- Preparation method of 4, 4 '-dihydroxy diphenyl ether
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The invention discloses a preparation method of 4, 4 '-dihydroxy diphenyl ether. The process is as follows. The preparation method comprises the following steps: reacting 4, 4 '-dibromo diphenyl etherwith an alkaline aqueous solution, dimethyl sulfoxide, a catalytic amount of an inorganic catalyst containing copper ions and a ligand compound A to generate sodium phenolate; precipitating, separating and removing the catalyst, then introducing carbon dioxide gas to replace 4, 4 '-dihydroxy diphenyl ether, and recrystallizing the 4, 4'-dihydroxy diphenyl ether crude product by using an organic solvent to obtain a 4, 4 '-dihydroxy diphenyl ether finished product with the purity of 99% or above. The invention provides a preparation method of 2, 3, 5-tetramethylpiperidine. High purity and simple process, the preparation method is low in pollution and low in production cost; according to the method, the problems of high-temperature and high-pressure hydrolysis, high energy consumption, low safety factor, low yield and the like in the prior art are solved by applying a catalytic amount of copper ion-containing inorganic catalyst and ligand, carbon dioxide is used for acidolysis, ions limited by electronic-grade products are prevented from being introduced, and meanwhile, the method is suitable for industrial production in the aspects of cost and operation.
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Paragraph 0020
(2020/06/20)
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- Highly productive α-alkylation of ketones with alcohols mediated by an Ir-oxalamidato/solid base catalyst system
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An Ir-oxalamidato complex in combination with a solid base (e.g., magnesium aluminometasilicate/Ca(OH)2) significantly improved the catalyst productivity in α-alkylation of methyl ketones with primary alcohols. Optimization through systematic variation of the oxalamidato ligand led to a practical turnover number (TON) of 10 000.40 000.
- Maeda, Hironori,Nara, Hideki,Shimizu, Hideo
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supporting information
p. 2772 - 2779
(2020/12/29)
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- Rhodium(I) Complexes of N-Aryl-Substituted Mono- and Bis(amidinates) Derived from Their Alkali Metal Salts
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The synthesis and characterization of several rhodium(I) complexes of amidinate and linker-bridged bis(amidinate) ligands are presented. The amidinate ligands for the mononuclear complexes CH3{C(NMes)2Rh(cod)} (1), CH3{C(NDipp)2Rh(cod)} (2), and HCC{C(NDipp)2Rh(cod)} (3) (cod = 1,5-cyclooctadiene) were synthesized by reacting the corresponding organometallic precursor [Rh(cod)Cl]2 with the alkali metal amidinates CH3{C(NR)2Li} L1Li (R = Mes = 2,4,6-Me3C6H2) and L2Li (R = Dipp = 2,6-iPr2C6H3). Analogously, the alkynyl-functionalized sodium amidinate (HCC{C(NDipp)2Na}·2DME, L3Na) could be further deprotonated and reacted with carbodiimine to form the alkyne-bridged bis(amidinate) CC{C(NDipp)2Na(thf)}2 (L4Na), which serves as suitable starting material for the synthesis of CC{C(NDipp)2Rh(cod)}2 (4). The bis(amidinate) ligands for the corresponding para- (5) and meta- (6) phenylene-bridged complexes p-/m-C6H4{C(NMes)2Rh(cod)}2 were accessible through the reaction of phthalic acids with trimethylsilyl polyphosphate and mesitylamine and subsequent deprotonation of the obtained amidines. Tetramesityl oxalamidinate was used to synthesize the dinuclear complex {C(NMes)2Rh(cod)}2 (7) and its carbonylation product {C(NMes)2Rh(CO)2}2 (8). All compounds under study were fully characterized by various spectroscopic methods. In particular the alkali metal salt of the linker-bridged bis(amidinate) L5Na forms a one-dimensional coordination polymer in the solid state. Reaction of L5Na and L6Na with [Rh(cod)Cl]2 leads to dinuclear complexes in which the metal–metal distance can be adjusted, enabling us to study their reactivity, including possible cooperative effects in catalysis.
- Moos, Eric M. B.,González-Gallardo, Sandra,Radius, Michael,Breher, Frank
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p. 3022 - 3035
(2018/07/29)
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- Copper-Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amides
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Cu2O/N,N′-bis(thiophen-2-ylmethyl)oxalamide is established to be an effective catalyst system for Goldberg amidation with inferior reactive (hetero)aryl chlorides, which have not been efficiently documented by Cu-catalysis to date. The reaction is well liberalized toward a variety of functionalized (hetero)aryl chlorides and a wide range of aromatic and aliphatic primary amides in good to excellent yields. Furthermore, the arylation of lactams and oxazolidinones is achieved. The present catalytic system also accomplished an intramolecular cross-coupling product.
- De, Subhadip,Yin, Junli,Ma, Dawei
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supporting information
p. 4864 - 4867
(2017/09/23)
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- Copper(I) Oxide/N,N′-Bis[(2-furyl)methyl]oxalamide-Catalyzed Coupling of (Hetero)aryl Halides and Nitrogen Heterocycles at Low Catalytic Loading
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An easily prepared oxalic diamide is a powerful ligand for the copper-catalyzed coupling of aryl halides with nitrogen heterocycles. Only 1–2 mol% each of copper(I) oxide and N,N′-bis[(2-furyl)methyl]oxalamide (BFMO) are needed to form N-arylation products under mild conditions. More than 10 different types of nitrogen heterocycles are compatible with these conditions, thereby giving the corresponding N-arylation products. (Figure presented.).
- Pawar, Govind Goroba,Wu, Haibo,De, Subhadip,Ma, Dawei
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supporting information
p. 1631 - 1636
(2017/05/22)
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- CuI/Oxalic Diamide Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amines
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A class of oxalic diamides are found to be effective ligands for promoting CuI-catalyzed aryl amination with less reactive (hetero)aryl chlorides. The reaction proceeds at 120 °C with K3PO4 as the base in DMSO to afford a wide range of (hetero)aryl amines in good to excellent yields. The bis(N-aryl) substituted oxalamides are superior ligands to N-aryl-N′-alkyl substituted or bis(N-alkyl) substituted oxalamides. Both the electronic nature and the steric property of the aromatic rings in ligands are important for their efficiency.
- Zhou, Wei,Fan, Mengyang,Yin, Junli,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 11942 - 11945
(2015/10/06)
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- Assembly of Primary (Hetero)Arylamines via CuI/Oxalic Diamide-Catalyzed Coupling of Aryl Chlorides and Ammonia
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A general and practical catalytic system for aryl amination of aryl chlorides with aqueous or gaseous ammonia has been developed, with CuI as the catalyst and bisaryl oxalic diamides as the ligands. The reaction proceeds at 105-120°C to provide a diverse set of primary (hetero)aryl amines in high yields with various functional groups.
- Fan, Mengyang,Zhou, Wei,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 5934 - 5937
(2015/12/11)
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- Improved microwave synthesis of unsymmetrical N,N'-diaryl-1,2-aminoethane and imidazolidinium salts as precursors of N-heterocyclic carbenes
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Lithium aluminium hydride reduction of bis-unsymmetric-diaryloxamides 3 is difficult to accomplish especially for the sterically hindered mesityl derivative. Using microwaves LAH reduction of 3a,d was successful in a short time, however, with cleavage of the ether linkage to give compounds 11a,d. Extension of this method enabled the reduction of bis-oxamide derivatives 13 to the corresponding tetraamine derivative 14 which was then converted to the bis-imidazolidinium salt 15. Application of this method led to rapid reduction of unsymmetric N,N'-diaryloxamides 16 to the corresponding N,N'- diarylethylenediamines 17 which were converted to their corresponding imidazolidinium salts 18. the Partner Organisations 2014.
- Ibrahim, Yehia A.,Al-Awadi, Nouria A.,Al-Azemi, Talal F.,John, Elizabeth
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p. 38869 - 38876
(2014/11/08)
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