JPS58154535A - Synthesis of acetoacetic acid ester - Google Patents
Synthesis of acetoacetic acid esterInfo
- Publication number
- JPS58154535A JPS58154535A JP57035795A JP3579582A JPS58154535A JP S58154535 A JPS58154535 A JP S58154535A JP 57035795 A JP57035795 A JP 57035795A JP 3579582 A JP3579582 A JP 3579582A JP S58154535 A JPS58154535 A JP S58154535A
- Authority
- JP
- Japan
- Prior art keywords
- acetone
- monohalogenated
- catalyst
- alcohol
- amount
- 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】 本発明はアセト酢酸エステルの合成方法に関す心。[Detailed description of the invention] The present invention relates to a method for synthesizing acetoacetate.
アセト酢酸エステルは染料、医薬品その他有機合成中間
体として重要な化合物である。従来工業的な!’i n
方法としては、酢酸をリン酸アルミニウム触媒を用いて
700℃で脱水してケテンを得、こt1全加工冷却して
ジケテ/とし、ジケテンを硫酸触媒の存在下にアルコー
ルと反応させてアセト酢酸エステルとする合成方法が採
用されて来た。Acetoacetate is an important compound as an intermediate for dyes, pharmaceuticals, and other organic synthesis. Traditionally industrial! 'i n
As a method, acetic acid is dehydrated at 700°C using an aluminum phosphate catalyst to obtain ketene, which is then completely processed and cooled to form diketene/diketene, and diketene is reacted with alcohol in the presence of a sulfuric acid catalyst to form acetoacetate. A synthetic method has been adopted.
しかしながらこめ方法は、反応温度が高く、多くの反応
1程を経過せねばならない欠点がある。However, the rice cracking method has the disadvantage that the reaction temperature is high and many reactions must be performed.
本発明の目的は、このような欠点のない低温度でしかも
一段階でアセト酢酸エステルを高収率で得る合成方法を
提供することである。The object of the present invention is to provide a synthetic method for obtaining acetoacetate in high yield at low temperatures and in one step, without such drawbacks.
本願発明者はこの目的を達成するため鋭意研究の結束、
本発明のモノハロゲン化アセトン、低級アルJ−ル及び
−酸化炭素全塩基物質及び触媒の在存において反応させ
ることから成るアセト酢酸エペー戸ルの合成方法に到達
した。すなわち、本発明のツノ法は、
X−ClI2−1:0−CIls+CO+R4→C1(
、−00−CH2−Coo Rなる反応を利用せんとす
るものである。(式中、Xは〕)ロゲン原子、Rはアル
キル基を示す)
本発明において原料として使用される七ツノ・ロゲン化
アセトンはクロロアセトン、ブロモアセトン、ヨードア
セト/である。In order to achieve this purpose, the inventor of the present application has conducted intensive research,
A process for the synthesis of acetoacetate, consisting of reacting monohalogenated acetone, lower alkyl and -carbon oxides in the presence of a total basic substance and a catalyst according to the invention has been achieved. That is, the horn method of the present invention is: X-ClI2-1:0-CIls+CO+R4→C1(
, -00-CH2-Coo R. (In the formula, X is a) rogen atom, and R is an alkyl group.) The heptadrogenated acetones used as raw materials in the present invention are chloroacetone, bromoacetone, and iodoacetone.
アルコールとしては、メチル、エチル、プロピル、イソ
プロピル、ブチルアルコール等の低級アルコールが使用
される。As the alcohol, lower alcohols such as methyl, ethyl, propyl, isopropyl, and butyl alcohol are used.
一酸化炭素は純粋なものが好ましいが、不活性な希ガス
類や、小量の水素を含むものでも使用する事が出来る。Although pure carbon monoxide is preferable, inert noble gases or those containing a small amount of hydrogen can also be used.
−酸化炭素の分圧は1〜100気圧、好ましくは1〜5
0気圧でるる。- The partial pressure of carbon oxide is between 1 and 100 atm, preferably between 1 and 5
It's 0 atm.
塩基物質としては、アルカリ金属及びアルカリ土類金属
の炭酸塩1重炭酸塩、酢酸塩、酸化物。Basic substances include carbonates, monobicarbonates, acetates, and oxides of alkali metals and alkaline earth metals.
水酸化物、アルコラード並びに、トリエチルアミン等の
第3級アミンや置換ピリジン等の有機塩基が使用され、
好適には、炭酸す) IJウム、炭酸カリウム、トリエ
チルアミン、ルチジン等が使用される。Hydroxides, alcoholades, and organic bases such as tertiary amines such as triethylamine and substituted pyridines are used;
Preferably, carbonate, potassium carbonate, triethylamine, lutidine, etc. are used.
塩基物質の使用量は、原料のモノノ・ロゲ/化アセトン
と等モルの・・ロゲ/化水素と反応して、/・ロゲ/化
物を生成するのに必要な理論値以上が使用される。The amount of the basic substance to be used is greater than the theoretical value required to react with mono-Rogge/acetone as a raw material and equimolar .-Rogge/hydrogen hydride to produce Rogge/hydrogen hydride.
触媒としては、ジコバルトオクタカルボニルが好適に使
用されるが、テトラコバルトドデカカルボニル、ヒドロ
コバルトテトラカルヂニル及びそのナトリウム塩及び、
コノマルト力ルポニルアニオ/溶液等も使用出来ろ。As the catalyst, dicobalt octacarbonyl is preferably used, but tetracobalt dodecacarbonyl, hydrocobalt tetracardinyl and its sodium salt,
You can also use Conomaltoluponylanio/solution etc.
触媒の縫は、モノノ10ゲン化アセト/1モルに対して
、l/1000〜115モル、好ましくは1、/100
〜1/lOモルが使用される。The amount of catalyst is 1/1000 to 115 mol, preferably 1/100 to 1 mol of mono-10-genated acetate.
~1/10 moles are used.
溶媒1丁、特になくとも反応は進行するが、炭化水素類
、エーテル、ケトン、エステル等の有機溶媒を使用する
事が出来る。Although the reaction proceeds without a single solvent, organic solvents such as hydrocarbons, ethers, ketones, and esters can be used.
!!た、無機塩基を用いる場合には、適量の水の添加が
反応速度を向上せしめる。! ! Furthermore, when an inorganic base is used, addition of an appropriate amount of water improves the reaction rate.
反応温度は10°〜150℃、好ましくは30〜70℃
である。Reaction temperature is 10° to 150°C, preferably 30 to 70°C
It is.
反応後、オートクレーブを冷却して反応液を取り出し、
既知の方法で触媒、塩基全除去した後。After the reaction, cool the autoclave and take out the reaction solution.
After completely removing the catalyst and base using a known method.
常圧または減圧蒸留によってアセト酢酸エステルを得る
事が出来る。Acetoacetate can be obtained by distillation at normal pressure or under reduced pressure.
次に、本発明の実施例を示すが、本発明の要旨を越えな
い限り、以下の実施例に限定されるものではない。Next, examples of the present invention will be shown, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.
〈実施例1〉
200 COステンレス製オートクレープニモノクo
/l/7 セ) 72.5d(30m’1jFIOt)
rエタノール10−。<Example 1> 200 CO stainless steel autoclave nimonoku o
/l/7 ce) 72.5d (30m'1jFIOt)
r ethanol 10-.
トルzンlOmL水2 wt、 Na、0032.1
? (20講m6L)。Toluzun lOmL water 2 wt, Na, 0032.1
? (20 lectures m6L).
002(10)a O,6f f仕込み、気相を一酸化
炭素で、e−ジ後、10kf/−まで−酸化炭素を圧入
した。002(10)a O, 6f f was charged, the gas phase was filled with carbon monoxide, and after e-digesting, -carbon oxide was injected up to 10 kf/-.
55℃で6時間反応を行なったところ、モノクロルアセ
トンの転化率88チ、アセト酢酸エチルの収率82%(
原料モノクロルアセトン基準)でめった。When the reaction was carried out at 55°C for 6 hours, the conversion rate of monochloroacetone was 88%, and the yield of ethyl acetoacetate was 82% (
(based on raw material monochloroacetone).
〈実施例2〉
水を添加しなかった事以外は、実施例1と同様に、55
℃で6時間反応を行なったところ、モノクロルアセトン
の転化率12チ、アセト酢酸エテルの収率10%であっ
た。<Example 2> Same as Example 1 except that water was not added.
When the reaction was carried out at .degree. C. for 6 hours, the conversion of monochloroacetone was 12% and the yield of ethyl acetoacetate was 10%.
〈実施例3〉
200 CCステンレス製オートクレーブにモノクロル
アセトン2.5 d (30mmot)、メタノール2
0tn!。<Example 3> 2.5 d (30 mmot) of monochloroacetone and 2 d of methanol in a 200 CC stainless steel autoclave
0tn! .
トリエチルアミン4.5 td (33mmot )
、 co、 (10)aO,69を仕込み、気相を一酸
化炭素でパージ後、30 kg/cr/Iまで一酸化炭
素を圧入した。Triethylamine 4.5 td (33 mmot)
, co, (10) aO,69 was charged, and after purging the gas phase with carbon monoxide, carbon monoxide was pressurized to 30 kg/cr/I.
55℃で4時間反応金行なったところ、モノクロルアセ
トンの転化率93%、アセト酢酸メチルの収率76%で
あった。When the reaction was carried out at 55° C. for 4 hours, the conversion of monochloroacetone was 93% and the yield of methyl acetoacetate was 76%.
〈実施例4〉
200 CCステンレス製オートクレーブにモノクロル
アセト72.5−(30mmot)、エタノール20ゴ
。<Example 4> 72.5 mm of monochloroacetate (30 mmot) and 20 mm of ethanol were placed in a 200 CC stainless steel autoclave.
26ルテジ/3.8 ml (33mraot)、 0
02(10)80.69を仕込み気相を一酸化炭素で、
o−ジ後 30 kg/crAまで一酸化炭素を圧入し
た。26 lutezi/3.8 ml (33 mraot), 0
02 (10) 80.69 and the gas phase with carbon monoxide,
After the O-ji, carbon monoxide was pressurized to 30 kg/crA.
55℃で4時間反応を行なったところ、モノクロルアセ
トンの転化率63%、アセト酢酸エチルの収率62%で
あった。When the reaction was carried out at 55° C. for 4 hours, the conversion rate of monochloroacetone was 63% and the yield of ethyl acetoacetate was 62%.
アルコールとしてn−プロノミノールを用いた事以外、
実施例4と同様にして55℃で4時間反応を行なったと
ころ、モノクロルアセトンの転化率62%、アセト酢酸
n−プロピルの収率60チであった。Other than using n-pronominol as alcohol,
When the reaction was carried out at 55° C. for 4 hours in the same manner as in Example 4, the conversion of monochloroacetone was 62% and the yield of n-propyl acetoacetate was 60%.
〈実施例6〉
20000ステンレス製オートクレーブにモノクロルア
セトン25ゴ(30溝”ot ) +メタノール20−
926ジーtert−ブチルピリジン7.4m(33諷
講ot)を仕込み、気相全一酸化炭素でパージ後、 3
0kV/cdまで一酸化炭素全圧入した。<Example 6> In a 20,000 stainless steel autoclave, 25 g of monochloroacetone (30 grooves) + 20 g of methanol
Charge 7.4 m (33 tons) of 926-tert-butylpyridine and purge with gas phase total carbon monoxide.
Carbon monoxide was fully pressurized to 0 kV/cd.
55℃で4時間反応を行なったところ、モノクロルアセ
トンの転化率23チ、アセト酢酸エチルの収率23%で
めった。When the reaction was carried out at 55° C. for 4 hours, the conversion of monochloroacetone was 23% and the yield of ethyl acetoacetate was 23%.
手 続 補 正 書(自発)
昭和58年1月11日
特許庁長官 若 杉 和 夫 殿
1、事件の表示
昭和57年特許願第035795号
2発明の名称
アセト酢酸エステルの合成方法
3補正をする者
事件との関係 特許出願人
住 所 千葉県千葉市用崎町1番地
名 称 川鉄化学株式会社
4代 理 人
住 所(〒104)東京都中央区銀座8丁目15番10
号銀座ダイヤハイツ410号電話03−542−091
76補正の内容
明細書6頁上から11行目、7頁上から5行目および1
4行目ノr 002(10)II J k r 002
(00)11 Jに訂正する。Procedural amendment (voluntary) January 11, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1. Indication of the case 1982 Patent Application No. 035795 2. Name of the invention Method for synthesizing acetoacetate 3. Amendment. Patent applicant address: 1 Yozakicho, Chiba City, Chiba Prefecture Name: 4th Director, Kawatetsu Kagaku Co., Ltd. Address: 8-15-10 Ginza, Chuo-ku, Tokyo, 104
No. Ginza Dia Heights No. 410 Telephone: 03-542-091
11th line from the top of page 6 of the specification of contents of the 76 amendment, 5th line from the top of page 7, and 1
4th line no r 002 (10) II J k r 002
(00)11 Corrected to J.
明細書8頁上から10行目の「ブチルピリジン7、4
ml (33rrvnoZ ) J の後にr 、 0
02(Co)II O,6t、 Jを挿入する。“Butylpyridine 7, 4” on page 8 of the specification, line 10 from the top
ml (33rrvnoZ) J followed by r, 0
Insert 02(Co)II O, 6t, J.
Claims (9)
び−酸化炭素を塩基物質及びフッ々ルトカルゼニル触媒
の存在において反応させることから成るアセト酢酸エス
テルの合成方法。(1) A method for synthesizing an acetoacetate, which comprises reacting a monohalogenated acetone, a lower alcohol, and a carbon oxide in the presence of a basic substance and a fluorocarzenyl catalyst.
ロモアセト/またはヨードアセトンである第1項の合成
方法。(2) The method of synthesis according to item 1, wherein the monohalogenated acetone is chloroacetone, bromoacetate/or iodoacetone.
ルコール、フロビルアルコール、イソゾロビルアルコー
ルまたはブチルアルコールである第1項の合成方法。(3) The method of synthesis according to item 1, wherein the lower alcohol is methyl alcohol, ethyl alcohol, flobyl alcohol, isozorobyl alcohol, or butyl alcohol.
項の合成方法。(4) The partial pressure of the carbon oxide is 1 to 100 atm.
How to combine terms.
、置換ピリジンなどの有機塩基でるる第1項の合成方法
。(5) The synthesis method according to item 1, wherein the basic substance is an organic base such as a tertiary amine, pyridine, or substituted pyridine.
属の炭酸塩1重炭酸塩、酢酸塩、酸化物。 水酸化物またはアルコラードでるる第1項の合成方法。(6) The basic substance is an alkali metal or alkaline earth metal carbonate monobicarbonate, acetate, or oxide. 1. Synthesis method using hydroxide or alcoholade.
項のいづれかの合成方法。(7) The reaction is carried out by adding an appropriate amount of water.
How to compose one of the terms.
ノ々ルトトテカカルIニル、ヒドロコバルトテトラカル
ゼニルまたはそのナトリウム塩またはコバルトカルダニ
ルアニオ/溶液である第1項の合成方法。(8) The method of synthesis according to item 1, wherein the catalyst is cobalt octacarzenyl, tetraconoltotecacarinyl, hydrocobalt tetracarzenyl or its sodium salt or cobalt cardanyl anion/solution.
。 01)該反応は溶媒中で行われる第1項の合成方法。(9) The amount of the catalyst is 1 mole of monohalogenated acetone. . . ~ ] "The synthetic method of the first term, in which the amount is molar. The synthetic method of the first term, in which the QO reaction temperature is 10 to 150°C. 01) The synthetic method of the first term, in which the reaction is carried out in a solvent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57035795A JPS58154535A (en) | 1982-03-09 | 1982-03-09 | Synthesis of acetoacetic acid ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57035795A JPS58154535A (en) | 1982-03-09 | 1982-03-09 | Synthesis of acetoacetic acid ester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58154535A true JPS58154535A (en) | 1983-09-14 |
JPH0354094B2 JPH0354094B2 (en) | 1991-08-19 |
Family
ID=12451851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57035795A Granted JPS58154535A (en) | 1982-03-09 | 1982-03-09 | Synthesis of acetoacetic acid ester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58154535A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57102836A (en) * | 1980-07-01 | 1982-06-26 | Montedison Spa | Manufacture of carboxylated organic compound |
-
1982
- 1982-03-09 JP JP57035795A patent/JPS58154535A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57102836A (en) * | 1980-07-01 | 1982-06-26 | Montedison Spa | Manufacture of carboxylated organic compound |
Also Published As
Publication number | Publication date |
---|---|
JPH0354094B2 (en) | 1991-08-19 |
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