JPH02235837A - Method for oxidizing aromatic alcohols - Google Patents
Method for oxidizing aromatic alcoholsInfo
- Publication number
- JPH02235837A JPH02235837A JP5594089A JP5594089A JPH02235837A JP H02235837 A JPH02235837 A JP H02235837A JP 5594089 A JP5594089 A JP 5594089A JP 5594089 A JP5594089 A JP 5594089A JP H02235837 A JPH02235837 A JP H02235837A
- Authority
- JP
- Japan
- Prior art keywords
- cyclodextrin
- aromatic
- oxidizing
- water
- formula
- 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
- -1 aromatic alcohols Chemical class 0.000 title claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 10
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002240 furans Chemical class 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract 2
- 150000002367 halogens Chemical class 0.000 claims abstract 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 7
- 150000001555 benzenes Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract description 4
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 3
- 150000002576 ketones Chemical class 0.000 abstract description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000003125 aqueous solvent Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 150000008365 aromatic ketones Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- HEZQRPHEDDAJTF-UHFFFAOYSA-N chloro(phenyl)methanol Chemical compound OC(Cl)C1=CC=CC=C1 HEZQRPHEDDAJTF-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N o-hydroxybenzyl alcohol Natural products OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
- Catalysts (AREA)
- 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〕
本発明は、芳香族アルコール類を酸化し、対応する芳香
族アルデヒドもしくは芳香族ケトンを製造する方法に関
する．更に詳しくは、芳香族アルコール類を水溶媒存在
下、シクロデキストリンを相間移動剤に用い、水溶性酸
化剤および／または酸化触媒により、温和な条件のもと
、速やかにかつ高収率で対応する芳香族アルデヒドもし
くは芳香族ケトンを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for oxidizing aromatic alcohols to produce the corresponding aromatic aldehydes or aromatic ketones. More specifically, aromatic alcohols are reacted quickly and in high yields under mild conditions using cyclodextrin as a phase transfer agent and a water-soluble oxidizing agent and/or oxidation catalyst in the presence of a water solvent. The present invention relates to a method for producing aromatic aldehydes or aromatic ketones.
従来、芳香族アルコール類の酸化により、対応するアル
デヒドやケトンを製造する方法として、無機系酸化剤も
くしは有機過酸化物などの酸化剤を用いる方法、あるい
は白金属系触媒を用いる方法が知られている．これらの
反応の多くは有機溶媒や水溶媒を使用して行なわれてい
るが、有機溶媒を用いる場合、溶媒回収や酸化剤もくし
は酸化触媒の生成物からの分離操作等に伴う種々のコス
トアップ要因を抱えている．一方、水溶媒を用いる場合
、反応に使用される酸化剤もくしは酸化触媒の多くは水
相に存在することもあり、前述のような問題点は本質的
に除外され得る．しかし、被反応物である芳香族アルコ
ール類の水への溶解性が低いこともあり、反応速度が遅
くなるという欠点を生ずることになる。Conventionally, methods using oxidizing agents such as inorganic oxidants or organic peroxides, or methods using platinum metal catalysts have been known as methods for producing the corresponding aldehydes and ketones by oxidizing aromatic alcohols. It is being done. Many of these reactions are carried out using organic or aqueous solvents, but when organic solvents are used, there are various costs involved in recovering the solvent and separating the oxidizing agent or oxidizing catalyst from the product. There are factors that increase this. On the other hand, when using an aqueous solvent, most of the oxidizing agent or oxidizing catalyst used in the reaction may be present in the aqueous phase, and the above-mentioned problems can essentially be eliminated. However, the solubility of aromatic alcohols as reactants in water is low, resulting in a disadvantage that the reaction rate is slow.
そこで、本発明者らは有機溶媒を用いる方法と比較して
問題点の少ない、水溶媒を用いる反応方法について鋭意
研究を行った結果、相間移動剤としてシクロデキストリ
ンを用いることにより水溶媒系においても極めて速やか
に、かつ高収率で芳香族アルコール類を対応するアルデ
ヒドもしくはケトン化合物に酸化し得ることを見い出し
、本発明を完成した．
即ち、本発明は芳香族アルコール類を水溶媒存在下、シ
クロデ本ストリンを相間移動剤に用い、水溶性酸化剤お
よび／または水溶性酸化触媒で酸化することを特徴とす
る芳香族アルデヒドもしくは芳香族ケトンの製造方法を
提供するものである。Therefore, the present inventors conducted intensive research on a reaction method using an aqueous solvent, which has fewer problems than methods using an organic solvent, and found that by using cyclodextrin as a phase transfer agent, it can be used in an aqueous solvent system. The present invention was completed based on the discovery that aromatic alcohols can be oxidized to the corresponding aldehyde or ketone compounds extremely rapidly and in high yields. That is, the present invention provides an aromatic aldehyde or an aromatic alcohol, which is characterized by oxidizing aromatic alcohols with a water-soluble oxidizing agent and/or a water-soluble oxidation catalyst in the presence of a water solvent using cyclodetrines as a phase transfer agent. A method for producing ketones is provided.
以下、本発明の内容を更に詳細に説明する．本発明で用
いられる酸化剤もくしは酸化触媒は水溶性でかつ選択的
に芳香族アルコール類から芳香族アルデヒドあるいは芳
香族ケトンを製造し得るものであるなら、基本的に全て
使用可能である．
水溶性の酸化剤として、次のような化合物が用いられる
。例えば、無機系酸化剤として、クロム酸あるいはその
エステル類、四価のセリウムから成る硝酸塩、酢酸塩お
よび硫酸塩、また五酸化バナジウム、三塩化酸化バナジ
ウム、メタバナジン酸ナトリウムおよびアンモニウム塩
などの五価のバナジウム化合物、ペルオキソ硫酸一銀（
Ｉ）塩あるいは次亜ハロゲン酸およびそれらの塩やエス
テル類が挙げられる。また、有機過酸化物として、過ギ
酸、過酢酸、トリフロロ過酢酸および過安息香酸などが
挙げられる。The contents of the present invention will be explained in more detail below. Basically, any oxidizing agent or oxidizing catalyst used in the present invention can be used as long as it is water-soluble and can selectively produce aromatic aldehydes or aromatic ketones from aromatic alcohols. The following compounds are used as water-soluble oxidizing agents. For example, inorganic oxidizing agents include chromic acid or its esters, nitrates, acetates and sulfates of tetravalent cerium, and pentavalent cerium such as vanadium pentoxide, vanadium trichloride oxide, sodium metavanadate and ammonium salts. Vanadium compounds, monosilver peroxosulfate (
I) Salts or hypohalous acids and their salts and esters. Examples of organic peroxides include performic acid, peracetic acid, trifluoroperacetic acid, and perbenzoic acid.
一方、酸化触媒としては白金属系触媒が用いられる．例
えば、ルテニウム、ロジウム、パラジウム、オスミウム
、イリジウムおよび白金などの白金属系触媒を用い、塩
基性水溶媒中で酸素含有ガスにより芳香族アルコール類
の酸化を行うことも可能である．この場合、白金属系触
媒に対し、鉛、ビスマス、銀あるいはスズなどを添加し
てもよい．
酸化剤を用い芳香族アルコール類の酸化を行う場合、酸
化剤の使用量は被酸化アルコール基に対しエないし１０
倍当量、好ましくは１．５ないし５倍当量である。反応
温度は、反応基質の酸化のされ易さや酸化剤の酸化力に
応じ決定されるが、一ａ的には１０ないし１００゜Ｃの
範囲で行われるのが望ましい。On the other hand, platinum metal catalysts are used as oxidation catalysts. For example, it is also possible to oxidize aromatic alcohols with an oxygen-containing gas in a basic aqueous solvent using platinum metal catalysts such as ruthenium, rhodium, palladium, osmium, iridium, and platinum. In this case, lead, bismuth, silver, tin, etc. may be added to the platinum metal catalyst. When aromatic alcohols are oxidized using an oxidizing agent, the amount of the oxidizing agent used is between
double equivalent, preferably 1.5 to 5 times equivalent. The reaction temperature is determined depending on the oxidizability of the reaction substrate and the oxidizing power of the oxidizing agent, but it is preferably carried out within the range of 10 to 100°C.
また、酸化触媒を用い反応を行う場合、触媒の使用量は
白金属系触媒の金属重量換算で、芳香族アルコール類に
対し５０ないし２０００ｐｐａ＋が好ましい．塩基性水
溶媒としては０．１ないし５規定の水酸化ナトリウムあ
るいは水酸化カリウム溶液が用いられる。反応温度は、
反応速度および選択性の面から１０ないし１００″Ｃと
するのが好ましい。Further, when the reaction is carried out using an oxidation catalyst, the amount of the catalyst used is preferably 50 to 2000 ppa+ relative to the aromatic alcohol, calculated in terms of metal weight of the platinum metal catalyst. As the basic aqueous solvent, a 0.1 to 5N sodium hydroxide or potassium hydroxide solution is used. The reaction temperature is
From the viewpoint of reaction rate and selectivity, the temperature is preferably 10 to 100''C.
本発明において使用されるシクロデキストリンとしては
α−シクロデキストリン、β−シクロデキストリンある
いはγ−シクロデキストリンが挙げられるが、これらシ
クロデキストリン骨格の一部を修飾した修飾シクロデキ
ストリン、例えばメチル化シクロデキストリン等の使用
も適宜可能である。Examples of the cyclodextrin used in the present invention include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Modified cyclodextrins in which a part of the cyclodextrin skeleton is modified, such as methylated cyclodextrin It can also be used as appropriate.
シクロデキストリンの使用量は、芳香族アルコール類に
対し０．１ないし１００モルパーセントであり、特に好
ましくは０．５ないし２０モルパーセントである．更に
、反応に使用されたシクロデキストリンは、回収後再度
反応に供することも可能である。The amount of cyclodextrin used is 0.1 to 100 mol percent, particularly preferably 0.5 to 20 mol percent, based on the aromatic alcohol. Furthermore, the cyclodextrin used in the reaction can be subjected to the reaction again after being recovered.
本発明では、反応溶媒に有機溶媒を使用しなくとも良い
．しかし、有機溶媒の使用は本発明においても本質的に
何等悪影響を及ぼさないことから、その使用については
別に制限を受けるものではない。このような有機溶媒と
しては、ヘキサン、ヘブタンなどの飽和炭化水素類、ベ
ンゼン、トルエン、キシレン、クロルベンゼン等が使用
できる。In the present invention, it is not necessary to use an organic solvent as a reaction solvent. However, since the use of an organic solvent essentially does not have any adverse effects in the present invention, its use is not particularly limited. As such organic solvents, saturated hydrocarbons such as hexane and hebutane, benzene, toluene, xylene, chlorobenzene, etc. can be used.
本発明で用いられる芳香族アルコール類とは、次の式（
Ｉ）で示される化合物を指す．式中＾はベンゼン核ある
いはフラン核を示し、Ｒｌはアルキル基、ヒドロキシ基
、アルコキシ基、ホルミル基及びハロゲン基から選ばれ
た少なくとも１種の置換基を、またＩＫは水素あるいは
アルキル基を示す．ここで、騰は１ないし６、ｎは０な
いし５の数を示す。The aromatic alcohol used in the present invention is expressed by the following formula (
Refers to the compound represented by I). In the formula, ^ represents a benzene nucleus or a furan nucleus, Rl represents at least one substituent selected from an alkyl group, a hydroxyl group, an alkoxy group, a formyl group, and a halogen group, and IK represents hydrogen or an alkyl group. Here, treble represents a number from 1 to 6, and n represents a number from 0 to 5.
上記芳香族アルコールとしては、Ａがベンゼン核から構
成される場合、ベンジルアルコール、メチルベンジルア
ルコール、α一エチルベンジルアルコール、イソブロビ
ルベンジルアルコール、ターシャリープチルベンジルア
ルコール、フタリルアルコール、ヒドロキシベンジルア
ルコール、メトキシベンジルアルコール、クロロベンジ
ルアルコールなどが、またＡがフラン核から構成される
場合、フルフリルアルコールやビスヒドロキシメチルフ
ランなどが例示され得る．
本発明の方法により得られる芳香族アルデヒドもしくは
芳香族ケトンは次の式（ＩＩ）で示される．
（Ａ＋ Ｒ’＋ Ｒ’＋ ｌｌｌｌ＋ ｎは式（Ｉ）と
同じ〕〔実施例〕
次に実施例を挙げ、本発明を更に詳細に説明するが、本
発明はこれらの実施例に限定されるものではない。When A is composed of a benzene nucleus, examples of the aromatic alcohol include benzyl alcohol, methylbenzyl alcohol, α-ethylbenzyl alcohol, isobrobyl benzyl alcohol, tert-butylbenzyl alcohol, phthalyl alcohol, hydroxybenzyl alcohol, methoxy Examples include benzyl alcohol, chlorobenzyl alcohol, and when A is composed of a furan nucleus, furfuryl alcohol and bishydroxymethylfuran. The aromatic aldehyde or aromatic ketone obtained by the method of the present invention is represented by the following formula (II). (A+ R'+ R'+ llll+ n is the same as in formula (I)) [Examples] Next, the present invention will be described in more detail with reference to Examples, but the present invention is limited to these Examples. It's not a thing.
実施例１〜７
ガラス製フラスコにｌＯ％次亜塩素酸ナトリウム水溶液
および所定量のシクロデキストリンを加え、芳香族アル
コールを添加後、５０″Ｃにおいて撹拌反応を行った．
酸化剤である次亜塩素酸ナトリウムの使用量は、反応基
質の被酸化アルコール基に対し３倍当量とし、シクロデ
キストリン添加量は反応基質の５ないし８モルパーセン
トである．反応終了後、反応液を分液ロ一トに移し、有
機層を分離した後、ガスクロマトグラフィーにより生成
物の分析を行った．比較例１〜７
上記各実施例に於いてシクロデキストリンを添加しない
ことを除いては、実施例と全く同一の条件において夫々
反応した結果を比較例とし、本発明の実施例において得
られた結果と併せて表１に示した．
２．
３．
４．
手
続
補
正
書
（自発）
発明の名称
芳香族アルコール類の酸化方法
補正をする者
事件との関係 特許出願人Examples 1 to 7 A 1O% aqueous sodium hypochlorite solution and a predetermined amount of cyclodextrin were added to a glass flask, and after addition of an aromatic alcohol, a stirring reaction was performed at 50''C.
The amount of sodium hypochlorite used as an oxidizing agent is 3 times equivalent to the alcohol group to be oxidized in the reaction substrate, and the amount of cyclodextrin added is 5 to 8 mole percent of the reaction substrate. After the reaction was completed, the reaction solution was transferred to a separating funnel, the organic layer was separated, and the product was analyzed by gas chromatography. Comparative Examples 1 to 7 Comparative Examples are the results of reactions conducted under the same conditions as in the Examples, except that cyclodextrin was not added, and the results obtained in the Examples of the present invention are It is also shown in Table 1. 2. 3. 4. Procedural amendment (voluntary) Name of the invention Relationship with the case of the person amending the method of oxidizing aromatic alcohols Patent applicant
Claims (1)
媒存在下、水溶性酸化剤および／または酸化触媒により
酸化し、下記の式（II）で示される化合物を製造するに
際し、シクロデキストリンを共存させることを特徴とす
る芳香族アルコール類の酸化方法。 ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） 〔式中、 Ａはベンゼン核あるいはフラン核、 Ｒ＾１はアルキル基、ヒドロキシ基、アルコキシ基、ホ
ルミル基及びハロゲンから選ばれた少なくとも１種、 Ｒ＾２はＨあるいはアルキル基を示し、 ｍは１≦ｍ≦６、ｎは０≦ｎ≦５の数を示す。〕[Claims] A compound represented by the following formula (II) is produced by oxidizing an aromatic alcohol represented by the following formula (I) with a water-soluble oxidizing agent and/or an oxidation catalyst in the presence of a water solvent. A method for oxidizing aromatic alcohols, which comprises coexisting cyclodextrin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, A is a benzene nucleus or furan nucleus, and R^1 is an alkyl group, hydroxyl group, or alkoxy group. , at least one selected from a formyl group and a halogen, R^2 represents H or an alkyl group, m represents a number of 1≦m≦6, and n represents a number of 0≦n≦5. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5594089A JP2575865B2 (en) | 1989-03-08 | 1989-03-08 | Method for oxidizing aromatic alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5594089A JP2575865B2 (en) | 1989-03-08 | 1989-03-08 | Method for oxidizing aromatic alcohols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02235837A true JPH02235837A (en) | 1990-09-18 |
| JP2575865B2 JP2575865B2 (en) | 1997-01-29 |
Family
ID=13013073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5594089A Expired - Lifetime JP2575865B2 (en) | 1989-03-08 | 1989-03-08 | Method for oxidizing aromatic alcohols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2575865B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016996A (en) * | 2014-04-25 | 2015-11-04 | 浙江工业大学 | Green preparing method of p-tert-butylcyclohexanone |
-
1989
- 1989-03-08 JP JP5594089A patent/JP2575865B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016996A (en) * | 2014-04-25 | 2015-11-04 | 浙江工业大学 | Green preparing method of p-tert-butylcyclohexanone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2575865B2 (en) | 1997-01-29 |
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