JPS6312876B2 - - Google Patents
Info
- Publication number
- JPS6312876B2 JPS6312876B2 JP54000978A JP97879A JPS6312876B2 JP S6312876 B2 JPS6312876 B2 JP S6312876B2 JP 54000978 A JP54000978 A JP 54000978A JP 97879 A JP97879 A JP 97879A JP S6312876 B2 JPS6312876 B2 JP S6312876B2
- Authority
- JP
- Japan
- Prior art keywords
- diacetone
- palladium
- reaction
- acid
- sorbose
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 42
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 15
- -1 diacetone ketogulonic acid ester Chemical class 0.000 claims description 15
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052716 thallium Inorganic materials 0.000 claims description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RGHNJXZEOKUKBD-KKQCNMDGSA-N D-gulonic acid Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-KKQCNMDGSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002211 L-ascorbic acid Substances 0.000 description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- 239000005711 Benzoic acid Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006567 deketalization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005837 enolization reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 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
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007273 lactonization reaction Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
Description
【発明の詳細な説明】
本発明は、ジアセトンケトグロン酸エステルの
製造方法に関する。２−ケトグロン酸エステルは
医薬品、食品添加剤として有用なＬ−アスコルビ
ン酸の中間原料として知られている化合物であ
る。従来、この２−ケトグロン酸エステルは、ジ
アセトンソルボースを過マンガン酸カリもしくは
次亜塩素酸ソーダ等により酸化し、ジアセトンケ
トグロン酸のアルカリ塩となし、中和後ジアセト
ンケトグロン酸とする。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diacetone ketogulonic acid ester. 2-ketogulonic acid ester is a compound known as an intermediate raw material for L-ascorbic acid, which is useful as a pharmaceutical and food additive. Conventionally, this 2-ketogulonic acid ester is produced by oxidizing diacetone sorbose with potassium permanganate or sodium hypochlorite to form an alkali salt of diacetone ketogulonic acid, which is then neutralized to form diacetone ketogulonic acid. .
その後アルコールとともに硫酸の存在下に脱ケ
タール化およびエステル化反応をおこない、２−
ケトグロン酸エステルを合成する方法が知られて
いる。最近では、この酸化反応の際に改良方法と
して水性のアルカリ性媒質中で貴金属触媒を用い
てジアセトンソルボースを酸素とともに反応せし
めることによりジアセトンケトグロン酸（アルカ
リ塩）を製造する方法特公昭53−28431号等が提
供されている。ここで得られた２−ケトグロン酸
エステルは、ナトリウムメトキサイドの存在下
に、ラクトン化およびエノール化反応をおこな
い、Ｌ−アスコルビン酸に導かれる。しかしなが
ら上記酸化反応等による方法は、工程数が多く、
煩雑な為工業的製造方法としては、コスト高とな
つている。そこで本発明者らは、Ｌ−アスコルビ
ン酸のより工業的に有利な製造方法について検討
をおこなつた結果、ジアセトンソルボースから一
挙にジアセトンケトグロン酸エステルを合成する
方法を見出し、本発明を達成した。すなわち本発
明方法は、ジアセトンソルボースをアルコール溶
媒中、酸素または酸素含有ガスとともにパラジウ
ム含有触媒を用い酸化反応せしめることによりジ
アセトンケトグロン酸エステルを一段で製造する
方法を提供するものである。 After that, deketalization and esterification reactions are carried out together with alcohol in the presence of sulfuric acid, and 2-
Methods for synthesizing ketogulonic acid esters are known. Recently, as an improved method for this oxidation reaction, a method for producing diacetone ketogulonic acid (alkaline salt) by reacting diacetone sorbose with oxygen using a noble metal catalyst in an aqueous alkaline medium has been proposed. No. 28431 etc. are provided. The 2-ketogulonic acid ester obtained here undergoes lactonization and enolization reactions in the presence of sodium methoxide, and is led to L-ascorbic acid. However, the method using the above-mentioned oxidation reaction etc. has a large number of steps;
Because it is complicated, it is expensive as an industrial manufacturing method. Therefore, the present inventors investigated a more industrially advantageous production method for L-ascorbic acid, and as a result, discovered a method for synthesizing diacetone ketogulonate from diacetone sorbose all at once, and developed the present invention. Achieved. That is, the method of the present invention provides a method for producing diacetone ketogulonic acid ester in one step by subjecting diacetone sorbose to an oxidation reaction in an alcohol solvent with oxygen or an oxygen-containing gas using a palladium-containing catalyst.
反応式で示せばつぎのとおりである。 The reaction formula is as follows.
上式においてR1およびR2は水素、低級アルキ
ル、アラルキルおよびアリールからなる群から選
ばれ、あるいはR1とR2とは一緒になつて低級ア
ルキレン基を形成するが、好ましくはR1、R2は
メチルが用いられる。R3は低級アルキル基であ
る。 In the above formula, R 1 and R 2 are selected from the group consisting of hydrogen, lower alkyl, aralkyl and aryl, or R 1 and R 2 together form a lower alkylene group, preferably R 1 , R 2 Methyl is used for 2 . R 3 is a lower alkyl group.
ここで得られたジアセトンケトグロン酸エステ
ルは酸触媒の存在下、脱ケタール化し容易に２−
ケトグロン酸エステルへ変換される。以上のごと
く本発明方法により、ジアセトンソルボースから
温和な条件下に、パラジウム含有触媒により高収
率でジアセトンケトグロン酸エステルが合成でき
ることにより、従来法と比較し、経済的に有利な
方法が見出された。 The diacetone ketogulonic acid ester obtained here is easily deketalized in the presence of an acid catalyst and 2-
Converted to ketogulonic acid ester. As described above, the method of the present invention allows the synthesis of diacetone ketogulonic acid ester from diacetone sorbose under mild conditions with a palladium-containing catalyst in high yield, making it an economically advantageous method compared to conventional methods. discovered.
ジアセトンソルボースの酸化反応は、いままで
は水性媒体中過マンガン酸カリウム等を用いた化
学量論反応であり、また貴金属触媒を用いた酸素
酸化反応においても水性媒体中当等以上のアルカ
リを用い、生成物をアルカリ塩とした後、中和後
ジアセトンケトグロン酸となす方法であつた。従
つて本発明方法は、従来の知見からは推測し難い
画期的反応方法と言える。 Up until now, the oxidation reaction of diacetone sorbose has been a stoichiometric reaction using potassium permanganate, etc. in an aqueous medium, and the oxygen oxidation reaction using a noble metal catalyst has also been carried out using an equivalent or more alkali in an aqueous medium. , the product was converted into an alkali salt, and then neutralized to form diacetone ketogulonic acid. Therefore, the method of the present invention can be said to be an epoch-making reaction method that is difficult to predict based on conventional knowledge.
又本発明触媒は、触媒の不活性化による反応の
停止の現象は見られず、くりかえし運転が可能で
ある。 Furthermore, the catalyst of the present invention does not exhibit the phenomenon of termination of the reaction due to deactivation of the catalyst, and can be operated repeatedly.
本発明で用いられるアルコール溶媒は、メチ
ル、エチル、プロピル、イソプロピル、ブチル、
イソブチルペンチル、イソペンチル、ヘキシル基
等を有する低級アルコールであり、特に好ましく
はメタノールが用いられる。上記、溶媒の使用量
は触媒種、反応温度、時間等により異なるが、ジ
アセトンソルボースに対して１〜500倍、好まし
くは10〜150倍の重量比がよい。次に本発明に用
いるパラジウム含有触媒はパラジウムもしくはパ
ラジウムと鉛、水銀、タリウムの金属あるいはそ
の化合物の少なくとも１つを含有する触媒が用い
られる。 The alcohol solvent used in the present invention includes methyl, ethyl, propyl, isopropyl, butyl,
It is a lower alcohol having an isobutylpentyl, isopentyl, or hexyl group, and methanol is particularly preferably used. The amount of the above-mentioned solvent to be used varies depending on the catalyst species, reaction temperature, time, etc., but the weight ratio is preferably 1 to 500 times, preferably 10 to 150 times, relative to diacetone sorbose. Next, the palladium-containing catalyst used in the present invention is a catalyst containing palladium or at least one of palladium and metals such as lead, mercury, and thallium, or compounds thereof.
パラジウムは０価であり、鉛、水銀、タリウム
の化合物は無機酸塩、有機酸塩、水酸化物、酸化
物として用いられる。無機酸塩は塩化物、臭化
物、ヨウ化物、フツ化物、硫酸塩、リン酸塩、ホ
ウ酸塩等のかたちで用いられ、有機酸塩はギ酸、
酢酸、プロピオン酸、ステアリン酸、マロン酸、
コハク酸、グルタル酸、マレイン酸、安息香酸、
フタル酸等が用いられる。上記触媒はパラジウム
単独でも使用されるが、担体を使うことが望まし
く、さらに鉛、水銀、タリウム金属もしくはその
化合物を担体に同時に担持して用いると活性、選
択性の向上が見られる。担体としては、通常の貴
金属の担体、例えば活性炭、シリカ、アルミナ等
がよい。担持されるパラジウム量は、特に制限は
ないが、0.1〜20％（重量比）、好ましくは１〜10
％である。又使用されるパラジウム量はジアセト
ンソルボースに対して0.001〜１モルが使用され、
さらに鉛、水銀、タリウムの添加量は、パラジウ
ム原子比で0.01〜30倍、好ましくは0.1〜10倍が
よい。 Palladium has a valence of zero, and compounds of lead, mercury, and thallium are used as inorganic acid salts, organic acid salts, hydroxides, and oxides. Inorganic acid salts are used in the form of chlorides, bromides, iodides, fluorides, sulfates, phosphates, borates, etc., and organic acid salts are used in the form of formic acid,
Acetic acid, propionic acid, stearic acid, malonic acid,
Succinic acid, glutaric acid, maleic acid, benzoic acid,
Phthalic acid and the like are used. Although palladium alone can be used in the above catalyst, it is preferable to use a carrier, and when lead, mercury, thallium metal or a compound thereof is simultaneously supported on the carrier, the activity and selectivity are improved. As the carrier, common noble metal carriers such as activated carbon, silica, alumina, etc. are suitable. The amount of palladium supported is not particularly limited, but is 0.1 to 20% (weight ratio), preferably 1 to 10%.
%. Moreover, the amount of palladium used is 0.001 to 1 mol relative to diacetone sorbose,
Furthermore, the amounts of lead, mercury, and thallium to be added are preferably 0.01 to 30 times, preferably 0.1 to 10 times, in palladium atomic ratio.
上記、触媒の調整方法は、通常実施されている
方法でよいが、例えばパラジウム塩の水溶液に担
体を浸漬させ、乾燥後、水素、ヒドラジン、ホル
マリン等で還元し金属態として反応に供すること
ができる。さらにパラジウムと酸化鉛の触媒系の
場合は、酢酸鉛の水溶液に担体を加え、数時間撹
拌後、酢酸鉛を吸着させ、500℃〜700℃に焼成す
る。さらにこのものを塩化パラジウムの水溶液に
加え、数時間撹拌後塩化パラジウムを吸着させた
後、ホルマリン還元、ヒドラジン還元、水素還元
等により還元処理することにより製造される。ま
た、鉛、水銀、タリウムの塩はパラジウムと担体
に同時に担持して使用するが、担体に担持せずに
反応系に直接添用して用いてもよい。 The catalyst may be prepared by any commonly used method, but for example, the carrier may be immersed in an aqueous solution of palladium salt, dried, and then reduced with hydrogen, hydrazine, formalin, etc., and subjected to the reaction as a metal. . Furthermore, in the case of a catalyst system of palladium and lead oxide, a carrier is added to an aqueous solution of lead acetate, and after stirring for several hours, lead acetate is adsorbed, and the solution is calcined at 500°C to 700°C. Further, this product is added to an aqueous solution of palladium chloride, stirred for several hours, adsorbed with palladium chloride, and then subjected to reduction treatment such as formalin reduction, hydrazine reduction, hydrogen reduction, etc. Further, salts of lead, mercury, and thallium are used by being supported on palladium and a carrier at the same time, but they may also be directly added to the reaction system without being supported on a carrier.
本発明における反応温度は、10゜〜200℃さらに
好ましくは20℃〜120℃の範囲である。また反応
圧力も常圧、加圧いずれの状態でも実施でき、さ
らに反応方法としては回分式、連続式のいずれで
もよい。本発明に使用される酸素とは純酸素のみ
ならず窒素のような反応に不活性なガスを含む酸
素、例えば空気をも使用することができ、酸素量
は特に制限はないが、化学量論量以上、好ましく
は化学量論量の1.5倍以上あれば充分である。 The reaction temperature in the present invention is in the range of 10°C to 200°C, more preferably 20°C to 120°C. Further, the reaction pressure can be either normal pressure or increased pressure, and the reaction method may be either batchwise or continuous. The oxygen used in the present invention is not only pure oxygen, but also oxygen containing a gas inert to the reaction such as nitrogen, such as air, and the amount of oxygen is not particularly limited. It is sufficient if the amount is at least 1.5 times the stoichiometric amount, preferably at least 1.5 times the stoichiometric amount.
以下、実施例をもつて本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
ジアセトン−１−ソルボース10ｇ、メタノール
50ｇ、パラジウム−活性炭（５％担持、エンゲル
ハルド社製）３ｇを100c.c.３つ口フラスコに入れ
撹拌下50℃、3hr反応をおこなつた。その間、酸
素をフイルター付導入管から反応液に毎分30c.c.導
入した。反応液はガスクロマトグラフイーにより
分析をおこなつた。Example 1 10 g of diacetone-1-sorbose, methanol
50 g of palladium and 3 g of palladium-activated carbon (5% supported, manufactured by Engelhard) were placed in a 100 c.c. three-necked flask, and a reaction was carried out at 50° C. for 3 hours with stirring. During this time, 30 c.c./min of oxygen was introduced into the reaction solution from an inlet tube with a filter. The reaction solution was analyzed by gas chromatography.
ジアセトン−１−ソルボース転化率 59％
ジアセトン−２−ケトグロン酸メチル 収率41％
ジアセトン−２−ケトグロン酸メチル選択率69％
実施例 ２
ジアセトン−１−ソルボース10ｇ、メタノール
100ｇ、パラジウム−アルミナ（５％パラジウム
担持、pd：pb＝１：１（原子比）pbはpboとして
担持）２ｇを200c.c.３つ口フラスコに入れ、撹拌
下50℃2hr反応をおこなつた。その間酸素をフイ
ルター付導入管から反応液に毎分30c.c.導入した。Diacetone-1-sorbose conversion rate 59% Methyl diacetone-2-ketogulonate Yield 41% Methyl diacetone-2-ketogulonate selectivity 69% Example 2 Diacetone-1-sorbose 10 g, methanol
Put 100 g and 2 g of palladium-alumina (5% palladium supported, pd: pb = 1:1 (atomic ratio), pb supported as pbo) into a 200 c.c. three-necked flask, and conduct a reaction for 2 hours at 50°C under stirring. Ta. During this time, oxygen was introduced into the reaction solution from an inlet tube with a filter at a rate of 30 c.c./min.
ジアセトン−１−ソルボース 転化率89％
ジアセトン−２−ケトグロン酸メチル 収率80％
ジアセトン−２−ケトグロン酸メチル選択率90％
実施例 ３
ジアセトン−１−ソルボース10ｇ、メタノール
60ｇ、パラジウム−シリカ（３％パラジウム担持
pd：Tl＝１：1TlはTlNO3として担持）５ｇを
200c.c.の３つ口フラスコに入れ撹拌下50℃、2hr反
応をおこなつた。Diacetone-1-sorbose Conversion rate 89% Methyl diacetone-2-ketogulonate Yield 80% Methyl diacetone-2-ketogulonate selectivity 90% Example 3 Diacetone-1-sorbose 10 g, methanol
60g, palladium-silica (3% palladium supported)
pd:Tl=1:1Tl is supported as TlNO3 ) 5g
The mixture was placed in a 200 c.c. three-necked flask and the reaction was carried out at 50° C. for 2 hours with stirring.
その間、空気をフイルター付導入管から反応液
に毎分70c.c.を導入した。 During this time, air was introduced into the reaction solution from the filtered inlet tube at a rate of 70 c.c. per minute.
ジアセトン−１−ソルボース 転化率79％
ジアセトン−２−ケトグロン酸メチル 収率69％
ジアセトン−２−ケトグロン酸メチル選択率87％
実施例 ４
ジアセトン−１−ソルボース10ｇ、ｎ−ブタノ
ール60ｇ、パラジウム−活性炭（５％パラジウム
担持、pd：Hg＝１：0.9HgはHgCl2として担持）
５ｇを200c.c.の３つ口フラスコに入れ、撹拌下90
℃、2hr反応をおこなつた。その間、酸素を毎分
50c.c.反応液に導入した。Diacetone-1-sorbose Conversion rate 79% Methyl diacetone-2-ketogulonate Yield 69% Methyl diacetone-2-ketogulonate selectivity 87% Example 4 10 g of diacetone-1-sorbose, 60 g of n-butanol, palladium-activated carbon ( 5% palladium supported, pd:Hg=1:0.9Hg supported as HgCl2 )
Put 5g into a 200c.c. three-necked flask and stir for 90 minutes.
The reaction was carried out at ℃ for 2 hours. Meanwhile, oxygen every minute
50 c.c. was introduced into the reaction solution.
ジアセトン−１−ソルボース 転化率67％ ジアセトン−２−ケトグロン酸ブチル 収率59％ ジアセトン−２−ケトグロン酸ブチル選択率88％Diacetone-1-sorbose Conversion rate 67% Butyl diacetone-2-ketogulonate Yield 59% Butyl diacetone-2-ketogulonate selectivity 88%
Claims (1)
ロン酸エステルを製造するに際し、アルコールの
存在下に、酸素または酸素含有ガスとともにパラ
ジウム含有触媒を用い酸化反応せしめることを特
徴とするジアセトンケトグロン酸エステルの製造
方法。 ２ パラジウム含有触媒がパラジウムと鉛、水
銀、タリウムの金属もしくはその化合物の少なく
とも１つを含有する触媒である特許請求の範囲第
１項記載の製造方法。[Scope of Claims] 1. A diacetone ketogulonic acid ester characterized in that an oxidation reaction is carried out in the production of diacetone ketogulonic acid ester from diacetone sorbose using a palladium-containing catalyst together with oxygen or an oxygen-containing gas in the presence of an alcohol. Method for producing gulonic acid ester. 2. The manufacturing method according to claim 1, wherein the palladium-containing catalyst is a catalyst containing palladium and at least one of metals such as lead, mercury, and thallium, or compounds thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP978A JPS53130716A (en) | 1977-01-03 | 1978-01-04 | Method and apparatus for bending plate glass method of forming plate glass and device for hanging plate glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5594395A JPS5594395A (en) | 1980-07-17 |
| JPS6312876B2 true JPS6312876B2 (en) | 1988-03-23 |
Family
ID=11462451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP97879A Granted JPS5594395A (en) | 1978-01-04 | 1979-01-11 | Preparation of diacetone ketogulonic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5594395A (en) |
-
1979
- 1979-01-11 JP JP97879A patent/JPS5594395A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5594395A (en) | 1980-07-17 |
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