KR100280925B1 - Method of preparing 2-nitrothioxanthone - Google Patents
Method of preparing 2-nitrothioxanthone Download PDFInfo
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- KR100280925B1 KR100280925B1 KR1019980049397A KR19980049397A KR100280925B1 KR 100280925 B1 KR100280925 B1 KR 100280925B1 KR 1019980049397 A KR1019980049397 A KR 1019980049397A KR 19980049397 A KR19980049397 A KR 19980049397A KR 100280925 B1 KR100280925 B1 KR 100280925B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
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Abstract
본 발명에 따르면, 2-카르복시-4'-니트로디페닐 설파이드를 폴리포스폰산-아세트산 혼합반응매질 중에서 고리화 반응시켜, 2-니트로티오잔톤을 고수율로 수득하는 방법에 제공된다.According to the present invention, a 2-carboxy-4'-nitrodiphenyl sulfide is cyclized in a polyphosphonic acid-acetic acid mixed reaction medium to provide 2-nitrothioxanthone in a high yield.
Description
본 발명은 다음식 (II)로 표시되는 2-니트로티오잔톤(2-nitrothioxanthone)[CAS No. : 72534-70-4 / 화학시 : C13H7NO3S]의 제조방법에 관한 것이다.The invention provides 2-nitrothioxanthone represented by the following formula (II) [CAS No. : 72534-70-4 / Chemistry: C 13 H 7 NO 3 S].
더욱 상세하게는, 본 발명은 폴리포스폰산-아세트산의 혼합 반응매질 중에서 2-카르복시-4′-니트로디페닐 설파이드를 고리화하여, 삼고리성(tricyclic) 화합물인 2-니트로티오잔톤을 고수율로 수득하는 방법에 관한 것이다.More specifically, the present invention cyclizes 2-carboxy-4′-nitrodiphenyl sulfide in a mixed reaction medium of polyphosphonic acid-acetic acid to yield a tricyclic compound 2-nitrothioxanthone in high yield. It relates to a method of obtaining.
본 발명에 따라 제조되는 2-니트로티오잔톤은 광화학 분야에서 광개시제(photoinitiator) 또는 광스위치의 소재(photoswitching agent)로 사용되며, 의약분야에서 항결핵제(antitubecular agent)의 합성 중간체(신톤, synthone)으로, 또한 농화학 분야에서의 합성 중간체로 유용하게 사용된다.2-nitrothioxanthone prepared according to the present invention is used as a photoinitiator or a photowitching agent in a photochemical field, and as a synthetic intermediate (synthone) of an antitubecular agent in the pharmaceutical field, It is also useful as a synthetic intermediate in the field of agrochemicals.
2-카르복시-4′-니트로디페닐 설파이드 화합물을 고리화하여 삼고리성(tricyclic) 헤테로 화합물을 합성하는 방법은 유기합성 분야, 특히, 광화학 및 의약화학 분야에서 매우 중요한 방법이다.The method of cyclizing a 2-carboxy-4′-nitrodiphenyl sulfide compound to synthesize tricyclic hetero compounds is a very important method in the field of organic synthesis, especially in the field of photochemistry and medicinal chemistry.
그러나, 니트로기가 도입된 2-카르복시-4′-니트로디페닐 설파이드 화합물을 고리화하는 방법은 알려져 있지 않고, 유사한 설파이드 화합물을 고리화하는데, 황산, 할로겐산, 무수산 등의 무기산을 이용하는 방법이 알려져 있다.However, a method of cyclizing a 2-carboxy-4′-nitrodiphenyl sulfide compound having a nitro group introduced is not known, and a method of cyclizing similar sulfide compounds using inorganic acids such as sulfuric acid, halogen acid, and anhydrous acid may be used. Known.
상기와 같은 종래의 방법을 도입하여 니트로 기를 갖는 화합물을 고리화하고자 할 경우에는, 치환기에 대한 선택성이 나타났고, 반응 결과 많은 양의 불순물이 포함된 생성물이 얻어지므로 수율이 낮아, 대응하는 화합물을 순수하게 고수율로 수득하는 것이 불가능하였다.In the case of introducing a conventional method as described above to cyclize a compound having a nitro group, selectivity to substituents was shown, and the reaction yielded a product containing a large amount of impurities, so that the yield was low. It was not possible to obtain pure high yields.
이에, 본 발명자는 위와 같은 문제점을 해결하여 2-니트로티오잔톤을 고수율로 수득할 방법을 개발하고자 연구노력을 거듭하여, 화합물에 대한 선택적 용해도를 갖는 특정의 혼합 반응매질을 사용할 경우, 만족할 만한 결과가 수득됨을 발견하고 본 발명을 완성하였다.Accordingly, the present inventors have made efforts to develop a method for obtaining 2-nitrothioxanthone in high yield by solving the above problems, and when using a specific mixed reaction medium having a selective solubility to the compound, satisfactory The results were found to complete and the present invention was completed.
즉, 본 발명은, 하기 식(I)의 화합물을 폴리포스폰산-아세트산의 혼합 반응 매질 중에서 고리화하여 하기 식(II)의 2-니트로티오잔톤을 제조하는 방법에 관한 것이다.That is, the present invention relates to a method of cyclizing a compound of formula (I) in a mixed reaction medium of polyphosphonic acid-acetic acid to prepare 2-nitrothioxanthone of formula (II).
본 발명의 방법에서 사용되는 아세트산은 단순한 반응 용매로서 뿐만 아니라 화합물의 선택적 용해도를 갖는 매체로서 사용되고 있다.Acetic acid used in the process of the invention is used not only as a simple reaction solvent but also as a medium having selective solubility of the compound.
본 발명의 고리화 반응에 사용되는 혼합 반응매질 중 폴리포스폰산과 아세트산의 비율은 3:1 내지 4:1 사이에서 선택되는 것이 바람직하다. 폴리포스폰산 대 아세트산의 비율이 상기 범위보다 적으면, 수득률이 좋지 않아 바람직하지 않으며, 위 비율이 상기 범위보다 크게 되면 저온에서 좋지 않아 바람직하지 않다.The ratio of polyphosphonic acid and acetic acid in the mixed reaction medium used in the cyclization reaction of the present invention is preferably selected from 3: 1 to 4: 1. If the ratio of polyphosphonic acid to acetic acid is less than the above range, the yield is not good, and it is not preferable.
용매의 양은 특별히 제한적이지 않으나, 반응물질인 2-카르복시-4′-니트로디페닐 설파이드의 중량을 기준으로 약 15배 내지 20배의 양으로 사용되는 것으로 바람직하다.The amount of the solvent is not particularly limited, but is preferably used in an amount of about 15 to 20 times based on the weight of the reactant 2-carboxy-4′-nitrodiphenyl sulfide.
본 발명의 고리화 반응은 촉매 없이, 또는 적절한 촉매의 존재 하에 수행될 수 있다.The cyclization reaction of the present invention can be carried out without catalyst or in the presence of a suitable catalyst.
본 발명의 따른 반응은 130℃ 내지 150℃의 반응온도에서 수행될 수 있으나, 상기 혼합매질의 환류온도에서 특히 바람직하게 수행되며, 일반적인 반응압력 하에서 바람직하게 수행된다.The reaction according to the invention can be carried out at a reaction temperature of 130 ℃ to 150 ℃, but is particularly preferably carried out at the reflux temperature of the mixed medium, it is preferably carried out under a general reaction pressure.
본 발명에서 출발물질로 사용되는 2-카르복시-4′-니트로디페닐 설파이드는 상업적으로 입수가능한 제품을 사용하거나, 통상의 방법으로 제조하여 사용할 수 있다. 특히, p-클로로니트로 벤젠을 티오살리실산과 수산화 나트륨으로 처리하는 방법에 의해 합성하여 재결정함으로써, 순수한 2-카르복시-4′-니트로디페닐 설파이드를 고수율로 합성할 수 있다.2-carboxy-4′-nitrodiphenyl sulfide to be used as a starting material in the present invention can be used using commercially available products or prepared by conventional methods. In particular, pure 2-carboxy-4′-nitrodiphenyl sulfide can be synthesized in high yield by synthesizing and recrystallizing p-chloronitrobenzene by a method of treating with thiosalicylic acid and sodium hydroxide.
[실시예]EXAMPLE
본 발명을 하기 제조예 및 실시예에 의해 더욱 상세히 설명한다. 그러나, 본 발명은 이들 실시예에 국한되는 것은 아니다.The invention is illustrated in more detail by the following preparation examples and examples. However, the present invention is not limited to these examples.
[제조예][Production example]
2-카르복시-4′-니트로디페닐 설파이드의 합성Synthesis of 2-carboxy-4′-nitrodiphenyl sulfide
300ml의 DMF에 수산화나트륨(93%) 20g(0.46몰)과 티오살리실산 32g(0.205몰)을 가하여 교반하여 주면서, 거기에 p-클로로니트로벤젠 36g(0.22몰)을 서서히 가한다. 상기 반응혼합물을 가열환류하면서 3시간 동안 반응을 진행시킨다. 반응이 종결되면 냉각시키고, 찬물을 과량 가한 후, 클로로포름으로 미반응 물질을 세척하여 제거한다. 분리된 물층을 합한 후, 35% 염산을 가하여 침전물을 형성하고, 이를 여과한다. 여과된 물질을 탄산 칼륨 수용액으로 중화시키고, 충분한 물로 여액이 중성이 될 때까지 세척한 후, 메탄올로 세척하고 건조하여 황색 분말을 수득한다. 정제를 위해 과량의 에탄올로 재결정한다.20 g (0.46 mole) of sodium hydroxide (93%) and 32 g (0.205 mole) of thiosalicylic acid are added to 300 ml of DMF and stirred, while 36 g (0.22 mole) of p-chloronitrobenzene is slowly added thereto. The reaction is allowed to proceed for 3 hours while refluxing the reaction mixture. After the reaction is completed, it is cooled, an excess of cold water is added and the unreacted material is washed off with chloroform. After the separated water layers were combined, 35% hydrochloric acid was added to form a precipitate, which was filtered. The filtered material is neutralized with aqueous potassium carbonate solution, washed with sufficient water until the filtrate is neutral, washed with methanol and dried to give a yellow powder. Recrystallize with excess ethanol for purification.
[실시예]EXAMPLE
2-니트로티오잔톤의 합성Synthesis of 2-nitrothioxanthone
250ml들이 이구 둥근 플라스크에 폴리포스폰산(116%) 90g과 아세트산 30g을 넣고, 교반에 의해 혼합한 후, 상기 제조예 1에서 수득된 2-카르복시-4′-니트로디페닐 설파이드 10g을 서서히 주의하면서 가한다. 상기 반응 혼합물을 가열하여 148℃의 온도조건 하에서 1시간 동안 반응시킨 다음, 실온으로 냉각시켜 얼음물에 붓고 교반하여 결정을 석출시킨다. 침전물을 과량의 클로로포름으로 추출하여 분리한 후, 5% 탄산 칼륨 수용액을 적당량 가하여 교반한다. 클로로포름 층을 분리하여 무수 황산 마그네슘으로 건조시키고, 여과한 뒤, 여액을 감압농축시켜 담황색의 침상 결정을 수득한다.90 g of polyphosphonic acid (116%) and 30 g of acetic acid were added to a 250 ml two-necked round flask, followed by mixing by stirring, while slowly paying attention to 10 g of 2-carboxy-4′-nitrodiphenyl sulfide obtained in Preparation Example 1 above. Add. The reaction mixture was heated to react for 1 hour under a temperature condition of 148 ° C, cooled to room temperature, poured into ice water, and stirred to precipitate crystals. The precipitate was extracted with an excess of chloroform and separated, then an appropriate amount of 5% aqueous potassium carbonate solution was added and stirred. The chloroform layer was separated, dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give pale yellow needle-like crystals.
상술한 바와 같이 본 발명의 방법에 의하여 목적물질인 2-니트로티오잔톤을 별도의 복잡한 정제과정 없이, 높은 수율로 수득할 수 있다.As described above, 2-nitrothioxanthone, which is a target substance, may be obtained by a method of the present invention in a high yield without a separate complicated purification process.
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| KR1019980049397A KR100280925B1 (en) | 1998-11-18 | 1998-11-18 | Method of preparing 2-nitrothioxanthone |
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| KR1019980049397A KR100280925B1 (en) | 1998-11-18 | 1998-11-18 | Method of preparing 2-nitrothioxanthone |
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