチル−２−イミダゾリジノン25
ml，ジメチルジフエニルメタン3.93ｇ，水酸化ナ
トリウム1.20ｇを用い、実施例１と同様の方法で
90〜100℃、８時間反応し、蒸留によりジメチル
ベンゾフエノン3.83ｇを得た。理論収率は91％。
生成物のNMR，IRおよび元素分析値は次の通り
であつた。 NMR (δ( CCl4 )ppm)
;7.4~8.0 (m, 10H) IR (cm -1 , CCl 4 solution)
; 3060, 1657, 1599, 700 Elemental analysis (%); C = 85.84, H = 5.47, calculated value C = 85.69, H = 5.53 Example 2 1,3-dimethyl-2-imidazolidinone 25
ml, dimethyldiphenylmethane 3.93g, and sodium hydroxide 1.20g in the same manner as in Example 1.
The reaction was carried out at 90 to 100°C for 8 hours, and 3.83 g of dimethylbenzophenone was obtained by distillation. Theoretical yield is 91%.
The NMR, IR and elemental analysis values of the product were as follows.
NMR（δ（CCl4）ppm） ；2.45（ｓ、6H）、
7.3〜7.7（ｍ、8H）
IR（cm-1、CCl4溶液）
；3120、2924、1667、1601
元素分析値（％）；Ｃ＝85.54、Ｈ＝6.90、
計算値Ｃ＝85.68、Ｈ＝6.71
実施例 ３
１，３−ジメチル−２−イミダゾリジノン25
ml，２−ベンジルピリジン3.38ｇ，水酸化ナトリ
ウム1.20ｇを用い、実施例１と同様の方法で70〜
80℃で８時間反応させ、蒸留によりフエニル−２
−ピリジルケトン3.00ｇを得た。理論収率は82％
であつた。生成物のNMR，IRおよび元素分析値
は次の通りであつた。 NMR (δ(CCl 4 ) ppm); 2.45 (s, 6H), 7.3-7.7 (m, 8H) IR (cm -1 , CCl 4 solution)
; 3120, 2924, 1667, 1601 Elemental analysis value (%); C = 85.54, H = 6.90, calculated value C = 85.68, H = 6.71 Example 3 1,3-dimethyl-2-imidazolidinone 25
ml, 3.38 g of 2-benzylpyridine, and 1.20 g of sodium hydroxide in the same manner as in Example 1.
After reacting at 80℃ for 8 hours, phenyl-2 was extracted by distillation.
-3.00 g of pyridyl ketone were obtained. Theoretical yield is 82%
It was hot. The NMR, IR and elemental analysis values of the product were as follows.
NMR（δ（CCl4）ppm） ；7.52（ｍ、3H）、
7.7〜8.3（ｍ、5H）、8.70（ｍ、1H）
IR（cm-1、CCl4溶液）
；3130、1681、1597、1580
元素分析値（％）；Ｃ＝78.42、Ｈ＝5.02
計算値Ｃ＝78.67、Ｈ＝4.95
実施例 ４
100mlのビーカーに１，３−ジメチル−２−イ
ミダゾリジノン25ml，フルオレン3.32ｇ，水酸化
ナトリウム0.12ｇを入れ、空気中室温で４時間撹
拌反応し、実施例１と同様に得られた粗結晶をエ
チルアルコールより再結して、フルオレノン2.92
ｇを得た。理論収率は81％であつた。生成物の
IRおよび元素分析値は次の通りであつた。 NMR (δ(CCl 4 ) ppm); 7.52 (m, 3H), 7.7-8.3 (m, 5H), 8.70 (m, 1H) IR (cm -1 , CCl 4 solution)
; 3130, 1681, 1597, 1580 Elemental analysis value (%); C = 78.42, H = 5.02 Calculated value C = 78.67, H = 4.95 Example 4 25 ml of 1,3-dimethyl-2-imidazolidinone in a 100 ml beaker , 3.32 g of fluorene, and 0.12 g of sodium hydroxide were stirred and reacted in air at room temperature for 4 hours. The crude crystals obtained in the same manner as in Example 1 were recrystallized from ethyl alcohol to obtain 2.92
I got g. The theoretical yield was 81%. of the product
The IR and elemental analysis values were as follows.
IR（cm-1、KBr）
；3050、1709、1610、1599、736
元素分析値（％）；Ｃ＝86.89、Ｈ＝4.42
計算値Ｃ＝86.65、Ｈ＝4.47
融点；80〜82℃
実施例 ５
１，３−ジメチル−２−イミダゾリジノン25
ml、９，10−ジヒドロアントラセン0.72ｇ、水酸
化ナトリウム0.24ｇを用い、実施例４と同様の方
法で得られた粗結晶をベンゼンより再結し、アン
トラキノン0.73ｇを得た。理論収率は88％であつ
た。生成物のIRおよび元素分析値は次の通りで
あつた。 IR (cm -1 , KBr)
; 3050, 1709, 1610, 1599, 736 Elemental analysis value (%); C = 86.89, H = 4.42 Calculated value C = 86.65, H = 4.47 Melting point: 80-82°C Example 5 1,3-dimethyl-2- imidazolidinone 25
The crude crystals obtained in the same manner as in Example 4 were recrystallized from benzene using 0.72 g of 9,10-dihydroanthracene and 0.24 g of sodium hydroxide to obtain 0.73 g of anthraquinone. The theoretical yield was 88%. The IR and elemental analysis values of the product were as follows.
IR（cm-1、KBr）
；3050、1674、1589、1282、690
元素分析値（％）；Ｃ＝80.70、Ｈ＝3.87
計算値Ｃ＝80.76、Ｈ＝3.87
融点；282〜284℃。 IR (cm -1 , KBr)
; 3050, 1674, 1589, 1282, 690 Elemental analysis value (%); C = 80.70, H = 3.87 Calculated value C = 80.76, H = 3.87 Melting point; 282-284°C.
Claims (1)
場合ベンゼン環またはピリジン環より選ばれ、式
（）および式（）の場合はベンゼン環を表
し、環Ａおよび環Ｂは、同一でも相異なつてもよ
い。） で示されるメチレン化合物を、含酸素雰囲気下、
溶媒中でアルカリ触媒の存在下で反応させて、そ
れぞれ対応する式（′）ないし式（′） （ただし式中、環Ａおよび環Ｂは前記定義に同
じ） で示されるケトン誘導体を製造するに際し、溶媒
として一般式（） （ただし式中、R1およびR2は、それぞれ同一
もしくは相異なる炭素数１ないし３のアルキル基
であり、R3は、水素原子またはメチル基であ
る。） で示されるアルキル−２−イミダゾリジノン化合
物を用いることを特徴とするケトン誘導体の製造
方法。 ２ アルキル−２−イミダゾリジノン化合物が、
１，３−ジメチル−２−イミダゾリジノン、１，
３−ジエチル−２−イミダゾリジノン、１，３−
ジイソプロピル−２−イミダゾリジノンおよび
１，３，４−トリメチル−２−イミダゾリジノン
から選ばれる少なくとも一種である特許請求の範
囲第１項記載の方法。 ３ アルカリ触媒が、アルカリ金属水酸化物また
はアルカリ金属アルコキシドである特許請求の範
囲第１項記載の方法。 ４ アルカリ金属水酸化物が、水酸化ナトリウム
または水酸化カリウムである特許請求の範囲第１
項記載の方法。 ５ アルカリ金属アルコキシドが、ナトリウムメ
トキシドナトリウムエトキシド、カリウム−ｔ−
ブトキシドおよびカリウムエトキシドから選ばれ
る特許請求の範囲第３項記載の方法。 ６ 反応が、０℃ないし220℃の温度で行われる
特許請求の範囲第１項記載の方法。 ７ アルカリ触媒が、メチレン化合物に対して
0.1ないし10モル当量の割合で用いられる特許請
求の範囲第１項記載の方法。[Claims] 1 Formula () to () (However, in the formula, ring A and ring B are selected from a benzene ring or a pyridine ring in the case of formula (), and represent a benzene ring in the case of formula () and formula (), and ring A and ring B may be the same or (They may be different.) A methylene compound represented by
By reacting in a solvent in the presence of an alkali catalyst, the corresponding formula (′) to formula (′) (However, in the formula, ring A and ring B are the same as defined above.) When producing a ketone derivative represented by the following, the general formula () is used as a solvent. (In the formula, R 1 and R 2 are respectively the same or different alkyl groups having 1 to 3 carbon atoms, and R 3 is a hydrogen atom or a methyl group.) A method for producing a ketone derivative, characterized by using a non-compound. 2 The alkyl-2-imidazolidinone compound is
1,3-dimethyl-2-imidazolidinone, 1,
3-diethyl-2-imidazolidinone, 1,3-
The method according to claim 1, which is at least one selected from diisopropyl-2-imidazolidinone and 1,3,4-trimethyl-2-imidazolidinone. 3. The method according to claim 1, wherein the alkali catalyst is an alkali metal hydroxide or an alkali metal alkoxide. 4 Claim 1 in which the alkali metal hydroxide is sodium hydroxide or potassium hydroxide
The method described in section. 5 Alkali metal alkoxides include sodium methoxide, sodium ethoxide, potassium-t-
4. The method of claim 3, wherein the method is selected from butoxide and potassium ethoxide. 6. The method according to claim 1, wherein the reaction is carried out at a temperature of 0°C to 220°C. 7 Alkaline catalysts react against methylene compounds
The method according to claim 1, wherein the amount is used in a proportion of 0.1 to 10 molar equivalents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5172978A JPS54144348A (en) | 1978-04-28 | 1978-04-28 | Preparation of ketone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5172978A JPS54144348A (en) | 1978-04-28 | 1978-04-28 | Preparation of ketone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54144348A JPS54144348A (en) | 1979-11-10 |
| JPS629098B2 true JPS629098B2 (en) | 1987-02-26 |
Family
ID=12894970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5172978A Granted JPS54144348A (en) | 1978-04-28 | 1978-04-28 | Preparation of ketone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54144348A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59122439A (en) * | 1982-12-28 | 1984-07-14 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of aromatic ketone |
| JPS59148731A (en) * | 1983-02-15 | 1984-08-25 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of aromatic ketone |
| JPS59219248A (en) * | 1983-05-27 | 1984-12-10 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of benzophenone |
| US5545760A (en) * | 1995-02-07 | 1996-08-13 | The Dow Chemical Company | Process for making fluorenones |
| CA2253746A1 (en) * | 1996-05-24 | 1997-12-04 | The Dow Chemical Company | Process for making fluorenones |
| JP2007182399A (en) * | 2006-01-06 | 2007-07-19 | Air Water Inc | Method for producing fluorenone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5154540A (en) * | 1974-11-07 | 1976-05-13 | Kawasaki Kasei Chemicals | Antorakinonno seizohoho |
| JPS51118754A (en) * | 1975-04-05 | 1976-10-18 | Kawasaki Kasei Chem Ltd | Process for preparation of anthraquinone |
-
1978
- 1978-04-28 JP JP5172978A patent/JPS54144348A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5154540A (en) * | 1974-11-07 | 1976-05-13 | Kawasaki Kasei Chemicals | Antorakinonno seizohoho |
| JPS51118754A (en) * | 1975-04-05 | 1976-10-18 | Kawasaki Kasei Chem Ltd | Process for preparation of anthraquinone |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54144348A (en) | 1979-11-10 |
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