JPS622001B2 - - Google Patents
Info
- Publication number
- JPS622001B2 JPS622001B2 JP59139410A JP13941084A JPS622001B2 JP S622001 B2 JPS622001 B2 JP S622001B2 JP 59139410 A JP59139410 A JP 59139410A JP 13941084 A JP13941084 A JP 13941084A JP S622001 B2 JPS622001 B2 JP S622001B2
- Authority
- JP
- Japan
- Prior art keywords
- dioxane
- reaction
- stirring
- highly reactive
- zinc powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- -1 zinc halide Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000005695 dehalogenation reaction Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000008282 halocarbons Chemical group 0.000 description 3
- ZTMQUWBTMOQSDL-UHFFFAOYSA-N 2,3,3-trichloroprop-2-enylbenzene Chemical compound ClC(Cl)=C(Cl)CC1=CC=CC=C1 ZTMQUWBTMOQSDL-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NGKSKVYWPINGLI-UHFFFAOYSA-N prop-2-ynylbenzene Chemical group C#CCC1=CC=CC=C1 NGKSKVYWPINGLI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は高反応性亜鉛粉末の製造方法、さらに
詳しくいえば、側鎖としてハロゲン化炭化水素基
を有する芳香族化合物を還元脱ハロゲン化して不
飽和炭化水素基をもつ芳香族化合物を製造する際
に使用するための高反応性亜鉛粉末を製造する方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing highly reactive zinc powder, and more specifically, a method for producing highly reactive zinc powder, and more specifically, a method for producing highly reactive zinc powder, and more specifically, a process for producing highly reactive zinc powder by reductive dehalogenation of an aromatic compound having a halogenated hydrocarbon group as a side chain. The present invention relates to a method for producing highly reactive zinc powder for use in producing aromatic compounds.
金属粉末を脱ハロゲン化剤として用い、側鎖と
してハロゲン化炭化水素基をもつ芳香族を還元脱
ハロゲン化して、不飽和炭化水素基をもつ芳香族
化合物を製造することは公知であり、この際に脱
ハロゲン化剤として用いる金属粉末については、
多種多様のものが提案されている。 It is known that an aromatic compound having an unsaturated hydrocarbon group is produced by reductively dehalogenating an aromatic compound having a halogenated hydrocarbon group as a side chain using a metal powder as a dehalogenating agent. Regarding metal powders used as dehalogenating agents,
A wide variety of options have been proposed.
ところで、この脱ハロゲン化反応が容易に進行
する場合には、問題はないが、この反応が容易に
進行しない場合、例えば２個以上のハロゲン原子
を同時に脱離して不飽和度の高い側鎖を形成する
場合には、反応性の高い金属粉末を用いる必要が
ある。 By the way, if this dehalogenation reaction proceeds easily, there is no problem, but if this reaction does not proceed easily, for example, two or more halogen atoms may be eliminated simultaneously to form a side chain with a high degree of unsaturation. When forming a metal powder, it is necessary to use a highly reactive metal powder.
本発明者は、このように脱ハロゲン化反応が困
難な場合においても、円滑かつ迅速に反応を進行
しうる高反応性の金属粉末、特に亜鉛粉末を製造
するための新規な製造方法を開発するために鋭意
研究を重ねた結果、ハロゲン化亜鉛を特定な条件
下で還元することにより、その目的を達成しうる
ことを見出し、本発明をなすに至つた。 The present inventors have developed a novel manufacturing method for manufacturing highly reactive metal powder, especially zinc powder, which allows the reaction to proceed smoothly and quickly even in cases where the dehalogenation reaction is difficult. As a result of intensive research for this purpose, the inventors discovered that the object can be achieved by reducing zinc halide under specific conditions, leading to the present invention.
すなわち、本発明に従えば、一般式
ZnX2
（式中のＸはハロゲン原子である）
で示されるハロゲン化亜鉛を、ジオキサン中、金
属ナトリウムを反応させることにより、所望の高
反応性亜鉛粉末を得ることができる。 That is, according to the present invention, a desired highly reactive zinc powder is produced by reacting zinc halide represented by the general formula ZnX 2 (X in the formula is a halogen atom) with metallic sodium in dioxane. Obtainable.
本発明方法を好適に実施するには、ハロゲン化
亜鉛例えばZnCl2に、所要量のジオキサン例えば
ｐ―ジオキサンを加え、加熱還流下にハロゲン化
亜鉛の１グラム当量に対し、約２グラム当量の金
属ナトリウムを、激しくかきまぜながら添加し反
応させる。反応完結後、溶媒のジオキサンを減圧
除去すれば、所望の高反応性亜鉛粉末が得られ
る。このものは精製することなく、そのまま脱ハ
ロゲン化剤として使用することができる。 To suitably carry out the method of the present invention, a required amount of dioxane, such as p-dioxane, is added to zinc halide, such as ZnCl 2 , and about 2 gram equivalents of metal are added to 1 gram equivalent of zinc halide under heating under reflux. Add the sodium and allow to react while stirring vigorously. After the reaction is completed, the solvent dioxane is removed under reduced pressure to obtain the desired highly reactive zinc powder. This product can be used as a dehalogenating agent as it is without purification.
この反応生成物を水又は含水アルコールで処理
し、副生した塩化ナトリウムを洗浄除去しようと
すると、生成した亜鉛粉末は酸化物に変換するの
で、このような精製手段をとることはできない。 If this reaction product is treated with water or an aqueous alcohol to wash and remove by-product sodium chloride, the zinc powder produced will be converted into an oxide, so such a purification method cannot be used.
本発明方法において、溶媒として用いるジオキ
サンは、ｏ―ジオキサン、ｍ―ジオキサン、ｐ―
ジオキサンのうずれでもよく、またこれらの混合
物であつてもよい。これらは、十分に脱水処理し
たのち分留することにより精製した状態で用いら
れる。このジオキサンの使用量としては、ハロゲ
ン化亜鉛に対し、５〜10倍容が適当であるが、触
媒活性の高いものを目的とする場合には、溶媒の
使用量を少なくする方がよい。 In the method of the present invention, dioxane used as a solvent includes o-dioxane, m-dioxane, p-dioxane,
It may be dioxane or a mixture thereof. These are used in a purified state by thorough dehydration treatment and fractional distillation. The appropriate amount of dioxane to be used is 5 to 10 times the volume of the zinc halide, but if a product with high catalytic activity is desired, it is better to use a smaller amount of solvent.
また、本発明方法でハロゲン化亜鉛の還元に用
いる金属ナトリウムは硫黄分の低いものが好まし
く、硫黄分が多いと触媒活性の低下の原因にな
る。金属ナトリウムの使用量としては、ハロゲン
化亜鉛１グラム当量に対し約２グラム当量とし、
未反応ナトリウムが残存しないようにするのが望
ましい。 Further, the metal sodium used for reducing zinc halide in the method of the present invention preferably has a low sulfur content; a high sulfur content causes a decrease in catalyst activity. The amount of metallic sodium used is approximately 2 gram equivalent per 1 gram equivalent of zinc halide,
It is desirable that no unreacted sodium remains.
本発明方法における還元反応は、約80〜105℃
の範囲、好ましくは反応混合物の還流温度（ｐ―
ジオキサンの場合は約101℃）において、約１〜
10時間、好ましくは３〜７時間反応させることに
より完結する。 The reduction reaction in the method of the present invention is carried out at approximately 80 to 105°C.
range, preferably the reflux temperature of the reaction mixture (p-
In the case of dioxane, at about 101℃), about 1 to
The reaction is completed for 10 hours, preferably 3 to 7 hours.
このようにして得られる高反応性亜鉛粉末は、
優れた脱ハロゲン化能力を有し、芳香族化合物の
ハロゲン化炭化水素側鎖の脱ハロゲン化におい
て、従来の亜鉛粉末の数倍の活性を示すので、不
飽和結合側鎖を有する芳香族化合物の製造用反応
剤として好適である。 The highly reactive zinc powder obtained in this way is
It has excellent dehalogenation ability and is several times more active than conventional zinc powder in dehalogenating the halogenated hydrocarbon side chains of aromatic compounds. Suitable as a manufacturing reactant.
次に実施例により本発明をさらに詳細に説明す
る。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
無水塩化亜鉛4.10ｇ（0.03モル）にｐ―ジオキ
サン25mlを加え、101℃に加熱し、かきまぜなが
らこの中へ金属ナトリウム1.38ｇ（0.06ｇ原子）
の細片をできるだけ短時間（通常30〜60分）に投
入する。投入後も加熱及びかきまぜを続行すると
内容物が黒変し、次第に高反応性亜鉛微粉末が生
成する。生成後さらに７時間反応を続けて完結さ
せたのち、窒素気流中で25mmHg以下に減圧し、
溶媒のｐ―ジオキサンを留去し、残留分8.05ｇを
得た。このものは高反応性亜鉛粉末1.96ｇを含
む。Example 1 Add 25 ml of p-dioxane to 4.10 g (0.03 mol) of anhydrous zinc chloride, heat to 101°C, and add 1.38 g (0.06 g atoms) of metallic sodium into the mixture while stirring.
the strips in as short a time as possible (usually 30 to 60 minutes). If heating and stirring are continued after the addition, the contents will turn black and a highly reactive fine zinc powder will gradually be produced. After the reaction was completed for another 7 hours, the pressure was reduced to 25 mmHg or less in a nitrogen stream.
The solvent p-dioxane was distilled off to obtain a residue of 8.05 g. This contains 1.96g of highly reactive zinc powder.
次いで残留分にエチルアルコール25mlを添加
し、さらに１，１，２―トリクロロ―３―フエニ
ル―１―プロペン2.21ｇ（0.01モル）を添加し還
流下に加熱かきまぜながら８時間反応させた。反
応液をガスクロマトグラフ法で分析したところ、
ベンジルアセチレン15.08％（収率28.6％）を含
むことが分つた。 Next, 25 ml of ethyl alcohol was added to the residue, followed by 2.21 g (0.01 mol) of 1,1,2-trichloro-3-phenyl-1-propene, and the mixture was reacted for 8 hours while stirring under reflux. When the reaction solution was analyzed by gas chromatography,
It was found to contain 15.08% benzylacetylene (yield 28.6%).
実施例 ２
無水塩化亜鉛4.10ｇ（0.03モル）にｐ―ジオキ
サン30mlを加え、101℃に加熱かきまぜながら、
この中へ金属ナトリウム1.38ｇ（0.06ｇ原子）の
細片を30分かけて投入する。投入後さらに同温度
で加熱かきまぜを続け７時間反応させた。反応完
了後窒素気流中でｐ―ジオキサンを25mmHg以下
の減圧度で回収し、残留分7.72ｇを得た。Example 2 30 ml of p-dioxane was added to 4.10 g (0.03 mol) of anhydrous zinc chloride, heated to 101°C while stirring,
A piece of 1.38 g (0.06 g atom) of metallic sodium is introduced into this over 30 minutes. After the addition, heating and stirring were continued at the same temperature for 7 hours of reaction. After the reaction was completed, p-dioxane was recovered under reduced pressure of 25 mmHg or less in a nitrogen stream to obtain 7.72 g of residue.
次いでこの残留分にエチルアルコール25mlを添
加し、さらに１，１，２―トリクロロ―３―フエ
ニル―１―プロペン2.21ｇ（0.01モル）を添加
し、還流下に加熱かきまぜながら８時間反応させ
た。反応液をガスクロマトグラフ法により分析し
たところ、ベンジルアセチレン含有率11.15％
（収率21.2％）であることが分つた。 Next, 25 ml of ethyl alcohol was added to the residue, followed by 2.21 g (0.01 mol) of 1,1,2-trichloro-3-phenyl-1-propene, and the mixture was reacted for 8 hours while stirring under reflux. Analysis of the reaction solution by gas chromatography revealed that the benzyl acetylene content was 11.15%.
(yield 21.2%).
実施例 ３
無水塩化亜鉛4.10ｇ（0.03モル）にｐ―ジオキ
サン25mlを加え、101℃に加熱かきまぜながらこ
の中へ金属ナトリウム1.38ｇ（0.06ｇ原子）の細
片を30分間で投入する。投入後さらに同温度で加
熱かきまぜを続け７時間反応させた。反応完了後
窒素気流中でｐ―ジオキサンを25mmHg以下の減
圧度で留去し、残留分8.62ｇを得た。Example 3 25 ml of p-dioxane is added to 4.10 g (0.03 mol) of anhydrous zinc chloride, and while stirring and heating to 101° C., 1.38 g (0.06 g atom) of metallic sodium is added into the mixture over 30 minutes. After the addition, heating and stirring were continued at the same temperature for 7 hours of reaction. After the reaction was completed, p-dioxane was distilled off under reduced pressure of 25 mmHg or less in a nitrogen stream to obtain a residue of 8.62 g.
この残留分にメチルアルコール25mlを添加し、
次に、α，β，β―トリクロロスチレン2.07ｇ
（0.01モル）を添加し、還流下に加熱かきまぜな
がら８時間反応させた。反応液をガスクロマトグ
ラフ法により分析したところ、フエニルアセチレ
ン17.54％（収率35.5％）を含むことが分つた。 Add 25ml of methyl alcohol to this residue,
Next, 2.07g of α,β,β-trichlorostyrene
(0.01 mol) was added, and the mixture was reacted for 8 hours under reflux with heating and stirring. When the reaction solution was analyzed by gas chromatography, it was found to contain 17.54% (yield: 35.5%) of phenylacetylene.
実施例 ４
無水塩化亜鉛4.10ｇ（0.03モル）にｐ―ジオキ
サン25mlを加え、101℃に加熱かきまぜながら、
この中に金属ナトリウム1.38ｇ（0.06ｇ原子）の
細片を30分間で投入する。投入後同温度でさらに
加熱かきまぜを続け７時間反応させた。反応完了
後窒素気流中、25mmHg以下の減圧度でｐ―ジオ
キサンを留去し、残留分7.16ｇを得た。Example 4 25 ml of p-dioxane was added to 4.10 g (0.03 mol) of anhydrous zinc chloride, heated to 101°C while stirring,
A strip of 1.38 g (0.06 g atom) of metallic sodium is introduced into this over a period of 30 minutes. After the addition, heating and stirring were continued at the same temperature for 7 hours of reaction. After the reaction was completed, p-dioxane was distilled off at a reduced pressure of 25 mmHg or less in a nitrogen stream to obtain a residue of 7.16 g.
この残留分にメチルアルコール25mlを添加し、
次いでα，β，β―トリクロロスチレン2.07ｇ
（0.01モル）を添加し、還流下に加熱かきまぜな
がら４時間反応させた。反応液をガスクロマトグ
ラフ法により分析したところ、フエニルアセチレ
ン7.90％（収率16.0％）を含むことが分つた。 Add 25ml of methyl alcohol to this residue,
Next, 2.07g of α,β,β-trichlorostyrene
(0.01 mol) was added, and the mixture was reacted for 4 hours under reflux with heating and stirring. When the reaction solution was analyzed by gas chromatography, it was found to contain 7.90% phenylacetylene (yield 16.0%).
Claims (1)
属ナトリウムと反応させることを特徴とする高反
応性亜鉛粉末の製造方法。[Claims] 1. Production of highly reactive zinc powder characterized by reacting zinc halide represented by the general formula ZnX 2 (X in the formula is a halogen atom) with metallic sodium in dioxane. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59139410A JPS6119707A (en) | 1984-07-05 | 1984-07-05 | Preparation of highly reactive metal powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59139410A JPS6119707A (en) | 1984-07-05 | 1984-07-05 | Preparation of highly reactive metal powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6119707A JPS6119707A (en) | 1986-01-28 |
| JPS622001B2 true JPS622001B2 (en) | 1987-01-17 |
Family
ID=15244592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59139410A Granted JPS6119707A (en) | 1984-07-05 | 1984-07-05 | Preparation of highly reactive metal powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6119707A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5507973A (en) * | 1991-04-26 | 1996-04-16 | Board Of Regents Of The University Of Nebraska | Highly reactive zerovalent metals from metal cyanides |
| WO1993015086A1 (en) * | 1992-02-04 | 1993-08-05 | Board Of Regents Of The University Of Nebraska | Highly reactive forms of zinc and reagents thereof |
| US5358546A (en) * | 1992-02-04 | 1994-10-25 | Board Of Regents Of The University Of Nebraska | Highly reactive forms of zinc and reagents thereof |
| KR100607027B1 (en) * | 2002-10-14 | 2006-07-31 | 주식회사 엘지생명과학 | New activation method of zinc metal |
-
1984
- 1984-07-05 JP JP59139410A patent/JPS6119707A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6119707A (en) | 1986-01-28 |
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