JPH0113699B2 - - Google Patents
Info
- Publication number
- JPH0113699B2 JPH0113699B2 JP60130506A JP13050685A JPH0113699B2 JP H0113699 B2 JPH0113699 B2 JP H0113699B2 JP 60130506 A JP60130506 A JP 60130506A JP 13050685 A JP13050685 A JP 13050685A JP H0113699 B2 JPH0113699 B2 JP H0113699B2
- Authority
- JP
- Japan
- Prior art keywords
- dichloroacetone
- ruthenium
- producing
- ruthenium compound
- reaction
- 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
- SUNMBRGCANLOEG-UHFFFAOYSA-N 1,3-dichloroacetone Chemical compound ClCC(=O)CCl SUNMBRGCANLOEG-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 6
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical compound CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000002085 enols Chemical class 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SMZHKGXSEAGRTI-UHFFFAOYSA-N 1,1,1-trichloropropan-2-one Chemical compound CC(=O)C(Cl)(Cl)Cl SMZHKGXSEAGRTI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- -1 hypochlorite ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material 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
Description
本発明は、１，３―ジクロルアセトンの製造に
関する。特に本発明は連続的に再生させた四酸化
ルテニウムを利用した１，３―ジクロルプロパン
―２―オールの酸化による１，３―ジクロルアセ
トンを高収率、高選択率で製造する優れた新規の
方法に関するものである。
１，３―ジクロルアセトンは塩素置換基が１お
よび３の位置にあるため化学反応性が高く、フア
インケミカルスの合成中間体として特に有用であ
る。これは医薬品や殺虫剤等の農薬の合成中間体
として有用である。
１，３―ジクロルアセトンの合成法として、
１，３―ジクロルプロパン―２―オールのクロム
酸による酸化（Chem.Ber.，４，562）が知られ
ているが、この方法では多量のクロムを含む廃棄
物が生じ、公害面の問題がある。アセトンの塩素
化による方法（特開昭54−130511）では危険な塩
素ガスを多量に使用し、トリクロルアセトン、
１，１―ジクロルアセトン等が副生し、選択率が
あまり高くない。
ところで四酸化ルテニウムは二級アルコールの
ケトンへの酸化剤としてしばしば利用されてい
る。
四酸化ルテニウムを用いた酸化反応は、化学量
論量の四酸化ルテニウムを用いる方法（J.Am.
Chem.Soc.，80，6682（1958））、触媒量のルテニ
ウム化合物を酸化剤の存在下に用いる方法１）J.
Chem.Soc.，D.1970，1420；２）USP.3997578）
がある。後者の方法では、酸化剤に安価で比較的
取り扱い易い次亜塩素酸ナトリウム水溶液を使用
している例（J.Chem.Soc.，D.1970，1420）があ
る。この方法でシクロヘキサノンの合成、糖類の
酸化等は行われているが、１，３―ジクロルプロ
パン―２―オールを酸化物して１，３―ジクロル
アセトンを合成した例は現在まで報告されていな
い、
この方法をジクロルアセトン合成に応用したと
ころ、反応率、選択択率が低く、製品の単離が困
難であつた。
本発明者らは、１，３―ジクロルプロパン―２
―オールを酸化して相当する１，３―ジクロルア
セトンを効率よく製造する方法の開発に鋭意努力
した結果、ルテニウム化合物を触媒に用い、次亜
塩素酸塩を酸化剤として使用する系で、反応系の
PHを調整することにより、高収率および高選択率
で目的とする１，３―ジクロルアセトンを製造す
る方法を見い出し、本発明を完成するに至つた。
ジクロルアセトンは、溶液中では式(1)で示すケ
ート型とエノール型の平衡状態で存在する。本発
明における反応条件下では、１，３―ジクロルア
セトンがエノール型となると、反応系内に存在す
る次亜塩素酸イオンと反応し、式(2)に示すトリク
ロルアセトンが副生する。
１，３―ジクロルアセトンを含む溶液のPHが高
くなると、エノール型の存在比率が高くなる。本
発明における反応条件下では、反応系のPHが高く
なると、トリクロルアセトンの副生が多くなり、
選択率が急激に低下する。
すなわち、本発明において、反応系のPHが重要
な因子であり、反応系のPHとしては、１ないし
４、好ましくは１ないし２の範囲である。
本発明において使用されるルテニウム化合物と
しては、ルテニウム金属またはその酸化物、各種
ルテニウム塩およびその錯体が使用できる。ルテ
ニウム化合物として具体的には、ルテニウム金
属；二酸化ルテニウム、四酸化ルテニウムなどの
酸化物；塩化ルテニウム、臭化ルテニウム、硫酸
ルテニウムなどの塩類；水酸化ルテニウム；ルテ
ニウムドデカカルボニル，ジクロロトリス（トリ
フエニルホスフイン）ルテニウムなどの錯体を例
示することができる。
これら化合物の触媒としての使用量は、反応基
質１モルに対して通常0.0001ないし１モル、好ま
しくは0.0005ないし0.1モルの範囲である。
本発明は水―反応基質の不均一系で行うことも
できるが、一般的には有機溶媒と水の不均一混合
溶液で行う。有機溶媒として四酸化ルテニウムの
酸化に対して安定でかつこれを溶解する溶媒は使
用可能である。具体的には、四塩化炭素、クロロ
ホルム、塩化メチレン、ジクロロエタン等のハロ
ゲン化炭化水素；ペンタン、ヘキサン、シクロヘ
キサンなどの脂肪族系または脂環式炭化水素；ア
セトン、メチルエチルケトン、メチルイソブチル
ケトンなどのケトン類；酢酸メチル、酢酸エチ
ル、酢酸イソプロピル、プロピオン酸メチルなど
のエステル類を例示することができる。
反応温度としては、50℃以下であればよいが、
好ましくは30℃以下がよい。
次に本発明の方法を実施例によつて具体的に説
明する。
実施例 １
１ガラス製反応器に１，３―ジクロルプロパ
ン―２―オール（92.9ｇ，0.72モル）、二酸化ル
テニウム（0.55ｇ，0.0033モル，アルコールに対
して0.45モル％）、酢酸エチル（170ｇ）および水
（180ｇ）を秤り取る。撹拌しながら12％次亜塩素
酸ナトリウム水溶液（492ｇ，1.1当量）を滴下し
た。滴下中、反応温度は20〜30℃、反応系の水層
のPHは１〜２に調整する。滴下終了後、20〜30℃
で１時間熟成を行つた。反応終了後、酢酸エチル
層と水層を分離し、水層は酢酸エチルで２回抽出
した。抽出液を酢酸エチル層に加え、濃縮、蒸留
することにより、１，３―ジクロルアセトン87.8
ｇ得た。
収率96.0％
実施例 ２
実施例１において用いた反応温度20〜30℃の代
わりに反応温度−５〜０℃で反応を行つた以外は
実施例１と同様の反応を行つた。
収量87.1ｇ，収率95.2％
実施例 ３〜６
実施例１において使用した二酸化ルテニウムの
代わりに表１に示したルテニウム化合物を使用し
た以外は実施例１と同様の反応を行つた。
The present invention relates to the production of 1,3-dichloroacetone. In particular, the present invention provides an excellent method for producing 1,3-dichloroacetone in high yield and high selectivity by oxidizing 1,3-dichloropropan-2-ol using continuously regenerated ruthenium tetroxide. It concerns a new method. Since 1,3-dichloroacetone has chlorine substituents at the 1 and 3 positions, it has high chemical reactivity and is particularly useful as a synthetic intermediate for fine chemicals. This is useful as a synthetic intermediate for pharmaceuticals and agricultural chemicals such as insecticides. As a method for synthesizing 1,3-dichloroacetone,
Oxidation of 1,3-dichloropropan-2-ol with chromic acid (Chem. Ber., 4 , 562) is known, but this method generates a large amount of waste containing chromium and poses pollution problems. There is. The method of chlorinating acetone (Japanese Unexamined Patent Publication No. 54-130511) uses a large amount of dangerous chlorine gas.
1,1-dichloroacetone and the like are produced as by-products, and the selectivity is not very high. By the way, ruthenium tetroxide is often used as an oxidizing agent for secondary alcohols to ketones. The oxidation reaction using ruthenium tetroxide is performed using a stoichiometric amount of ruthenium tetroxide (J.Am.
Chem.Soc., 80 , 6682 (1958)), method using a catalytic amount of a ruthenium compound in the presence of an oxidizing agent 1) J.
Chem.Soc., D.1970, 1420; 2) USP.3997578)
There is. In the latter method, there is an example (J.Chem.Soc., D.1970, 1420) in which an inexpensive and relatively easy-to-handle sodium hypochlorite aqueous solution is used as an oxidizing agent. This method has been used to synthesize cyclohexanone, oxidize sugars, etc., but to date, no example has been reported in which 1,3-dichloroacetone was synthesized by oxidizing 1,3-dichloropropan-2-ol. When this method was applied to the synthesis of dichloroacetone, the reaction rate and selectivity were low, and it was difficult to isolate the product. The present inventors have discovered that 1,3-dichloropropane-2
As a result of intensive efforts to develop a method to efficiently produce the corresponding 1,3-dichloroacetone by oxidizing -ol, a system using a ruthenium compound as a catalyst and hypochlorite as an oxidizing agent was developed. reaction system
The present inventors have discovered a method for producing the desired 1,3-dichloroacetone in high yield and high selectivity by adjusting the pH, and have completed the present invention. Dichloroacetone exists in a solution in an equilibrium state of cate type and enol type as shown by formula (1). Under the reaction conditions of the present invention, when 1,3-dichloroacetone becomes an enol form, it reacts with hypochlorite ions present in the reaction system, and trichloroacetone shown in formula (2) is produced as a by-product. As the pH of a solution containing 1,3-dichloroacetone increases, the proportion of enol forms increases. Under the reaction conditions of the present invention, as the pH of the reaction system increases, more trichloroacetone is produced as a by-product.
Selectivity drops rapidly. That is, in the present invention, the pH of the reaction system is an important factor, and the pH of the reaction system is in the range of 1 to 4, preferably 1 to 2. As the ruthenium compound used in the present invention, ruthenium metal or its oxide, various ruthenium salts, and complexes thereof can be used. Examples of ruthenium compounds include: ruthenium metal; oxides such as ruthenium dioxide and ruthenium tetroxide; salts such as ruthenium chloride, ruthenium bromide, and ruthenium sulfate; ruthenium hydroxide; ruthenium dodecacarbonyl, dichlorotris (triphenylphosphine); ) Examples include complexes such as ruthenium. The amount of these compounds used as a catalyst is generally in the range of 0.0001 to 1 mol, preferably 0.0005 to 0.1 mol, per 1 mol of the reaction substrate. Although the present invention can be carried out in a heterogeneous water-reactive substrate system, it is generally carried out in a heterogeneous mixed solution of an organic solvent and water. Any solvent that is stable against oxidation of ruthenium tetroxide and that dissolves it can be used as the organic solvent. Specifically, halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and dichloroethane; aliphatic or alicyclic hydrocarbons such as pentane, hexane, and cyclohexane; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. ; Examples include esters such as methyl acetate, ethyl acetate, isopropyl acetate, and methyl propionate. The reaction temperature should be 50℃ or less, but
Preferably, the temperature is 30°C or lower. Next, the method of the present invention will be specifically explained using examples. Example 1 1,3-dichloropropan-2-ol (92.9 g, 0.72 mol), ruthenium dioxide (0.55 g, 0.0033 mol, 0.45 mol % based on alcohol), and ethyl acetate (170 g) were placed in a glass reactor. ) and water (180g). A 12% aqueous sodium hypochlorite solution (492 g, 1.1 equivalents) was added dropwise while stirring. During the dropwise addition, the reaction temperature is adjusted to 20-30°C, and the pH of the aqueous layer of the reaction system is adjusted to 1-2. After dropping, 20-30℃
It was aged for 1 hour. After the reaction was completed, the ethyl acetate layer and the aqueous layer were separated, and the aqueous layer was extracted twice with ethyl acetate. By adding the extract to the ethyl acetate layer, concentrating and distilling it, 1,3-dichloroacetone 87.8
I got g. Yield: 96.0% Example 2 The same reaction as in Example 1 was carried out except that the reaction temperature was -5 to 0°C instead of the reaction temperature of 20 to 30°C used in Example 1. Yield: 87.1 g, yield: 95.2% Examples 3 to 6 The same reaction as in Example 1 was carried out, except that the ruthenium compounds shown in Table 1 were used instead of the ruthenium dioxide used in Example 1.
【表】【table】
【表】
実施例 ７
実施例１において用いた反応系の水層のPH１〜
２を３〜４に変更した以外は実施例１と同様の反
応行つた。収率87％。
実施例 ８〜11
実施例１において使用した酢酸エチルの代わり
に表２に示した有機溶媒を使用した以外は実施例
１と同様の反応を行つた。[Table] Example 7 PH1~ of the aqueous layer of the reaction system used in Example 1
The same reaction as in Example 1 was carried out except that 2 was changed to 3 or 4. Yield 87%. Examples 8 to 11 The same reactions as in Example 1 were carried out except that the organic solvents shown in Table 2 were used instead of ethyl acetate used in Example 1.
Claims (1)
により高原子価ルテニウム化合物を生成させ、そ
れを用いて１，３―ジクロルプロパン―２―オー
ルを酸化することを特徴とする１，３―ジクロル
アセトンの製造法。 ２ ルテニウム化合物として、ルテニウム金属、
その酸化物、各種ルテニウム塩およびその錯体か
ら選ばれた少なくとも一種を使用する第１項記載
の１，３―ジクロルアセトンの製造法。 ３ ルテニウム化合物の使用量が反応基質の１，
３―ジクロルプロパン―２―オール１モルに対し
て0.001モルないし0.05モルである第１項または
第２項記載の１，３―ジクロルアセトンの製造
法。 ４ 酸化剤が次亜塩素酸ナトリウムである第１項
ないし第３項のいずれかに記載の１，３―ジクロ
ルアセトンの製造法。 ５ 反応系は水層と有機溶媒からなる混合溶液で
ある第１項ないし第４項のいずれかに記載の１，
３―ジクロルアセトンの製造法。 ６ 反応系の混合溶液中の水層のPHが４以下であ
る第５項記載の１，３―ジクロルアセトンの製造
法。 ７ 反応温度が50℃以下、好ましくは30℃以下で
ある第１項ないし第６項のいずれかに記載の１，
３―ジクロルアセトンの製造法。[Claims] 1. A method characterized in that a high-valent ruthenium compound is produced by a ruthenium compound and an oxidizing agent that is continuously added, and 1,3-dichloropropan-2-ol is oxidized using the ruthenium compound. Method for producing 1,3-dichloroacetone. 2 As a ruthenium compound, ruthenium metal,
2. The method for producing 1,3-dichloroacetone according to item 1, which uses at least one selected from oxides thereof, various ruthenium salts, and complexes thereof. 3 The amount of ruthenium compound used is 1,
The method for producing 1,3-dichloroacetone according to item 1 or 2, wherein the amount is 0.001 mol to 0.05 mol per mol of 3-dichloropropan-2-ol. 4. The method for producing 1,3-dichloroacetone according to any one of items 1 to 3, wherein the oxidizing agent is sodium hypochlorite. 5. 1, according to any one of paragraphs 1 to 4, wherein the reaction system is a mixed solution consisting of an aqueous layer and an organic solvent.
Method for producing 3-dichloroacetone. 6. The method for producing 1,3-dichloroacetone according to item 5, wherein the pH of the aqueous layer in the mixed solution of the reaction system is 4 or less. 7. 1, according to any one of paragraphs 1 to 6, wherein the reaction temperature is 50°C or lower, preferably 30°C or lower.
Method for producing 3-dichloroacetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60130506A JPS61289053A (en) | 1985-06-14 | 1985-06-14 | Production of 1,3-dichloroacetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60130506A JPS61289053A (en) | 1985-06-14 | 1985-06-14 | Production of 1,3-dichloroacetone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61289053A JPS61289053A (en) | 1986-12-19 |
| JPH0113699B2 true JPH0113699B2 (en) | 1989-03-07 |
Family
ID=15035907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60130506A Granted JPS61289053A (en) | 1985-06-14 | 1985-06-14 | Production of 1,3-dichloroacetone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61289053A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4650714B2 (en) * | 2003-09-01 | 2011-03-16 | ナガセケムテックス株式会社 | Method for producing carbonyl compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59195161A (en) * | 1983-04-21 | 1984-11-06 | Fujirebio Inc | Magnetic particle and its production |
| JPS62118255A (en) * | 1985-11-19 | 1987-05-29 | Toshimitsu Musha | Detection of immunological reaction by using magnetic field |
-
1985
- 1985-06-14 JP JP60130506A patent/JPS61289053A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59195161A (en) * | 1983-04-21 | 1984-11-06 | Fujirebio Inc | Magnetic particle and its production |
| JPS62118255A (en) * | 1985-11-19 | 1987-05-29 | Toshimitsu Musha | Detection of immunological reaction by using magnetic field |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61289053A (en) | 1986-12-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |