JPH0124138B2 - - Google Patents
Info
- Publication number
- JPH0124138B2 JPH0124138B2 JP16635781A JP16635781A JPH0124138B2 JP H0124138 B2 JPH0124138 B2 JP H0124138B2 JP 16635781 A JP16635781 A JP 16635781A JP 16635781 A JP16635781 A JP 16635781A JP H0124138 B2 JPH0124138 B2 JP H0124138B2
- Authority
- JP
- Japan
- Prior art keywords
- acenaphthenes
- acenaphthylenes
- metal
- peroxide
- reaction
- 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
- 238000000034 method Methods 0.000 claims description 25
- 150000001240 acenaphthylenes Chemical class 0.000 claims description 14
- 150000001239 acenaphthenes Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000004972 metal peroxides Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012442 inert solvent Substances 0.000 claims description 4
- DRZNOPRRQNUPSF-UHFFFAOYSA-N 1-bromo-1,2-dihydroacenaphthylene Chemical compound C1=CC(C(Br)C2)=C3C2=CC=CC3=C1 DRZNOPRRQNUPSF-UHFFFAOYSA-N 0.000 claims description 3
- ANIXIIYQBGBGRI-UHFFFAOYSA-N 1-chloro-1,2-dihydroacenaphthylene Chemical compound C1=CC(C(Cl)C2)=C3C2=CC=CC3=C1 ANIXIIYQBGBGRI-UHFFFAOYSA-N 0.000 claims description 3
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims description 3
- -1 nickel peroxide Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JJENRBJFTBKLOV-UHFFFAOYSA-N 1,2,2-tribromo-1H-acenaphthylene Chemical compound BrC1C(C=2C=CC=C3C=CC=C1C=23)(Br)Br JJENRBJFTBKLOV-UHFFFAOYSA-N 0.000 description 1
- UUOJQDOCFHDSBH-UHFFFAOYSA-N 1,2,2-trichloro-1h-acenaphthylene Chemical compound C1=CC(C(C2Cl)(Cl)Cl)=C3C2=CC=CC3=C1 UUOJQDOCFHDSBH-UHFFFAOYSA-N 0.000 description 1
- SGVYNSUGXGDLGL-UHFFFAOYSA-N 1,2-dichloroacenaphthylene Chemical group C1=CC(C(Cl)=C2Cl)=C3C2=CC=CC3=C1 SGVYNSUGXGDLGL-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
- GJVBRRZHNXEIID-UHFFFAOYSA-N 2,2-dibromo-1H-acenaphthylene Chemical compound BrC1(CC2=CC=CC3=CC=CC1=C23)Br GJVBRRZHNXEIID-UHFFFAOYSA-N 0.000 description 1
- NZHXMSNRVKBDMH-UHFFFAOYSA-N 2,2-dichloro-1h-acenaphthylene Chemical compound C1=CC(C(Cl)(Cl)C2)=C3C2=CC=CC3=C1 NZHXMSNRVKBDMH-UHFFFAOYSA-N 0.000 description 1
- QQTNONSQLWTQPU-UHFFFAOYSA-N 5,6-dichloro-1,2-dihydroacenaphthylene Chemical compound C1CC2=CC=C(Cl)C3=C2C1=CC=C3Cl QQTNONSQLWTQPU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000005486 naphthalic acid group Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は金属過酸化物によるアセナフチレン類
の新規製造方法に関するものである。
更に詳しくは、アセナフテン及びクロルアセナ
フテン、ブロムアセナフテンなどのアセナフテン
類を、不活性溶媒の存在下、金属過酸化物を作用
させて酸化し、相当するアセナフチレン類を極め
て高い収率で得る製造方法を提供せんとするもの
である。
アセナフチレン類を製造する方法としては、次
の方法が一般的に知られている。即ち
(1) アセナフテン類の自動酸化による方法
(2) アセナフテン類の重金属酸化剤による脱水素
方法
(3) アセナフテン類の１位の光塩素化及び脱塩化
水素による方法
(4) アセナフテン類を赤熱した酸化鉛（）上で
脱水素する方法等がある。(1)、(2)の方法はいづ
れも原料アセナフテン類の転化率を高めると、
過剰に酸化を受けた化合物との共存状態として
得られ、選択的にアセナフチレン類を製造する
方法としては極めて不満足な方法である。加え
て、精製の為の付加工程を必要とし、経済的な
損失は大きい。特に(2)の方法の如く重金属類に
よる酸化方法の場合には、精製工程及び安全衛
生上公害防止上の諸対策を必要とし、又それら
に要する用役費等も莫大なものとなり工業的製
法としては適していない。(3)の方法の場合は、
塩素化時、脱塩化水素時に各々副生物が生成さ
れ、それらの精製に多大の労力を要し、これも
又経済的でない。(4)の方法の場合については製
造設備費、ユーテイリテイー等が嵩むと予想さ
れる。
アセナフチレン及びハロゲノアセナフチレン
類については、それらの合成法の研究例は少な
く殊にハロゲノアセナフチレン類の選択的合成
法についての文献は見当らない。その様な背景
から本発明者はここに新規なアセナフチレン類
の製造方法を提供することとなつた。
アセナフチレン類の用途としては、該化合物
中の五員環に含まれる二重結合が酸化反応に対
して敏感なところから種々の酸化方法により容
易に染、顔料の中間物として極めて有用なナフ
タル酸誘導体を合成する事が可能である。又、
ハロゲノ基を含むアセナフチレン類の場合は、
ハロゲノ基が反応性に富むところから置換反応
等を利用して、高度の誘導体の合成も可能であ
る。この事は各種化合物の前駆中間体としての
価値を一層高めるものといえ極めて有用な化合
物である。
本発明者等は、金属過酸化物の特異な酸化力
に着目し鋭意研究を続けてきた結果、極めて高
品質なアセナフチレン類を高収率で得る工業的
製法を見出すに至り本発明を完成した。
以下に本発明の詳細を記述する。
重金属過酸化物は重金属の塩に次亜塩素酸塩と
水酸化アルカリを作用させることにより得られ
る。この中で好ましいものはニツケルパーオキサ
イド（NiPO）又はコバルトパーオキサイド
（CoPO）であつてこれらは例えば以下のように
して得られる。即ち、硫酸ニツケルあるいは硫酸
コバルトの水溶液に水酸化ナトリウムと次亜塩素
酸ソーダを加える事により容易に黒色のNiPO及
びCoPOが生成する。生成したNiPO及びCoPOは
別後、風乾し、反応に供する事ができる。
アセナフテン類としてはアセナフテン、モノク
ロルアセナフテン、モノブロムアセナフテン、ジ
クロルアセナフテン、ジブロムアセナフテン、ト
リクロルアセナフテン、トリブロムアセナフテン
等が包含される。これらのアセナフテン類を実質
的に、本発明方法によつて変質を受けない有機溶
媒系に溶解させ、先に得られたNiPOもしくは
CoPO、又はそれらの混合物を対アセナフテン類
重量比で100〜2000％加え、加熱下で反応を行う。
金属過酸化物使用量は200％〜800％の範囲で充分
効果的であり、実用性、経済性も良好であるが、
該範囲を超える使用であつても反応上の不利はな
い。これらの金属過酸化物は、有機溶媒に対し
て、実質的にほとんど不溶であり、酸化反応終了
後も不溶性の金属酸化物として存在するので目的
のアセナフチレン類は使用する有機溶媒に溶解し
うるものを選択しておけば、容易に金属酸化物と
の別分離が可能である。分離された金属酸化物
は、希硫酸に溶解後再度、水酸化アルカリと次亜
塩素酸ソーダを加える事により容易に黒色の金属
過酸化物の再生が可能であり、循環再使用でき
る。再生率は90％以上と極めて良好であり、再生
の容易さ、再生に要する薬剤費、用役費の低価格
等が、より本発明方法の経済性、工業的価値を一
層高める極めて有利な製造方法といえる。
本発明で使用する不活性溶媒としては、本発明
の反応によつて実質的に変質を受けない溶媒であ
つて具体的には例えばベンゼン、モノクロルベン
ゼン、ジクロベンゼン、ニトロベンゼンなどの芳
香族化合物、酢酸、プロピオン酸などの低級脂肪
酸、オクタン、ノナン又はデカンなどの脂肪族炭
化水素などが挙げられる。
又、NiPO及びCoPOは水と共沸化合物を形成
する溶媒系を選択することにより水性のプレスケ
ーキの状態のまま本発明方法に適用可能である。
即ちアセナフテン類を溶解させた有機溶媒中に
金属過酸化物の水性プレスケーキを添加し、徐々
に加熱する。共沸温度で水の留去を行い、その後
本発明方法の反応を実施することが可能である。
この点でも工業的製法としての価値を一層高める
ものである。
本発明方法の一実施態様を以下に示す。
本発明の不活性溶媒にアセナフテン類を溶解さ
せ、金属過酸化物を所定量加える。その後徐々に
加熱し、50℃〜200℃の範囲で反応させる。好ま
しくは80℃〜150℃の範囲が実用的である。
反応終了後、アセナフチレン類が溶解している
状態であれば懸濁状態にある金属酸化物は容易に
別され、極めて高純度のアセナフチレン類の溶
液が高収率で得られる。この反応液から減圧蒸留
下、溶媒類を留去すると褐色のタール状物が得ら
れる。エタノールを用い再結晶する事により板状
の淡黄色〜黄色のアセナフチレン類の結晶が得ら
れる。しかしながら金属酸化物を別分離したア
セナフチレン類を含む反応液は、そのまま次工程
の反応に供する事が充分可能な程高純度であり、
むしろこの方法による方が実用上、経済上有利と
いえる。
以上、本発明を一般的に記述したが、更に具体
的に説明する為、以下に実施例を掲る。しかしな
がら本発明は、以下の実施例のみに制約されるも
のではない。
尚、実施例中で使用したNiPOおよびCoPOの
活性酸素原子量は単位重量当り0.326×10-2重量
比であつた（ヨードメトリーによる分析）。又実
施例中の「部」は全て重量を示すものである。
実施例 １
容量200mlの四つ口フラスコに撹拌機及び温度
計、冷却器を装着し、モノクロルベンゼン100部
と５，６−ジクロルアセナフテン12部を加える。
続いてNiPO60部を加え撹拌下、徐々に加熱す
る。131℃の還流状態のまま充分な撹拌下に７時
間反応を続け、その後約30℃迄放冷し黒色不溶性
のニツケル酸化物を別する。得られた液を島
津製作所製のガスクロマトグラフイーGC−6AM
（カラム充填剤；シリコンOV−17）にて分析し
たところ以下の結果を得た。
The present invention relates to a new method for producing acenaphthylenes using metal peroxides. More specifically, a manufacturing method in which acenaphthenes such as acenaphthene, chloroacenaphthene, and bromoacenaphthene are oxidized by the action of a metal peroxide in the presence of an inert solvent to obtain the corresponding acenaphthylenes in an extremely high yield. We aim to provide the following. The following method is generally known as a method for producing acenaphthylenes. Namely, (1) a method of autooxidation of acenaphthenes, (2) a method of dehydrogenating acenaphthenes using a heavy metal oxidizing agent, (3) a method of photochlorination and dehydrochlorination of the first position of acenaphthenes, and (4) a method of red-hot acenaphthenes. There are methods such as dehydrogenation on lead oxide (). In both methods (1) and (2), if the conversion rate of the raw material acenaphthenes is increased,
It is obtained in coexistence with an excessively oxidized compound, and is an extremely unsatisfactory method for selectively producing acenaphthylenes. In addition, additional steps for purification are required, resulting in a large economic loss. In particular, in the case of the oxidation method using heavy metals, such as method (2), various measures are required for the purification process and for safety and health to prevent pollution, and the utility costs required for these are also enormous, making it difficult to use industrial production methods. It is not suitable as such. In the case of method (3),
By-products are produced during chlorination and dehydrochlorination, and their purification requires a great deal of effort, which is also uneconomical. In the case of method (4), manufacturing equipment costs, utilities, etc. are expected to increase. Regarding acenaphthylene and halogenoacenaphthylenes, there are few research examples of their synthesis methods, and in particular, no literature has been found on selective synthesis methods of halogenoacenaphthylenes. Against this background, the present inventors have now provided a novel method for producing acenaphthylenes. Acenaphthylenes are used as naphthalic acid derivatives, which are easily dyed by various oxidation methods because the double bond contained in the five-membered ring in these compounds is sensitive to oxidation reactions, and are extremely useful as intermediates for pigments. It is possible to synthesize. or,
In the case of acenaphthylenes containing halogeno groups,
Due to the high reactivity of the halogeno group, it is possible to synthesize highly advanced derivatives using substitution reactions and the like. This fact further increases its value as a precursor intermediate for various compounds, making it an extremely useful compound. The present inventors have focused on the unique oxidizing power of metal peroxides, and as a result of intensive research, they have discovered an industrial manufacturing method for obtaining extremely high-quality acenaphthylenes in high yield, and have completed the present invention. . The details of the invention are described below. Heavy metal peroxides are obtained by reacting heavy metal salts with hypochlorite and alkali hydroxide. Preferred among these are nickel peroxide (NiPO) and cobalt peroxide (CoPO), which can be obtained, for example, as follows. That is, black NiPO and CoPO are easily produced by adding sodium hydroxide and sodium hypochlorite to an aqueous solution of nickel sulfate or cobalt sulfate. The generated NiPO and CoPO can be separated, air-dried, and used for reaction. The acenaphthenes include acenaphthene, monochloroacenaphthene, monobromoacenaphthene, dichloroacenaphthene, dibromoacenaphthene, trichloroacenaphthene, tribromoacenaphthene, and the like. These acenaphthenes are substantially dissolved in an organic solvent system that does not undergo modification by the method of the present invention, and the previously obtained NiPO or
CoPO or a mixture thereof is added in a weight ratio of 100 to 2000% to acenaphthenes, and the reaction is carried out under heating.
It is sufficiently effective when the amount of metal peroxide used is in the range of 200% to 800%, and it is also practical and economical.
There is no disadvantage in terms of reaction even if the amount exceeds this range. These metal peroxides are virtually insoluble in organic solvents and remain as insoluble metal oxides even after the oxidation reaction is complete, so the target acenaphthylenes are those that can be dissolved in the organic solvent used. By selecting , it is possible to easily separate the metal oxide from the metal oxide. The separated metal oxide can be easily regenerated into a black metal peroxide by dissolving it in dilute sulfuric acid and adding alkali hydroxide and sodium hypochlorite again, and can be recycled and reused. The regeneration rate is extremely good at over 90%, and the ease of regeneration and the low cost of chemicals and utilities required for regeneration are extremely advantageous production methods that further enhance the economic efficiency and industrial value of the method of the present invention. It can be said to be a method. The inert solvent used in the present invention is a solvent that is not substantially altered by the reaction of the present invention, and specifically includes aromatic compounds such as benzene, monochlorobenzene, dichlorobenzene, and nitrobenzene, and acetic acid. , lower fatty acids such as propionic acid, and aliphatic hydrocarbons such as octane, nonane or decane. Furthermore, NiPO and CoPO can be applied to the method of the present invention in the form of an aqueous presscake by selecting a solvent system that forms an azeotrope with water. That is, an aqueous presscake of metal peroxide is added to an organic solvent in which acenaphthenes are dissolved, and the mixture is gradually heated. It is possible to carry out the distillation of water at the azeotropic temperature and then carry out the reaction of the process according to the invention.
This point also further enhances the value as an industrial manufacturing method. One embodiment of the method of the present invention is shown below. Acenaphthenes are dissolved in the inert solvent of the present invention, and a predetermined amount of metal peroxide is added. Thereafter, the mixture is gradually heated and reacted at a temperature ranging from 50°C to 200°C. Preferably, a range of 80°C to 150°C is practical. After the reaction is completed, if the acenaphthylenes are dissolved, the metal oxides in suspension are easily separated, and a highly purified solution of acenaphthylenes can be obtained in high yield. When the solvent is distilled off from this reaction solution under reduced pressure, a brown tar-like substance is obtained. By recrystallizing with ethanol, plate-shaped pale yellow to yellow crystals of acenaphthylenes are obtained. However, the reaction solution containing acenaphthylenes from which the metal oxides have been separated is sufficiently pure that it can be used as it is in the next reaction step.
Rather, this method can be said to be more advantageous from a practical and economic point of view. The present invention has been generally described above, but in order to explain it more specifically, examples are given below. However, the present invention is not limited only to the following examples. The active oxygen atomic weight of NiPO and CoPO used in the examples was 0.326 x 10 -2 weight ratio per unit weight (analysis by iodometry). In addition, all "parts" in the examples indicate weight. Example 1 A four-neck flask with a capacity of 200 ml is equipped with a stirrer, a thermometer, and a condenser, and 100 parts of monochlorobenzene and 12 parts of 5,6-dichloroacenaphthene are added thereto.
Next, add 60 parts of NiPO and gradually heat while stirring. The reaction was continued for 7 hours under reflux at 131°C with sufficient stirring, and then allowed to cool to about 30°C to separate the black insoluble nickel oxide. The obtained liquid was subjected to gas chromatography GC-6AM manufactured by Shimadzu Corporation.
(Column packing material: Silicon OV-17), the following results were obtained.
【表】
得られた液はロータリーエバポレーターにて
減圧下モノクロルベンゼンを留去すると褐色のタ
ール状物を得る。このタール状物をエタノールか
ら再結晶させると黄色の板状結晶が得られた。こ
れはGC−MS及び元素分析にてジクロルアセナ
フチレンである事を確認した。
以下に元素分析値を示す。[Table] When monochlorobenzene is distilled off from the obtained liquid under reduced pressure using a rotary evaporator, a brown tar-like substance is obtained. When this tar-like substance was recrystallized from ethanol, yellow plate-like crystals were obtained. This was confirmed to be dichloroacenaphthylene by GC-MS and elemental analysis. The elemental analysis values are shown below.
【表】
実施例１と同様な方法にて、実験条件を一部変
更した実施例を表−３に示した。
実施例 ２〜８
各種の原料を用い、表−３中の各条件下で実施
した結果を示す。[Table] Table 3 shows an example in which the same method as Example 1 was used, but the experimental conditions were partially changed. Examples 2 to 8 The results were shown using various raw materials and under each condition in Table 3.
Claims (1)
酸化物を作用させ酸化することを特徴とするアセ
ナフチレン類の製造方法。 ２ アセナフテン類として、アセナフテン、クロ
ルアセナフテン、ブロムアセナフテンを使用する
特許請求の範囲第１項記載の方法。 ３ 金属過酸化物として、ニツケルパーオキサイ
ド、コバルトパーオキサイドを、対原料重量比
100％〜2000％使用する特許請求の範囲第１、２
項記載の方法。 ４ 反応を50℃〜200℃の温度で実施する特許請
求の範囲第１、２、３項記載の方法。[Claims] 1. A method for producing acenaphthylenes, which comprises oxidizing acenaphthenes with a metal peroxide in the presence of an inert solvent. 2. The method according to claim 1, wherein acenaphthene, chloroacenaphthene, and bromoacenaphthene are used as the acenaphthenes. 3. As metal peroxides, nickel peroxide and cobalt peroxide were used at the weight ratio to the raw material.
Claims 1 and 2 using 100% to 2000%
The method described in section. 4. The method according to claims 1, 2 and 3, wherein the reaction is carried out at a temperature of 50°C to 200°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16635781A JPS5869823A (en) | 1981-10-20 | 1981-10-20 | Preparation of acenaphthylenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16635781A JPS5869823A (en) | 1981-10-20 | 1981-10-20 | Preparation of acenaphthylenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5869823A JPS5869823A (en) | 1983-04-26 |
| JPH0124138B2 true JPH0124138B2 (en) | 1989-05-10 |
Family
ID=15829881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16635781A Granted JPS5869823A (en) | 1981-10-20 | 1981-10-20 | Preparation of acenaphthylenes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5869823A (en) |
-
1981
- 1981-10-20 JP JP16635781A patent/JPS5869823A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5869823A (en) | 1983-04-26 |
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