JPS62263141A - Production of 2,2-bis(hydroxymethyl)alkanoic acid - Google Patents
Production of 2,2-bis(hydroxymethyl)alkanoic acidInfo
- Publication number
- JPS62263141A JPS62263141A JP61105161A JP10516186A JPS62263141A JP S62263141 A JPS62263141 A JP S62263141A JP 61105161 A JP61105161 A JP 61105161A JP 10516186 A JP10516186 A JP 10516186A JP S62263141 A JPS62263141 A JP S62263141A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxymethyl
- bis
- hydrogen peroxide
- alkanal
- compound
- 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
- 239000002253 acid Substances 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 239000010955 niobium Substances 0.000 claims abstract description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 abstract description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000011135 tin Substances 0.000 abstract description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 10
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 8
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- CBIFNLUPCWCNQT-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)-2-methylpropanal Chemical compound OCC(C)(CO)C=O CBIFNLUPCWCNQT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000755266 Kathetostoma giganteum Species 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- 235000002492 Rungia klossii Nutrition 0.000 description 1
- 244000117054 Rungia klossii Species 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 eva methacrolein Natural products 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は２．コービス（ヒドロキシメチル）アルカン酸
の製造方法に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention comprises 2. The present invention relates to a method for producing corbis(hydroxymethyl)alkanoic acid.
コ、λ−ビス（ヒドロキシメチル）アルカン酸、例えば
λ、−一ビス（ヒドロキシメチル）プロピオン酸、コ、
−一ビス（ヒドロキシメチル）酪酸等は、ウレタン等の
高分子材料の原料として有用な化合物である。Co, λ-bis(hydroxymethyl)alkanoic acid, such as λ,-monobis(hydroxymethyl)propionic acid, co,
- Monobis(hydroxymethyl)butyric acid and the like are compounds useful as raw materials for polymeric materials such as urethane.
コ、コービス（ヒドロキシメチル）アルカン酸の製造方
法として、
■ α位にメチレン基を有するアルカナールとホルムア
ルデヒドとを縮合して得られるλ、２−ビス（ヒドロキ
シメチル）アルカナールを過酸化水素により酸化する方
法（例えば米国特許第３，３／２，７３４号明細書）、
及び■ 上記方法において、酸化剤に過イン酪酸を用い
る方法（有機合成化生協会誌、ＬらｌＯりｊ（／り７Ｊ
ｒ）、
が知られている。As a method for producing co-bis(hydroxymethyl)alkanoic acid, ■ λ,2-bis(hydroxymethyl)alkanal obtained by condensing an alkanal having a methylene group at the α position with formaldehyde is oxidized with hydrogen peroxide. (e.g., U.S. Pat. No. 3,3/2,734),
and ■ In the above method, a method using perimbutyric acid as an oxidizing agent (Journal of the Society for Organic Synthesis,
r), is known.
低く、多量の副生成物があり、そのため精製に手間を要
する。また上記■の方法も収率が高いとは言えず、更に
安全面での問題がある。There are many by-products, which makes purification laborious. Moreover, the above method (1) cannot be said to have a high yield, and there are also safety problems.
本発明者らはかかる従来技術の問題点を解決するため、
コ、２−ビス（ヒドロキシメチル）アルカナールの過酸
化水素による酸化反応を詳細に検討し、収率向上のため
の手段を探索した。In order to solve the problems of the prior art, the present inventors
The oxidation reaction of co-,2-bis(hydroxymethyl)alkanal with hydrogen peroxide was studied in detail, and a means for improving the yield was searched for.
その結果、酸化反応時に、触媒として特定の元素の化合
物を存在させると、目的物の収率が向上することを見出
し、本発明に到達した。As a result, it was discovered that the yield of the target product was improved when a compound of a specific element was present as a catalyst during the oxidation reaction, and the present invention was achieved.
即ち、本発明の要旨は、λ、ココ−ス（ヒドロキシメチ
ル）アルカナールを過酸化水素により１’ｆｆ１（ｔし
てλ、ココ−ス（ヒドロキシメチル）アルカン酸を製造
するに際し、触媒としてセリウム。That is, the gist of the present invention is to produce cocose (hydroxymethyl) alkanal with hydrogen peroxide to produce cocose (hydroxymethyl) alkanoic acid (λ) with cerium as a catalyst. .
チタン、ジルコニウム、スズ、ニオブ、モリブデン及び
タングステンからなる群から選ばれた少なくとも一種の
元素の化合物を使用することを特徴とする２、２−ビス
（ヒドロキシメチル）アルカン酸の否遣方法、に存する
。A method for discarding 2,2-bis(hydroxymethyl)alkanoic acid, characterized by using a compound of at least one element selected from the group consisting of titanium, zirconium, tin, niobium, molybdenum and tungsten. .
以下に本発明方法につき詳細に説明する。The method of the present invention will be explained in detail below.
本発明方法において原料として用いるコ、λ−ビス（ヒ
ドロキシメチル）アルカナールは、例えば、α位にメチ
レン基を有するアルカナール、例えばプロピオンアルデ
ヒド、ｎ−ブチルアルデヒド等を、ホルムアルデヒドと
、公知の手段により縮合すること罠よって製造される。The co,λ-bis(hydroxymethyl)alkanal used as a raw material in the method of the present invention is prepared by, for example, alkanal having a methylene group at the α-position, such as propionaldehyde, n-butyraldehyde, etc., with formaldehyde and known means. It is produced by condensation traps.
ホルムアルデヒド源としては通常、ホルマリン水溶液が
用いられるが、他の状懇のものでも良い。As the formaldehyde source, an aqueous formalin solution is usually used, but other sources may also be used.
触媒としては水酸化ナトリウム、トリエチルアミン等の
一般的な塩基性物質が用いられる。ホルムアルデヒドの
アルカナールに対するモル比は当址より過剰であること
が好ましく、通常コないしλＯ程度の範囲で選ばれる。As the catalyst, common basic substances such as sodium hydroxide and triethylamine are used. The molar ratio of formaldehyde to alkanal is preferably in excess, and is usually selected from a range of approximately 0 to λO.
°マタλ、コービス（ヒドロキシメチル）アルカナール
はα−アルキルアクロレイン、例エバメタクロレインと
ホルムアルデヒドとの付加反応によっても製造すること
ができる。Corbis(hydroxymethyl) alkanals can also be prepared by the addition reaction of α-alkyl acrolein, e.g. eva methacrolein, with formaldehyde.
コ、２−ビス（ヒドロキシメチル）アルカナールは、一
般に不安定な物質である。従って、コ、コービス（ヒド
ロキシメチル）アルカン酸の原料として用いる場合、一
旦ｒＩ製して純粋な形で填り出しても良いが、ひしろ、
縮合反応液をその１１、めるいはこれから未反応の原料
、縮。Co,2-bis(hydroxymethyl) alkanals are generally unstable materials. Therefore, when using it as a raw material for co-corbis(hydroxymethyl)alkanoic acid, it is possible to make rI and fill it in pure form, but
The condensation reaction solution is 11, and the unreacted raw materials are condensed.
金触媒等のみを除去して得られる租λ、２−ビス（ヒド
ロキシメチル）アルカナール溶液を用いるのが良い。It is preferable to use a 2-bis(hydroxymethyl) alkanal solution obtained by removing only the gold catalyst and the like.
過ば化水素によるλ、ｉ−ビス（ヒドロキシメチル）ア
ルカナールの酸化反応に２いて、過酸化水素の１史用漣
は、２．ノービス（ヒドロキシメチル）アルカナールに
対しモル比で通常０．１ないし２．好ましくはＯｏｌな
いし１．ｊである。もらろん、原料中に残存ホルムアル
デヒド等、過酸化水素を消費する物質が混入している場
合はそれに応じて過酸化水素の使用量を増加させる。In the oxidation reaction of λ, i-bis(hydroxymethyl) alkanal with hydrogen peroxide, the amount of hydrogen peroxide used is 2. The molar ratio to novis(hydroxymethyl) alkanal is usually 0.1 to 2. Preferably Ool to 1. It is j. Of course, if the raw materials contain substances that consume hydrogen peroxide, such as residual formaldehyde, the amount of hydrogen peroxide used will be increased accordingly.
−ｉた、酸化を完全に行なυうとする余り、大過剰のＡ
酸化水素を用いるときは、目的物の二次重分Ｍをひき起
こす恐れがあり、好ましくない。- In addition, in an attempt to completely oxidize, there was a large excess of A.
When hydrogen oxide is used, it is not preferable because it may cause secondary polymerization M of the target product.
過酸化水素は通常、水溶液として用いられる。Hydrogen peroxide is usually used as an aqueous solution.
反応のｂ媒とじ又は水が好ましい。反応温度は通常１，
２ｏ′ｃ：’ｘいしｉｏｏ℃、好’ＥＬ＜は１０℃ない
しり０℃である。The reaction medium B or water is preferred. The reaction temperature is usually 1,
2o'c: 'x is ioo°C,'EL< is 10°C to 0°C.
本発明方法の特徴とするところは酸化反応において特定
の触媒を用いることにある。該触媒としては周期律表第
μ周期から第６周期の第Ｊ族から第６族に属する元素の
化合物が挙げられるが、特にセリウム、チタン、ジルコ
ニウム、スズ、ニオブ、モリブデンおよびタングステン
の化合物が好１しく、本発明においてはこれらの化合物
を使用する。より具体的には、塩化セリウム、硝酸セリ
ウム、硫酸セリ９ムアンモニウム、塩化チタン、硝酸ジ
ルコニル、塩化スズ、シュウ酸ニオブ、モリブデン酸ア
ンモニウム、リンタングステン酸ナトリウム等が挙げら
れる。The method of the present invention is characterized by the use of a specific catalyst in the oxidation reaction. Examples of the catalyst include compounds of elements belonging to groups J to 6 of the μth period to the 6th period of the periodic table, and compounds of cerium, titanium, zirconium, tin, niobium, molybdenum, and tungsten are particularly preferred. First, these compounds are used in the present invention. More specifically, cerium chloride, cerium nitrate, ammonium cerium sulfate, titanium chloride, zirconyl nitrate, tin chloride, niobium oxalate, ammonium molybdate, sodium phosphotungstate, and the like can be mentioned.
特に反応系に可溶なものを用いるのが好筐しい。In particular, it is preferable to use one that is soluble in the reaction system.
触媒の使用量は過酸化水素１モルに対し、金属原子換算
で通常、／×１０ ’ないし／／Ｘ１０”モル、好１
しくは／Ｘ１０ ’ ナイＬ／ ！×１０ ”モルであ
る。The amount of catalyst used is usually /×10' to //X10'' mole, preferably 1 in terms of metal atoms, per 1 mole of hydrogen peroxide.
How/X10' Nai L/! ×10” moles.
反応は未反応の２，２−ビス（ヒドロキシメチル）アル
カナールが消失するまで行なうのが好ましい。生成物は
、まず過剰の過酸化水素が残存しておれば適当な方法で
分解したのち、溶媒を留去し、残留分から目的とする２
、コービス（ヒドロキシメチル）アルカン酸を晶析させ
る。The reaction is preferably carried out until unreacted 2,2-bis(hydroxymethyl)alkanal disappears. The product is first decomposed by an appropriate method if excess hydrogen peroxide remains, then the solvent is distilled off and the residue is converted to the desired 2
, to crystallize Corbis(hydroxymethyl)alkanoic acid.
必要により再結晶等によりさらに高純度化を計ることが
できる。If necessary, further purification can be achieved by recrystallization or the like.
次に実施例によって本発明の態様を更に具体的に説明す
るが、本発明はその要旨を越えない限り、以下の実施例
によって限定されるべきものではない。Next, embodiments of the present invention will be explained in more detail with reference to Examples, but the present invention should not be limited by the following Examples unless the gist thereof is exceeded.
実施例／−１０及び比較例１
（Ａ）、？、、？−ビス（ヒドロキシメチル）プロピオ
ンアルデヒドの合成：
３５％ホルマリン水溶液りＯａｔにブロピオンアルデヒ
ドタｔｘｌ及び２０％水酸化ナトリウム水溶液２．Ｏｆ
を加えて室温で２時間攪拌し、最後に脱塩水により全体
をｌ００ｘｌに希釈した。この希釈液を２，２−ビス（
ヒドロキシメチル）プロピオン酸合成の原料とし丸。Example/-10 and Comparative Example 1 (A), ? ,,? -Synthesis of bis(hydroxymethyl)propionaldehyde: 35% formalin aqueous solution, propionaldehyde txl and 20% sodium hydroxide aqueous solution 2. Of
was added and stirred for 2 hours at room temperature, and finally the whole was diluted to 100xl with demineralized water. This diluted solution was mixed with 2,2-bis(
Toshimaru is a raw material for the synthesis of hydroxymethyl)propionic acid.
（Ｂ）、２．λ−ビス（ヒドロキシメチル）プロピオン
酸の合成：上８ｄ希釈液ＪｄにＪＯＩ）過酸化水素水Ｊ
ｔｘｌ及び水２ｍｌに溶解した谷ｄ金属塩を加え、７
０℃で５時間反応させた。生成物ｔ−液体クロマトグラ
フィーで分析した結果を第１表に示す。(B), 2. Synthesis of λ-bis(hydroxymethyl)propionic acid: Add JOI to the above 8d diluted solution J) Hydrogen peroxide solution J
Add txl and Tani d metal salt dissolved in 2 ml of water,
The reaction was carried out at 0°C for 5 hours. The results of product t-liquid chromatography analysis are shown in Table 1.
第１表
第１表つづく
一１＋／）対プロピオンアルデヒド
１２） タ！℃、１時間反応
実施例／Ｉ及び比較例コ
３ｊ俤ホルマリンｕｎｔｉｌ、グロビオンアルデ℃ドタ
耐及び２０％水酸化ナトリウム水溶液２、Ｏｆを混合し
、２０℃において３時間反応させたのち、水で全体を１
００ｍ１に希釈してλ、２−上２−ヒドロキシメチル）
プロピオンアルデヒド水溶液を製造した。Table 1 Table 1 continued 1+/) versus propionaldehyde 12) Ta! ℃, 1 hour Reaction Example/I and Comparative Example 1 whole
00ml diluted with λ, 2-2-hydroxymethyl)
An aqueous propionaldehyde solution was produced.
１０％項化詐−セリウム水溶液２ ｙｔｌを混合し、７
０℃で５時間反応させた。目的物の２．λ−ビス（ヒド
ロキシメチル）プロピオン酸の収率はｔ ！、コチであ
った。Mix 2 ytl of 10% aqueous cerium solution, and
The reaction was carried out at 0°C for 5 hours. Objective 2. The yield of λ-bis(hydroxymethyl)propionic acid is t! , it was a flathead.
や
塩化第セリウムを用いなかったほかは同様に操作した場
合、収率はｔｌ、≠チであった。When the same procedure was performed except that cerium chloride and cerium chloride were not used, the yield was tl,≠t.
本発明方法により、λ、２−上２−ヒドロキシメチル）
アルカナールから高収率で、合成原料として有用な２．
２−ビス（ヒドロキシメチル）アルカン酸を製造するこ
とができる。By the method of the present invention, λ, 2-supra-2-hydroxymethyl)
2. High yield from alkanal and useful as a synthetic raw material.
2-bis(hydroxymethyl)alkanoic acid can be produced.
特許出願人 三菱化成工業株式会社 代 理 人 弁理士 長谷用 −ほか１名Patent applicant: Mitsubishi Chemical Industries, Ltd. Representative: Patent Attorney Hase - 1 other person
Claims (1)
ルを過酸化水素により酸化して２，２−ビス（ヒドロキ
シメチル）アルカン酸を製造するに際し、触媒としてセ
リウム、チタン、ジルコニウム、スズ、ニオブ、モリブ
デン及びタングステンからなる群から選ばれた少なくと
も一種の元素の化合物を使用することを特徴とする２，
２−ビス（ヒドロキシメチル）アルカン酸の製造方法。(1) When oxidizing 2,2-bis(hydroxymethyl)alkanal with hydrogen peroxide to produce 2,2-bis(hydroxymethyl)alkanoic acid, cerium, titanium, zirconium, tin, and niobium are used as catalysts. 2, characterized in that a compound of at least one element selected from the group consisting of molybdenum and tungsten is used;
A method for producing 2-bis(hydroxymethyl)alkanoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61105161A JPH0745430B2 (en) | 1986-05-08 | 1986-05-08 | Method for producing 2,2-bis (hydroxymethyl) alkanoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61105161A JPH0745430B2 (en) | 1986-05-08 | 1986-05-08 | Method for producing 2,2-bis (hydroxymethyl) alkanoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62263141A true JPS62263141A (en) | 1987-11-16 |
| JPH0745430B2 JPH0745430B2 (en) | 1995-05-17 |
Family
ID=14399976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61105161A Expired - Lifetime JPH0745430B2 (en) | 1986-05-08 | 1986-05-08 | Method for producing 2,2-bis (hydroxymethyl) alkanoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745430B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0751223A3 (en) * | 1995-06-26 | 1998-01-14 | Showa Denko Kabushiki Kaisha | Method for preparing dimethylolcarboxylic acid derivatives |
| CN107189052A (en) * | 2017-07-18 | 2017-09-22 | 温州南力实业有限公司 | A kind of preparation of loaded catalyst and its application in poly- carbonic acid hexylene glycol ester polyol is prepared |
| CN108658753A (en) * | 2018-06-20 | 2018-10-16 | 江西吉煜新材料有限公司 | A kind of continuous production device and technique of 2,2- dihydromethyl propionic acids |
| CN108658752A (en) * | 2018-06-20 | 2018-10-16 | 江西吉煜新材料有限公司 | A method of preparing 2,2- dihydromethyl propionic acids |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3312736A (en) * | 1963-07-29 | 1967-04-04 | Trojan Powder Co | Method of making polymethylol-alkanoic acids |
| JPS5615237A (en) * | 1979-06-29 | 1981-02-14 | Interox Sa | Manufacture of carboxyl compound |
-
1986
- 1986-05-08 JP JP61105161A patent/JPH0745430B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3312736A (en) * | 1963-07-29 | 1967-04-04 | Trojan Powder Co | Method of making polymethylol-alkanoic acids |
| JPS5615237A (en) * | 1979-06-29 | 1981-02-14 | Interox Sa | Manufacture of carboxyl compound |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0751223A3 (en) * | 1995-06-26 | 1998-01-14 | Showa Denko Kabushiki Kaisha | Method for preparing dimethylolcarboxylic acid derivatives |
| US5716815A (en) * | 1995-06-26 | 1998-02-10 | Showa Denko K.K. | Method for preparing dimethylcarboxylic acid compounds |
| CN107189052A (en) * | 2017-07-18 | 2017-09-22 | 温州南力实业有限公司 | A kind of preparation of loaded catalyst and its application in poly- carbonic acid hexylene glycol ester polyol is prepared |
| CN108658753A (en) * | 2018-06-20 | 2018-10-16 | 江西吉煜新材料有限公司 | A kind of continuous production device and technique of 2,2- dihydromethyl propionic acids |
| CN108658752A (en) * | 2018-06-20 | 2018-10-16 | 江西吉煜新材料有限公司 | A method of preparing 2,2- dihydromethyl propionic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745430B2 (en) | 1995-05-17 |
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