- Conformational Studies by Dynamic NMR. 35. Structure, Conformation, and Stereodynamics of Hindered Naphthylamines
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The low-temperature 1H and 13C NMR spectra of a number of N-ethyl- and of N-isopropyl-N-alkyl-1-naphthylamines allowed the measurement of the interconversion barriers between the two twisted enantiomeric conformers.The free energyes of activation increased substantially with the dimension of the N-alkyl groups (e.g., δG**173 is 8.3 Kcal mol-1 when N-alkyl is a methyl group, and δG**373 is 19.85 Kcal mol-1 when N-alkyl is a tert-butyl group in N-ethyl-N-alkyl-1-naphthylamines).Nuclear Overhauser enhancement (NOE) experiments confirmed that these molecules adopt a twist conformation and indicated that in N-methyl as well as in N-ethyl-N-isopropyl-1-naphthylamines the N-isopropyl moiety is closer to H-8 than to H-2.Thes results, obtained in solution, were confirmed by the X-ray investigation of an analogous derivative in the solid state.On the other hand, the less hindered secundary 1-naphthylamines turned out to be planar in solution (NOE experiments) as well as in the solid state (X-ray diffraction).Finally it was found that electron-releasing (e.g., -NH2) and electron attracting (e.g., -NO2) substitunets in position 4 increase and reduce, respectively, the interconversion barriers of the twisted tertiary 1-naphthylamines.As expected this trend is opposite to that reported in the case of planar N-methylanilines containing analogous substituents in position 4.
- Casarini, D.,Foresti, E.,Lunazzi, L.,Macciantelli, D.
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- Development of dimeric triarylmethine derivatives with improved thermal and photo stability for color filters
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Five novel triarymethine derivatives containing a two chromophore moiety within the molecule have been designed, synthesized and investigated as potential color filter dyes. These new “dimer-type” triarylmethines showed increased photostability and thermal stability compared to the Victoria Blue BO unit and notably manipulation of the dye counter ion also led to increased thermal stability. To evaluate the dyes in color filters, filters were fabricated and the photo- and thermo-stability was determined after heat treatment (230 °C for 30 min). The fabricated color filters showed approximately 80% transmittance at 450 nm and the ΔEab values were in the range 3.03–9.26. These results indicate that the synthesized dimer-type triarylmethine derivatives have the potential for application as color filters for blue dyes.
- Kong, Nam Sik,Jung, Hyocheol,Kim, Beomjin,Lee, Chan Kyu,Kong, Hoyoul,Jun, Kun,Kim, Jin Chul,Noh, Seung Man,Cheong, In Woo,Park, Jongwook,Park, Young IL
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- Dimer-type triarylmethane dye compounds, blue resin composition comprising the same for color filter and color filter using the same
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The present invention relates to a blue dye compound for a color filter, and more particularly, to a novel dimer-type triarylmethane dye compound having enhanced solubility, high heat resistance, high light resistance and high brightness compared to a conventional dye, and to a blue resin composition for a color filter comprising the same and a color filter using the same. When the dimer type triarylmethane dye compound according to the present invention is used in the blue resin composition for a color filter, a dye compound which has excellent solubility in propylene glycol monomethyl ether acetate (PGMEA) used as a solvent in a process and which has high heat resistance and high brightness can be provided. Therefore, a color filter with high brightness and a high contrast ratio compared to the conventional pigment type color filter can be manufactured through the manufacture of color filters using the same.(AA) Compound 6(BB) Compound 7(CC) Compound 8(DD) Compound 9(EE) Compound 10(FF) Compound 11(GG) Compound 12COPYRIGHT KIPO 2018
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Paragraph 0070-0074
(2018/05/03)
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- Synthesis of Arylamines via Aminium Radicals
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Arylamines constitute the core structure of many therapeutic agents, agrochemicals, and organic materials. The development of methods for the efficient and selective construction of these structural motifs from simple building blocks is desirable but stil
- Svejstrup, Thomas D.,Ruffoni, Alessandro,Juliá, Fabio,Aubert, Valentin M.,Leonori, Daniele
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supporting information
p. 14948 - 14952
(2017/11/20)
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- Direct N-alkylation of aromatic amines using a microflow reactor: Enhancement of selectivity and reactivity
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A simple and highly atom-economical method for the direct N-alkylation of aromatic amines by using a microflow reactor was developed to overcome the problem of over-alkylation. In the developed method, high-yield conversion (up to 100%) was achieved in a relatively short reaction time. The ratio of mono- to di-benzylated products (3.57:1) was higher than that achieved with batch reactions conducted in a 1 L scale flask (0.87:1). The structural features of the microflow reactor meant that short-chain alkyl halides could be converted into products with high reactivity and selectivity under superheating conditions, although their boiling point was much lower than the reaction temperature. This method was successfully applied to the synthesis of a range of secondary amines including an intermediate of indobufen synthesis.
- Choi, Yong-Sung,Kim, Yoon-Jung,Shen, Liu-Lan,Lee, Yong Sup,Jeong, Jin-Hyun
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supporting information
p. 970 - 974
(2015/04/27)
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- CuI/DMPAO-catalyzed N-arylation of acyclic secondary amines
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DMPAO has been found to be a powerful ligand to enable copper-catalyzed coupling of aryl halides with aliphatic acyclic secondary amines take place under relatively mild conditions, and coupling of aryl halides with primary amines and cyclic secondary amines proceeds at low catalyst loading.
- Zhang, Yu,Yang, Xinye,Yao, Qizheng,Ma, Dawei
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supporting information; experimental part
p. 3056 - 3059
(2012/07/28)
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- peri-interactions in naphthalenes, 10 [1]. In search of independent criteria for N→P bonding: Protonation studies on (8-diethylamino-naphth-1-yl)-diphenyl-phosphine
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Enhancement of the basicity of the amino group in (8-dialkylamino-naphth-1-yl)-diphenylphosphines diverts protonation from the P to the N atom. Thus the cation 8-Et2N+(H)-C 10H6-PPh2 becomes available whose 1H and 31P NMR spectra provide arguments against dative N→P interactions in the phosphines and their quaternary phosphonium salts. Likewise, the X-ray structure of 8-Et2N-C10H6-PPh 2 does not indicate such interactions.
- Schiemenz, Günter Paulus,N?ther, Christian,P?rksen, Simon
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p. 663 - 671
(2007/10/03)
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- Hydrogen-bonding-induced electron transfer from triplet N,N-dialkyl-1-naphthylamines to benzophenone via triplet exciplexes
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Laser flash photolysis studies at 355-nm on the photoreactions of the benzophenone (BP) and N,N-dialkyl-1-naphthylamine, DANA (N,N-dimethyl-1-naphthylamine, DMNA, and N,N-diethyl-1-naphthylamine, DENA) system have been carried out with and without H2O and methanol in acetonitrile (ACN) at 295 K. In the nanosecond time scale, triplet energy transfer from triplet BP (3BP*) to DANA occurs with the efficiency φTET (0.74 for DMNA and 0.61 for DENA) regardless of the presence of H2O and methanol. After the formation of triplet DANA (3DANA*), the triplet exciplex 3(DANA...BP)* with weak charge-transfer character is produced with the equilibrium constant K1 (10 M-1 for DMNA and 9 M-1 for DENA) between 3DANA* and BP. The mechanism for the formation of 3(DANA...BP)* is shown in Scheme 1. In the presence of H2O and methanol, it is found that the intraexciplex electron transfer takes place to give the BP anion (BP?-) and DANA cation (DANA?+) radicals in the hydrogen-bonded triplet exciplex 3(DANA...BP)*HB by H2O or methanol. The mechanism for the production of DANA?+ and BP?- is proposed in Scheme 2. The equilibrium constants K2 for the formation of 3(DANA...BP)*HB with H2O and methanol obtained are 0.55 and 0.45 M-1 for DMNA, 0.50 and 0.40 M-1 for DENA. The rate constants ket for the intraexciplex electron transfer induced by hydrogen bonding are determined to be 2.5 × 107 s-1 for DMNA and 1.4 × 107 s-1 for DENA. It was revealed that the driving force for intraexciplex electron transfer is the negatively enlarged reduction potential of BP in 3(DANA...BP)*HB due to the hydrogen bonding to the carbonyl group of BP in 3(DANA... BP)*.
- Kiyota, Tatsuya,Yamaji, Minoru,Shizuka, Haruo
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p. 672 - 679
(2007/10/03)
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- Photosubstitution of 1-Methoxy-4-nitronaphthalene with Amine Nucleophiles: Dual Pathways
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The photosubstitution of 1-methoxy-4-nitronaphthalene (MNN) with amines has been investigated by a combination of continuous and time-resolved experiments.Primary amines cause replacement of the nitro group, while secondary amines displace the methoxy substituent.Both reactions involve attack of the amine upon the triplet excited state of MNN.Spectroscopic evidence for the radical anion MNN*- has been obtained; the yield of this species depends upon the structure of the amine in the order RNH2*-, but that the reaction with primary amines is most probably an example of an SN2 Ar* process.The results for MNN and related compounds are discussed in the context of the orientation rules proposed by Mutai et al.
- Bunce, Nigel J.,Cater, Stephen R.,Scaiano, J. C.,Johnston, Linda J.
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p. 4214 - 4223
(2007/10/02)
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