JP2002265391A - Method for reducing organic compound - Google Patents
Method for reducing organic compoundInfo
- Publication number
- JP2002265391A JP2002265391A JP2001135817A JP2001135817A JP2002265391A JP 2002265391 A JP2002265391 A JP 2002265391A JP 2001135817 A JP2001135817 A JP 2001135817A JP 2001135817 A JP2001135817 A JP 2001135817A JP 2002265391 A JP2002265391 A JP 2002265391A
- Authority
- JP
- Japan
- Prior art keywords
- group
- organic compound
- reduction
- compound
- compounds
- 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
- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002346 iodo group Chemical group I* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000006722 reduction reaction Methods 0.000 abstract description 11
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 6
- 150000002896 organic halogen compounds Chemical class 0.000 abstract description 6
- 230000002829 reductive effect Effects 0.000 abstract description 6
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 4
- 238000006149 azo coupling reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005695 dehalogenation reaction Methods 0.000 abstract description 4
- 150000002466 imines Chemical class 0.000 abstract description 4
- 150000002828 nitro derivatives Chemical class 0.000 abstract description 4
- 238000006578 reductive coupling reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- -1 lithium aluminum hydride Chemical compound 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- FPWNLURCHDRMHC-UHFFFAOYSA-N 4-chlorobiphenyl Chemical group C1=CC(Cl)=CC=C1C1=CC=CC=C1 FPWNLURCHDRMHC-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- GWQSENYKCGJTRI-UHFFFAOYSA-N 1-chloro-4-iodobenzene Chemical compound ClC1=CC=C(I)C=C1 GWQSENYKCGJTRI-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- 101100000419 Autographa californica nuclear polyhedrosis virus AC41 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- UVEWQKMPXAHFST-SDNWHVSQSA-N chembl1256376 Chemical compound C=1C=CC=CC=1/C=N/C1=CC=CC=C1 UVEWQKMPXAHFST-SDNWHVSQSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical compound C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 1
- GTWJETSWSUWSEJ-UHFFFAOYSA-N n-benzylaniline Chemical compound C=1C=CC=CC=1CNC1=CC=CC=C1 GTWJETSWSUWSEJ-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Fire-Extinguishing Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は有機ハロゲン化合物
の還元・脱ハロゲン化反応、イミン類の還元によるアミ
ンの合成、カルボニル類の還元・還元的カップリング反
応、及びニトロ化合物のジアゾカップリング反応に関す
るものである。特にＰＣＢに代表される有害塩素化合物
の無害化において有効な技術である。The present invention relates to reduction and dehalogenation reactions of organic halogen compounds, synthesis of amines by reduction of imines, reduction and reductive coupling reactions of carbonyls, and diazo coupling reactions of nitro compounds. Things. In particular, it is an effective technique for detoxifying harmful chlorine compounds represented by PCB.
【０００２】[0002]
【従来の技術】有機化合物の還元、有機ハロゲン化合物
の脱ハロゲン化方法には水素添加触媒を用いる方法、ナ
トリウム、イットリウム、サマリウム、インジウムなど
の金属を用いる方法、水素化アルミニウムリチウムや水
素化ホウ素ナトリウムなどの水素化物を用いる方法など
が知られているが、使用する金属は高価であり、かつ無
水の有機溶媒中で反応を行う必要があるため、簡便かつ
環境に優しい還元方法としては極めて不満足なものであ
る。2. Description of the Related Art Methods for reducing organic compounds and dehalogenating organic halogen compounds include a method using a hydrogenation catalyst, a method using metals such as sodium, yttrium, samarium and indium, lithium aluminum hydride and sodium borohydride. Although a method using a hydride such as is known, the metal used is expensive, and since it is necessary to carry out the reaction in an anhydrous organic solvent, it is extremely unsatisfactory as a simple and environmentally friendly reduction method. Things.
【０００３】また、有害塩素化合物の無害化に関する技
術では、ＰＣＢを含んだトランスオイルをＮａＯＨやＣ
ａＯなどのアルカリ類と高温処理する方法、ナトリウム
金属とともに高温加熱処理する方法などが知られている
が、操作は容易でない上に、有機化合物は回収できな
い。また、ＰＣＢを焼却する方法では、ダイオキシン、
塩化水素ガス等の各種ガスが発生して、大気汚染、焼却
炉の腐蝕などが問題となる。[0003] In the technology relating to detoxification of harmful chlorine compounds, trans-oil containing PCB is converted to NaOH or C.
A method of performing high-temperature treatment with an alkali such as aO, a method of performing high-temperature heat treatment with sodium metal, and the like are known, but the operation is not easy and an organic compound cannot be recovered. In the method of incinerating PCB, dioxin,
Various gases such as hydrogen chloride gas are generated, causing problems such as air pollution and corrosion of incinerators.
【０００４】[0004]
【発明が解決しようとする課題】そこで本発明の目的は
有機化合物をアルコール類と金属カルシウムのみを使用
して、短時間かつ容易な操作で、しかも穏和な条件下に
効率よく還元する新規な方法を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel method for efficiently reducing an organic compound by using only alcohols and calcium metal in a short and easy manner and under mild conditions. Is to provide.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記の目
的を達成すべく鋭意検討を重ねた結果、金属カルシウム
を使用してアルコール類中で、有機ハロゲン化合物の還
元・脱ハロゲン化反応、イミン類の還元によるアミンの
合成、カルボニル類の還元・還元的カップリング反応、
及びニトロ化合物のジアゾカップリング反応が進行する
ことを見出した。そして、有害塩素化合物の場合に、そ
の無害化ができるとの知見を得た。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that reduction and dehalogenation of organic halogen compounds in alcohols using metallic calcium. , Synthesis of amines by reduction of imines, reduction and reductive coupling of carbonyls,
And that the diazo coupling reaction of nitro compounds proceeds. And, in the case of a harmful chlorine compound, it has been found that it can be made harmless.
【０００６】本発明は、上記の知見を基に完成されたも
のであり、 「有機化合物とアルコール類に金属カルシウムを添加混
合して反応させることを特徴とする有機化合物の還元方
法（第１発明）」 「前記有機化合物が、下記一般式（ａ）The present invention has been completed on the basis of the above-mentioned findings, and provides a method for reducing an organic compound characterized by adding and mixing metallic calcium to an organic compound and an alcohol to cause a reaction (first invention). "The organic compound is represented by the following general formula (a)
【化３】 「式中、Ｘはクロロ基、ブロム基、ヨード基、水素原子
を示し、Ｒは水素原子、フェニル基、カルボニル基、ア
ルキル基、アリル基、アミノ基、ヒドロキシル基、ニト
ロ基、シアノ基、アルコキシ基、イミノ基、フルオロ
基、クロロ基、ブロム基、ヨード基を示し、これらは更
に置換基を有してもよい。」 又は下記一般式（ｂ）Embedded image In the formula, X represents a chloro group, a bromo group, an iodine group, or a hydrogen atom, and R represents a hydrogen atom, a phenyl group, a carbonyl group, an alkyl group, an allyl group, an amino group, a hydroxyl group, a nitro group, a cyano group, an alkoxy group. A group, an imino group, a fluoro group, a chloro group, a bromo group, or an iodo group, which may further have a substituent. "Or the following general formula (b)
【化４】 「式中、Ｘはクロロ基、ブロム基、フルオル基、ヨード
基を示す。」で表される化合物である上記発明記載の有
機化合物の還元方法（第２発明）」 本発明は上記第１又は第２発明記載の有機化合物の還元
方法によって構成される。Embedded image (Wherein X represents a chloro group, a bromo group, a fluoro group or an iodo group.) The method for reducing an organic compound according to the above-mentioned invention, which is a compound represented by the following formula (second invention): It is constituted by the method for reducing an organic compound according to the second invention.
【０００７】[0007]
【発明の実施の形態】以下、本発明の有機化合物の還元
方法（以下、「本発明の方法」という）について詳細に
説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the method for reducing an organic compound of the present invention (hereinafter, referred to as “method of the present invention”) will be described in detail.
【０００８】本発明において使用される一般式（ａ）で
示される有機化合物としては、４−クロロビフェニル、
４−クロロニトロベンゼン、４−クロロヨードベンゼ
ン、ｐ−ジブロモベンゼン、４−ブロモクロロベンゼ
ン、４−ブロモヨードベンゼン、１，４−ジクロロベン
ゼン、ベンズアルデヒド、およびそのオルト、メタ、パ
ラ位にメチル基、エチル基、メトキシ基、エトキシ基、
フルオロ基などを含有するもの、アセトフェノン、ベン
ジリデンアニリンなどがあげられる。一般式（ｂ）で示
される有機ハロゲン化合物としては、１−クロロナフタ
レン、１−ブロモナフタレンなどがあげられる。The organic compound represented by the general formula (a) used in the present invention includes 4-chlorobiphenyl,
4-chloronitrobenzene, 4-chloroiodobenzene, p-dibromobenzene, 4-bromochlorobenzene, 4-bromoiodobenzene, 1,4-dichlorobenzene, benzaldehyde, and its ortho, meta, para-methyl and ethyl groups , Methoxy group, ethoxy group,
Examples thereof include those containing a fluoro group and the like, acetophenone, benzylideneaniline, and the like. Examples of the organic halogen compound represented by the general formula (b) include 1-chloronaphthalene and 1-bromonaphthalene.
【０００９】原料有機化合物に対する金属カルシウムの
使用量は０．２〜５倍重量であることが好ましい。カル
シウムの形状は特に問わない。The amount of metal calcium used is preferably 0.2 to 5 times the weight of the starting organic compound. The shape of calcium is not particularly limited.
【００１０】溶媒にはメタノール、エタノール、プロパ
ノールなどのアルコール類が使用されるが、エタノール
が最も好ましい。As the solvent, alcohols such as methanol, ethanol and propanol are used, and ethanol is most preferable.
【００１１】反応温度は一般には室温が選ばれるが、好
ましくは−７０℃〜加熱還流である。The reaction temperature is generally selected from room temperature, and preferably from -70 ° C. to reflux.
【００１２】[0012]
【実施例】以下、実施例により本発明を具体的に説明す
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。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
【００１３】実施例１ フラスコに４−クロロビフェニル（１．０５３７ｇ）と
金属カルシウム２０ｍｍｏｌ（０．８ｇ）を入れ、１０
ｍｌのエタノールを加え、この混合溶液を室温で２４時
間撹拌した。反応終了後、２０ｍｌのジエチルエーテル
で２回抽出した。この抽出液を無水硫酸マグネシウムで
乾燥後、溶媒を減圧下に溜去することにより有機層（ビ
フェニル、シクロヘキセニル類、シクロヘキシル類）を
回収した。ＧＣ−ＭＳにより回収した有機層中の４−ク
ロロビフェニルの濃度は０．３９２２７ｍｇ／ｇ（脱塩
素率９９．９６３ｗｔ％）であった。Example 1 A flask was charged with 4-chlorobiphenyl (1.0537 g) and 20 mmol (0.8 g) of metallic calcium.
ml of ethanol was added and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, extraction was performed twice with 20 ml of diethyl ether. After the extract was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to recover an organic layer (biphenyl, cyclohexenyl, cyclohexyl). The concentration of 4-chlorobiphenyl in the organic layer recovered by GC-MS was 0.39227 mg / g (dechlorination rate 99.963 wt%).
【００１４】実施例２ フラスコにモノクロロビフェニル類、ジクロロビフェニ
ル類、トリクロロビフェニル類、テトラクロロビフェニ
ル類等の芳香族塩素化合物の混合物を含むトランスオイ
ル１ｇ（芳香族塩素化合物の含量８．６１６ｍｇ）と金
属カルシウム２０ｍｍｏｌ（０．８ｇ）を入れ、１０ｍ
ｌのエタノールを加え、この混合溶液を室温で２４時間
撹拌した。反応終了後、２０ｍｌのジエチルエーテルで
２回抽出した。この抽出液を無水硫酸マグネシウムで乾
燥後、溶媒を減圧下に溜去することによりトランスオイ
ルを回収した。ＧＣ−ＭＳにより回収したトランスオイ
ル中の芳香族塩素化合物の含量は０．００３５ｍｇ／ｇ
（脱塩素率９９．９６ｗｔ％）であった。Example 2 1 g of a trans oil containing a mixture of aromatic chlorine compounds such as monochlorobiphenyls, dichlorobiphenyls, trichlorobiphenyls, and tetrachlorobiphenyls in a flask (8.616 mg of an aromatic chlorine compound) and metal Add 20 mmol (0.8 g) of calcium and add 10 m
One liter of ethanol was added and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, extraction was performed twice with 20 ml of diethyl ether. After the extract was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to recover the trans oil. The content of the aromatic chlorine compound in the trans oil recovered by GC-MS is 0.0035 mg / g.
(Dechlorination rate: 99.96 wt%).
【００１５】実施例３ フラスコにＮ−ベンジリデンアニリン５ｍｍｏｌ（９０
６ｍｇ）と金属カルシウム２０ｍｍｏｌ（０．８ｇ）を
入れ、１０ｍｌのエタノールを加え、この混合溶液を室
温で２４時間撹拌した。反応終了後、２０ｍｌのジエチ
ルエーテルで２回抽出した。この抽出液を無水硫酸マグ
ネシウムで乾燥後、溶媒を減圧下に溜去することにより
Ｎ−ベンジルアニリン（９０５ｍｇ，９９％）を得た。Example 3 A flask was charged with 5 mmol of N-benzylideneaniline (90 mmol).
6 mg) and 20 mmol (0.8 g) of metallic calcium were added, 10 ml of ethanol was added, and the mixed solution was stirred at room temperature for 24 hours. After completion of the reaction, extraction was performed twice with 20 ml of diethyl ether. After the extract was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain N-benzylaniline (905 mg, 99%).
【００１６】実施例４ フラスコにベンズアルデヒド５ｍｍｏｌ（５３１ｍｇ）
と金属カルシウム２０ｍｍｏｌ（０．８ｇ）を入れ、１
０ｍｌのエタノールを加え、この混合溶液を室温で２４
時間撹拌した。反応終了後、２０ｍｌのジエチルエーテ
ルで２回抽出した。この抽出液を無水硫酸マグネシウム
で乾燥後、溶媒を減圧下に溜去することによりベンジル
アルコール（３１３ｍｇ，５８％）と１，２−ジフェニ
ル−１，２−エタンジオール（１９８ｍｇ，３７％）を
得た。EXAMPLE 4 5 mmol (531 mg) of benzaldehyde was placed in a flask.
And 20 mmol (0.8 g) of metallic calcium
0 ml of ethanol was added and the mixed solution was allowed to stand at room temperature for 24 hours.
Stirred for hours. After completion of the reaction, extraction was performed twice with 20 ml of diethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain benzyl alcohol (313 mg, 58%) and 1,2-diphenyl-1,2-ethanediol (198 mg, 37%). Was.
【００１７】[0017]
【発明の効果】本発明の方法によれば、極めて簡便な操
作で有機ハロゲン化合物の脱ハロゲン化、イミン類の還
元によるアミンの合成、カルボニル類の還元・還元的カ
ップリング反応、及びニトロ化合物のジアゾカップリン
グ等を行うことができる。According to the method of the present invention, dehalogenation of an organic halogen compound, synthesis of an amine by reduction of an imine, reduction / reductive coupling reaction of a carbonyl, and reaction of a nitro compound can be carried out by extremely simple operations. Diazo coupling or the like can be performed.
【００１８】また、近年問題となっているＰＣＢを含ん
だトランスオイル、また未処理のＰＣＢなどの処理につ
いて、本発明方法が経済的で操作も容易で極めて有効で
ある。そして、その母化合物すなわちビフェニル及びそ
の還元体がほぼ定量的に回収できるので資源の再利用に
も貢献できる。さらに、脱塩素化処理後、脱離した塩素
は本反応の過程で生成する固形物中に塩化物イオンとし
て取り込まれ、無毒な塩として回収することができる。
そのため、有害塩素化合物より脱離した塩素はガスとし
て放出されることはなく装置が腐蝕される心配がない。Further, the method of the present invention is economical, easy to operate, and very effective for treating transformer oil containing PCB, which has been a problem in recent years, and untreated PCB. Since the mother compound, that is, biphenyl and its reduced form can be recovered almost quantitatively, it can contribute to the reuse of resources. Further, after the dechlorination treatment, the desorbed chlorine is taken in as a chloride ion in a solid substance generated in the course of the present reaction, and can be recovered as a non-toxic salt.
Therefore, chlorine desorbed from the harmful chlorine compound is not released as a gas, and there is no fear that the apparatus is corroded.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 33/22 Ｃ０７Ｃ 33/22 33/26 33/26 209/52 209/52 211/48 211/48 Ｆターム(参考） 2E191 BA13 BC01 BD11 4H006 AA02 AA05 AC11 AC13 AC41 AC52 BA92 BB14 BE21 EA22 FC52 FE11 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C07C 33/22 C07C 33/22 33/26 33/26 209/52 209/52 211/48 211 / 48F Term (reference) 2E191 BA13 BC01 BD11 4H006 AA02 AA05 AC11 AC13 AC41 AC52 BA92 BB14 BE21 EA22 FC52 FE11
Claims (2)
金属カルシウムを添加混合することを特徴とする有機化
合物の還元方法。1. A method for reducing an organic compound, comprising adding and mixing calcium metal to a mixed solution of an organic compound and an alcohol.
を示し、Ｒは水素原子、フェニル基、カルボニル基、ア
ルキル基、アリル基、アミノ基、ヒドロキシル基、ニト
ロ基、シアノ基、アルコキシ基、イミノ基、フルオロ
基、クロロ基、ブロム基、ヨード基を示し、これらは更
に置換基を有してもよい。」又は下記一般式（ｂ） 【化２】 「式中、Ｘはクロロ基、ブロム基、ヨード基を示す。」
で表される化合物である請求項１に記載の有機化合物の
還元方法。2. The method according to claim 1, wherein the organic compound is represented by the following general formula (a): In the formula, X represents a chloro group, a bromo group, an iodine group, or a hydrogen atom, and R represents a hydrogen atom, a phenyl group, a carbonyl group, an alkyl group, an allyl group, an amino group, a hydroxyl group, a nitro group, a cyano group, an alkoxy group. A group, an imino group, a fluoro group, a chloro group, a bromo group, or an iodo group, which may further have a substituent. ”Or the following general formula (b): "In the formula, X represents a chloro group, a bromo group, or an iodo group."
The method for reducing an organic compound according to claim 1, which is a compound represented by the formula:
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001000731 | 2001-01-05 | ||
| JP2001-731 | 2001-01-05 | ||
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ID=26607372
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3533389B2 (en) | 2002-08-08 | 2004-05-31 | 独立行政法人 科学技術振興機構 | Method of detoxifying dioxins |
| WO2008038801A1 (en) | 2006-09-29 | 2008-04-03 | Japan Science And Technology Agency | Method of producing diol, polydiol, secondary alcohol or diketone compound |
| JP2008088082A (en) * | 2006-09-29 | 2008-04-17 | Japan Science & Technology Agency | Method for producing diol or polydiol |
| JP2008214302A (en) * | 2007-03-07 | 2008-09-18 | Japan Science & Technology Agency | Method for producing secondary alcohol or diketone compound using ketone compound |
| JP2009185025A (en) * | 2008-01-07 | 2009-08-20 | Nagoya Industrial Science Research Inst | Method for dehalogenating aromatic halide |
| JP2009221351A (en) * | 2008-03-17 | 2009-10-01 | Koji Mitoma | Method of processing polyphenol-based substance or phenol-based substance |
-
2001
- 2001-05-07 JP JP2001135817A patent/JP2002265391A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3533389B2 (en) | 2002-08-08 | 2004-05-31 | 独立行政法人 科学技術振興機構 | Method of detoxifying dioxins |
| WO2008038801A1 (en) | 2006-09-29 | 2008-04-03 | Japan Science And Technology Agency | Method of producing diol, polydiol, secondary alcohol or diketone compound |
| JP2008088082A (en) * | 2006-09-29 | 2008-04-17 | Japan Science & Technology Agency | Method for producing diol or polydiol |
| US7696386B2 (en) | 2006-09-29 | 2010-04-13 | Japan Science And Technology Agency | Method of producing diol, polydiol, secondary alcohol or diketone compound |
| JP2008214302A (en) * | 2007-03-07 | 2008-09-18 | Japan Science & Technology Agency | Method for producing secondary alcohol or diketone compound using ketone compound |
| JP2009185025A (en) * | 2008-01-07 | 2009-08-20 | Nagoya Industrial Science Research Inst | Method for dehalogenating aromatic halide |
| JP2009221351A (en) * | 2008-03-17 | 2009-10-01 | Koji Mitoma | Method of processing polyphenol-based substance or phenol-based substance |
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