175854-39-4

Basic information

• Product Name: 1,4,7-tris-Boc-1,4,7,10-tetraaza-cyclododecane
• Synonyms: 1,4,7-tris-Boc-1,4,7,10-tetraaza-cyclododecane;1,4,7-Tri-Boc-1,4,7,10-tetraazacyclododecane;Tri-tert-butyl 1,4,7,10-tetraazacyclotetradecane-1,4,7-tricarboxylate;N,N',N''-tris-Boc-cyclen;1,4,7,10-Tetraazacyclododecane-1,4,7-tricarboxylic acid, tris(1,1-diMethylethyl) ester;TriBoc-Cyclen;Tri-tert-Butyl 1,4,7,10-tetraazacyclododecane-1,4,7-tricarboxylate;1,4,7,10-Tetraazacyclododecane-1,4,7-tricarboxylic acid, 1,4,7-tris(1,1-dimethylethyl) ester
• CAS NO: 175854-39-4
• Molecular Formula: C₂₃H₄₄N₄O₆
• Molecular Weight: 472.63
• Mol File: 175854-39-4.mol
• Article Data: 44

Chemical Properties

• Melting Point: 72-73℃
• Boiling Point: 541.1°Cat760mmHg
• Flash Point: 281°C
• Appearance: /
• Density: 1.065
• Vapor Pressure: 9E-12mmHg at 25°C
• Refractive Index: 1.513
• Storage Temp.: 2-8°C
• PKA: 9.52±0.20(Predicted)
• Sensitive: Hygroscopic
• CAS DataBase Reference: 1,4,7-tris-Boc-1,4,7,10-tetraaza-cyclododecane(CAS DataBase Reference)
• NIST Chemistry Reference: 1,4,7-tris-Boc-1,4,7,10-tetraaza-cyclododecane(175854-39-4)
• EPA Substance Registry System: 1,4,7-tris-Boc-1,4,7,10-tetraaza-cyclododecane(175854-39-4)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26
• WGK Germany: 3
• Hazardous Substances Data: 175854-39-4(Hazardous Substances Data)

Usage

Chemical Properties

White powder

Uses

Building block used to attach the Cyclen azacrown to a molecular scaffold, building block for a trifold cyclen Zn complex as phosphate dianion receptor in aqueous solution

InChI:InChI=1/C23H44N4O6/c1-21(2,3)18(28)33-27-13-11-24-10-12-25(19(29)31-22(4,5)6)14-15-26(16-17-27)20(30)32-23(7,8)9/h24H,10-17H2,1-9H3

Upstream product

• 24424-99-5 di-tert-butyl dicarbonate 
• 294-90-6 1,4,7,10-tetraazacyclododecan 
• 10045-25-7 1,4,7,10-tetraazacyclododecane tetrahydrochloride 
• 52667-88-6 cyclen tetratosylate 
• 188903-14-2 1-benzyloxycarbonyl-4,7,10-tris-tert-butoxycarbonyl-1,4,7,10-tetraazacyclododecane 

Downstream Products

• 188903-14-2 1-benzyloxycarbonyl-4,7,10-tris-tert-butoxycarbonyl-1,4,7,10-tetraazacyclododecane 
• 133587-10-7 1,1'-<1,3-phenylenebis(methylene)>bis<1,4,7,10-tetraazacyclododecane> 
• 257280-68-5 1-bromomethyl-4-(4,7,10-tris(tert-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane-1-ylmethyl)benzene 
• 390362-13-7 1,3-bis(1,4,7-tris[tert-butyloxycarbonyl]-1,4,7,10-tetraaza-cyclododecan-1-yl)-4,6-dinitro-benzene 
• 849238-63-7 1-((4-bromophenyl)methylcarbamoylmethyl)-4,7,10-tris(tret-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane 
• 25070-74-0 1-benzyloxycarbonylpyrrolidine 
• 957829-63-9 10-(6-benzyloxycarbonylamino-hexyl)-1,4,7,10-tetraaza-cyclododecane-1,4,7-tricarboxylic acid tri-tert-butyl ester 
• 960054-47-1 1-(2-mesitylenesulfonylaminoethyl)-4,7,10-tris(tert-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane 
• 1198150-49-0 1-(N-benzyloxycarbonyl-2-pyrrolidinecarbonyl)-4,7,10-tris(tert-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane 
• 1206885-01-9 1-[8-(benzenesulfonyloxy)-5,7-bis(N,N-dimethylaminosulfonyl)quinolin-2-ylmethyl]-4,7,10-tris(tert-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane 

Relevant articles and documents

Fuel-Selective Transient Activation of Nanosystems for Signal Generation

The transient activation of function using chemical fuels is common in nature, but much less in synthetic systems. Progress towards the development of systems with a complexity similar to that of natural ones requires chemical fuel selectivity. Here, we show that a self-assembled nanosystem, composed of monolayer-protected gold nanoparticles and a fluorogenic peptide, is activated for transient signal generation only in case the chemical fuel matches the recognition site present at the nanoparticle surface. A modification of the recognition site in the nanosystem completely changes the chemical fuel selectivity. When two nanosystems are simultaneously present, the selectivity expressed by the system depends on the concentration of nucleotide added.

Dinuclear macrocyclic polyamine zinc(II) complexes linked with flexible spacers: Synthesis, characterization, and DNA cleavage

Dinuclear macrocyclic polyamine zinc(II) complexes, which have two cyclen groups linked by flexible spacers, have been synthesized as DNA cleavage agents. The structures of these new dinuclear complexes are consistent with the data obtained from elemental analysis, MS and 1H NMR spectroscopy. The catalytic activity of these dinuclear complexes on DNA cleavage was studied. The results showed that the dinuclear zinc(II) complexes can catalyze the cleavage of supercoiled DNA (pUC 19 plasmid DNA) (Form I) under physiological conditions to produce selectively nicked DNA (Form II).

Synthesis of calix[4]arene-cyclen conjugates

Novel calix[4]arene derivatives constrained in the cone or 1,3-alternate conformations, bearing one or two cyclen (1,4,7,10-tetraazacyclododecane) moieties directly connected to the upper rim, have been synthesized using Buchwald-Hartwig coupling reaction. The complexation ability and hydrolytic activities of selected Zn(II) complexes of these calixarenes were studied. Although the attempts to hydrolyze activated phosphodiester bonds were unsuccessful, the NMR titration experiments revealed binding affinity for chloride, acetate, and benzoate anions in defined stoichiometry.

Vesicles and micelles from amphiphilic Zinc(II)-cyclen complexes as highly potent promoters of hydrolytic DNA cleavage

Phosphate esters are essential to any living organism and their specific hydrolysis plays an important role in many metabolic processes. As phosphodiester bonds can be extraordinary stable, as in DNA, great effort has been put into mimicking the active sites of hydrolytic enzymes which can easily cleave these linkages and were often found to contain one or more coordinated metal ions. With this in mind, we report micellar and vesicular Zn(II)-cyclen complexes which considerably promote the hydrolytic cleavage of native DNA and the activated model substrate bis(4-nitrophenyl)phosphate (BNPP). They are formed by self-assembly from amphiphilic derivatives of previously employed complexes in aqueous solution and therefore allow a simple and rapid connection of multiple active metal sites without great synthetic effort. Considering the hydrolytic cleavage of BNPP at 25 °C and pH 8, the micellar and vesicular metal catalysts show an increase of second-order rate constants (k2) by 4-7 orders of magnitude compared to the unimolecular complexes under identical conditions. At neutral pH, they produce the highest k2 values reported so far. For pBR322 plasmid DNA, both a conversion of the supercoiled to the relaxed and linear form, and also a further degradation into smaller fragments by double strand cleavages could be observed after incubation with the vesicular Zn(II)-complexes. Finally, even the cleavage of nonactivated single-stranded oligonucleotides could be considerably promoted compared to background reaction.

Coordination chemistry of a mono-dibenzofuran derivative of 1,4,7,10-tetraazacyclododecane

Copper(II) and cadmium(II) complex of a mono-dibenzofuran derivative of 1,4,7,10-tetraazacyclododecane (cyclen), L1, have been prepared by reaction of the mono-dibenzofuran-substituted cyclen with either copper(II) or cadmium(II) perchlorate in acetonitrile. This yielded the corresponding divalent metal complexes, [Cu(L1)](ClO4)2·H2O (C1) and [Cd(L1)](ClO4)2·H2O (C2), which were isolated as single crystals suitable for X-ray crystallography by diffusing diethyl ether into an acetonitrile solution of each complex. For the copper(II) complex, C1, the X-ray crystal structure revealed a distorted square pyramidal Cu(II) coordination sphere occupied by four amine nitrogens from the cyclen ring and one oxygen from the amide linkage present in L1. On the other hand, the metal center in the cadmium complex is seven coordinate, with two weakly bound acetonitrile molecules occupying two additional coordination sites about the Cd(II) center; these bind cis to the amide oxygen. The coordination geometry is best described as monocapped trigonal prismatic. In both complexes, the secondary amine nitrogens on the cyclen macrocycle form hydrogen bonds with perchlorate counterions present in the crystal lattice. Titration of L1 with various metal ions (Mn2+, Co2+, Ni2+, Cu2+, Zn2+, and Cd2+) in acetonitrile revealed a gradual quenching of the benzofuran emission with increasing [M2+] consistent with formation of metal complexes with a 1: 1 M2+: L1 stoichiometry. From the emission data, the conditional stability constant was determined to be 10-20 times higher for the Cu(II) complex than the other divalent metal complexes investigated.

Cooperative self-assembly of adenosine and uridine nucleotides on a 2D synthetic template

(Figure Presented) Double plane: Base pairing mediates sterically induced, cooperative self-assembly of complementary nucleotides on a template formed from amphiphilic bis(ZnII-cyclen) derivatives ordered on thiolated surface. Real-time monitoring of binding events proved precise harboring of equal amounts of A and U nucleotides from their arbitrary combinations in solution into planar bilayers (see picture).

Cu(II)-Based Paramagnetic Probe to Study RNA-Protein Interactions by NMR

Paramagnetic NMR techniques allow for studying three-dimensional structures of RNA-protein complexes. In particular, paramagnetic relaxation enhancement (PRE) data can provide valuable information about long-range distances between different structural components. For PRE NMR experiments, oligonucleotides are typically spin-labeled using nitroxide reagents. The current work describes an alternative approach involving a Cu(II) cyclen-based probe that can be covalently attached to an RNA strand in the vicinity of the protein's binding site using "click" chemistry. The approach has been applied to study binding of HIV-1 nucleocapsid protein 7 (NCp7) to a model RNA pentanucleotide, 5′-ACGCU-3′. Coordination of the paramagnetic metal to glutamic acid residue of NCp7 reduced flexibility of the probe, thus simplifying interpretation of the PRE data. NMR experiments showed attenuation of signal intensities from protein residues localized in proximity to the paramagnetic probe as the result of RNA-protein interactions. The extent of the attenuation was related to the probe's proximity allowing us to construct the protein's contact surface map.

Design, Synthesis, and Biological Evaluation of Boron-Containing Macrocyclic Polyamines and Their Zinc(II) Complexes for Boron Neutron Capture Therapy

Boron neutron capture therapy (BNCT) is a binary therapeutic method for cancer treatment based on the use of a combination of a cancer-specific drug containing boron-10 (10B) and thermal neutron irradiation. For successful BNCT,10B-containing molecules need to accumulate specifically in cancer cells, because destructive effect of the generated heavy particles is limited basically to boron-containing cells. Herein, we report on the design and synthesis of boron compounds that are functionalized with 9-, 12-, and 15-membered macrocyclic polyamines and their Zn2+complexes. Their cytotoxicity, intracellular uptake activity into cancer cells and normal cells, and BNCT effect are also reported. The experimental data suggest that mono- and/or diprotonated forms of metal-free [12]aneN4- and [15]aneN5-type ligands are uptaken into cancer cells, and their complexes with intracellular metals such as Zn2+would induce cell death upon thermal neutron irradiation, possibly via interactions with DNA.

Catalytic Hydrolysis of Phosphate Monoester by Supramolecular Phosphatases Formed from a Monoalkylated Dizinc(II) Complex, Cyclic Diimide Units, and Copper(II) in Two-Phase Solvent System

Design and synthesis of enzyme mimic with programmed molecular interaction among several building blocks including metal complexes and metal chelators is of intellectual and practical significance. The preparation of artificial enzymes that mimic the natu