JPH11246471A - Oxidation of aliphatic primary alcohol - Google Patents
Oxidation of aliphatic primary alcoholInfo
- Publication number
- JPH11246471A JPH11246471A JP10046782A JP4678298A JPH11246471A JP H11246471 A JPH11246471 A JP H11246471A JP 10046782 A JP10046782 A JP 10046782A JP 4678298 A JP4678298 A JP 4678298A JP H11246471 A JPH11246471 A JP H11246471A
- Authority
- JP
- Japan
- Prior art keywords
- group
- metal
- primary alcohol
- reaction
- oac
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/20—Pins, blades, or sockets shaped, or provided with separate member, to retain co-operating parts together
- H01R13/207—Pins, blades, or sockets shaped, or provided with separate member, to retain co-operating parts together by screw-in connection
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R31/00—Coupling parts supported only by co-operation with counterpart
- H01R31/08—Short-circuiting members for bridging contacts in a counterpart
- H01R31/085—Short circuiting bus-strips
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/28—Clamped connections, spring connections
- H01R4/30—Clamped connections, spring connections utilising a screw or nut clamping member
- H01R4/34—Conductive members located under head of screw
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は脂肪族１級アルコー
ルの酸化方法に関し、詳しくは、操作性が簡便で大量合
成の容易な、且つ安全性の高い脂肪族１級アルコールの
酸化方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for oxidizing an aliphatic primary alcohol, and more particularly, to a method for oxidizing an aliphatic primary alcohol which is easy to operate, easy to mass-produce, and highly safe. is there.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】アルコ
ールの酸化は、化学反応における重要な官能基変換の１
つであり、幅広く研究が行われている。代表的な方法と
しては、下記〜に示す方法が挙げられる。BACKGROUND OF THE INVENTION Alcohol oxidation is one of the key functional group transformations in chemical reactions.
It has been widely studied. Representative methods include the following methods.
【０００３】 CrO3による酸化方法(Jones Oxidation
etc.) 活性化DMSOを用いる方法(Swern Oxidation, Corey-
Kim Oxidation etc.) Al(OCH(CH3)2)3を用いる Redox反応(Oppenauer Oxi
dation) しかしこれらの方法は少量合成においては便利である
が、反応の後処理が繁雑であったり、有害な廃棄物を多
量に副生する等の問題を有しており、大量合成には適さ
なかった。工業的な生産を考えた場合、触媒的な酸化法
が必須となり、酸化剤は安全かつ安価なものが望まし
い。古くよりPt又はPd触媒によるアルコールの酸化が報
告されているが、高温、アルカリ性条件等の厳しい反応
条件が必要であった（特開平６−３２１８４５、ＥＰ−
２０１９５７、特開昭５０−９６５１６など）。一方、
Ru触媒を用いるアルコールの効率的な酸化方法が報告さ
れている(J. Org. Chem., 1993, 58, 7318.)。しかしな
がら、Ru金属は高価である為、しばしば大量合成におい
ては問題となってくる。この様な状況により、反応性の
低い脂肪族１級アルコールにおける実用的な酸化方法は
殆ど報告されていないのが現状であった。An oxidation method using CrO 3 (Jones Oxidation
etc.) Method using activated DMSO (Swern Oxidation, Corey-
Kim Oxidation etc.) Redox reaction using Al (OCH (CH 3 ) 2 ) 3 (Oppenauer Oxi
However, these methods are convenient for small-scale synthesis, but have problems such as complicated post-reaction of the reaction and large amounts of harmful waste by-products. Did not. When considering industrial production, a catalytic oxidation method is essential, and safe and inexpensive oxidizing agents are desirable. Oxidation of alcohols with Pt or Pd catalysts has been reported for a long time, but severe reaction conditions such as high temperature and alkaline conditions were required (Japanese Patent Laid-Open No. 6-321845;
201957, JP-A-50-96516). on the other hand,
An efficient oxidation method of alcohol using Ru catalyst has been reported (J. Org. Chem., 1993, 58, 7318.). However, Ru metal is expensive and often poses a problem in mass synthesis. Under such circumstances, practically no practical oxidation method has been reported for aliphatic primary alcohols having low reactivity.
【０００４】このため、反応操作が簡単で安全な、また
使用する触媒が安価で大量合成に適した脂肪族１級アル
コールの実用的な酸化方法が強く望まれている。従っ
て、本発明の目的は、上記問題を解決できる実用的な脂
肪族１級アルコールの酸化方法を提供することにある。[0004] Therefore, there is a strong demand for a practical method for oxidizing an aliphatic primary alcohol which is simple and safe in reaction operation, inexpensive in the catalyst used, and suitable for mass synthesis. Accordingly, an object of the present invention is to provide a practical method for oxidizing an aliphatic primary alcohol which can solve the above-mentioned problems.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、特定の第
１群及び第２群より選ばれる金属触媒の共存下、アルデ
ヒドを添加して反応を行うことにより上記目的が達成で
きることを見出し、本発明を完成した。Means for Solving the Problems The present inventors have found that the above object can be achieved by adding an aldehyde and performing a reaction in the presence of a specific metal catalyst selected from the first group and the second group. Thus, the present invention has been completed.
【０００６】すなわち本発明は、一般式（Ｉ） R1-OH （Ｉ） 〔式中、R1は炭素数５〜22の直鎖のアルキル基を示
す。〕で表される脂肪族１級アルコールを酸化するに際
し、Co0 、Co2+、Fe2+、Fe3+、Cu2+、Mn2+又はNi2+を含
有する金属化合物からなる第１群から選ばれる金属触媒
の１種以上、及びCr、Mo、Ｖ、Mn、Fe、Ni、Cu、Pd、Ｗ
又はこれらの金属化合物からなる第２群から選ばれる金
属触媒であって第１群から選ばれた金属触媒以外の金属
触媒の１種以上の存在下、一般式（II） R2-CHO （II） 〔式中、R2は炭素数１〜22の直鎖又は分岐鎖のアルキル
基、アルケニル基、あるいは置換又は無置換のフェニル
基、ベンジル基又はシクロアルキル基を示す。〕で表さ
れるアルデヒドを添加して反応を行うことを特徴とす
る、脂肪族１級アルコールの酸化方法を提供するもので
ある。That is, the present invention provides a compound represented by the general formula (I) R 1 -OH (I) wherein R 1 is a linear alkyl group having 5 to 22 carbon atoms. When oxidizing the aliphatic primary alcohol represented by the formula (1), a first compound comprising a metal compound containing Co 0 , Co 2+ , Fe 2+ , Fe 3+ , Cu 2+ , Mn 2+ or Ni 2+ is used. One or more metal catalysts selected from the group and Cr, Mo, V, Mn, Fe, Ni, Cu, Pd, W
Or, in the presence of one or more metal catalysts selected from the second group consisting of these metal compounds and other than the metal catalysts selected from the first group, a compound represented by the general formula (II) R 2 -CHO (II Wherein R 2 represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or a substituted or unsubstituted phenyl group, benzyl group or cycloalkyl group. Wherein the reaction is carried out by adding an aldehyde represented by the formula (1):
【０００７】[0007]
【発明の実施の形態】以下、本発明の実施の形態を詳細
に説明する。一般式（Ｉ）において、R1は炭素数５〜2
2、好ましくは８〜22の直鎖のアルキル基を示す。Embodiments of the present invention will be described below in detail. In the general formula (I), R 1 has 5 to 2 carbon atoms.
2, preferably 8 to 22 linear alkyl groups.
【０００８】一般式（II）において、R2は炭素数１〜22
の直鎖又は分岐鎖のアルキル基、アルケニル基（ビニル
基等）、あるいは置換基としてハロゲン原子等を有して
いてもよいフェニル基、ベンジル基又はシクロアルキル
基（シクロヘキシル基等）を示すが、炭素数１〜４の直
鎖又は分岐鎖のアルキル基、置換フェニル基又はフェニ
ル基が反応性の点で好ましく、特にメチル基、エチル
基、ｎ−プロピル基、iso −プロピル基、ｎ−ブチル
基、tert−ブチル基、フェニル基、ｍ−クロロフェニル
基が好ましく、更にはメチル基が価格の点で好ましい。In the general formula (II), R 2 has 1 to 22 carbon atoms.
Represents a linear or branched alkyl group, alkenyl group (such as vinyl group), or a phenyl group, benzyl group or cycloalkyl group (such as cyclohexyl group) which may have a halogen atom or the like as a substituent, A linear or branched alkyl group having 1 to 4 carbon atoms, a substituted phenyl group or a phenyl group is preferred in terms of reactivity, and particularly a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group Tert-butyl group, phenyl group and m-chlorophenyl group are preferred, and a methyl group is more preferred in terms of price.
【０００９】本発明で用いられる第１群の金属触媒は、
Co0 、Co2+、Fe2+、Fe3+、Cu2+、Mn2+又はNi2+を含有す
る金属化合物から選ばれるが、金属は単核であっても複
核であっても良い。また、これらの水和物であっても良
い。対イオンもしくは配位子としては塩素イオン、臭素
イオン、ヨウ素イオン、酸素原子、カルボニル、オレフ
ィン、Ｐ含有配位子、Ｎ含有配位子、Ｏ含有配位子、カ
ルボン酸アニオン、アルコキシド等が挙げられる。The first group of metal catalysts used in the present invention is:
Co 0 , Co 2+ , Fe 2+ , Fe 3+ , Cu 2+ , selected from metal compounds containing Mn 2+ or Ni 2+ , the metal may be mononuclear or polynuclear . Also, these hydrates may be used. Examples of the counter ion or ligand include chlorine ion, bromide ion, iodine ion, oxygen atom, carbonyl, olefin, P-containing ligand, N-containing ligand, O-containing ligand, carboxylate anion, alkoxide and the like. Can be
【００１０】第１群の金属触媒の具体例としては、Co,
Co(OAc)2・4H2O, Co(OCOC17H35)2,Co(NO3)2・6H2O, CoC
l2, CoSO4・7H2O, Co(acac)2, Co(hexadecafluorophtha
locyanine), FeCl2, Fe(OAc)2, FeCp2, Fe(Cp-PPh2)2,
Fe(phthalocyanine), FeCl(tetraphenylporphyrinato),
Fe2O3, FeCl3, Fe(OCOC17H35)3, Fe(NO3)3・9H2O,Fe(a
cac)3, Fe(hexafluoroacetylacetonato)3, CuCl2, CuO,
Cu(acac)2, Cu(OAc)2, Cu(CF3CO2)2, Cu(CF3SO3)2, Cu
(OH)2, Cu(0Me)2, Cu(NO3)2・3H2O, CuSO4,Mn(OAc)2・4
H2O, NiCl2, NiO, Ni(OAc)2・4H2O, Ni(OOC-COO), Ni(a
cac)2, NiCp2, NiCl2(PPh3)2 等が挙げられ、Co, Co(OA
c)2・4H2O, Co(NO3)2・6H2O, Fe2O3,FeCl3, Fe(NO3)3・
9H2O, Cu(OAc)2, Cu(NO3)2・3H2O, Mn(OAc)2・4H2O, Ni
(OAc)2・4H2Oが好ましく、Co, Co(OAc)2・4H2O, Fe2O3,
Cu(OAc)2, Mn(OAc)2・4H2O,Ni(OAc)2・4H2Oが特に好ま
しい。[0010] Specific examples of the first group of metal catalysts include Co,
Co (OAc) 2・ 4H 2 O, Co (OCOC 17 H 35 ) 2 , Co (NO 3 ) 2・ 6H 2 O, CoC
l 2 , CoSO 4・ 7H 2 O, Co (acac) 2 , Co (hexadecafluorophtha
locyanine), FeCl 2 , Fe (OAc) 2 , FeCp 2 , Fe (Cp-PPh 2 ) 2 ,
Fe (phthalocyanine), FeCl (tetraphenylporphyrinato),
Fe 2 O 3, FeCl 3, Fe (OCOC 17 H 35) 3, Fe (NO 3) 3 · 9H 2 O, Fe (a
cac) 3 , Fe (hexafluoroacetylacetonato) 3 , CuCl 2 , CuO,
Cu (acac) 2 , Cu (OAc) 2 , Cu (CF 3 CO 2 ) 2 , Cu (CF 3 SO 3 ) 2 , Cu
(OH) 2, Cu (0Me ) 2, Cu (NO 3) 2 · 3H 2 O, CuSO 4, Mn (OAc) 2 · 4
H 2 O, NiCl 2 , NiO, Ni (OAc) 2・ 4H 2 O, Ni (OOC-COO), Ni (a
cac) 2 , NiCp 2 , NiCl 2 (PPh 3 ) 2 and the like, Co, Co (OA
c) 2 · 4H 2 O, Co (NO 3) 2 · 6H 2 O, Fe 2 O 3, FeCl 3, Fe (NO 3) 3 ·
9H 2 O, Cu (OAc) 2, Cu (NO 3) 2 · 3H 2 O, Mn (OAc) 2 · 4H 2 O, Ni
(OAc) 2 · 4H 2 O are preferable, Co, Co (OAc) 2 · 4H 2 O, Fe 2 O 3,
Cu (OAc) 2 , Mn (OAc) 2 .4H 2 O and Ni (OAc) 2 .4H 2 O are particularly preferred.
【００１１】本発明で用いられる第２群の金属触媒は、
Cr、Mo、Ｖ、Mn、Fe、Ni、Cu、Pd、Ｗ又はこれらの金属
化合物であるが、金属は単核であっても複核であっても
良い。また、これらの水和物であっても良い。対イオン
もしくは配位子としては塩素イオン、臭素イオン、ヨウ
素イオン、酸素原子、カルボニル、オレフィン、Ｐ含有
配位子、Ｎ含有配位子、Ｏ含有配位子、カルボン酸アニ
オン、アルコキシド等が挙げられる。これらの金属触媒
はそのまま用いても良いし、又はシリカ、アルミナ、ゼ
オライト、活性炭、高分子樹脂等の担体に担持させて用
いても良い。The second group of metal catalysts used in the present invention is:
Cr, Mo, V, Mn, Fe, Ni, Cu, Pd, W or a metal compound thereof, but the metal may be mononuclear or polynuclear. Also, these hydrates may be used. Examples of the counter ion or ligand include chlorine ion, bromide ion, iodine ion, oxygen atom, carbonyl, olefin, P-containing ligand, N-containing ligand, O-containing ligand, carboxylate anion, alkoxide and the like. Can be These metal catalysts may be used as they are, or may be used by being supported on a carrier such as silica, alumina, zeolite, activated carbon, or a polymer resin.
【００１２】第２群の金属触媒の具体例としては、Cr,
CrO3, Cr2O3, CrCl2, Cr(CO)6, Cr(CO)3(benzene), [Cr
(OAc)2・H2O]2, CrK(SO4)2・12H2O, Cr(H2NCH2CH2NH2)3
Cl3・3.5H2O, Mo, Mo(CO)6, Mo2C, MoB, [Mo(OAc)2]2,
MoCl3, MoO2, MoS2, MoSe2,MoO2Cl2, MoO2(acac)2, MoC
l5, MoO3, Mo(CO)3(cycloheptatriene), H2MoO4・H2O,
NaMoO4・2H2O, (NH4)6Mo7O24・2H2O, Na3[PO4・12Mo
O3]・nH2O, V, VCl3,V(acac)3, VO(acac)2, V2O5, NaVO
3, VO(OC3H7)3, VO(phthalocyanine), Mn, Mn2(CO)10,
MnO2, Mn(OAc)2・4H2O, Mn(OAc)3・2H2O, Mn(acac)3, M
nCl(tetraphenylporphyrinato), Mn(ClO4)2・6H2O, MnF
2, MnCO3, MnWO4, MnCl(salen), Fe, FeSi2, Fe(CO)5,
Fe3(CO)12, FeCl2, Fe(OAc)2, FeCp2, Fe(ClO4)2・6H
2O, Fe(Cp-PPh2)2, Fe(phthalocyanine), FeCl(tetraph
enylporphyrinato), Fe2O3, FeCl3,Fe(OCOC17H35)3, Fe
(NO3)3・9H2O, Fe(ClO4)3・nH2O, Fe(acac)3, Fe(hexaf
luoroacetylacetonato)3, FePO4・nH2O, Ni, Ni(COD)2,
NiCl2(PPh3)2, NiCl2, NiO, Ni(OAc)2・4H2O, Ni(OOC
-COO), Ni(acac)2, NiCp2, NiCl2(PPh3)2, Ni2O3, Cu,
Cu(1,10-phenanthroline)2, CuCl, CuBr, CuI, Cu2O, C
u2S, CuCl2, CuO,Cu(acac)2, Cu(OAc)2, Cu(CF3CO2)2,
Cu(CF3SO3)2, Cu(OH)2, Cu(OMe)2, Cu(NO3)2・3H2O, C
uSO4, CuSCN, Cu(phthalocyanine), Pd, Pd/C, Pd/Al2O
3, PdO, PdCl2, PdCl2(MeCN)2, Pd(OAc)2, Pd(acac)2,
W, W(CO)6, WC, WB, WO3, WOCl4,Na2WO4・2H2O, H2WO4,
Na3[PO4・12WO3]・nH2O等が挙げられ、Cr、Mo又はこれ
らの金属化合物が好ましく、Cr, CrO3, MoB, Mo(CO)6,
MoCl3, MoO2 が特に好ましい。Specific examples of the second group of metal catalysts include Cr,
CrO 3 , Cr 2 O 3 , CrCl 2 , Cr (CO) 6 , Cr (CO) 3 (benzene), (Cr
(OAc) 2・ H 2 O] 2 , CrK (SO 4 ) 2・ 12H 2 O, Cr (H 2 NCH 2 CH 2 NH 2 ) 3
Cl 3・ 3.5H 2 O, Mo, Mo (CO) 6 , Mo 2 C, MoB, [Mo (OAc) 2 ] 2 ,
MoCl 3 , MoO 2 , MoS 2 , MoSe 2 , MoO 2 Cl 2 , MoO 2 (acac) 2 , MoC
l 5 , MoO 3 , Mo (CO) 3 (cycloheptatriene), H 2 MoO 4・ H 2 O,
NaMoO 4・ 2H 2 O, (NH 4 ) 6 Mo 7 O 24・ 2H 2 O, Na 3 (PO 4・ 12Mo
O 3 ] ・ nH 2 O, V, VCl 3 , V (acac) 3 , VO (acac) 2 , V 2 O 5 , NaVO
3 , VO (OC 3 H 7 ) 3 , VO (phthalocyanine), Mn, Mn 2 (CO) 10 ,
MnO 2 , Mn (OAc) 2・ 4H 2 O, Mn (OAc) 3・ 2H 2 O, Mn (acac) 3 , M
nCl (tetraphenylporphyrinato), Mn (ClO 4 ) 2・ 6H 2 O, MnF
2 , MnCO 3 , MnWO 4 , MnCl (salen), Fe, FeSi 2 , Fe (CO) 5 ,
Fe 3 (CO) 12, FeCl 2, Fe (OAc) 2, FeCp 2, Fe (ClO 4) 2 · 6H
2 O, Fe (Cp-PPh 2 ) 2 , Fe (phthalocyanine), FeCl (tetraph
enylporphyrinato), Fe 2 O 3 , FeCl 3 , Fe (OCOC 17 H 35 ) 3 , Fe
(NO 3 ) 3・ 9H 2 O, Fe (ClO 4 ) 3・ nH 2 O, Fe (acac) 3 , Fe (hexaf
luoroacetylacetonato) 3 , FePO 4・ nH 2 O, Ni, Ni (COD) 2 ,
NiCl 2 (PPh 3 ) 2 , NiCl 2 , NiO, Ni (OAc) 2・ 4H 2 O, Ni (OOC
-COO), Ni (acac) 2 , NiCp 2 , NiCl 2 (PPh 3 ) 2 , Ni 2 O 3 , Cu,
Cu (1,10-phenanthroline) 2 , CuCl, CuBr, CuI, Cu 2 O, C
u 2 S, CuCl 2 , CuO, Cu (acac) 2 , Cu (OAc) 2 , Cu (CF 3 CO 2 ) 2 ,
Cu (CF 3 SO 3) 2 , Cu (OH) 2, Cu (OMe) 2, Cu (NO 3) 2 · 3H 2 O, C
uSO 4 , CuSCN, Cu (phthalocyanine), Pd, Pd / C, Pd / Al 2 O
3 , PdO, PdCl 2 , PdCl 2 (MeCN) 2 , Pd (OAc) 2 , Pd (acac) 2 ,
W, W (CO) 6 , WC, WB, WO 3 , WOCl 4 , Na 2 WO 4・ 2H 2 O, H 2 WO 4 ,
Na 3 [PO 4 .12WO 3 ] .nH 2 O and the like, and Cr, Mo or a metal compound thereof is preferable, and Cr, CrO 3 , MoB, Mo (CO) 6 ,
MoCl 3 and MoO 2 are particularly preferred.
【００１３】本発明において第１群の金属触媒と第２群
の金属触媒の好ましい組合せは第１群の金属触媒として
Co, Co(OAc)2・4H2O, Fe2O3, Cu(OAc)2, Mn(OAc)2・4H2
O又はNi(OAc)2・4H2Oを用い、第２群の金属触媒としてC
r, CrO3, MoB, Mo(CO)6, MoCl3 又はMoO2を用いる組合
せであり、より好ましい組合せは第１群の金属触媒とし
てCo(OAc)2・4H2O, Fe2O3, Cu(OAc)2 又はNi(OAc)2・4H
2Oを用い、第２群の金属触媒としてCrO3, Mo(CO)6, MoC
l3又はMoO2を用いる組合せであり、特に好ましい組合せ
は第１群の金属触媒としてCo(OAc)2・4H2Oを用いる上記
の組合せである。In the present invention, a preferred combination of the first group metal catalyst and the second group metal catalyst is as the first group metal catalyst.
Co, Co (OAc) 2・ 4H 2 O, Fe 2 O 3 , Cu (OAc) 2 , Mn (OAc) 2・ 4H 2
Using O or Ni (OAc) 2 .4H 2 O, the second group of metal catalysts is C
r, CrO 3 , MoB, Mo (CO) 6 , MoCl 3 or a combination using MoO 2 , a more preferred combination is Co (OAc) 2 .4H 2 O, Fe 2 O 3 , Cu (OAc) 2 or Ni (OAc) 2 · 4H
With 2 O, CrO 3 as the metal catalyst of the second group, Mo (CO) 6, MoC
a combination of using l 3 or MoO 2, particularly preferred combinations are the above combination of using Co (OAc) 2 · 4H 2 O as the metal catalyst of the first group.
【００１４】本発明の方法によると、前記一般式（Ｉ）
で表される脂肪族１級アルコールを酸化するに際し、前
記第１群より選ばれる金属触媒、及び前記第２群より選
ばれる金属触媒であって第１群から選ばれた金属触媒以
外の金属触媒の存在下、前記一般式（II）で表されるア
ルデヒドを添加することにより反応を行うが、本発明の
酸化方法の好ましい実施様態を以下に示す。According to the method of the present invention, the above general formula (I)
A metal catalyst selected from the first group and a metal catalyst other than the metal catalyst selected from the first group when oxidizing the aliphatic primary alcohol represented by The reaction is carried out by adding an aldehyde represented by the above general formula (II) in the presence of the above. A preferred embodiment of the oxidation method of the present invention is shown below.
【００１５】反応器に一般式（Ｉ）で表される脂肪族１
級アルコール、第１群より選ばれる金属触媒、第２群よ
り選ばれる金属触媒、さらに必要なら溶媒を仕込み、一
般式（II）で表されるアルデヒドを添加する。In the reactor, the aliphatic 1 represented by the general formula (I)
A secondary alcohol, a metal catalyst selected from the first group, a metal catalyst selected from the second group, and, if necessary, a solvent are charged, and the aldehyde represented by the general formula (II) is added.
【００１６】第１群より選ばれる金属触媒、及び第２群
より選ばれる金属触媒の仕込み量は、それぞれ、一般式
（Ｉ）で表される１級アルコールに対し 0.001〜10mol
％が好ましく、0.01〜５ mol％が更に好ましい。0.001m
ol％より少ないと添加による効果が減少し、反応時間が
長くなり好ましくない。また10 mol％を超えて用いる
と、好ましくない副反応が起こるようになり、また経済
的に不利である。The charged amounts of the metal catalyst selected from the first group and the metal catalyst selected from the second group are each 0.001 to 10 mol based on the primary alcohol represented by the general formula (I).
%, More preferably 0.01 to 5 mol%. 0.001m
If the amount is less than ol%, the effect of the addition decreases, and the reaction time becomes longer, which is not preferable. On the other hand, if it is used in excess of 10 mol%, undesirable side reactions will occur and it is economically disadvantageous.
【００１７】反応で用いる溶媒は、一般式（Ｉ）で表さ
れる脂肪族１級アルコールの性質により使用の有無、及
び種類を選択することが出来る。例えば、一般式（Ｉ）
で表される１級アルコールの融点や粘度が高くそのまま
では撹拌が困難な場合、一般式（Ｉ）で表される１級ア
ルコールの濃度と反応収率の間に相関がある場合等は、
適当な量の反応溶媒を使用することが出来る。本反応で
用いられる溶媒としては、一般的に有機合成で用いられ
ている溶媒なら何でも良く、例えばヘキサン、アセト
ン、トルエン、ジクロロメタン、クロロホルム、酢酸エ
チル、アセトニトリル、酢酸、ジメチルスルホキシド、
ジメチルホルムアミド、メタノール、水等が挙げられ、
単独で用いても混合して用いても良い。The solvent used in the reaction can be selected depending on the nature of the aliphatic primary alcohol represented by the general formula (I), and whether or not it is used, can be selected. For example, the general formula (I)
In the case where the melting point and the viscosity of the primary alcohol represented by the formula (1) are so high that stirring is difficult as it is, the case where there is a correlation between the concentration of the primary alcohol represented by the general formula (I) and the reaction yield, etc.
An appropriate amount of reaction solvent can be used. As the solvent used in this reaction, any solvent generally used in organic synthesis may be used, for example, hexane, acetone, toluene, dichloromethane, chloroform, ethyl acetate, acetonitrile, acetic acid, dimethyl sulfoxide,
Dimethylformamide, methanol, water and the like,
They may be used alone or as a mixture.
【００１８】前記一般式（II）で表されるアルデヒドの
添加量は、一般式（Ｉ）で表される脂肪族１級アルコー
ルに対し 0.1〜20当量が好ましく、１〜10当量が更に好
ましい。0.1 当量より少ないと反応が完全には進行しな
くなり、故意に原料を残存させる場合を除き好ましくな
い。また、20当量を超えて用いても効果は同じである
が、経済的に不利である。添加の方法は、反応の開始時
に一括して仕込んでもよいし、滴下により添加を行って
もよい。The amount of the aldehyde represented by the general formula (II) is preferably 0.1 to 20 equivalents, more preferably 1 to 10 equivalents, based on the aliphatic primary alcohol represented by the general formula (I). If the amount is less than 0.1 equivalent, the reaction does not proceed completely, which is not preferable unless the raw materials are intentionally left. Use of more than 20 equivalents has the same effect, but is economically disadvantageous. The method of addition may be batch charging at the start of the reaction, or may be added dropwise.
【００１９】反応は空気雰囲気下、酸素雰囲気下、若し
くはこれらの混合気体の雰囲気下で行うが、酸素雰囲気
下の方が反応が速く進行し好ましい。また、反応スケー
ルが大きい場合、これらの気体との接触効率を高くする
為に、これらの気体をバブリングにより供給するのが好
ましい。The reaction is carried out in an air atmosphere, an oxygen atmosphere, or an atmosphere of a mixed gas thereof. An oxygen atmosphere is preferred because the reaction proceeds rapidly. When the reaction scale is large, it is preferable to supply these gases by bubbling in order to increase the contact efficiency with these gases.
【００２０】酸化反応時の温度は、一般式（Ｉ）で表さ
れる脂肪族１級アルコールもしくは溶媒の融点以上、沸
点以下であれば何ら問題ないが、−30〜150 ℃が好まし
く、更に好ましくは０〜100 ℃である。酸化反応の時間
は、0.5 〜48時間が好ましい。The temperature at the time of the oxidation reaction is not critical as long as it is higher than or equal to the melting point and lower than the boiling point of the aliphatic primary alcohol or the solvent represented by the general formula (I), but is preferably -30 to 150 ° C., more preferably. Is from 0 to 100 ° C. The oxidation reaction time is preferably 0.5 to 48 hours.
【００２１】[0021]
【発明の効果】本発明の酸化方法によると、実質的に用
いる反応剤は一般式（II）で表されるアルデヒドと酸素
だけである。これは従来の金属反応剤や過酸化物等の危
険な酸化剤を用いる方法と比較して、著しく安全であり
且つ操作が簡便である。また従来の方法の様に、有害な
廃棄物は副生しない。また、従来のPt又はPd触媒による
酸化方法の様に高温やアルカリ性条件下で反応を行う必
要がなく、この点においても、従来法と比較して著しく
安全であり、且つ操作が簡便である。According to the oxidation method of the present invention, the only reactants substantially used are the aldehyde represented by the general formula (II) and oxygen. This is significantly safer and easier to operate than conventional methods using dangerous oxidizing agents such as metal reactants and peroxides. Also, unlike the conventional method, no harmful waste is produced as a by-product. Further, unlike the conventional oxidation method using a Pt or Pd catalyst, there is no need to carry out the reaction under high temperature or alkaline conditions, and in this respect, the operation is extremely safe and the operation is simple as compared with the conventional method.
【００２２】これらの理由は、まず、一般式（II）で表
されるアルデヒドと酸素より、第１群より選ばれる金属
触媒の存在下、反応系中で酸化剤である過酸（R2-COOO
H) を調製していることにある。これにより、危険な酸
化剤である過酸の取り扱いに伴う種々の問題が解決され
た。更にこの過酸（R2-COOOH) の作用により、第２群よ
り選ばれる金属触媒が酸化活性種となるが、この酸化活
性種が一般式（Ｉ）で表される１級アルコールに対し
て、極めて高活性を示すことにある。これにより、厳し
い条件下で反応を行う必要がなくなった。The reasons for this are as follows. First, a peracid (R 2- ) which is an oxidizing agent is converted from an aldehyde represented by the general formula (II) and oxygen in a reaction system in the presence of a metal catalyst selected from the first group. COOO
H). This has solved various problems associated with handling peracid, which is a dangerous oxidizing agent. Further, by the action of this peracid (R 2 —COOOH), the metal catalyst selected from the second group becomes an oxidizing active species, and the oxidizing active species reacts with the primary alcohol represented by the general formula (I). , Exhibiting extremely high activity. This eliminates the need to perform the reaction under severe conditions.
【００２３】第１群に示す金属触媒の存在下、アルデヒ
ドと酸素より過酸が生成することは以前より知られてお
り(Trans. Faraday Soc., 1951, 47, 721., Advances i
n Chemistry Series, 1968, 76, 363.など）、またこれ
をオレフィンのエポキシ化反応(Chem. Lett., 1991, 1.
など）やBacycr-Villiger 反応(Chem. Lett., 1991,64
1., Tetrahedron Lett., 1992, 33, 7557.など）等に応
用した例は報告されている(Bull. Chem. Soc. Jpn., 19
95, 68, 17.)。しかし、これをアルコールの酸化に応用
した例は、前記のRu触媒を用いる方法しか知られていな
い(J. Org. Chem., 1993, 58, 7318.)。It has long been known that peracid is formed from aldehyde and oxygen in the presence of the metal catalysts shown in Group 1 (Trans. Faraday Soc., 1951, 47, 721., Advances i.
n Chemistry Series, 1968, 76, 363.) and epoxidation of olefins (Chem. Lett., 1991, 1.
And Bacycr-Villiger reaction (Chem. Lett., 1991, 64).
1., Tetrahedron Lett., 1992, 33, 7557, etc.) have been reported (Bull. Chem. Soc. Jpn., 19
95, 68, 17.). However, as an example of applying this method to the oxidation of alcohol, only a method using the above-mentioned Ru catalyst is known (J. Org. Chem., 1993, 58, 7318.).
【００２４】本発明の方法で得られた一般式（Ｉ）で表
される１級アルコールの酸化物がカルボン酸もしくはカ
ルボン酸エステルである場合、塩基性物質で中和もしく
は加水分解することによりカルボン酸塩にすることが出
来る。更に一般式（Ｉ）で表される１級アルコールが長
鎖の脂肪族アルコールである場合、この様にして得られ
るカルボン酸塩は、各種洗浄剤の基剤もしくは添加剤と
して使用することができる。When the oxide of the primary alcohol represented by the general formula (I) obtained by the method of the present invention is a carboxylic acid or a carboxylic ester, the carboxylic acid is neutralized or hydrolyzed with a basic substance. It can be an acid salt. Further, when the primary alcohol represented by the general formula (I) is a long-chain aliphatic alcohol, the carboxylate obtained in this manner can be used as a base or additive for various cleaning agents. .
【００２５】[0025]
【実施例】実施例１ 酸素入りの風船を備えた50ミリリットル・ナスフラスコ
にｎ−ドデカノール0.3873ｇ(2.079mmol) 、Co(OAc)2・
4H2O 0.0012ｇ (0.0048mmol；ｎ−ドデカノールに対し
て0.2mol％) 、CrO3 0.0020ｇ(0.020mmol；ｎ−ドデカ
ノールに対して１ mol％) 及び酢酸エチル６mlを仕込
み、室温下で撹拌した。そこへ、酢酸エチル２mlに溶解
させたアセトアルデヒド0.37ｇ（ｎ−ドデカノールに対
して４当量) を30分間かけて滴下した。その後、25℃で
4.5 時間撹拌して反応物を得た。ガス・クロマトグラフ
ィーによる分析を行ったところ、反応率は100 ％、ラウ
リン酸の収率は69％であった。EXAMPLE 1 0.3873 g (2.079 mmol) of n-dodecanol, Co (OAc) 2 .multidot.-in a 50 ml eggplant flask equipped with a balloon containing oxygen.
0.0012 g (0.0048 mmol; 0.2 mol% based on n-dodecanol) of 4H 2 O, 0.0020 g (0.020 mmol; 1 mol% based on n-dodecanol) of CrO 3 and 6 ml of ethyl acetate were charged and stirred at room temperature. . Thereto, 0.37 g of acetaldehyde (4 equivalents to n-dodecanol) dissolved in 2 ml of ethyl acetate was added dropwise over 30 minutes. Then at 25 ° C
The reaction was obtained after stirring for 4.5 hours. Analysis by gas chromatography revealed that the conversion was 100% and the yield of lauric acid was 69%.
【００２６】比較例１〜３ 実施例１と同様の反応条件で、各触媒の有無、及びアセ
トアルデヒドの使用量を変化させて反応を行った。反応
条件及び結果を表１にまとめて示した。なお、表１中、
触媒の使用量はｎ−ドデカノールに対する mol％、アセ
トアルデヒドの使用量はｎ−ドデカノールに対する当量
で示した。Comparative Examples 1 to 3 Reactions were carried out under the same reaction conditions as in Example 1 except for the presence or absence of each catalyst and the amount of acetaldehyde used. Table 1 summarizes the reaction conditions and results. In Table 1,
The amount of the catalyst used was shown in mol% based on n-dodecanol, and the amount of acetaldehyde used was shown in equivalents based on n-dodecanol.
【００２７】[0027]
【表１】 [Table 1]
【００２８】実施例２〜47及び比較例４〜６ 実施例１と同様の反応条件で、ｎ−ドデカノールに対し
て0.2mol% のCo(OAc)2・4H2O、ｎ−ドデカノールに対し
て４当量のアセトアルデヒドを用いて、第２群より選ば
れる金属触媒（ｎ−ドデカノールに対して0.2mol％）の
種類を表２及び表３に示すように変化させて反応を行な
った。反応温度は25℃、反応時間は５時間で行なった。
結果を表２及び表３にまとめて示した。Examples 2 to 47 and Comparative Examples 4 to 6 Under the same reaction conditions as in Example 1, 0.2 mol% of Co (OAc) 2 .4H 2 O with respect to n-dodecanol, and with respect to n-dodecanol The reaction was carried out using 4 equivalents of acetaldehyde while changing the type of metal catalyst (0.2 mol% based on n-dodecanol) selected from the second group as shown in Tables 2 and 3. The reaction was performed at a reaction temperature of 25 ° C. for a reaction time of 5 hours.
The results are summarized in Tables 2 and 3.
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【表３】 [Table 3]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 31/36 Ｂ０１Ｊ 31/36 Ｚ Ｃ０７Ｃ 51/235 Ｃ０７Ｃ 51/235 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification symbol FI B01J 31/36 B01J 31/36 Z C07C 51/235 C07C 51/235 // C07B 61/00 300 C07B 61/00 300
Claims (2)
す。〕で表される脂肪族１級アルコールを酸化するに際
し、Co0 、Co2+、Fe2+、Fe3+、Cu2+、Mn2+又はNi2+を含
有する金属化合物からなる第１群から選ばれる金属触媒
の１種以上、及びCr、Mo、Ｖ、Mn、Fe、Ni、Cu、Pd、Ｗ
又はこれらの金属化合物からなる第２群から選ばれる金
属触媒であって第１群から選ばれた金属触媒以外の金属
触媒の１種以上の存在下、一般式（II） R2-CHO （II） 〔式中、R2は炭素数１〜22の直鎖又は分岐鎖のアルキル
基、アルケニル基、あるいは置換又は無置換のフェニル
基、ベンジル基又はシクロアルキル基を示す。〕で表さ
れるアルデヒドを添加して反応を行うことを特徴とす
る、脂肪族１級アルコールの酸化方法。1. A compound of the general formula (I) R 1 —OH (I) wherein R 1 represents a linear alkyl group having 5 to 22 carbon atoms. When oxidizing the aliphatic primary alcohol represented by the formula (1), a first compound comprising a metal compound containing Co 0 , Co 2+ , Fe 2+ , Fe 3+ , Cu 2+ , Mn 2+ or Ni 2+ is used. One or more metal catalysts selected from the group and Cr, Mo, V, Mn, Fe, Ni, Cu, Pd, W
Or, in the presence of one or more metal catalysts selected from the second group consisting of these metal compounds and other than the metal catalysts selected from the first group, a compound represented by the general formula (II) R 2 -CHO (II Wherein R 2 represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or a substituted or unsubstituted phenyl group, benzyl group or cycloalkyl group. And oxidizing the aliphatic primary alcohol.
はこれらの金属化合物である請求項１記載の酸化方法。2. The oxidation method according to claim 1, wherein the metal catalyst selected from the second group is Cr, Mo or a metal compound thereof.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04678298A JP4030646B2 (en) | 1998-02-27 | 1998-02-27 | Method for oxidizing aliphatic primary alcohol |
| EP19990301228 EP0939454B1 (en) | 1998-02-27 | 1999-02-19 | Electrical wiring construction including a bus bar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04678298A JP4030646B2 (en) | 1998-02-27 | 1998-02-27 | Method for oxidizing aliphatic primary alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11246471A true JPH11246471A (en) | 1999-09-14 |
| JP4030646B2 JP4030646B2 (en) | 2008-01-09 |
Family
ID=12756910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04678298A Expired - Fee Related JP4030646B2 (en) | 1998-02-27 | 1998-02-27 | Method for oxidizing aliphatic primary alcohol |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0939454B1 (en) |
| JP (1) | JP4030646B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002201144A (en) * | 2000-12-28 | 2002-07-16 | Kao Corp | Method for producing compound having carboxy and/or carbonyl group |
| CN110963947A (en) * | 2019-12-23 | 2020-04-07 | 张家港格瑞特化学有限公司 | Preparation method of surfactant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS509794B1 (en) * | 1969-03-11 | 1975-04-16 | ||
| JPS591443A (en) * | 1982-06-28 | 1984-01-06 | Nikka Chem Ind Co Ltd | Preparation of polyethylene glycolic acid |
| JPH06321845A (en) * | 1993-05-11 | 1994-11-22 | Otsuka Chem Co Ltd | Production of carboxilic acid |
| JPH11246473A (en) * | 1998-02-27 | 1999-09-14 | Kao Corp | Oxidation of primary alcohol |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5851479A (en) * | 1981-09-18 | 1983-03-26 | 富士通株式会社 | Terminal board for power source |
| US4639819A (en) * | 1984-08-06 | 1987-01-27 | Lutron Electronics Co., Inc. | Protective bypass for electronic circuits |
| US5064384A (en) * | 1990-12-04 | 1991-11-12 | Square D Company | Jumper assembly for multiple breaker application |
| JP2929838B2 (en) * | 1992-06-17 | 1999-08-03 | 住友電装株式会社 | Wire harness and method of manufacturing the same |
| JPH07154914A (en) * | 1993-11-29 | 1995-06-16 | Sumitomo Wiring Syst Ltd | Branch connection box |
| JP3269920B2 (en) * | 1994-07-28 | 2002-04-02 | 三菱電機株式会社 | connector |
-
1998
- 1998-02-27 JP JP04678298A patent/JP4030646B2/en not_active Expired - Fee Related
-
1999
- 1999-02-19 EP EP19990301228 patent/EP0939454B1/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS509794B1 (en) * | 1969-03-11 | 1975-04-16 | ||
| JPS591443A (en) * | 1982-06-28 | 1984-01-06 | Nikka Chem Ind Co Ltd | Preparation of polyethylene glycolic acid |
| JPH06321845A (en) * | 1993-05-11 | 1994-11-22 | Otsuka Chem Co Ltd | Production of carboxilic acid |
| JPH11246473A (en) * | 1998-02-27 | 1999-09-14 | Kao Corp | Oxidation of primary alcohol |
Non-Patent Citations (2)
| Title |
|---|
| Ｊ．ＯＲＧ．ＣＨＥＭ．, vol. 58, JPN6007000796, 1993, pages 7318 - 7319, ISSN: 0000906631 * |
| 第4版 実験化学講座23 有機合成Ｖ, JPN6007000797, 7 October 1991 (1991-10-07), pages 225 - 229, ISSN: 0000906632 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002201144A (en) * | 2000-12-28 | 2002-07-16 | Kao Corp | Method for producing compound having carboxy and/or carbonyl group |
| CN110963947A (en) * | 2019-12-23 | 2020-04-07 | 张家港格瑞特化学有限公司 | Preparation method of surfactant |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0939454A3 (en) | 2001-08-01 |
| EP0939454B1 (en) | 2004-10-06 |
| EP0939454A2 (en) | 1999-09-01 |
| JP4030646B2 (en) | 2008-01-09 |
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