21161-11-5Relevant articles and documents
3,3′-Diiodobinaphthol and 3,3′-Diiodobiphenol Derivatives as Hypervalent Iodine Organocatalysts for the α-Oxytosylation of Ketones
Brenet, Simon,Minozzi, Clémentine,Clarens, Bastien,Amiri, Lilia,Berthiol, Florian
, p. 3859 - 3873 (2015)
New series of enantiopure 3,3′-diiodobinaphthol- and 3,3′-diiodobiphenol-based molecules have been synthesized and used as chiral hypervalent iodine oxidation organocatalysts in the α-oxytosylation of propiophenone. When we compared these new organocatalysts to our previous series of 3,3′-diiodo-1,1′-binaphthalene-2,2′-diol-fused maleimides, we have made two important observations: the maleimide moiety is the best moiety for obtaining moderate enantioselectivities, and the presence of an aliphatic substituent on the biaryl part of the catalyst enhances the enantioselectivity.
Photodegradable bridged silane and preparation method thereof
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Paragraph 0065-0067; 0072-0076; 0080-0084; 0088-0092; 0096, (2020/12/29)
The invention relates to photodegradable bridged silane and a preparation method thereof. The photodegradable bridged silane has a structure as shown in a formula I which is described in the specification. The method comprises the following steps: taking 1, 3-dimethyl-2-nitrobenzene as a raw material, carrying out oxidation reaction to obtain 2-nitro 1, 3-phthalic acid, carrying out reduction reaction on a carboxylic acid group to obtain 2-nitro-1, 3-benzenedimethanol, carrying out acylation reaction on the 2-nitro-1, 3-benzenedimethanol and chloroacetyl chloride to obtain 2-nitro-1, 3-benzenedichloroacetate, and finally carrying out substitution reaction on the 2-nitro-1, 3-benzenedichloroacetate and amino-containing silane to obtain the photodegradable bridged silane containing 2-nitrobenzyl. The photodegradable bridged silane obtained in the invention has good photoresponse performance, can be used for designing and preparing photoresponsive functional materials, and has important application value. The synthesis process is simple, raw materials are easy to obtain, reaction conditions are mild, and operability is high.
SELF-IMMOLATIVE SYSTEMS
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Page/Page column 11; 26; 27, (2020/05/28)
The present invention is concerned with self-immolative recognition and/or responsive systems for electrophilic compounds, especially alkylating agents, which systems may comprise disclosure or detection of the alkylating agent. The present invention is especially concerned with non-protic triggered self-immolative systems, molecules, and methods, and in particular for detection of non- protic electrophilic agents, and especially alkylating agents, for example alkyl or benzylic halides, which may be found in pesticides or fumigants, or chemical warfare agents.
DOX-UCNPs@mSiO2-TiO2 nanocomposites for near-infrared photocontrolled chemo/photodynamic therapy
Chen, Yuhua,Tong, Ruihan,An, Na,Lin, Huiming,Qu, Fengyu
supporting information, p. 7292 - 7301 (2017/08/02)
Currently, incorporating multiple therapeutic functions into one nanostructure has attracted more and more attention for the development of efficient anticancer agents. In this study, a uniform core-shell UCNPs@mSiO2 nanocomposite was prepared as the carrier to develop the NIR light-controlled chemotherapy associated with photodynamic therapy (PDT). In view of the novel UV emission, the semiconductor photosensitizer TiO2 was exploited due to its high efficiency and chemical stability. The host modification method was used to integrate TiO2 doping and mesoporous structure, which can store anticancer drug molecules (doxorubicin, DOX). To improve the utilization of emission, a photolabile o-nitrobenzyl derivative was incorporated to form a sensitive linker (NB linker) as a "gate" to make sure the few leak. Upon NIR irradiation, the UV emission can not only excite TiO2 to produce reactive oxygen species (ROS), but also induce the breaking of NB linker as well as drug release. The NIR-triggered performances were further demonstrated by the cell experiment using HeLa cells as the model cancer cell. The synergistic effect of chemotherapy and PDT induces enhanced cytotoxicity, which is more powerful than their simple effects added together. Therefore, the novel NIR light-controlled double-therapeutic nanocomposite should be a potential candidate for anticancer agents.
PROGRAMMED DEGRADATION OF POLYMERS DERIVED FROM BIOMASS
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, (2016/05/10)
Novel photodegradable polymers derived from biomass are provided, together with methods of making and methods of using said polymers.
Multistimuli-responsive hydrogel particles prepared via the self-assembly of PEG-based hyperbranched polymers
Chen, Qian-Bao,You, Ye-Zi
supporting information, p. 677 - 679 (2015/05/27)
Generally, it is very difficult to obtain multistimuli-responsive hydrogel particles. Here, we introduce a novel method for the preparation of multistimuli-responsive hydrogel particles by adding water into the poly(ethylene glycol) (PEG)-based hyperbranched polymers. The produced PEG-base polymers via reversible addition-fragmentation chain transfer (RAFT) polymerization become temperature-sensitive and less soluble when heated above the lower critical solution temperature (LCST) after directly adding water. Subsequently, the hydrogel particles can be formed via hyperbranch-hyperbranch coupling through disulfide exchange. The resulting hydrogel particles are temperature-, photo-, and redox-responsive.
Programmed photodegradation of polymeric/oligomeric materials derived from renewable bioresources
Rajendran, Saravanakumar,Raghunathan, Ramya,Hevus, Ivan,Krishnan, Retheesh,Ugrinov, Angel,Sibi, Mukund P.,Webster, Dean C.,Sivaguru, Jayaraman
supporting information, p. 1159 - 1163 (2015/01/30)
Renewable polymeric materials derived from biomass with built-in phototriggers were synthesized and evaluated for degradation under irradiation of UV light. Complete decomposition of the polymeric materials was observed with recovery of the monomer that was used to resynthesize the polymers.
Hydrogen bonding behavior of amide-functionalized α-diimine palladium complexes
Zhai, Feng,Jordan, Richard F.
supporting information, p. 7176 - 7192 (2015/08/19)
A class of (N,N′-diaryl-α-diimine)Pd complexes bearing amide substituents on the N-aryl rings is described. Hydrogen bonding interactions involving the amide groups influence the structures, isomer distributions, and ligand coordination behavior of these compounds. The amide-functionalized α-diimine ligands (2,6-iPr2-Ph)N=CMeCMe=N(2-C(=O)NMe2-6-iPr-Ph) (4a), (2,6-iPr2-Ph)N=CMeCMe=N(2,6-(C(=O)NMe2)2-Ph) (4b), and (2-C(=O)NMe2-6-iPr-Ph)N=CMeCMe=N(2-C(=O)NMe2-6-iPr-Ph) (4c) were prepared by condensation reactions of 2,3-butanedione and the appropriate anilines. The attempted preparation of (2,6-iPr2-Ph)N=CMeCMe=N(2-C(=O)NHMe-6-iPr-Ph) (4d) yielded the corresponding 1,2-dihydroquinazolinone derivative 4d′ formed by nucleophilic attack of the amide nitrogen at the proximal imine carbon. 4a and 4b react with (cod)PdMeCl to yield square planar (α-diimine)PdMeCl complexes 5a,a′ and 5b,b′, respectively, which exist as two isomers that differ in the orientation (trans/cis) of the Pd-Me ligand and the amide-substituted arylimine unit. 4c reacts with (MeCN)2PdCl2 and (cod)PdMeCl to yield (4c)PdCl2 (6c-anti,syn) and (4c)PdMeCl (5c-anti,syn), which exhibit anti/syn isomerism due to hindered rotation of the Caryl-N bonds. In the solid state, the amide oxygen atoms in 6c-anti and 5c-syn engage in hydrogen bonding with cocrystallized CH2Cl2 solvent molecules. 4d′ reacts with (MeCN)2PdCl2 via ring-opening metalation to afford the α-diimine complex (4d)PdCl2 (6d). Transmetalation of 6d with SnMe4 yields (4d)PdMeCl (5d,d′) as a mixture of trans and cis isomers. The reaction of 5d,d′ with AgOAc yields (4d)PdMe(OAc) (7d) as a single isomer in which the Pd-Me group is trans to the amide-functionalized arylimine unit. 5d, 6d, and 7d exhibit intramolecular N-H···Cl and N-H···O hydrogen bonding interactions involving the amide NH units. The reactions of 5a,a′, 5c-anti, and 5d,d′ with AgSbF6 in the presence of pyrazole yield the corresponding (α-diimine)PdMe(pz)+SbF6- salts (8a,c,d; pz = pyrazole), which exhibit an intramolecular hydrogen bond between the amide oxygen and the pyrazole NH unit. 8a,c,d undergo partial dissociation of pyrazole in CD3CN solution to generate the corresponding CD3CN complexes 9a,c,d. The non-hydrogen-bonded complex {(2,6-iPr2-Ph)N=CMeCMe=N(2,6-iPr2-Ph)}PdMe(pz)+SbF6- (8e) and its pyrazole dissociation product {(2,6-iPr2-Ph)N=CMeCMe=N(2,6-iPr2-Ph)}PdMe(CD3CN)+SbF6- (9e) were generated in a similar fashion. The pyrazole dissociation constants, Keq = [(α-diimine)PdMe(CD3CN)+] × [pz] × [(α-diimine)PdMe(pz)+]-1, vary in the order 8e > 8d > 8a > 8c, span more than 2 orders of magnitude, and reflect the enhancement of pyrazole binding in 8a,c,d by amide-pyrazole hydrogen bonding. The intramolecular hydrogen bonding in 8c strengthens pyrazole binding by a factor of ca. 120 (i.e., ΔΔG = 2.8(1) kcal mol-1) relative to the case of 8e.
PROCESS TO PREPARE 3-METHYL-2-NITROBENZOIC ACID BY AIR OXIDATION
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Page/Page column 40; 41; 42, (2016/01/30)
A method for preparing 3-methyl-2-nitrobenzoic acid is disclosed wherein 1, 3 -dimethyl-2-nitrobenzene is combined with an oxidation catalayst in the presence of an oxygen source and an initiator, provided that less than 99% of the 1,3 -dimethyl-2- nitrobenzene is oxidized. A method for preparing compounds of Formula 7 and Formula 11 is also disclosed wherein the method is characterized by using 3-methyl-2-nitrobenzoic acid as prepared by the method disclosed above. wherein R1 is C1-C7 alkyl, C3-C6 cycloalkyl or C4-C7 alkylcycloalkyl
Inclusion complex containing epoxy resin composition for semiconductor encapsulation
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, (2014/03/21)
The invention is an epoxy resin composition for sealing a semiconductor, including (A) an epoxy resin and (B) a clathrate complex. The clathrate complex is one of (b1) an aromatic carboxylic acid compound, and (b2) at least one imidazole compound represented by formula (II): wherein R2 represents a hydrogen atom, C1-C10 alkyl group, phenyl group, benzyl group or cyanoethyl group, and R3 to R5 represent a hydrogen atom, nitro group, halogen atom, C1-C20 alkyl group, phenyl group, benzyl group, hydroxymethyl group or C1-C20 acyl group. The composition has improved storage stability, retains flowability when sealing, and achieves an effective curing rate applicable for sealing delicate semiconductors.
