- Recyclable Oxofluorovanadate-Catalyzed Formylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes
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An efficient method has been developed for the reductive amination of CO2 by using readily available and recyclable oxofluorovanadates as catalysts. Various amines are transformed into the desired N-formylated products in moderate to excellent yields at room temperature in the presence of phenylsilane. Mechanistic studies based on in situ infrared spectroscopy suggest a reaction pathway initiated through F?Si interactions. The activated phenylsilane allows for CO2 insertion to produce phenylsilyl formate, which undergoes attack by the amine to generate the target product.
- Wu, Shanxuan,Huang, Zijun,Jiang, Xiaolin,Yan, Fachao,Li, Yuehui,Du, Chen-Xia
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p. 1763 - 1766
(2021/03/01)
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- Ligand-Enabled Ni-Al Bimetallic Catalysis for Nonchelated Dual C-H Annulation of Arylformamides and Alkynes
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A bifunctional secondary phosphine oxide (SPO) ligand-controlled method was developed for Ni-Al-catalyzed nonchelated dual C-H annulation of arylformamides with alkynes, providing a series of substituted amide-containing heterocycles in ≤97% yield. The SPO-bound bimetallic catalysis proved to be critical to the reaction efficiency.
- Luan, Yu-Xin,Wang, Yin-Xia,Ye, Mengchun,Zhang, Feng-Ping
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supporting information
(2020/03/19)
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- Design of Lewis base functionalized ionic liquids for the N-formylation of amines with CO2 and hydrosilane: The cation effects
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A series of functionalized ionic liquids (ILs) were developed for the reductive functionalization of CO2 with amine and hydrosilane to afford formamides under mild conditions. It was found that 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-based IL i.e. [DBUC12]Br showed high efficiency for the N-formylation reaction of amines without using any organic solvents or additives. Furthermore, control experiments suggested the cations with active hydrogen may weaken the nucleophilicity of anions through ion pairing interactions, thereby affecting the activation of hydrosilane. The reaction mechanism was then investigated by Density Functional Theory (DFT) calculations. This protocol represents a highly efficient and environmentally friendly example for catalytic conversion of CO2 into value-added chemicals such as formamide derivatives by employing DBU functionalized ILs.
- Li, Xiao-Ya,Fu, Hong-Chen,Liu, Xiao-Fang,Yang, Shu-Han,Chen, Kai-Hong,He, Liang-Nian
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p. 563 - 569
(2020/02/05)
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- Selective: N-formylation/N-methylation of amines and N-formylation of amides and carbamates with carbon dioxide and hydrosilanes: Promotion of the basic counter anions of the zinc catalyst
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A catalyst composed of commercially available Zn(OAc)2 and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO2 as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH3 under a CO2 atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph2SiH2 produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pKa values and lower reactivities than the corresponding amines. The present Zn(OAc)2/phen catalyst was found to show versatility in the conversion of CO2 and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si-H and N-H bonds.
- Zhang, Qiao,Lin, Xiao-Tao,Fukaya, Norihisa,Fujitani, Tadahiro,Sato, Kazuhiko,Choi, Jun-Chul
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supporting information
p. 8414 - 8422
(2020/12/29)
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- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
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We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
- Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
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supporting information
p. 5317 - 5324
(2020/09/17)
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- Catalyst-free selective: N -formylation and N -methylation of amines using CO2 as a sustainable C1 source
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We herein describe catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source. By tuning the reaction solvent and temperature, the selective synthesis of formamides and methylamines is achieved in good to excellent yields using sodium borohydride (NaBH4) as a sustainable reductant.
- Zou, Qizhuang,Long, Guangcai,Zhao, Tianxiang,Hu, Xingbang
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supporting information
p. 1134 - 1138
(2020/03/11)
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- An efficient method for the N-formylation of amines under catalyst- and additive-free conditions
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A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.
- Xu, Zhuo-Wei,Xu, Wen-Yi,Pei, Xiao-Jun,Tang, Fei,Feng, Yi-Si
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supporting information
p. 1254 - 1258
(2019/04/10)
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- Mn-Catalyzed Selective Double and Mono-N-Formylation and N-Methylation of Amines by using CO2
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Functionalization of amines by using CO2 is of fundamental importance considering the abundance of amines and CO2. In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO2 utilization as a C1 building block. This study represents the first example of selective catalytic double N-formylation of aryl amines by using a dinuclear Mn complex in the presence of phenylsilane. This robust system also allows for selective formylation and methylation of amines under a range of conditions.
- Huang, Zijun,Jiang, Xiaolin,Zhou, Shaofang,Yang, Peiju,Du, Chen-Xia,Li, Yuehui
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p. 3054 - 3059
(2019/04/10)
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- N-aryl formamide prepared by using ethyl bromodifluoroacetate as formylating reagent
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The invention discloses a compound of N-aryl formamide prepared by using ethyl bromodifluoroacetate as a formylating reagent. The compound is prepared by using N-alkyl arylamine as a raw material, ethyl bromodifluoroacetate as a formylating reagent and copper as a catalyst, adding different ligands, bases, etc., performing reaction under stirring in a reaction solvent at 100-120 DEG C for 10-14 hours; then filtering the reaction solution to obtain filtrate after reaction ending; concentrating the filtrate, removing the solvent by using a rotary evaporator to obtain a residue, treating the residue by silica gel column chromatography, eluting with an eluent, collecting the effluent according to the actual gradient; combining the effluent containing the product, concentrating the combined effluent to remove the solvent, and performing vacuum drying to obtain the target product. The compound has the advantages of simple and easily obtained raw materials, simple preparation process, less pollution, low energy consumption and high yield.
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Paragraph 0031
(2018/12/02)
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- Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate
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Ethyl bromodifluoroacetate (BrCF2COOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.
- Li, Xiao-Fang,Zhang, Xing-Guo,Chen, Fan,Zhang, Xiao-Hong
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p. 12815 - 12821
(2018/10/20)
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- DBU-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2 and Polymethylhydrosiloxane
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We describe herein an efficient organocatalytic system for the selective N-methylation and N-formylation of amines with carbon dioxide (CO2) as a sustainable C1 feedstock and polymethylhydrosiloxane (PMHS) as a cost-effectvie reducing reagent. High-yielding N-methylation products are obtained with low catalyst loading (1%) of DBU. Selective N-formylation of amines is achieved using the same catalytic system at a lower reaction temperature. (Figure presented.).
- Li, Gang,Chen, Jie,Zhu, Dao-Yong,Chen, Ye,Xia, Ji-Bao
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supporting information
p. 2364 - 2369
(2018/05/07)
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- Photoinduced Oxidative Formylation of N,N-Dimethylanilines with Molecular Oxygen without External Photocatalyst
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A photoinduced oxidative formylation of N,N-dimethylanilines with molecular oxygen in the absence of an external photocatalyst was developed and provided the corresponding formamides in good yields under mild reaction conditions. Investigations indicated that both the starting material and product act as photosensitizers and that 1O2 coexists with O2?- during the reaction through energy transfer and single electron transfer process.
- Yang, Shuai,Li, Pinhua,Wang, Zhihui,Wang, Lei
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supporting information
p. 3386 - 3389
(2017/07/15)
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- Zinc phthalocyanine as an efficient catalyst for halogen-free synthesis of formamides from amines via carbon dioxide hydrosilylation under mild conditions
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The combination of a zinc phthalocyanine (ZnPc) catalyst and a stoichiometric amount of dimethyl formamide (DMF) provided a simple route to formamide derivatives from amines, CO2, and hydrosilanes under mild conditions. We deduced that formation of an active zinc-hydrogen (Zn-H) species promoted hydride transfer from the hydrosilane to CO2. The cooperative activation of the Lewis acidic ZnPc by strongly polar DMF, led to formation of activated amines and hydrosilanes, which promoted the chemical reduction of CO2. Consequently, the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity, representing a simple and sustainable pathway for the reductive transformation of CO2 into valuable chemicals as an alternative to conventional halogen-containing process.
- Luo, Rongchang,Lin, Xiaowei,Lu, Jing,Zhou, Xiantai,Ji, Hongbing
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p. 1382 - 1389
(2017/08/22)
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- Catalyst-free: N -formylation of amines using BH3NH3 and CO2 under mild conditions
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The catalyst-free N-formylation of amines using CO2 as the C1 source and BH3NH3 as the reductant has been developed for the first time. The corresponding formylated products of both primary and secondary amines are obtained in good to excellent yields (up to 96% of isolated yield) under mild conditions.
- Zhao, Tian-Xiang,Zhai, Gao-Wen,Liang, Jian,Li, Ping,Hu, Xing-Bang,Wu, You-Ting
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supporting information
p. 8046 - 8049
(2017/07/22)
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- Transformation of carbon dioxide into valuable chemicals over bifunctional metallosalen catalysts bearing quaternary phosphonium salts
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The chemical transformation of CO2 under mild conditions remains a great challenge because of its exceptional kinetic and thermodynamic stability. Two important reactions in the transformation of CO2 are the N-formylation reaction of amines using hydrosilanes and CO2, and the cycloaddition of CO2 to epoxides. Here, we report the high efficiency of bifunctional metallosalen complexes bearing quaternary phosphonium salts in catalyzing both of these reactions under solvent-free, mild conditions without the need for co-catalysts. The catalysts' bifunctionality is attributed to an intramolecular cooperative process between the metal center and the halogen anion. Depending on the reaction, this activates CO2 by permitting either the synergistic activation of Si–H bond via metal–hydrogen coordinative bond (M–H) or the dual activation of epoxide via metal–oxygen coordinative bond (M–O). The one-component catalysts are also shown to be easily recovered and reused five times without significant loss of activity or selectivity. The current results are combined with previous work in the area to propose the relevant reaction mechanisms.
- Zhang, Wuying,Luo, Rongchang,Xu, Qihang,Chen, Yaju,Lin, Xiaowei,Zhou, Xiantai,Ji, Hongbing
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p. 736 - 744
(2017/04/24)
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- A N-methyl-N-(3-methyl phenyl) dithio-2-clamping the method for the preparation of
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The invention discloses a method for preparing N-methyl-N-(3-methyl phenyl) thiocarbamate-2-naphthyl. By adopting the method, usage of harmful and toxic thiophosgene or chlorine can be avoided, and physical health of staff can be protected. The method is suitable for large-scale industrial production and application, and good enterprise benefits and social benefits can be obtained.
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Paragraph 0031; 0033-0035
(2017/05/26)
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- Fluoro-functionalized polymeric N-heterocyclic carbene-zinc complexes: Efficient catalyst for formylation and methylation of amines with CO2 as a C1-building block
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A fluoro-functionalized polymeric N-heterocyclic carbene (NHC)-Zn complex (F-PNHC-Zn) was designed and synthesized by taking fluorous imidazolium salts as precursors through a two-step alkylation. The resultant F-PNHC-Zn was applied in catalyzing the formylation and methylation of amines using CO2 as a C1 building block in the presence of organosilane, which showed much higher activity than the corresponding non-fluorous PNHC-Zn under identical conditions. N-Methylanilines with both electron-withdrawing and electron-donating groups all could be converted to the corresponding formamides and methylamines in >90% conversion. Quantitative conversion of N-methylaniline was obtained even under very low CO2 pressure (0.05 MPa diluted by N2). Moreover, F-PNHC-Zn was highly stable and easily recyclable for these reactions. This journal is
- Yang, Zhen-Zhen,Yu, Bo,Zhang, Hongye,Zhao, Yanfei,Ji, Guipeng,Liu, Zhimin
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p. 19613 - 19619
(2015/06/09)
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- Direct condensation of functionalized sp3 carbons with formanilides for enamine synthesis using an in situ generated HMDS amide catalyst
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The efficient synthesis of functionalized enamines including β-enaminoesters was effectively accomplished by the direct condensation of functionalized sp3 carbanions such as acetates with formamides using in situ generated HMDS base from catalytic cesium fluoride and stoichiometric tristrimethylsilylamine. This journal is the Partner Organisations 2014.
- Taneda, Hiroshi,Inamoto, Kiyofumi,Kondo, Yoshinori
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supporting information
p. 6523 - 6525
(2014/06/09)
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- Oxidative cleavage of the carbon-carbon σ-bond using reusable copper on iron
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An efficient and resuble copper on iron catalyst has been prepared for the cleavage of the carbon-carbon σ-bond in α-aminocarbonyl compounds leading to the corresponding formylamides and acids with a maximal TON of up to 51,000. It is noteworthy that the copper on iron catalyst can be easily separated from the reaction mixture, and retains its activity after several reuses. Copyright
- Song, Ren-Jie,Liu, Yu,Hu, Rui-Xiang,Liu, Yan-Yun,Wu, Ji-Cheng,Yang, Xu-Heng,Li, Jin-Heng
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supporting information; experimental part
p. 1467 - 1473
(2011/08/03)
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- Indium-catalyzed N -formylation of amines under solvent-free conditions
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We have developed a simple, mild method for N-formylation of a wide variety of amines in the presence of indium metal as a catalyst under solvent-free conditions. This reaction is applicable to the chemoselective N-formylation of amino groups and -amino acid esters without epimerization. Georg Thieme Verlag Stuttgart.
- Kim, Joong-Gon,Jang, Doo Ok
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experimental part
p. 1231 - 1234
(2010/07/08)
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- A METHOD OF PREPARING A PORPHYRIN DERIVATIVE, A PORPHYRIN DERIVATIVE, USE OF SAID PORPHYRIN
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The present invention relates to a method of preparing a porphyrin derivative from a meso-acrylonitrile-substituted porphyrin compound. According to the invention a Vilsmeier reagent carrying an aromatic ring is used, wherein said Vilsmeier reagent is a s
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Page/Page column 22
(2008/06/13)
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- Investigations of Steric and Electronic Factors Influencing the Cyclopalladation of meta-Toluidine Analogues
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The cyclopalladation of two different types of aniline derivatives is described: the acetylated anilines N-(3-methylphenyl)acetamide (2a), 3-(acetylamino)-4-chlorobenzoic acid (2c), and N-(2-chlorophenyl)acetamide (2d) are cyclometalated easily with palladium(II) acetate and trifluoroacetic acid to yield the corresponding complexes 4a, 4c, and 4d, respectively, whereas the acetylated meta-toluidine N-(2-chloro-5-methylphenyl)acetamide (2b) cannot be metalated at the only accessible site between the acetylamino and the methyl group.This aromatic C-H bond can be activated, however, with the second type of meta-toluidine derivatives: the 2-chloro-5,N-dimethyl-N-nitrosoaniline (3b) readily undergoes cyclopalladation to yield the corresponding Pd(II) complex di-μ-trifluoroacetato-bisdipalladium(II) (5b) containing a five-membered palladacylce with coordination of Pd(II) at the nitroso N-atom, which is established by 15N-NMR spectroscopy.
- Mossi, Waldo,Klaus, Alfred J.,Rys, Paul
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p. 2531 - 2537
(2007/10/02)
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- One-Pot Monomethylation of Substituted Anilines by Phase Transfer Catalyst
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A one-pot monomethylation of substituted anilines (1) by phase transfer catalysis has been developed.The primary amino function of 1 is protected by treatment with formic acid to give N-formylanilines (2) which are methylated in situ with dimethyl sulphate in the presence of tetrabutylammonium hydrogen sulphate, anhyd.K2CO3 and powdered NaOH.The resultant N-formyl-N-methylanilines (3) on deformylation by boiling with water furnish N-methyl-anilines (4) in high yields with >95percent purity.
- Sharma, V. K.,Kumar, A.,Agarwal, K. P.
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