JPH0149343B2 - - Google Patents
Info
- Publication number
- JPH0149343B2 JPH0149343B2 JP60173291A JP17329185A JPH0149343B2 JP H0149343 B2 JPH0149343 B2 JP H0149343B2 JP 60173291 A JP60173291 A JP 60173291A JP 17329185 A JP17329185 A JP 17329185A JP H0149343 B2 JPH0149343 B2 JP H0149343B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- compound
- catalyst
- produced
- acetate
- 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
- -1 malonic acid diester Chemical class 0.000 claims description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 10
- 150000002504 iridium compounds Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 150000003284 rhodium compounds Chemical class 0.000 claims description 8
- 150000002497 iodine compounds Chemical class 0.000 claims description 7
- 150000001241 acetals Chemical class 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 20
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000010948 rhodium Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052703 rhodium Inorganic materials 0.000 description 6
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000000460 chlorine Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- 238000011049 filling Methods 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
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture 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
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000005907 alkyl ester 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 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
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 229960003750 ethyl chloride Drugs 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve 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
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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)
Description
（産業上の利用分野）
本発明はハロゲン化酢酸エステルと一酸化炭素
を反応させる、マロン酸ジエステルの製法の改良
法に関する。マロン酸ジエステルは医薬、農薬、
染料等の原料として利用されており、その安価な
製造方法の確立が望まれているものである。
（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を製造する方法が
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
提案されている。本発明者らは、先に特願昭60−
48156号明細書（特開昭61−97245号公報）におい
て、エステル類またエーテル類またはアセタール
類の存在下または不存在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。
（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と一
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を有するもので
あつた。
(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。
(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。
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。
（問題点を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。
以下本発明を更に詳しく説明する。
本発明に使用するハロゲン化酢酸エステルは沸
点250℃以下のものであれば特に限定されないが、
メチル、エチル、ｎ―プロピル、イソプロピル等
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。
本発明に使用するエステル類は沸点200℃以下
のものであれば特に限定されないが、好ましくは
酢酸メチル、酢酸メチル、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
キ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、
ハロゲン化酢酸イソプロピルであれば酢酸イソプ
ロピルの如くである。
本発明に使用するエーテル類は、沸点200℃以
下のものであれば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キル基を
有するジアルキルエーテル類が有利である。例え
ば、ハロゲン化酢酸メチルであればジメチルエー
テル、ハロゲン化酢酸イソプロピルであれば、ジ
イソプロピルエーテルの如くである。
本発明に使用するアセタール類は沸点200℃以
下のものであれば特に限定れないが、好ましくは
メチラール、ジエチルアセタール等である。
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。
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RhCl3・3H2O、
RhBr3・2H2O、Rh（NO3）、Rh2（CO）4Cl2、Rh
（CO）Cl〔Ｐ（C6H5）3〕2、RhCl〔Ｐ（C6H5）3〕3、
Rh2O3・5H2O、（NH4）3RhCl6、RhI3・xH2O、
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。
イリジウム化合物としてイリジウムのハロゲン
化物、無機酸塩または錯化合物であり、例をあげ
ればIrCl3・3H2O、IrCl4、IrBr3・4H2O、
（NH4）2IrCl6、IrCl（CO）3等である。これら化合
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。
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。例をあげれば、
LiI、KI、NaI、BaI2、CsI、RbI、CoI2、CaI2、
等であるが、好ましくは、NaI、KI、BaI2であ
る。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は、通常
活性炭、アルミナ、シリカ、珪藻土、軽石、ゼオ
ライト、モレキユラシーブなど不活性な担体に担
持させて使用するが、特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重量％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なわれる。
沃素化合物はロジウム化合物及びイリジウム化
合物と同様に担体に担持させて使用する。この場
合、ロジウム化合物またはイリジウム化合物と同
時に担持させても、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ることが有利
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１：0.01〜１：50、好ましくは１：0.1〜
１：10である。
本発明の反応は、一酸化炭素及び気体状のハロ
ゲン化酢酸エステル、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
をそのまま、あるいは不活性ガスで希釈して気相
状態で触媒上に導いて行われる。反応装置は気相
反応に用いる通常の固定床反応器が用いられる。
反応温度は、100℃〜300℃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。
原料の使用比率はハロゲン化酢酸エステル１モ
ルに対して一酸化炭素は１〜100モル、エステル
類は１〜50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
スの触媒層との触媒時間は0.2〜10秒の範囲が好
ましい。
反応後反応管から排出された反応物は、常法に
従つて冷却凝縮し、蒸留操作を得て、マロン酸ジ
エステルが取得される。
（実施例）
次に実施例により、本発明を具体的に説明す
る。
実施例 １
RhCl3・3H2O1ｇを球状活性炭10ｇに吸着させ
た後、さらにKI0.63ｇを吸着させた触媒を内径25
mm、高さ600mmの耐熱ガラス製反応管に充填した
後、200℃に加熱して一酸化炭素を毎時0.13モル
の速度で１時間導入した。次に、一酸化炭素及び
モノクロロ酢酸メ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。
反応生成物をガスクロマトグラフイーで分析し
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／Kg―触媒であ
つた。
(Industrial Application Field) The present invention relates to an improved method for producing malonic acid diester by reacting a halogenated acetate with carbon monoxide. Malonic acid diester is used for pharmaceuticals, agricultural chemicals,
It is used as a raw material for dyes, etc., and it is desired to establish an inexpensive manufacturing method. (Prior Art) Conventionally, a method has been proposed for producing malonic acid diester by reacting a halogenated acetate with carbon monoxide. For example, Japanese Patent Publication No. 56-16134 proposes a method in which the reaction is carried out in a liquid phase in the presence of an alcohol, a base, a rhodium catalyst, and optionally an iodine compound. The inventors previously filed a patent application in 1983-
In specification No. 48156 (Japanese Unexamined Patent Publication No. 61-97245), a method is proposed in which a gas phase catalytic reaction is carried out using a rhodium compound or an iridium compound as a catalyst in the presence or absence of esters, ethers, or acetals. did. (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. (1) All of these methods produce a small amount of malonic acid diester per unit amount of catalyst. (2) The method of reacting liquid halogenated acetate requires a large amount of basic compound to capture the halogen produced in the reaction.
It involves a technique for uniformly mixing the reactants and the basic compound, and requires complex operations such as filtration and extraction to separate the halogenated metal salt from the malonic acid diester and catalyst after the reaction. 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. (Means for Solving the Problems) The present invention involves reacting a 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. This is a method for producing malonic acid diester, which is characterized by carrying out a gas phase catalytic reaction in the presence of an iodine compound. The present invention will be explained in more detail below. The halogenated acetate used in the present invention is not particularly limited as long as it has a boiling point of 250°C or less, but
Lower alkyl esters such as methyl, ethyl, n-propyl, and isopropyl are preferred, and any halogen substituent may be used, but chlorine and bromine are particularly preferred. The esters used in the present invention are not particularly limited as long as they have a boiling point of 200°C or less, but are preferably acetate esters such as methyl acetate, methyl acetate, n-propyl acetate, isopropyl acetate, etc., and halogenated acetate esters. Preference is given to acetate esters which have the same alkyl group as the ester residue. For example, for halogenated methyl acetate, methyl acetate,
If it is a halogenated isopropyl acetate, it is like isopropyl acetate. The ethers used in the present invention are not particularly limited as long as they have a boiling point of 200°C or less, but are preferably dimethyl ether, diethyl ether, di-n
- Lower dialkyl ethers such as propyl ether and diisopropyl ether, and dialkyl ethers having the same alkyl group as the ester residue of the halogenated acetate ester are advantageous. For example, dimethyl ether is used for halogenated methyl acetate, and diisopropyl ether is used for halogenated isopropyl acetate. The acetals used in the present invention are not particularly limited as long as they have a boiling point of 200°C or less, but methylal, diethyl acetal, etc. are preferable. Carbon monoxide used in the present invention does not need to be particularly pure, and carbon monoxide containing an inert gas may be used. 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 include RhCl 3 .3H 2 O,
RhBr 3・2H 2 O, Rh (NO 3 ), Rh 2 (CO) 4 Cl 2 , Rh
(CO)Cl[P( C6H5 ) 3 ] 2 , RhCl [ P( C6H5 ) 3 ] 3 ,
Rh 2 O 3・5H 2 O, (NH 4 ) 3 RhCl 6 , RhI 3・xH 2 O,
etc. These compounds do not need to be highly pure, and may contain salts such as sodium chloride and potassium chloride. Iridium compounds include iridium halides, inorganic acid salts, or complex compounds, such as IrCl 3.3H 2 O, IrCl 4 , IrBr 3.4H 2 O,
( NH4 ) 2IrCl6 , IrCl(CO) 3 , etc. These compounds do not need to be highly pure, and may contain salts such as sodium chloride and potassium chloride. In the present invention, a metal iodide is used as the iodine compound added to the catalyst. For example,
LiI, KI, NaI, BaI 2 , CsI, RbI, CoI 2 , CaI 2 ,
etc., but preferably NaI, KI, BaI 2 . In addition, these iodine compounds may be hydrated. Rhodium compounds and iridium compounds are usually supported on an inert carrier such as activated carbon, alumina, silica, diatomaceous earth, pumice, zeolite, and molecular sieve, and activated carbon is particularly preferred. In this case, the amount of supported rhodium or iridium compound is expressed in terms of rhodium or iridium metal.
It is sufficient to use it in a range of 0.5 to 20% by weight. The rhodium or iridium compound is supported on the carrier by a known catalyst preparation method. The iodine compound is used by being supported on a carrier in the same manner as the rhodium compound and the iridium compound. In this case, the rhodium compound or iridium compound may be supported simultaneously or separately, but it is advantageous to support them separately. In this case, the amount of the iodine compound added is 1:0.01 to 1:50, preferably 1:0.1 to 1:50 in molar ratio to the rhodium compound or iridium compound.
It was 1:10. The reaction of the present invention is catalyzed in the gas phase using carbon monoxide and gaseous halogenated acetate, and if necessary, gaseous esters, ethers, or acetals as they are or diluted with an inert gas. It is carried out by leading upwards. The reactor used is a conventional fixed bed reactor used for gas phase reactions.
The reaction temperature is preferably 100°C to 300°C, and the reaction proceeds under normal pressure, but it can also be carried out under slightly increased pressure. The ratio of raw materials to be used is preferably in the range of 1 to 100 moles of carbon monoxide, 1 to 50 moles of esters, 1 to 50 moles of ethers, and 1 to 50 moles of acetals per mole of halogenated acetic ester. . The catalytic time of the raw material gas with the catalyst layer is preferably in the range of 0.2 to 10 seconds. After the reaction, the reactant discharged from the reaction tube is cooled and condensed according to a conventional method, followed by a distillation operation to obtain malonic acid diester. (Example) Next, the present invention will be specifically explained with reference to Examples. Example 1 After adsorbing 1 g of RhCl 3 3H 2 O on 10 g of spherical activated carbon, a catalyst with an inner diameter of 25 cm was adsorbed with 0.63 g of KI.
After filling a heat-resistant glass reaction tube with a diameter of 600 mm and a height of 600 mm, the mixture was heated to 200° C. and carbon monoxide was introduced at a rate of 0.13 mol/hour for 1 hour. Next, carbon monoxide and methyl monochloroacetate were added at 0.25 mol/hour each.
A mixed gas was introduced into the reaction tube through a preheater maintained at 175° C. at a rate of 0.06 mol. reaction temperature
The reaction was carried out at 175°C and under normal pressure. As a result of analyzing the reaction product by gas chromatography, dimethyl malonate was produced at the production rate shown in Table 1. Furthermore, the total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 432 mol/Kg of catalyst.
【表】
実施例 ２
KI0.63ｇをNaI・2H2O0.57ｇに変えて実施例
１と同様に行つた。
反応生成物をガスクロマトグラフイーで分析し
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。
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／Kg―触媒であつた。[Table] Example 2 The same procedure as in Example 1 was carried out except that 0.63 g of KI was replaced with 0.57 g of NaI.2H 2 O. As a result of gas chromatography analysis of the reaction product, dimethyl malonate was produced at the production rate shown in Table 2. The total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 468 mol/Kg of catalyst.
【表】
実施例 ３
KI0.63ｇをBaI2・2H2O1.62ｇに変えて実施例
１と同様に行なつた。
反応生成物をガスクロマトグラフイーで分析し
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。
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／Kg―触媒であつた。[Table] Example 3 The same procedure as in Example 1 was carried out except that 0.63 g of KI was replaced with 1.62 g of BaI 2.2H 2 O. As a result of gas chromatography analysis of the reaction product, dimethyl malonate was produced at the production rate shown in Table 3. The total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 396 mol/Kg of catalyst.
【表】
実施例 ４
RhCl3・3H2OをIrCl3・3H2Oに変えて実施例１
と同様に行つた。
反応生成物をガスクロマトグラフイーで分析し
た結果、マロン酸ジメチルが第４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158モル／Kg―触媒であつた。[Table] Example 4 Example 1 by changing RhCl 3・3H 2 O to IrCl 3・3H 2 O
I went in the same way. As a result of gas chromatography analysis of the reaction product, dimethyl malonate was produced at the production rate shown in Table 4. Furthermore, the total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 158 mol/Kg of catalyst.
【表】
実施例 ５
RhCl3・3H2O1ｇを球状活性炭10ｇに吸着させ
た後、さらにKI0.63ｇを吸着させた触媒を内径25
mm、高さ600mmの耐熱ガラス製反応管に充填した
後、200℃に加熱して一酸化炭素を毎時0.13モル
の速度で１時間導入した。次に一酸化炭素、モノ
クロロ酢酸メチル、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、0.16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。
反応生成物をガスクロマトグラフイーで分析し
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。
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／Kg―触媒であつた。[Table] Example 5 After adsorbing 1 g of RhCl 3 3H 2 O on 10 g of spherical activated carbon, a catalyst with an inner diameter of 25 cm was adsorbed with 0.63 g of KI.
After filling a heat-resistant glass reaction tube with a diameter of 600 mm and a height of 600 mm, the mixture was heated to 200° C. and carbon monoxide was introduced at a rate of 0.13 mol/hour for 1 hour. Next, carbon monoxide, methyl monochloroacetate, and diethyl ether were added at a rate of 0.25 mol, 0.03 mol, and 0.16 mol per hour, respectively.
A mixed gas was introduced into the reaction tube through a preheater maintained at 175°C. The reaction was carried out at a reaction temperature of 175°C and under normal pressure. Analysis of the reaction products by gas chromatography revealed that diethyl malonate was produced at the production rate shown in Table 5, and ethyl chloride was produced as a by-product. Furthermore, the total amount of diethyl malonate produced up to 72 hours after the start of the reaction was 439 mol/Kg of catalyst.
【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を第６
表に示す。
なお、マロン酸ジエステ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。[Table] Examples 6 to 15 The results of experiments conducted according to Examples with different monochloroacetic esters, solvents, catalysts, and additives are shown in the 6th table.
Shown in the table. Note that the total amount of malonic acid diester produced indicates the cumulative amount produced up to 72 hours after the start of the reaction.
【表】【table】
【表】
比較例 １
実施例１の方法においてKIを添加しない場合
の試験を行つたところ、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216モル／Kg―触
媒であつた。
比較例 ２
実施例４の方法においてKIを添加しない場合
の試験を行なつたところ、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79モル／Kg―触
媒であつた。
比較例 ３
実施例５の方法においてKIを添加しない場合
の試験を行なつたところ、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230モル／Kg―
触媒であつた。
（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
物の取得が容易であり、また、触媒効率が高く、
簡単な操作で容易にマロン酸ジエステルを製造す
ることができる。[Table] Comparative Example 1 When a test was conducted using the method of Example 1 without adding KI, the total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 216 mol/Kg of catalyst. Comparative Example 2 When a test was conducted using the method of Example 4 without adding KI, the total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 79 mol/Kg of catalyst. Comparative Example 3 When a test was conducted using the method of Example 5 without adding KI, the total amount of dimethyl malonate produced up to 72 hours after the start of the reaction was 230 mol/Kg.
It was a catalyst. (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 catalyst efficiency is high.
Malonic acid diester can be easily produced by simple operations.
Claims (1)
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。1 Gas phase catalytic reaction in the presence of a rhodium compound or iridium compound, in the presence or absence of esters, ethers, or acetals, in the presence of an iodine compound, when halogenated acetate and carbon monoxide are reacted. A method for producing malonic acid diester characterized by
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 JPS6236343A (en) | 1987-02-17 |
| JPH0149343B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62260444A (en) * | 1986-05-06 | 1987-11-12 | Mitsubishi Electric Corp | Two-way elastsic storage circuit |
-
1985
- 1985-08-08 JP JP60173291A patent/JPS6236343A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6236343A (en) | 1987-02-17 |
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