JPS59210028A - Method for oxidation - Google Patents
Method for oxidationInfo
- Publication number
- JPS59210028A JPS59210028A JP8381083A JP8381083A JPS59210028A JP S59210028 A JPS59210028 A JP S59210028A JP 8381083 A JP8381083 A JP 8381083A JP 8381083 A JP8381083 A JP 8381083A JP S59210028 A JPS59210028 A JP S59210028A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- nitric acid
- concentration
- aqueous solution
- oxidation
- 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
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 79
- 239000002253 acid Substances 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- -1 alkyl compound Chemical class 0.000 claims abstract description 4
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 abstract description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 20
- 229940015043 glyoxal Drugs 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 150000001299 aldehydes Chemical class 0.000 abstract description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 abstract description 4
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000272209 Coraciiformes Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004157 Nitrosyl chloride Substances 0.000 description 1
- 241000238413 Octopus Species 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 1
- 235000019392 nitrosyl chloride Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 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)
この発明は有機化合物の酸化方法に関するものであり、
アルデヒド・カルボン酸なと含酸素有機化合物の製造に
用いることができる。[Detailed Description of the Invention] (Industrial Application Field) This invention relates to a method for oxidizing organic compounds,
It can be used to produce oxygen-containing organic compounds such as aldehydes and carboxylic acids.
(従来技術)
有機化学の分野における酸化方法のひとつとしで、硝酸
酸化法か占くがら知られでいる。(Prior Art) One of the oxidation methods in the field of organic chemistry is the nitric acid oxidation method.
例えば西トイソ特許932369号によるとクリオキザ
ールを30〜50%(重量%以ド同し)硝酸で酸化する
ことて高濃度のグリオキシル酸水溶7rシか得られる。For example, according to Nishi Toiso Patent No. 932369, a highly concentrated glyoxylic acid aqueous solution 7r can be obtained by oxidizing cryoxal with 30 to 50% (wt%) nitric acid.
硝酸酸化は活性アルキル化合物や、炭素炭素工(【、結
合化合物の酸化にも用いられる。。Nitric acid oxidation is also used to oxidize active alkyl compounds and carbon-carbon compounds.
活性アルキル化合物の例としでは、アルキルカルホニル
化合物(アルデヒド・ケトン)、芳fi 族佃I鎖アル
キル化合物か挙げられる。これらの化合物ではカルボニ
ル基や芳香核に隣るα炭素原子−1−の炭素水素結合か
qノ断され炭素酸素結合を形成した7 ルテヒ+” ヤ
カルボン酸を生ずる。アセトアルデヒド
ンからトリメリント
る。また炭素炭素二重結合化合物の硝酸酸化の例として
は、テトラヒドロフタル
挙りられ、炭素炭素結合が切断され、炭素酸素結合か形
成されたブタンテトラカルボン酸を生ずる。Examples of active alkyl compounds include alkylcarbonyl compounds (aldehydes and ketones) and aromatic I-chain alkyl compounds. In these compounds, the carbon-hydrogen bond of the alpha carbon atom -1- adjacent to the carbonyl group or aromatic nucleus is cleaved to form a carbon-oxygen bond, resulting in 7 lutehi+" yacarboxylic acid. It is trimelinated from acetaldehydone. An example of nitric acid oxidation of a carbon double bond compound is tetrahydrophthal, where the carbon carbon bond is broken and a carbon oxygen bond is formed to produce butane tetracarboxylic acid.
これらの硝酸酸化反応において用いられる硝酸濃度はい
ろいろである。例えば小方芳部著、有機化合物の酸化と
還凡(南江堂)p。436〜452に示されている多数
の例からひろうと、低いもので5〜15%、1島いもの
では90%に」二る。しがル硝酸濃度1%以下というよ
うなきわめて低い濃度て満足すべき速度で酸化のおこな
われる例は、知られていないようであり、また反応を順
調に進行させるためにしはしは過剰性の硝酸が用いられ
る。The nitric acid concentration used in these nitric acid oxidation reactions varies. For example, Yoshibe Ogata, Oxidation and Return of Organic Compounds (Nankodo), p. From the numerous examples shown in 436-452, it can be as low as 5-15%, and as high as 90% for one island. There seems to be no known example of oxidation occurring at a satisfactory rate at an extremely low concentration of nitric acid, such as 1% or less; Nitric acid is used.
硝酸は滴下なとの逐次添加法で用いられることも多いか
、反応液中には5%前後又はそれ以上の濃度で硝酸か存
在するのか普通である。例え(1特開昭51 2944
1に5〜7%なとの記載がある。Nitric acid is often used by a sequential addition method such as dropwise addition, or it is usually present in the reaction solution at a concentration of around 5% or more. Example (1 Japanese Patent Publication No. 51/1944 2944
1 states that it is 5 to 7%.
このように著量の硝酸を含む混合物か得られた場合精製
処理を必要とするが、蒸留法や晶析法の適用しにくいも
のについではイオン交換樹脂処理、電気透析たとコスI
・の高い特別の精製法を用いなければならなかった。精
製工程は更に目的物の一部及び残留硝酸のロスをもたし
でいた。If a mixture containing a significant amount of nitric acid is obtained in this way, purification treatment is required, but if it is difficult to apply distillation or crystallization methods, ion exchange resin treatment, electrodialysis, and cost-effective treatment are necessary.
・Special purification methods with high levels of The purification process also resulted in the loss of some of the target product and residual nitric acid.
グリオキザール水溶液の硝酸酸化に際して硫酸、塩酸、
リン酸及び硝酸アルミニウムからなる群より選ばれた化
合物を存在させて反応を促進させる方法か知られでいる
(特開昭48−103517 )。Sulfuric acid, hydrochloric acid,
A method is known in which the reaction is accelerated by the presence of a compound selected from the group consisting of phosphoric acid and aluminum nitrate (Japanese Unexamined Patent Publication No. 103517/1983).
これらの物質はグリオキザールに刻して通常0.02〜
02モルの使用で未反応グリオキザールを減少させると
同時にグリオキシル酸収率を高める1、しかし、反応液
中の硝酸濃度は滴下終了後80’CI肋間の熟成を経た
後でも約3%あり、硝酸の滴下反応中に5%1]1■後
又はそれ以−にの濃度である点に一ついては従来の硝酸
酸化と特に異なるものではなかった。These substances are chopped into glyoxal and are usually 0.02~
The use of 0.2 mol of unreacted glyoxal reduces unreacted glyoxal and increases the yield of glyoxylic acid. There was no particular difference from conventional nitric acid oxidation in that the concentration was 5% 1] 1 or more during the dropping reaction.
濃硝酸1容と濃塩酸3容とを混合してなる酸化剤組成物
は、ト水の名で古くから知られておりHNOl−3HC
1−CQ +NOC,6+−21−103←
22
のように発生期の塩素や塩化ニトロシルを含むの−(強
力な酸化溶解性かある。また王水を水て倍にうずめた希
王水や、組成を逆転した硝酸3 塩酸1の逆王水も知ら
れているが、普通の王水も含めて金属や鉱石など無機r
ビ学の分野の酸化溶解剤としでの利用にととまっていた
。An oxidizing agent composition made by mixing 1 volume of concentrated nitric acid and 3 volumes of concentrated hydrochloric acid has been known for a long time as HNOl-3HC.
1-CQ +NOC, 6+-21-103←
22 Contains nascent chlorine and nitrosyl chloride (has strong oxidation solubility.Also, dilute aqua regia is diluted with aqua regia, and inverted aqua regia with 3 nitric acid and 1 hydrochloric acid. Water is also known, but it also contains minerals such as metals and ores, including ordinary aqua regia.
Its use was limited to as an oxidizing solubilizer in the field of biology.
このように硝酸と塩酸とを含む公知の水性酸化剤t11
成物は、いずれもがなり高い濃度の硝酸を含むものてあ
り、また活性アルキル化合物や二重結合化合物がら含酸
素有機化合物を製造する反応に用いられたものでもなか
った。従って硝酸塩酸混合物を用い残存イ萌酸がきわめ
で低濃度の反応混合物を直接にt!jる酸化方法は知ら
れていない。Thus, the known aqueous oxidizing agent t11 containing nitric acid and hydrochloric acid
All of the products contained a high concentration of nitric acid, and none of them were used in the reaction to produce oxygen-containing organic compounds from active alkyl compounds or double bond compounds. Therefore, using a nitrate acid mixture, a reaction mixture with a very low concentration of residual sulfuric acid can be directly prepared. There is no known oxidation method.
(発明の目的)
木発萌は、公知の硝酸酸化法で必要とされた数%又はそ
れ以上(こ比べてきわめて低い1%以下、例えIi’
0.1%曲後又はそれ以上の硝酸濃度においで1,11
,17足ずべき反応速度て有機基τ1を酸化、含酸素有
機化合物を得る方法である。この方法は反応混合物から
の硝酸の除去工程を不・県にし、また硝酸ロスをなくす
利点かある。(Objective of the invention) Wood sprouting is reduced to several percent or more than that required by the known nitric acid oxidation method (compared to 1% or less, which is extremely low, for example, Ii'
1,11 at a nitric acid concentration of 0.1% or higher
, 17, the organic group τ1 is oxidized to obtain an oxygen-containing organic compound at a reaction rate of less than 17. This method has the advantage of eliminating the step of removing nitric acid from the reaction mixture and eliminating nitric acid loss.
(発明の構成)
本発明者は硝酸は・酸化源とはするか、それを直接に有
機基質と反応させるのでなく、硝酸濃度1%以上になる
ように非酸化性強酸水溶液中に逐次添加して系内に形成
される水性酸化剤組成物υ)形て有機基質を酸化−1−
ることにより、系内の蛸酸濃1q、をきわめて低濃度に
保ったま\、しかも満hl 1−へさ速度て酸化剤組成
物か得られることを見出した1゜(非酸化性強酸)
非酸化性強酸としでは塩酸か代表的なもσ)であるか、
臭化水素酸、希硫酸、トノジエンスルホンのことく、水
溶液中ではに゛完全に解削して(・る強酸( pK a
<0 )であって、過塩素酸の.J: :)な酸化性
のものでない酸は回しように使用できる3。(Structure of the Invention) The present inventor uses nitric acid as an oxidation source, and instead of directly reacting it with an organic substrate, it is added sequentially to a non-oxidizing strong acid aqueous solution so that the nitric acid concentration is 1% or more. The aqueous oxidant composition υ) formed in the system oxidizes the organic substrate.
It was discovered that an oxidizing agent composition can be obtained at a rate of 1 liter while keeping the concentration of octopus acid in the system at an extremely low concentration of 1 q (non-oxidizing strong acid). A strong oxidizing acid is hydrochloric acid or the typical σ).
Strong acids (pK a
<0) of perchloric acid. J: :) Non-oxidizing acids can be used as usual.3.
酸の種類や濃度のちがいかあるので、(1ちか(・に−
1,水と同様とに1凸゛えないか、非酸化性強酸、水、
硝酸の3つを出発物とする酸化剤組成物IIIて化パを
反応により硝1′Iヲ自身より強力な酸化種かできて(
・るものと思われる。このような観点から非酸[ヒ+1
1強酸濃度は」−記酸化剤組成物11(g中のモ/lz
数て表わず。逐次添加1−る硝酸中の水分により希釈さ
オ′シてこの濃度は下ってゆくか、反応のはしめには1
七ル/1<g以上、約1時でも05モル/Kg以−に即
持することか好ましい。この限界濃度は反応液中の硝酸
濃度をチェック1−ることにより実験的にきめることか
てきる、。Since there are many different types and concentrations of acids,
1.A non-oxidizing strong acid, water,
Oxidizing agent composition III starting with nitric acid produces an oxidizing species more powerful than nitric acid itself (
・It seems that From this point of view, non-acid [H+1
1.The concentration of strong acid is 11 (mol/lz in g) of oxidizing agent composition 11 (g).
There are no numbers. As the water in the nitric acid is successively added, the concentration of the nitric acid decreases, or at the end of the reaction, the concentration of nitric acid decreases.
It is preferable that the ratio is 7 mol/1<g or more, and it is preferably maintained immediately at 0.5 mol/Kg or more even for about 1 hour. This limit concentration can be determined experimentally by checking the nitric acid concentration in the reaction solution.
他ノハ不必“歩に高す感度にすることはなく、硫酸の場
合、高濃度(こすとると酸1′ヒ性になり、濃硫酸、硝
酸、:老醜は二1・口化削であるというように別のはた
らきをもつ3、塩酸の場合、通常供給される濃度(すI
Qモル/ K g以上てあり、この点も実用上の上限に
なる。結局好ましい初濃度は1〜5モル/1りg程度で
ある。この値1;よ滴下され系内に現存している硝酸濃
度(1% 016%以下)に比べて6倍以」二(こあた
る。In the case of sulfuric acid, there is no need to increase the sensitivity to an unnecessarily high level. 3. In the case of hydrochloric acid, which has a different function as shown in FIG.
Q mol/Kg or more, which is also a practical upper limit. After all, the preferred initial concentration is about 1 to 5 mol/g. This value is more than 6 times the concentration of nitric acid (1% or less) that is present in the system after being dropped.
非酸化性強酸の11じCも、塩酸は、有[穴石素化反応
の副生物として太(IYに余剰か出るなど入手か容易で
あり、あまり高濃度てなくても有効であり、反応1選4
〕<率向上や、所望により除去する場合の蒸発法か■げ
能である点なと最も好ましいものである。Hydrochloric acid is also a non-oxidizing strong acid, and it is easily obtained as a by-product of the mineralization reaction. 4
] It is most preferable in that it improves the rate and can be removed by evaporation if desired.
酢酸のような弱酸はもとより、リン酸のような中程度の
強さの酸も反応液中の硝酸濃度を低下させる本発明の作
用はない。Not only weak acids such as acetic acid but also moderately strong acids such as phosphoric acid do not have the effect of the present invention of reducing the nitric acid concentration in the reaction solution.
((+l’i酸の逐次添加)
低い硝酸濃度で反応を進めるという本発明の1−1的か
らして、下水のような高濃度の硝酸を含む組成物自体を
そのま(の形で用いるイつけにはゆかない。硝酸濃度を
できるたけ低くおさえ、塩酸や硫酸の濃度を有効に使う
ために基質と、i’sA酸や硫酸とを含む水溶液中に硝
酸を滴下する。もちろんy+゛i:il・″以外の形で
逐次添加しでもよい。((Sequential addition of +l'i acid)) Considering the objective 1-1 of the present invention, which is to proceed with the reaction at a low nitric acid concentration, the composition itself containing a high concentration of nitric acid, such as sewage, is used as it is. In order to keep the nitric acid concentration as low as possible and use the concentrations of hydrochloric acid and sulfuric acid effectively, nitric acid is dropped into the aqueous solution containing the substrate and i'sA acid and sulfuric acid.Of course, y+゛i :il·'' may be added sequentially.
これにより基質に対して当量的にはごく少し・酸化剤組
成物で反応をはしめ、消費された酸化パリは逐次添加さ
れた硝酸と系内に多量に存在する非酸化性強酸とから1
1f生する。相対的に多量:に存在する非酸化性強酸は
、硝酸を直ちに油量酸化剤組成物に変え、基質を速やか
に酸化するので系内硝酸濃度を1%以下に保つことは容
易である。従来技術と同様の高濃度、例えは40〜50
%の硝酸を滴トシでも反応液中の硝酸濃度は019a以
1このことか多い。As a result, the reaction is carried out with a very small amount of the oxidizing agent composition equivalently to the substrate, and the consumed oxidized paris is separated from the nitric acid successively added and the non-oxidizing strong acid present in large amounts in the system.
Live 1f. The non-oxidizing strong acid present in a relatively large amount immediately converts nitric acid into an oil oxidizer composition and quickly oxidizes the substrate, making it easy to maintain the nitric acid concentration in the system at 1% or less. High concentration similar to conventional technology, e.g. 40-50
Even if 1% nitric acid is added dropwise, the nitric acid concentration in the reaction solution is about 1% higher than 0.019a.
(有(幾基質)
上記酸化法はまず含酸素有機化合物をより高次の酸化段
階の含酸素有機化合物に酸化する反応について見出され
た1、この4ノ1(の反応として、カルボニル化合物か
らカルホン、酸、アルコールからカルボニル化合物を得
ろ反応が挙けられる。クリオキザールからクリオキシル
酸、ヘンツインからヒベノンイルなと従来のfj1冒俊
1′り化法が適用できた反応と同種の基質につ(・て適
用できる。また活性アルキル化合物の酸化に用いること
もてきる。アルテヒトやケトンの如きアルキルヵルホニ
ル化合物を酸化するとアルギル基はカルボニルの隣(α
−位)で酸化される。アセトアルデヒドからクリオキザ
ールの生成はその例℃ある。芳香族側鎖のアルキル基も
粘性なα−位て酸化されること同(羨であり芳香族アル
テヒトや芳香族カルボン酸を生り−る。(Presence (many substrates)) The above oxidation method is based on 1, which was discovered regarding the reaction of oxidizing an oxygen-containing organic compound to an oxygen-containing organic compound at a higher oxidation stage. Examples include reactions to obtain carbonyl compounds from carphones, acids, and alcohols.Reactions to obtain carbonyl compounds from cryoxal to cryoxylic acid, from henzin to hibenonyl, etc. It can also be used for the oxidation of active alkyl compounds.When oxidizing alkylcarbonyl compounds such as artechite and ketones, the argyl group is oxidized next to the carbonyl (α
- position). An example is the formation of cryoxal from acetaldehyde. The alkyl group in the aromatic side chain is also oxidized at the viscous α-position, producing aromatic artefacts and aromatic carboxylic acids.
キンシン類、フッイドクメン、デュレン、 ヒ ス(3
4−ジメチルフェニル)エタンなとのメチル基を酸化す
ることができる。p−二1・ロトルエンの如き二1・口
基舎もつ芳香核の側鎖アルギル基はIIG 記のものに
比べて酸化しにくい。Kingfishers, Huidokumen, Duren, Hiss (3
The methyl group can be oxidized such as 4-dimethylphenyl)ethane. The side chain argyl group of an aromatic nucleus having a 21-group base, such as p-21-rotoluene, is less likely to be oxidized than those listed in IIG.
炭素炭素二重結合をもつ化合物の酸化も本発明の方法で
実施できる1、テトラヒドロフタル物かC,はフタ/デ
トラカルホ/酸−う・rllられる,、f−のIUL、
/クロ・\キセノ、キノリンなとかこのイ小のノ1シ′
白の例として挙i−Jられる。The oxidation of compounds with carbon-carbon double bonds can also be carried out by the method of the present invention.
/ Kuro \ xeno, kinoline, etc.
Examples of white are i-J.
( イ1肖 酸 )
硝酸は従来の硝酸酸化法に:J6ける・とれと同し.J
、う石、品′e1、濃度、添IJ11失を用いることか
てぎる、、例えば45ゾお前後の11業用(ll″i酸
4・反1,1″・膚イレ中に滴)・。(I1 Portion) Nitric acid is used in the conventional nitric acid oxidation method: Same as J6. J
, Calcium, product'e1, concentration, use of added IJ11 loss, for example, 11 industrial use after 45 zo (ll"i acid 4, anti-1,1", drops in skin irritation). .
(71)応させる。硝酸の酸1′に能力は非酸11Z性
強酸づ(溶i(シとの作111て1111られる水性酸
化削絹放物;こ移り、有機部質は速やかに酸化される.
、 /iii費された硝1%(こ刈し1°・、:する酸
化窒素は反L1’.:器の気相部に111でくる,。(71) Make them respond. The ability of nitric acid to react with acid 1' is transferred to a non-acid 11Z strong acid (dissolved in a water-based oxidation product made with 1111), and the organic parts are quickly oxidized.
, /iii 1% of the nitric oxide (removed 1°): The nitrogen oxide that is consumed comes to the gas phase of the vessel at 111.
オフカス中の酸化窒素は空/,IC.酸化、水吸収塔4
・通す/fと公知り))7法で硝酸として回収できる。The nitrogen oxide in the off-gas is empty/, IC. Oxidation, water absorption tower 4
・Publicly known as pass/f)) It can be recovered as nitric acid using method 7.
(反ル15条件)
反応i’iirj度は基I,r!Jや[]的物;こLi
’fi j;遂1宜凍択てさる、。(Reaction 15 conditions) The reaction i'iirj degree is the group I, r! J and [] things; koLi
'fi j;Finally, I've made my choice.
−・liljL的には0〜+ 0 0 ’Cの範囲から
、カスの発生やイと熱で知られるj叉1,F二の進行を
確1,,(にしなからrillj. L”t:6・ζ1
!−一定に保ちつつ硝酸を滴下する,F記の記述は詳細
な検i?Jをもこ〆fつだクリオギリーールがらクリオ
キシル酸〜・の実幹データにもとっ・′.1でいるか、
他のJ、いご↓の場合にもはg゛あてはまる。即ち滴下
の末期Oこは反応液中の硝酸濃度かり5%というように
多少」二るか1 %を超えることはない。硝酸濃度はi
i:iij下終r後史(ニドってゆき1時間もたては通
常0005〜003%迄−トす、特にrll、製・?必
要どせずに残存前11俊濃度01%以下のクリオキシル
酸溶液か得られる、従来の硝1峻酸化の場合は0.1モ
ル程度の硫酸や塩酸を添加して反応を促進した場合ても
40℃前後における硝酸滴下だけてはグリオキサール−
ルの変(ヒ率自体が向−1二し難く、滴ド終了後s o
”cイ・′11度に:F?’ tll+’+’t L
で熟成することが行なわれでいたか、本発明の場合は特
に昇温しで熟成する必要はない。From a range of 0 to + 0 0'C, the progress of j-1 and F-2, which are known for the generation of scum and heat, can be confirmed. 6・ζ1
! - Is the description in F about dropping nitric acid while keeping it constant? We also looked at actual data on cryoxylic acid, including cryoxylic acid. Are you at 1?
G゛ also applies to other cases of J and Igo↓. That is, at the end of the dropping, the concentration of nitric acid in the reaction solution does not exceed 5%, or more than 2% or 1%. Nitric acid concentration is i
i: Iij lower end history (after 1 hour, it usually reaches 0005-003%, especially rll, production, etc., without any need for residual pre-11 concentration of cryoxyl of 01% or less) In the case of conventional nitric acid oxidation, in which an acid solution is obtained, glyoxal-
(The rate itself is difficult to move -12, and after the drop is completed, so
``C I・'11 degrees: F?'tll+'+'t L
In the case of the present invention, it is not necessary to ripen at elevated temperature.
反応には亜哨酸力l・リウムの如き公知の開始剤を用い
ることもでざる1、また、アルミナ、バノーシン酸、ア
ンモニウノ・、銅粉末などを加えで反応させることもで
きる。In the reaction, a known initiator such as sulfuric acid, chloride, etc. can be used, or alumina, vanosic acid, ammonium chloride, copper powder, etc. can be added to the reaction.
(発明の作用・効果)
多量の非酸化性強酸を含む水溶液中に硝酸を滴下すると
強力な酸化剤組成物が形成され、従来の硝酸酸化法ては
酸化か進行しなかったような低硝酸濃度(1%以1’
)を保ったよ(含酸素有機化合物−\の酸化か進行する
。これにより残存硝酸をほとんと含まない[目的物の水
溶液か容易に得られる、これにより従来必要とされてい
た残存硝酸除去の]:稈を省いて面接イ〕機合成反応に
供することかてぎるようになった。父、用途に、より強
酸を含まない目的物を必・及1とする場合は、例えは塩
酸の蒸発なとの処理を行なえはよい。(Actions and Effects of the Invention) When nitric acid is dropped into an aqueous solution containing a large amount of non-oxidizing strong acid, a strong oxidizing agent composition is formed, and the nitric acid concentration is so low that oxidation does not proceed in the conventional nitric acid oxidation method. (1% or more 1'
) was maintained (the oxidation of oxygenated organic compounds progresses. As a result, it contains almost no residual nitric acid [an aqueous solution of the target product can be easily obtained; this removes residual nitric acid, which was previously required) :It has become possible to omit the culm and use it for organic synthesis reaction.If the purpose requires a target product that does not contain a stronger acid, for example, evaporation of hydrochloric acid. It is better to do the processing with
酸化剤として硝酸は大部分オフノJス中の酸化窒素から
回収り能であるので、T業的には回収不能′Cロスとな
る硝酸は反応液中の残存硝酸(こもとつくものか多かっ
た。本発明は、この残存硝酸を激減させるので副原料節
減の効果も大きい。また、従来の(il!i酸酸化酸酸
化−でしくましくまみられた硝酸の蓄積か起きないため
反応か暴走するとか、−11,’jにNOxを含む排ガ
スを多量に出すことか無いため運転管理あるいは環境保
全の立場から見でも非常に有利である。Since nitric acid as an oxidizing agent can be recovered mostly from nitrogen oxide in off-gas, the nitric acid that cannot be recovered in the T industry and results in C loss is the residual nitric acid in the reaction solution. Since the present invention drastically reduces this residual nitric acid, it has a great effect in saving auxiliary materials.Also, since the accumulation of nitric acid that was seen in the conventional method (il!i acid oxidation) does not occur, the reaction may run out of control. Since there is no need to emit a large amount of exhaust gas containing NOx, it is very advantageous from the standpoint of operation management and environmental conservation.
例1. 水59.3 g 、硫酸30g(水溶液中の濃
度34モル/+<g)とテI・ラヒドロフタル酸無水物
45.6 g、銅粉末0.7 gバナンン酸アンモニウ
l\0. :3 gと共に仕込み、加熱したところ70
〜80℃で1イj−になっl’:o63%イ+f’i
l’i*を滴ドし、90〜100−Cで反応を続けた1
、反応終了IL’jまての滴下量5 Q g +:11
の水を加えると終了11、テの水性酸化剤#−1成物中
の硫酸div度は288モル/<gであった。反応混合
物から析出した結晶(4,s g)はブタンテトラカル
ホン酸であった。漏液ヲメチルエステル化して分析した
ところフタンテトラカルポン酸かエステルの形て漏液中
にも見出された。Example 1. 59.3 g of water, 30 g of sulfuric acid (concentration in aqueous solution 34 mol/+<g), 45.6 g of teI-rahydrophthalic anhydride, 0.7 g of copper powder, ammonium vananate \0. : 70 when prepared with 3 g and heated
It becomes 1 j- at ~80℃ l': o63% i + f'i
l'i* was added dropwise and the reaction was continued at 90-100-C.
, dripping amount until reaction completion IL'j 5 Q g +: 11
When water was added, the degree of sulfuric acid div in the aqueous oxidizer #1 composition was 288 mol/<g. The crystals (4, s g) precipitated from the reaction mixture were butanetetracarphonic acid. When the leaked liquid was converted into methyl ester and analyzed, phthanetetracarboxylic acid or ester was also found in the leaked liquid.
例2355%塩酸149g、10%rn;、硝酸ソータ
水溶液8g(HCβ93モル/ 1<g )をアセトア
ルjとド355gと混i’ff1L+44%硝酸乏;8
8gを40−42℃て、15時間かりて滴ドした。反応
液中ソ)硝酸濃度t・10.25・29以ドてあり、ア
セトアルデヒド約5579が反応した、、355%塩h
ネの代ζ・に5.15′も塩酸j 4 9 1:を用い
、10%111I。Example 2 149 g of 355% hydrochloric acid, 10% rn;, 8 g of nitric acid sorter aqueous solution (HCβ93 mol/1<g) were mixed with 355 g of acetal and 1L + 44% nitric acid deficient;8
8 g was added dropwise at 40-42°C over 15 hours. The concentration of nitric acid in the reaction solution was t.
5.15' was also used for ζ and 10% 111I using hydrochloric acid j 4 9 1:.
硝酸ソーダ水溶液を加え(HC&1.34モル/ K.
g )、355gのアセ:・アルデートと共に40″0
に加熱しアルミナ5gを加え、44%硝酸288gを滴
下しく 4 0 ”C 1. 5時間)反応させた,、
反応フィシ及びトう/゛ゾ甲残っていたアセトアルデヒ
ド
デヒドをさしひくと変化率は約31%てあり、反応液中
に得られたグリオキサールは659gであ′)だ6反応
液( 6 9 6. 1 g )中にはこの他・)・酸
(30%)、酢酸(4.4%)、クリ」ギシル酸なとそ
の他の酸分(111男・)か分析された。Add sodium nitrate aqueous solution (HC & 1.34 mol/K.
g), 355g of ace:・40″0 with aldate
5 g of alumina was added, and 288 g of 44% nitric acid was added dropwise to react (40"C 1.5 hours).
Subtracting the reaction mixture and the remaining acetaldehyde dehyde, the rate of change was approximately 31%, and the glyoxal obtained in the reaction solution was 659 g. It was also analyzed that 1 g of the sample contained 1 g of other acids (30%), acetic acid (4.4%), chloroformic acid, and other acids (111 g).
[り11 3. 1 8. 2%硫酸1. 3 9
g、3%硫酸10g、10%+11(硝酸ソーダtog
(H2SOi。[ri11 3. 1 8. 2% sulfuric acid 1. 3 9
g, 3% sulfuric acid 10g, 10% + 11 (sodium nitrate tog
(H2SOi.
16モル/ Kg ) f 用イ、アセトアルデヒド3
5514、アルミナl O gと共にlL+:合し、4
4%硝酸288gを40℃て滴下した。16 mol/Kg) f A, acetaldehyde 3
5514, lL+: combined with alumina lOg, 4
288 g of 4% nitric acid was added dropwise at 40°C.
反応液( 717.2 g )中にはアセトアルデヒド
( 2 6. 6 2’%)とパラアルデヒド(496
%)か残っているか、反応生成物としてグリオキサール
(9,37%) a 7.2 gか得られた。この他ギ
酸(227%)、酢酸(4,26%)、クリオキシル酸
メfとの酸分(+ 2. Ci 4 ’(お)か分析さ
れた。The reaction solution (717.2 g) contained acetaldehyde (26.62%) and paraaldehyde (496%).
%) remained, and 7.2 g of glyoxal (9.37%) was obtained as the reaction product. In addition, the acid content of formic acid (227%), acetic acid (4.26%), and cryoxylic acid mef (+2.Ci 4 '(O)) was analyzed.
例4. 濃塩酸(i(Cβ97モル/+<g ) 30
0 g中にテユレン40.3 ((を加え、68%硝酸
167gを滴下した。反応温度70〜95℃てカスの発
生、原料の消失などから酸化反応の進行が認められた。Example 4. Concentrated hydrochloric acid (i (Cβ97 mol/+<g) 30
40.3 g of Teyulene was added to the solution, and 167 g of 68% nitric acid was added dropwise. At a reaction temperature of 70 to 95° C., progress of the oxidation reaction was observed from the generation of scum and the disappearance of raw materials.
原料としてヒス(34−ジメチルフェニル)エタンヲ用
いた場合も同様に活性メチル基の酸化がみられた。Similar oxidation of active methyl groups was observed when his(34-dimethylphenyl)ethane was used as the raw material.
例5. シクロヘキセンと塩酸(濃度153%)の不均
一相混合物中に40°Cて45%硝酸を滴下したところ
酸化反応か進み、酵素と塩素の尋人された生成物が得ら
れた1、例6. グリオキサール1996%、グリオキ
シル酸049%、塩酸1002%を含む水溶液435g
に45%硝酸154gを反応湿度40 ’Cて4時間か
けで滴下し、その場でつくられる酸化剤ス:[↓酸物(
開始時FIC君345モル/1\g)によりグリオキサ
ールを40°Cて酸化したつ滴下終了後1時間(同?j
ul+L’史)てクリオキシル酸1658%を含み、硝
酸わずかに0007%の反応液を得た。この反応液中に
はグリオキサール084%I J’lin”l酸7.3
4%、蓚酸3.31%を含んでいた2、クリオキザール
変1ヒ率(ま947%、クリオキシル酸選)ノI! 率
84.7%、収率821%であった7、水性酸化剤組人
物中の塩酸濃度を(・ろいろ;こ変えてはg同様の反応
を行なった結果をあhせて第1表に示す。Example 5. When 45% nitric acid was dropped into a heterogeneous phase mixture of cyclohexene and hydrochloric acid (concentration 153%) at 40°C, the oxidation reaction proceeded and a complex product of enzyme and chlorine was obtained.1, Example 6. 435g of an aqueous solution containing 1996% glyoxal, 049% glyoxylic acid, and 1002% hydrochloric acid.
154 g of 45% nitric acid was added dropwise over 4 hours at a reaction humidity of 40'C to form an oxidizing agent on the spot: [↓Acid (
At the start, glyoxal was oxidized at 40°C using FIC-kun (345 mol/1\g) for 1 hour after the dropwise addition was completed (same?j).
A reaction solution containing 1,658% of cryoxylic acid and only 0,007% of nitric acid was obtained. This reaction solution contained 084% glyoxal and 7.3% IJ'lin'l acid.
4%, oxalic acid 3.31%2, Cryoxylic acid concentration (947%, Cryoxylic acid selection) No I! The concentration of hydrochloric acid in the aqueous oxidizing agent mixture was 84.7% and the yield was 821%. Shown below.
第 1 表
例7.塩酸の代りに、初濃度14.16%(144モル
/ Kg )の硫酸を含む水溶液を用い、反応rAii
度を60゛Cとした他は、はV実施例2、;うと同様に
してグリオキサールを酸化した。Table 1 Example 7. Instead of hydrochloric acid, an aqueous solution containing sulfuric acid with an initial concentration of 14.16% (144 mol/Kg) was used to conduct the reaction rAii.
Glyoxal was oxidized in the same manner as in Example 2, except that the temperature was changed to 60°C.
滴下終了後1時間(60°C)て、硝酸0011%に迄
1・′つたクリオキシル酸く1357%)水溶液を得た
。グリオキザール変化率975%、クリオキシル酸選択
率66.8%であった。One hour after the completion of the dropwise addition (at 60°C), an aqueous solution of cryoxylic acid (1357%) containing nitric acid (0011%) was obtained. The glyoxal conversion rate was 975% and the cryoxylic acid selectivity was 66.8%.
例8.(比較例)
硫酸の代りに初濃度15.05%のリン酸を含む水溶液
を用いた他は例7.とはV同様にしてグリオキザールを
酸化した。滴下終了後]、 l+、’1間(60℃)で
1174%のグリオキシル酸水浴液か得られたか、硝酸
か、3、04 %も残ッテイタ。A、、e(NO3)3
9 H20としての初濃度27.6%の硝酸アルミニウ
ムを用いた場合(反応温度40“C:も得らJl、た1
067%グリオキシル酸水溶液中の硝酸濃度761%で
あった。このように強酸以外の添加剤は多量に用いても
従来の硝酸酸化を本質的・1こ変える作用をもつでいな
い。Example 8. (Comparative Example) Example 7 except that an aqueous solution containing phosphoric acid with an initial concentration of 15.05% was used instead of sulfuric acid. Glyoxal was oxidized in the same manner as V. After completion of the dropwise addition], a glyoxylic acid solution of 1174% was obtained between 1 and 1 (60°C), and 3.04% of nitric acid remained. A,,e(NO3)3
9 When using aluminum nitrate with an initial concentration of 27.6% as H20 (reaction temperature 40"C:
The concentration of nitric acid in the glyoxylic acid aqueous solution was 761%. As described above, even if additives other than strong acids are used in large amounts, they do not have the effect of essentially changing conventional nitric acid oxidation.
Claims (1)
ように硝酸を逐次添加して系内に形成される水性酸化剤
組成物により有機基質(クリオキザールを除く)を酸化
し含酸素有機化合物を得ることを特徴とする酸化方法 2、 有機基質か活性アルキル化合物又は炭素炭素二重
結合化合物である特許請求の範囲第1項記載の酸化方法 3 非酸化性強酸か塩酸又は硫酸である特許請求の範囲 第1項又は第2項記載の酸化方法[Claims] 1. Organic substrates (excluding cryoxal) are removed by an aqueous oxidant composition formed in the system by sequentially adding nitric acid to an aqueous solution of a non-oxidizing strong acid so as to maintain the nitric acid concentration at 1% or less. Oxidation method 2 characterized in that the organic substrate is oxidized to obtain an oxygen-containing organic compound; Oxidation method 3 according to claim 1, wherein the organic substrate is an active alkyl compound or a carbon-carbon double bond compound; Non-oxidizing strong acid or hydrochloric acid or sulfuric acid, the oxidation method according to claim 1 or 2.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8381083A JPS59210028A (en) | 1983-05-13 | 1983-05-13 | Method for oxidation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8381083A JPS59210028A (en) | 1983-05-13 | 1983-05-13 | Method for oxidation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59210028A true JPS59210028A (en) | 1984-11-28 |
JPH0469131B2 JPH0469131B2 (en) | 1992-11-05 |
Family
ID=13813020
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8381083A Granted JPS59210028A (en) | 1983-05-13 | 1983-05-13 | Method for oxidation |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59210028A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2654428A1 (en) * | 1989-11-16 | 1991-05-17 | Hoechst France | NEW PROCESS FOR THE CONTINUOUS INDUSTRIAL MANUFACTURE OF AN AQUEOUS GLYOXYLIC ACID SOLUTION. |
-
1983
- 1983-05-13 JP JP8381083A patent/JPS59210028A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2654428A1 (en) * | 1989-11-16 | 1991-05-17 | Hoechst France | NEW PROCESS FOR THE CONTINUOUS INDUSTRIAL MANUFACTURE OF AN AQUEOUS GLYOXYLIC ACID SOLUTION. |
EP0428429A2 (en) * | 1989-11-16 | 1991-05-22 | Societe Francaise Hoechst | Process for a continuous industrial preparation of an aqueous solution of glyoxylic acid |
Also Published As
Publication number | Publication date |
---|---|
JPH0469131B2 (en) | 1992-11-05 |
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