CN102391199A - Preparation method of low-temperature bleaching catalyst ligand - Google Patents
Preparation method of low-temperature bleaching catalyst ligand Download PDFInfo
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- CN102391199A CN102391199A CN2011102764054A CN201110276405A CN102391199A CN 102391199 A CN102391199 A CN 102391199A CN 2011102764054 A CN2011102764054 A CN 2011102764054A CN 201110276405 A CN201110276405 A CN 201110276405A CN 102391199 A CN102391199 A CN 102391199A
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Abstract
The invention relates to a preparation method of a low-temperature bleaching catalyst ligand, which comprises the following steps of: dissolving a sulfonyl-contained diethylenetriamine into an organic solvent, then, adding an alkaline agent, further dropwise adding an organic solvent solution of sulfonylated glycol, cooling to room temperature after finishing reacting, pouring the reacted mixture solution into water, filtering, and carrying out recrystallization to obtain 1,4,7-trisulfonyl-1,4,7-triazacyclononane; and (2) stirring the 1,4,7-trisulfonyl-1,4,7-triazacyclononane in concentrated sulfuric acid at a temperature of 100-200 DEG C, adding alkali to neutralize after cooling, and then, preparing 1,4,7-trimethyl-1,4,7-triazacyclononane through adding formaldehyde and formic acid and refluxing. According to the preparation method provided by the invention, the operation is simple, the process route is short, the reacting raw materials are easy to get, the cost is low, the yield is high, and thus, the preparation method is applicable to industrial production.
Description
Technical field
The invention belongs to the preparation field of bleaching catalyst part, particularly a kind of preparation method of cold bleaching catalyst ligand.
Background technology
The fabric whiteness of hydrogen peroxide bleaching is pure, not yellowing, degradation production is pollution-free, equipment is not had corrosion and is applicable to multiple fiber bleachedly, since promoting, has obtained using widely at dyeing and finishing industry.But bleaching needs under nearly boiling temperature and strong alkaline condition, just can reach best effect usually, has shortcomings such as energy consumption is big, the fabric strength loss is serious.Therefore research and utilization has the catalyzer of high-efficiency catalytic activity, and fabric is carried out cold bleaching, has very important practical sense.
1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) manganese complex Mn
2(μ-O)
3(Me
3TACN)
2(PF
6)
2.XH
2O is one type of effective catalyst, and it can effectively be bleached textiles by the catalysis ydrogen peroxide 50 under low temperature (60～80 ℃) and low alkalinity (pH is 9～10.5) condition, and the fabric whiteness after the bleaching is high, and strength damage is little.The excellent performance of this catalyzer comes from its special ligand 1, and 4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN), still up to the present there is not a simple and economic preparation 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) method is applied thereby limited above-mentioned catalyzer, therefore, develops a rational preparation route and has very big economic benefit and social benefit.
Preparation 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) and the method for midbody by document [Stetter H, Roos E E, Chem.Ber., 1954,87 (4): 566～571; Stetter H, Mayer K H Chem.Ber., 1961,94 (6): 1410～1416; Richman J E, Atkins T J,, J.Am.Chem.Soc., 1974,96 (7): 2268～2270; Atkins T J, Richman J E, Org.Synth.; 1978,58,86～98] summarize below six steps: (1) diethylenetriamine and Tosyl chloride add sodium hydroxide and under room temperature, react 2～4h and make N in toluene; N ', N "-three p-toluenesulfonyl diethylenetriamines; (2) N, N ', N "-three p-toluenesulfonyl diethylenetriamines and sodium ethylate are in absolute ethanol, and reflux makes the disodium salt of three p-toluenesulfonyl diethylenetriamines under the nitrogen protection; (3) terepthaloyl moietie and Tosyl chloride are that alkaline agent stirring reaction 12～14h in ice-water bath makes two tosic acid glycol esters with the triethylamine in methylene dichloride; The disodium salt of (4) two tosic acid glycol esters and three p-toluenesulfonyl diethylenetriamines is heated to 90～100 ℃ of reaction 4～6h and makes 1,4 of cyclisation, 7-three p-toluenesulfonyls-1,4,7-7-triazacyclononane in inert solvent DMF under the nitrogen protection; (5) 1,4,7-three p-toluenesulfonyls-1,4,7-7-triazacyclononane after stirring 48～72h under 110～150 ℃, add alkaline agent and make 1,4, the 7-7-triazacyclononane in the vitriol oil; (6) 1,4,7-7-triazacyclononane and formaldehyde and formic acid get final ligand 1 at 90～120 ℃ of refluxed 24～48h through aftertreatment, and 4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN).It reacts as follows:
In this method, synthesizing 1,4,7-three p-toluenesulfonyls-1; 4, during the 7-7-triazacyclononane, need earlier three p-toluenesulfonyl diethylenetriamines to be prepared into corresponding disodium salt; The preparation of disodium salt is comparatively loaded down with trivial details and need nitrogen protection, and is wayward, can not directly carry out annulation by one kettle way.And at preparation 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) time, need elder generation by 1,4 usually, 7-three p-toluenesulfonyls-1; 4, the 7-7-triazacyclononane synthesizes 1,4,7-7-triazacyclononane or 1; 4,7-7-triazacyclononane tri hydrochloride, this procedure is loaded down with trivial details, inefficiency; And 1,4, the 7-7-triazacyclononane needs the secluding air sealing to preserve, and is wayward.In addition, above-mentioned synthetic 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) method synthetic route is long, and synthesis cycle is long, though the single step yield is higher, overall yield is lower, and needs in the building-up process to consume a large amount of organic solvents, and cost is higher, is not suitable in enormous quantities synthetic.
Summary of the invention
Problem to be solved by this invention provides a kind of preparation method of cold bleaching catalyst ligand, and this preparation method is simple to operate, and operational path is short, and reaction raw materials is easy to get, and cost is low, and productive rate is high, is fit to suitability for industrialized production.
The preparation method of a kind of cold bleaching catalyst ligand of the present invention comprises:
(1) will be dissolved in the diethylenetriamine of alkylsulfonyl in the organic solvent, and add alkaline agent then, and drip the organic solvent solution of the terepthaloyl moietie behind the sulfonylation again, and dropwise afterreaction 1～24h, temperature of reaction is 0～150 ℃, and reaction is cooled to room temperature after finishing; In reacted mixed solution impouring water, filter, recrystallization gets midbody 1,4,7-three alkylsulfonyls-1,4,7-7-triazacyclononane;
(2) with above-mentioned 1,4,7-three alkylsulfonyls-1,4; The 7-7-triazacyclononane stirs 10～100min deprotection base in 100～200 ℃ the vitriol oil, add the alkali neutralization after the cooling, adds the backflow of formaldehyde and formic acid then and makes 1,4; 7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN).
The diethylenetriamine of the band alkylsulfonyl in the said step (1) is N, N ', N "-three p-toluenesulfonyl diethylenetriamines.
Organic solvent in the said step (1) is N, N '-N, N, and N '-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, 2-Pyrrolidone, toluene, methylene dichloride or trichloromethane are preferably methylene dichloride or N, N '-N,N-DIMETHYLACETAMIDE.
Alkaline agent in the said step (1) is yellow soda ash, salt of wormwood, Quilonum Retard, cesium carbonate, sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, triethylamine or pyridine, is preferably salt of wormwood or yellow soda ash.
Alkaline agent in the said step (1) is 2 with the ratio of the amount of substance of the diethylenetriamine of alkylsulfonyl: 1-10: 1.
Terepthaloyl moietie behind the sulfonylation in the said step (1) is two tosic acid glycol esters.
The amount of substance ratio of the diethylenetriamine of the band alkylsulfonyl in the said step (1) and the terepthaloyl moietie of sulfonylation is 1: 1～1: 10, is preferably 1: 1～1: 3.
Temperature of reaction in the said step (1) is 30～150 ℃, and the reaction times is 9～12h.
1,4 of the middle gained of said step (2), 7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) be used for synthetic textiles cold bleaching catalyzer Mn
2(μ-O)
3(Me
3TACN)
2(PF
6)
2XH
2O.
Step (2) is by 1,4,7-three alkylsulfonyls-1,4, and 7-7-triazacyclononane one kettle way is synthetic 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN); One kettle way is synthetic to be meant: in same reaction vessel, need not to isolate intermediate product and direct synthetic ligands 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN), promptly need not by 1,4,7-three alkylsulfonyls-1,4, the 7-7-triazacyclononane makes 1,4 earlier, and the 7-7-triazacyclononane is separated it with the raw material as the introducing methyl separately again.
The part of gained is 1,4 shown in the formula (I), 7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN):
The preparing method's of cold bleaching catalyst ligand of the present invention reaction formula is following:
Wherein R is an alkylsulfonyl.
The present invention can directly prepare 1,4,7-three alkylsulfonyls-1,4 by the diethylenetriamine of band alkylsulfonyl and the terepthaloyl moietie generation annulation of sulfonylation; The 7-7-triazacyclononane, and directly by 1,4,7-three alkylsulfonyls-1; 4,7-7-triazacyclononane one kettle way short period of time in same reaction vessel can be prepared final ligand 1,4; 7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN).
Method provided by the invention begins from the initial raw material diethylenetriamine, also only needs for four steps just can prepare final ligand 1, and 4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN), saved preparation sulphonamide disodium salt and 1,4,7-7-triazacyclononane tri hydrochloride or 1,4, loaded down with trivial details and uppity committed steps such as 7-7-triazacyclononane have greatly reduced the reaction times, enhance productivity.In addition, method provided by the invention not only operational path is short, and reaction raw materials be easy to get, simple to operate, cost is low, productive rate is high, is fit to suitability for industrialized production.
Beneficial effect
(1) preparation method of the present invention is simple to operate, and operational path is short, and reaction raw materials is easy to get, and cost is low, and productive rate is high, is fit to suitability for industrialized production.
(2) ligand 1 of gained of the present invention, 4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) can be used for preparing cold bleaching catalyzer 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) manganese complex Mn
2(μ-O)
3(Me
3TACN)
2(PF
6)
2.XH
2O, this catalyzer is used for Cotton Fabric Low Temperature Bleaching, to the ecological, environmental protective of dyeing, energy-saving and cost-reducingly have a remarkable meaning.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) raw material N, N ', N " preparation of-three p-toluenesulfonyl diethylenetriamines
In the there-necked flask of 500mL, add the 4.2g diethylenetriamine, there-necked flask is placed ice-water bath, mechanical stirring.Other gets the 25.2g Tosyl chloride and 18.2g yellow soda ash is dissolved in respectively in 200mL acetone and the 150ml water, and constant pressure funnel is poured in gradation into, slowly splashes into there-necked flask simultaneously, and the dropping time is no less than 45min.After dripping, at room temperature stir 8～12h, suction filtration gets white solid matter, and water and ether washed twice are treated its dry back recrystallization in ethanol respectively, the final white solid powder 22.78g that gets, and productive rate is 91.5%, fusing point: 172～174 ℃.
(2) preparation of raw material two tosic acid glycol esters
Take by weighing 5g terepthaloyl moietie and be dissolved in the 50mL toluene, be cooled to 0 ℃ with ice-water bath after, under agitation slowly splash into simultaneously toluene (250mL) solution and the 20g triethylamine of 50g Tosyl chloride; At room temperature continue reaction 12h after dripping off, evaporate to dryness toluene, the white solid that obtains is with water washing three times; The absolute ethyl alcohol recrystallization; Get white crystal 20g, yield 68.7%, 119～120 ℃ of fusing points.
(3) 1,4,7-three p-toluenesulfonyls-1,4, the preparation of 7-7-triazacyclononane
Take by weighing 10.8gN, N ', N "-three p-toluenesulfonyl diethylenetriamines dissolve in the 250ml methylene dichloride, place there-necked flask, mechanical stirring, a colourless transparent solution.Add 3.95g salt of wormwood, 50 ℃ are stirred 1h down, get a yellow turbid solution.Other gets 14.2g two tosic acid glycol esters and is dissolved in the 150ml methylene dichloride, is added drop-wise to then in the above-mentioned mixed solution, drips off the back and continues reaction 9h down at 50 ℃.Obtain khaki color solution after having reacted, filter faint yellow solid with getting faint yellow emulsion in its impouring water, crossing, with getting white needle-like crystals 6.39g behind the ethyl alcohol recrystallization, productive rate is 56.6%.Fusing point: 216～218 ℃.
(4) 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) preparation
Get 4.3g1,4,7-three p-toluenesulfonyls-1,4; The 7-7-triazacyclononane adds the 10ml vitriol oil in the 100ml there-necked flask, 200 ℃ are stirred 20min down; After being cooled to room temperature, there-necked flask is placed ice-water bath, with among the NaOH with excessive sulfuric acid; Add 5.0ml formic acid solution and 5.0ml formaldehyde solution then, be placed on and be heated to 100 ℃ of backflows 24 hours in the oil bath, get a bright yellow solution.Reaction mixture is cooled off in ice bath, to pH＞12, add the 20ml normal hexane and stir the after-filtration in a moment with concentrated NaOH solution; And use the normal hexane washing leaching cake, and filtrating is told organic phase, and water is used n-hexane extraction; Merge organic phase, add anhydrous sodium sulfate drying, revolve to steam and remove normal hexane; A final faint yellow oily material 1.02g, the productive rate 82.2% of getting.
Embodiment 2
With the described N among the embodiment 1, N ', N "-three p-toluenesulfonyl diethylenetriamines and two tosic acid glycol esters are raw material, synthetic 1; 4,7-three p-toluenesulfonyls-1,4,7-7-triazacyclononane and 1; 4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN).
(1) 1,4,7-three p-toluenesulfonyls-1,4, the preparation of 7-7-triazacyclononane
Take by weighing 10.8g N, N ', N "-three p-toluenesulfonyl diethylenetriamines dissolve in the 200ml N-Methyl pyrrolidone, place there-necked flask, mechanical stirring, a colourless transparent solution.Add 4.62g salt of wormwood, 80 ℃ are stirred 45min down, get a yellow turbid solution.Other gets 7.07g two tosic acid glycol esters and is dissolved in the 100ml N-Methyl pyrrolidone, is added drop-wise to then in the above-mentioned mixed solution, drips off the back and continues reaction 6h down at 80 ℃.Obtain khaki color solution after having reacted, filter faint yellow solid with getting faint yellow emulsion in its impouring water, crossing, with getting white needle-like crystals 6.01g behind the ethyl alcohol recrystallization, productive rate is 53.3%.Fusing point: 217～218 ℃.
(2) 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) preparation
Get 4.3g1,4,7-three p-toluenesulfonyls-1,4; The 7-7-triazacyclononane adds the 15ml vitriol oil in the 100ml there-necked flask, 190 ℃ are stirred 30min down; After being cooled to room temperature, there-necked flask is placed ice-water bath, with among the NaOH with excessive sulfuric acid; Add 10ml formic acid solution and 10ml formaldehyde solution then, be placed on and be heated to 100 ℃ of backflows 16 hours in the oil bath, get a bright yellow solution.Reaction mixture is cooled off in ice bath, to pH＞12, add 30ml and stir the after-filtration in a moment with concentrated NaOH solution; And use the normal hexane washing leaching cake, and filtrating is told organic phase, and water is used n-hexane extraction; Merge organic phase, add anhydrous sodium sulfate drying, revolve to steam and remove normal hexane; A final faint yellow oily material 1.02g, the productive rate 88.6% of getting.
Embodiment 3
With the described N among the embodiment 1, N ', N "-three p-toluenesulfonyl diethylenetriamines and two tosic acid glycol esters are raw material, synthetic 1; 4,7-three p-toluenesulfonyls-1,4,7-7-triazacyclononane and 1; 4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN).
(1) 1,4,7-three p-toluenesulfonyls-1,4, the preparation of 7-7-triazacyclononane
Take by weighing 10.8g N, N ', N "-three p-toluenesulfonyl diethylenetriamines dissolve in the 200ml DMAC N,N, place there-necked flask, mechanical stirring, a colourless transparent solution.Add 8g salt of wormwood, 100 ℃ are stirred 30min down, get a yellow turbid solution.Other gets 21.2g two tosic acid glycol esters and is dissolved in the 200ml DMAC N,N, is added drop-wise to then in the above-mentioned mixed solution, drips off the back and continues reaction 8h down at 100 ℃.Obtain khaki color solution after having reacted, filter faint yellow solid with getting faint yellow emulsion in its impouring water, crossing, with getting white needle-like crystals 7g behind the ethyl alcohol recrystallization, productive rate is 62.1%.Fusing point: 217～218 ℃.
(2) 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) preparation
Get 8.6g 1,4,7-three p-toluenesulfonyls-1,4; The 7-7-triazacyclononane adds the 25ml vitriol oil in the 100ml there-necked flask, 180 ℃ are stirred 1h down; After being cooled to room temperature, there-necked flask is placed ice-water bath, with among the NaOH with excessive sulfuric acid; Add 15ml formic acid solution and 15ml formaldehyde solution then, be placed on and be heated to 100 ℃ of backflows 16 hours in the oil bath, get a bright yellow solution.Reaction mixture is cooled off in ice bath, to pH＞12, add the 50ml normal hexane and stir the after-filtration in a moment with concentrated NaOH solution; And use the normal hexane washing leaching cake, and filtrating is told organic phase, and water is used n-hexane extraction; Merge organic phase, add anhydrous sodium sulfate drying, revolve to steam and remove normal hexane; A final faint yellow oily material 2.1g, the productive rate 88.9% of getting.
Claims (10)
1. the preparation method of a cold bleaching catalyst ligand comprises:
(1) will be dissolved in the diethylenetriamine of alkylsulfonyl in the organic solvent, and add alkaline agent then, and drip the organic solvent solution of the terepthaloyl moietie behind the sulfonylation again, and dropwise, in 0～150 ℃ of temperature of reaction reaction 1～24h down, reaction is cooled to room temperature after finishing; In reacted mixed solution impouring water, filter, recrystallization gets midbody 1,4,7-three alkylsulfonyls-1,4,7-7-triazacyclononane;
(2) with above-mentioned 1,4,7-three alkylsulfonyls-1,4, the 7-7-triazacyclononane stirs 10～100min in 100～200 ℃ the vitriol oil, add the alkali neutralization after the cooling, adds the backflow of formaldehyde and formic acid then and makes 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane.
2. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1 is characterized in that: the diethylenetriamine of the band alkylsulfonyl in the said step (1) is N, N ', N "-three p-toluenesulfonyl diethylenetriamines.
3. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1; It is characterized in that: the organic solvent in the said step (1) is N; N '-N, N, N '-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, 2-Pyrrolidone, toluene, methylene dichloride or trichloromethane.
4. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1 is characterized in that: the alkaline agent in the said step (1) is yellow soda ash, salt of wormwood, Quilonum Retard, cesium carbonate, sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, triethylamine or pyridine.
5. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1 is characterized in that: the alkaline agent in the said step (1) is 2 with the ratio of the amount of substance of the diethylenetriamine of alkylsulfonyl: 1-10: 1.
6. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1 is characterized in that: the terepthaloyl moietie behind the sulfonylation in the said step (1) is two tosic acid glycol esters.
7. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1 is characterized in that: the amount of substance ratio of the diethylenetriamine of the band alkylsulfonyl in the said step (1) and the terepthaloyl moietie of sulfonylation is 1: 1～1: 10.
8. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1 is characterized in that: the amount of substance ratio of the diethylenetriamine of the band alkylsulfonyl in the said step (1) and the terepthaloyl moietie of sulfonylation is 1: 1～1: 3.
9. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1 is characterized in that: the temperature of reaction in the said step (1) is 30～150 ℃, and the reaction times is 9～12h.
10. the preparation method of a kind of cold bleaching catalyst ligand according to claim 1 is characterized in that: 1,4 of the middle gained of said step (2), 7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TACN) be used for synthetic textiles cold bleaching catalyzer Mn
2(μ-O)
3(Me
3TACN)
2(PF
6)
2XH
2O.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103232403A (en) * | 2013-05-09 | 2013-08-07 | 浙江凯普化工有限公司 | Preparation method of azacyclo |
| CN103360332A (en) * | 2013-07-29 | 2013-10-23 | 苏州天马精细化学品股份有限公司 | Preparation method of catalyst ligand for bleaching paper pulp and textile |
| CN104529922A (en) * | 2014-12-12 | 2015-04-22 | 沈阳感光化工研究院有限公司 | Preparation method of 1,4,7-triazacyclononane hydrochloride |
| CN113444055A (en) * | 2021-06-23 | 2021-09-28 | 仪征市海帆化工有限公司 | Synthesis method of 1, 4-bis (p-toluenesulfonyl) -7-benzoyl triazacyclononane |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232403A (en) * | 2013-05-09 | 2013-08-07 | 浙江凯普化工有限公司 | Preparation method of azacyclo |
| CN103232403B (en) * | 2013-05-09 | 2016-04-27 | 浙江凯普化工有限公司 | A kind of preparation method of nitrogen heterocyclic |
| CN103360332A (en) * | 2013-07-29 | 2013-10-23 | 苏州天马精细化学品股份有限公司 | Preparation method of catalyst ligand for bleaching paper pulp and textile |
| CN103360332B (en) * | 2013-07-29 | 2016-04-27 | 苏州天马精细化学品股份有限公司 | The preparation method of a kind of paper pulp, fabric bleaching catalyst ligand |
| CN104529922A (en) * | 2014-12-12 | 2015-04-22 | 沈阳感光化工研究院有限公司 | Preparation method of 1,4,7-triazacyclononane hydrochloride |
| CN113444055A (en) * | 2021-06-23 | 2021-09-28 | 仪征市海帆化工有限公司 | Synthesis method of 1, 4-bis (p-toluenesulfonyl) -7-benzoyl triazacyclononane |
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