KR101062900B1 - Method for preparing arenadiazonium tosylate - Google Patents

Method for preparing arenadiazonium tosylate Download PDF

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KR101062900B1
KR101062900B1 KR1020080096538A KR20080096538A KR101062900B1 KR 101062900 B1 KR101062900 B1 KR 101062900B1 KR 1020080096538 A KR1020080096538 A KR 1020080096538A KR 20080096538 A KR20080096538 A KR 20080096538A KR 101062900 B1 KR101062900 B1 KR 101062900B1
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methylbenzenesulfonate
tosylate
resin
nmr
mhz
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지기환
필리모노프 빅터
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울산대학교 산학협력단
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Abstract

본 발명은 아렌디아조늄 토실레이트의 신규 제조방법에 관한 것으로, 본 발명의 제조방법에 따라 제조된 아렌디아조늄 토실레이트는 쉽게 제조될 수 있고, 오랜기간 동안 고체 상태에서 폭발하지 않고 안정적으로 보관될 수 있고, 많은 용매들에서 높은 용해도를 나타내며, 디아조늄 염의 전형적인 반응에서 높은 반응성을 나타내므로, 유기합성에서 다양하고 유용한 빌딩블록으로서 매우 유용하게 사용될 수 있다. The present invention relates to a novel process for the preparation of arenadiazonium tosylate, wherein the arenadiazonium tosylate prepared according to the preparation method of the present invention can be easily prepared and can be stably stored in a solid state for a long time without being exploded. It has high solubility in many solvents and high reactivity in typical reactions of diazonium salts, which can be very useful as various and useful building blocks in organic synthesis.

아렌디아조늄, 토실레이트, 제조방법, 톨루엔설폰산, 수지 Arendiazonium, Tosylate, Manufacturing Method, Toluenesulfonic Acid, Resin

Description

아렌디아조늄 토실레이트의 제조방법{Preparation method of arenediazonium tosylate}Preparation method of arendiazonium tosylate {Preparation method of arenediazonium tosylate}

본 발명은 쉽게 제조될 수 있고, 보관시 고체 상태에서 안정하고 폭발하지 않으며, 유기 반응에서 다양한 융통성을 지니므로, 유기합성에서 다양하고 유용한 빌딩블록으로서 매우 유용하게 사용될 수 있는 아렌디아조늄 토실레이트의 신규 제조방법에 관한 것이다. The present invention can be easily prepared, is stable in the solid state when stored, does not explode, and has a variety of flexibility in organic reactions, so that it is very useful as various and useful building blocks in organic synthesis. It relates to a novel manufacturing method.

방향족 디아조늄 염은 고전 유기합성에서 뿐 아니라 현대 유기 나노화합물의 준비 및 금속 또는 비금속 표면에 대한 유기 분자의 그래프팅에서도 중요한 빌딩 블록이다. 디아조늄 모티브를 지닌 화합물의 합성에 있어서 상기 화합물의 폭넓은 응용에도 불구하고, 디아조늄 염은 본질적인 불안정 및 폭발성 등의 심각한 결점을 지닌다.Aromatic diazonium salts are important building blocks not only in classical organic synthesis but also in the preparation of modern organic nanocompounds and in the grafting of organic molecules to metallic or nonmetallic surfaces. Despite the wide application of these compounds in the synthesis of compounds with diazonium motifs, diazonium salts have serious drawbacks such as inherent instability and explosiveness.

이러한 불안정성으로 인해, 디아조늄 염을 이용한 이하의 모든 반응들은 디아조늄 염이 생산되었던 동일 매체에서 수행되어야 한다. 이러한 이유로 인해 많은 화학자들은 디아조늄 염의 중요한 변형에 접근하기 곤란하였다. 따라서, 쉽게 제조될 수 있고, 보관시 고체 상태에서 안정하며 폭발하지 않으며, 유기 반응에서 다양한 융통성을 지니는 새로운 디아조늄 염의 개발이 시급한 실정이었다. Due to this instability, all of the following reactions with diazonium salts must be carried out in the same medium in which the diazonium salts were produced. For this reason, many chemists have difficulty accessing important modifications of diazonium salts. Therefore, it is urgent to develop new diazonium salts which can be easily prepared, are stable in the solid state during storage, do not explode, and have various flexibility in organic reactions.

이러한 특성은 아릴디아조늄 테트라플루오로보레이트, 헥사플루오로포스페이트 및 아렌디아조늄 o-벤젠디설폰이미드에 특이한 것이며, 또 이러한 특성을 만족하는 다른 가능한 디아조늄 염으로는 아렌디아조늄 아릴설포네이트(Ar1N2 + Ar2SO3 -)가 있다. 그러나 아렌디아조늄 아릴설포네이트의 특성들이 보고된 이래로 벌써 반세기가 경과되었음에도 불구하고, 이를 유기 합성에 응용한 어떠한 새로운 보고도 없었다. These properties are specific to aryldiazonium tetrafluoroborate, hexafluorophosphate and arenadiazonium o -benzenedisulfonimide, and other possible diazonium salts that satisfy these properties are arenadiazonium arylsulfonates ( Ar 1 N 2 + Ar 2 SO 3 − ). However, despite the fact that half a century has passed since the properties of arenadiazonium arylsulfonate were reported, there were no new reports of application to organic synthesis.

한편, 본 발명자는 중간체인 아렌디아조늄 토실레이트를 거치는 아릴아민의 디아조늄화-요오드화 공정에서 p-톨루엔설폰산(TsOH)이 온화한 산성화제로서 역할을 수행함을 밝혔고, 몇몇 정제 아렌디아조늄 토실레이트는 수분 페이스트에서 NaNO2를 이용한 아릴아민의 디아조늄화에 의해 제조될 수 있다는 것을 발견하였다.On the other hand, the present inventors have found that p -toluenesulfonic acid (TsOH) plays a role as a mild acidifying agent in the diazonation-iodization process of arylamine via the intermediate arrendiazonium tosylate, and several purified arrendiazonium tosylate It has been found that can be prepared by diazoniumation of arylamines with NaNO 2 in a moisture paste.

Figure 112008069036196-pat00001
Figure 112008069036196-pat00001

그러나, 얻어진 산물인 아렌디아조늄 토실레이트 및 TsONa의 유사한 용해도로 인해 이들의 분리가 복잡하고 정제과정에서 디아조늄 산물의 원치않는 손실 문제를 야기한다. 따라서, 이러한 문제점을 해결할 수 있는 새로운 방법의 개발이 필요하다.However, the similar solubility of the resulting products, arendiazonium tosylate and TsONa, makes their separation complicated and leads to the problem of unwanted loss of diazonium products during purification. Therefore, there is a need for the development of new methods that can solve these problems.

상기 종래기술의 문제점을 해결하기 위하여, 본 발명자는 NaNO2를 이용한 종래의 아릴아민의 디아조늄화 방법을 개선하고자 수지로 지지된 디아조화제를 이용한 아렌디아조늄 토실레이트의 신규 제조방법을 개발함으로써 본 발명을 완성한 것이다.In order to solve the above problems of the prior art, the present inventors have developed a method for producing arendiazonium tosylate using a diazonating agent supported with a resin in order to improve the diazonation of conventional arylamines using NaNO 2 . The present invention has been completed.

따라서, 본 발명의 목적은 수지로 지지된 디아조화제를 이용한 아렌디아조늄 토실레이트의 신규 제조방법을 제공하는 데에 있다.Accordingly, it is an object of the present invention to provide a novel method for producing arenadiazonium tosylate using a diazotizing agent supported by a resin.

상기 목적을 달성하기 위하여, 본 발명은 수지로 지지된 디아조화제를 이용한 하기 화학식 1 또는 화학식 2로 표시되는 아렌디아조늄 토실레이트의 제조방법을 제공한다:In order to achieve the above object, the present invention provides a method for producing an arenadiazonium tosylate represented by the following formula (1) or formula (2) using a diazotizing agent supported by resin:

Ar-N2 +·TsO- Ar-N 2 + · TsO -

+N2-Ar-CH2-Ar-N2 +·2TsO- + N 2 -Ar-CH 2 -Ar -N 2 + · 2TsO -

상기 화학식 1 및 화학식 2에서, In Chemical Formula 1 and Chemical Formula 2,

Ar은 페닐, 피리딜, 피페로닐, 나프틸, 안트라닐, 푸릴, 인돌릴, 퀴놀릴, 이 소퀴놀릴, 벤조옥사졸릴, 페난트릴, 피리미딜, 옥사졸릴, 티아졸릴, 이소옥사졸릴, 이소티아졸릴, 아미다졸릴, 피라졸릴, 옥사디아졸릴 및 티오디아졸릴로 구성된 군에서 선택된 임의로 치환된 아릴 및 헤테로아릴기이며,Ar is phenyl, pyridyl, piperonyl, naphthyl, anthranyl, furyl, indolyl, quinolyl, isoquinolyl, benzooxazolyl, phenanthryl, pyrimidyl, oxazolyl, thiazolyl, isoxazolyl, iso An optionally substituted aryl and heteroaryl group selected from the group consisting of thiazolyl, amidazolyl, pyrazolyl, oxdiazolyl and thiodiazolyl,

이때, 임의의 치환체는 할로, 알킬, 알콕시, 할로알콕시, 알콕시알킬, 시아노, 니트로, 아미노, 알킬아미노, 카르복시, 알콕시카르보닐 또는 히드록시에서 선택된다.Wherein any substituent is selected from halo, alkyl, alkoxy, haloalkoxy, alkoxyalkyl, cyano, nitro, amino, alkylamino, carboxy, alkoxycarbonyl or hydroxy.

본 발명에 따른 제조방법은 수지로 지지된 디아조화제를 제조하는 단계; 톨루엔설폰산 존재 하에서 상기 디아조화제를 이용하여 아미노아렌 화합물을 디아조화하는 단계; 및 수지를 여과하여 제거하고, 에테르를 가하여 산물을 침전시키는 단계를 포함하여 구성된다.The manufacturing method according to the present invention comprises the steps of preparing a diazotizing agent supported by a resin; Diazotizing an aminoarene compound using the diazotizing agent in the presence of toluenesulfonic acid; And filtering off the resin and adding ether to precipitate the product.

본 발명의 수지로 지지된 디아조화제에 사용되는 수지는 다공성 테트라알킬암모늄 수산화물 또는 다공성 테트라알킬암모늄 할로겐화물에서 선택된 어느 하나이다.The resin used in the diazotizing agent supported by the resin of the present invention is either selected from porous tetraalkylammonium hydroxides or porous tetraalkylammonium halides.

상기 디아조화하는 단계는 용매로서 아세트산 또는 C1 내지 C4의 알코올에서 선택된 어느 하나를 사용하며, 바람직하게는 아세트산 또는 메탄올을 사용한다. The step of diazotizing uses acetic acid or any one selected from alcohols of C1 to C4 as a solvent, preferably acetic acid or methanol.

상기 디아조화하는 단계는 실온에서 5 내지 60분 동안 수행되는 것이 바람직 하며, 만약 상기 시간 범위를 벗어나 단시간 수행되면 반응의 미완성 문제가 야기될 수 있고, 장기간 수행되면 부반응의 발생 문제가 야기될 수 있다.The diazotizing step is preferably performed at room temperature for 5 to 60 minutes, and if performed for a short time out of the time range, it may cause an incomplete reaction of the reaction, and if it is performed for a long time, it may cause a problem of occurrence of side reactions. .

또한, 상기 디아조화하는 단계는 아미노아렌 1 당량에 대하여, 수지로 지지된 디아조화제 1 내지 8 당량 및 톨루엔설폰산 1 내지 8 당량을 포함하여 반응하며, 바람직하게는 아미노아렌 1 당량에 대하여, 수지로 지지된 디아조화제 3 내지 6 당량 및 톨루엔설폰산 3 내지 6 당량을 포함하여 반응할 수 있다.In addition, the step of diazotizing is carried out with respect to 1 equivalent of aminoarene, including 1 to 8 equivalents of diazotizing agent supported by resin and 1 to 8 equivalents of toluenesulfonic acid, and preferably to 1 equivalent of aminoarene, 3 to 6 equivalents of the diazotizing agent supported by resin and 3 to 6 equivalents of toluenesulfonic acid may be reacted.

상기 아미노아렌, 수지로 지지된 디아조화제 및 톨루엔설폰산의 함량 비율에 따라 본 발명의 최종 산물인 아렌디아조늄 토실레이트의 수득율이 변화할 수 있다.Depending on the content ratio of the aminoarene, the diazotizing agent and toluenesulfonic acid supported by the resin, the yield of the arenediazonium tosylate, which is the final product of the present invention, may be changed.

또한, 상기 아렌디아조늄 토실레이트는 벤젠디아조늄 4-메틸벤젠셀포네이트(Benzenediazonium 4-methylbenzenesulfonate; 1a), 2-메틸벤젠디아조늄 4-메틸벤젠설포네이트(2-Methylbenzenediazonium 4-methylbenzenesulfonate; 2a), 3-메틸벤젠디아조늄 4-메틸벤젠설포네이트(3-Methylbenzenediazonium 4-methylbenzenesulfonate; 3a), 4-메틸벤젠디아조늄 4-메틸벤젠설포네이트(4-Methylbenzenediazonium 4-methylbenzenesulfonate; 4a), 3,4-디메틸벤젠디아조늄 4-메틸벤젠설포네이트(3,4-Dimethylbenzenediazonium 4-methylbenzenesulfonate; 5a), 2-메톡시벤젠디아조늄 4-메틸벤젠설포네이트(2-Methoxybenzenediazonium 4-methylbenzenesulfonate; 6a), 4-메톡시벤젠디아조늄 4-메틸벤젠설포네이트(4-Methoxybenzenediazonium 4-methylbenzenesulfonate; 7a), 4-아미노벤젠디아조늄 4-메틸벤젠설포네이트(4-Aminobenzenediazonium 4-methylbenzenesulfonate; 8a), 2-니트로벤젠디아조늄 4-메틸벤젠설포네이트(2-Nitrobenzenediazonium 4- methylbenzenesulfonate; 9a), 3-니트로벤젠디아조늄 4-메틸벤젠설포네이트(3-Nitrobenzenediazonium 4-methylbenzenesulfonate; 10a), 4-니트로벤젠디아조늄 4-메틸벤젠설포네이트(4-Nitrobenzenediazonium 4-methylbenzenesulfonate; 11a), 4-시아노벤젠디아조늄 4-메틸벤젠설포네이트(4-Cyanobenzenediazonium 4-methylbenzenesulfonate; 12a), 2-카르복시벤젠디아조늄 4-메틸벤젠설포네이트(2-Carboxybenzenediazonium 4-methylbenzenesulfonate; 13a), 4-카르복시벤젠디아조늄 4-메틸벤젠설포네이트(4-Carboxybenzenediazonium 4-methylbenzenesulfonate; 14a), 4-아이오도벤젠디아조늄 4-메틸벤젠설포네이트(4-Iodobenzenediazonium 4-methylbenzenesulfonate; 15a), 2,4,6-트리브로모벤젠디아조늄 4-메틸벤젠설포네이트(2,4,6-Tribromobenzenediazonium 4-methylbenzenesulfonate; 16a), 나프탈렌-1-디아조늄 4-메틸벤젠설포네이트(Naphthalene-1-diazonium 4-methylbenzenesulfonate; 17a) 및 4-벤질벤젠디아조늄 4-메틸벤젠설포네이트(4-Benzylbenzenediazonium 4-methylbenzenesulfonate; 18a)로 이루어진 군에서 선택된 어느 하나이다. In addition, the arenadiazonium tosylate is benzenediazonium 4-methylbenzenesulfonate (Benzenediazonium 4-methylbenzenesulfonate; 1a), 2-methylbenzenediazonium 4-methylbenzenesulfonate (2-Methylbenzenediazonium 4-methylbenzenesulfonate; 2a), 3-Methylbenzenediazonium 4-methylbenzenesulfonate (3a), 4-Methylbenzenediazonium 4-methylbenzenesulfonate (4a), 3,4- Dimethylbenzenediazonium 4-methylbenzenesulfonate (3,4-Dimethylbenzenediazonium 4-methylbenzenesulfonate; 5a), 2-methoxybenzenediazonium 4-methylbenzenesulfonate (2-aethoxybenzenediazonium 4-methylbenzenesulfonate; 6a) 4-Methoxybenzenediazonium 4-methylbenzenesulfonate (7a), 4-aminobenzenediazonium 4-methylbenzenesulfonate (8a), 2-nitrobenzenediazonium 4-methyl Zenysulfonate (2-Nitrobenzenediazonium 4-methylbenzenesulfonate; 9a), 3-nitrobenzenediazonium 4-methylbenzenesulfonate (10a), 4-nitrobenzenediazonium 4-methylbenzenesulfonate ( 4-Nitrobenzenediazonium 4-methylbenzenesulfonate; 11a), 4-cyanobenzenediazonium 4-methylbenzenesulfonate (4-Cyanobenzenediazonium 4-methylbenzenesulfonate; 12a), 2-carboxybenzenediazonium 4-methylbenzenesulfonate (2-Carboxybenzenediazonium 4-methylbenzenesulfonate; 13a), 4-carboxybenzenediazonium 4-methylbenzenesulfonate (14a), 4-iodobenzenediazonium 4-methylbenzenesulfonate (4-Iodobenzenediazonium 4-methylbenzenesulfonate; 15a), 2,4,6-tribromobenzenediazonium 4-methylbenzenesulfonate (2,4,6-Tribromobenzenediazonium 4-methylbenzenesulfonate; 16a), naphthalene-1-diazonium 4-methylbenzenesulfonate (Naphthalene-1- diazonium 4-methylbenzenesulfonate; 17a) and 4-benzylbenzenediazonium 4-methylbenzenesulfonate (4-Benzylbenzenediazonium 4-methylbenzenesulfonate; 18a).

이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명자는 TsOH의 존재 하에서 수지로 지지된 디아조화제를 이용함으로써 아미노아렌의 신규 디아조화 방법을 개발하였다. 이때, 수지로 지지된 디아조화제(resin-NO2 -)의 제조는 NaNO2 수용액을 이용하여 다공성 테트라알킬암모늄 수산화물 수지 엠버리스트(Amberlyst) A26 또는 테트라알킬암모늄 할로겐화물 수지를 이 온교환 함으로써 얻어진다. The inventors have developed a new method of diazoation of aminoarene by using a diazotizing agent supported with a resin in the presence of TsOH. At this time, the diazotizing agent (resin-NO 2 -) the support with a resin producing a is obtained by the ion exchange porous tetraalkylammonium hydroxide resin amber list (Amberlyst) A26 or tetraalkylammonium halide resin using NaNO 2 aqueous solution Lose.

하기 반응식 2와 같이, 다양한 방향족 아민의 디아조화는 아민, p-톨루엔설폰산 및 폴리머-NO2 -를 지닌 차가운 AcOH 또는 MeOH 용액을 실온에서 5-20분 동안 출발기질이 없어질 때까지 교반함으로써 제조한다. 이때 수지는 여과에 의해 제거되고 최종산물인 아렌디아조늄 염은 디에틸에테르를 가하여 침전시켜 얻는다.As shown in Scheme 2, the diazotization of various aromatic amines is accomplished by stirring a cold AcOH or MeOH solution with amine, p-toluenesulfonic acid and polymer-NO 2 - until there is no starting substrate for 5-20 minutes at room temperature. Manufacture. At this time, the resin is removed by filtration, and the end product, the arendiazonium salt, is obtained by adding diethyl ether to precipitate.

Figure 112008069036196-pat00002
Figure 112008069036196-pat00002

본 발명의 방법에 따르면, 종래 알킬 나이트리트를 이용한 디아조화보다 더 값싸며 보다 편리하게 아렌디아조늄 염을 제조할 수 있다. 본 디아조화 방법은 전자수용체 뿐 아니라 전자제공체를 지닌 다양한 아닐린, 입체적으로 복잡한 아닐린의 제조에도 유용하다.According to the process of the present invention, arehendiazonium salts can be prepared more cheaply and more conveniently than diazotization with conventional alkyl nitrites. The diazotization method is useful for the preparation of various anilines, three-dimensionally complex anilines with electron acceptors as well as electron acceptors.

예를들어, 하기 반응식 3과 같이 본 발명에서 제조된 아렌디아조늄 토실레이트를 요오드칼륨(KI), 브롬칼륨(KBr) 또는 아질산나트륨(NaNO2)과 같은 화합물과 실온에서 반응시켜 4-아이오도아닐린(4-iodoaniline), 4-브로모벤조니트릴(4-bromobenzonitrile) 또는 1,4-디니트로벤젠(1,4-dinitrobenzene)을 제조할 수 있다.For example, alendiazonium tosylate prepared in the present invention is reacted at room temperature with a compound such as potassium iodine (KI), potassium bromide (KBr) or sodium nitrite (NaNO 2 ) as shown in Scheme 3 below. Aniline (4-iodoaniline), 4-bromobenzonitrile or 1,4-dinitrobenzene can be prepared.

또, 4-니트로벤젠디아조늄 4-메틸벤젠설포네이트(4-Nitrobenzenediazonium 4-methylbenzenesulfonate; 11a)를 피페리딘과 반응시켜 1-((4-니트로페닐)디아제닐)피페리딘[1-((4-Nitrophenyl)diazenyl)piperidine; 19]을 제조할 수 있으며, 4-니트로벤젠디아조늄 4-메틸벤젠설포네이트(4-Nitrobenzenediazonium 4-methylbenzenesulfonate; 11a), 2-카르복시벤젠디아조늄 4-메틸벤젠설포네이트(2-Carboxybenzenediazonium 4-methylbenzenesulfonate; 13a) 또는 4-카르복시벤젠디아조늄 4-메틸벤젠설포네이트(4-Carboxybenzenediazonium 4-methylbenzenesulfonate; 14a)를 스티렌 화합물과 반응시켜 (E)-4-니트로스틸벤[(E)-4-Nitrostilbene; 20], (E)-2-스티릴벤조산[(E)-2-Styrylbenzoic acid; 21] 또는 (E)-4-스티릴벤조산[(E)-4-styrylbenzoic acid; 22]을 제조할 수 있다.Also, 4-nitrobenzenediazonium 4-methylbenzenesulfonate (11a) was reacted with piperidine to give 1-((4-nitrophenyl) diazenyl) piperidine [1- ( (4-Nitrophenyl) diazenyl) piperidine; 19], 4-nitrobenzenediazonium 4-methylbenzenesulfonate (4-nitrobenzenediazonium 4-methylbenzenesulfonate; 11a), 2-carboxybenzenediazonium 4-methylbenzenesulfonate (2-Carboxybenzenediazonium 4-methylbenzenesulfonate); ; 13a) or 4-carboxy-4-methyl benzene diazonium sulfonate (4-Carboxybenzenediazonium 4-methylbenzenesulfonate; 14a) of a styrene compound to yield (E) -4- nitro-stilbene [(E) -4-Nitrostilbene; 20], ( E ) -2-styrylbenzoic acid [( E ) -2-Styrylbenzoic acid; 21] or ( E ) -4-styrylbenzoic acid [( E ) -4-styrylbenzoic acid; 22] can be prepared.

Figure 112008069036196-pat00003
Figure 112008069036196-pat00003

또한, 본 발명에 따라 합성된 아렌디아조늄 염은 양성자성 용매 뿐 아니라, 극성 비양성자성 용매에서 좋은 용해도를 나타내며, 실온의 암실에서 몇 달 동안 어떠한 변화도 없이 저장될 수 있는 안정성을 나타낸다.In addition, the arenadiazonium salts synthesized according to the present invention exhibit good solubility in protic solvents as well as polar aprotic solvents and show stability that can be stored for several months in the dark at room temperature without any change.

또한, 본 발명에 따라 합성된 아렌디아조늄 염의 열 안정성을 질소 분위기 하에서 0-600℃에서 DSC에 의해 검증한 결과, 어떠한 염에서도 폭발 현상을 관찰할 수 없었다.In addition, as a result of verifying the thermal stability of the arenadiazonium salt synthesized according to the present invention by DSC at 0-600 ° C. under a nitrogen atmosphere, no explosion phenomenon could be observed in any salt.

또한, 본 발명에 따라 합성된 아렌디아조늄 염에 대한 싱크로트론복사(synchrotron radiation)를 이용한 X-레이 분석 결과, 도 1에 도시된 바와 같이 하나의 독립된 아렌디아조늄 양이온이 3개의 토실레이트 음이온에 의해 둘러싸인 것을 확인하였다. 특히, 아렌디아조늄 토실레이트는 전하-전하 상호작용에 의해 디아조늄 양이온에 있는 질소 원자와 토실레이트 음이온의 산소 원자 간의 복수의 밀접한 결합을 나타내므로, 본 발명에 따른 아렌디아조늄 토실레이트에 특별한 안정성을 부여할 수 있다.In addition, as a result of X-ray analysis using synchrotron radiation for the arenadiazonium salts synthesized according to the present invention, as shown in FIG. 1, one independent arenadiazonium cation is formed by three tosylate anions. It confirmed that it was surrounded. In particular, the arendiazonium tosylate exhibits a plurality of intimate bonds between the nitrogen atom in the diazonium cation and the oxygen atom of the tosylate anion by charge-charge interactions, and thus have particular stability to the arerendiazonium tosylate according to the invention. Can be given.

본 발명의 제조방법에 따라 제조된 알렌디아조늄 토실레이트는 쉽게 제조될 수 있고, 오랜기간 동안 고체 상태에서 폭발하지 않고 안정적으로 보관될 수 있고, 많은 용매들에서 높은 용해도를 나타내며, 디아조늄 염의 전형적인 반응에서 높은 반응성을 나타내므로, 유기합성에서 다양하고 유용한 빌딩블록으로서 매우 유용하게 사용될 수 있다.Allendiazonium tosylate prepared according to the preparation method of the present invention can be easily prepared, can be stored stably without exploding in a solid state for a long time, exhibits high solubility in many solvents, and is typical of diazonium salts. Because of the high reactivity in the reaction, it can be very useful as various and useful building blocks in organic synthesis.

이하, 하기 실시예를 통해 본 발명을 보다 상세하게 설명한다. 다만, 이러한 실시예에 의해 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by these examples.

<실시예 1 내지 18> 아렌디아조늄 염의 제조Examples 1 to 18 Preparation of Arendiazonium Salts

AcOH(8ml)에서 p-톨루엔설폰산(2.97g, 15.75mmol)의 모노하이드레이트 용액에 실온에서 수지-NO2 -(4.5g, 15.75mmol NO2 - 함유)을 첨가하고 5분 동안 교반하였다. Toluene sulfonic acid resin -NO 2 at room temperature to a solution of the monohydrate (2.97g, 15.75mmol) - - AcOH (8ml) p from the addition of - (4.5g, 15.75mmol NO 2 content) and stirred for 5 minutes.

이때, 상기 수지-NO2 -는 다공성 테트라알킬암모늄 수산화물 수지 AV-17-8(3.5g)을 물 30ml에 용해된 NaNO2 수용액(2.07g, 30mmol)에 첨가하여 실온에서 10분동안 이온교환 함으로써 얻어졌다. 얻어진 수지-NO2 -를 여과하고 여액의 pH가 중성이 될 때까지 물로 세정하여 준비된 수지-NO2 -는 3.5mmol의 NO2 -/g을 함유하였다. 상기 AV-17-8은 엠버리스트 A26 수산화 형태의 러시아 동족체로서, 16% DVB 가교제 및 4.3mmol/g의 로딩을 지닌 0.4-1.2mm 폴리스티렌 비즈이다. At this time, the resin-NO 2 - by adding the porous tetraalkylammonium hydroxide resin AV-17-8 (3.5g) to NaNO 2 aqueous solution (2.07g, 30mmol) dissolved in 30ml of water and ion-exchanged at room temperature for 10 minutes Obtained. The obtained resin-NO 2 - was filtered and washed with water until the pH of the filtrate became neutral. The prepared resin-NO 2 - contained 3.5 mmol of NO 2 − / g. AV-17-8 is a Russian homologue of the Amberlyst A26 hydroxide form, 0.4-1.2 mm polystyrene beads with a 16% DVB crosslinker and a loading of 4.3 mmol / g.

각각 관련 아닐린(5.25mmol)을 가하고 5-20분 동안 교반하고 아민의 완전한 소비를 TLC(헥산-에테르=1:1)로 확인하였다. 반응 혼합물을 수지로부터 여과한 여액을 에테르(100-140ml)에 가하였다. 얻어진 결과 고상을 여과하고 에테르(20-40ml)로 세정하고 진공 하에서 건조하였다. 그 결과, 얻어진 화합물을 표 1에 정리하였고, 각각의 NMR 데이터를 하기에 기재하였다. Relevant aniline (5.25 mmol) was added respectively, stirred for 5-20 minutes and complete consumption of the amine was confirmed by TLC (hexane-ether = 1: 1). The filtrate was filtered from the resin and the filtrate was added to ether (100-140 ml). The resulting solid was filtered, washed with ether (20-40 ml) and dried under vacuum. As a result, the obtained compound is summarized in Table 1, and each NMR data is described below.

이때, 하기 표 1에서 a는 디아조화 반응을 20분 동안 물, 실온에서 수행한 것이고, 아민/수지-NO2 -/TsOH는 a의 경우 1:1:1이고, b의 경우 1:3:3이고, c의 경우 1:6:6이며, d는 반응시간이 5분이고, e는 메탄올을 용매로 사용한 것이고, f는 lit.mp가 131-132℃이며, g는 lit.mp가 141-142℃이다.In this case, in Table 1, a is a diazolation reaction performed for 20 minutes at water and room temperature, and amine / resin-NO 2 − / TsOH is 1: 1: 1 for a and 1: 3 for b: 3, c is 1: 6: 6, d is a reaction time of 5 minutes, e is methanol as a solvent, f is lit.mp is 131-132 ° C, and g is lit.mp is 141- 142 ° C.

Figure 112008069036196-pat00004
Figure 112008069036196-pat00004

벤젠디아조늄 4-메틸벤젠셀포네이트(Benzenediazonium 4-methylbenzenesulfonate; 1a). mp 224 ℃. IR (KBr): 2295 (N

Figure 112008069036196-pat00005
N). 1H NMR (300 MHz, DMSO): δ 2.29 (s, 3H), 7.13 (d, J=7.5 Hz, 2H), 7.35 (d, J=7.5 Hz, 2H), 7.36-7.52 (m, 5H). 13C NMR (75 MHz, DMSO): δ 20.50, 123.15, 123.54, 128.25, 128.38, 129.91, 131.84, 138.41, 144.72. Benzenediazonium 4-methylbenzenesulfonate (1a) . mp 224 ° C. IR (KBr): 2295 (N
Figure 112008069036196-pat00005
N). 1 H NMR (300 MHz, DMSO): δ 2.29 (s, 3H), 7.13 (d, J = 7.5 Hz, 2H), 7.35 (d, J = 7.5 Hz, 2H), 7.36-7.52 (m, 5H) . 13 C NMR (75 MHz, DMSO): δ 20.50, 123.15, 123.54, 128.25, 128.38, 129.91, 131.84, 138.41, 144.72.

2-메틸벤젠디아조늄 4-메틸벤젠설포네이트(2-Methylbenzenediazonium 4-methylbenzenesulfonate; 2a). mp 182 ℃. IR (KBr): 2064 (N

Figure 112008069036196-pat00006
N). 1H NMR (300 MHz, DMSO): δ 2.29 (s, 3H), 2.32 (s, 3H), 7.14 (d, J = 7.5 Hz, 2H), 7.25-7.40 (m, 4H), 7.51 (d, J = 7.5 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 16.78, 20.85, 123.10, 125.44, 127.20, 128.24, 130.60, 131.42, 131.60, 138.13, 144.85. 2-Methylbenzenediazonium 4-methylbenzenesulfonate; 2a . mp 182 ° C. IR (KBr): 2064 (N
Figure 112008069036196-pat00006
N). 1 H NMR (300 MHz, DMSO): δ 2.29 (s, 3H), 2.32 (s, 3H), 7.14 (d, J = 7.5 Hz, 2H), 7.25-7.40 (m, 4H), 7.51 (d, J = 7.5 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 16.78, 20.85, 123.10, 125.44, 127.20, 128.24, 130.60, 131.42, 131.60, 138.13, 144.85.

3-메틸벤젠디아조늄 4-메틸벤젠설포네이트(3-Methylbenzenediazonium 4-methylbenzenesulfonate; 3a). mp 158-161 ℃. IR (KBr): 2068 (N

Figure 112008069036196-pat00007
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 2.31 (s, 3H), 7.13-7.24 (m, 5H), 7.34-7.39 (m, 1H), 7.52 (d, J = 7.5 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 20.86, 120.26, 123.54, 125.53, 128.35, 128.98, 129.72, 131.49, 138.36, 139.61, 144.76. 3-Methylbenzenediazonium 4-methylbenzenesulfonate (3a) . mp 158-161 ° C. IR (KBr): 2068 (N
Figure 112008069036196-pat00007
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 2.31 (s, 3H), 7.13-7.24 (m, 5H), 7.34-7.39 (m, 1H), 7.52 (d, J = 7.5 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 20.86, 120.26, 123.54, 125.53, 128.35, 128.98, 129.72, 131.49, 138.36, 139.61, 144.76.

4-메틸벤젠디아조늄 4-메틸벤젠설포네이트(4-Methylbenzenediazonium 4-methylbenzenesulfonate; 4a). mp 120 ℃. IR (KBr): 2288 (N

Figure 112008069036196-pat00008
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 2.31 (s, 3H), 7.13 (d, J = 7.5 Hz, 2H), 7.24-7.71 (m, 4H), 7.51 (d, J =7.5 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 20.59, 20.86, 123.12, 125.54, 128.30, 128.76, 130.27, 138.00, 138.22, 144.96. 4-Methylbenzenediazonium 4-methylbenzenesulfonate; 4a . mp 120 ° C. IR (KBr): 2288 (N
Figure 112008069036196-pat00008
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 2.31 (s, 3H), 7.13 (d, J = 7.5 Hz, 2H), 7.24-7.71 (m, 4H), 7.51 (d, J = 7.5 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 20.59, 20.86, 123.12, 125.54, 128.30, 128.76, 130.27, 138.00, 138.22, 144.96.

3,4-디메틸벤젠디아조늄 4-메틸벤젠설포네이트(3,4-Dimethylbenzenediazonium 4-methylbenzenesulfonate; 5a). mp 182 ℃. IR (KBr): 2280 (N

Figure 112008069036196-pat00009
N). 1H NMR (300 MHz, DMSO): δ 2.20 (s, 6H), 2.28 (s, 3H), 7.05-7.16 (m, 4H), 7.24 (d, J = 7.8 Hz, 1H), 7.51 (d, J = 7.5 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 19.16, 19.58, 21.06, 120.48, 123.94, 125.69, 128.55, 129.12, 130.82, 136.64, 138.36, 138.62, 144.77. 3,4-dimethylbenzenediazonium 4-methylbenzenesulfonate (5a) . mp 182 ° C. IR (KBr): 2280 (N
Figure 112008069036196-pat00009
N). 1 H NMR (300 MHz, DMSO): δ 2.20 (s, 6H), 2.28 (s, 3H), 7.05-7.16 (m, 4H), 7.24 (d, J = 7.8 Hz, 1H), 7.51 (d, J = 7.5 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 19.16, 19.58, 21.06, 120.48, 123.94, 125.69, 128.55, 129.12, 130.82, 136.64, 138.36, 138.62, 144.77.

2-메톡시벤젠디아조늄 4-메틸벤젠설포네이트(2-Methoxybenzenediazonium 4-methylbenzenesulfonate; 6a). mp 149-151 ℃. IR (KBr): 2209 (N

Figure 112008069036196-pat00010
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 3.87 (s, 3H), 7.02 (m, 1H), 7.12 (d, J = 7.5 Hz, 2H), 7.20 (d, J =7.8 Hz, 1H), 7.35-7.41 (m, 2H), 7.50 (d, J = 7.5 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 20.82, 56.10, 112.49, 120.89, 120.91, 123.83, 125.48, 128.18, 129.55, 138.00, 145.00, 152.80. 2-Methoxybenzenediazonium 4-methylbenzenesulfonate; 6a . mp 149-151 ° C. IR (KBr): 2209 (N
Figure 112008069036196-pat00010
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 3.87 (s, 3H), 7.02 (m, 1H), 7.12 (d, J = 7.5 Hz, 2H), 7.20 (d, J = 7.8 Hz, 1H), 7.35-7.41 (m, 2H), 7.50 (d, J = 7.5 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 20.82, 56.10, 112.49, 120.89, 120.91, 123.83, 125.48, 128.18, 129.55, 138.00, 145.00, 152.80.

4-메톡시벤젠디아조늄 4-메틸벤젠설포네이트(4-Methoxybenzenediazonium 4-methylbenzenesulfonate; 7a). mp 118-120 ℃. IR (KBr): 2243 (N

Figure 112008069036196-pat00011
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 3.76 (s, 3H), 7.03 (d, J = 8.7 Hz, 2H), 7.12 (d, J = 7.5 Hz, 2H), 7.29 (d, J =8.7 Hz, 2H), 7.49 (d, J = 7.5 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 20.82, 55.54, 114.96, 123.86, 124.40, 125.49, 128.19, 138.02, 145.19, 158.89. 4-Methoxybenzenediazonium 4-methylbenzenesulfonate; 7a . mp 118-120 ° C. IR (KBr): 2243 (N
Figure 112008069036196-pat00011
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 3.76 (s, 3H), 7.03 (d, J = 8.7 Hz, 2H), 7.12 (d, J = 7.5 Hz, 2H), 7.29 (d, J = 8.7 Hz, 2H), 7.49 (d, J = 7.5 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 20.82, 55.54, 114.96, 123.86, 124.40, 125.49, 128.19, 138.02, 145.19, 158.89.

4-아미노벤젠디아조늄 4-메틸벤젠설포네이트(4-Aminobenzenediazonium 4-methylbenzenesulfonate; 8a). mp 149-151 ℃. IR (KBr): 2234 (N

Figure 112008069036196-pat00012
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 6.81 (d, J = 9.0 Hz, 2H), 7.13 (d, J =7.5 Hz, 2H), 7.51 (d, J = 7.5 Hz, 2H), 8.12 (d, J = 9.0 Hz, 2H), 8.36 (s, 2H, NH2). 13C NMR (75 MHz, DMSO): δ 21.01, 89.04, 115.55, 125.67, 128.48, 135.32, 138.45, 145.06, 159.42. 4-Aminobenzenediazonium 4-methylbenzenesulfonate; 8a . mp 149-151 ° C. IR (KBr): 2234 (N
Figure 112008069036196-pat00012
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 6.81 (d, J = 9.0 Hz, 2H), 7.13 (d, J = 7.5 Hz, 2H), 7.51 (d, J = 7.5 Hz , 2H), 8.12 (d, J = 9.0 Hz, 2H), 8.36 (s, 2H, NH 2 ). 13 C NMR (75 MHz, DMSO): δ 21.01, 89.04, 115.55, 125.67, 128.48, 135.32, 138.45, 145.06, 159.42.

2-니트로벤젠디아조늄 4-메틸벤젠설포네이트(2-Nitrobenzenediazonium 4-methylbenzenesulfonate; 9a). mp 155 ℃. IR (KBr): 2303 (N

Figure 112008069036196-pat00013
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.37-8.60 (m, 2H), 8.77 (d, J = 8.4 Hz, 1H), 9.11 (d, J = 8.4 Hz, 1H). 13C NMR (75 MHz, DMSO): δ 20.89, 120.30, 123.58, 125.56, 128.40, 129.02, 129.74, 131.51, 138.49, 139.80, 144.87. 2-nitrobenzenediazonium 4-methylbenzenesulfonate; 9a . mp 155 ° C. IR (KBr): 2303 (N
Figure 112008069036196-pat00013
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.37-8.60 (m, 2H) , 8.77 (d, J = 8.4 Hz, 1H), 9.11 (d, J = 8.4 Hz, 1H). 13 C NMR (75 MHz, DMSO): δ 20.89, 120.30, 123.58, 125.56, 128.40, 129.02, 129.74, 131.51, 138.49, 139.80, 144.87.

3-니트로벤젠디아조늄 4-메틸벤젠설포네이트(3-Nitrobenzenediazonium 4-methylbenzenesulfonate; 10a). mp 134 ℃. IR (KBr): 2307 (N

Figure 112008069036196-pat00014
N). 1H NMR (300 MHz, DMSO): δ 2.29 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.20-8.26 (m, 1H), 8.97 (d, J = 8.1 Hz, 1H), 9.05 (d, J = 8.1 Hz, 1H), 9.61 (s, 1H). 13C NMR (75 MHz, DMSO): δ 20.85, 118.31, 125.54, 128.22, 132.79, 134.99, 138.02, 145.34, 147.60. 3-nitrobenzenediazonium 4-methylbenzenesulfonate; 10a . mp 134 ° C. IR (KBr): 2307 (N
Figure 112008069036196-pat00014
N). 1 H NMR (300 MHz, DMSO): δ 2.29 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.20-8.26 (m, 1H) , 8.97 (d, J = 8.1 Hz, 1H), 9.05 (d, J = 8.1 Hz, 1H), 9.61 (s, 1H). 13 C NMR (75 MHz, DMSO): δ 20.85, 118.31, 125.54, 128.22, 132.79, 134.99, 138.02, 145.34, 147.60.

4-니트로벤젠디아조늄 4-메틸벤젠설포네이트(4-Nitrobenzenediazonium 4-methylbenzenesulfonate; 11a). mp 132 ℃. IR (KBr): 2308 (N

Figure 112008069036196-pat00015
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.10 (d, J=7.5 Hz, 2H), 7.47 (d, J=7.5 Hz, 2H), 8.69 (d, J=9.3 Hz, 2H), 8.89 (d, J=9.3 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 20.84, 121.96, 125.57, 126.04, 128.18, 134.60, 137.85, 145.55, 153.22. 4-nitrobenzenediazonium 4-methylbenzenesulfonate (11a) . mp 132 ° C. IR (KBr): 2308 (N
Figure 112008069036196-pat00015
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.10 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.69 (d, J = 9.3 Hz , 2H), 8.89 (d, J = 9.3 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 20.84, 121.96, 125.57, 126.04, 128.18, 134.60, 137.85, 145.55, 153.22.

4-시아노벤젠디아조늄 4-메틸벤젠설포네이트(4-Cyanobenzenediazonium 4-methylbenzenesulfonate; 12a). mp 124 ℃. IR (KBr): 2235 (N

Figure 112008069036196-pat00016
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.10 (d, J=7.5 Hz, 2H), 7.46 (d, J=7.5 Hz, 2H), 8.42 (d, J=9.0 Hz, 2H), 8.85 (d, J=9.0 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 20.87, 116.45, 121.11, 121.72, 125.57, 128.25, 133.17, 134.81, 137.97, 145.39. 4-Cyanobenzenediazonium 4-methylbenzenesulfonate; 12a . mp 124 ° C. IR (KBr): 2235 (N
Figure 112008069036196-pat00016
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.10 (d, J = 7.5 Hz, 2H), 7.46 (d, J = 7.5 Hz, 2H), 8.42 (d, J = 9.0 Hz , 2H), 8.85 (d, J = 9.0 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 20.87, 116.45, 121.11, 121.72, 125.57, 128.25, 133.17, 134.81, 137.97, 145.39.

2-카르복시벤젠디아조늄 4-메틸벤젠설포네이트(2-Carboxybenzenediazonium 4-methylbenzenesulfonate; 13a). mp 128 ℃. IR (KBr): 2289 (N

Figure 112008069036196-pat00017
N). 1H NMR (300 MHz, DMSO): δ 2.27 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.12-8.17 (m, 1H), 8.27-8.37 (m, 2H), 8.90 (d, J = 8.1 Hz, 1H). 13C NMR (75 MHz, DMSO): δ 21.14,116.02, 125.75, 128.61, 132.75, 134.91, 135.50, 138.59, 141.12, 144.96, 162.70. 2-Carboxybenzenediazonium 4-methylbenzenesulfonate; 13a . mp 128 ° C. IR (KBr): 2289 (N
Figure 112008069036196-pat00017
N). 1 H NMR (300 MHz, DMSO): δ 2.27 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.12-8.17 (m, 1H) , 8.27-8.37 (m, 2H), 8.90 (d, J = 8.1 Hz, 1H). 13 C NMR (75 MHz, DMSO): δ 21.14,116.02, 125.75, 128.61, 132.75, 134.91, 135.50, 138.59, 141.12, 144.96, 162.70.

4-카르복시벤젠디아조늄 4-메틸벤젠설포네이트(4-Carboxybenzenediazonium 4-methylbenzenesulfonate; 14a). mp 114-115 ℃. IR (KBr): 2303 (N

Figure 112008069036196-pat00018
N). 1H NMR (300 MHz, DMSO): δ 2.27 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.36 (d, J =8.7 Hz, 2H), 8.76 (d, J = 8.7 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 21.11, 119.78, 125.77, 128.57, 131.55, 133.38, 138.55, 140.98, 145.03, 165.14. 4-Carboxybenzenediazonium 4-methylbenzenesulfonate (14a) . mp 114-115 ° C. IR (KBr): 2303 (N
Figure 112008069036196-pat00018
N). 1 H NMR (300 MHz, DMSO): δ 2.27 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.36 (d, J = 8.7 Hz , 2H), 8.76 (d, J = 8.7 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 21.11, 119.78, 125.77, 128.57, 131.55, 133.38, 138.55, 140.98, 145.03, 165.14.

4-아이오도벤젠디아조늄 4-메틸벤젠설포네이트(4-Iodobenzenediazonium 4-methylbenzenesulfonate; 15a). mp 124-126 ℃. IR (KBr): 2210 (N

Figure 112008069036196-pat00019
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.34-8.41 (m, 4H). 13C NMR (75 MHz, DMSO): δ 20.86, 113.60, 115.12, 125.49, 128.17, 132.91, 137.87, 140.20, 145.31. 4-Iodobenzenediazonium 4-methylbenzenesulfonate; 15a . mp 124-126 ° C. IR (KBr): 2210 (N
Figure 112008069036196-pat00019
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.11 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.34-8.41 (m, 4H) . 13 C NMR (75 MHz, DMSO): δ 20.86, 113.60, 115.12, 125.49, 128.17, 132.91, 137.87, 140.20, 145.31.

2,4,6-트리브로모벤젠디아조늄 4-메틸벤젠설포네이트(2,4,6-Tribromobenzenediazonium 4-methylbenzenesulfonate; 16a). mp 152 ℃. IR (KBr): 2284 (N

Figure 112008069036196-pat00020
N). 1H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.12 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.71 (s, 2H). 13C NMR (75 MHz, DMSO): δ 20.93,92.00, 124.95, 125.54, 126.21, 128.35, 138.34, 144.65. 2,4,6-tribromobenzenediazonium 4-methylbenzenesulfonate (2,4,6-Tribromobenzenediazonium 4-methylbenzenesulfonate; 16a) . mp 152 ° C. IR (KBr): 2284 (N
Figure 112008069036196-pat00020
N). 1 H NMR (300 MHz, DMSO): δ 2.28 (s, 3H), 7.12 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 7.5 Hz, 2H), 8.71 (s, 2H). 13 C NMR (75 MHz, DMSO): δ 20.93,92.00, 124.95, 125.54, 126.21, 128.35, 138.34, 144.65.

나프탈렌-1-디아조늄 4-메틸벤젠설포네이트(Naphthalene-1-diazonium 4-methylbenzenesulfonate; 17a). mp 134-136 ℃. IR (KBr): 2222 (N

Figure 112008069036196-pat00021
N). 1H NMR (300 MHz, DMSO): δ 2.27 (s, 3H), 7.13 (d, J = 7.5 Hz, 2H), 7.46-7.78 (m, 5H), 7.90-8.07 (m, 4H). 13C NMR (75 MHz, DMSO): δ 20.89,121.43, 125.57, 127.07, 127.50, 127.82, 127.98, 128.37, 128.83, 129.00, 130.06, 132.00, 132.87, 138.48, 144.86. Naphthalene-1-diazonium 4-methylbenzenesulfonate (17a) . mp 134-136 ° C. IR (KBr): 2222 (N
Figure 112008069036196-pat00021
N). 1 H NMR (300 MHz, DMSO): δ 2.27 (s, 3H), 7.13 (d, J = 7.5 Hz, 2H), 7.46-7.78 (m, 5H), 7.90-8.07 (m, 4H). 13 C NMR (75 MHz, DMSO): δ 20.89,121.43, 125.57, 127.07, 127.50, 127.82, 127.98, 128.37, 128.83, 129.00, 130.06, 132.00, 132.87, 138.48, 144.86.

4-벤질벤젠디아조늄 4-메틸벤젠설포네이트(4-Benzylbenzenediazonium 4-methylbenzenesulfonate; 18a). mp 246 ℃. IR (KBr): 2293 (N

Figure 112008069036196-pat00022
N). 1H NMR (300 MHz, DMSO): δ 2.27 (s, 3H), 7.13 (d, J = 7.5 Hz, 2H), 7.26 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 7.5 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 21.10, 123.53, 125.73, 128.57, 129.84, 130.33, 138.60, 141.45, 144.92. 4-benzylbenzenediazonium 4-methylbenzenesulfonate (18a) . mp 246 ° C. IR (KBr): 2293 (N
Figure 112008069036196-pat00022
N). 1 H NMR (300 MHz, DMSO): δ 2.27 (s, 3H), 7.13 (d, J = 7.5 Hz, 2H), 7.26 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz , 2H), 7.49 (d, J = 7.5 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 21.10, 123.53, 125.73, 128.57, 129.84, 130.33, 138.60, 141.45, 144.92.

<실시예 19 내지 36> 아렌디아조늄 염을 이용한 다른 화합물 합성 Examples 19 to 36 Synthesis of Other Compounds Using Arendiazonium Salts

1. 4-아이오도아닐린(4-iodoaniline)4-iodoaniline

물(6ml)에 용해된 상기 화합물 8a 용액(0.40 g, 1.0 mmol)에 요오드칼륨(KI; 0.42 g, 2.5 mmol)을 실온에서 첨가하고, 2-나프톨에 의한 네거티브 디아조늄 시험때까지 50분 동안 교반하였다. 침전물을 여과하고 증류수로 세정하여 4-아이오도아닐린(0.20g, 100%, mp 64℃)을 얻었다.Potassium iodine (KI; 0.42 g, 2.5 mmol) was added to the solution of Compound 8a (0.40 g, 1.0 mmol) dissolved in water (6 ml) at room temperature, and for 50 minutes until negative diazonium test with 2-naphthol. Stirred. The precipitate was filtered and washed with distilled water to give 4-iodoaniline (0.20 g, 100%, mp 64 ℃).

2. 4-브로모벤조니트릴(4-Bromobenzonitrile)2. 4-Bromobenzonitrile

물(6ml)에 용해된 상기 화합물 12a 용액(0.30 g, 1.0 mmol)에 브롬칼륨(KBr; 0.52 g, 2.5 mmol)을 실온에서 첨가하고, 2-나프톨에 의한 네거티브 디아조늄 시험때까지 100분 동안 교반하였다. 침전물을 여과하고 증류수로 세정하여 4-브로모벤조니트릴(0.13g, 74%, mp 113℃)을 얻었다. Potassium bromide (KBr; 0.52 g, 2.5 mmol) was added to a solution of Compound 12a (0.30 g, 1.0 mmol) dissolved in water (6 ml) at room temperature and allowed to undergo negative diazonium test with 2-naphthol for 100 minutes. Stirred. The precipitate was filtered off and washed with distilled water to give 4-bromobenzonitrile (0.13 g, 74%, mp 113 ° C.).

3. 1,4-디니트로벤젠(1,4-Dinitrobenzene)3. 1,4-Dinitrobenzene

물(6ml)에 용해된 상기 화합물 11a 용액(0.32 g, 1.0 mmol)에 아질산나트륨(NaNO2; 0.17 g, 2.5 mmol)을 실온에서 첨가하고, 2-나프톨에 의한 네거티브 디아조늄 시험때까지 30분 동안 교반하였다. 침전물을 여과하고 증류수로 세정하여 1,4-디니트로벤젠(0.12g, 74%, mp 171-173℃)을 얻었다. To the compound 11a solution (0.32 g, 1.0 mmol) dissolved in water (6 ml) was added sodium nitrite (NaNO 2 ; 0.17 g, 2.5 mmol) at room temperature and 30 minutes until negative diazonium test with 2-naphthol. Was stirred. The precipitate was filtered and washed with distilled water to give 1,4-dinitrobenzene (0.12 g, 74%, mp 171-173 ° C).

4. 기타 화합물들의 합성4. Synthesis of Other Compounds

상기와 동일한 방법으로 하기 표 2에 있는 총 11종의 다른 화합물들도 합성하였다.A total of 11 other compounds in Table 2 were also synthesized in the same manner as above.

Figure 112008069036196-pat00023
Figure 112008069036196-pat00023

5. 1-((4-니트로페닐)디아제닐)피페리딘[1-((4-Nitrophenyl)diazenyl)piperidine; 19]. 5. 1-((4-nitrophenyl) diazenyl) piperidine [1-((4-Nitrophenyl) diazenyl) piperidine; 19].

메탄올(20ml)에 용해된 피페리딘(0.34 g, 4 mmol)을 0-5℃로 냉각시켜 준비하였다. 메탄올(10ml)에 용해된 상기 화합물 11a 용액(0.64 g, 2 mmol)에 냉각된 피페리딘 용액을 첨가하고, 2-나프톨에 의한 네거티브 디아조늄 시험때까지 20분 동안 0-5℃에서 교반하였다. 반응 혼합물을 물(50ml)에 넣고 고체 산물을 여과하고 증류수로 세정하며 건조하여 1-((4-니트로페닐)디아제닐)피페리딘[0.40g, 97%, mp 88-90℃(EtOH) (lit.mp 87-88℃)]을 얻었다. Piperidine (0.34 g, 4 mmol) dissolved in methanol (20 ml) was prepared by cooling to 0-5 ° C. To the compound 11a solution (0.64 g, 2 mmol) dissolved in methanol (10 ml) was added a cooled piperidine solution and stirred at 0-5 ° C. for 20 minutes until negative diazonium test with 2-naphthol. . The reaction mixture was poured into water (50 ml), the solid product was filtered off, washed with distilled water and dried to give 1-((4-nitrophenyl) diazenyl) piperidine [0.40 g, 97%, mp 88-90 ° C. (EtOH) (lit.mp 87-88 ° C.)].

1H NMR (300 MHz, DMSO): δ 1.69 (m, 3H), 3.85 (m, 2H), 7.48 (d, J=8.7 Hz, 2H), 8.18 (d, J=8.7 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 23.5, 43.7, 53.2, 120.5, 125.2, 144.0, 156.0 MS m/z 234 (M+). 1 H NMR (300 MHz, DMSO): δ 1.69 (m, 3H), 3.85 (m, 2H), 7.48 (d, J = 8.7 Hz, 2H), 8.18 (d, J = 8.7 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 23.5, 43.7, 53.2, 120.5, 125.2, 144.0, 156.0 MS m / z 234 (M + ).

6. (6. ( EE )-4-니트로스틸벤[() -4-nitrostilbene (( EE )-4-Nitrostilbene; 20]) -4-Nitrostilbene; 20]

상기 화합물 11a(0.55 g, 1.5 mmol), 스티렌(0.19 g, 1.8 mmol) 및 Pd(OAc)2(0.004 g, 0.015 mmol)의 95% EtOH 수용액(15ml)에서의 혼합물을 2-나프톨에 의한 네거티브 디아조늄 시험때까지 20분 동안 70℃에서 교반하였다. 반응 혼합물을 실리카겔을 거쳐 여과하고 냉각시켰다. 여과에 의해 (E)-4-니트로스틸벤[0.25g, 75%, mp 154-157℃(EtOH) (lit.mp 155-156℃)]을 얻었다. Negative mixture of the compound 11a (0.55 g, 1.5 mmol), styrene (0.19 g, 1.8 mmol) and Pd (OAc) 2 (0.004 g, 0.015 mmol) in an aqueous 95% EtOH solution (15 ml) with 2-naphthol Stir at 70 ° C. for 20 minutes until diazonium test. The reaction mixture was filtered through silica gel and cooled. Filtration yielded ( E ) -4-nitrostyrene ben [0.25 g, 75%, mp 154-157 ° C (EtOH) (lit.mp 155-156 ° C)].

1H NMR (300 MHz, CDCl3): δ 7.11 (d, J = 16.5 Hz, 1H), 7.24 (d, J = 16.5 Hz, 1H), 7.38 (m, 1H), 7.54 (d, J = 6.3 Hz, 1H), 7.61 (d, J = 7.8 Hz, 1H), 8.20 (d, J = 7.8 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ 124.0, 126.2, 126.8, 126.9, 128.8, 133.3, 136.0, 143.7, 146.6. 1 H NMR (300 MHz, CDCl 3 ): δ 7.11 (d, J = 16.5 Hz, 1H), 7.24 (d, J = 16.5 Hz, 1H), 7.38 (m, 1H), 7.54 (d, J = 6.3 Hz, 1H), 7.61 (d, J = 7.8 Hz, 1H), 8.20 (d, J = 7.8 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ): δ 124.0, 126.2, 126.8, 126.9, 128.8, 133.3, 136.0, 143.7, 146.6.

7. (7. ( EE )-2-스티릴벤조산[() -2-styrylbenzoic acid [( EE )-2-Styrylbenzoic acid; 21] 및 () -2-Styrylbenzoic acid; 21] and ( EE )-4-스티릴벤조산[() -4-styryl benzoic acid [( EE )-4-styrylbenzoic acid; 22]) -4-styrylbenzoic acid; 22]

상기 화합물 13a 및 14a를 이용하여 상기와 동일한 방법으로 (E)-2-스티릴벤조산[0.21 g, 65%, mp 153-155℃ (EtOH) (lit mp 159-160℃ 3 )] 및 (E)-4-스티릴벤조산[0.22 g, 67%, mp 250-253℃ (EtOH) (lit. mp. 257-258℃ 4 )]을 각각 제조하였다.( E ) -2-styrylbenzoic acid [0.21 g, 65%, mp 153-155 ° C. (EtOH) (lit mp 159-160 ° C. 3 )] and ( E using the same compound 13a and 14a as above. ) -4-styrylbenzoic acid [0.22 g, 67%, mp 250-253 ° C. (EtOH) (lit. mp. 257-258 ° C. 4 )], respectively.

21: 1H NMR (300 MHz, (CD3)2CO): δ 7.14 (d, J = 16.2 Hz, 1H), 7.26-7.42 (m, 4H), 7.56-7.61 (m, 3H), 7.85-7.87 (m, 1H), 7.99-8.02 (m, 1H), 8.12 (d, J = 16.2 Hz, 1H); 13C NMR (75 MHz, (CD3)2CO) 127.5, 128.1, 128.2, 128.6, 129.5, 129.8, 131.7, 131.9, 133.1, 138.5, 139.8, 160.9; 21 : 1 H NMR (300 MHz, (CD 3 ) 2 CO): δ 7.14 (d, J = 16.2 Hz, 1H), 7.26-7.42 (m, 4H), 7.56-7.61 (m, 3H), 7.85- 7.87 (m, 1 H), 7.99-8.02 (m, 1 H), 8.12 (d, J = 16.2 Hz, 1 H); 13 C NMR (75 MHz, (CD 3 ) 2 CO) 127.5, 128.1, 128.2, 128.6, 129.5, 129.8, 131.7, 131.9, 133.1, 138.5, 139.8, 160.9;

22: 1H NMR (300 MHz, DMSO): δ 7.27 (d, J = 16.5 Hz, H), 7.29-7.41 (m, 4H), 7.61 (d, J = 7.5 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.92 (d, J = 8.1 Hz, 2H). 13C NMR (75 MHz, DMSO): δ 126.7, 127.0, 127.5, 128.4, 128.9, 129.6, 129.9, 131.2, 136.7, 141.5, 167.2. 22 : 1 H NMR (300 MHz, DMSO): δ 7.27 (d, J = 16.5 Hz, H), 7.29-7.41 (m, 4H), 7.61 (d, J = 7.5 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.92 (d, J = 8.1 Hz, 2H). 13 C NMR (75 MHz, DMSO): δ 126.7, 127.0, 127.5, 128.4, 128.9, 129.6, 129.9, 131.2, 136.7, 141.5, 167.2.

<실험예 1> 열 안정성 검토 및 결정구조 분석Experimental Example 1 Thermal Stability Review and Crystal Structure Analysis

본 발명에 따른 화합물의 열 안정성을 질소 분위기 하에서 0-600℃에서 DSC에 의해 검증하였고, 어떠한 염에서도 폭발 현상을 관찰할 수 없었다.The thermal stability of the compounds according to the invention was verified by DSC at 0-600 ° C. under a nitrogen atmosphere and no explosion phenomenon could be observed in any salt.

또한, X-레이 결정학에 의해 이들 화합물들의 결정 구조를 조사하였다. 싱크로트론복사(synchrotron radiation)를 이용한 X-레이 분석에 의해 하나의 독립된 아렌디아조늄 양이온이 3개의 토실레이트 음이온에 의해 둘러싸인 것을 확인하였다. In addition, the crystal structure of these compounds was investigated by X-ray crystallography. X-ray analysis using synchrotron radiation confirmed that one independent arenadiazonium cation was surrounded by three tosylate anions.

특히, 도 1에 도시된 바와 같이 아렌디아조늄 토실레이트는 전하-전하 상호작용에 의해 디아조늄 양이온에 있는 질소 원자와 토실레이트 음이온의 산소 원자 간의 다수 밀접한 결합을 확인할 수 있었다. 양이온 및 음이온 간의 이러한 상호작용으로 인해 본 발명에 따른 아렌디아조늄 토실레이트에 특별한 안정성이 부여되는 것으로 판단된다. 각각 화합물의 X-레이 데이터는 하기와 같다.In particular, as shown in FIG. 1, the arendiazonium tosylate was able to confirm many intimate bonds between the nitrogen atom in the diazonium cation and the oxygen atom of the tosylate anion by charge-charge interaction. It is believed that this interaction between the cation and anion imparts special stability to the arereniazonium tosylate according to the present invention. X-ray data of each compound is as follows.

X-ray data of 9a: C13H11N3O5S M = 321.31, Triclinic, P-1 (No. 2), a = 7.509(2) Å, b = 7.546(2) Å, c = 13.672(3) Å, α = 78.64(3)°, β = 75.67(3)°, γ = 75.60(3)°, V = 719.4(2) Å3, Z = 2, T = 90 K, μ(λ= 0.80000 Å) = 0.343 mm-1, dcalc = 1.483 g/cm3, 2571 reflections measured, 2571 unique, R1 = 0.0392, wR2 =0.1220 (I > 2(I)), R1 = 0.0398, wR2 =0.1231 (all data), GOF = 1.055. X-ray data of 9a : C 13 H 11 N 3 O 5 SM = 321.31, Triclinic, P-1 (No. 2), a = 7.509 (2) Å, b = 7.546 (2) Å, c = 13.672 ( 3) Å, α = 78.64 (3) °, β = 75.67 (3) °, γ = 75.60 (3) °, V = 719.4 (2) Å 3 , Z = 2, T = 90 K, μ (λ = 0.80000 Å) = 0.343 mm -1 , d calc = 1.483 g / cm 3 , 2571 reflections measured, 2571 unique, R 1 = 0.0392, wR 2 = 0.1220 (I> 2 (I)), R 1 = 0.0398, wR 2 = 0.1231 (all data), GOF = 1.055.

X-ray data of 12a: C14H11N3O3S M = 301.32, monoclinic, P21/c (No. 14), a = 5.845(1) Å, b = 8.847(2) Å, c = 26.65(1) Å, β = 94.29(3)°, V = 1374.2(5) Å3, Z = 4, T = 90 K, μ(λ = 0.80000 Å) = 0.338 mm-1, dcalc = 1.456 g·cm-3, 4808 reflections measured, 2681 unique (Rint = 0.0476), R1 = 0.0429, wR2 =0.1242 (I > 2(I)), R1 = 0.0438, wR2 = 0.1256 (all data), GOF = 1.036. X-ray data of 12a : C 14 H 11 N 3 O 3 SM = 301.32, monoclinic, P2 1 / c (No. 14), a = 5.845 (1) Å, b = 8.847 (2) Å, c = 26.65 (1) Å, β = 94.29 (3) °, V = 1374.2 (5) Å 3 , Z = 4, T = 90 K, μ (λ = 0.80000 Å) = 0.338 mm -1 , d calc = 1.456 g cm -3 , 4808 reflections measured, 2681 unique (R int = 0.0476), R 1 = 0.0429, wR 2 = 0.1242 (I> 2 (I)), R 1 = 0.0438, wR 2 = 0.1256 (all data), GOF = 1.036.

X-ray data of 15a: C13H11N2O3SI M = 402.20, Triclinic, P-1 (No. 2), a = 7.678(2) Å, b = 10.149(2) Å, c = 18.657(4) Å, α = 77.15(3)°, β = 88.73(3)°, γ = 77.04(3)°, V = 1380.7(5) Å3, Z = 4, T = 90 K, μ(λ = 0.80000 Å) = 3.367 mm-1, dcalc = 1.935 g/cm3, 4411 reflections measured, 4411 unique, R1 = 0.0793, wR2 =0.2202 (I > 2(I)), R1 = 0.0814, wR2 = 0.2253 (all data), GOF = 1.041. X-ray data of 15a : C 13 H 11 N 2 O 3 SI M = 402.20, Triclinic, P-1 (No. 2), a = 7.678 (2) Å, b = 10.149 (2) Å, c = 18.657 (4) Å, α = 77.15 (3) °, β = 88.73 (3) °, γ = 77.04 (3) °, V = 1380.7 (5) Å 3 , Z = 4, T = 90 K, μ (λ) = 0.80000 μs) = 3.367 mm -1 , d calc = 1.935 g / cm 3 , 4411 reflections measured, 4411 unique, R 1 = 0.0793, wR 2 = 0.2202 (I> 2 (I)), R 1 = 0.0814, wR 2 = 0.2253 (all data), GOF = 1.041.

도 1은 본 발명에 따른 아렌디아조늄 토실레이트 중 화합물 9a(a), 화합물 12a(b) 및 화합물 15a(c)에 대한 X-레이 결정 구조를 나타낸 이미지 사진이다.1 is an image photograph showing the X-ray crystal structure of the compound 9a (a), 12a (b) and 15a (c) in the arereniazonium tosylate according to the present invention.

Claims (7)

삭제delete 수지로 지지된 디아조화제를 제조하는 단계;Preparing a diazotizing agent supported by a resin; 톨루엔설폰산 존재 하에서 상기 디아조화제를 이용하여 아미노아렌 화합물을 디아조화하는 단계; 및 Diazotizing an aminoarene compound using the diazotizing agent in the presence of toluenesulfonic acid; And 수지를 여과하여 제거하고, 에테르를 가하여 산물을 침전시키는 단계Filtering off the resin and adding ether to precipitate the product 를 포함하여 구성되는 것을 특징으로 하는, 하기 화학식 1 또는 화학식 2로 표시되는 아렌디아조늄 토실레이트의 제조방법:Method for producing an arenadiazonium tosylate represented by the formula (1) or formula (2), characterized in that comprising a: [화학식 1][Formula 1] Ar-N2 +·TsO- Ar-N 2 + · TsO - [화학식 2][Formula 2] +N2-Ar-CH2-Ar-N2 +·2TsO- + N 2 -Ar-CH 2 -Ar -N 2 + · 2TsO - 상기 화학식 1 및 화학식 2에서, In Chemical Formula 1 and Chemical Formula 2, Ar은 페닐이며,Ar is phenyl, 이때, 임의의 치환체는 할로, 메틸, 메톡시, 시아노, 니트로, 아미노, 카르복시 또는 히드록시에서 선택됨.Wherein any substituent is selected from halo, methyl, methoxy, cyano, nitro, amino, carboxy or hydroxy. 제 2항에 있어서, 상기 수지는 다공성 테트라알킬암모늄 수산화물 또는 다공성 테트라알킬암모늄 할로겐화물에서 선택된 어느 하나인 것을 특징으로 하는 아렌디아조늄 토실레이트의 제조방법.The method of claim 2, wherein the resin is any one selected from porous tetraalkylammonium hydroxides and porous tetraalkylammonium halides. 제 2항에 있어서, 상기 디아조화하는 단계는 용매로서 아세트산 또는 C1 내지 C4의 알코올에서 선택된 어느 하나를 사용한 것을 특징으로 하는 아렌디아조늄 토실레이트의 제조방법.The method of claim 2, wherein the diazotizing is carried out using acetic acid or any one selected from alcohols of C1 to C4 as a solvent. 제 2항에 있어서, 상기 디아조화하는 단계는 실온에서 5 내지 60분 동안 수행되는 것을 특징으로 하는 아렌디아조늄 토실레이트의 제조방법.The method of claim 2, wherein the diazotizing is performed for 5 to 60 minutes at room temperature. 제 2항에 있어서, 상기 디아조화하는 단계는 아미노아렌 1 당량에 대하여, 수지로 지지된 디아조화제 1 내지 8 당량 및 톨루엔설폰산 1 내지 8 당량을 포함하여 반응하는 것을 특징으로 하는 아렌디아조늄 토실레이트의 제조방법.The method of claim 2, wherein the diazotization is carried out with respect to 1 equivalent of aminoarene, including 1 to 8 equivalents of a diazolating agent supported by resin and 1 to 8 equivalents of toluenesulfonic acid. Method for preparing tosylate. 제 2항에 있어서, 상기 아렌디아조늄 토실레이트는 벤젠디아조늄 4-메틸벤젠셀포네이트(Benzenediazonium 4-methylbenzenesulfonate; 1a), 2-메틸벤젠디아조늄 4-메틸벤젠설포네이트(2-Methylbenzenediazonium 4-methylbenzenesulfonate; 2a), 3-메틸벤젠디아조늄 4-메틸벤젠설포네이트(3-Methylbenzenediazonium 4-methylbenzenesulfonate; 3a), 4-메틸벤젠디아조늄 4-메틸벤젠설포네이트(4-Methylbenzenediazonium 4-methylbenzenesulfonate; 4a), 3,4-디메틸벤젠디아조늄 4-메틸벤젠설포네이트(3,4-Dimethylbenzenediazonium 4-methylbenzenesulfonate; 5a), 2-메톡시벤젠디아조늄 4-메틸벤젠설포네이트(2-Methoxybenzenediazonium 4-methylbenzenesulfonate; 6a), 4-메톡시벤젠디아조늄 4-메틸벤젠설포네이트(4-Methoxybenzenediazonium 4-methylbenzenesulfonate; 7a), 4-아미노벤젠디아조늄 4-메틸벤젠설포네이트(4-Aminobenzenediazonium 4-methylbenzenesulfonate; 8a), 2-니트로벤젠디아조늄 4-메틸벤젠설포네이트(2-Nitrobenzenediazonium 4-methylbenzenesulfonate; 9a), 3-니트로벤젠디아조늄 4-메틸벤젠설포네이트(3-Nitrobenzenediazonium 4-methylbenzenesulfonate; 10a), 4-니트로벤젠디아조늄 4-메틸벤젠설포네이트(4-Nitrobenzenediazonium 4-methylbenzenesulfonate; 11a), 4-시아노벤젠디아조늄 4-메틸벤젠설포네이트(4-Cyanobenzenediazonium 4-methylbenzenesulfonate; 12a), 2-카르복시벤젠디아조늄 4-메틸벤젠설포네이트(2-Carboxybenzenediazonium 4-methylbenzenesulfonate; 13a), 4-카르복시벤젠디아조늄 4-메틸벤젠설포네이트(4-Carboxybenzenediazonium 4-methylbenzenesulfonate; 14a), 4-아이오도벤젠디아조늄 4-메틸벤젠설포네이트(4-Iodobenzenediazonium 4-methylbenzenesulfonate; 15a), 2,4,6-트리브로모벤젠디아조늄 4-메틸벤젠설포네이트(2,4,6-Tribromobenzenediazonium 4-methylbenzenesulfonate; 16a) 및 4-벤질벤젠디아조늄 4-메틸벤젠설포네이트(4-Benzylbenzenediazonium 4-methylbenzenesulfonate; 18a)로 이루어진 군에서 선택된 어느 하나인 것을 특징으로 하는 아렌디아조늄 토실레이트의 제조방법.The method of claim 2, wherein the arenadiazonium tosylate is Benzenediazonium 4-methylbenzenesulfonate (1a), 2-methylbenzenediazonium 4-methylbenzenesulfonate (2-Methylbenzenediazonium 4-methylbenzenesulfonate 2a), 3-Methylbenzenediazonium 4-methylbenzenesulfonate (3a), 4-methylbenzenediazonium 4-methylbenzenesulfonate (4-Methylbenzenediazonium 4-methylbenzenesulfonate; 4a), 3,4-dimethylbenzenediazonium 4-methylbenzenesulfonate (5a), 2-methoxybenzenediazonium 4-methylbenzenesulfonate (6a) , 4-Methoxybenzenediazonium 4-methylbenzenesulfonate (7a), 4-aminobenzenediazonium 4-methylbenzenesulfonate (4-aminobenzenediazonium 4-methylbenzenesulfonate; 8a), 2- Nitrobenzenedia 2-Nitrobenzenediazonium 4-methylbenzenesulfonate (9a), 3-nitrobenzenediazonium 4-methylbenzenesulfonate (10a), 4-nitrobenzenediazonium 4-methyl 4-Nitrobenzenediazonium 4-methylbenzenesulfonate (11a), 4-cyanobenzenediazonium 4-methylbenzenesulfonate (12a), 2-carboxybenzenediazonium 4-methylbenzenesulfonate (2-Carboxybenzenediazonium 4-methylbenzenesulfonate; 13a), 4-carboxybenzenediazonium 4-methylbenzenesulfonate (14a), 4-iodobenzenediazonium 4-methylbenzenesulfonate (4-Iodobenzenediazonium 4-methylbenzenesulfonate; 15a), 2,4,6-tribromobenzenediazonium 4-methylbenzenesulfonate (2,4,6-Tribromobenzenediazonium 4-methylbenzenesulfonate; 16a) and 4-benzylbenzenediazonium 4-methylbenzenesulfonate (4-Benzylbenzenediazonium 4 -methylbenzenesulfonate; 18a) a method for producing arerendiazonium tosylate, characterized in that any one selected from the group consisting of.
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US5036142A (en) 1989-12-26 1991-07-30 Allied-Signal Inc. Process for making electro-optically active polymers
US5061404A (en) 1989-12-26 1991-10-29 Allied-Signal Inc. Electro-optical materials and light modulator devices containing same

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US5036142A (en) 1989-12-26 1991-07-30 Allied-Signal Inc. Process for making electro-optically active polymers
US5061404A (en) 1989-12-26 1991-10-29 Allied-Signal Inc. Electro-optical materials and light modulator devices containing same

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Title
Tetrahedron Letters. 2008, Vol.49, pp.1080-1082

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