2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine

• CAS: 3584-23-4
• Catalog Number: ACM3584234-2
• Category: Main Products
• Molecular Weight: 421.9g/mol
• Molecular Formula: C12H7Cl6N3O
• Synonyms: 3,6-Triazine,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1
• IUPAC Name: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine
• Canonical SMILES: COC1=CC=C(C=C1)C2=NC(=NC(=N2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl
• InChI: InChI=1S/C12H7Cl6N3O/c1-22-7-4-2-6(3-5-7)8-19-9(11(13,14)15)21-10(20-8)12(16,17)18/h2-5H,1H3
• InChI Key: QRHHZFRCJDAUNA-UHFFFAOYSA-N
• Appearance: Slightly pale yellow to Yellow; solid
• Complexity: 345
• Covalently-Bonded Unit Count: 1
• EC Number: 222-711-7
• Exact Mass: 420.869078g/mol
• Formal Charge: 0
• H-Bond Acceptor: 4
• H-Bond Donor: 0
• Heavy Atom Count: 22
• Monoisotopic Mass: 418.872028g/mol
• Rotatable Bond Count: 2
• XLogP3: 4.9

Case Study

2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine for efficient 3D printing

Zhao, Xiaoyu, et al. Nature Communications 12.1 (2021): 2873.

An efficient 3D printing method via photooxidation based on photopolymerization of ketocoumarins (e.g., KCD) was proposed and demonstrated, which achieved high printing speed (5.1 cm h) and high printing resolution (23 μm). The printing speed is much faster than the state-of-the-art 3D printing method using common bottom-up DLP 3D printers without compromising printing resolution. The light energy efficiency is also 12 times higher than that of conventional systems containing non-reactive light absorbers. Mechanistically, the generated free radicals lead to rapid photopolymerization, enabling facile 3D printing, while deethylated KCD limits light penetration, thereby improving printing resolution. In contrast, when KCD encounters photoreduction, the printing resolution drops dramatically because the increased light transmittance of the printed polymer parts leads to increased lateral photopolymerization. The ketocoumarin photooxidation-based 3D printing method proposed here paves the way for efficient additive manufacturing by controlling the photoreaction of photosensitizers during photopolymerization.
Efficient 3D printing was achieved by photooxidation based on ketocoumarin photopolymerization. For proof of concept, commercially available KCD was used as a photosensitizer. KCD exhibits high intersystem crossing (ISC) efficiency up to 92% and maximum molar extinction coefficient (ε) up to 8.8 × 10L mol cmat 458 nm, both of which are conducive to efficient photoreaction of KCD with co-initiators under visible light irradiation. The photooxidation of KCD by 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine (TA) is expected to occur in the presence of water, resulting in initiating radicals and deethylated products. TA˙ functions to initiate rapid photopolymerization for facile 3D printing, while KCD_2 is a promising photosensitive molecule due to its high photocatalytic activity in the visible wavelength region (ε = 4.3 × 10L molcmat 448 nm). First, the photooxidation products of KCD by TA were identified. It is noteworthy that although the ketocoumarin/triazine system and other ketocoumarin- or triazine-based systems have been shown to effectively mediate visible light photopolymerization, the relevant mechanisms and products during the photoreaction process have not been fully disclosed, thus hindering the development of efficient 3D printing. According to the electron transfer free energy (-0.14 eV) calculated using the Rehm-Weller equation, the photooxidation of KCD by TA is thermodynamically favored under visible light irradiation. Mechanistically, KCD may undergo two oxidations when reacting with TA under visible light irradiation, which is supported by transient absorption spectroscopy and density functional theory calculations. Among them, TA is first reduced by accepting one electron from excited KCD. Subsequently, the C-Cl bond undergoes isolytic cleavage to generate TA˙ radicals, which is demonstrated by electron paramagnetic resonance spectroscopy in the presence of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as a radical stabilizer. The detected free radical showed a g value of 2.0062 and two hyperfine coupling constants of 20.1 G (H3) and 13.5 G (N2), which are highly consistent with previous reports. In addition, the generated KCD_2 was separated and identified by 1 H and 13 C nuclear magnetic resonance (NMR) spectroscopy and high-performance liquid chromatography-high-resolution mass spectrometry. In addition, the generated acetaldehyde (CH2CHO) was identified using gas chromatography-mass spectrometry.

2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine in 3D printing

B. Metral, A. Bischoff, C. Ley, A. Ibrahim, X. Allonas, ChemPhotoChem 2019, 3, 1109.

A novel three-component photoinitiator system based on safranin O, tetraphenylborate as a co-initiator and 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine as a redox additive. Laser flash photolysis studies demonstrated the photocycling behavior of the system as well as the ability to form initiating free radicals. RT-FTIR photopolymerization experiments using diacrylate monomers showed surprisingly good reactivity of the three-component system, while the corresponding two-component system had very low reactivity. Analysis at different light intensities allowed to fully characterize the response of the resin to irradiation and propose a predictive empirical model. Then, experiments on curing depth at different irradiations were performed and Jacobs parameters were determined. It was found that the critical energy (Ec) and penetration depth (Dp) were almost constant regardless of the irradiation. On the other hand, when SFHis increased, both Ec and Dp decreased due to the dual effects of SFH as a photoinitiator and a light absorber. In addition, the model was used to calculate the time corresponding to Ec, i.e. the critical time, and the conversion (Conv) at Ec for each intensity.
Curing depth experiments. Each formulation was placed on a glass plate that held up to 1 cm high resin to reproduce 3D printing conditions. A different point of each plate was then illuminated with a 530nm LED connected to an LED driver, forming a 1x1cm square. The setup was such that the incident light from the LED passed through an aperture controlled by an electronic shutter controller, allowing fine control of the exposure time. The light was reflected by a mirror below the plate. As a result, the resin at the bottom of the glass was illuminated, mimicking the 3D printing process. For a given irradiance, each square had a different exposure time, producing a different thickness. The process was repeated at different light intensities by placing a filter of the desired optical density between the shutter and the mirror. After exposure, the excess monomer was carefully removed with ethanol. The film thickness was then measured with a profilometer. The measurements are made with a 2mm focal length color probe at a speed of approximately 5500μm/s with a resolution of 10μm in X and 150-200μm in Y. The glass and film regions of interest are manually selected in the processing software, providing more accurate values than conventional micrometer averaging measurements.

Custom Q&A

What is the molecular formula of the keyword?

The molecular formula of the keyword is C12H7Cl6N3O.

What is the molecular weight of the keyword?

The molecular weight of the keyword is 421.9 g/mol.

What is the IUPAC name of the keyword?

The IUPAC name of the keyword is 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

What is the CAS number of the keyword?

The CAS number of the keyword is 3584-23-4.

What is the InChIKey of the keyword?

The InChIKey of the keyword is QRHHZFRCJDAUNA-UHFFFAOYSA-N.

How many hydrogen bond donor counts does the keyword have?

The keyword has 0 hydrogen bond donor counts.

How many hydrogen bond acceptor counts does the keyword have?

The keyword has 4 hydrogen bond acceptor counts.

How many rotatable bond counts does the keyword have?

The keyword has 2 rotatable bond counts.

What is the topological polar surface area of the keyword?

The topological polar surface area of the keyword is 47.9Ų.

How many heavy atom counts does the keyword have?

The keyword has 22 heavy atom counts.