JPS5929052B2 - Production method of triketone hydrate - Google Patents
Production method of triketone hydrateInfo
- Publication number
- JPS5929052B2 JPS5929052B2 JP2329375A JP2329375A JPS5929052B2 JP S5929052 B2 JPS5929052 B2 JP S5929052B2 JP 2329375 A JP2329375 A JP 2329375A JP 2329375 A JP2329375 A JP 2329375A JP S5929052 B2 JPS5929052 B2 JP S5929052B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- hydrate
- triketone
- iodine
- triketones
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229910001511 metal iodide Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000001624 naphthyl group Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 150000003462 sulfoxides Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 di-substituted carbonylmethane Chemical class 0.000 description 2
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 2
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical class C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OYBDPLQZAOFKOT-UHFFFAOYSA-N 1,3-diphenylpropane-1,2,3-trione hydrate Chemical compound O.C=1C=CC=CC=1C(=O)C(=O)C(=O)C1=CC=CC=C1 OYBDPLQZAOFKOT-UHFFFAOYSA-N 0.000 description 1
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 1
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 description 1
- GSWSUDFFJVJMLG-UHFFFAOYSA-N 2,2-dibromo-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(Br)(Br)C(=O)C1=CC=CC=C1 GSWSUDFFJVJMLG-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、種々の合成中間体として有用なトリケトン類
の新規製法に係り、詳記すれば、ジ置換カルボニルメタ
ン類と触媒量のヨウド、触媒量の金属ヨウ化物又はそれ
らの混合物と、触媒量のプロトン酸とを、ジアルキルス
ルホキシド中で反応させることを特徴とする、トリケト
ン類水加物及びトリケトン類の新規製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing triketones useful as various synthetic intermediates. The present invention relates to a novel method for producing triketone hydrates and triketones, which is characterized by reacting a mixture thereof with a catalytic amount of protonic acid in a dialkyl sulfoxide.
従来トリケトン類の製法としては、例えば、オルガニッ
ク スインシセス（ＯｒｇａｎｉｃＳｙｎｔｈｅｓｅｓ
）、Ｃｏｌｌ、Ｖｏｌ■２４４頁に記載の如く、クロロ
ホルム中、ジベンゾイルメタンに臭素を反応させ、生じ
たジベンゾイルジブロムメタンを酢酸ソーダと反応させ
、得られたジフェニルトリケトン水加物を蒸留して製造
する方法が知られていた。Conventional methods for producing triketones include, for example, Organic Syntheses.
), Coll, Vol. 244, dibenzoylmethane is reacted with bromine in chloroform, the resulting dibenzoyldibromomethane is reacted with sodium acetate, and the resulting diphenyltriketone hydrate is distilled. A method of manufacturing was known.
しかしながらこの方法は、高価で毒性の強い臭素を使用
する点と収率が低（・と（・う点が欠点であり、工業的
製法としては不満足であつた。本発明の目的は、トリケ
トン類水加物及びトリケトン類の工業的容易な製法を提
供することである。即ち本発明は、ジ置換カルボニルメ
タン類と触媒量のヨウド、触媒量の金属ヨウ化物又はそ
れらの混合物と、触媒量のプロトン酸とを反応させるこ
とにより、高収率で目的物を与えることを見出し、達成
されたものである。However, this method has disadvantages of using expensive and highly toxic bromine and low yield, and is unsatisfactory as an industrial production method. It is an object of the present invention to provide an industrially easy method for producing hydrates and triketones.That is, the present invention provides an industrially easy method for producing hydrates and triketones. This was achieved by discovering that the desired product could be obtained in high yield by reacting it with a protonic acid.
本発明の方法を反応式で示せば次の如くである。The reaction formula of the method of the present invention is as follows.
即ちジアルキルスルホキシド沖、ジ置換カルボニルメタ
ン類〔１〕と触媒量のヨウド又は触媒量のナトリウム、
カリウム等の金属ヨウ化物と、触媒量のプロトン酸とを
混合し、好ましくは加熱し反応させる。この金属ヨウ化
物は、系内に入れられるとすぐにジアルキルスルホキシ
ドにより酸化されてヨウドとなるので、ヨウドの代わり
に用見・ることができる。本発明に使用するジ置換カル
ボニルメタン類としては、式
（式中Ｒは、フエニル、アルキル置換フエニル、アルコ
キシ置換フエニル 、ナフチル、アルキル 二置換ナフ
チル、アルコキシ置換ナフチル基を示す。That is, a dialkyl sulfoxide, a di-substituted carbonylmethane [1] and a catalytic amount of iodine or a catalytic amount of sodium,
A metal iodide such as potassium and a catalytic amount of protic acid are mixed and reacted, preferably by heating. This metal iodide is oxidized to iodine by dialkyl sulfoxide as soon as it is introduced into the system, so it can be used in place of iodine. The disubstituted carbonylmethanes used in the present invention are represented by the formula (wherein R represents phenyl, alkyl-substituted phenyl, alkoxy-substituted phenyl, naphthyl, alkyl-disubstituted naphthyl, or alkoxy-substituted naphthyl group).
）なる化合物が挙げられ、ジアルキルスルホキシド類と
しては、例えば、ジメチルスルホキシドＪ壮チルスルホ
キシド、ジ一ｎ−プロピルスルホキシド、ジ一ｎ−ブチ
ルスルホキシド等が挙げられ、原料 ５の入手しやすさ
、価格等の理由でジメチルスルホキシドを用℃・るのが
好まし（・。本発明に使用される、ヨウド又は金属ヨウ
化物は、ジ置換カルボニルメタン類に対し、好ましくは
、１〜２０重量％使用され、ヨウドと金属ヨウ化物とは
、単独又はそ ３れらを混合して使用される。本発明方
法により、副生するジアルキルスルフイド類は、酸化し
て、反応溶媒として再使用するのが好まし（・ｏ反応終
了後、反応液より生成物を単離するには、例えば反応終
了液を水中に投入し、溶媒により抽出後溶媒を留去する
。), and the dialkyl sulfoxides include, for example, dimethyl sulfoxide, dimethyl sulfoxide, di-n-propyl sulfoxide, di-n-butyl sulfoxide, etc., and the ease of availability of raw material 5, price, etc. For this reason, it is preferable to use dimethyl sulfoxide (.) The iodine or metal iodide used in the present invention is preferably used in an amount of 1 to 20% by weight based on the disubstituted carbonylmethane, Iodine and metal iodide may be used alone or as a mixture of the three. By the method of the present invention, dialkyl sulfides produced as by-products are preferably oxidized and reused as a reaction solvent. To isolate the product from the reaction solution after the reaction is complete, for example, the reaction solution is poured into water, extracted with a solvent, and then the solvent is distilled off.
生成物は、トリケトン類水加物として得られ、蒸留する
ことにより無水のトリケトン類が得られる。かくして得
られたトリケトン類は、光重合開始剤、特殊な用途に供
せられる還元剤等として有用である。The product is obtained as a hydrate of triketones, and anhydrous triketones are obtained by distillation. The triketones thus obtained are useful as photopolymerization initiators, reducing agents for special uses, and the like.
以上述べた如く、本発明方法は、毒性が強く、取り扱（
・の難しい臭素を使用せず、高収率で目的物を与える等
の利点を有する、新規トリケトン類水加物及びトリケト
ン類の製法を提供するものであり、斯業に貢献する処極
めて大き（・ｏ以下に実施例を述べ、本発明を更に説明
する。As mentioned above, the method of the present invention is highly toxic and difficult to handle.
・It provides a new triketone hydrate and a method for producing triketones, which has the advantage of providing the target product in high yield without using difficult bromine, and it is an extremely important contribution to this industry.・O Examples will be described below to further explain the present invention.
実施例中数量を表わす部は重量部である。実施例
ジメチルスルホキシド５１中、ジベンゾイルメタン４４
８部とヨウド２５部と硫酸２０部とを混合し、１００℃
、５時間加熱反応した。In the examples, parts expressed are parts by weight. Example Dibenzoylmethane 44 in dimethyl sulfoxide 51
Mix 8 parts of iodine, 25 parts of iodine, and 20 parts of sulfuric acid, and heat at 100°C.
The mixture was heated and reacted for 5 hours.
Claims (1)
ル、アルキル置換ナフチル基を示す。 ）なる化合物と、触媒量のヨウド、触媒量の金属ヨウ化
物又はそれらの混合物と触媒量のプロトン酸とを、ジア
ルキルスルホキシド中で反応させることを特徴とする、
式 ▲数式、化学式、表等があります▼ （式中Ｒは前記と同じ。 ）なる化合物の製造法。[Claims] 1 A compound of the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents phenyl, alkyl-substituted phenyl, naphthyl, or alkyl-substituted naphthyl group.), a catalytic amount of iodine, and a catalyst. characterized in that an amount of a metal iodide or a mixture thereof and a catalytic amount of a protic acid are reacted in a dialkyl sulfoxide,
A method for producing a compound with the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is the same as above.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2329375A JPS5929052B2 (en) | 1975-02-25 | 1975-02-25 | Production method of triketone hydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2329375A JPS5929052B2 (en) | 1975-02-25 | 1975-02-25 | Production method of triketone hydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS51100035A JPS51100035A (en) | 1976-09-03 |
| JPS5929052B2 true JPS5929052B2 (en) | 1984-07-18 |
Family
ID=12106552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2329375A Expired JPS5929052B2 (en) | 1975-02-25 | 1975-02-25 | Production method of triketone hydrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5929052B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60189958A (en) * | 1984-03-09 | 1985-09-27 | Nec Kansai Ltd | Semiconductor device |
| JPS6356950A (en) * | 1986-08-28 | 1988-03-11 | Fuji Electric Co Ltd | Composite integrated circuit device |
-
1975
- 1975-02-25 JP JP2329375A patent/JPS5929052B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60189958A (en) * | 1984-03-09 | 1985-09-27 | Nec Kansai Ltd | Semiconductor device |
| JPS6356950A (en) * | 1986-08-28 | 1988-03-11 | Fuji Electric Co Ltd | Composite integrated circuit device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51100035A (en) | 1976-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69206423T2 (en) | Process for the preparation of 5- (2,4-difluorophenyl) salicylic acid. | |
| EP0597329A2 (en) | Process for the preparation of alpha-fluor-beta dicarbonyle compounds | |
| JPS5929052B2 (en) | Production method of triketone hydrate | |
| JPH0610158B2 (en) | Method for producing 3-fluorobenzoic acids | |
| JPS629098B2 (en) | ||
| JP2517304B2 (en) | Method for producing bromoacetonitrile | |
| JPH072690B2 (en) | Method for producing 3-methyl-4-nitrophenol | |
| US4057585A (en) | Method of preparing 2,3-dichloroanisole | |
| IL31463A (en) | 1-formyl-3-nitro-azacycloalkan-2-ones and process for their production | |
| JPH02286637A (en) | Production of aliphatic-substituted fluorobenzene | |
| DE4225763A1 (en) | Process for the production of halogen aromatics | |
| JP2706554B2 (en) | 4-trifluoromethylaniline derivative and method for producing the same | |
| JPS61180736A (en) | Manufacture of 3-bromobenzaldehyde | |
| SU591456A1 (en) | Method of preparing w-nitroacetophenones | |
| SU466208A1 (en) | Method for preparing 4-aryl-3-bromo-2,4-diketomyl acid esters | |
| JPS6197240A (en) | Preparation of polyhydroxybenzophenone | |
| SU767081A1 (en) | Method of preparing propargyl bromide | |
| JPH04224525A (en) | Production of 9,9-dialkylfluorene | |
| JPS63258836A (en) | Production of ethene derivative | |
| SU395355A1 (en) | The method of producing alkoxy or dialkoxy | |
| JPH0128013B2 (en) | ||
| JPS6366131A (en) | Method for producing fluorine-containing aliphatic substituted aromatic compounds | |
| SU1077877A1 (en) | Process for preparing methyl-derivatives of cyclohexane-1,4-dione | |
| SU544654A1 (en) | Method for producing dianyl glutaconaldehyde hydrochloride | |
| SU568648A1 (en) | Method of obtaining 3-phenyl-delta- 3-butenolides |