KR20190001284A - Filter material for removing heavy metals and formaldehyde - Google Patents

Abstract

The present invention provides a filter having a function of removing heavy metal and formaldehyde, which includes, as an active component, one or more selected among trientine or a trientine derivative indicated as chemical formula 1, cyclene or a cyclene derivative indicated as chemical formula 2, and cyclam or a cyclam derivative indicated as chemical formula 3. In the chemical formulae: R_1, R_2, R_3, R_4, R_5, and R_6 are independently hydrogen, -R_7-COOH, or salt thereof; and R_7 is an aliphatic of C_1 to C_5, a substituted or non-substituted aromatic ring, or a heterocyclic six-membered or five-membered ring.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a filter for removing heavy metals and formaldehyde,

The present invention relates to a filter for effectively removing heavy metals and formaldehyde, and more particularly, to an air filter, a cigarette filter, and an air mask that can be used in various air conditioning systems such as home air cleaners for automobiles and air conditioners.

Today, the generation of fine dust due to air pollution is increasing day by day, and it is becoming an environmental problem. The use of air masks when going out for the purpose of blocking fine dust is now becoming commonplace, and various air cleaners large and small are sold for indoor air purification, ventilation systems equipped with various filters are introduced for the construction of houses such as apartments In fact.

The fine dust (PM ₁₀ ) has an average particle diameter of 10 μm or less and the ultrafine dust (PM _2.5 ) has an average particle diameter of 2.5 μm or less. It is a kind of dust that causes various skin diseases such as asthma, lung function, and various respiratory diseases such as dermatitis, It is known as a factor.

Fine dusts may vary depending on the area, environment, and season, but may include Hg, Pb, Cd, As, Cr, Cu, Ni, Zinc), Mn (manganese), Co (cobalt), and Sn (tin) are contained in a large amount of about 20%, causing various diseases.

In order to remove such fine dust and heavy metals, filters of various materials and specifications are developed and sold for the system. These filters are divided into filtration type, electrostatic type, collision adhesion type, adsorption type filter, dust type filter, dust type filter, dust type filter and gas removing filter according to dust collection type. Have been used.

The materials of the filter include paper filters, nonwoven filters, vinyl chloride filters, HEPA filters, and materials to which various adsorbents such as carbon, activated carbon, zeolite, silica gel, alumina and ferric oxide are added, In particular, the adsorption performance of heavy metals and formaldehyde, a primary carcinogen, is not yet satisfactory. The HEPA filter can remove fine dust of 0.3 μm or less depending on the grade, but it is expensive, and the adsorption performance of heavy metals and formaldehyde is still limited.

On the other hand, harmful heavy metals such as As (arsenic), cadmium (Cd) and Ni (nickel) are included in tobacco as well as fine dust, and they are introduced into the respiratory tract together with nicotine, It is known to cause the same disease. Common cigarettes include an Acetate Tow fiber tobacco filter to filter tar, nicotine, and carbon monoxide during smoking, and activated carbon or zeolite, which is a porous adsorbent, to enhance filter performance. However, such activated carbon and zeolite have some effect on the removal of nicotine and tar, but they do not have a great effect on adsorption removal of heavy metals, formaldehyde and the like.

The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an air filter material capable of effectively removing heavy metals and formaldehyde, and to provide an air filter material that can be used in various air conditioners such as air cleaners, air conditioners, The purpose is to provide air filter, cigarette filter, air mask.

In order to accomplish the above object, the present invention provides a process for producing a compound of formula (I), which comprises, as an active ingredient for removing heavy metals and formaldehyde, a trientine or trientine derivative represented by the following formula And a cyclic or cyclic derivative represented by the general formula (3).

[Chemical Formula 1]

(2)

(3)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, -R ₇ -COOH or a salt thereof, R ₇ is a C ₁ to C ₅ aliphatic, A substituted or unsubstituted aromatic ring, or a heterocyclic 6-atom or 5-membered ring.

The active ingredient is preferably selected from the group consisting of trienetine of the following general formula (1a), cyclane of the general formula (2a), cyclam of the general formula (3a) or salts thereof.

[Formula 1a]

(2a)

[Chemical Formula 3]

The triethyne derivative is preferably selected from compounds represented by the following formulas (1b) to (1d) or salts thereof.

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

(Wherein R ₈ and R ₉ are each independently hydrogen or a C ₁ -C ₄ alkyl group and X is oxygen (O), sulfur (S) or nitrogen (N).)

The cyclic derivatives are preferably selected from compounds represented by the following formulas (2b) to (2d) or salts thereof.

(2b)

[Chemical Formula 2c]

(2d)

(Wherein R ₈ and R ₉ are each independently hydrogen or a C ₁ -C ₄ alkyl group and X is oxygen (O), sulfur (S) or nitrogen (N).)

The cyclic derivative is preferably selected from compounds represented by the following formulas (3b) to (3d) or salts thereof.

(3b)

[Chemical Formula 3c]

(3d)

(Wherein R ₈ and R ₉ are each independently hydrogen or a C ₁ -C ₄ alkyl group and X is oxygen (O), sulfur (S) or nitrogen (N).)

The filter containing the active ingredient according to the present invention is excellent in the removal of heavy metals present in fine dust, and is excellent in an air filter, a cigarette filter, and an air filter which can be used in various air conditioners such as an air purifier, an air conditioner, And can be usefully used as a mask material.

In the present invention, the term " filter " includes an air filter that can be used in various air conditioners such as an air purifier, an air conditioner, and an air circulation system, as well as a filter for a cigarette filter and an air mask.

The present inventors have conducted various studies on heavy metal chelating agents in order to develop a filter material capable of effectively removing heavy metals and formaldehyde as a first-level carcinogen, and have found that trienetine, acycene, cyclam And derivatives thereof as a heavy metal and formaldehyde adsorbent of the filter, the present invention has been accomplished.

Trientine is represented by the following formula (1a) and is named Triethylenetetramine (TETA).

[Formula 1a]

Triethylenetetramine dihydrochloride has been shown to participate in the metabolism of copper in mouse experiments (FW Sunderman et al., Toxicol. Appl. Pharmacol . 38, 177 (1976)), pharmacologically, copper (JM Walshe, Prog. Clin. Biol . Res. 34, 271 (1979); RH Haslam et al., Dev. Pharmacol. Ther . 318 (1980)).

Cyclen is a generic name of 1,4,7,10-tetraazacyclododecane represented by the following formula (2a), which forms a chelate through coordination bond with gadolinium (Gd) and is used as a nuclear medicine contrast agent.

(2a)

Cyclam is a general name of 1,4,8,11-tetraazacyclotetradecane represented by the following formula (3a), and is used for nuclear medicine contrast agents and the like.

[Chemical Formula 3]

The chelating agents such as trienetine, cyclamen, and cyclam are widely known to be used for oral administration or vascular administration of copper or for pharmaceutical use as a contrast agent, but no studies have been reported on their use as filter materials.

The present inventors have found that trien- tine, acycene, and cyclam compounds are useful as filter components for removing heavy metals. As a filter material in the present invention, results of removing heavy metals in fine dust, skin irritation, and toxicity are disclosed. The trienetine, cyclamen and cyclam compounds are known to be harmful to the skin in the past. As a result of the experiments of the present invention, it has been found that the use of an effective amount for removing heavy metals on the skin results in no skin irritation or toxicity, .

On the other hand, it has been confirmed by the present invention that trien- tine, cyclane, cyclam and their derivative compounds are highly effective for the removal of formaldehyde as a primary carcinogen.

The present invention relates to a triene or triene derivative represented by the following general formula (1), a cyclane or a cyclene derivative represented by the following general formula (2), a cyclam or cyclam derivative represented by the general formula A filter having heavy metal and formaldehyde removing ability.

[Chemical Formula 1]

(2)

(3)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, -R ₇ -COOH or a salt thereof, R ₇ is a C ₁ to C ₅ aliphatic, A substituted or unsubstituted aromatic ring, or a heterocyclic 6-atom or 5-membered ring.

The air filter of the present invention is characterized in that it contains trientine, cyclane, cyclam or salts thereof as an effective ingredient for removing heavy metals and formaldehyde.

On the other hand, in the present invention, it has been confirmed that when a carboxyl group is introduced into the amine position of the trienetine, the cyclane and cyclam compounds to improve the degree of coordination of heavy metal, and the aromatic or heterocyclic group is introduced, skin irritation is remarkably reduced .

The trienetine derivatives, cyclic derivatives and cyclam derivatives according to the present invention are preferably selected from the compounds represented by the following formulas (1b) to (3d).

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

(2b)

[Chemical Formula 2c]

(2d)

(3b)

[Chemical Formula 3c]

(3d)

(Wherein R ₈ and R ₉ are each independently hydrogen or a C ₁ -C ₄ alkyl group and X is oxygen (O), sulfur (S) or nitrogen (N).)

The content of the trienetine or trientine derivative, cyclane or cyclane derivative, cyclam or cyclam derivative of the present invention can be changed depending on the use of the filter and the material thereof. The active ingredient of the present invention is not limited to the weight of the filter containing the active ingredient but may be contained in an amount of 0.001 to 5.0% by weight, preferably 0.1 to 3.0% by weight, more preferably 0.2 to 2.0% by weight.

The trienetine or trientine derivatives, cyclans or cyclane derivatives, cyclam or cyclam derivative compounds of the present invention can be used in the form of water-soluble salts. The compounds of the present invention include the hydrochloride salt, the sodium salt, and the potassium salt. More preferably, the compound of the present invention is in the form of a dihydrochloride salt or a tetrachloride salt. The preparation of the salt can be carried out by a known method.

The filter of the present invention can be produced by preparing the active ingredient in the form of an aqueous solution or a solution, impregnating the filter material with a conventionally used filter material, or spraying it with a spraying method followed by drying. The filter material of the present invention is generally used for filter materials to which various adsorbents such as paper filters, nonwoven filters, fiber filters, vinyl chloride filters, HEPA filters, carbon, activated carbon, zeolite, silica gel, alumina, Lt; / RTI > filter material.

The filter of the present invention can be used as a single filter and can be used as a composite filter in a form overlapped with other filter materials.

Hereinafter, the filter having the heavy metal and formaldehyde removing ability of the present invention will be described in detail through examples. However, the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention.

≪ Synthesis of trientine derivative >

Example 1: Preparation of 3,6,9,12-tetrakis (carboxymethyl) -3,6,9,12-tetraazatetradecanedioic acid (Formula 1e)

Triethylenetetramine (10.0 g) and acetonitrile (ACN) (400.0 ml) were added and stirred. 66.1 g of K ₂ CO ₃ and 78.8 g of ethyl bromoacetate were added. The mixture was heated and refluxed for 48 hours to terminate the reaction. After cooling to room temperature, the solid is discarded by filtration and the filtrate is concentrated in vacuo. Add 200 ml of methylene chloride (MC) and 300 ml of purified water to the concentrate, stir for 30 minutes, and separate into layers. The organic layer was treated with MgSO _4, concentrated in vacuo and then subjected to column purification using MC-MeOH to obtain 29.6 g of diethyl 3,6,9,12-tetrakis (2-ethoxy-2-oxoethyl) -3,6,9,12-tetraazatetradecanedioate . (Yield: 64.8%)

_{^{1 H NMR (CDCl 3):}} 4.16 (q, 8H), 4.14 (q, 4H), 3.57 (s, 8H), 3.44 (s, 4H), 2.85 (t, 4H), 2.78 (t, 4H), 2.74 (s, 4H), 1.27 (t, 12H), 1.26 (t, 6H)

29.6 g of the prepared diethyl 3,6,9,12-tetrakis (2-ethoxy-2-oxoethyl) -3,6,9,12-tetraazatetradecanedioate, 12.33 g of NaOH, 180 ml of MeOH and 120 ml of purified water, Lt; 0 > C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. Add 400 ml of MC to extract. The extracted organic layer was treated with MgSO ₄ to obtain 15.9 g of the title compound (Yield: 72.3.0%).

¹ H NMR (DMSO): 4.57 (s, 8H), 4.55 (s, 4H), 4.22 (s, 12H)

Example 2: Preparation of 4,4 ', 4 ", 4"' - (((ethane-1,2-diylbis ((4- carboxyphenyl) azanediyl) azanetriyl)) < / RTI > tetrabenzoic acid (1f)

10.0 g of triethylenetetramine, 108.1 g of ethyl 4-bromobenzoate, 46.0 g of t-BuONa and 600 ml of toluene are stirred and stirred. The temperature was raised to 35 ° C and 2.8 g of 50% (t-Bu) ₃ P toluene solution was added. After stirring for 30 minutes, the temperature was raised to 50 ° C. and 2.0 g of Pd (dba) 2 was added. . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was treated with MgSO _4, concentrated in vacuo and purified by MC-MeOH column to obtain tetraethyl 4,4 ', 4'',4''- (((ethane-1,2-diylbis (4- (ethoxycarbonyl) phenyl) azanediyl )) bis (ethane-2,1-diyl)) bis (azanetriyl)) tetrabenzoate. (Yield: 32.4%)

¹ H NMR (CDCl ₃ ): 7.82 (m, 4H), 7.71 (m, 8H), 7.25 (m, 8H) 3.45 ~ 3.18 (m, 12H), 1.27 (t, 12H), 1.26 (t, 6H)

bis (ethane-2,1-diyl) bis ((4-ethoxycarbonyl) phenyl) azethenyl) azanetriyl)) tetrabenzoate, 6.1 g of NaOH, 180 ml of MeOH and 140 ml of purified water were charged, the temperature was raised to 55 to 60 ° C and the reaction was terminated by stirring for 12 hours. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. 200 ml of MC is added to extract. The extracted organic layer was treated with MgSO ₄ to obtain 17.0 g of the title compound. (Yield: 89.0%).

¹ H NMR (DMSO): 7.80 (m, 4H), 7.68 (m, 8H)

Example 3: Synthesis of 5,5 '- ((2 - ((5-carboxypyridin-3-yl) 2-carboxypyridin-4-yl) amino) ethyl) amino) ethyl) amino) ethyl) azanediyl) dinicotinic acid (Formula 1g)

10.0 g of triethylenetetramine, 108.5 g of ethyl 5-bromonicotinate, 46.0 g of t-BuONa and 600 ml of xylene are added and stirred. The temperature was raised to 35 ° C and 2.8 g of 50% (t-Bu) ₃ P toluene solution was added. After stirring for 30 minutes, the temperature was raised to 50 ° C. and 2.0 g of Pd (dba) 2 was added. . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was treated with MgSO _4, concentrated in vacuo and purified by MC-MeOH column to obtain diethyl 5,5 '- ((2- ((5- (ethoxycarbonyl) pyridin- Pyridin-4-yl) amino) ethyl) amino) ethyl) amino) ethyl) azanediyl) dinicotinate . (Yield: 27.8%)

_{^{1 H NMR (CDCl 3):}} 8.92 (d, 4H), 8.85 (d, 2H), 8.45 (d, 4H), 8.43 (d, 2H), 7.89 (d, 4H), 7.76 (d, 2H), 12H), 1.26 (t, 6H), 4.23 (q, 8H), 4.15

pyridin-3-yl) (2 - ((5- (ethoxycarbonyl) pyridin-3-yl) (2- (5- (ethoxycarbonyl) pyridin- Amino) ethyl) azanediyl) dinicotinate, 5.3 g of NaOH, 160 ml of MeOH and 120 ml of purified water were charged, and the mixture was stirred at 55 to 60 ° C And the mixture was stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. Add 160 ml of MC to extract. The extracted organic layer was treated with MgSO ₄ to obtain 13.0 g of the title compound. (Yield: 78.4%).

^{1 H NMR (DMSO): 8.95} (d, 4H), 8.87 (d, 2H), 8.46 (d, 4H), 8.44 (d, 2H), 7.89 (d, 4H), 7.75 (d, 2H), 3.41 ~ 3.11 (m, 12H)

Example 4: Synthesis of 5,5 ', 5' ', 5 "' - (((ethane-1,2-diylbis (5-carboxyfuran- )) bis (azanetriyl)) tetrakis (furan-2-carboxylic acid)

10.0 g of triethylenetetramine, 103.3 g of ethyl 5-bromofuran-2-carboxylate, 46.0 g of t-BuONa and 600 ml of toluene are added and stirred. The temperature was raised to 35 ° C and 2.8 g of 50% (t-Bu) ₃ P toluene solution was added. After stirring for 30 minutes, the temperature was raised to 50 ° C. and 2.0 g of Pd (dba) 2 was added. . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was treated with MgSO _4, concentrated in vacuo and purified by MC-MeOH column to obtain tetraethyl 5,5 ', 5'',5''' - (((ethane-1,2-diylbis (5- (ethoxycarbonyl) furan- -yl) azanediyl) bis (ethane-2,1-diyl)) bis (azanetriyl)) tetrakis (furan-2-carboxylate). (Yield: 37.9%).

¹ H NMR (CDCl ₃ ): 7.42 (m, 12H), 4.31 (q, 8H), 4.28 (q, 4H), 3.65-3.15 )

(ethane-1,2-diylbis (5- (ethoxycarbonyl) furan-2-yl) azanediyl) bis (ethane-2,1-diyl )) bis (azanetriyl)) tetrakis (furan-2-carboxylate), 7.2 g of NaOH, 200 ml of MeOH and 150 ml of purified water were charged and the mixture was heated to 55 to 60 ° C and stirred for 12 hours. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. 200 ml of MC is added to extract. The extracted organic layer was treated with MgSO ₄ to obtain 15.0 g of the title compound. (Yield: 71.8%)

¹ H NMR (DMSO): 7.41 (m, 12H), 3.67-3.15 (m, 12H)

≪ Synthesis of cyclic derivatives &

Example 5: Preparation of 2,2 ', 2 ", 2' '- (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl) tetraacetic acid (Formula 2e)

10.0 g of Cyclen and 400.0 ml of acetonitrile are added and stirred, 40.1 g of K ₂ CO ₃ and 42.7 g of ethyl bromoacetate are added, and the mixture is heated to reflux for 40 hours to complete the reaction. After cooling to room temperature, the solid is discarded by filtration and the filtrate is concentrated in vacuo. Add 200 ml of MC and 300 ml of purified water to the concentrate, stir for 30 minutes, and separate. The organic layer was dried over MgSO _4, concentrated in vacuo and column-purified with MC-MeOH to give tetraethyl 2,2 ', 2'',2''' - (1,4,7,10-tetraazacyclododecane- tetrayl) tetraacetate (yield: 52.3%).

¹ H NMR (CDCl ₃ ): 4.19 (q, 8H), 3.19 (s, 8H), 2.48

15.7 g of tetraethyl 2,2 ', 2'',2''- (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl) tetraacetate, 5.6 g of NaOH, 95 ml of MeOH, The mixture was heated to 55 to 60 ° C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. 200 ml of MC is added to extract. The organic layer was extracted to give the title compound, 9.9g MgSO ₄ and treated. (Yield: 80.5%).

^{1 H NMR (DMSO): 3.88} (s, 8H), 3.23 (s, 16H)

Example 6: Preparation of 4,4 ', 4 ", 4"' - (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl) tetrabenzoic acid (2f)

Cyclen, 58.5 g of ethyl 4-bromobenzoate, 27.9 g of t-BuONa, and 400 ml of toluene are stirred. 2.4 g of 50% (t-Bu) ₃ P toluene solution was added to the mixture, and the mixture was stirred for 30 minutes. After heating to 50 ° C, 1.7 g of Pd (dba) 2 was added and the mixture was heated to reflux . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was dried over MgSO _4, concentrated in vacuo, and purified by MC-MeOH column to obtain tetraethyl 4,4 ', 4'',4''' - (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl ) tetrabenzoate. < / RTI > (Yield: 35.6%).

¹ H NMR (CDCl ₃ ): 7.81 (d, 8H), 6.98 (d, 8H), 4,15 (q, 8H)

15.8 g of tetraethyl 4,4 ', 4'',4''- (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl) tetrabenzoate, 3.8 g of NaOH, 130 ml of MeOH, The mixture was heated to 55 to 60 ° C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. Add 130 ml of MC to extract. The extracted organic layer was treated with MgSO ₄ to obtain 11.5 g of the title compound. (Yield: 85.2%).

¹ H NMR (DMSO): 7.82 (d, 8H), 6.97 (d, 8H), 3.45

Example 7: Preparation of 5,5 ', 5 ", 5"' - (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl) tetranicotinic acid (Formula 2g)

Cyclen, 58.7 g of ethyl 5-bromonicotinate, 27.9 g of t-BuONa, and 400 ml of xylene are added and stirred. 2.4 g of 50% (t-Bu) ₃ P toluene solution was added to the mixture, and the mixture was stirred for 30 minutes. After heating to 50 ° C, 1.7 g of Pd (dba) 2 was added and the mixture was heated to reflux . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was dried over MgSO _4, concentrated in vacuo and purified by MC-MeOH column to obtain tetraethyl 5,5 ', 5'',5''- (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl ) tetranicotinate. (Yield: 40.1%).

¹ H NMR (CDCl ₃ ): 8.95 (d, 4H), 8.46 (d, 4H), 7.83 , 12H)

17.9 g of tetraethyl 5,5 ', 5'',5''' - (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl) tetranicotinate, 4.3 g of NaOH, 150 ml of MeOH, The mixture was heated to 55 to 60 ° C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. Add 160 ml of MC to extract. The extracted organic layer was treated with MgSO ₄ to obtain 11.6 g of the title compound. (Yield: 75.6%).

¹ H NMR (DMSO): 8.96 (d, 4H), 8.44 (d, 4H), 7.84

Example 8: Synthesis of 5,5 ', 5 "', 5" '- (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl) tetrakis (furan- 2h)

Cyclen, 56.0 g of ethyl 5-bromofuran-2-carboxylate, 27.9 g of t-BuONa and 400 ml of toluene. 2.4 g of 50% (t-Bu) ₃ P toluene solution was added to the mixture, and the mixture was stirred for 30 minutes. After heating to 50 ° C, 1.7 g of Pd (dba) 2 was added and the mixture was heated to reflux . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was dried over MgSO _4, concentrated in vacuo and purified by MC-MeOH column to obtain tetraethyl 5,5 ', 5'',5''- (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl ) < / RTI > tetrakis (furan-2-carboxylate). (Yield: 30.0%).

¹ H NMR (CDCl ₃ ): 7.39 (d, 8H), 4,35 (q, 8H), 3.28

tetraethyl 5,5 ', 5''- (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl) tetrakis (furan-2-carboxylate) , MeOH (100 ml) and purified water (75 ml). The mixture was heated to 55 to 60 ° C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. Add 100 ml of MC to extract. The organic layer was extracted to give the title compound, 7.9g MgSO ₄ and treated. (Yield: 73.9%).

¹ H NMR (DMSO): 7.40 (d, 8H), 3.29 (s, 16H)

≪ Synthesis of cyclam derivative >

Example 9: Preparation of 2,2 ', 2 ", 2' '- (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl) tetraacetic acid (Formula 3e)

Cyclam (10.0 g) and acetonitrile (400.0 ml) were added and stirred, 34.5 g of K ₂ CO ₃ and 36.7 g of ethyl bromoacetate were added, and the mixture was heated to reflux for 40 hours to complete the reaction. After cooling to room temperature, the solid is discarded by filtration and the filtrate is concentrated in vacuo. Add 200 ml of MC and 300 ml of purified water to the concentrate, stir for 30 minutes, and separate. The organic layer was dried over MgSO _4, concentrated in vacuo and column-purified with MC-MeOH to give tetraethyl 2,2 ', 2'',2''' - (1,4,8,11-tetraazacyclotetradecane- tetrayl) tetraacetate. (Yield: 56.8%)

¹ H NMR (CDCl ₃ ): 4.12 (q, 8H), 3.36 (s, 8H), 2.69-2.73 (m, 16H)

15.4 g of tetraethyl 2,2 ', 2'',2''- (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl) tetraacetate, 5.2 g of NaOH, 90 ml of MeOH, The mixture was heated to 55 to 60 ° C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. 200 ml of MC is added to extract. The extracted organic layer was treated with MgSO ₄ to obtain 9.3 g of the title compound. (Yield: 75.9%).

¹ H NMR (D ₂ O): 3.51 (s, 8H), 3.14 (s, 8H)

Example 10: Preparation of 4,4 ', 4 ", 4"' - (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl) tetrabenzoic acid (Formula 3f)

Cyclam (10.0 g), ethyl 4-bromobenzoate (50.3 g), t-BuONa (24.0 g) and toluene (400 ml). The temperature was raised to 35 ° C and 2.0 g of 50% (t-Bu) ₃ P toluene solution was added. After stirring for 30 minutes, the temperature was raised to 50 ° C. and 1.5 g of Pd (dba) 2 was added. . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was dried over MgSO _4, concentrated in vacuo and purified by MC-MeOH column to obtain tetraethyl 4,4 ', 4'',4''' - (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl ) tetrabenzoate. < / RTI > (Yield: 31.0%).

¹ H NMR (CDCl ₃ ): 7.80 (d, 8H), 6.94 (d, 8H), 4.13 (q, 8H), 2.65-2.71 (t, 12H)

tetrabenzoate tetrabenzoate, 2.6 g of NaOH, 100 ml of MeOH, and 70 ml of purified water were added to a solution of 4,4 ', 4'',4''- (1,4,8,11-tetraazacyclotetradecane-1,4,8,11- The mixture was heated to 55 to 60 ° C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. Add 100 ml of MC to extract. The extracted organic layer was treated with MgSO ₄ to obtain 8.6 g of the title compound. (Yield: 81.2%).

¹ H NMR (DMSO): 7.83 (d, 8H), 6.95 (d, 8H), 2.63-2.73

Example 11: Preparation of 5,5 ', 5 ", 5"' - (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl) tetranicotinic acid (Formula 3g)

Cyclam (10.0 g), ethyl 5-bromonicotinate (50.3 g), t-BuONa (24.0 g) and xylene (400 ml). The temperature was raised to 35 ° C and 2.0 g of 50% (t-Bu) ₃ P toluene solution was added. After stirring for 30 minutes, the temperature was raised to 50 ° C. and 1.5 g of Pd (dba) 2 was added. . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was dried over MgSO _4, concentrated in vacuo and purified by MC-MeOH column to obtain tetraethyl 5,5 ', 5'',5''' - (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl ) tetranicotinate. (Yield: 27.8%)

¹ H NMR (CDCl ₃ ): 8.91 (d, 4H), 8.37 (d, 4H), 7.85 (m, 4 H), 1.24 (t, 12 H)

tetraethyl 5,5 ', 5'',5''- (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl) tetranicotinate, 2.6 g of NaOH, 90 ml of MeOH, The mixture was heated to 55 to 60 ° C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. Add 120 ml of MC to extract. The organic layer was extracted to give the title compound, 7.4g MgSO ₄ and treated. (Yield: 77.6%).

^{1 H NMR (DMSO): 8.93} (d, 4H), 8.38 (d, 4H), 7.85 (d, 4H), 2,67 ~ 2.66 (m, 16H), 1,72 (m, 4H)

Example 12: 5,5 ', 5 "' - (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl) tetrakis (furan-2-carboxylic acid) 3h)

Cyclam, 48.1 g of ethyl 5-bromofuran-2-carboxylate, 24.0 g of t-BuONa and 400 ml of toluene are stirred. The temperature was raised to 35 ° C and 2.0 g of 50% (t-Bu) ₃ P toluene solution was added. After stirring for 30 minutes, the temperature was raised to 50 ° C. and 1.5 g of Pd (dba) 2 was added. . After cooling to room temperature, 1000 ml of purified water is added, and the mixture is left to stand for 30 minutes to separate the layers, and the aqueous layer is discarded. The organic layer was dried over MgSO _4, concentrated in vacuo and purified by MC-MeOH column to obtain tetraethyl 5,5 ', 5'',5''' - (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl ) tetrakis (furan-2-carboxylate). (Yield: 37.5%).

¹ H NMR (CDCl ₃ ): 7.40 (d, 8H), 4.23 (q, 8H), 2.65-2.71 (m, 16H)

tetraethyl 5,5 ', 5''- (1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrayl) tetrakis (furan-2-carboxylate) , MeOH (110 ml) and purified water (85 ml). The mixture was heated to 55 to 60 ° C and stirred for 12 hours to terminate the reaction. Cool to 40 < 0 > C and concentrate in vacuo to remove the solvent, adjust the pH to 5-6 with 10% aqueous HCl and stir for 30 min. Add 120 ml of MC to extract. The extracted organic layer was treated with MgSO ₄ to obtain 9.4 g of the title compound (yield: 78.1%).

¹ H NMR (DMSO): 7.41 (d, 8H), 2.69-2.72 (m, 16H), 1.68 (m, 4H)

Example  13 to 27: Manufacture of air filter

Triene, cyclane, cyclam, and the trientine derivatives, cyclic derivatives and cyclam derivatives prepared in the above Examples 1 to 12 were prepared in a 1% aqueous solution and then commercially available 5T nonwoven fabric for air filters PET material) was cut into 10 cm * 10 cm, sprayed for 30 seconds in the aqueous solution, sufficiently wetted, and dried for 3 hours to prepare a filter containing the active ingredient according to the present invention.

The effective components of the air filter are shown in Table 1 below.

Air filter Active ingredient Example 13 Trientine Example 14 Example 1 Example 15 Example 2 Example 16 Example 3 Example 17 Example 4 Example 18 Cyclen Example 19 Example 5 Example 20 Example 6 Example 21 Example 7 Example 22 Example 8 Example 23 Cyclam Example 24 Example 9 Example 25 Example 10 Example 26 Example 11 Example 27 Example 12 Comparative Example 1 -

Experimental Example  1: Heavy metal of air filter Removability  exam

The prepared filters were placed in a closed space and a large amount of fine dust collected from the outside was put in. Then, the fans installed inside the filters were moved for one day so that fine dusts adhered to the filters, (Cu, Zn, Mn, Ni, Cd) of the fine dust water solution was measured using a total heavy metal test kit (WAK-Me ^™ , Kyoritsu Chemical-Check Lab. Respectively.

The total amount of heavy metals was measured by comparing the color of the aqueous solution with the standard color, and the results are shown in Table 2.

(Yellow) 0 ppm 0.2 ppm 0.5 ppm 1.0 ppm 2.0 ppm? 5 ppm (red)

filter Active ingredient Total amount of heavy metals (Cu, Zn, Mn, Ni, Cd) (ppm) Example 13 Trientine ≤5 (red) Example 14 Example 1 ≤ 5 Example 15 Example 2 ≤ 5 Example 16 Example 3 ≤ 5 Example 17 Example 4 ≤ 5 Example 18 Cyclen ≤ 5 Example 19 Example 5 ≤ 5 Example 20 Example 6 ≤ 5 Example 21 Example 7 ≤ 5 Example 22 Example 8 ≤ 5 Example 23 Cyclam ≤ 5 Example 24 Example 9 ≤ 5 Example 25 Example 10 ≤ 5 Example 26 Example 11 ≤ 5 Example 27 Example 12 ≤ 5 Comparative Example 1 - 2.0

As shown in Table 2, the total amount of heavy metals contained in the filter according to the present invention was 5 ppm or more (≤5) in the filter of Comparative Example 1 which did not contain the active ingredient of the present invention, It can be seen that the filters according to the present invention have a remarkable ability to adsorb harmful heavy metals.

Experimental Example  2: Skin irritation test of active ingredient

A total of 20 subjects, 20 men and 10 women in their 20s and 30s, underwent a primary skin irritation test using the patch method according to the CTFA guidelines (The Cosmetic, Toiletry & Fragrance Association, Inc., Washington, DC, Respectively.

First, a filter paper disk for a chamber was placed in a 8-mm diameter, 10-panel pin chamber, 20 ㎕ each of the composition for a skin according to Experimental Example 1 was dropped, naturally dried for 10 minutes, Respectively.

After 24 hours, the pin chamber was removed, and skin changes were observed with the naked eye. The skin irritation degree and the judgment grade were calculated according to the following formula (2), and the results are shown in the following Table 3.

[Criteria for skin irritation]

(-): No erythema or particularly no symptoms; (+ Slightly redder than ±; (+): markedly redder than surrounding; (++): more reddened and swollen than surrounding.

[Skin irritation judgment level]

Stimulation 0 to 0.1: Grade I (unstimulated range); 0.11-0.3: grade II (light stimulus range); 0.31-0.5: grade III (moderate stimulus range); 0.51 or higher: Grade IV (range of strong stimulus)

sample Judgment result (person) Irritation degree Rating Active ingredient Content (% by weight) (-) (± (+) (++) Trientine 0.1% 20 0 0 0 0 I 0.5% 19 One 0 0 0.05 I 1.0% 17 3 0 0 0.15 II Example 1 0.1% 20 0 0 0 0 I 0.5% 19 One 0 0 0.05 I 1.0% 16 4 0 0 0.20 II Example 2 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 19 One 0 0 0.05 I Example 3 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 19 One 0 0 0.05 I Example 4 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 19 One 0 0 0.05 I Cyclen 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 18 One One 0 0.15 II Example 5 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 19 One 0 0 0.05 I Example 6 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 19 One 0 0 0.05 I Example 7 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 20 0 0 0 0 I Example 8 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 18 2 0 0 0.10 I Cyclam 0.1% 20 0 0 0 0 I 0.5% 19 One 0 0 0.05 I 1.0% 17 3 0 0 0.15 II Example 9 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 18 2 0 0 0.10 I Example 10 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 19 One 0 0 0.05 I Example 11 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 18 2 0 0 0.10 I Example 12 0.1% 20 0 0 0 0 I 0.5% 20 0 0 0 0 I 1.0% 19 One 0 0 0.05 I Comparative Example 1
(EDTA) 0.1% 20 2 0 0 0.10 I 0.5% 17 2 One 0 0.20 II 1.0% 15 3 2 0 0.35 III

As shown in Table 3, the heavy metal chelating compound according to the present invention showed grade I in a non-stimulated range up to a concentration of 0.5 wt% in a human skin irritation test. In the concentration range of 1.0 wt% Tin, cyclane, and cyclam showed grade II (light stimulus range) while all of these aromatics and heterocyclic derivatives showed grade I, indicating reduced skin irritation. On the other hand, the EDTA of Comparative Example 1 was judged to be grade III (moderate irritation range) at a concentration of 1.0 wt%, indicating that the skin irritancy is higher than that of the compound of the present invention. Therefore, it can be seen that the filter according to the present invention is harmless to the human body and can be used for a cigarette filter, an air mask or the like.

Example  28 to 42: Preparation of a tobacco filter

Trienetine, cyclane, cyclam and the trientine derivatives, cyclic derivatives and cyclam derivatives prepared in Examples 1 to 12 were prepared in aqueous solutions of 0.5%, 1.0% and 2.0%, respectively, And the lower 1/4 portion of the cigarette filter was immersed in the aqueous solution for 4 seconds to allow the active ingredient of the present invention to be appropriately impregnated into the filter and then dried for 1 hour to prepare a cigarette filter containing the active ingredient of the present invention .

The active ingredients of the tobacco filter are shown in Table 4 below.

filter Active ingredient Example 28 Trientine Example 29 Example 1 Example 30 Example 2 Example 31 Example 3 Example 32 Example 4 Example 33 Cyclen Example 34 Example 5 Example 35 Example 6 Example 36 Example 7 Example 37 Example 8 Example 38 Cyclam Example 39 Example 9 Example 40 Example 10 Example 41 Example 11 Example 42 Example 12 Comparative Example 2 -

Experimental Example  3: Heavy metals of tobacco filter Removability

Four cigarettes of the same effective ingredient were prepared as one sample of filter cigarettes containing the active ingredient prepared in Example 2, fixed to a suction device set in a similar condition to actual smoking, then fired, and then the suction device was operated Smoking was performed.

The smoked tobacco filters were collected and placed in 100 ml of methanol for each sample (4 quadrants). After cooling for 60 minutes with ultrasonic shaking, the mixture was cooled to room temperature and methanol was added to make 100 ml. To prepare a sample solution.

The prepared sample solution was analyzed for heavy metal components using an inductively coupled plasma mass spectrometer (ICP-MS, Xseries ^™ 2, Thermo Fisher Scientific, UK).

The measured mass (m / z) of arsenic (As) in ICP-MS was 75, the values of cadmium (Cd) were 114 and nickel (Ni) 60 were measured and the heavy metal adsorption rate Are shown in Table 1.

sample Arsenic (As) Cadmium (Cd) Nickel (Ni) Active ingredient content Adsorption amount
(ppm) Adsorption rate
(%) Adsorption amount
(ppm) Adsorption rate
(%) Adsorption amount
(ppm) Adsorption rate
(%) Trientine 0.5% 46 200% 79 176% 102 155% 1.0% 53 230% 84 187% 125 189% 2.0% 62 270% 96 213% 131 198% Example 1 0.5% 43 187% 77 171% 89 135% 1.0% 48 209% 79 176% 101 153% 2.0% 63 274% 84 187% 122 185% Example 2 0.5% 44 191% 75 167% 94 142% 1.0% 48 209% 84 187% 98 148% 2.0% 58 252% 93 207% 103 156% Example 3 0.5% 48 209% 75 167% 89 135% .0% 53 230% 81 180% 102 155% .0% 63 274% 86 191% 126 191% Example 4 0.5% 47 204% 67 149% 91 138% 1.0% 56 243% 75 167% 98 148% 2.0% 61 265% 80 178% 104 158% Cyclen 0.5% 39 170% 65 144% 89 135% 1.0% 43 187% 78 173% 93 141% 2.0% 56 243% 82 182% 98 148% Example 5 0.5% 41 178% 59 131% 83 126% 1.0% 46 200% 66 147% 88 133% 2.0% 51 222% 70 156% 89 135% Example 6 0.5% 40 174% 61 136% 79 120% 1.0% 41 178% 68 151% 83 126% 2.0% 46 200% 73 162% 87 132% Example 7 0.5% 39 170% 64 142% 92 139% 1.0% 46 200% 71 158% 97 147% 2.0% 55 239% 78 173% 102 155% Example 8 0.5% 37 161% 58 129% 86 130% 1.0% 48 209% 61 136% 91 138% 2.0% 49 213% 70 156% 99 150% Cyclam 0.5% 37 161% 60 133% 79 120% 1.0% 41 178% 71 158% 86 130% 2.0% 56 243% 78 173% 89 135% Example 9 0.5% 41 178% 61 136% 76 115% 1.0% 46 200% 63 140% 85 129% 2.0% 45 196% 70 156% 96 145% Example 10 0.5% 36 157% 58 129% 81 123% 1.0% 39 170% 63 140% 89 135% 2.0% 51 222% 71 158% 94 142% Example 11 0.5% 37 161% 59 131% 79 120% 1.0% 45 196% 63 140% 90 136% 2.0% 51 222% 70 156% 89 135% Example 12 0.5% 34 148% 58 129% 77 117% 1.0% 39 170% 67 149% 85 129% 2.0% 43 187% 72 160% 89 135% Control 1 - 23 45 66

As shown in Table 5, the adsorption rate of arsenic (Pb) of the tobacco filter containing the heavy metal chelating compound according to the present invention was about 148-274% and the adsorption rate of cadmium (Cd) 213% and nickel (Ni) adsorption rate was 117 ~ 191%. As the content of active ingredient increased, the adsorption rate of heavy metal was significantly increased.

This means that the tobacco filter containing the active ingredient according to the present invention has a remarkably excellent heavy metal removal ability as compared with the active ingredient-free tobacco filter.

Experimental Example  4: formaldehyde Removability  exam

Purified water was added to a 35.0% formaldehyde solution to prepare a 2.0% formaldehyde diluted solution. To the diluted solution, trientine, cyclane, cyclam, and derivative compounds of the present invention corresponding to 3 molar equivalents were added, and the amount of formaldehyde change was analyzed by GC analysis while stirring at room temperature .

The content of formaldehyde was measured under the following analysis conditions, and the contents of formaldehyde after the initial, 30 minutes, and 180 minutes were shown in Table 6.

<GC analysis conditions>

 - Detector: Flame ionization detector

 Column: ZB-1 (0.32 mm x 30 m, 3.00 m) or a similar column.

 - Headspace conditions: equilibrium temperature 60 캜, equilibration time 10 min, transfer line temperature 65 캜

 - Column temperature: keep at 50 ° C for the first 5 minutes, then increase the temperature to 200 ° C by 30 ° C per minute and maintain at 200 ° C for 10 minutes.

 - Specimen inlet temperature: constant temperature around 140 ℃.

 - Detector temperature: constant temperature around 250 ℃.

 - Carrier gas: nitrogen

 - Split ratio: about 1:20

 - Flow rate: 2.5 mL / min

 - Injection amount: 5 uL of the test solution is injected into the vial with microcirrins. Before and after the milling, keep it according to the head space conditions and inject 1 mL of the vapor phase into the column.

 - Analysis time: 20 minutes

Active ingredient Area (mAU * min) Initial 30 minutes 180 minutes Trientine 0.305 0.168 0 Example 1 0.305 0.170 0 Example 2 0.305 0.168 0 Example 3 0.305 0.171 0 Example 4 0.305 0.173 0 Cyclen 0.305 0.181 0 Example 5 0.305 0.179 0 Example 6 0.305 0.183 0 Example 7 0.305 0.181 0 Example 8 0.305 0.168 0 Cyclam 0.305 0.172 0 Example 9 0.305 0.182 0 Example 10 0.305 0.171 0 Example 11 0.305 0.174 0 Example 12 0.305 0.170 0

As shown in Table 6, GC analysis showed that the formaldehyde was reduced by 40 to 45% in 30 minutes after the addition of the compound of the present invention, but was completely undetected after 180 minutes. This means that the active ingredient of the present invention adsorbs effectively with formaldehyde, and that the composition for cleaning households according to the present invention can be effectively used for removing formaldehyde, which is a causative substance of shedding syndrome.

Claims (13)

A triene or triene derivative represented by the following general formula (1), a cyclane or a cyclene derivative represented by the following general formula (2), a cyclam or a cyclam derivative represented by the general formula (3) , Heavy metals and formaldehyde.
[Chemical Formula 1]

(2)

(3)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, -R ₇ -COOH or a salt thereof, R ₇ is a C ₁ to C ₅ aliphatic, A substituted or unsubstituted aromatic ring, or a heterocyclic 6-atom or 5-membered ring.
The method according to claim 1,
Wherein the active ingredient is selected from the group consisting of trienes of the following general formula (1a), cyclans of the general formula (2a), cyclam of the general formula (3a) or salts thereof.
[Formula 1a]

(2a)

[Chemical Formula 3]

The method according to claim 1,
Wherein the trienetine derivative is selected from the group consisting of compounds represented by the following formulas (1b) to (1d) or salts thereof: a heavy metal and a formaldehyde-removing filter.
[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

(Wherein R ₈ and R ₉ are each independently hydrogen or a C ₁ -C ₄ alkyl group and X is oxygen (O), sulfur (S) or nitrogen (N).)
The method according to claim 1,
Wherein the cyclic derivative is selected from the group consisting of compounds represented by the following formulas (2b) to (2d) or salts thereof.
(2b)

[Chemical Formula 2c]

(2d)

(Wherein R ₈ and R ₉ are each independently hydrogen or a C ₁ -C ₄ alkyl group and X is oxygen (O), sulfur (S) or nitrogen (N).)
The method according to claim 1,
Wherein the cyclic derivative is selected from the group consisting of compounds represented by the following formulas (3b) to (3d) or salts thereof: (1) a heavy metal and a formaldehyde-removing filter.
(3b)

[Chemical Formula 3c]

(3d)

(Wherein R ₈ and R ₉ are each independently hydrogen or a C ₁ -C ₄ alkyl group and X is oxygen (O), sulfur (S) or nitrogen (N).)
The method according to claim 1,
Wherein the trientine derivative is selected from compounds represented by the following formulas (1e) to (1h) or salts thereof.
[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

The method according to claim 1,
Wherein the cyclic derivative is selected from the group consisting of compounds represented by the following formulas (2e) to (2h) or salts thereof.
[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

The method according to claim 1,
Wherein the cyclic derivative is selected from the group consisting of compounds represented by the following formulas (3e) to (3h) or salts thereof.
[Formula 3e]

(3f)

[Formula 3g]

[Chemical Formula 3h]

9. The method according to any one of claims 1 to 8,
Characterized in that said trienetine or trienetine derivative, cyclane or cyclene derivative, cyclam or cyclam derivative component is contained in an amount of 0.001 to 5.0% by weight, based on the total weight of the filter, of heavy metal and formaldehyde filter.
The method according to claim 1,
Wherein the filter is used as an air-cleaning filter, an air-conditioner filter, a filter having heavy metal and formaldehyde removing ability.
The method according to claim 1,
Wherein the filter is used as a cigarette filter, the filter having heavy metal and formaldehyde removal ability.
A filter cigarette comprising the cigarette filter of claim 10.
A mask comprising the filter according to claim 1.