JPS6145990B2 - - Google Patents
Info
- Publication number
- JPS6145990B2 JPS6145990B2 JP11236178A JP11236178A JPS6145990B2 JP S6145990 B2 JPS6145990 B2 JP S6145990B2 JP 11236178 A JP11236178 A JP 11236178A JP 11236178 A JP11236178 A JP 11236178A JP S6145990 B2 JPS6145990 B2 JP S6145990B2
- Authority
- JP
- Japan
- Prior art keywords
- glucose
- lactone
- palladium
- glucono delta
- reaction
- 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 36
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 30
- 239000008103 glucose Substances 0.000 claims description 30
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 23
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 23
- 239000000182 glucono-delta-lactone Substances 0.000 claims description 23
- 229960003681 gluconolactone Drugs 0.000 claims description 23
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- -1 amide compound Chemical class 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- 235000013527 bean curd Nutrition 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000010855 food raising agent Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- UNYNVICDCJHOPO-UHFFFAOYSA-N quabalactone III Natural products CC1OC(=O)C(O)=C1C UNYNVICDCJHOPO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、グルコースからグルコノデルタラク
トンを製造する方法、さらに詳しくは、グルコー
スを有機溶媒存在下にパラジウム触媒を用い、分
子状酸素とともに反応せしめることを特徴とする
グルコノデルタラクトンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing glucono delta lactone from glucose, and more specifically, a method for producing glucono delta lactone from glucose, which is characterized by reacting glucose with molecular oxygen in the presence of an organic solvent using a palladium catalyst. This invention relates to a method for producing nodeltalactone.
グルコノデルタラクトンは、食品添加物に許可
されている唯一の糖ラクトンであり、従来よりパ
ン、ケーキ等製菓の膨剤として用いられており、
さらには、豆腐、ハム、ソーセージ、かまぼこ等
の添加剤としても使用され、用途が拡大しつつあ
る。最近では、土木、建築、医薬、化粧品、洗剤
方面においても需要が増大しつつある重要な化合
物である。現在、グルコノデルタラクトンは、グ
ルコースから得られるグルコン酸をラクトン化す
ることにより製造されており、また、グルコン酸
はグルコースを微生物学的に酸化して製造する方
法、あるいは電解酸化させる方法、さらには次亜
塩素酸を用いた化学的酸化等がおこなわれてき
た。従つて、グルコノデルタラクトンは、一度グ
ルコン酸とした後、ラクトン化して製造する２段
階の方法による煩雑な工程を必要としていた。 Glucono delta-lactone is the only sugar lactone that is permitted as a food additive, and has traditionally been used as a leavening agent in confectionery such as bread and cakes.
Furthermore, it is also used as an additive for tofu, ham, sausage, kamaboko, etc., and its uses are expanding. Recently, it is an important compound whose demand is increasing in the fields of civil engineering, architecture, medicine, cosmetics, and detergents. Currently, glucono delta-lactone is produced by lactonizing gluconic acid obtained from glucose, and gluconic acid is produced by microbiological oxidation of glucose, or by electrolytic oxidation. Chemical oxidation using hypochlorous acid has been carried out. Therefore, glucono delta-lactone requires a complicated two-step process in which it is first converted into gluconic acid and then lactonized.
そこで本発明者らは１段階でグルコノデルタラ
クトンの製造法について検討していたところ、高
収率、高選択率で製造できる方法を見出した。す
なわち本発明方法は、パラジウム触媒を用い、有
機溶媒存在下に分子状酸素とともに反応せしめる
ことにより、一挙にグルコノデルタラクトンを得
ることができ、かつパラジウムを用いる触媒反応
である。従つて、本発明方法は、従来法と比較
し、経済的に極めて有利であり、工業的規模での
製造方法として好都合である。 Therefore, the present inventors investigated a method for producing glucono delta-lactone in one step, and found a method capable of producing it with high yield and high selectivity. That is, the method of the present invention is a catalytic reaction in which glucono delta-lactone can be obtained all at once by using a palladium catalyst and reacting with molecular oxygen in the presence of an organic solvent, and which uses palladium. Therefore, the method of the present invention is economically extremely advantageous compared to conventional methods, and is convenient as a production method on an industrial scale.
本発明方法はグルコースからグルコノデルタラ
クトンを１段で製造する方法に関するが原料を溶
解もしくは分散する有機溶媒の存在下で運転する
ことができ、その際、有機溶媒としては、例えば
アミド化合物、アルコール、脂肪族エーテル、エ
ステル化合物等が通常的に用いられる。このうち
アミド化合物としては、ジメチルホルムアミド、
ジメチルアセトアミド、Ｎ−メチルピロリドン、
テトラメチルウレア、ヘキサメチルホスホルアミ
ド等、アルコールとしては、メタノール、エタノ
ール、プロパノール、ｎ−ブタノール等、脂肪族
エーテル化合物としてはジエチルエーテル、ジメ
トキシエタン、ジエチレングリコールジメチルエ
ーテル、トリエチレングリコールジメチルエーテ
ル、ジオキサン等、エステル化合物としては、ギ
酸メチル、ギ酸エチル、酢酸メチル、酢酸エチ
ル、酢酸プロピル、酢酸ブチル等を用いることが
できる。溶媒によつては20％（重量）以下の水を
添加し、反応をおこなうこともできる。またさら
に触媒として用いられるパラジウムは、金属単独
でも使用できるが、担体を使用する方が望まし
く、担体としては、通常の貴金属の担体である例
えば、活性炭、シリカ、シリカアルミナ、アルミ
ナ、炭酸カルシウム、リン酸カルシウム、硫酸バ
リウム、アルミナ・マグネシア等が良い。担体に
パラジウムを含浸させたパラジウム触媒の調製法
は、通常の方法、例えば塩化パラジウム水溶液に
活性炭を加え、数時間撹拌後、塩化パラジウムを
吸着させる。その後水素還元、ホルマリン還元、
あるいはヒドラジン還元等によつて還元処理す
る。このようにして調製したパラジウムの担持率
は特に臨界値はないが、0.1〜15％（重量）、好ま
しくは１〜10％（重量）である。 Although the method of the present invention relates to a method for producing glucono delta lactone from glucose in one step, it can be operated in the presence of an organic solvent that dissolves or disperses the raw materials. , aliphatic ethers, ester compounds, etc. are commonly used. Among these, amide compounds include dimethylformamide,
dimethylacetamide, N-methylpyrrolidone,
Tetramethylurea, hexamethylphosphoramide, etc. Alcohols include methanol, ethanol, propanol, n-butanol, etc. Aliphatic ether compounds include diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dioxane, etc., esters As the compound, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc. can be used. Depending on the solvent, the reaction may be carried out by adding up to 20% (by weight) of water. Palladium used as a catalyst can be used as a metal alone, but it is preferable to use a carrier. Examples of carriers include activated carbon, silica, silica alumina, alumina, calcium carbonate, and calcium phosphate. , barium sulfate, alumina/magnesia, etc. are good. A palladium catalyst in which a carrier is impregnated with palladium is prepared by a conventional method, for example, activated carbon is added to an aqueous solution of palladium chloride, and after stirring for several hours, palladium chloride is adsorbed. After that, hydrogen reduction, formalin reduction,
Alternatively, reduction treatment is performed by hydrazine reduction or the like. The supporting ratio of palladium thus prepared has no particular critical value, but is 0.1 to 15% (by weight), preferably 1 to 10% (by weight).
反応の際使用するパラジウムの量は、限定され
るものではないが、例えばバツチ反応では使用グ
ルコースに対して、0.001〜１モルが使用され、
触媒の活性は充分維持される。 The amount of palladium used during the reaction is not limited, but for example, in a batch reaction, 0.001 to 1 mol is used relative to the glucose used,
The activity of the catalyst is sufficiently maintained.
本発明において使用される分子状酸素とは、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できる。反応
圧力は常圧ないし加圧下でおこなうことができ
る。反応温度は10℃から200℃、さらに好ましく
は20℃から130℃がよい。 The molecular 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. The reaction can be carried out at normal pressure or elevated pressure. The reaction temperature is preferably 10°C to 200°C, more preferably 20°C to 130°C.
本発明を実施するには、槽形式の反応装置、塔
形式の反応装置も可能であり、それらに用いられ
るパラジウム触媒は、粉状、粒状いずれでもよ
く、触媒上での気液の触媒を良好にするような方
法を用いてやればよい。 To carry out the present invention, a tank-type reaction device or a column-type reaction device is also possible, and the palladium catalyst used in these may be either powder or granule, and the palladium catalyst can be used to catalyze gas and liquid on the catalyst. You can do it using a method that does this.
実施例 １
充分に微粉化したグルコース５ｇ、パラジウム
活性炭５ｇ（パラジウム５％担持）（エンゲルハ
ルト社製）およびメタノール260ｇを500c.c.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
供給した。反応後触媒を別し、液中のグルコ
ノデルタラクトンをガスクロマトグラフイーによ
り定量をおこなつた。Example 1 5 g of sufficiently pulverized glucose, 5 g of palladium activated carbon (supporting 5% palladium) (manufactured by Engelhard), and 260 g of methanol were placed in a 500 c.c. flask, and a reaction was carried out at 50° C. for 2 hours with stirring.
During this time, oxygen was supplied to the reaction solution from an inlet tube with a filter. After the reaction, the catalyst was separated and the glucono delta-lactone in the liquid was determined by gas chromatography.
ガスクロマトグラフイー分析条件、
充てん剤：OV−17（ShimaliteW、島律製作所
製）
カラムの長さ：２ｍ
カラムの温度：180℃
インジエクシヨン温度：220℃
又、未反応グルコースの定量は、高速液体クロ
マトグラフイーによりおこなつた。Gas chromatography analysis conditions: Packing material: OV-17 (Shimalite W, manufactured by Shima Ritsu Seisakusho) Column length: 2 m Column temperature: 180°C In-die extraction temperature: 220°C In addition, unreacted glucose was quantified using high-performance liquid chromatography. This was done by E.
高速液体クロマトグラフイーの分析条件
カラム充てん剤：マイクロボンダパツクCH
溶媒：水：アセトニトリル＝15：85（体積比）
溶媒流量：１ml/min
グルコース転化率（％）61％
グルコノデルタラクトン収率（％）56％
実施例 ２
充分に微粉化したグルコース５ｇ、パラジウム
−アルミナ（５％担持）粒状５ｇおよびジメチル
ホルムアミド70ｇを200c.c.フラスコに入れ、撹拌
下、46℃、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供給した。反
応終了後、触媒を別し、未反応グルコースは高
速液体クロマトグラフイーにより、グルコノデル
タラクトンはガスクロマトグラフイーにより、定
量をおこなつた。Analysis conditions for high performance liquid chromatography Column packing material: Microbondapak CH Solvent: Water: Acetonitrile = 15:85 (volume ratio) Solvent flow rate: 1 ml/min Glucose conversion rate (%) 61% Glucono delta-lactone yield ( %) 56% Example 2 5 g of well-pulverized glucose, 5 g of palladium-alumina (5% supported) granules, and 70 g of dimethylformamide were placed in a 200 c.c. flask, and a reaction was carried out at 46°C for 2 hours under stirring. . During this time, oxygen was supplied to the reaction solution from an inlet tube with a filter. After the reaction was completed, the catalyst was separated, and unreacted glucose was determined by high performance liquid chromatography, and glucono delta-lactone was determined by gas chromatography.
グルコース転化率76％
グルコノデルタラクトン68％
実施例 ３
グルコース５ｇ、パラジウム−シリカ（５％担
持）５ｇおよびＮ・メチルピロリドン100ｇを200
c.c.フラスコに入れ、酸素を供給しながら撹拌下、
100℃、30分反応をおこなつた。 Glucose conversion rate 76% Glucono delta lactone 68% Example 3 5 g of glucose, 5 g of palladium-silica (5% supported) and 100 g of N-methylpyrrolidone were
Place in a cc flask and stir while supplying oxygen.
The reaction was carried out at 100°C for 30 minutes.
反応終了後、触媒を別し、液中の未反応グ
ルコース、グルコノデルタラクトンの分析をおこ
なつた。 After the reaction was completed, the catalyst was separated and the unreacted glucose and glucono delta-lactone in the solution were analyzed.
グルコース転化率47％
グルコノデルタラクトン収率43％
実施例 ４
グルコース５ｇ、パラジウム−活性炭（５％担
持）５ｇ、ジメトキシエタン200ｇを500c.c.フラス
コに入れ、80℃、1hr酸素を吹き込みながら撹拌
下反応をおこなつた。 Glucose conversion rate: 47% Glucono delta lactone yield: 43% Example 4 5 g of glucose, 5 g of palladium-activated carbon (5% supported), and 200 g of dimethoxyethane were placed in a 500 c.c. flask and stirred at 80°C for 1 hour while blowing oxygen. The following reaction was performed.
グルコース転化率42％
グルコノデルタラクトン収率39％
実施例 ５
グルコース５ｇ、パラジウム−アルミナ（５％
担持）５ｇ、ジオキサン200ｇ、水１ｇを500c.c.フ
ラスコに入れ、50℃、1hr、酸素を吹き込みなが
ら撹拌下反応をおこなつた。 Glucose conversion rate 42% Glucono delta lactone yield 39% Example 5 Glucose 5g, palladium-alumina (5%
5 g of the support), 200 g of dioxane, and 1 g of water were placed in a 500 c.c. flask, and the reaction was carried out at 50° C. for 1 hr with stirring while blowing oxygen.
グルコース転化率40％
グルコノデルタラクトン収率34％
実施例 ６
グルコース５ｇ、パラジウム−活性炭10ｇ、
（５％担持）メタノール100ｇ、水１ｇを200c.c.フ
ラスコに入れ、実施例１と同様の反応条件下にお
いて反応をおこなつた。 Glucose conversion rate 40% Glucono delta lactone yield 34% Example 6 Glucose 5g, palladium-activated carbon 10g,
(5% loading) 100 g of methanol and 1 g of water were placed in a 200 c.c. flask, and a reaction was carried out under the same reaction conditions as in Example 1.
グルコース転化率（％）60％
グルコノデルタラクトン収率51％
実施例 ７
グルコース５ｇ、パラジウム−炭酸バリウム
（３％担持）７ｇ、酢酸メチル200ｇ、水0.5ｇを
200c.c.フラスコに入れ、実施例１と同様の反応条
件下において反応をおこなつた。 Glucose conversion rate (%) 60% Glucono delta lactone yield 51% Example 7 5 g of glucose, 7 g of palladium-barium carbonate (3% supported), 200 g of methyl acetate, and 0.5 g of water
The mixture was placed in a 200 c.c. flask, and a reaction was carried out under the same reaction conditions as in Example 1.
グルコース転化率（％）38％
グルコノデルタラクトン収率（％）33％
実施例 ８
充分に微粉化したグルコース５ｇ、パラジウム
−アルミナ10ｇ（パラジウム３％担持）およびｎ
−ブタノール200ｇ、を実施例１と同様の反応条
件下において反応をおこなつた。 Glucose conversion rate (%) 38% Glucono delta lactone yield (%) 33% Example 8 5 g of well-pulverized glucose, 10 g of palladium-alumina (supporting 3% palladium) and n
-Butanol (200 g) was reacted under the same reaction conditions as in Example 1.
グルコース転化率40％
グルコノデルタラクトン収率35％
実施例 ９
充分に微粉化したグルコース５ｇ、パラジウム
−活性炭５ｇ（パラジウム３％担持）およびジエ
チレングリコールジメチルエーテル150ｇを実施
例１と同様の反応条件下において反応をおこなつ
た。 Glucose conversion rate: 40% Glucono delta-lactone yield: 35% Example 9 5 g of fully pulverized glucose, 5 g of palladium-activated carbon (supporting 3% palladium) and 150 g of diethylene glycol dimethyl ether were reacted under the same reaction conditions as in Example 1. I did this.
グルコース転化率43％ グルコノデルタラクトン収率36％ Glucose conversion rate 43% Glucono delta lactone yield 36%
Claims (1)
造するに際し、グルコースを有機溶媒存在下にパ
ラジウム触媒を用い、分子状酸素とともに反応せ
しめることを特徴とするグルコノデルタラクトン
の製造方法。 ２ 有機溶媒としてアミド化合物、アルコール、
脂肪族エーテル又はエステル化合物を用いる特許
請求の範囲第１項記載のグルコノデルタラクトン
の製造方法。[Scope of Claims] 1. A method for producing glucono delta-lactone, which comprises reacting glucose with molecular oxygen in the presence of an organic solvent using a palladium catalyst in producing glucono delta-lactone from glucose. 2 As an organic solvent, amide compound, alcohol,
The method for producing glucono delta-lactone according to claim 1, which uses an aliphatic ether or ester compound.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11236178A JPS5540606A (en) | 1978-09-14 | 1978-09-14 | Preparation of glucono-delta-lactone |
| DE2936652A DE2936652C2 (en) | 1978-09-14 | 1979-09-11 | Process for the production of gluconic acid delta lactone |
| GB7931828A GB2031884B (en) | 1978-09-14 | 1979-09-13 | Process for producing glucono-delta-lactone from glucose |
| US06/075,457 US4256645A (en) | 1978-09-14 | 1979-09-14 | Process for producing glucona-delta-lactone from glucose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11236178A JPS5540606A (en) | 1978-09-14 | 1978-09-14 | Preparation of glucono-delta-lactone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5540606A JPS5540606A (en) | 1980-03-22 |
| JPS6145990B2 true JPS6145990B2 (en) | 1986-10-11 |
Family
ID=14584758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11236178A Granted JPS5540606A (en) | 1978-09-14 | 1978-09-14 | Preparation of glucono-delta-lactone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5540606A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0328725U (en) * | 1989-07-28 | 1991-03-22 |
-
1978
- 1978-09-14 JP JP11236178A patent/JPS5540606A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5540606A (en) | 1980-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0006611B1 (en) | Process for preparing diesters of malonic acid | |
| RU2057747C1 (en) | Method for production of metacycline or its additive acid salts | |
| US4772729A (en) | Hydrogenation of citric acid and substituted citric acids to 3-substituted tetrahydrofuran, 3- and 4-substituted butyrolactones and mixtures thereof | |
| JPS636056B2 (en) | ||
| JP2903187B2 (en) | Method for producing (poly) oxyethylene alkyl ether acetic acid | |
| KR870000035B1 (en) | Process for the production of a diester or oxalic acid | |
| JPS6145990B2 (en) | ||
| EP0289725B1 (en) | Method for producing an unsaturated glycol diester | |
| US4256645A (en) | Process for producing glucona-delta-lactone from glucose | |
| JPH01294643A (en) | Production of oxygen-containing compound | |
| JPS63295528A (en) | Production of glyoxylic acids | |
| JPS6312075B2 (en) | ||
| JPS62258335A (en) | Production of methyl isobutyl ketone | |
| KR820000822B1 (en) | Process for producing salts of pyruvic acid | |
| EP0597298A1 (en) | Process for producing alpha-hydroxyisobutyramide | |
| JP2552513B2 (en) | Method for oxidizing (poly) oxyethylene alkyl ether compound | |
| JPS6115863B2 (en) | ||
| JP7168565B2 (en) | Method for producing bisacyloxylated exomethylene compound | |
| JP2550473B2 (en) | Process for producing acetal and hemiacetal ester | |
| JP3066423B2 (en) | Method for producing β-hydroxyethoxyacetic acid | |
| KR100710543B1 (en) | Continuous Process for the Production of Optically Pure S- ?-hydroxy- ?-butyrolactone | |
| CN110563582A (en) | Process for preparing 2-hydroxy-2-phenyl-malonamide | |
| US4415475A (en) | Mixed metal oxide catalyst containing titanium, boron and molybdenum values | |
| US4358601A (en) | Process for preparing 2-butenolide | |
| JP2599969B2 (en) | Method for producing pyruvic acid |