KR20100037289A - Preparation method of arenediazonium tosylate - Google Patents

Abstract

PURPOSE: An arenediazonium tosylate is provided to be stably stored without explosion in a solid state for a long time, to show high reactivity in a typical reaction of a diazonium salt. CONSTITUTION: A method for preparing arenediazonium tosylate represented by chemical formula 1: Ar-N_2^+ · TsO^- or chemical formula 2: +N_2-Ar-CH_2-Ar-N_2^+ · TsO^- using a diazotizing agent supported with a resin comprises the steps of: preparing a diazotizing agent supported with a resin; diazotizing an aminoarene compound using the diazotizing agent in the presence of toluene sulfonic acids; and precipitating the product by removing the resin through filtration and adding ether.

Description

Preparation method of arendiazonium tosylate {Preparation method of arenediazonium tosylate}

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.

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.

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.

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.

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.

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.

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.

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.

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-N ₂ ⁺ · TsO ^-

^{_{+ N 2 -Ar-CH 2 -Ar}} -N 2 + · TsO -

In Chemical Formula 1 and Chemical Formula 2,

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,

Wherein any substituent is selected from halo, alkyl, alkoxy, haloalkoxy, alkoxyalkyl, cyano, nitro, amino, alkylamino, carboxy, alkoxycarbonyl or hydroxy.

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.

The resin used in the diazotizing agent supported by the resin of the present invention is any one selected from porous tetraalkylammonium hydroxide or porous tetraalkylammonium halide, preferably porous tetramethylammonium hydroxide, porous tetraethylammonium hydroxide Side, porous tetrapropylammonium hydroxide, porous tetrabutylammonium hydroxide, porous tetramethylammonium chloride, porous tetraethylammonium chloride, porous tetrapropylammonium chloride or porous tetrabutylammonium chloride.

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.

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. .

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.

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.

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).

Hereinafter, the present invention will be described in more detail.

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.

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.

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.

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.

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.

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.

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.

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 present invention. Can be given.

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.

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.

Examples 1 to 18 Preparation of Arendiazonium Salts

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.

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.

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.

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

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

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.

Examples 19 to 36 Synthesis of Other Compounds Using Arendiazonium Salts

4-iodoaniline

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-Bromobenzonitrile

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-Dinitrobenzene

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. Synthesis of Other Compounds

A total of 11 other compounds in Table 2 were also synthesized in the same manner as above.

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

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.)].

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. ( E ) -4-nitrostilbene (( E ) -4-Nitrostilbene; 20]

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)].

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. ( E ) -2-styrylbenzoic acid [( E ) -2-Styrylbenzoic acid; 21] and ( E ) -4-styryl benzoic acid [( E ) -4-styrylbenzoic acid; 22]

( 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 : 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 : 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.

Experimental Example 1 Thermal Stability Review and Crystal Structure Analysis

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.

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.

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 : 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 : 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 : 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.

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)

Method for producing an arenadiazonium tosylate represented by the following formula (1) or formula (2) using a diazolating agent supported by a resin: [Formula 1] Ar-N ₂ ⁺ · TsO ^- [Formula 2] ^{_{+ N 2 -Ar-CH 2 -Ar}} -N 2 + · TsO - In Chemical Formula 1 and Chemical Formula 2, 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, Wherein any substituent is selected from halo, alkyl, alkoxy, haloalkoxy, alkoxyalkyl, cyano, nitro, amino, alkylamino, carboxy, alkoxycarbonyl or hydroxy. The method of claim 1, wherein the manufacturing method 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 Method for producing an arenadiazonium tosylate, characterized in that comprising a. The method of claim 1 or 2, wherein the resin is any one selected from porous tetraalkylammonium hydroxides and porous tetraalkylammonium halides. The method of claim 1 or 2, wherein the diazotizing is performed by using one selected from acetic acid or C1 to C4 alcohol as a solvent. The method of claim 1 or 2, wherein the diazotizing is performed for 5 to 60 minutes at room temperature. The method of claim 1 or 2, wherein the diazotizing step comprises reacting 1 to 8 equivalents of the resin-supported diazotizing agent and 1 to 8 equivalents of toluenesulfonic acid with respect to 1 equivalent of aminoarene. A method for producing arendiazonium tosylate. The method of claim 1 or 2, wherein the arenadiazonium tosylate is Benzenediazonium 4-methylbenzenesulfonate (1a), 2-methylbenzenediazonium 4-methylbenzenesulfonate (2- Methylbenzenediazonium 4-methylbenzenesulfonate; 2a), 3-methylbenzenediazonium 4-methylbenzenesulfonate (3-a), 4-methylbenzenediazonium 4-methylbenzenesulfonate (4-Methylbenzenediazonium 4-methylbenzenesulfonate 4a), 3,4-dimethylbenzenediazonium 4-methylbenzenesulfonate (5a), 2-methoxybenzenediazonium 4-methylbenzenesulfonate (2-Methoxybenzenediazonium 4- methylbenzenesulfonate; 6a), 4-methoxybenzenediazonium 4-methylbenzenesulfonate; 4-aminobenzenediazonium 4-methylbenzenesulfonate; 4-aminobenzenediazonium 4-methylbenzenesulfonate; 8a ), 2-knit 2-Nitrobenzenediazonium 4-methylbenzenesulfonate (9a), 3-nitrobenzenediazonium 4-methylbenzenesulfonate (10a), 4-nitrobenzenediazonium 4 4-Methylbenzenesulfonate (4-nitrobenzenediazonium 4-methylbenzenesulfonate; 11a), 4-cyanobenzenediazonium 4-methylbenzenesulfonate (4-cyanobenzenediazonium 4-methylbenzenesulfonate; 12a), 2-carboxybenzenediazonium 4-methylbenzene Sulfonates (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) A method for producing an arenadiazonium tosylate, characterized in that any one selected from the group consisting of. .

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