KR890002552B1 - Process for the preparation of alkoxy nitrobenzene - Google Patents
Process for the preparation of alkoxy nitrobenzene Download PDFInfo
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- KR890002552B1 KR890002552B1 KR1019860008493A KR860008493A KR890002552B1 KR 890002552 B1 KR890002552 B1 KR 890002552B1 KR 1019860008493 A KR1019860008493 A KR 1019860008493A KR 860008493 A KR860008493 A KR 860008493A KR 890002552 B1 KR890002552 B1 KR 890002552B1
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- nitrochlorobenzene
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- nitrobenzene
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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Abstract
Description
본 발명은 일반식(I)로 표시되는 알콕시 니트로 벤젠을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing alkoxy nitro benzene represented by formula (I).
(식중 R은 메틸(IV) 및 에틸(V)등의 저급 알킬기를 의미한다.) 알콕시 니트로 벤젠은 의약, 염료, 산화방지제 및 산패방지제등의 유기합성을 위한 원료 및 중간체로서 많이 사용되고 있는 물질이다.(Wherein, R means lower alkyl groups such as methyl (IV) and ethyl (V).) Alkoxy nitrobenzene is a substance that is widely used as raw materials and intermediates for organic synthesis, such as medicine, dyes, antioxidants and antiseptics. .
따라서 이에 대한 제조방법이 오래전부터 제안되고 오고 있는데 그중 반응조건과 경제성등 때문에 니트로크로로벤젠과 저급 알콜류를 가성소다 또는 가성카리 존재하에서 반응시키는 방법이 널리 이용되어 왔다.Therefore, a preparation method for this has been proposed for a long time, and among them, a method of reacting nitrochlorobenzene and lower alcohols in the presence of caustic soda or caustic carry has been widely used because of reaction conditions and economical efficiency.
그 예를 들면 다음과 같다.For example:
미합중국 특허 제 1, 801, 901호의 리차드슨(Richardson)법은 파라니트로크로로벤젠과 가성소다를 95% 알콜중에서 상압, 60℃로 140시간 반응시켜서 파라에톡시니트로 벤젠을 약 90% 수율로 얻었다.The Richardson method of US Pat. Nos. 1, 801, and 901 was made to react paranitrochlorobenzene and caustic soda in 95% alcohol for 140 hours at atmospheric pressure and 60 ° C. to obtain paraethoxynitrobenzene in about 90% yield.
그러나 이 방법은 알콜을 용매로 사용하므로 반응 후 과잉의 알콜을 회수하여 재정제하여야 하며 알콜중에 알데히드가 함유되어 있으면 디크로로 아족시 벤젠이 부산물로 생성되어 착색된다.However, since this method uses alcohol as a solvent, the excess alcohol must be recovered and refined after the reaction. If the alcohol contains aldehyde, dichloro azoxy benzene is produced as a by-product and colored.
또한 반응시간이 140시간을 요하는 단점이 있다. 또한 1931년 발표된 슈바이저(Schwyzer)법은 (Unit Process in Synthesis 841) 45℃에서 알콜에 가성카리를 녹인 후 촉매로서 아황산카리를 가하고 단계별로 온도를 상승시켜서 80℃가 되면 12시간 반응 시킨후 침전된 포타시움크로라이드를 여과하고 여액에 다시 아황산 카리를 넣고 3시간 반응시키는 방법이 기술되어 있다.In addition, there is a disadvantage that the reaction time requires 140 hours. In addition, the Schwyzer method, released in 1931 (Unit Process in Synthesis 841), dissolved caustic in alcohol at 45 ° C, and then added sulfurous acid as a catalyst and increased the temperature step by step. The method of filtering the precipitated potassium chloride and adding the sulfurous acid sulfur to the filtrate and reacting for 3 hours is described.
이 방법은 리차드슨법 보다는 반응시간을 줄일 수 있으나 약 70시간의 장시간 반응과 반응중간에 한번 여과를 해야하는 단점이 있다.This method can reduce the reaction time than the Richardson method, but there are disadvantages of requiring a long time reaction of about 70 hours and one time filtration during the reaction.
그후 1967년과 1972년에 크레바노브(Klebanov)(C. A 66, 51160v) 및 울리치(Ulrich)(C. A 76, 72217)에 의해 발표된 방법은 망간옥사이드, 코발트옥사이드등을 촉매로 사용하여 파라니트로크로로벤젠과 알콜, 가성소다를 75℃에서 산소를 주입하여 반응시켜서 85-90%의 수율을 얻었다.Later, in 1967 and 1972, the method published by Klebanov (C. A 66, 51160v) and Ulrich (C. A 76, 72217) was catalyzed by manganese oxide and cobalt oxide. Paranitrochlorobenzene, alcohol and caustic soda were reacted by injecting oxygen at 75 ° C. to obtain a yield of 85-90%.
그리고 비슷한 방법으로 1975년 한국약학회지에는 촉매로 망간옥사이드를 사용하여 파라니트로크로로벤젠으로부터 파라니트로 페네틀의 제조를 반응속도론 적으로 각 첨가제에 따른 영향을 검토한 바 있다.In a similar way, the Korean Journal of Pharmacy in 1975 examined the effects of each additive on the reaction kinetics of the production of paranitrophenetine from paranitrochlorobenzene using manganese oxide as a catalyst.
그러나 이들 방법은 과량의 촉매를 사용하여야 하며(니트로크로로벤젠에 대해 50중량%이상)반응시간도 15시간 이상을 요한다.However, these methods require the use of excess catalyst (more than 50% by weight relative to nitrochlorobenzene) and require a reaction time of more than 15 hours.
위에서 설명한 바와 같이 니트로크로로벤젠으로부터 알콕시니트로 벤젠을 제조하는 데는 과량의 촉매를 사용하고 장시간의 반응을 시켜야 하는 큰 단점을 갖고 있다.As described above, the production of alkoxynitrobenzene from nitrochlorobenzene has a big disadvantage of using an excessive amount of catalyst and allowing a long time reaction.
이와 같은 단점을 보완하기 위하여 1963년 몬산토에서는(미합중국 특허 제 3, 085, 113호)공기 압력하에서 파라니트로크로로벤젠에 가성소다를 녹인 알콜용액을 적가하여 7시간 반응시켜서 90% 정도의 전환율을 얻고 미반응된 니트로크로로벤젠을 감압증류하여 회수하는 방법을 기술하였다.To compensate for this drawback, Monsanto in 1963 (US Patent No. 3, 085, 113) added an alcohol solution in which caustic solubility was dissolved in paranitrochlorobenzene under air pressure for 7 hours to achieve 90% conversion. The method for obtaining and recovering the unreacted nitrochlorobenzene by distillation under reduced pressure was described.
그러나 이 방법도 미반응 니트로크로로벤젠이 고비점 물질이며 알콕시니트로 벤젠과는 증류온도차가 아주 근소하기 때문에 완전한 분별증류가 안되며, 압력하에서 가성소다를 적가하는등 반응조작에도 어려운 점이 있다.However, this method also does not have complete fractional distillation because unreacted nitrochlorobenzene is a high boiling point material and the difference in distillation temperature with alkoxynitrobenzene is very small, and it is difficult to operate the reaction such as dropping caustic soda under pressure.
일본 규격 협회에서 1984년 7월에 발행된 일본 공업규격에서도 파라니트로 페네톨(파라에톡시니트로벤젠)의 제조방법으로는 미합중국 특허 제 3, 085, 113호의 방법에 기준을 두고 있다.Japanese Industrial Standards published in July 1984 by the Japan Standards Association also use paranitro phentol (paraethoxynitrobenzene) as a method of manufacturing U.S. Patent Nos. 3, 085, 113.
따라서 본 발명의 목적은 종래의 방법에서 나타나는 문제점을 해결함과 동시에 경제적인 알콕시니트로 벤젠의 새로운 제조방법을 제공하는데 있다.Accordingly, an object of the present invention is to solve the problems in the conventional process and at the same time provide an economical method for producing alkoxynitrobenzene.
본 발명은 니트로크로로벤젠(II)과 일반식(III)의 알콜을 가성소다 또는 가성카리와 상간 이동 촉매를 사용하여 일반식(I)로 표시되는 알콕시니트로 벤젠을 제조하는 방법에 관한 것이다.The present invention relates to a process for producing an alkoxynitrobenzene represented by the general formula (I) by using a caustic soda or caustic soda with an alcohol of the general formula (III) and nitrochlorobenzene (II).
여기서 R은 앞에서 정의한 바와 동일한 의미를 지니며(II)의 화합물은 파라-니트로크로로벤젠과 오르토-니트로크로로벤젠을 나타낸다.Wherein R has the same meaning as defined above and the compound of (II) represents para-nitrochlorobenzene and ortho-nitrochlorobenzene.
본 발명에 따른 방법에 있어서 사용되는 촉매는 암모니움 및 포스포니움계 상간 이동 촉매로서 반응에 악영향을 주지 않는 어떤 종류의 상가 이동 촉매도 사용할 수 있으나 그 대표적인 것으로는 테트라브틸 암모니움 크로라이드, 테트라브틸 암무니움 브로마이드, 테트라메틸 암모니움 브로마이드, 테트라메틸 암모니움 크로라이드, 테트라프로필 암모니움 크로라이다, 등과 같은 테트라 알킬 암모니움 할라이드계와 벤질 트리메틸 암모니움 크로라이드, 벤질 트리에틸 암모니움 크로라이드, 벤질 디메틸 에틸 암모니움 크로라이드등과 같은 벤질 알킬 암모니움 할라이드계, 테트라 페닐포스포니움 크로라이드, 테트라부틸 포스포니움 크로라이드, 테트라에틸 포스포니움 브로마이드, 메틸 트리에틸 포스포니움 크로라이드 등과 같은 알킬 또는 페닐알킬 포스포니움 할라이드계 등을 예로 들 수 있다.The catalyst used in the process according to the present invention may be any kind of a phase transfer catalyst which does not adversely affect the reaction as an ammonium and phosphonium-based phase transfer catalyst, but representative examples thereof include tetrabutyl ammonium chromide and tetrabutyl. Tetra alkyl ammonium halides such as ammonium bromide, tetramethyl ammonium bromide, tetramethyl ammonium chromide, tetrapropyl ammonium chromidae, benzyl trimethyl ammonium chromide, benzyl triethyl ammonium chromide, Benzyl alkyl ammonium halides such as benzyl dimethyl ethyl ammonium chromide and the like, tetra phenylphosphonium chromide, tetrabutyl phosphonium chromide, tetraethyl phosphonium bromide, methyl triethyl phosphonium chromide and the like Alkyl or phenyl And the like can be given help kill phosphonium halide-based example.
이들 촉매들은 대체로 저렴한 가격으로 쉽게 제조할 수 있으며 또한 수용성이므로 최종 생성물로부터 제거가 용이한 장점이 있다.These catalysts are generally easy to manufacture at low cost and are water soluble, so they are easy to remove from the final product.
촉매의 사용량은 니트로크로로벤젠(II)에 대하여 0.01-1당량배의 범위가 적당하나 경제성을 볼 때 0.05-0.15당량배가 더욱 좋다.The amount of the catalyst used is in the range of 0.01-1 equivalent times to nitrochlorobenzene (II), but 0.05-0.15 equivalent times is more preferable in view of economics.
촉매의 사용량이 많을수록 반응은 온화하고 빠르게 진행되며 1당량배 사용시는 상압, 상온하에서도 2-5시간에 완전한 반응을 이룰 수 있다.As the amount of catalyst used increases, the reaction proceeds mildly and quickly. When using 1 equivalent, the reaction can be completed in 2-5 hours under normal pressure and room temperature.
최종 생성물인 화합물( I )의 제조시 사용되는 알코올(III)의 사용량은 반응조건에 따라 다양하게 할 수 있으나 일반적으로 니트로크로로벤젠(II)에 대해 1-10당량배가 적당하다.The amount of the alcohol (III) used in the preparation of the final product (I) may vary depending on the reaction conditions, but in general, 1 to 10 equivalent times of nitrochlorobenzene (II) is appropriate.
화합물( I )의 제조시 사용되는 용매로는 반응에 악영항을 미치지 않는 것이면 되며 합성에 사용되는 알콜자체를 용매로 사용하는 것이 편리한다.The solvent used in the preparation of the compound (I) may be any one which does not adversely affect the reaction, and it is convenient to use the alcohol itself used as the solvent as the solvent.
또한 용매를 사용하지 않고 사용 알콜도 소량의 과잉량만을 첨가하는 것도 좋은 방법이다.It is also a good idea to add a small excess of alcohol without using a solvent.
반응 진행에 따라 생성되는 염화수소를 제거하기 위하여 첨가되는 가성소다 또는 가성카리는 니트로크로로벤젠(II)에 대하여 0.85-2 당량배의 범위가 적당하나 1.05-1.3당량배가 더욱 좋다.Caustic soda or caustic added to remove hydrogen chloride produced as the reaction proceeds is suitably in the range of 0.85-2 equivalents to nitrochlorobenzene (II), but more preferably 1.05-1.3 equivalents.
한편 본 발명의 방법은 10-150℃의 범위가 적당하나 25-90℃가 더욱 좋다.On the other hand, the method of the present invention is a suitable range of 10-150 ℃ but 25-90 ℃ is more preferred.
압력은 상압 -10kg/㎠이 적당하며 압력 반응시 사용하는 기체는 공기나 산소등이 적당하다.The normal pressure is -10kg / ㎠ and the gas used for pressure reaction is air or oxygen.
지금까지 살펴본 바와같이 본 방법에 있어서 일반식( I )의 화합물은 한 반응기내에서 단시간내에 온화한 반응조건하에서 고순도 고수율로 얻을 수 있게 되었으며 종래와 같이 장시간에 걸쳐 반응시키는 방법이나 미 반응된 출발물질인 니트로크로로벤젠을 감압하에 고온으로 증류하여 재사용하는 방법보다 반응 시간이 월등히 짧고 공정이 간단하며 경제적인 이점이 있다.As described above, in the present method, the compound of formula (I) can be obtained in high purity and high yield under mild reaction conditions in a reactor within a short time, and is reacted for a long time as in the prior art or unreacted starting materials. The reaction time is much shorter, the process is simpler, and economical than the method of distilling phosphorus nitrochlorobenzene at a high temperature under reduced pressure and reusing it.
[실시예 1]Example 1
온도계, 교반기, 액체 및 기체 주입구가 부착된 300ml 압력반응기에 95% 에탄올 75ml(1.24몰)과 벤질트리메틸 암모니움 크로라이드 5.9g(0.031몰)을 넣고 교반한다.In a 300 ml pressure reactor equipped with a thermometer, agitator, liquid and gas inlet, 75 ml (1.24 mol) of 95% ethanol and 5.9 g (0.031 mol) of benzyltrimethyl ammonium chromide are stirred.
여기에 파라니트로크로로벤젠 50g(0.31몰), 95%가성소다 15.7g(0.37몰)을 주입한다.Into this, 50 g (0.31 mole) of paranitrochlorobenzene and 15.7 g (0.37 mole) of 95% caustic soda are injected.
반응기를 완전히 밀폐시킨 공기를 주입하여 3kg/㎠까지 압력을 올린다.Inject air that completely seals the reactor up to 3 kg / cm 2.
강하게 교반하면서 85℃로 가온한다. 4시간동안 유지한 후 반응을 종결시킨다.Warm to 85 ° C. with vigorous stirring. Hold for 4 hours and then terminate the reaction.
압력을 상압으로 낮추고 물을 주입, 냉각하면 과립형태로 응고된 파라에톡시 니트로벤젠(V) 50.7g을 얻는다.When the pressure was lowered to atmospheric pressure, water was injected and cooled to obtain 50.7 g of paraethoxy nitrobenzene (V) solidified in the form of granules.
이것은 파라니트로크로로벤젠에 대하여 98%의 수율이며 액체크로마토그램 분석결과 순도는 97.1%이고 미반응 파라니트로크로로벤젠의 함량은 0.5%였다.This was 98% yield for paranitrochlorobenzene, the purity of the liquid chromatogram analysis was 97.1%, the content of unreacted paranitrochlorobenzene was 0.5%.
이 생성물(V)의 융점은 56-58℃이고 비점은 15Torr에서 168℃이다.The melting point of this product (V) is 56-58 ° C. and the boiling point is 168 ° C. at 15 Torr.
프로톤 NMR은 다음과 같다.Proton NMR is as follows.
1H NMR(CDCL3)δ1.3-1.5(m, 3H), 3.9-4.2(m, 2H), 6.7-6.9(d, 2H), 8.0-8.2(d, 2H)1 H NMR (CDCL 3 ) δ1.3-1.5 (m, 3H), 3.9-4.2 (m, 2H), 6.7-6.9 (d, 2H), 8.0-8.2 (d, 2H)
[실시예 2]Example 2
실시예 1에서 95% 에탄올 75ml 20.7ml(0.34몰)로 줄여서 첨가하여 실시예 1의 실험을 하였다.In Example 1 was reduced to 95% ethanol 750.7 20.7ml (0.34 mol) was added to the experiment of Example 1.
(V)의 수율은 97%였다. 액체크로마토그램 분석결과 순도는 96.5%이고 미반응 파라니트로크로로벤젠의 함량은 0.7%였다.The yield of (V) was 97%. Purity was 96.5% and the content of unreacted paranitrochlorobenzene was 0.7%.
[실시예 3]Example 3
실시예 1에서 벤젠트리메틸 암모니움 크로라이드 대신 테트라브틸 포스포니움 브로마이드 5.2g(0.0155몰)을 첨가하여 실시예 1의 실험을 하였다.The experiment of Example 1 was carried out by adding 5.2 g (0.0155 mol) of tetrabutyl phosphonium bromide instead of benzenetrimethyl ammonium chromide in Example 1.
(V)의 수율은 99%였고 순도는 98%, 미반응 파라니트로크로로벤젠의 함량은 0.2%였다.The yield of (V) was 99%, the purity was 98%, and the content of unreacted paranitrochlorobenzene was 0.2%.
[실시예 4]Example 4
실시예 3에서 에탄올 대신 메탄올 17ml(0.372몰)을 첨가하여 실시예 3의 실험을 하였다.In Example 3, 17 ml (0.372 mol) of methanol was added instead of ethanol to perform the experiment of Example 3.
파라메톡시 니트로벤젠(IV)의 수율은 98였고 순도는 97%, 미반응 파라니트로크로로벤젠의 함량은 0.5%였다.The yield of paramethoxy nitrobenzene (IV) was 98, the purity was 97%, and the content of unreacted paranitrochlorobenzene was 0.5%.
[실시예 5]Example 5
온도계, 교반기, 환류냉각기가 부착된 300ml 4구 플라스크에 95% 에탄올 75ml(1.24몰)과 벤질트리메틸 암모니움 크로라이드 59g(0.31몰)을 넣고 교반한다.In a 300 ml four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 75 ml (1.24 mol) of 95% ethanol and 59 g (0.31 mol) of benzyltrimethyl ammonium chromide were stirred.
여기에 파라니트로크로로벤젠 50g(0.31몰), 95%가성소다 26.1g(0.62몰)을 주입한다.50 g (0.31 mol) of paranitrochlorobenzene and 26.1 g (0.62 mol) of 95% caustic soda were injected thereto.
상압 25℃를 유지하며 5시간동안 반응시킨다. 반응완료후 물을 주입하여 과립형태로 응고시키면 파라에톡시 니트로벤젠(V) 50g을 얻는다.The reaction is carried out for 5 hours while maintaining a normal pressure of 25 ℃. After completion of the reaction, water was injected to coagulate in the form of granules to obtain 50 g of paraethoxy nitrobenzene (V).
이것은 파라니트로크로로벤젠에 대하여 96.6%의 수율이며 액체크로마토그램 분석결과 순도는 99.8%이고 미반응 파라니트로크로로벤젠은 없었다.This was 96.6% yield for paranitrochlorobenzene, the purity of liquid chromatogram analysis was 99.8% and there was no unreacted paranitrochlorobenzene.
[실시예 6]Example 6
실시예 5에서 가성소다 26.1g 대신 13.7g(0.326몰)을 첨가하여 실시예 5의 실험을 하였다.In Example 5, 13.7 g (0.326 mol) was added instead of 26.1 g of caustic soda, and the experiment of Example 5 was performed.
반응은 14시간이 경과후에 종결되었으며 (V)의 수율은 97%였고 순도는 99.5%였다.The reaction was terminated after 14 hours, with (V) yield of 97% and purity 99.5%.
[실시예 7]Example 7
실시예 5에서 벤질트리메틸 암모니움 크로라이드 대신 테트라브틸 암모니움 크로라이드 86.2g(0.31몰)을 첨가하여 실시예1의 실험을 하였다.In Example 5, 86.2 g (0.31 mole) of tetravyl ammonium fluoride was added instead of benzyltrimethyl ammonium fluoride to carry out the experiment of Example 1.
반응 시간이 5시간 경과후 (V)의 수율은 97%이고 순도는 99.8%였다.After 5 hours of reaction time, the yield of (V) was 97% and the purity was 99.8%.
[실시예 8]Example 8
실시예 5에서 벤질트리메틸 암모니움 크로라이드 대신 벤질트리에틸 암모니움 크로라이드 71g(0.31몰)을 첨가하여 실시예 5의 실험을 하였다.In Example 5, 71 g (0.31 mole) of benzyl triethyl ammonium fluoride was added instead of benzyl trimethyl ammonium chromide to carry out the experiment of Example 5.
반응시간이 4.5시간 경과후(V)의 수율은 98%이고 순도는 99.7%였다.After 4.5 hours of reaction time, the yield was 98% and the purity was 99.7%.
[실시예 9]Example 9
실시예 1에서 파라니트로크로로벤젠 대신 올소니트로크로로벤젠을 사용하여 실시예 1의 실험을 하였다.In Example 1, the experiment of Example 1 was carried out using allonitrochlorobenzene instead of paranitrochlorobenzene.
오르토 메톡시 니트로벤젠(V)을 97%의 수율로 얻었고 액체크로마토그램 분석결과 순도는 98%였다.Ortho methoxy nitrobenzene (V) was obtained in 97% yield and the purity of liquid chromatogram analysis was 98%.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019860008493A KR890002552B1 (en) | 1986-10-10 | 1986-10-10 | Process for the preparation of alkoxy nitrobenzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019860008493A KR890002552B1 (en) | 1986-10-10 | 1986-10-10 | Process for the preparation of alkoxy nitrobenzene |
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| Publication Number | Publication Date |
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| KR880005066A KR880005066A (en) | 1988-06-27 |
| KR890002552B1 true KR890002552B1 (en) | 1989-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019860008493A KR890002552B1 (en) | 1986-10-10 | 1986-10-10 | Process for the preparation of alkoxy nitrobenzene |
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| KR (1) | KR890002552B1 (en) |
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| KR880005066A (en) | 1988-06-27 |
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