Cyclen synthesis

7synthesis methods

Product Name:Cyclen
CAS Number:294-90-6
Molecular formula:C8H20N4
Molecular Weight:172.27

Some syntheses exploit the Thorpe-Ingold effect to facilitate ring-formation. Illustrative is the reaction of the deprotonated tosylamides with ditosylates:
TsN(CH2CH2NTsNa)2 + TsN(CH2CH2OTs)2 → (TsNCH2CH2)4
The resulting macrocycle can be deprotected with strong acid. Base gives the tetramine.
High dilution conditions result in a low reaction rate penalty and this disadvantage is removed in an alternative procedure starting from triethylenetetraamine and dithiooxamide to a bisamidine – also a bis(imidazoline) – followed by reduction and ring expansion with DIBAL.
Synthesis of Cyclen

In one study cyclen is covalently bonded through a propylene molecular spacer to adenine and chelated with zinc diperchlorate. This complex is able to selectively bind uracil and uridine in a 1:2 ratio both through the adenine part and cyclen part of the molecule as evidenced by mass spectrometry.
wiki/Cyclen

1,4,7,10-TETRAAZACYCLODODECANE TETRAHYDROCHLORIDE

10045-25-7
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294-90-6
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$5.00/1g

Yield:294-90-6 95%

Reaction Conditions:

with hydrogenchloride

Steps:

1-10 1,4,7-tetraazacyclododecane

Dowex TM 1 × 8 200-400 mesh strong basic type I anion exchange resin (Cl type) was placed in a 300 mL beaker and dissolved in 1 M HCl.After filtering this with Nutche, the obtained filtrate was dissolved in distilled water and poured into a chromatographic tube filled with cotton and sea sand.After adding 1 M HCl until the pH of the droplet became 1, the pH was adjusted to 5 with distilled water. Then add 1 M NaOH until the pH reaches 12 and thenThe pH was adjusted to 7 using distilled water. A solution prepared by dissolving 1,4,7,10-tetraazacyclododecane tetrahydrochloride (1.50 g, 4.72 mmol) in the smallest amount of distilled water was put therein, and droplets having a basic pH were collected.This solution is concentrated on a rotary evaporator andVacuum drying gave a yellow solid. Dissolve this in CHCl3, add Na2SO4 to dehydrate it, filter it with Nutche, wash it with a small amount of CHCl3, collect the filtrate, and concentrate it with a rotary evaporator.Vacuum dried and left in the refrigerator to give a yellow solid(0.772 g, Yield 95%).

References:

JP2021/42186,2021,A Location in patent:Paragraph 0058-0059