JPS6236343A - Production of malonic acid diester - Google Patents
Production of malonic acid diesterInfo
- Publication number
- JPS6236343A JPS6236343A JP60173291A JP17329185A JPS6236343A JP S6236343 A JPS6236343 A JP S6236343A JP 60173291 A JP60173291 A JP 60173291A JP 17329185 A JP17329185 A JP 17329185A JP S6236343 A JPS6236343 A JP S6236343A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- rhodium
- iridium
- reaction
- catalyst
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- -1 malonic acid diester Chemical class 0.000 title claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims description 9
- 150000002504 iridium compounds Chemical class 0.000 claims abstract description 14
- 150000003284 rhodium compounds Chemical class 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- 150000002497 iodine compounds Chemical class 0.000 claims abstract description 10
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 8
- 150000001241 acetals Chemical class 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010948 rhodium Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 150000002168 ethanoic acid esters Chemical class 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 abstract 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 11
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical class [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010457 zeolite 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
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】
（産業上の利用分野）
の原料とし【利用され℃おり、その安価な製造方法の確
立が望まれているものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) It is used as a raw material for industrial applications, and it is desired to establish an inexpensive manufacturing method.
（従来の技術）
従来、ハロゲン化酢酸エステルと一酸化炭素を反応させ
てマロン酸ジエステル？Ｉ−１！！造する方法が提案さ
れている。例えば特公昭５６−１６１３４号公報には、
液相でアルコールと塩基及びロジウム触媒及び場合によ
り沃素化合物の存在で行なう方法が提案布下でロジウム
化合物またはイリジウム化合物を触媒として気相接触反
応させて行なう方法を提案した。(Prior art) Conventionally, malonic acid diester was produced by reacting halogenated acetate and carbon monoxide. I-1! ! A method has been proposed to create For example, in Japanese Patent Publication No. 56-16134,
A method in which the reaction is carried out in the liquid phase in the presence of an alcohol, a base, a rhodium catalyst, and optionally an iodine compound has been proposed.A method in which a gas phase catalytic reaction is carried out in the presence of a rhodium compound or an iridium compound as a catalyst has been proposed.
（発明が解決しようとする問題点）
従来技術のこれらハロゲン化酢酸エステルを一酸化炭素
と反応させてマロン酸ジエステルを製造する方法は、以
下のような問題点ｔ′４ｉ″ｆるものであった。(Problems to be Solved by the Invention) The conventional methods of producing malonic acid diester by reacting these halogenated acetic esters with carbon monoxide have the following problems. Ta.
（１） これらの方法はいずれも単位触媒量あたりの
マロン酸ジエステルの生成量が少ない。(1) All of these methods produce a small amount of malonic acid diester per unit amount of catalyst.
（２）液体状のハロゲン化酢酸エステルを反応させる方
法は、反応で生成するハロゲンを捕捉するために多量の
塩基性化合物を必要とするため、反応物と塩基性化合物
との均一な混合に工夫を有し、反応後のハロゲン化金属
塩をマロン酸ジエステルや触媒と分離するのに濾過や抽
出などの複雑な操作を必要とする。(2) The method of reacting liquid halogenated acetate ester requires a large amount of basic compound to capture the halogen produced in the reaction, so we devised ways to uniformly mix the reactant and basic compound. It requires complicated operations such as filtration and extraction to separate the metal halide salt from the malonic acid diester and catalyst after the reaction.
本発明はこれらの問題点を解決し、より簡単な操作で効
率の良いマロン酸ジエステルの製法を提供すべく鋭意研
究を重ねたものである。The present invention is the result of extensive research aimed at solving these problems and providing a method for producing malonic acid diester that is simpler and more efficient.
（問題Ａ’ｌ解決するための手段）
本発明は、ロジウム化合物またはイリジウム化合物の存
在下、エステル類、エーテル類またはアセタール類を存
在させまたはさせずして、ハロゲン化酢酸エステルと一
酸化炭素を反応させるにあたり、沃素化合物の共存下、
気相接触反応させることを特徴とするマロン酸ジエステ
ルの製法である。(Means for Solving Problem A'l) The present invention provides a method for combining halogenated acetate and carbon monoxide in the presence of a rhodium compound or an iridium compound, with or without the presence of esters, ethers, or acetals. During the reaction, in the presence of an iodine compound,
This is a method for producing malonic acid diester, which is characterized by carrying out a gas phase catalytic reaction.
以下本発明を更に詳しく説明する。The present invention will be explained in more detail below.
本発明に使用するハロゲン化酢酸エステルは沸点２５０
℃以下のものであれはＷｔＣＶ＆定されないが、メチル
、エチル、ｎ−プロピル、イソゾロぎル等の低級アルキ
ルエステルが好ましく、ハロゲン置換基としてはいずれ
でもよいが、特に塩素および臭素が好ましい。The halogenated acetate used in the present invention has a boiling point of 250
℃ or less, WtCV& is not specified, but lower alkyl esters such as methyl, ethyl, n-propyl, and isozologyl are preferred, and any halogen substituent may be used, but chlorine and bromine are particularly preferred.
本発明に使用するエステル類は沸点２００℃以下のもの
であれば４ｖＩＣ限定されないが、好ましくは酢酸メチ
ル、酢酸エチル、酢酸ｎ−プロピル、酢酸イソプロピル
等の酢酸エステル類であり、ハロゲン化酢酸エステルの
エステル残基と同一のアルヤル基を有する酢酸エステル
が有利である。例えば、ハロゲン化酢酸メチルであれば
酢酸メチル、ハロゲン化酢飯インプロｔルであれば酢酸
イソゾロビルの如（である。The esters used in the present invention are not limited to 4vIC as long as they have a boiling point of 200°C or lower, but are preferably acetate esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and halogenated acetate esters. Preference is given to acetate esters which have the same aryal group as the ester residue. For example, methyl acetate is used for halogenated methyl acetate, and isozorovir acetate is used for halogenated vinegar improt.
本発明に使用するエーテル類は、沸点２００℃以下のも
のであれは特に限定されないが、好ましくはジメチルエ
ーテル、ジエチルエーテル、ジ−ｎ−プロピルエーテル
、ジイソプロピルエーテル等の低級ジアルキルエーテル
であり、ハロゲン化酢酸エステルのエステル残基と同一
のアル千ル基を有するジアルキルエーテル類が有利であ
る。例えば、）・ロゲン化酢酸メチルであればジノチル
エーテル、ノ・ロデン化酢酸イソノロビルであれは、ジ
イソプロぎルエーテルの如くである。The ethers used in the present invention are not particularly limited as long as they have a boiling point of 200°C or lower, but are preferably lower dialkyl ethers such as dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, and halogenated acetic acid. Preference is given to dialkyl ethers which have the same alkyl group as the ester residue of the ester. For example, dinotyl ether is used for methyl acetate, and diisoprogyl ether is used for isonorovir acetate.
本−Ｈ６明に便用するアセタール類は沸点２００ ”Ｏ
以下のものであればｔ＃に限定されないが、好ましくは
メチラール、ジエチルアセタール等である。The acetals commonly used in this book have a boiling point of 200 ”O
The following compounds are not limited to t#, but methylal, diethyl acetal, etc. are preferable.
本発明に使用する一酸化炭素は特に純粋である必要はな
く、不活性ガスが共存するものを用いても良□い。Carbon monoxide used in the present invention does not need to be particularly pure, and carbon monoxide containing an inert gas may be used.
本発明において触媒として用いるロジウム化合物は、ロ
ジウムのハロゲン化物、無機酸塩または錯化合物であり
、例をあげればｈｑ＊、５Ｈ２ｏ 、 ’ ＲｈＢｒ５
ｅ２Ｈ２０、Ｒｈ（ＮＯｓ）３．Ｒｈ５（Ｃｏ）４ｃｊ
ｓ ＊Ｒｈ（Ｃｏ）Ｃｊ（Ｐ（ＣａＨｓ）ｓ〕２ 、
ＲｈＣｊ（Ｐ（０，６Ｈ６）ｓ１３ 、 ｎｈｇｏ３＠
５Ｈ２０、（ＮＨ４）３ＲｈＣｊ６ ＊ ＲｈＸ３”Ｘ
Ｈ２Ｏ、等である。これらの化合物は高純度の必要はな
く、例えば塩化ナトリウム、塩化カリウムのような塩類
が含まれていてもさしつかえない。The rhodium compound used as a catalyst in the present invention is a rhodium halide, an inorganic acid salt, or a complex compound, and examples thereof include hq*, 5H2o, 'RhBr5
e2H20, Rh(NOs)3. Rh5(Co)4cj
s *Rh(Co)Cj(P(CaHs)s)2,
RhCj(P(0,6H6)s13, nhgo3@
5H20, (NH4)3RhCj6 *RhX3”X
H2O, etc. These compounds do not need to be highly pure, and may contain salts such as sodium chloride and potassium chloride.
イリジウム化合物としてはイリジウムのハロゲン化物、
無根酸塩または鉛化合物であり、例をあげればＩｒＣｌ
４１１３■２０．工ｒｃｊ４ ＠ ＸｒＢｒ３”４Ｈ１
０ｍＣＮＨ４）！Ｉ工ｒツ６．工ｒα（ｃｏ）、等であ
る。これら化合物は高純度の必会はな（、例えば塩化ナ
トリウム、塩化カリウムのような塩類が含まれてい【も
さしつかえない。Iridium compounds include iridium halides,
Root-free salts or lead compounds, such as IrCl
4113■20. Engineering rcj4 @XrBr3”4H1
0mCNH4)! I-engineering6. engineering rα(co), etc. These compounds must be of high purity (for example, they may contain salts such as sodium chloride and potassium chloride).
本発明において触媒に添加する沃素化合物としては、金
属沃化物が使用される。例２あげれば、Ｌｉ工。In the present invention, a metal iodide is used as the iodine compound added to the catalyst. For example, li engineering.
Ｋｍ 、 Ｎａ工、 Ｂａ工２．Ｃ８工、 Ｒ１）工、
Ｃｏ工２ 、 Ｏａ工２９等であるが、好ましくは、
）Ｔａ工、 Ｋｘ、 Ｂａ工２である。Km, Na engineering, Ba engineering 2. C8 engineering, R1) engineering,
Co work 2, Oa work 29, etc., but preferably,
) Ta work, Kx, Ba work 2.
またこれら沃素化合物は水和物でもさしつかえない。□
ロジウム化合物及びイリジウム化合物を工、通常活性炭
、アルミナ、シリカ、珪藻土、軽石、ゼオライト、モレ
キエラシーデなど不活性な担体に担持させて使用するが
、！＃に活性炭が好ましい。この場合、ロジウム化合物
またはイリジウム化合物の担持量はロジウムまたはイリ
ジウム金属換算で０．５〜２０重ＸＳの範囲で用いれば
十分である。ロジウムまたはイリジウム化合物の担体へ
の担持は公知の触媒調製法で行われる。In addition, these iodine compounds may be hydrated. □
Rhodium compounds and iridium compounds are usually supported on inert carriers such as activated carbon, alumina, silica, diatomaceous earth, pumice, zeolite, and molechielase. Activated carbon is preferred for #. In this case, it is sufficient to use the supported amount of the rhodium compound or iridium compound in the range of 0.5 to 20 weight XS in terms of rhodium or iridium metal. The rhodium or iridium compound is supported on the carrier by a known catalyst preparation method.
沃素化合物はロジウム化合物及びイリジウム化合物と一
様に担体Ｋａ持させて使用する。この場合、ロジウム化
合物またはイリジウム化合物と同時に担持させ【も、あ
るいは別々に担持させても良いが、好ましくは別々に担
持させ４・ことが有利である。この場合、沃素化合物の
添加量は、ロジウム化合物またはイリジウム化合物に対
して、モル比で１ ： ０．０１〜ｉ：ｓｏ、好ましく
は１ ： ０．１〜１：１０である。The iodine compound and the rhodium compound and the iridium compound are used in a state where they are supported on a carrier Ka. In this case, the rhodium compound or the iridium compound may be supported simultaneously or separately, but it is advantageous to support them separately. In this case, the molar ratio of the iodine compound to the rhodium compound or iridium compound is 1:0.01 to i:so, preferably 1:0.1 to 1:10.
本発明の反応に、−酸化炭素及び気体状のハロゲン化酢
急エステル、更に必要に応じて気体状のエステル類また
はエーテル類またはアセタール類をその筐ま、あるいは
不活性ガスで希釈して気相状態で触蝋上に→いて行われ
る。反応装置は気相反応に用いる過電の固定床反応器が
用いられる。反応温度はｉｏｏ’ｃ〜３００ ”Ｃが好
ましく、圧力は常圧下で進行するが、若干加圧しても行
うことができる。In the reaction of the present invention, -carbon oxide and gaseous halogenated acetic acid ester, and if necessary, gaseous esters, ethers, or acetals are added in a gaseous phase by placing them in a container or diluting them with an inert gas. It is performed while standing on a touch wax. The reactor used is a supercharged fixed bed reactor used for gas phase reactions. The reaction temperature is preferably ioo'c to 300''C, and the reaction proceeds under normal pressure, but it can also be carried out under slightly increased pressure.
原料の使用比率はハロゲン化酢Ｉ賀エステル１モルに対
して一酩化炭素は１〜１００モル、エステル類は１〜５
０モル、エーテル類は１〜５０モル、アセタール類は１
〜５０モルの範囲が好ましい。原料ガスの触媒Ｗｌとの
触媒時間は０．２〜１０秒の範囲が好筐しい。The ratio of raw materials used is 1 to 100 moles of carbon monodrunide and 1 to 5 moles of esters per 1 mole of halogenated vinegar Iga ester.
0 mol, 1 to 50 mol for ethers, 1 for acetals
A range of 50 moles is preferred. The catalytic time of the raw material gas with the catalyst Wl is preferably in the range of 0.2 to 10 seconds.
反応後反応管からＤト出された反応物は、常法に従って
冷却凌栂し、盛ｗ操作を得゛Ｃ１マロン酸ジメチルとし
て取得される。After the reaction, the reactant discharged from the reaction tube is cooled in accordance with a conventional method and obtained as C1 dimethyl malonate.
（実施例） 次に実施例により、本発明を具体的に説明する。(Example) Next, the present invention will be specifically explained with reference to Examples.
実施例１
ＲｈＣｌ３・５ａ、ｏ １９ ｋ球状活性炭ｉｏｇに１
＆看させた後、さらＫＫＫＯ２６！ｔ Ｎを吸着させた
触媒を内径２５膓、高さ６００鵬の耐熱ガラス製反応管
に充填した後、２００℃に加熱して一鹸化炭素を毎時０
．１３モルの速度で１時間尋人した。次に、−酸化炭素
及びモノクロ覧酢醗ノチルをそれぞれ毎時０．２５モル
、０．０６モルの速度で１７５℃に維持された予熱器を
通し【混合ガスとし反応管に導入した。反応温度１７５
“０、常圧下に反応させた。Example 1 RhCl3.5a, o 19k spherical activated carbon iog 1
&After watching over, KKKO26! A heat-resistant glass reaction tube with an inner diameter of 25mm and a height of 600mm was filled with the catalyst adsorbed with tN, and then heated to 200°C to generate monosaponified carbon at 0% per hour.
．． It was heated for 1 hour at a rate of 13 moles. Next, carbon oxide and monochrome acetate were introduced into the reaction tube as a mixed gas through a preheater maintained at 175° C. at a rate of 0.25 mol and 0.06 mol per hour, respectively. Reaction temperature 175
“0, the reaction was carried out under normal pressure.
反応生成物をガスクロマトグラフィーで分析した結果、
マロン酸ジメチルが第１表の生成速度で生成した。また
反応開始後７２時間までのマロン酸ジメチルの総生成量
は４３２モル／ＫＰ−触媒であった。As a result of analyzing the reaction product by gas chromatography,
Dimethyl malonate was produced at the production rate shown in Table 1. The total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 432 mol/KP-catalyst.
第１表
実施例２
に工０．６５９ ｋ Ｎａ工＠２Ｈ，ＯＯ，５７！ｉに
変え【実施例１と同様に行った。Table 1 Example 2 Ni 0.659 k Na 2H, OO, 57! i [The same procedure as in Example 1 was performed.
反応生成物をガスクロマトグラフィーで分析した結果、
マロン酸ジメチルが第２表の生成速度で生成した。As a result of analyzing the reaction product by gas chromatography,
Dimethyl malonate was produced at the production rate shown in Table 2.
また反応開始後７２時間までのマロン酸ジメチルの総生
成量は４６８モル／を一触媒であった。The total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 468 mol/catalyst.
第２表
実施例３
に工０．６５ ＩＩ’ｋ Ｂａ工寓５２Ｈ２０１，６２
１Ｋ変えて実施例１と同様に行った＠
反応生成物をガスクロマトグラフィーで分析した結果、
マロン酸ジメチルが第３表の生成速度で生成した。Table 2 Example 3 Ni 0.65 II'k Ba 52H201,62
The reaction was carried out in the same manner as in Example 1 with 1K changed. The reaction product was analyzed by gas chromatography, and the results were as follows:
Dimethyl malonate was produced at the production rate shown in Table 3.
また反応開始後７２時間までのマロン酸ジメチルの総生
成量は３９６モル／卆−触媒であった。The total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 396 mol/liter of catalyst.
第６表
実施例４
ＲｈＣｊ、 ＠ ３ａ、ｏ ｋ ＩｒＣｌ４１１３ａ、
ｏ Ｋ変えて実施例１と同様に行った。Table 6 Example 4 RhCj, @ 3a, o k IrCl4113a,
o The same procedure as in Example 1 was carried out except that K was changed.
反応生成物をガスクロマトグラフィーで分析した結果、
マ四ン酸ジメチｋが第４表の生成速度で生成した。As a result of analyzing the reaction product by gas chromatography,
Dimethic acid matetra-k was produced at the production rate shown in Table 4.
また反応開始後７２時間までのマロン酸ジエチルの総生
成量は１５８モル／１ｉｐ−触媒であった。Further, the total amount of diethyl malonate produced up to 72 hours after the start of the reaction was 158 mol/1ip-catalyst.
第４表
実施例５
ＲｈＣｊ、 ＊３ａ、ｏ １ ＃ ｔ−球状活性炭１０
ＩＩＫａ着させた後、さらＫＫＸｏ、６５１ｔ−吸着さ
せた触媒を内径２５鵡、高さ６００鋤の耐熱ガラス表反
応管に充填した後、２００℃に加熱して一酸化炭素を毎
時０１３モルの速度で１時間導入した。次に一酸化炭素
、モノクロロ酢酸エチル、及びジエチルエーテルをそれ
ぞれ毎時０．２５モル、０．０３モル、（）、１６モル
の速度で１７５℃に維持された予熱器を通して混合ガス
とし反応管に導入した。反応温度１７５℃、常圧下に反
応させた。Table 4 Example 5 RhCj, *3a, o 1 #t-spherical activated carbon 10
After IIKa deposition, KKXo and 651t-adsorbed catalyst was packed into a heat-resistant glass reaction tube with an inner diameter of 25mm and a height of 600mm, and heated to 200°C to release carbon monoxide at a rate of 0.13mol/hour. It was installed for 1 hour. Next, carbon monoxide, ethyl monochloroacetate, and diethyl ether are introduced into the reaction tube as a mixed gas through a preheater maintained at 175°C at a rate of 0.25 mol, 0.03 mol, (), and 16 mol per hour, respectively. did. The reaction was carried out at a reaction temperature of 175° C. and under normal pressure.
反応生成物をガスクロマトグラフィーで分析した結果、
マロン酸ジエチルが第５表の生成速度で生成し、その他
塩化エチルが副生していた。As a result of analyzing the reaction product by gas chromatography,
Diethyl malonate was produced at the production rate shown in Table 5, and ethyl chloride was also produced as a by-product.
また、反応開始後７２時間までのマロン酸ジエチルの総
生成量は４３９モル／Ｉ！Ｐ−触媒であった。Furthermore, the total amount of diethyl malonate produced up to 72 hours after the start of the reaction was 439 mol/I! It was a P-catalyst.
第５表
実施例６〜１５
実施例に準じて、モノクロロ酢酸エステル、溶媒、触媒
及び添加物を変えて実施した結果會第６表に示す。Table 5 Examples 6 to 15 Table 6 shows the results of experiments carried out in accordance with Examples 6 to 15 using different monochloroacetic esters, solvents, catalysts, and additives.
なお、マロン酸ジエチルの総生成量は反応開始後７２時
間までの累計生成量を示す。Note that the total production amount of diethyl malonate indicates the cumulative production amount up to 72 hours after the start of the reaction.
比較例１
実施例１の方法においてＫｘｔ−添加しない場合の試験
を行ったところ、反る開始後７２時間までのマロン酸ジ
メチルの線生成量は２１６モル／に？−触［であった。Comparative Example 1 When a test was conducted using the method of Example 1 without adding Kxt, the amount of dimethyl malonate line produced up to 72 hours after the start of warping was 216 mol/? -It was a touch.
比較例２
実施例４の方法においてに工ｔ−ａ加しない場合の試験
を行なったところ、反応開始後７２時間までのフロン酸
ジメチルの線生成量は７９モル／１ｉｐ−触媒であった
。Comparative Example 2 When a test was conducted using the method of Example 4 without adding t-a, the linear production amount of dimethyl fluoroate up to 72 hours after the start of the reaction was 79 mol/ip-catalyst.
比較例６
実施例５の方法においてに工ｉｆ添加しない場合の試験
を行なったところ、反応開始後７２時間までのマロン酸
ジメチルの線生成量は２３０モル／ＩＩＦ−触媒であっ
た。Comparative Example 6 When a test was conducted using the method of Example 5 without addition of IIF, the linear production amount of dimethyl malonate up to 72 hours after the start of the reaction was 230 mol/IIF-catalyst.
（発明の効果）
本発明によれば、気相反応で塩基性化合物を必要としな
いために、原料の混合が容易で且つ生成物の取得が容易
てあり、また、触媒効率が高（、簡単な操作で容易にマ
ロン酸ジエステルｔ−製造することができる。(Effects of the Invention) According to the present invention, since a basic compound is not required in the gas phase reaction, it is easy to mix the raw materials and obtain the product, and the catalytic efficiency is high ( Malonic acid diester t-can be easily produced by simple operations.
Claims (1)
テル類、エーテル類またはアセタール類を存在させまた
はさせずして、ハロゲン化酢酸エステルと一酸化炭素を
反応させるにあたり、沃素化合物の共存下、気相接触反
応させることを特徴とするマロン酸ジエステルの製法。When reacting halogenated acetate and carbon monoxide in the presence of a rhodium compound or iridium compound, with or without the presence of esters, ethers, or acetals, a gas phase catalytic reaction is carried out in the presence of an iodine compound. A method for producing malonic acid diester characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60173291A JPS6236343A (en) | 1985-08-08 | 1985-08-08 | Production of malonic acid diester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60173291A JPS6236343A (en) | 1985-08-08 | 1985-08-08 | Production of malonic acid diester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6236343A true JPS6236343A (en) | 1987-02-17 |
| JPH0149343B2 JPH0149343B2 (en) | 1989-10-24 |
Family
ID=15957720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60173291A Granted JPS6236343A (en) | 1985-08-08 | 1985-08-08 | Production of malonic acid diester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6236343A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4819208A (en) * | 1986-05-06 | 1989-04-04 | Mitsubishi Denki Kabushiki Kaisha | Biodirectional elastic store circuit |
-
1985
- 1985-08-08 JP JP60173291A patent/JPS6236343A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4819208A (en) * | 1986-05-06 | 1989-04-04 | Mitsubishi Denki Kabushiki Kaisha | Biodirectional elastic store circuit |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0149343B2 (en) | 1989-10-24 |
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