JPH05163189A - Production of 3,3,4-trimethyl-4-pentene-2-one - Google Patents
Production of 3,3,4-trimethyl-4-pentene-2-oneInfo
- Publication number
- JPH05163189A JPH05163189A JP3328763A JP32876391A JPH05163189A JP H05163189 A JPH05163189 A JP H05163189A JP 3328763 A JP3328763 A JP 3328763A JP 32876391 A JP32876391 A JP 32876391A JP H05163189 A JPH05163189 A JP H05163189A
- Authority
- JP
- Japan
- Prior art keywords
- trimethyl
- acetic anhydride
- reaction
- dimethylbutenes
- penten
- 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.)
- Granted
Links
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
【０００１】[0001]
【産業上の利用分野】本発明は、農薬、特に殺虫剤の中
間体として有用な３，３，４−トリメチル−４−ペンテ
ン−２−オンの製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing 3,3,4-trimethyl-4-penten-2-one which is useful as an intermediate for agricultural chemicals, especially insecticides.
【０００２】[0002]
【従来技術及び発明が解決しようとする課題】３，３，
４−トリメチル−４−ペンテン−２−オンの製造方法に
関しては、２，３−ジメチル−２−ブテンおよび無水酢
酸を原料として、陽イオン交換樹脂を用いる方法が知ら
れている（Zh. Vses. Khim. O-va. im. D. I. Mendelee
va 1988, 33(3), 350-2 ）。しかしながらこの方法は、
高価なイオン交換樹脂を多量に用いており、しかも収率
が５０〜６５％と低く、工業的な製造法としては、満足
できるものではなかった。本発明者らは工業的に有利な
３，３，４−トリメチル−４−ペンテン−２−オンの製
造方法を見出すべく、触媒について種々検討の結果、触
媒として硫酸と無水酢酸との縮合物または三フッ化ホウ
素類を用いることにより、２，３−ジメチルブテン類と
無水酢酸から、３，３，４−トリメチル−４−ペンテン
−２−オンが高収率でしかも選択的に得られることを見
出し、本発明に到った。2. Prior Art and Problems to be Solved by the Invention
Regarding a method for producing 4-trimethyl-4-penten-2-one, a method using a cation exchange resin with 2,3-dimethyl-2-butene and acetic anhydride as raw materials is known (Zh. Vses. Khim. O-va. Im. DI Mendelee
va 1988, 33 (3), 350-2). However, this method
Since a large amount of expensive ion exchange resin is used and the yield is as low as 50 to 65%, it is not satisfactory as an industrial production method. The present inventors have conducted various studies on the catalyst in order to find an industrially advantageous method for producing 3,3,4-trimethyl-4-penten-2-one, and as a result, a condensate of sulfuric acid and acetic anhydride or a catalyst was obtained. By using boron trifluorides, 3,3,4-trimethyl-4-penten-2-one can be selectively obtained in high yield from 2,3-dimethylbutenes and acetic anhydride. Heading, the present invention was reached.
【０００３】[0003]
【課題を解決するための手段】即ち、本発明は、触媒と
して硫酸と無水酢酸との縮合物または三フッ化ホウ素類
を用いて、２，３−ジメチルブテン類と無水酢酸とを反
応させることを特徴とする３，３，４−トリメチル−４
−ペンテン−２−オンの製造方法に関するものである。
以下、本発明を詳細に説明する。That is, the present invention is to react 2,3-dimethylbutenes with acetic anhydride using a condensate of sulfuric acid and acetic anhydride or boron trifluoride as a catalyst. 3,3,4-trimethyl-4 characterized by
-The present invention relates to a method for producing penten-2-one.
Hereinafter, the present invention will be described in detail.
【０００４】本発明の一方の原料である２，３−ジメチ
ルブテン類としては、２，３−ジメチル−２−ブテン、
２，３−ジメチル−１−ブテンが挙げられる。これらは
それぞれ単独で用いてもよいし、両者の混合物を用いて
もよい。The 2,3-dimethylbutenes which are one of the starting materials of the present invention include 2,3-dimethyl-2-butene,
2,3-dimethyl-1-butene can be mentioned. These may be used alone or as a mixture of both.
【０００５】本発明の他方の原料である無水酢酸として
は、通常市販されているものを使用することができる。
その量は通常、２，３−ジメチルブテン類に対し、０．
１〜５重量倍であり、好ましくは０．５〜２重量倍であ
る。As the acetic anhydride which is the other raw material of the present invention, commercially available products can be used.
The amount is usually 0. 2, relative to 2,3-dimethylbutenes.
It is 1 to 5 times by weight, preferably 0.5 to 2 times by weight.
【０００６】本発明において使用される触媒のうち、硫
酸と無水酢酸との縮合物としては、例えば硫酸と無水酢
酸とを混合して得られる縮合物、スルホ酢酸等を挙げる
ことができる。硫酸と無水酢酸とを混合して得られる縮
合物を用いる場合、予め調整したものを用いてもよい
し、反応前に反応に用いられる無水酢酸を全量仕込んだ
後に硫酸を添加して調整してもよい。混合する硫酸の濃
度としては、９４％以上が好ましく、無水硫酸を用いる
こともできる。その調整温度は通常３０〜９０℃であ
る。三フッ化ホウ素類としては、例えば三フッ化ホウ素
−エーテル錯体、三フッ化ホウ素−酢酸錯体等を挙げる
ことができる。用いられる触媒の量は、無水酢酸に対
し、通常０．１〜２０重量％、好ましくは１〜１０重量
％である。Among the catalysts used in the present invention, examples of the condensate of sulfuric acid and acetic anhydride include condensates obtained by mixing sulfuric acid and acetic anhydride, sulfoacetic acid and the like. When a condensate obtained by mixing sulfuric acid and acetic anhydride is used, it may be prepared in advance, or adjusted by adding sulfuric acid after charging all the acetic anhydride used in the reaction before the reaction. Good. The concentration of sulfuric acid to be mixed is preferably 94% or more, and anhydrous sulfuric acid can also be used. The adjustment temperature is usually 30 to 90 ° C. Examples of boron trifluorides include boron trifluoride-ether complex and boron trifluoride-acetic acid complex. The amount of the catalyst used is usually 0.1 to 20% by weight, preferably 1 to 10% by weight, based on acetic anhydride.
【０００７】反応方法としては、例えば、触媒と無水酢
酸からなる溶液に、２，３−ジメチルブテン類を添加す
る方法を挙げることができる。反応温度は通常、０〜５
０℃であり、好ましくは１０〜４０℃である。本発明に
おいては反応に対して不活性な溶媒を用いることもでき
るが、通常は無溶媒で反応を行うことが容積効率の点か
ら好ましい。反応後、例えば通常のアルカリ水溶液によ
る中和、分液後、得られる有機層を蒸留することによ
り、高収率で３，３，４−トリメチル−４−ペンテン−
２−オン〔１〕が得られる。未反応の２，３−ジメチル
ブテン類も高純度、高収率で回収することができる。Examples of the reaction method include a method of adding 2,3-dimethylbutenes to a solution containing a catalyst and acetic anhydride. The reaction temperature is usually 0 to 5
The temperature is 0 ° C, preferably 10 to 40 ° C. In the present invention, a solvent inert to the reaction can be used, but it is usually preferable to carry out the reaction without a solvent from the viewpoint of volumetric efficiency. After the reaction, for example, neutralization with an ordinary alkaline aqueous solution, liquid separation, and then distillation of the resulting organic layer are carried out to give 3,3,4-trimethyl-4-pentene-in a high yield.
2-one [1] is obtained. Unreacted 2,3-dimethylbutenes can also be recovered with high purity and high yield.
【０００８】ここで得られた３，３，４−トリメチル−
４−ペンテン−２−オン〔１〕は、例えば下記に示す経
路により、２，２，３，３−テトラメチルシクロプロパ
ン−１−カルボン酸へと導くことができる。 3,3,4-trimethyl-obtained here
4-Penten-2-one [1] can be led to 2,2,3,3-tetramethylcyclopropane-1-carboxylic acid by, for example, the route shown below.
【０００９】[0009]
【発明の効果】本発明により、農薬、特に殺虫剤の中間
体として有用な３，３，４−トリメチル−４−ペンテン
−２−オンが高収率でしかも選択的に得られる。INDUSTRIAL APPLICABILITY According to the present invention, 3,3,4-trimethyl-4-penten-2-one, which is useful as an intermediate for agricultural chemicals, especially insecticides, can be selectively obtained in high yield.
【００１０】[0010]
【実施例】本発明を実施例により、さらに詳細に説明す
るが、本発明は実施例に限定されるものではない。 実施例１ 無水酢酸１２１．３０ｇ（１．１９モル）を反応容器に
仕込み４０℃に保温し、９８％硫酸６．０７ｇ（無水酢
酸に対し５重量％）を１時間で滴下する。滴下終了後、
２０℃まで冷却し、同温度で２，３−ジメチル−２−ブ
テン１００ｇ（１．１９モル）を２時間で滴下する。そ
の後同温度で１２時間保温する。反応後２２７．１ｇの
反応液（ＧＣ分析値：３，３，４−トリメチル−４−ペ
ンテン−２−オン含量３７．５％、２，３−ジメチル−
２−ブテン含量１８．０％、２，３−ジメチル−１−ブ
テン含量１．２％）を得る。この結果より、３，３，４
−トリメチル−４−ペンテン−２−オンの収率は９６．
２％（対消費２，３−ジメチルブテン類）であり、２，
３−ジメチル−２−ブテンの回収率は４１．０％であ
る。この反応液に２７％苛性ソーダ水溶液２３５．２１
ｇを２０℃以下で２時間で滴下する。滴下終了後、分液
し、有機層として１２８．３５ｇを得、これを蒸留し、
３，３，４−トリメチル−４−ペンテン−２−オン８
４．１７ｇ（純度９５．７％）、２，３−ジメチルブテ
ン類３８．８ｇを得る。EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. Example 1 121.30 g (1.19 mol) of acetic anhydride was charged into a reaction vessel and kept at 40 ° C., and 6.07 g of 98% sulfuric acid (5% by weight based on acetic anhydride) was added dropwise over 1 hour. After finishing the dropping
After cooling to 20 ° C., 100 g (1.19 mol) of 2,3-dimethyl-2-butene is added dropwise at the same temperature in 2 hours. Then, the temperature is kept at the same temperature for 12 hours. After the reaction, 227.1 g of reaction liquid (GC analysis value: 3,3,4-trimethyl-4-penten-2-one content 37.5%, 2,3-dimethyl-
2-butene content 18.0%, 2,3-dimethyl-1-butene content 1.2%) is obtained. From this result, 3, 3, 4
The yield of -trimethyl-4-penten-2-one is 96.
2% (consumed 2,3-dimethylbutenes), 2,
The recovery rate of 3-dimethyl-2-butene is 41.0%. A 23% aqueous solution of 27% caustic soda was added to this reaction liquid.
g at 20 ° C. or lower in 2 hours. After completion of dropping, liquid separation was performed to obtain 128.35 g as an organic layer, which was distilled,
3,3,4-trimethyl-4-penten-2-one 8
4.17 g (purity 95.7%) and 2,3-dimethylbutenes 38.8 g are obtained.
【００１１】実施例２ 無水酢酸７６．５５ｇ（０．７５モル）を反応容器に仕
込み４０℃に保温し、９８％硫酸３．８３ｇ（無水酢酸
に対し５重量％）を１時間で滴下する。滴下終了後、２
５℃まで冷却し、同温度で２，３−ジメチル−２−ブテ
ンと２，３−ジメチル−１−ブテンとの１／１混合物４
２．０８ｇ（０．５０モル）を２時間で滴下する。その
後２５〜３０℃で２時間保温する。反応後、反応液を分
析する。その結果、３，３，４−トリメチル−４−ペン
テン−２−オンの収率は９０．３％（対消費２，３−ジ
メチルブテン類）であり、２，３−ジメチルブテン類の
回収率は４３．７％である。Example 2 76.55 g (0.75 mol) of acetic anhydride was charged into a reaction vessel and kept at 40 ° C., and 3.83 g of 98% sulfuric acid (5% by weight based on acetic anhydride) was added dropwise over 1 hour. 2 after the dropping
Cool to 5 ° C., and at the same temperature, 1/1 mixture of 2,3-dimethyl-2-butene and 2,3-dimethyl-1-butene 4
2.08 g (0.50 mol) is added dropwise over 2 hours. Then, the temperature is kept at 25 to 30 ° C. for 2 hours. After the reaction, the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 90.3% (based on the consumption 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was Is 43.7%.
【００１２】実施例３ 無水酢酸７６．５５ｇ（０．７５モル）を反応容器に仕
込み４０℃に保温し、９８％硫酸３．８３ｇ（無水酢酸
に対し５重量％）を１時間で滴下する。滴下終了後、２
５℃まで冷却し、同温度で２，３−ジメチル−２−ブテ
ンと２，３−ジメチル−１−ブテンとの９／１混合物４
２．０８ｇ（０．５０モル）を２時間で滴下する。その
後２５〜３０℃で２時間保温する。反応後、反応液を分
析する。その結果、３，３，４−トリメチル−４−ペン
テン−２−オンの収率は９１．０％（対消費２，３−ジ
メチルブテン類）であり、２，３−ジメチルブテン類の
回収率は３９．０％である。Example 3 76.55 g (0.75 mol) of acetic anhydride was charged into a reaction vessel and kept at 40 ° C., and 3.83 g of 98% sulfuric acid (5% by weight based on acetic anhydride) was added dropwise over 1 hour. 2 after the dropping
Cool to 5 ° C. and at the same temperature mix 9/1 of 2,3-dimethyl-2-butene and 2,3-dimethyl-1-butene 4
2.08 g (0.50 mol) is added dropwise over 2 hours. Then, the temperature is kept at 25 to 30 ° C. for 2 hours. After the reaction, the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 91.0% (based on the consumption 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was Is 39.0%.
【００１３】実施例４ 無水酢酸７６．５５ｇ（０．７５モル）を反応容器に仕
込み４０℃に保温し、９８％硫酸３．８３ｇ（無水酢酸
に対し５重量％）を１時間で滴下する。滴下終了後、２
５℃まで冷却し、同温度で２，３−ジメチル−１−ブテ
ン４２．０８ｇ（０．５０モル）を２時間で滴下する。
その後２５〜３０℃で２２時間保温する。反応後、反応
液を分析する。その結果、３，３，４−トリメチル−４
−ペンテン−２−オンの収率は７９．４％（対消費２，
３−ジメチルブテン類）であり、２，３−ジメチルブテ
ン類の回収率は９．８％である。Example 4 76.55 g (0.75 mol) of acetic anhydride was charged into a reaction vessel and kept at 40 ° C., and 3.83 g of 98% sulfuric acid (5% by weight based on acetic anhydride) was added dropwise over 1 hour. 2 after the dropping
After cooling to 5 ° C., 42.08 g (0.50 mol) of 2,3-dimethyl-1-butene is added dropwise at the same temperature in 2 hours.
Then, the temperature is kept at 25 to 30 ° C. for 22 hours. After the reaction, the reaction solution is analyzed. As a result, 3,3,4-trimethyl-4
-Penten-2-one yield was 79.4% (consumed to 2,
3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes is 9.8%.
【００１４】実施例５ 無水酢酸５１．０５ｇ（０．５０モル）及びBF3-ジエチ
ルエーテル錯体２．１３ｇ（無水酢酸に対し４．１７重
量％）を反応容器に仕込み、２０℃で２，３−ジメチル
−２−ブテン４２．０８ｇ（０．５０モル）を２時間で
滴下する。その後２０〜２５℃で２２時間保温する。反
応後、反応液を分析する。その結果、３，３，４−トリ
メチル−４−ペンテン−２−オンの収率は９４．７％
（対消費２，３−ジメチルブテン類）であり、２，３−
ジメチルブテン類の回収率は１９．９％である。Example 5 51.05 g (0.50 mol) of acetic anhydride and 2.13 g of BF 3 -diethyl ether complex (4.17% by weight with respect to acetic anhydride) were charged into a reaction vessel, and the mixture was heated at 20 ° C. for 2-3 hours. -Dimethyl-2-butene 42.08 g (0.50 mol) is added dropwise over 2 hours. Then, the temperature is kept at 20 to 25 ° C for 22 hours. After the reaction, the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 94.7%.
(Vs consumption of 2,3-dimethylbutenes), 2,3-
The recovery rate of dimethylbutenes is 19.9%.
【００１５】実施例６ 触媒としてスルホ酢酸を２．５５ｇ（無水酢酸に対し５
重量％）用い、２，３−ジメチル−２−ブテン滴下後の
保温を２７〜３２℃で２０時間行う以外は実施例５と同
様に反応を行い、反応液を分析する。その結果、３，
３，４−トリメチル−４−ペンテン−２−オンの収率は
９０．０％（対消費２，３−ジメチルブテン類）であ
り、２，３−ジメチルブテン類の回収率は４０．５％で
ある。Example 6 2.55 g of sulfoacetic acid as a catalyst (5 to acetic anhydride was used)
(% By weight), and the reaction is performed in the same manner as in Example 5 except that the temperature after the dropwise addition of 2,3-dimethyl-2-butene is maintained at 27 to 32 ° C. for 20 hours, and the reaction solution is analyzed. As a result, 3,
The yield of 3,4-trimethyl-4-penten-2-one was 90.0% (based on consumption of 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was 40.5%. Is.
【００１６】実施例７ 無水酢酸６０．６５ｇ（０．５９モル）を反応容器に仕
込み４０℃に保温し、９８％硫酸３．０３ｇ（無水酢酸
に対し５重量％）を１時間で滴下する。滴下終了後、２
０℃まで冷却し、同温度で２，３−ジメチル−２−ブテ
ン１００ｇ（１．１９モル）を２時間で滴下する。その
後同温度で１４時間保温する。反応後、反応液を分析す
る。その結果、３，３，４−トリメチル−４−ペンテン
−２−オンの収率は８６．９％（対消費２，３−ジメチ
ルブテン類）であり、２，３−ジメチルブテン類の回収
率は６０．７％である。Example 7 60.65 g (0.59 mol) of acetic anhydride was placed in a reaction vessel and kept at 40 ° C., and 3.03 g of 98% sulfuric acid (5% by weight based on acetic anhydride) was added dropwise over 1 hour. 2 after the dropping
After cooling to 0 ° C., 100 g (1.19 mol) of 2,3-dimethyl-2-butene is added dropwise at the same temperature in 2 hours. After that, it is kept at the same temperature for 14 hours. After the reaction, the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 86.9% (based on consumption 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was Is 60.7%.
【００１７】実施例８ 無水酢酸８４．９１ｇ（０．８３モル）、９８％硫酸
４．２５ｇ（無水酢酸に対し５重量％）を用いる以外は
実施例７と同様に反応を行い、反応液を分析する。その
結果、３，３，４−トリメチル−４−ペンテン−２−オ
ンの収率は８８．５％（対消費２，３−ジメチルブテン
類）であり、２，３−ジメチルブテン類の回収率は５
０．８％である。Example 8 Reaction was carried out in the same manner as in Example 7 except that 84.91 g (0.83 mol) of acetic anhydride and 4.25 g of 98% sulfuric acid (5% by weight relative to acetic anhydride) were used. analyse. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 88.5% (based on consumption 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was Is 5
0.8%.
【００１８】実施例９ 無水酢酸１２１．３０ｇ（１．１９モル）、９８％硫酸
１２．１１３（無水酢酸に対し１０重量％）を用い、
２，３−ジメチル−２−ブテン滴下後の保温時間を２３
時間行う以外は実施例７と同様に反応を行い、反応液を
分析する。その結果、３，３，４−トリメチル−４−ペ
ンテン−２−オンの収率は９２．７％（対消費２，３−
ジメチルブテン類）であり、２，３−ジメチルブテン類
の回収率は３０．４％である。Example 9 Using 121.30 g (1.19 mol) of acetic anhydride and 12.113 of 98% sulfuric acid (10% by weight based on acetic anhydride),
The incubation time after dropping 2,3-dimethyl-2-butene was 23
The reaction is carried out in the same manner as in Example 7 except that the reaction is carried out for a time, and the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 92.7% (compared to 2,3-consumption).
Dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes is 30.4%.
【００１９】実施例１０ 無水酢酸１５７．６９ｇ（１．５４モル）、９８％硫酸
７．８８ｇ（無水酢酸に対し５重量％）を用い、２，３
−ジメチル−２−ブテン滴下後の保温時間を１２時間行
う以外は実施例７と同様に反応を行い、反応液を分析す
る。その結果、３，３，４−トリメチル−４−ペンテン
−２−オンの収率は９２．５％（対消費２，３−ジメチ
ルブテン類）であり、２，３−ジメチルブテン類の回収
率は２８．２％である。Example 10 Using 157.69 g (1.54 mol) of acetic anhydride and 7.88 g of 98% sulfuric acid (5% by weight based on acetic anhydride), 2,3
-A reaction is conducted in the same manner as in Example 7 except that the heat retention time after dropping dimethyl-2-butene is 12 hours, and the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 92.5% (based on consumption 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was Is 28.2%.
【００２０】実施例１１ 無水酢酸１２１．３０ｇ（１．１９モル）を反応容器に
仕込み４０℃に保温し、９４．６４％硫酸６．０７ｇ
（無水酢酸に対し５重量％）を１時間で滴下する。滴下
終了後、２５℃まで冷却し、同温度で２，３−ジメチル
−２−ブテン４２．０８ｇ（０．５０モル）を２時間で
滴下する。その後２５〜３０℃で１２時間保温する。反
応後、反応液を分析する。その結果、３，３，４−トリ
メチル−４−ペンテン−２−オンの収率は８６．２％
（対消費２，３−ジメチルブテン類）であり、２，３−
ジメチルブテン類の回収率は１６．６％である。Example 11 121.30 g (1.19 mol) of acetic anhydride was charged into a reaction vessel and kept at 40 ° C., and 6.07 g of 94.64% sulfuric acid was added.
(5% by weight with respect to acetic anhydride) is added dropwise over 1 hour. After completion of the dropping, the mixture is cooled to 25 ° C., and 42.08 g (0.50 mol) of 2,3-dimethyl-2-butene is added dropwise at the same temperature in 2 hours. Then, the temperature is kept at 25 to 30 ° C. for 12 hours. After the reaction, the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 86.2%.
(Vs consumption of 2,3-dimethylbutenes), 2,3-
The recovery rate of dimethylbutenes is 16.6%.
【００２１】比較例１ 無水酢酸１２１．３０ｇ（１．１９モル）及び２，３−
ジメチル−２−ブテン１００ｇ（１．１９モル）を反応
器に仕込み、２０℃で９８％硫酸６．０７ｇ（無水酢酸
に対し５重量％）を２時間で滴下する。その後同温度で
１２時間保温する。反応後、反応液を分析する。その結
果、３，３，４−トリメチル−４−ペンテン−２−オン
の収率は５％（対消費２，３−ジメチルブテン類）未満
である。Comparative Example 1 121.30 g (1.19 mol) of acetic anhydride and 2,3-
100 g (1.19 mol) of dimethyl-2-butene was charged into the reactor, and 6.07 g of 98% sulfuric acid (5% by weight with respect to acetic anhydride) was added dropwise at 20 ° C. over 2 hours. Then, the temperature is kept at the same temperature for 12 hours. After the reaction, the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one is less than 5% (based on consumption 2,3-dimethylbutenes).
【００２２】比較例２ 触媒として塩化第２鉄を２．４３ｇ（無水酢酸に対し
４．８重量％）用い、２，３−ジメチル−２−ブテン滴
下後の保温を２０時間行う以外は実施例５と同様に反応
を行い、反応液を分析する。その結果、３，３，４−ト
リメチル−４−ペンテン−２−オンの収率は６９．９％
（対消費２，３−ジメチルブテン類）であり、２，３−
ジメチルブテン類の回収率は３３．６％である。Comparative Example 2 Example except that 2.43 g of ferric chloride (4.8% by weight with respect to acetic anhydride) was used as a catalyst and the temperature was kept for 20 hours after dropping 2,3-dimethyl-2-butene. The reaction is performed in the same manner as in 5, and the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 69.9%.
(Vs consumption of 2,3-dimethylbutenes), 2,3-
The recovery rate of dimethylbutenes is 33.6%.
【００２３】比較例３ 触媒として過塩素酸マグネシウム４水和物を２．５５ｇ
（無水酢酸に対し５重量％）用い、２，３−ジメチル−
２−ブテン滴下後の保温を２７〜３２℃で２０時間行う
以外は実施例５と同様に反応を行い、反応液を分析す
る。その結果、３，３，４−トリメチル−４−ペンテン
−２−オンの収率は６２．３％（対消費２，３−ジメチ
ルブテン類）であり、２，３−ジメチルブテン類の回収
率は６９．１％である。Comparative Example 3 2.55 g of magnesium perchlorate tetrahydrate as a catalyst
(5% by weight with respect to acetic anhydride), 2,3-dimethyl-
The reaction is carried out in the same manner as in Example 5 except that the temperature after the dropwise addition of 2-butene is maintained at 27 to 32 ° C. for 20 hours, and the reaction solution is analyzed. As a result, the yield of 3,3,4-trimethyl-4-penten-2-one was 62.3% (based on consumption 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was Is 69.1%.
【００２４】比較例４ 触媒としてメタンスルホン酸を２．５５ｇ（無水酢酸に
対し５重量％）用い、２，３−ジメチル−２−ブテン滴
下後の保温を２７〜３２℃で２０時間行う以外は実施例
５と同様に反応を行い、反応液を分析する。その結果、
３，３，４−トリメチル−４−ペンテン−２−オンの収
率は２４．４％（対消費２，３−ジメチルブテン類）で
あり、２，３−ジメチルブテン類の回収率は９１．０％
である。Comparative Example 4 Except that 2.55 g of methanesulfonic acid (5% by weight with respect to acetic anhydride) was used as a catalyst, and the temperature was kept at 27 to 32 ° C. for 20 hours after dropping 2,3-dimethyl-2-butene. The reaction is carried out in the same manner as in Example 5, and the reaction solution is analyzed. as a result,
The yield of 3,3,4-trimethyl-4-penten-2-one was 24.4% (based on consumption of 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was 91. 0%
Is.
【００２５】比較例５ 触媒として酢酸ニッケル４水和物を２．５５ｇ（無水酢
酸に対し５重量％）用い、２，３−ジメチル−２−ブテ
ン滴下後の保温を７５〜８０℃で８時間行う以外は実施
例５と同様に反応を行い、反応液を分析する。その結
果、３，３，４−トリメチル−４−ペンテン−２−オン
は全く得られず、２，３−ジメチルブテン類の回収率は
８６．９％である。Comparative Example 5 2.55 g of nickel acetate tetrahydrate (5% by weight with respect to acetic anhydride) was used as a catalyst, and the temperature was kept at 75-80 ° C. for 8 hours after the dropwise addition of 2,3-dimethyl-2-butene. The reaction is performed in the same manner as in Example 5 except that the reaction is performed, and the reaction solution is analyzed. As a result, 3,3,4-trimethyl-4-penten-2-one was not obtained at all, and the recovery rate of 2,3-dimethylbutenes was 86.9%.
【００２６】比較例６ 触媒として五酸化リンを２．５５ｇ（無水酢酸に対し５
重量％）用い、２，３−ジメチル−２−ブテン滴下後の
保温を２４〜２８℃で８時間行う以外は実施例５と同様
に反応を行い、反応液を分析する。その結果、３，３，
４−トリメチル−４−ペンテン−２−オンは全く得られ
ず、２，３−ジメチルブテン類の回収率は８１．６％で
ある。Comparative Example 6 As a catalyst, 2.55 g of phosphorus pentoxide (5 to acetic anhydride was used)
% By weight), and the reaction is conducted in the same manner as in Example 5 except that the temperature after the dropping of 2,3-dimethyl-2-butene is maintained at 24-28 ° C. for 8 hours, and the reaction solution is analyzed. As a result, 3, 3,
4-Trimethyl-4-penten-2-one was not obtained at all, and the recovery rate of 2,3-dimethylbutenes was 81.6%.
【００２７】比較例７ 触媒としてタングストケイ酸を２．５５ｇ（無水酢酸に
対し５重量％）用い、２，３−ジメチル−２−ブテン滴
下後の保温を２４〜２８℃で２３時間行う以外は実施例
５と同様に反応を行い、反応液を分析する。その結果、
３，３，４−トリメチル−４−ペンテン−２−オンの収
率は５２．８％（対消費２，３−ジメチルブテン類）で
あり、２，３−ジメチルブテン類の回収率は８０．３％
である。Comparative Example 7 Tungstosilicic acid was used as a catalyst in an amount of 2.55 g (5% by weight based on acetic anhydride), and the temperature was kept at 24 to 28 ° C. for 23 hours after the dropping of 2,3-dimethyl-2-butene. The reaction is carried out in the same manner as in Example 5 and the reaction solution is analyzed. as a result,
The yield of 3,3,4-trimethyl-4-penten-2-one was 52.8% (based on consumption of 2,3-dimethylbutenes), and the recovery rate of 2,3-dimethylbutenes was 80. 3%
Is.
【００２８】参考例１ 実施例１で得られた３，３，４−トリメチル−４−ペン
テン−２−オン（純度９５．７％）８４．１７ｇ及びｎ
−ヘキサン９．０ｇを反応器に仕込み、触媒として塩化
亜鉛２１７ｍｇを添加する。攪拌下、内温を２５〜３０
℃に保ちつつ塩化水素ガス２７．９ｇを５時間かけて反
応液中に吹き込む。脱ガス後、反応液として１１８．４
６ｇ（３，３，４−トリメチル−４−クロロペンタン−
２−オン含量７９．０％、３，３，４−トリメチル−４
−ペンテン−２−オン含量２．０％）が得られる。３，
３，４−トリメチル−４−ペンテン−２−オン転化率９
７．０％、３，３，４−トリメチル−４−クロロペンタ
ン−２−オン選択率９３．０％、３，３，４−トリメチ
ル−４−クロロペンタン−２−オン収率９０．２％（対
仕込み３，３，４−トリメチル−４−ペンテン−２−オ
ン）である。上記で得られた反応液１１８．４６ｇ
（３，３，４−トリメチル−４−クロロペンタン−２−
オン純度７９．０％）にメタノール１８８．７ｇを仕込
み、塩化亜鉛３９２ｍｇを添加後、攪拌下、臭素５０．
６３ｇを２０℃で３．５時間をかけて滴下する。更に塩
素２０．４１ｇを２０℃で２時間かけて反応液中に吹き
込む。その後同温度で０．５時間保温し、反応液３７
８．２０ｇ（３，３，４−トリメチル−４−クロロ−１
−ブロモペンタン−２−オン含量３４．５％、３，３，
４−トリメチル−４−クロロペンタン−２−オン含量
０．５％）を得る。３，３，４−トリメチル−４−クロ
ロペンタン−２−オン転化率９８．０％、３，３，４−
トリメチル−４−クロロ−１−ブロモペンタン−２−オ
ン選択率９６．０％、３，３，４−トリメチル−４−ク
ロロ−１−ブロモ−ペンタン−２−オン収率９４．０％
（対仕込み３，３，４−トリメチル−４−クロロペンタ
ン−２−オン）。反応液を氷水にチャージし、トルエン
３００ｇで抽出し、該トルエン溶液４３８．９０ｇ
（３，３，４−トリメチル−４−クロロ−１−ブロモ−
ペンタン−２−オン含量２９．７５％）が得られる。上
記で得られた３，３，４−トリメチル−４−クロロ−１
−ブロモ−ペンタン−２−オンのトルエン溶液４３８．
９０ｇ（含量２９．７５％）を反応器に仕込み、塩化ト
リエチルベンジルアンモニウム６．１６ｇを添加後、５
％苛性ソーダ水溶液１８４０ｇを内温３０℃で２時間か
けて滴下する。その後同温度で４時間保温する。反応後
分液して得られる水層を９８％硫酸を滴下することによ
り酸析し、析出した結晶を濾集、水洗後乾燥することに
より、２，２，３，３−テトラメチルシクロプロパン−
１−カルボン酸７６．７０ｇ（純度９９．７％、収率９
９．５％／仕込み３，３，４−トリメチル−４−クロロ
−１−ブロモ−ペンタン−２−オン）が得られる。Reference Example 1 84.17 g of 3,3,4-trimethyl-4-penten-2-one (purity 95.7%) obtained in Example 1 and n
-9.0 g of hexane are charged into the reactor, and 217 mg of zinc chloride is added as a catalyst. The internal temperature is 25 to 30 with stirring.
While keeping the temperature at 0 ° C., 27.9 g of hydrogen chloride gas was blown into the reaction solution over 5 hours. After degassing, the reaction solution was 118.4
6 g (3,3,4-trimethyl-4-chloropentane-
2-one content 79.0%, 3,3,4-trimethyl-4
-Penten-2-one content 2.0%) is obtained. Three
3,4-trimethyl-4-penten-2-one conversion 9
7.0%, 3,3,4-trimethyl-4-chloropentan-2-one selectivity 93.0%, 3,3,4-trimethyl-4-chloropentan-2-one yield 90.2% (Countercharged 3,3,4-trimethyl-4-penten-2-one). 118.46 g of the reaction solution obtained above
(3,3,4-trimethyl-4-chloropentane-2-
On-purity 79.0%) was charged with 188.7 g of methanol, 392 mg of zinc chloride was added, and then 50.
63 g are added dropwise at 20 ° C. over 3.5 hours. Further, 20.41 g of chlorine is blown into the reaction solution at 20 ° C. for 2 hours. After that, the reaction solution 37 was kept at the same temperature for 0.5 hours.
8.20 g (3,3,4-trimethyl-4-chloro-1
-Bromopentan-2-one content 34.5%, 3,3
4-Trimethyl-4-chloropentan-2-one content 0.5%) is obtained. 3,3,4-Trimethyl-4-chloropentan-2-one conversion 98.0%, 3,3,4-
Trimethyl-4-chloro-1-bromopentan-2-one selectivity 96.0%, 3,3,4-trimethyl-4-chloro-1-bromo-pentan-2-one yield 94.0%.
(Countercharged 3,3,4-trimethyl-4-chloropentan-2-one). The reaction solution was charged with ice water and extracted with 300 g of toluene, and 438.90 g of the toluene solution.
(3,3,4-trimethyl-4-chloro-1-bromo-
A pentan-2-one content of 29.75%) is obtained. 3,3,4-trimethyl-4-chloro-1 obtained above
-Bromo-pentan-2-one in toluene 438.
90 g (content 29.75%) was charged into a reactor, and after adding 6.16 g of triethylbenzylammonium chloride, 5
% Aqueous sodium hydroxide solution (1840 g) is added dropwise at an internal temperature of 30 ° C. over 2 hours. After that, keep the same temperature for 4 hours. After the reaction, the aqueous layer obtained by liquid separation is subjected to acid precipitation by dropping 98% sulfuric acid, and the precipitated crystals are collected by filtration, washed with water and dried to give 2,2,3,3-tetramethylcyclopropane-.
76.70 g of 1-carboxylic acid (purity 99.7%, yield 9
9.5% / charged 3,3,4-trimethyl-4-chloro-1-bromo-pentan-2-one) is obtained.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年４月２８日[Submission date] April 28, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００２[Name of item to be corrected] 0002
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００２】[0002]
【従来技術及び発明が解決しようとする課題】３，３，
４−トリメチル−４−ペンテン−２−オンの製造方法に
関しては、２，３−ジメチル−２−ブテンおよび無水酢
酸を原料として、陽イオン交換樹脂を用いる方法が知ら
れている（Zh. Vses. Khim. O-va. im. D. I. Mendelee
va 1988, 33(3), 350-2 ）。しかしながらこの方法は、
高価なイオン交換樹脂を多量に用いており、しかも収率
が５０〜６５％と低く、工業的な製造法としては、満足
できるものではなかった。本発明者らは工業的に有利な
３，３，４−トリメチル−４−ペンテン−２−オンの製
造方法を見出すべく、種々検討の結果、硫酸と無水酢酸
との縮合物または三フッ化ホウ素類の存在下に、２，３
−ジメチルブテン類と無水酢酸とを反応させることによ
り、３，３，４−トリメチル−４−ペンテン−２−オン
が高収率でしかも選択的に得られることを見出し、本発
明に到った。2. Prior Art and Problems to be Solved by the Invention
Regarding a method for producing 4-trimethyl-4-penten-2-one, a method using a cation exchange resin with 2,3-dimethyl-2-butene and acetic anhydride as raw materials is known (Zh. Vses. Khim. O-va. Im. DI Mendelee
va 1988, 33 (3), 350-2). However, this method
Since a large amount of expensive ion exchange resin is used and the yield is as low as 50 to 65%, it is not satisfactory as an industrial production method. The present inventors to find a method for producing industrially advantageous 3,3,4-trimethyl-4-penten-2-one, the species' s study results, sulfuric acid and acetic anhydride
In the presence of a condensate of
By reacting dimethylbutenes with acetic anhydride
As a result, they have found that 3,3,4-trimethyl-4-penten-2-one can be obtained selectively in high yield and have reached the present invention.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００３[Name of item to be corrected] 0003
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００３】[0003]
【課題を解決するための手段】即ち、本発明は、硫酸と
無水酢酸との縮合物または三フッ化ホウ素類の存在下
に、２，３−ジメチルブテン類と無水酢酸とを反応させ
ることを特徴とする３，３，４−トリメチル−４−ペン
テン−２−オンの製造方法に関するものである。以下、
本発明を詳細に説明する。That is, the present invention relates to sulfuric acid and
In the presence of condensate with acetic anhydride or boron trifluoride
The present invention relates to a method for producing 3,3,4-trimethyl-4-penten-2-one, which comprises reacting 2,3-dimethylbutenes with acetic anhydride. Less than,
The present invention will be described in detail.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００６】使用される硫酸と無水酢酸との縮合物とし
ては、例えば硫酸と無水酢酸とを混合して得られる縮合
物、スルホ酢酸等を挙げることができる。硫酸と無水酢
酸とを混合して得られる縮合物を用いる場合、予め調整
したものを用いてもよいし、反応前に反応に用いられる
無水酢酸を全量仕込んだ後に硫酸を添加して調整しても
よい。混合する硫酸の濃度としては、９４％以上が好ま
しく、無水硫酸を用いることもできる。その調整温度は
通常３０〜９０℃である。三フッ化ホウ素類としては、
例えば三フッ化ホウ素−エーテル錯体、三フッ化ホウ素
−酢酸錯体等を挙げることができる。硫酸と無水酢酸と
の縮合物または三フッ化ホウ素類の量は、無水酢酸に対
し、通常０．１〜２０重量％、好ましくは１〜１０重量
％である。[0006] The condensation product of use for is Ru sulfate and acetic anhydride, and examples thereof include condensates obtained by mixing the sulfuric acid and acetic anhydride, sulfo acetate. When a condensate obtained by mixing sulfuric acid and acetic anhydride is used, it may be prepared in advance, or adjusted by adding sulfuric acid after charging all the acetic anhydride used in the reaction before the reaction. Good. The concentration of sulfuric acid to be mixed is preferably 94% or more, and anhydrous sulfuric acid can also be used. The adjustment temperature is usually 30 to 90 ° C. As boron trifluoride,
Examples thereof include boron trifluoride-ether complex and boron trifluoride-acetic acid complex. With sulfuric acid and acetic anhydride
The amount of the condensate or boron trifluoride is usually 0.1 to 20% by weight, preferably 1 to 10% by weight, based on acetic anhydride.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】反応方法としては、例えば、無水酢酸なら
びに、硫酸と無水酢酸との縮合物または三フッ化ホウ素
類からなる溶液に、２，３−ジメチルブテン類を添加す
る方法を挙げることができる。反応温度は通常、０〜５
０℃であり、好ましくは１０〜４０℃である。本発明に
おいては反応に対して不活性な溶媒を用いることもでき
るが、通常は無溶媒で反応を行うことが容積効率の点か
ら好ましい。反応後、例えば通常のアルカリ水溶液によ
る中和、分液後、得られる有機層を蒸留することによ
り、高収率で３，３，４−トリメチル−４−ペンテン−
２−オン〔１〕が得られる。未反応の２，３−ジメチル
ブテン類も高純度、高収率で回収することができる。As a reaction method, for example, in the case of acetic anhydride,
And condensate of sulfuric acid and acetic anhydride or boron trifluoride
To a solution consisting of the class, and a method of adding the 2,3-dimethyl butenes. The reaction temperature is usually 0 to 5
The temperature is 0 ° C, preferably 10 to 40 ° C. In the present invention, a solvent inert to the reaction can be used, but it is usually preferable to carry out the reaction without a solvent from the viewpoint of volumetric efficiency. After the reaction, for example, neutralization with an ordinary alkaline aqueous solution, liquid separation, and then distillation of the resulting organic layer are carried out to give 3,3,4-trimethyl-4-pentene-in a high yield.
2-one [1] is obtained. Unreacted 2,3-dimethylbutenes can also be recovered with high purity and high yield.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location // C07B 61/00 300
Claims (1)
は三フッ化ホウ素類を用いて、２，３−ジメチルブテン
類と無水酢酸とを反応させることを特徴とする３，３，
４−トリメチル−４−ペンテン−２−オンの製造方法。1. A method of reacting 2,3-dimethylbutenes with acetic anhydride using a condensate of sulfuric acid and acetic anhydride or boron trifluoride as a catalyst.
A method for producing 4-trimethyl-4-penten-2-one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3328763A JP2995969B2 (en) | 1991-12-12 | 1991-12-12 | Method for producing 3,3,4-trimethyl-4-penten-2-one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3328763A JP2995969B2 (en) | 1991-12-12 | 1991-12-12 | Method for producing 3,3,4-trimethyl-4-penten-2-one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05163189A true JPH05163189A (en) | 1993-06-29 |
| JP2995969B2 JP2995969B2 (en) | 1999-12-27 |
Family
ID=18213878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3328763A Expired - Fee Related JP2995969B2 (en) | 1991-12-12 | 1991-12-12 | Method for producing 3,3,4-trimethyl-4-penten-2-one |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2995969B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111433336A (en) * | 2017-10-17 | 2020-07-17 | 丝趣科尔卡有限公司 | Odorants and compositions comprising odorants |
-
1991
- 1991-12-12 JP JP3328763A patent/JP2995969B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111433336A (en) * | 2017-10-17 | 2020-07-17 | 丝趣科尔卡有限公司 | Odorants and compositions comprising odorants |
| JP2021503517A (en) * | 2017-10-17 | 2021-02-12 | エス エイチ ケルカル アンド カンパニー リミテッド | Odorants and compositions containing odorants |
| CN111433336B (en) * | 2017-10-17 | 2024-02-23 | 丝趣科尔卡有限公司 | Odorants and compositions comprising odorants |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2995969B2 (en) | 1999-12-27 |
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