JPS6239544A - Production of malonic acid diester - Google Patents
Production of malonic acid diesterInfo
- Publication number
- JPS6239544A JPS6239544A JP17699585A JP17699585A JPS6239544A JP S6239544 A JPS6239544 A JP S6239544A JP 17699585 A JP17699585 A JP 17699585A JP 17699585 A JP17699585 A JP 17699585A JP S6239544 A JPS6239544 A JP S6239544A
- Authority
- JP
- Japan
- Prior art keywords
- malonic acid
- reaction
- acid diester
- butanol
- tert
- 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.)
- Pending
Links
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- -1 malonic acid diester Chemical class 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000004185 ester group Chemical group 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims description 2
- 150000002690 malonic acid derivatives Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 13
- 238000004821 distillation Methods 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- XPSYZCWYRWHVCC-UHFFFAOYSA-N 3-o-tert-butyl 1-o-methyl propanedioate Chemical compound COC(=O)CC(=O)OC(C)(C)C XPSYZCWYRWHVCC-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical group CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 1
- CLPHAYNBNTVRDI-UHFFFAOYSA-N ditert-butyl propanedioate Chemical compound CC(C)(C)OC(=O)CC(=O)OC(C)(C)C CLPHAYNBNTVRDI-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、エステル基の異なるマロン酸ジエステルの製
造法に関する。更に詳しくは、ターシャリブチル基と該
ターシャリブチル基と異なるエステル基を有するマロン
酸ジエステル（以下クロスエステルと称す）の製造法に
関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing malonic acid diesters having different ester groups. More specifically, the present invention relates to a method for producing a malonic acid diester (hereinafter referred to as cross ester) having a tertiary butyl group and an ester group different from the tertiary butyl group.
クロスエステルは、医薬、農薬等の原料として有用な物
質であり、その安価な製造方法の確立が望まれている。Cross ester is a substance useful as a raw material for medicines, agricultural chemicals, etc., and it is desired to establish an inexpensive method for producing it.
本発明は、同一のエステル基を有するマロン酸ジエステ
ルとターシャリブタノールを接触させ部分エステル交換
反応を行なわせてクロスエステルを製造する方法に関す
る。The present invention relates to a method for producing a cross ester by bringing a malonic acid diester having the same ester group into contact with tertiary butanol to carry out a partial transesterification reaction.
（従来の技術）
マロン酸クロスエステルの製造法としては従来より次の
方法が知られている。■酢酸エステルを触媒存在下でカ
ルボキシル化してマロン酸七ノエステルとした後、エス
テル化する方法。(Prior Art) The following method is conventionally known as a method for producing malonic acid cross ester. ■A method in which acetic acid ester is carboxylated in the presence of a catalyst to form malonic acid heptanoester, and then esterified.
（例えば、特開昭４９−３６６１２号公報）、■モノク
ロル酢酸エステルをエステル残基と異なるアルコール中
でカルボニル化する方法（％開昭５０−１１１０１５号
公報、特開昭５６−７３０４４号公報及び特開昭５６−
７５４３６号公報）、■マロン酸ジエステルをマロン酸
モノエステルトシｔ、ニー後、ａ酸存在下でイソブチレ
ンと反応させる方法（オーガニック・シン上９１，１９
５フ年、ａ’ｙｓ、３４頁＋＋、 Ｑｒｇ、 ５ｙｎｔ
ｈｅｓ＠ｓ＋ ３ヱ、３４ （１９５７））、■マロ
ン酸ジエステルをマロン酸モノエステルに導き、さらに
フタル酸クロリドでマロン酸モノエステルの酸フロリド
にした後、ターシャリ−ブタノ−Ｎを作用させる方法（
ジャーナルオブアメリカンケミカルソサイアテイ１９４
４年、６６巻、１２８６頁： Ｊ、Ａｍ＊ｒ＋Ｃｈ＊ｍ
ｅ ８ｏｃ、＊ ｊｊ２−１１２８６（１９４４））。(For example, JP-A-49-36612), ■ A method of carbonylating monochloroacetate in an alcohol different from the ester residue (% JP-A-50-111015, JP-A-56-73044, and 1977-
75436 Publication), ■ A method of reacting malonic acid diester with isobutylene in the presence of malonic acid monoester, t, and a acid (Organic Shin 91, 19).
5th year, a'ys, 34 pages ++, Qrg, 5ynt
hes@s+ 3ヱ, 34 (1957)), ■ A method in which malonic acid diester is converted into malonic acid monoester, which is further converted into acid fluoride of malonic acid monoester with phthalic acid chloride, and then treated with tertiary-butano-N (
Journal of American Chemical Society 194
Year 4, Volume 66, Page 1286: J, Am*r+Ch*m
e 8oc, * jj2-11286 (1944)).
（発明が解決しようとする問題点）
従来のマロン酸クロスエステルの製造法においては以下
に示す欠点を有していた。(Problems to be Solved by the Invention) Conventional methods for producing malonic acid cross esters have the following drawbacks.
■高価な触媒（Ｌｌ、Ｃｏ触媒など）を使用するため分
離・回収が必要６
■特殊な溶媒、試剤を用いるため（ジメチルホル；ア菰
ド、ジアゾメタン、フタル酸り・す・ドなど）分離が必
要であったり保安上の問題を有する。■Separation and recovery are necessary because expensive catalysts (Ll, Co catalysts, etc.) are used.6 ■Separation is difficult because special solvents and reagents are used (dimethylform; acomide, diazomethane, phthalate, etc.). It is necessary or has security issues.
本発明は、これらの問題点を解決し、より簡単な操作及
び触媒不存在下で効率の良いクロスエステルの製造法を
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 in order to solve these problems and provide a method for producing cross esters that is simpler and more efficient in the absence of a catalyst.
（問題点を解決するための手段）
本発明は、下記一般式（Ｉ）で示されるマロン酸ジエス
テルとターシャリブタノールとを無触媒下で加熱接触さ
せて、下記一般式（Ｉｔ）で示されるターシャリブチル
基を含むエステル基の異なるマロン酸ジエステルの製造
法である。(Means for Solving the Problems) The present invention provides a malonic acid diester represented by the following general formula (I) and tertiary butanol that are brought into contact with each other under heating in the absence of a catalyst, and a malonic acid diester represented by the following general formula (It) is This is a method for producing malonic acid diesters having different ester groups including a tert-butyl group.
（式中、Ｒはメチル基、エチル基、ｎ−プロピル基、ま
たは１−プロピル基である。）以下本発明を更に詳しく
説明する。(In the formula, R is a methyl group, an ethyl group, an n-propyl group, or a 1-propyl group.) The present invention will be explained in more detail below.
本発明は、触媒を使用しないことが特徴の１つである。One of the characteristics of the present invention is that no catalyst is used.
常法のエステル変換反応では酸触媒、が用いられるが、
ターシャリブタノールは酸触媒と反応してインブチレン
を生成するため、クロスエステルを工業的に製造するこ
とは不可能である。無触媒下で反応を促進させるため、
本発明の接触温度は８０〜１８０℃が好ましい。Acid catalysts are used in conventional ester conversion reactions, but
It is not possible to produce crossesters industrially because tertiary butanol reacts with acid catalysts to produce imbutylene. To accelerate the reaction without catalyst,
The contact temperature in the present invention is preferably 80 to 180°C.
接触温度は、反応速度の点からは高い方が効率的である
カ、マロン酸ジエステルやクロスエステルの熱安定性を
配慮すると１８０℃以下が好ましい。しかし、接触温度
が低すぎると接触時間が長くなるために８０〜１８０℃
が好ましい。The contact temperature is preferably 180° C. or lower in view of the thermal stability of the malonic acid diester and cross ester, although it is more efficient from the viewpoint of reaction rate. However, if the contact temperature is too low, the contact time will be longer, so
is preferred.
本発明に使用する同一のエステル基を有するマロン酸ジ
エステルは、特に純粋である必要はなり、マロン酸ジエ
ステルト同一のエステル基を有するマロン酸モノエステ
ルや不活性溶媒が共存するものを用いてもよい。The malonic acid diester having the same ester group used in the present invention does not need to be particularly pure, and a malonic acid monoester having the same ester group or an inert solvent may be used. .
本発明において使用する原料の使用比率は同一のエステ
ル基を有スるマロン酸ジエステル１モルに対してターシ
ャリブタノールが１〜１０モルの範囲であることが好ま
しい。The ratio of raw materials used in the present invention is preferably in the range of 1 to 10 moles of tertiary butanol per mole of malonic acid diester having the same ester group.
ターシャリブタノールがこの範囲より少ない場合は反応
速度が小さくなるので不適であり、また、ターシャリブ
タノールがこの範囲より多い場合は、クロスエステルの
生成にそれほど効果は望めず、マロン酸ジターシャリブ
チルの生成が多くなるので好ましくない。If the amount of tert-butanol is less than this range, it is unsuitable because the reaction rate will be low, and if the amount of tert-butanol is more than this range, it will not be very effective in producing cross-esters, and di-tert-butyl malonate will be This is not preferable because it generates more.
本発明は、バッチ方式、連続方式のいずれの方式も採用
できる。バッチ方式の場合、例えば、同一のエステル基
を有スるマロン酸ジエステルとターシャリブタノールを
反応缶に仕込み、密閉状態で部分エステル交換反応させ
る方法が、または、蒸留塔を備えた反応缶に同一のエス
テル基を有するマロン酸ジエステルを仕込み、次に反応
缶にターシャリブタノールを所定量分割添加し、エステ
ル変換されて副生したアルコールと未反応ターシャリブ
タノールを蒸留塔塔頂から留出させて反応させろ方法が
とられる。連続方式の場合は、例えば、上記バッチ方式
のうち分割添加すを方法に続けて、反応缶に同一のエス
テル基を有するマロン酸ジエステルとターシャリブタノ
ールを連続的に添加し、エステル交換されて副生したア
ルコールと未反応ターシャリブタノールを蒸留塔塔頂か
ら留出させると共に反応缶底部より生成したクロスエス
テルを抜き取る方法がとられる。The present invention can employ either a batch method or a continuous method. In the case of a batch method, for example, malonic acid diester and tertiary butanol having the same ester group may be charged in a reaction vessel and subjected to a partial transesterification reaction in a closed state; A malonic acid diester having an ester group is charged, and then a predetermined amount of tertiary butanol is added in portions to the reaction vessel, and alcohol by-produced by ester conversion and unreacted tertiary butanol are distilled out from the top of the distillation column. A method is used to make it react. In the case of a continuous method, for example, following the divided addition method of the above batch method, malonic acid diester and tertiary butanol having the same ester group are continuously added to the reaction vessel, and transesterification is performed to produce a by-product. A method is adopted in which the produced alcohol and unreacted tertiary butanol are distilled off from the top of the distillation column, and the produced cross ester is extracted from the bottom of the reaction vessel.
本発明における反応は常圧下で進行するが、密閉反応容
器中、加圧下で行なってもよ（、さらにエステル交換さ
れて副生じたアルコールや未反応ターシャリブタノール
を積極的に系外に留出させるために若干減圧下で行なっ
てもよい。The reaction in the present invention proceeds under normal pressure, but may also be carried out in a closed reaction vessel under pressure (in addition, alcohol by-produced by transesterification and unreacted tertiary butanol are actively distilled out of the system). It may be carried out under slightly reduced pressure in order to achieve this.
反応後、反応缶から排出された反応物は常法に従い、例
えば、蒸留によってクロスエステルが取得できる。After the reaction, the reactant discharged from the reaction vessel can be subjected to a conventional method, for example, by distillation, to obtain a cross ester.
（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゜
内容積１ｔのステンレス製オートクレーブにマロン酸ジ
メチル２モルとターシャリブタノール６モルを仕込み反
応缶の温度を１５０℃に保ちながら、密閉反応容器中で
部分エステル化反応を行なわせた。この時反応缶内の圧
力は０．７贅であった。Example 1 2 moles of dimethyl malonate and 6 moles of tert-butanol were charged into a stainless steel autoclave having an internal volume of 1 ton, and a partial esterification reaction was carried out in a closed reaction vessel while maintaining the temperature of the reactor at 150°C. At this time, the pressure inside the reaction vessel was 0.7 mm.
反応５時間後の生成物をガスクロマトグラフィーで分析
した結果マロン酸メチルターシャリブチルエステルが１
．１５モル生成していた（選択＄９６．３％、収＄ ５
７．５％）。Gas chromatography analysis of the product after 5 hours of reaction revealed that methyl tert-butyl malonate was 1.
．． 15 mol was produced (selection $96.3%, yield $5
7.5%).
実施例２゜
ＩＡインチ磁製ラシヒリングを充填した内径２０ｍ、高
さ２００箇の蒸留塔を備えつけた内容積５００−の反応
缶にマロン酸ジメチル２モルを仕込み、反応缶の温度を
１５０℃に保ちながら、常圧下でターシャリブタノール
を毎時０．５モルの速度で合計２．５モル分１Ｆｌｌ添
加すると同時に未反応のターシャリブタノール及び反応
で生成したメタノールを蒸留塔塔頂から系外に留出させ
ながらエステル交換反応させた。Example 2 2 moles of dimethyl malonate was charged into a reaction vessel with an internal volume of 500 mm and equipped with a distillation column with an inner diameter of 20 m and a height of 200 filled with IA inch porcelain Raschig rings, and the temperature of the reaction vessel was maintained at 150 °C. Meanwhile, under normal pressure, tertiary butanol was added at a rate of 0.5 mol per hour for a total of 2.5 mol of 1F, and at the same time unreacted tertiary butanol and methanol produced by the reaction were distilled out of the system from the top of the distillation column. The transesterification reaction was carried out while
反応５時間後の生成物をガスクロマトグラフィーで分析
した結果マロン散メチルターシャリブチルエステルが１
．１モル生成していた（選択率９５．３チ、収率５５％
）。Analysis of the product after 5 hours of reaction by gas chromatography revealed that malon powder methyl tert-butyl ester was 1
．． 1 mol was produced (selectivity 95.3, yield 55%)
).
実施例３゜
マロン酸ジメチルをマロン酸ジイソプロピルに変えて実
施例１と同様に行なった。Example 3 The same procedure as in Example 1 was carried out except that dimethyl malonate was replaced with diisopropyl malonate.
反応生成物をガスクロマトグラフィーで分析した結果、
マロン酸イソプロピルターシャリブチルエステルが０，
８６モル生成していた（選択率９４．１％、収率４３％
）。As a result of analyzing the reaction product by gas chromatography,
Isopropyl tertiary butyl malonate ester is 0,
86 mol was produced (selectivity 94.1%, yield 43%)
).
実施例４゜
実施例２で示した試験後、缶液中にターシャリブタノー
ル及びマロン酸ジメチルをそれぞれ毎時０．５モル及び
０．１モルの速度で連続的に供給し、１５０℃で反応さ
せた。未反応のターシャリブタノール及び反応で生成し
たメタノールを蒸留塔塔頂から系外に留出させると同時
に缶液の液面を一定に保ちながら連続的に反応缶底部よ
り生成りロスエステルを抜き取り、連続的にエステル交
換反応させた。Example 4 After the test shown in Example 2, tert-butanol and dimethyl malonate were continuously fed into the bottom liquid at a rate of 0.5 mol and 0.1 mol per hour, respectively, and reacted at 150°C. Ta. Unreacted tertiary butanol and methanol produced by the reaction are distilled out of the system from the top of the distillation column, and at the same time, the produced loss ester is continuously extracted from the bottom of the reaction vessel while keeping the liquid level of the bottom constant. The transesterification reaction was carried out continuously.
反応生成物をガスクロマトグラフィーで分析した結果、
マロン酸メチルターシャリブチルエステルが表の生成速
度で生成した。As a result of analyzing the reaction product by gas chromatography,
Methyl tert-butyl malonate ester was produced at the production rate shown in the table.
比較例１゜
３００ｍ１７５スコにマロン酸ジメチル０．５モル、タ
ーシャリブタノール２．０モルを仕込み反応温度６０℃
で５時間反応させた。Comparative Example 1 0.5 mol of dimethyl malonate and 2.0 mol of tertiary butanol were charged into a 300 m 175 Sco, and the reaction temperature was 60°C.
The reaction was carried out for 5 hours.
反応生成物をガスクロマトグラフィーで分析した結果、
マロン酸メチルターシャリブチルエステルが０．０１モ
ルしか生成していなかった（収率２％）。As a result of analyzing the reaction product by gas chromatography,
Only 0.01 mol of methyl tert-butyl malonate was produced (yield 2%).
比較例２゜
実施例２の方法において、触媒として硫酸を０．２モル
仕込み試験を行なったところ、インブチレンが発生し、
蒸留塔塔頂より留出した。反応生成物をガスクロマトグ
ラフィーで分析した結果、マロン酸メチルターシャリブ
チルエステルが０．０８モルしか生成していなかった（
収率４％）。Comparative Example 2 When a test was conducted using the method of Example 2 with 0.2 mol of sulfuric acid as a catalyst, inbutylene was generated.
Distilled from the top of the distillation column. Analysis of the reaction product by gas chromatography revealed that only 0.08 mol of methyl tert-butyl malonate was produced (
yield 4%).
（発明の効果）
本発明は同一のエステル基を有するｉロン酸ジエステル
とターシャリブタノールを触媒不存在で直接部分エステ
ル交換反応させるために、工程が短く、副生物の生成も
少なく、クロスエステルの取得が容易であり、また簡単
な操作で容易に実施できるすぐれた方法である。(Effects of the Invention) The present invention allows a direct partial transesterification reaction between an ironic acid diester and tertiary butanol having the same ester group in the absence of a catalyst, resulting in a short process, less generation of by-products, and the formation of cross-esters. It is an excellent method that is easy to obtain and can be easily implemented with simple operations.
特許出願人 電気化学工業株式会社 手続補正書 昭和６０年９月９日Patent applicant: Denki Kagaku Kogyo Co., Ltd. Procedural amendment September 9, 1985
Claims (2)
ルとターシヤリブタノールとを無触媒下で加熱接触させ
て、下記一般式（II）で示されるターシヤリブチル基を
含むエステル基の異なるマロン酸ジエステルの製造法。 ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） （式中、Ｒはメチル基、エチル基、ｎ−プロピル基、ま
たは１−プロピル基である。）(1) A malonic acid diester represented by the following general formula (I) and tertiary butanol are brought into contact with each other by heating in the absence of a catalyst to produce malonates having different ester groups containing a tertiary butyl group represented by the following general formula (II). Method for producing acid diesters. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R is a methyl group, ethyl group, n-propyl group, or 1-propyl group. .)
範囲第（１）項記載の製造法。(2) The manufacturing method according to claim (1), wherein the heating contact is carried out at 80 to 180°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17699585A JPS6239544A (en) | 1985-08-13 | 1985-08-13 | Production of malonic acid diester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17699585A JPS6239544A (en) | 1985-08-13 | 1985-08-13 | Production of malonic acid diester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6239544A true JPS6239544A (en) | 1987-02-20 |
Family
ID=16023339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17699585A Pending JPS6239544A (en) | 1985-08-13 | 1985-08-13 | Production of malonic acid diester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6239544A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980059274A (en) * | 1996-12-31 | 1998-10-07 | 박영구 | Method for producing malonic acid dialkyl ester |
| KR19980059273A (en) * | 1996-12-31 | 1998-10-07 | 박영구 | Method for producing malonic acid dialkyl ether |
| JP2014043418A (en) * | 2012-08-27 | 2014-03-13 | Toho Titanium Co Ltd | Method for producing asymmetric malonic acid diesters |
-
1985
- 1985-08-13 JP JP17699585A patent/JPS6239544A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980059274A (en) * | 1996-12-31 | 1998-10-07 | 박영구 | Method for producing malonic acid dialkyl ester |
| KR19980059273A (en) * | 1996-12-31 | 1998-10-07 | 박영구 | Method for producing malonic acid dialkyl ether |
| JP2014043418A (en) * | 2012-08-27 | 2014-03-13 | Toho Titanium Co Ltd | Method for producing asymmetric malonic acid diesters |
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