JPS6215060B2 - - Google Patents
Info
- Publication number
- JPS6215060B2 JPS6215060B2 JP6308581A JP6308581A JPS6215060B2 JP S6215060 B2 JPS6215060 B2 JP S6215060B2 JP 6308581 A JP6308581 A JP 6308581A JP 6308581 A JP6308581 A JP 6308581A JP S6215060 B2 JPS6215060 B2 JP S6215060B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- glyoxylic acid
- alcohol
- hemiacetal
- acid
- 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
- HHLFWLYXYJOTON-UHFFFAOYSA-N Glyoxylic acid Natural products OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 32
- -1 Glyoxylic acid hemiacetal ester Chemical class 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- SOEVVANXSDKPIY-UHFFFAOYSA-M sodium glyoxylate Chemical compound [Na+].[O-]C(=O)C=O SOEVVANXSDKPIY-UHFFFAOYSA-M 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- DBPFRRFGLYGEJI-UHFFFAOYSA-N ethyl glyoxylate Chemical compound CCOC(=O)C=O DBPFRRFGLYGEJI-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
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003899 tartaric acid esters Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
グリオキシル酸エステルの製造法として(1)酒石
酸エステルを過沃素酸で酸化する方法、(2)グリオ
キシル酸ヘミアセタールエステルを五酸化燐で処
理する方法、(3)無水酢酸中でグリオキシル酸ナト
リウムとアリールハライドを反応させる方法等が
報告されているが、(1)、(2)はそれぞれ過沃素酸、
五酸化燐という取扱い上特殊な試薬を使用する点
で、(3)は無水系での反応のために要求されるグリ
オキシル酸ナトリウムの実質的に無水の固体の調
製に困難がある点でいずれも工業的実施は有利で
あると言えない。
しかるに、本発明者等はグリオキシル酸ヘミア
セタールエステルを120℃以上に加熱すると共に
副生するアルコールを系外に除去しながら、該エ
ステルを熱分解する場合、容易にグリオキシル酸
エステルが製造出来ることを見出し本発明を完成
するに至つた。本発明の方法は原料の調製、ある
いは製造手段のいずれも簡単であるので、従来法
に比べて工業的規模での実施に当つて大きな利点
がある。
本発明ではグリオキシル酸ヘミアセタールエス
テルを(1)120℃以上に加熱して分解すること及び
(2)副生するアルコールを系外に除去好ましくは精
留下に除去することが不可欠の要件であり、いず
れか一方でもかかる条件が満たされない場合、目
的物の取得は不可能である。
本発明における出発原料であるグリオキシル酸
ヘミアセタールエステルは任意の方法で調製出
来、例えばシユウ酸エステルの電解還元法等が挙
げられるが、実用的にはグリオキシル酸とアルコ
ールを反応させる方法が有利である。グリオキシ
ル酸とアルコールとを反応させてグリオキシル酸
ヘミアセタールエステルを製造するには、グリオ
キシル酸にアルコール及びベンゼン等の適当な共
沸剤を添加し、共沸脱水すれば良い。この場合、
通常のエステル化反応に用いられる酸触媒を使用
することは反応がグリオキシル酸フルアセタール
エステルにまで進行する恐れがあり、一旦フルア
セタールエステルに変化すると熱分解によるグリ
オキシル酸エステルの製造が困難となるので、酸
触媒の不存在下で、ヘミアセタール化反応を行な
うのが有利である。
該グリオキシル酸ヘミアセタールエステルを熱
分解するに当つては、該液を120℃以上に加熱す
ると共に、副生するアルコールを系外に除去する
ことが必要である。加熱温度が120℃以下では充
分な分解がおこらず、目的物の収率が低く実用不
可能である。又、副生するアルコールを系外に除
去しないと、一旦生成したグリオキシル酸エステ
ルが再びグリオキシル酸ヘミアセタールエステル
に変化しこれ又、実用に供し得ない。
熱分解を実施する場合、例えば系内に選択的に
アルコールを吸収するアルコール吸収剤を添加し
て、加熱することが出来るが、工業的な規模での
実施では、精留塔にヘミアセタールエステルを導
入し120℃以上の温度で適当な環流比下に蒸留を
行なつて熱分解と脱アルコールを同時に行なうの
が有利である。まずアルコール等の低沸分を留去
したあと、留出するグリオキシル酸エステル分を
捕集すれば目的物が得られる。該グリオキシル酸
エステルは通常の目的には充分実用可能であるが
必要であれば、適宜精製を行つて差支えない。又
留去されたアルコールはグリオキシル酸ヘミアセ
タールエステルの調製用として再使用される。
本発明におけるグリオキシル酸ヘミアセタール
エステルのエステル基としては特に限定はなく任
意のエステルであつて良く、メチル、エチル、プ
ロピル、ブチル、アミル、ヘキシル、ヘプチル、
オクチル、カプリル、ノニル、デシル、ドデシ
ル、ミリスチル、ヘプタデシル、ステアリル、ベ
ンジル、フエネチル等が例示されるが、必ずしも
これらに限定されるものではない。
次に実例を挙げて本発明の方法を更に詳しく説
明する。
実施例 １
52.7％グリオキシル酸水溶液426ｇ（３モル）
にエチルアルコール500ml、ベンゼン100mlを加え
共酸脱水しながら、グリオキシル酸ヘミアセター
ルエチルエステルを調製した。
このエステルを精留塔（長さ１ｍ、内径20mmの
Vigreuxカラム）を用いてバス温145〜180℃にて
蒸留を行ない130〜131℃留分を捕集した。
該留分はグリオキシル酸エチルエステルであつ
た。実験の結果を表に示す。
実施例２〜３、対照例１〜２
表に示した条件下で実施例１に準じて各種のグ
リオキシル酸エステルを製造した。その結果を表
に示す。
【表】[Detailed description of the invention] Methods for producing glyoxylic acid ester include (1) a method of oxidizing tartaric acid ester with periodic acid, (2) a method of treating glyoxylic acid hemiacetal ester with phosphorus pentoxide, and (3) acetic anhydride. Among them, a method of reacting sodium glyoxylate and aryl halide has been reported, but methods (1) and (2) are performed using periodic acid and aryl halide, respectively.
(3) both require the use of a special reagent, phosphorus pentoxide, and the difficulty in preparing the substantially anhydrous solid sodium glyoxylate required for the reaction in an anhydrous system. Industrial implementation cannot be said to be advantageous. However, the present inventors have found that glyoxylic acid ester can be easily produced by heating glyoxylic acid hemiacetal ester to 120°C or higher and thermally decomposing the ester while removing by-product alcohol from the system. Heading: The present invention has been completed. Since the method of the present invention is simple in both the preparation of raw materials and the manufacturing method, it has a great advantage in implementation on an industrial scale compared to conventional methods. In the present invention, glyoxylic acid hemiacetal ester is decomposed by (1) heating to 120°C or higher;
(2) It is essential to remove by-product alcohol from the system, preferably by rectification, and if either of these conditions is not met, it is impossible to obtain the target product. Glyoxylic acid hemiacetal ester, which is the starting material in the present invention, can be prepared by any method, such as the electrolytic reduction method of oxalic acid ester, but for practical purposes, the method of reacting glyoxylic acid and alcohol is advantageous. . In order to produce glyoxylic acid hemiacetal ester by reacting glyoxylic acid and alcohol, alcohol and a suitable azeotropic agent such as benzene may be added to glyoxylic acid, followed by azeotropic dehydration. in this case,
If you use an acid catalyst that is used in a normal esterification reaction, there is a risk that the reaction will progress to glyoxylic acid full acetal ester, and once it changes to full acetal ester, it will be difficult to produce glyoxylic acid ester by thermal decomposition. , it is advantageous to carry out the hemiacetalization reaction in the absence of an acid catalyst. In thermally decomposing the glyoxylic acid hemiacetal ester, it is necessary to heat the liquid to 120° C. or higher and to remove by-product alcohol from the system. If the heating temperature is below 120°C, sufficient decomposition will not occur and the yield of the target product will be low, making it impractical. In addition, unless the by-produced alcohol is removed from the system, the glyoxylic acid ester once produced will change again to glyoxylic acid hemiacetal ester, which again cannot be put to practical use. When carrying out thermal decomposition, for example, an alcohol absorbent that selectively absorbs alcohol can be added to the system and heated, but when carried out on an industrial scale, hemiacetal ester is added to the rectification column. It is advantageous to carry out thermal decomposition and dealcoholization simultaneously by introducing and distilling at a temperature of 120° C. or higher and a suitable reflux ratio. First, low-boiling components such as alcohol are distilled off, and then the distilled glyoxylic acid ester component is collected to obtain the desired product. The glyoxylic acid ester is fully usable for ordinary purposes, but if necessary, it may be purified as appropriate. The alcohol distilled off is also reused for the preparation of glyoxylic acid hemiacetal ester. The ester group of glyoxylic acid hemiacetal ester in the present invention is not particularly limited and may be any ester, such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl,
Examples include, but are not limited to, octyl, capryl, nonyl, decyl, dodecyl, myristyl, heptadecyl, stearyl, benzyl, phenethyl and the like. Next, the method of the present invention will be explained in more detail by giving examples. Example 1 426 g (3 mol) of 52.7% glyoxylic acid aqueous solution
Glyoxylic acid hemiacetal ethyl ester was prepared by adding 500 ml of ethyl alcohol and 100 ml of benzene to the mixture and dehydrating the co-acid. This ester is transferred to a rectification column (1 m long, 20 mm inner diameter).
Distillation was performed using a Vigreux column at a bath temperature of 145 to 180°C, and a 130 to 131°C fraction was collected. The fraction was glyoxylic acid ethyl ester. The results of the experiment are shown in the table. Examples 2-3, Comparative Examples 1-2 Various glyoxylic acid esters were produced according to Example 1 under the conditions shown in the table. The results are shown in the table. 【table】
Claims (1)
120℃以上に加熱すると共に副生するアルコール
を系外に除去しながら、該エステルを熱分解する
ことを特徴とするグリオキシル酸エステルの製造
方法。 ２ グリオキシル酸ヘミアセタールエステルがグ
リオキシル酸とアルコールとの反応生成物である
特許請求の範囲第１項記載の製造方法。[Claims] 1. Glyoxylic acid hemiacetal ester
A method for producing glyoxylic acid ester, which comprises thermally decomposing the ester while heating to 120°C or higher and removing by-product alcohol from the system. 2. The manufacturing method according to claim 1, wherein the glyoxylic acid hemiacetal ester is a reaction product of glyoxylic acid and alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6308581A JPS57176929A (en) | 1981-04-24 | 1981-04-24 | Preparation of glyoxylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6308581A JPS57176929A (en) | 1981-04-24 | 1981-04-24 | Preparation of glyoxylic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57176929A JPS57176929A (en) | 1982-10-30 |
| JPS6215060B2 true JPS6215060B2 (en) | 1987-04-06 |
Family
ID=13219135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6308581A Granted JPS57176929A (en) | 1981-04-24 | 1981-04-24 | Preparation of glyoxylic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57176929A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4820385A (en) * | 1988-02-18 | 1989-04-11 | Monsanto Company | Purification of alkyl glyoxylate in a continuous column by azeotropic distillation |
| US4867849A (en) * | 1988-07-25 | 1989-09-19 | Cova Dario R | Purification of alkyl glyoxylate |
| JP2934605B2 (en) * | 1995-08-24 | 1999-08-16 | 株式会社日本触媒 | Method for producing α-oxocarboxylic acid ester and catalyst used therefor |
-
1981
- 1981-04-24 JP JP6308581A patent/JPS57176929A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57176929A (en) | 1982-10-30 |
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