JPH08259528A - Method for producing arylalkyl hydroperoxides - Google Patents
Method for producing arylalkyl hydroperoxidesInfo
- Publication number
- JPH08259528A JPH08259528A JP6659495A JP6659495A JPH08259528A JP H08259528 A JPH08259528 A JP H08259528A JP 6659495 A JP6659495 A JP 6659495A JP 6659495 A JP6659495 A JP 6659495A JP H08259528 A JPH08259528 A JP H08259528A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- arylalkyl
- metal ion
- formula
- hydrocarbon
- 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.)
- Pending
Links
- -1 arylalkyl hydroperoxides Chemical class 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 13
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000007514 bases Chemical class 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 2
- PZRFMNQRPVQCIT-UHFFFAOYSA-N 4-[2-(4-oxopentan-2-ylideneamino)ethylimino]pentan-2-one Chemical compound CC(=O)CC(C)=NCCN=C(C)CC(C)=O PZRFMNQRPVQCIT-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- 229910001429 cobalt ion Inorganic materials 0.000 claims 1
- 229910001437 manganese ion Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000009825 accumulation Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 150000002432 hydroperoxides Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical class CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical class C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- GDEQPEBFOWYWSA-UHFFFAOYSA-N 1,2-dimethyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C)=C1C GDEQPEBFOWYWSA-UHFFFAOYSA-N 0.000 description 1
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 1
- MLXMBIUVXPMUPK-UHFFFAOYSA-N 1-butan-2-yl-2-ethylbenzene Chemical compound CCC(C)C1=CC=CC=C1CC MLXMBIUVXPMUPK-UHFFFAOYSA-N 0.000 description 1
- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical class C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 description 1
- GWLLTEXUIOFAFE-UHFFFAOYSA-N 2,6-diisopropylnaphthalene Chemical compound C1=C(C(C)C)C=CC2=CC(C(C)C)=CC=C21 GWLLTEXUIOFAFE-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- TVYVQNHYIHAJTD-UHFFFAOYSA-N 2-propan-2-ylnaphthalene Chemical compound C1=CC=CC2=CC(C(C)C)=CC=C21 TVYVQNHYIHAJTD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
- C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
- C07C409/08—Compounds containing six-membered aromatic rings
- C07C409/10—Cumene hydroperoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
- C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
- C07C409/08—Compounds containing six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【目的】遷移金属錯体を触媒として用い、アリールアル
キル炭化水素を酸素含有気体にて酸化して、対応するア
リールアルキルヒドロペルオキシド類を製造する方法に
おいて、反応速度及び選択率を高めることにある。
【構成】本発明によるアリールアルキルヒドロペルオキ
シド類の製造方法は、配位構造
【化１】
（式中、Ｍは遷移金属イオンを示す。）を形成する配位
子と遷移金属イオンとからなる遷移金属錯体を触媒とし
て用いて、酸素含有気体にて酸化して、対応するアリー
ルアルキルヒドロペルオキシド類に選択的に転化するこ
とを特徴とする。(57) [Summary] [Objective] In a method for producing a corresponding arylalkyl hydroperoxide by oxidizing an arylalkyl hydrocarbon with an oxygen-containing gas using a transition metal complex as a catalyst, the reaction rate and selectivity are To raise. The method for producing arylalkyl hydroperoxides according to the present invention has a coordination structure: (In the formula, M represents a transition metal ion.) A transition metal complex composed of a transition metal ion and a ligand forming the transition metal ion is used as a catalyst to oxidize with an oxygen-containing gas to obtain a corresponding arylalkyl hydroperoxide. It is characterized in that it is selectively converted into a class.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、窒素原子及び酸素原子
を電子供与原子とするある種の遷移金属錯体を触媒とし
て用いて、アリールアルキル炭化水素を酸素含有気体に
て酸化して、対応するアリールアルキルヒドロペルオキ
シド類に選択的に且つ高濃度に転化することによるアリ
ールアルキルヒドロペルオキシド類の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention corresponds to the oxidation of arylalkyl hydrocarbons with an oxygen-containing gas using certain transition metal complexes having nitrogen and oxygen atoms as electron donor atoms as catalysts. The present invention relates to a method for producing arylalkyl hydroperoxides by selectively and highly converting to arylalkyl hydroperoxides.
【０００２】[0002]
【従来の技術】触媒の存在下にアリールアルキル基を有
する炭化水素を酸素含有気体にて酸化して、対応するア
リールアルキルヒドロペルオキシド類を製造する方法
は、従来、種々知られている。例えば、特公昭５５−５
００２０号公報には、エチレンジアミン四酢酸（ＥＤＴ
Ａ）等のポリアミノカルボン酸類を配位子とするコバル
ト、ニッケル、マンガン、銅又は鉄の水溶性錯体（キレ
ート化合物）を触媒として用いて、水の存在下に、3,５
−ジメチルクメン等のような第２級アルキル基を有する
アリールアルキル炭化水素を酸素含有気体にて酸化し
て、対応するヒドロペルオキシド類に転化する方法が記
載されている。2. Description of the Related Art Various methods for producing a corresponding arylalkyl hydroperoxide by oxidizing a hydrocarbon having an arylalkyl group with an oxygen-containing gas in the presence of a catalyst are conventionally known. For example, Japanese Patent Publication Sho 55-5
Japanese Patent No. 0020 discloses that ethylenediaminetetraacetic acid (EDT
Using a water-soluble complex (chelate compound) of cobalt, nickel, manganese, copper or iron having a polyaminocarboxylic acid such as A) as a ligand as a catalyst, the presence of
-A method is described in which an arylalkyl hydrocarbon having a secondary alkyl group such as dimethylcumene is oxidized with an oxygen-containing gas and converted to the corresponding hydroperoxides.
【０００３】しかし、この方法によれば、ヒドロペルオ
キシド類の熱分解が無視できる８０℃程度の比較的低い
温度領域においては、酸化反応を実用的な反応速度で進
行させることができない。他方、特開昭５１−３４１３
８号公報には、α, α−（エチレンジニトリロ）ジ−ｏ
−クレゾールのニッケル錯化合物がβ−イソプロピルナ
フタレンの酸化触媒として提案されているが、触媒性能
は十分ではない。However, according to this method, the oxidation reaction cannot proceed at a practical reaction rate in a relatively low temperature range of about 80 ° C. at which thermal decomposition of hydroperoxides can be ignored. On the other hand, JP-A-51-3413
No. 8 discloses α, α- (ethylenedinitrilo) di-o.
A cresol nickel complex compound has been proposed as an oxidation catalyst for β-isopropylnaphthalene, but the catalytic performance is not sufficient.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、アリールア
ルキル炭化水素を酸素含有気体にて酸化して、対応する
アリールアルキルヒドロペルオキシド類を製造する従来
の方法における上述したような問題を解決するためにな
されたものであって、ある種の遷移金属錯体がアリール
アルキル炭化水素を酸素含有気体にて酸化して、対応す
るアリールアルキルヒドロペルオキシド類に転化するの
に有用な触媒であることを見出して、本発明に至ったも
のである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems in the prior art process of oxidizing arylalkyl hydrocarbons with an oxygen-containing gas to produce the corresponding arylalkylhydroperoxides. And found that certain transition metal complexes are useful catalysts for the oxidation of arylalkyl hydrocarbons with oxygen-containing gases and conversion to the corresponding arylalkylhydroperoxides. The present invention has been achieved.
【０００５】即ち、本発明は、窒素原子及び酸素原子を
電子供与原子とするある種の遷移金属錯体を触媒として
用いて、アリールアルキル炭化水素を酸素含有気体にて
酸化して、対応するアリールアルキルヒドロペルオキシ
ド類を製造する方法を提供することを目的とする。That is, according to the present invention, an arylalkyl hydrocarbon is oxidized with an oxygen-containing gas by using a certain transition metal complex having a nitrogen atom and an oxygen atom as an electron donor atom as a catalyst to obtain a corresponding arylalkyl. It is an object to provide a method for producing hydroperoxides.
【０００６】[0006]
【課題を解決するための手段】本発明によるアリールア
ルキルヒドロペルオキシド類の製造方法は、一般式
（Ｉ）The process for preparing arylalkyl hydroperoxides according to the present invention comprises a compound of the general formula (I)
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】（式中、Ｐ及びＱは、水素又はアルキル基
を示し、相互に同じであってもよく、異なっていてもよ
く、ｘは１〜３の整数を示し、Ａｒはｘ価の芳香族炭化
水素基を示す。）で表わされるアリールアルキル炭化水
素を、配位構造（II）(In the formula, P and Q represent hydrogen or an alkyl group, which may be the same or different from each other, x represents an integer of 1 to 3, and Ar represents an aromatic valence of x. Arylalkylhydrocarbon represented by Group II hydrocarbon group) has a coordination structure (II)
【０００９】[0009]
【化５】 Embedded image
【００１０】（式中、Ｍは遷移金属イオンを示す。）を
形成する配位子と遷移金属イオンとからなる遷移金属錯
体を触媒として用いて、酸素含有気体にて酸化して、対
応するアリールアルキルヒドロペルオキシド類に選択的
に転化することを特徴とする。(Wherein M represents a transition metal ion), a transition metal complex consisting of a ligand forming a transition metal ion and a transition metal ion is used as a catalyst, and is oxidized with an oxygen-containing gas to give a corresponding aryl. It is characterized in that it is selectively converted into alkyl hydroperoxides.
【００１１】本発明による方法において、原料として用
いるアリールアルキル炭化水素は、一般式（Ｉ）In the method according to the present invention, the arylalkyl hydrocarbon used as a raw material has the general formula (I).
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】（式中、Ｐ及びＱは、水素又はアルキル基
を示し、相互に同じであってもよく、異なっていてもよ
く、ｘは１〜３の整数を示し、Ａｒはｘ価の芳香族炭化
水素基を示す。）で表わされる。(In the formula, P and Q represent hydrogen or an alkyl group, which may be the same or different from each other, x represents an integer of 1 to 3, and Ar represents an x-valent fragrance. It represents a group hydrocarbon group.).
【００１４】本発明によれば、上記一般式（Ｉ）で表わ
されるアリールアルキル炭化水素は、α水素を有するこ
とが必要であり、特に、第３級水素を有することが好ま
しい。従って、本発明によれば、上記一般式（Ｉ）にお
いて、Ｐ及びＱの少なくともいずれかがアルキル基であ
ることが好ましく、特に、いずれもがアルキル基である
ことが好ましい。上記アルキル基としては、特に、メチ
ル基が好ましい。芳香族炭化水素基として、例えば、ベ
ンゼン、ナフタレン、ビフェニル、ジフェニルエーテル
等から導かれるｘ価の炭化水素基を挙げることができる
が、好ましくは、ベンゼン又はナフタレンから導かれる
ｘ価の炭化水素基である。According to the present invention, the arylalkyl hydrocarbon represented by the above general formula (I) is required to have α hydrogen, and it is particularly preferable to have tertiary hydrogen. Therefore, according to the present invention, in the above general formula (I), at least one of P and Q is preferably an alkyl group, and particularly preferably both are alkyl groups. As the above alkyl group, a methyl group is particularly preferable. Examples of the aromatic hydrocarbon group include an x-valent hydrocarbon group derived from benzene, naphthalene, biphenyl, diphenyl ether, etc., and an x-valent hydrocarbon group derived from benzene or naphthalene is preferable. .
【００１５】従って、本発明において、アリールアルキ
ル炭化水素の好ましい具体例としては、例えば、クメ
ン、サイメン、ｍ−ジイソプロピルベンゼン、ｐ−ジイ
ソプロピルベンゼン等のジイソプロピルベンゼン類、1,
3,５−トリイソプロピルベンゼン等のトリイソプロピル
ベンゼン類、エチルベンゼン、ｓｅｃ−ブチルベンゼ
ン、ｓｅｃ−ブチルエチルベンゼン、イソプロピルナフ
タレン類、2,６−ジイソプロピルナフタレン等のジイソ
プロピルナフタレン類、イソプロピルビフェニル類、4,
4'−ジイソプロピルビフェニル等のジイソプロピルビフ
ェニル類や、これらの２種以上の混合物を挙げることが
できる。しかし、これらに限定されるものではない。Therefore, in the present invention, preferred specific examples of arylalkyl hydrocarbons include diisopropylbenzenes such as cumene, cymen, m-diisopropylbenzene and p-diisopropylbenzene, 1,
Triisopropylbenzenes such as 3,5-triisopropylbenzene, ethylbenzene, sec-butylbenzene, sec-butylethylbenzene, isopropylnaphthalenes, diisopropylnaphthalenes such as 2,6-diisopropylnaphthalene, isopropylbiphenyls, 4,
Examples thereof include diisopropyl biphenyls such as 4′-diisopropyl biphenyl, and mixtures of two or more thereof. However, it is not limited to these.
【００１６】本発明によれば、窒素原子及び酸素原子を
電子供与原子とし、中心金属イオンである遷移金属イオ
ンに窒素原子及び酸素原子が窒素原子／酸素原子の比１
／１にて配位している錯体、即ち、下記配位構造（II）According to the present invention, a nitrogen atom and an oxygen atom are electron donor atoms, and a transition metal ion, which is a central metal ion, has a nitrogen atom / oxygen atom ratio of 1 to 1.
/ 1 complex, that is, the following coordination structure (II)
【００１７】[0017]
【化７】 [Chemical 7]
【００１８】（式中、Ｍは遷移金属イオンを示す。）を
形成する配位子と遷移金属イオンとからなる遷移金属錯
体を触媒として用いて上述したようなアリールアルキル
炭化水素を酸素含有気体にて酸化して、対応するアリー
ルアルキルヒドロペルオキシド類に選択的に転化する。
特に、本発明によれば、上記遷移金属錯体は、好ましく
は、一般式（III)(Wherein M represents a transition metal ion) and a transition metal complex consisting of a transition metal ion and a ligand forming the transition metal ion is used as a catalyst to convert the above arylalkyl hydrocarbon into an oxygen-containing gas. Oxidize and selectively convert to the corresponding arylalkyl hydroperoxides.
In particular, according to the present invention, the transition metal complex preferably has the general formula (III)
【００１９】[0019]
【化８】 Embedded image
【００２０】（式中、Ｍは遷移金属イオンを示し、Ｒ1
からＲ8 は水素又は有機基であり、それぞれ同一であっ
ても、異なっていてもよく、また、隣接する有機基と共
に環を形成していてもよい。）で表わされる。(In the formula, M represents a transition metal ion, and R 1
To R 8 are hydrogen or an organic group, which may be the same or different, and may form a ring with an adjacent organic group. ).
【００２１】上記一般式（III)で表わされる遷移金属錯
体において、Ｒ1 からＲ8 は、水素のほか、特に、限定
されるものではなく、種々の有機基であってよく、例え
ば、そのような有機基として、アルキル基、アリール
基、アリールアルキル基等を例示することができ、それ
ぞれ同一であっても、異なっていてもよい。また、Ｒ1
からＲ8 は、隣接する有機基と結合していてもよく、ま
た、隣接する有機基と共に環を形成していてもよい。例
えば、Ｒ1 とＲ5 は相互に結合して、アルキレン基、特
に、エチレン基やトリメチレン基を形成してもよく、ま
た、Ｒ3 とＲ4 は相互に結合して芳香環（代表的にはベ
ンゼン環）を形成してもよく、同様に、Ｒ 7 とＲ8 も相
互に結合して芳香環（代表的にはベンゼン環）を形成し
てもよい。また、Ｒ2 やＲ6 は、例えば、メチル基のよ
うなアルキル基や、フェニル基のようなアリール基であ
ってもよい。The transition metal complex represented by the above general formula (III)
In the body, R1To R8Is, in addition to hydrogen, especially limited
However, it may be various organic groups, for example,
Examples of such organic groups include alkyl groups and aryl groups.
Group, arylalkyl group, etc.
They may be the same or different. Also, R1
To R8May be bonded to an adjacent organic group,
Further, a ring may be formed with the adjacent organic group. An example
For example, R1And RFiveAre bonded to each other to form an alkylene group,
In addition, an ethylene group or trimethylene group may be formed.
R3And RFourAre bonded to each other by an aromatic ring (typically
Ring group), and similarly, R 7And R8Mou
Bond together to form an aromatic ring (typically a benzene ring)
May be. Also, R2And R6Is a methyl group, for example
Such as an alkyl group or an aryl group such as a phenyl group.
You may.
【００２２】従って、前記遷移金属錯体を形成する配位
子の好ましい具体例としては、例えば、N,N'−ビス（１
−メチル−３−オキソブチリデン）エチレンジアミン、
N,N'−ビス（１−フェニル−３−オキソブチリデン）エ
チレンジアミン、N,N'−ジサリチラルエチレンジアミ
ン、N,N'−ジサリチラルトリメチレンジアミン、N,N'−
ジサリチラル−（ｏ−フェニレン）ジアミン等を挙げる
ことができる。Therefore, a preferred specific example of the ligand forming the transition metal complex is, for example, N, N'-bis (1
-Methyl-3-oxobutylidene) ethylenediamine,
N, N'-bis (1-phenyl-3-oxobutylidene) ethylenediamine, N, N'-disalicyrethylenediamine, N, N'-disalicylic trimethylenediamine, N, N'-
Examples thereof include disalicyral- (o-phenylene) diamine.
【００２３】他方、前記一般式（III)で表わされる遷移
金属錯体において、上記遷移金属イオンは、マンガン、
コバルト、鉄、銅、ロジウム、クロム又はルテニウムの
イオンであり、特に、コバルト、マンガン又はルテニウ
ムのイオンであることが好ましい。On the other hand, in the transition metal complex represented by the general formula (III), the transition metal ion is manganese,
It is an ion of cobalt, iron, copper, rhodium, chromium or ruthenium, particularly preferably an ion of cobalt, manganese or ruthenium.
【００２４】本発明の方法において、遷移金属錯体は、
通常、出発物質である前記アリールアルキル炭化水素１
００重量部に対して、0.００００１〜5.０重量部の範囲
で用いられ、好ましくは、0.０００１〜0.１重量部の範
囲で用いられる。In the method of the present invention, the transition metal complex is
Usually, the starting arylalkyl hydrocarbon 1
It is used in the range of 0.0001 to 5.0 parts by weight, preferably 0.0001 to 0.1 part by weight, based on 00 parts by weight.
【００２５】酸化剤としての酸素含有気体としては、通
常、空気が用いられるが、酸素や、酸素と窒素の任意の
混合ガスを用いてもよい。反応は、通常、常圧下で行な
えばよいが、必要に応じて、加圧下に行なってもよい。
反応温度は、通常、４０〜１２０℃の範囲であるが、好
ましくは、５０〜１００℃の範囲である。Air is usually used as the oxygen-containing gas as the oxidant, but oxygen or an arbitrary mixed gas of oxygen and nitrogen may be used. The reaction may be carried out under normal pressure, but may be carried out under pressure if necessary.
The reaction temperature is usually in the range of 40 to 120 ° C, preferably 50 to 100 ° C.
【００２６】また、本発明によれば、反応は、固体の塩
基性化合物又は塩基性化合物の水溶液共存下に行なって
もよい。上記塩基性化合物の具体例としては、例えば、
炭酸ナトリウム、炭酸水素ナトリウム、水酸化ナトリウ
ム、炭酸カリウム、炭酸水素カリウム、水酸化カリウ
ム、酸化バリウム、酸化マグネシウム等を挙げることが
できる。このような塩基性化合物は、通常、出発物質で
ある前記アリールアルキル炭化水素１００重量部に対し
て、0.０００１〜１0.０重量部の範囲で用いられ、好ま
しくは、0.００１〜5.０重量部の範囲で用いられる。Further, according to the present invention, the reaction may be carried out in the presence of a solid basic compound or an aqueous solution of a basic compound. Specific examples of the basic compound include, for example,
Examples thereof include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium hydroxide, barium oxide and magnesium oxide. Such a basic compound is usually used in the range of 0.0001 to 10.0 parts by weight, preferably 0.001 to 5.50 parts by weight, relative to 100 parts by weight of the starting arylalkyl hydrocarbon. Used in the range of 0 parts by weight.
【００２７】本発明においては、反応は、回分式、連続
式のいずれでも行なうことができる。回分式で反応を行
なう場合は、出発物質であるアリールアルキル炭化水素
が反応温度で液体であれば、それに触媒を加え、加熱攪
拌下に、通常、空気を吹き込むことによって、酸化反応
を行なう。必要であれば、反応に不活性な有機溶剤や水
を反応溶剤として用いてもよい。他方、出発物質である
アリールアルキル炭化水素が反応温度で固体であれば、
反応に不活性な有機溶剤に溶解させて、溶液とし、それ
に触媒を加え、加熱攪拌下に、空気を吹き込んで、酸化
反応を行なえばよい。In the present invention, the reaction can be carried out batchwise or continuously. When the reaction is carried out in a batch system, if the starting arylalkyl hydrocarbon is a liquid at the reaction temperature, a catalyst is added thereto, and the air is usually blown into the mixture under heating and stirring to carry out the oxidation reaction. If necessary, an organic solvent or water inert to the reaction may be used as the reaction solvent. On the other hand, if the starting arylalkyl hydrocarbon is a solid at the reaction temperature,
The solution may be dissolved in an organic solvent inert to the reaction to form a solution, a catalyst may be added thereto, and air may be blown into the solution under heating and stirring to carry out the oxidation reaction.
【００２８】更に、本発明においては、必要に応じて、
反応の開始に際して、アリールアルキル炭化水素に、こ
れに対応する少量のアリールアルキルヒドロペルオキシ
ド等を開始剤として存在させてもよい。また、触媒を固
定床に形成し、出発物質であるアリールアルキル炭化水
素又はその溶液と空気を混合しつつ、この固定床を通過
させてもよい。Further, in the present invention, if necessary,
At the start of the reaction, a small amount of the corresponding arylalkyl hydroperoxide or the like may be present as an initiator in the arylalkyl hydrocarbon. Alternatively, the catalyst may be formed in a fixed bed, and the arylalkyl hydrocarbon as a starting material or a solution thereof may be mixed with air and passed through the fixed bed.
【００２９】本発明の方法によれば、目的とするアリー
ルアルキルヒドロペルオキシドは、反応終了後、得られ
た反応混合物を蒸留する等の通常の手段によって、反応
混合物から容易に回収することができる。According to the method of the present invention, the desired arylalkyl hydroperoxide can be easily recovered from the reaction mixture by a usual means such as distillation of the obtained reaction mixture after the reaction is completed.
【００３０】[0030]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれら実施例により何ら限定されるものではな
い。以下において、反応混合物中のクメンヒドロペルオ
キシドの濃度は、ヨードメトリー及びガスクロマトグラ
フィーにより求めた。また、生成したクメンヒドロペル
オキシドの選択率は、ガスクロマトグラフィーにより求
めた。The present invention will be described below with reference to examples.
The present invention is not limited to these examples. In the following, the concentration of cumene hydroperoxide in the reaction mixture was determined by iodometry and gas chromatography. The selectivity of the cumene hydroperoxide produced was determined by gas chromatography.
【００３１】実施例１ クメン９０ｇとクメンヒドロペルオキシド１０ｇの混合
物にN,N'−ビス（１−メチル−３−オキソブチリデン）
エチレンジアミン−コバルト錯体２ｍｇを加えて、全量
を溶解させた。これを８０℃に加熱し、強攪拌下、空気
を６０ｍｌ／分の割合にて吹き込み、８時間、クメンを
空気酸化した。この間のクメンヒドロペルオキシド蓄積
速度は1.８重量％／時であった。また、生成したクメン
ヒドロペルオキシドの選択率は８６モル％であった。Example 1 A mixture of 90 g of cumene and 10 g of cumene hydroperoxide was added to N, N'-bis (1-methyl-3-oxobutylidene).
2 mg of ethylenediamine-cobalt complex was added to dissolve the whole amount. This was heated to 80 ° C., air was blown at a rate of 60 ml / min under strong stirring, and cumene was air-oxidized for 8 hours. The cumene hydroperoxide accumulation rate during this period was 1.8% by weight / hour. The selectivity of cumene hydroperoxide produced was 86 mol%.
【００３２】実施例２ N,N'−ジサリチラルエチレンジアミン−銅錯体を触媒と
して用いた以外は、実施例１と同様にして反応を行なっ
た。クメンヒドロペルオキシド蓄積速度は0.７重量％／
時であり、生成したクメンヒドロペルオキシドの選択率
は９２モル％であった。Example 2 The reaction was carried out in the same manner as in Example 1 except that N, N'-disalicyral ethylenediamine-copper complex was used as a catalyst. Cumene hydroperoxide accumulation rate is 0.7% by weight /
And the selectivity of the cumene hydroperoxide produced was 92 mol%.
【００３３】実施例３ N,N'−ジサリチラルエチレンジアミン−マンガン錯体を
触媒として用いた以外は、実施例１と同様にして反応を
行なった。反応開始から１時間の間は、クメンヒドロペ
ルオキシドの分解が認められたが、反応開始から２〜８
時間の間のクメンヒドロペルオキシドの蓄積速度は1.６
重量％／時であり、その間に生成したクメンヒドロペル
オキシドの選択率は８７モル％であった。Example 3 The reaction was carried out in the same manner as in Example 1 except that N, N'-disalicyral ethylenediamine-manganese complex was used as a catalyst. Decomposition of cumene hydroperoxide was observed for 1 hour from the start of the reaction, but 2 to 8 from the start of the reaction.
Cumene hydroperoxide accumulation rate over time is 1.6
% By weight, and the selectivity for cumene hydroperoxide formed during that time was 87 mol%.
【００３４】実施例４ N,N'−ジサリチラルエチレンジアミン−ニッケル錯体を
触媒として用いた以外は、実施例１と同様にして反応を
行なった。クメンヒドロペルオキシドの蓄積速度は1.５
重量％／時であり、生成したクメンヒドロペルオキシド
の選択率は７２モル％であった。Example 4 A reaction was carried out in the same manner as in Example 1 except that N, N'-disalicyral ethylenediamine-nickel complex was used as a catalyst. Cumene hydroperoxide accumulation rate is 1.5
% By weight, and the selectivity of cumene hydroperoxide produced was 72 mol%.
【００３５】比較例１ 触媒として、Ｎａ2 〔Ｃｏ（ＥＤＴＡ）〕２００ｍｇを
用いた以外は、実施例１と同様にして反応を行なった。
クメンヒドロペルオキシドの蓄積速度は0.１３重量％／
時であり、生成したクメンヒドロペルオキシドの選択率
は６４モル％であった。Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that 200 mg of Na 2 [Co (EDTA)] was used as the catalyst.
Cumene hydroperoxide accumulation rate is 0.13% by weight /
And the selectivity of the cumene hydroperoxide produced was 64 mol%.
【００３６】実施例５ クメン１００ｇにN,N'−ジサリチラルエチレンジアミン
−コバルト錯体２ｍｇを加えて、全量を溶解させた。こ
れを８０℃に加熱し、強攪拌下、空気を６０ｍｌ／分の
割合にて吹き込み、２時間、クメンを空気酸化した。こ
の間のクメンヒドロペルオキシド蓄積速度は3.２重量％
／時であり、その間に生成したクメンヒドロペルオキシ
ドの選択率は８０モル％であった。Example 5 To 100 g of cumene, 2 mg of N, N'-disalicyral ethylenediamine-cobalt complex was added and the whole amount was dissolved. This was heated to 80 ° C., and air was blown at a rate of 60 ml / min under strong stirring to air-oxidize cumene for 2 hours. Cumene hydroperoxide accumulation rate during this period was 3.2% by weight
/ H, the selectivity of cumene hydroperoxide formed during that time was 80 mol%.
【００３７】比較例２ 実施例５において、N,N'−ジサリチラルエチレンジアミ
ン−コバルト錯体に代えて、Ｎａ2 〔Ｃｏ（ＥＤＴ
Ａ）〕２００ｍｇを触媒として用いた以外は、実施例５
と同様にして反応を試みたが、反応は進行しなかった。Comparative Example 2 In Example 5, instead of the N, N'-disalicyral ethylenediamine-cobalt complex, Na 2 [Co (EDT
A)] Example 5 except that 200 mg was used as the catalyst.
The reaction was tried in the same manner as, but the reaction did not proceed.
【００３８】[0038]
【発明の効果】以上のように、本発明によれば、窒素原
子及び酸素原子を電子供与原子とする遷移金属錯体を触
媒として用いて、アリールアルキル炭化水素を酸素含有
気体にて酸化することによって、少量の触媒量で、高い
反応速度で対応するヒドロペルオキシド類を高選択率に
て得ることができる。As described above, according to the present invention, a transition metal complex having a nitrogen atom and an oxygen atom as an electron donor atom is used as a catalyst to oxidize an arylalkyl hydrocarbon with an oxygen-containing gas. The corresponding hydroperoxides can be obtained with a high selectivity at a high reaction rate with a small amount of catalyst.
Claims (7)
に同じであってもよく、異なっていてもよく、ｘは１〜
３の整数を示し、Ａｒはｘ価の芳香族炭化水素基を示
す。）で表わされるアリールアルキル炭化水素を、配位
構造（II） 【化２】 （式中、Ｍは遷移金属イオンを示す。）を形成する配位
子と遷移金属イオンとからなる遷移金属錯体を触媒とし
て用いて、酸素含有気体にて酸化して、対応するアリー
ルアルキルヒドロペルオキシド類に選択的に転化するこ
とを特徴とするアリールアルキルヒドロペルオキシド類
の製造方法。1. A compound represented by the general formula (I): (In the formula, P and Q represent hydrogen or an alkyl group, which may be the same or different from each other, and x is 1 to
3 represents an integer of 3 and Ar represents an x-valent aromatic hydrocarbon group. ), An arylalkyl hydrocarbon represented by the formula (II) (In the formula, M represents a transition metal ion.) A transition metal complex composed of a transition metal ion and a ligand forming the transition metal ion is used as a catalyst to oxidize with an oxygen-containing gas to obtain a corresponding arylalkyl hydroperoxide. A process for producing arylalkyl hydroperoxides, which comprises selectively converting into aryls.
素又は有機基であり、それぞれ同一であっても、異なっ
ていてもよく、また、隣接する有機基と結合していても
よく、また、隣接する有機基と共に環を形成していても
よい。）で表わされる請求項１記載の方法。2. A transition metal complex represented by the general formula (III): (In the formula, M represents a transition metal ion, and R 1 to R 8 are hydrogen or an organic group, which may be the same or different, and may be bonded to an adjacent organic group. Or may form a ring with an adjacent organic group).
鉄、銅、ロジウム、クロム又はルテニウムのイオンであ
る請求項１又は２記載の方法。3. The transition metal ion is manganese, cobalt,
3. The method according to claim 1, which is an ion of iron, copper, rhodium, chromium or ruthenium.
キソブチリデン）エチレンジアミン、N,N'−ビス（１−
フェニル−３−オキソブチリデン）エチレンジアミン、
N,N'−ジサリチラルエチレンジアミン、N,N'−ジサリチ
ラルトリメチレンジアミン又はN,N'−ジサリチラル−
（ｏ−フェニレン）ジアミンである請求項１記載の方
法。4. The ligand is N, N'-bis (1-methyl-3-oxobutylidene) ethylenediamine, N, N'-bis (1-
Phenyl-3-oxobutylidene) ethylenediamine,
N, N'-disalicylic ethylenediamine, N, N'-disalicylic trimethylenediamine or N, N'-disalicyral-
The method according to claim 1, which is (o-phenylene) diamine.
請求項１記載の方法。5. The method of claim 1, wherein the arylalkyl hydrocarbon is cumene.
イオンである請求項１記載の方法。6. The method according to claim 1, wherein the transition metal ion is a cobalt or manganese ion.
の存在下に酸化する請求項１記載の方法。7. The method according to claim 1, wherein the arylalkyl hydrocarbon is oxidized in the presence of a basic compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6659495A JPH08259528A (en) | 1995-03-24 | 1995-03-24 | Method for producing arylalkyl hydroperoxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6659495A JPH08259528A (en) | 1995-03-24 | 1995-03-24 | Method for producing arylalkyl hydroperoxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08259528A true JPH08259528A (en) | 1996-10-08 |
Family
ID=13320423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6659495A Pending JPH08259528A (en) | 1995-03-24 | 1995-03-24 | Method for producing arylalkyl hydroperoxides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08259528A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007302656A (en) * | 2006-04-25 | 2007-11-22 | Air Products & Chemicals Inc | POLYDENTATE beta-KETOIMINATE METAL COMPLEX |
| US8617305B2 (en) | 2011-01-25 | 2013-12-31 | Air Products And Chemicals, Inc. | Metal complexes for metal-containing film deposition |
| US9079923B2 (en) | 2010-08-05 | 2015-07-14 | Air Products And Chemicals, Inc. | Multidentate ketoimine ligands for metal complexes |
-
1995
- 1995-03-24 JP JP6659495A patent/JPH08259528A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007302656A (en) * | 2006-04-25 | 2007-11-22 | Air Products & Chemicals Inc | POLYDENTATE beta-KETOIMINATE METAL COMPLEX |
| US7947814B2 (en) | 2006-04-25 | 2011-05-24 | Air Products And Chemicals, Inc. | Metal complexes of polydentate beta-ketoiminates |
| US9079923B2 (en) | 2010-08-05 | 2015-07-14 | Air Products And Chemicals, Inc. | Multidentate ketoimine ligands for metal complexes |
| US8617305B2 (en) | 2011-01-25 | 2013-12-31 | Air Products And Chemicals, Inc. | Metal complexes for metal-containing film deposition |
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