- Hydrogenation of 1-nitroanthraquinone to 1-aminoanthraquinone catalyzed by bimetallic cuptx nanoparticles
-
Bimetallic CuPtx nanoparticles were prepared in ethanol solution by the wet chemical reduction method using Cu(NO3)2 and H2PtCl6 as starting materials, hydrazine hydrate as a reductant, and polyvinyl pyrrolidone as an organic modifier. The average particle sizes of Cu and Pt nanoparticles were 60 nm and 3 nm, respectively. The small-sized Pt nanoparticles were evenly anchored at the surfaces of large-sized Cu nanoparticles, forming Cu@Pt core-shell structured nanocomposites. In the bimetallic CuPtx nanoparticles, electron was transferred from platinum to copper species, which increased the selectivity of 1-aminoanthraquinone by suppressing the high hydrogenation activity of metallic platinum. The CuPt0.1 bimetallic nanoparticles exhibited higher catalytic activity for the hydrogenation of 1-nitroanthraquinone to 1-aminoanthraquinone than both monometallic Cu and Pt nanoparticles. Over the CuPt0.1 catalyst, the selectivity of 1-aminoanthraquinone was 99.3% at the 1-nitroanthraquinone conversion of 98.9%.
- Yang, Chenchen,Wang, Aili,Yin, Hengbo
-
-
Read Online
- Efficient Selective Reduction of Aromatic Nitro Compounds Affording Aromatic Amines under CO/H2O Conditions Catalyzed by Amine-Added Rhodium-Carbonyl Complexes
-
Remarkably high catalytic activities for the reduction of aromatic nitro compounds affording aromatic amines using CO (1 atm) and water at room temperature were exhibited by using amine-added rhodium carbonyl complexes (Rh(CO)2(acac), Rh4(CO)12, and Rh6(CO)16) in 2-methoxyethanol or diglyme (diethylene glycol dimethyl ether) containing a 5 equiv NaOH aqueous solution.The reduction proceeded not only with high catalytic activities, but also with remarkably high nitro-group selectivities, as exhibited in the case of 1-nitroanthraquinone affording 1-aminoanthraquinone, wit hout any other unsaturated groups, such as C=O, being reduced.The T.O.F. (turnovers/time) of 1776 mol-cat-1 h-1 (296 g-atom Rh-1 h-1) was attained for the reduction of p-nitroanisole yielding p-anisidine using Rh6(CO)16-1,8-bis(dimethylamino)-naphthalene catalyst.
- Nomura, Kotohiro,Ishino, Masaru,Hazama, Motoo
-
-
Read Online
- Preparation method of 1-aminoanthraquinone
-
A preparation method of 1-aminoanthraquinone comprises the following steps: by taking nickel carbonyl loaded by superparamagnetic nanoparticles as a catalyst and 1-nitroanthraquinone as a reaction substrate, adding a solvent, introducing hydrogen, and conducting reacting at 60-80 DEG C and 0.3-0.5 MPa for 2-8 hours; and applying a magnetic field to the reaction product to recover the catalyst, and performing post-treatment to obtain 1-aminoanthraquinone, wherein the mass of the catalyst is 0.003 times that of the 1-nitroanthraquinone, and the mass ratio of the 1-nitroanthraquinone to the solvent is 15:4. The 1-aminoanthraquinone synthesis process is simple and convenient, high in selectivity, environment-friendly, small in equipment investment and suitable for industrial production. The nickel carbonyl loaded by the superparamagnetic nanoparticles has moderate catalytic activity, nitryl can be selectively reduced, excessive reduction of carbonyl is avoided, the yield of the 1-aminoanthraquinone is high, and the catalyst can be collected and reused through an external magnetic field and can be repeatedly used for at least five times.
- -
-
Paragraph 0010
(2021/07/01)
-
- Copper-catalyzed one-pot relay synthesis of anthraquinone based pyrimidine derivative as a probe for antioxidant and antidiabetic activity
-
Synthetic compounds have modernized the globe due to its vast applicable fields. Anthraquinones, as well as pyrimidine derivatives, are used as essential pharmacophores in the field of medicine. Maintenance of a green disease-free environment by using these derivatives is being acknowledged in developed as well as developing countries of the world. Considering the use of active catalysts in the synthesis of anthraquinone based derivatives are the era of concern for researchers due to their distinctive properties. Owing to the remarkable activities of anthraquinone and pyrimidine derivative, we synthesize compounds having both functionalities with the utilization of novel synergically active copper catalysts. This study explores the application of synthesized compounds using fast, ecofriendly and cost-effective approaches.1H and 13C NMR, antioxidant, antidiabetic, molecular docking and QSAR studies were used for characterization and evaluation of newly synthesized anthraquinone based pyrimidine derivatives. The result of these techniques shows that our desired compounds were successfully synthesized and have potent applications. Among all synthesized compounds, G2 and G3 showed a remarkable antioxidant activity with IC50 of 15.09 and 21.88 μg/ml respectively. While the compound G2 and G4 showed a strong inhibitory antidiabetic activity with the IC50 value of 24.23 and 28.94 μg/ml respectively. Furthermore, molecular docking results for both of the proteins assist the experimental data and confirms the different interactions between binding domains and substituent moieties. SAR study also relates to the experimental facts by giving us positive results of synthesized compounds. According to the QSAR study, G4 and G2 emerged as the most stable and most reactive compound among other compounds respectively. While MEP shows moderate to good nucleophilic and electrophilic reactivity of all four compounds.
- Ahmad, Zaheer,Arshad, Uzma,Parveen, Shagufta,Rafiq, Naila,Shafiq, Nusrat,Zarren, Gul
-
-
- TARGETED BIFUNCTIONAL DEGRADERS
-
The present invention provides, in one aspect, bifunctional compounds that can be used to promote or enhance degradation of certain circulating proteins. In another aspect, the present invention provides bifunctional compounds that can be used to promote or enhance degradation of certain autoantibodies. In certain embodiments, treatment or management of a disease and/or disorder requires degradation, removal, or reduction in concentration of the circulating protein or the autoantibody in the subject. Thus, in certain embodiments, administration of a compound of the invention to the subject removes or reduces the circulation concentration of the circulating protein or the autoantibody, thus treating, ameliorating, or preventing the disease and/or disorder. In certain embodiments, the circulating protein is TNF.
- -
-
-
- Solvent-free, microwave assisted oxidation of alcohols with 4-hydroxypyridinium chlorochromate functionalized silica gel
-
4-Hydroxypyridinium chlorochromate functionalized silica gel was found to be an efficient and reusable oxidant for the very fast oxidation of primary and secondary alcohols to the corresponding carbonyl compounds under solventfree conditions and microwave irradiation in excellent yields.
- AHMADI, Sayed Ali,GHALEHBANDI, Shermineh Sadat,GHAZANFARI, Dadkhoda,SHEIKHHOSSEINI, Enayatollah
-
p. 283 - 289
(2020/10/06)
-
- BIFUNCTIONAL SMALL MOLECULES TO TARGET THE SELECTIVE DEGRADATION OF CIRCULATING PROTEINS
-
The present invention is directed to bifunctional small molecules which contain a circulating protein binding moiety (CPBM) linked through a linker group to a cellular receptor binding moiety (CRBM) which is a membrane receptor of degrading cell such as a hepatocyte or other degrading cell. In embodiments, the (CRBM) is a moiety which binds to asialoglycoprotein receptor (an asialoglycoprotein receptor binding moiety, or ASGPRBM) of a hepatocyte. In additional embodiments, the (CRBM) is a moiety which binds to a receptor of other cells which can degrade proteins, such as a LRP1, LDLR, FcyRI, FcRN, Transferrin or Macrophage Scavenger receptor. Pharmaceutical compositions based upon these bifunctional small molecules represent an additional aspect of the present invention. These compounds and/or compositions may be used to treat disease states and conditions by removing circulating proteins through degradation in the hepatocytes or macrophages of a patient or subject in need of therapy. Methods of treating disease states and/or conditions in which circulating proteins are associated with the disease state and/or condition are also described herein.
- -
-
-
- SMALL MOLECULE BASED ANTIBODY-RECRUITING COMPOUNDS FOR CANCER TREATMENT
-
The present invention relates to chimeric (including bifunctional) compounds, compositions comprising those compounds and methods of treating cancer in a patient or subject, especially including metastatic cancer where cancer cells exhibit overexpression (heightened expression) of cell surface urokinase-type plasminogen activator receptor (urokinase receptor) compared to normal (non-cancerous) cells. The compounds bind to the urokinase-type plasminogen activator receptor (uPAR) on the surface of a cancer cell, including a metastatic cancer cell, and consequently recruit native antibodies of the patient or subject where the antibodies can selectively degrade and/or deactivate targeted cancer cells through antibody-dependent cellular phagocytosis and antibody-dependent cellular cytotoxicity (ADCC) and/or complement dependent cytotoxicity (CDC) against a large number and variety of cancers, thus providing cancer cell death and an inhibition of growth, elaboration and/or metastasis of the cancer, including remission and cure of the patient's cancer.
- -
-
Page/Page column 53; 54
(2017/03/08)
-
- 1-method for synthesizing amino-anthraquinone
-
The invention relates to a synthetic method of 1-amino-anthraquinone. The mixture of sodium sulfide and sulfur is used as a reducing agent to generate 1-amino-anthraquinone through reduction, and consequently, the 1-amino-anthraquinone is obtained. The synthetic method provided by the technical solution of the invention is characterized in that the mixture of sodium sulfide and sulfur is used as the reducing agent, 150-230 kg of sulfur is added to industrial sodium sulfide per ton, the reducing capacity of the mixture is equivalent to that of 1.305-1.467 tons of industrial sodium sulfide and the reducing agent cost is reduced by 20-30%, the dosage of the sodium sulfide is greatly reduced in the new process and the cost of the reducing agent is reduced; in addition, the concentration of free alkali in a medium is reduced, the generation of hydrolysis side reaction is effectively controlled, the yield of reduction is improved by about 4% and the reducing waste residue is reduced; the obtained product is excellent in quality; the sulfur used in the new method is rich in source and low in cost; the reducing cost is reduced by about 1/4 and the yield of reduction is improved by about 4%; the synthetic method of 1-amino-anthraquinone has excellent environmental protection and economic benefit.
- -
-
Paragraph 0035; 0036
(2017/03/14)
-
- Continuous hydrogenation of a commercial aqueous phase synthesis of 1-amino-anthraquinone method
-
The invention discloses a method for synthesizing 1-amino anthraquinone via continuous hydrogenation of industrial water phases. 1-nitro anthraquinone and hydrogen are taken as raw materials. The method is characterized by comprising the following steps: adding water taken as a reaction solvent and a catalyst into a first reduction kettle, and respectively adding a 1-nitro anthraquinone alkali solution and the hydrogen to carry out a reduction reaction; enabling the reaction liquid to continuously and sequentially flow out from a liquid outlet when the reaction liquid in the reduction kettle reaches the liquid outlet and then flow into a second-stage reduction kettle and a third-stage reduction kettle which are connected in series with the first reduction kettle; carrying out catalyst separation after the reaction liquid flows out from a liquid outlet of the third-stage reduction kettle and flows into sedimentation and filtration equipment, and feeding a filtrate into an oxidation kettle; and carrying out oxidization to obtain a filter cake, namely the 1-amino anthraquinone. According to the method, the continuous hydrogenation reaction can be realized, so that the quality of the obtained 1-amino anthraquinone is improved, the yield of the obtained 1-amino anthraquinone is increased and the cost of the obtained 1-amino anthraquinone is lowered. In addition, the method is stable in production and is suitable for industrialized mass production. The environment-friendly water is taken as a reaction medium, so that the recycling of the catalyst and the solvent is realized, i.e., the discharge of waste residue, waste gas and the waste water is avoided. Therefore, the environment stress is lightened.
- -
-
Paragraph 0027-0034
(2017/03/14)
-
- Method for preparing 1-amino-anthraquinone from 1-nitro-anthraquinone by catalytic hydrogenation
-
The invention provides a method for preparing 1-amino-anthraquinone from 1-nitro-anthraquinone by catalytic hydrogenation. The method comprises the following steps: step 1, placing 1-nitro-anthraquinone and N,N-dimethylformamide into a high pressure reaction kettle; adding a certain amount of nano-copper/nickel binary alloy catalyst; mounting a reacting device well; feeding N2 to exhaust air; feeding high-purity hydrogen to exhaust the N2; and starting a stirring device; step 2, feeding a certain pressure of hydrogen into a system obtained in step 1 under a constant temperature condition for reacting; after the reaction is ended, reducing the temperature to be below 45 DEG C; diluting the reacting product 1-amino-anthraquinone; and finally analyzing and calculating a result by using high performance liquid chromatography. During a preparation procedure of a catalyst disclosed by the invention, different organic modifiers are used for controlling the size of particles; the nano-copper/nickel binary alloy catalyst of different structures and shapes is prepared; the catalytic performance of the catalyst is effectively improved.
- -
-
Paragraph 0026; 0030; 0031; 0036; 0037-0039; 0044-0047
(2017/08/25)
-
- A 1-aminoanthraquinone method for the synthesis of
-
The invention relates to a method for synthesizing 1-aminoanthraquinone. According to the method, the dosage of anthraquinone and nitric acid is adjusted in a mixed solvent in the presence of a catalyst, the depth of nitrification is controlled, anthraquinone is subjected to partial nitrification by using a mixed-acid nitrification method, so as to produce 1-nitroanthraquinone, and then, 1-aminoanthraquinone is synthesized through reduction reaction; the solvent used is one or more of dichloroethane, dimethyl formamide, xylene, chlorobenzene and toluene; mixed acid used means a mixture prepared from fuming nitric acid and fuming sulfuric acid; the catalyst used is para-toluenesulfonic acid and salt thereof; during the nitrification of the method, 1-nitroanthraquinone is mainly produced, and 1,8-dinitroanthraquinone, 1,5-dinitroanthraquinone, 1,7-dinitroanthraquinone, 1,6-dinitroanthraquinone and 2-nitroanthraquinone are not produced; the yield of the product, namely 1-aminoanthraquinone, is 95-99%, the purity is high (over 99%), refining is not required, the production cost is low, the operation is simple and convenient, and the industrial production is convenient to realize.
- -
-
Paragraph 0016; 0032; 0034-0036; 0038-0039; 0040; 0042-0043
(2019/02/02)
-
- Re-engineering the Immune Response to Metastatic Cancer: Antibody-Recruiting Small Molecules Targeting the Urokinase Receptor
-
Developing selective strategies to treat metastatic cancers remains a significant challenge. Herein, we report the first antibody-recruiting small molecule (ARM) that is capable of recognizing the urokinase-type plasminogen activator receptor (uPAR), a uniquely overexpressed cancer cell-surface marker, and facilitating the immune-mediated destruction of cancer cells. A co-crystal structure of the ARM-U2/uPAR complex was obtained, representing the first crystal structure of uPAR complexed with a non-peptide ligand. Finally, we demonstrated that ARM-U2 substantially suppresses tumor growth in vivo with no evidence of weight loss, unlike the standard-of-care agent doxorubicin. This work underscores the promise of antibody-recruiting molecules as immunotherapeutics for treating cancer.
- Rullo, Anthony F.,Fitzgerald, Kelly J.,Muthusamy, Viswanathan,Liu, Min,Yuan, Cai,Huang, Mingdong,Kim, Minsup,Cho, Art E.,Spiegel, David A.
-
supporting information
p. 3642 - 3646
(2016/03/23)
-
- Visible-light photocatalytic activity of chitosan/polyaniline/CdS nanocomposite: Kinetic studies and artificial neural network modeling
-
Chitosan/polyaniline (CS/PAni), chitosan/CdS (CS/CdS) and chitosan/polyaniline/CdS nanocomposite were synthesized and characterized using X-ray diffraction pattern analysis, FT-IR spectroscopy and scanning electronic microscopy. The adsorption performance and photocatalytic activity of CS/PAni/CdS was compared with CS/PAni and CS/CdS in the removal of Reactive Blue 19 (RB19) dye. After five cycles of experiments under visible light irradiation, CS/PAni/CdS retained high photocatalytic activity which confirmed good stability of nanocomposite. Moreover, the kinetics of decolorization was investigated and novel equation rate for dye removal was established by considering two parallel mechanisms including adsorption and surface photocatalytic degradation of dye by CS/PAni/CdS. Artificial neural network was employed to develop a model for predicting the decolorization efficiency and determining the relative importance of operational parameters. A 3-layer perceptron network with optimized 5:10:1 topology could provide adequate predictive performance (R2 = 0.983). Moreover, the photocatalytic degradation of RB19 was monitored by measuring the total organic carbon (TOC) and GC-MS analysis, enabling the evaluating the mineralization and identifying the intermediates. During 120 min of experiment, more than 80% of TOC was removed.
- Rasoulifard,Seyed Dorraji,Amani-Ghadim,Keshavarz-Babaeinezhad
-
-
- Pd-catalyzed α-selective C(sp3)-H acetoxylation of amides through an unusual cyclopalladation mechanism
-
We report the first example of Pd-catalyzed site-selective α-C(sp3)-H oxidation/acetoxylation of amides through an unusual [4,6]-bicyclic metallacycle intermediate with 1-aminoanthraquinone as a new bidentate directing group. In addition to the distinct mechanism and high efficiency, the reaction is highly appealing due to the ample commercial source, low-cost, as well as easy removal and recycling of the auxiliary group.
- Wang, Meining,Yang, Yang,Fan, Zhoulong,Cheng, Zhen,Zhu, Weiliang,Zhang, Ao
-
p. 3219 - 3222
(2015/06/01)
-
- Synthesis of S,S-dialkyl-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl) sulfoximides and specificities of their base-catalyzed intramolecular heterocyclizations into naphtho[1,2,3-cd]-indol-6(2H)-ones
-
Heating of 6H-anthra[1,9-cd][1,2]oxazol-6-ones with dialkyl sulfoxides in sulfolane gave S,S-dialkyl-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)sulfoximides which underwent cyclization to naphtho-[1,2,3-cd]indol-6(2H)-one derivatives on heating in boiling tetrahydrofuran in the presence of sodium methoxide. p-Toluenesulfinic acid was isolated as by-product in the cyclization of S-methyl-S-(4-methylphenyl)-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl) sulfoximide. The heterocyclizations of S,S-dipropyl- and S,S-dibutyl-N-(9,10- dioxo-9,10-dihydroanthracen-1-yl)sulfoximides to 1-ethyl- and 1-propylnaphtho[1,2,3-cd]-indol-6(2H)-ones were accompanied by formation of the corresponding 1-[1-hydroxyethyl(propyl)]naphtho-[1,2,3-cd]indol-6(2H)-ones.
- Kargina,Gornostaev,Nefedov
-
-
- Highly chemo-and regioselective transfer reduction of aromatic nitro compounds using ammonium formate catalyzed by supported gold nanoparticles
-
A highly chemo-and regioselective reduction of a wide diversity of aromatic nitro compounds to the corresponding amines has been achieved by a combination of gold nanoparticles supported on titania and ammonium formate (HCOONH 4) in ethanol at room temperature. Furthermore, a direct and mild route to formanilides from aromatic nitro compounds bearing different functional groups by reductive N-formylation using the gold-mediated transfer reduction protocol is also established.
- Lou, Xia-Bing,He, Lin,Qian, Yue,Liu, Yong-Mei,Cao, Yong,Fan, Kang-Nian
-
supporting information; experimental part
p. 281 - 286
(2011/04/16)
-
- Direct and ketone-sensitized photoconversion of 1-nitro-9,10-anthraquinone to 1-amino-9,10-anthraquinone mediated by donor radicals
-
The full photoreduction of 1-nitro-2-R-9,10-anthraquinone (R = H: N1, methyl: N2) was studied in benzene, acetonitrile and acetonitrile-water mixtures in the presence of 2-propanol and triethylamine (TEA). The major photoproduct is the fluorescing 1-amino-2-R-AQ (A1, A2). The quantum yield of full reduction increases with the donor concentration, approaching ΦNH2 = 0.1. The intermediates involved are assigned on the basis of spectral and kinetic characteristics. The short-lived triplet state (≤20 ns) of N2 can be intercepted by 2-propanol or TEA, thereby forming the spectroscopically hidden donor radicals and the nitroAQ radicals which absorb at 400 and 540 nm; the latter band is due to the radical anion. The triplet state of N1 was not observed at room temperature, but the radical properties and decay in the nitrosoAQ are similar for N1 and N2. For donors in lower concentrations ΦNH2 is strongly increased in the presence of benzophenone, acetophenone or acetone, approaching 0.22. The results under direct and sensitized conditions are compared and major dependences and the effects of mixtures of acetonitrile with water are outlined.
- G?rner, Helmut,Gruen, Henry
-
experimental part
p. 20 - 27
(2010/04/25)
-
- 2,2-Bis(ethoxycarbonyl)vinyl (BECV) as a versatile amine protecting group for selective functional-group transformations
-
A 2,2-Bis(ethoxycarbonyl) vinyl- (BECV) group was used for the selective protection of amines at room temperature in the presence of potentially interfering functional groups such as OH, SH, COOH as well as other NH 2 groups. Several functional group transformations such as esterification, O-alkylation, O-acylation, N-alkylation, N-acylation, S-alkylation can selectively be carried out in the presence of the BECV group. The selective deprotection of the BECV group was achieved in a short time using ethylenediamine at room temperature while several other functional groups such as benzoate, aliphatic esters, amides and ethers remain intact. The BECV group shows orthogonal stability against the common protecting groups such as Fmoc, Cbz and Boc.
- Ilangovan, Andivelu,Kumar, Rajendran Ganesh
-
supporting information; experimental part
p. 2938 - 2943
(2010/07/02)
-
- Efficient and selective room-temperature gold-catalyzed reduction of nitro compounds with CO and H2O as the hydrogen source
-
[Chemical equation presented] Taking hydrogen from water: Gold catalysis enabled the selective reduction of nitro compounds under very mild conditions with a combination of H2O and CO as the reductant (see scheme). This environmentally friendly reaction proceeded in high yield and with high chemoselectivity in the presence of a wide range of functional groups
- He, Lin,Wang, Lu-Cun,Sun, Hao,Ni, Ji,Cao, Yong,He, Yong,Fan, Kang-Nian
-
supporting information; experimental part
p. 9538 - 9541
(2010/03/24)
-
- Chemoselective reduction of azides with sodium sulfide hydrate under solvent free conditions
-
Sodium sulfide hydrate has been employed for an efficient reduction of a variety of azides to the primary amines in good-to-excellent yields under solvent-free system and without perturbing many active functionalities such as ether, carbonyl, sulfonyl, and nitro.
- Kazemi, Foad,Kiasat, Ali Reza,Sayyahi, Sohyl
-
p. 1813 - 1817
(2007/10/03)
-
- Thioxanthone dyes with improved solubility and a method of preparing 2-oxybenzanthrones as intermediate materials for making of these dyes
-
The invention relates to new thioxanthone compounds having utility as fluorescent dyes and processes for their manufacture.
- -
-
-
- A facile reduction of aromatic nitro compounds to aromatic amines with bis(cyclopentadienyl)titanium(IV) dichloride-indium system
-
Cp2TiCl2/In system was found to be a new reagent for reducing various aromatic nitro compounds to the corresponding aromatic amines in good yields under mild and neutral conditions.
- Yoo, Byung Woo,Lee, Sung Jae,Yoo, Byoung Seung,Choi, Kyung Il,Kim, Joong Hyup
-
p. 2489 - 2493
(2007/10/03)
-
- Preparation of glycosyltriazenes
-
O-Unprotected glycosyltriazenes are prepared for the first time by coupling of 1-anthraquinone-1-diazonium hydrogensulfate with β-glycopyranosylamines to afford 1-(anthraquinone-1-yl)-3-(β-glycopyranosyl)triazenes 3a-h. Acetylation of compounds 3 furnished the O-acetates 4a-g. The stability of triazenes 3 results from fixation of the NH proton in an intramolecular hydrogen bond to one of the anthraquinone carbonyl oxgen atoms. Treatment of triazenes 4 with tert-butyl hypochlorite afforded acetoglycosyl chlorides 6 and 1-azidoanthraquinone 7. With acetic acid the triazene 4a formed tetra-O-acetyl-D-xylopyranose 9 together with 1-aminoanthraquinone 10. WIiley-VCH Verlag GmbH, 2000.
- Weng, Min,Jochims, Johannes C.
-
p. 530 - 536
(2007/10/03)
-
- Reactions of 9-chloro-1,10-anthraquinone 1-dichlorophosphorylimine with N- and C-nucleophiles
-
9-Chloro-1,10-anthraquinone 1-dichlorophosphorylimine formed in the reaction of 1-amino-9,10-anthraquinone with PCl5 followed by dehydrochlorination reacts with primary amines with substitution of chlorine atoms. In the case of aliphatic amines, the reaction occurs further concurrently in two directions: the addition of the amine molecule with the formation of 9,9-di(alkylamino) derivatives of the anthrone and the substitution of hydrogen atom at position 4 with the formation of 4,9-di(alkylamino) derivatives of 1,10-anthraquinone 1-imine. In the case of aromatic amines, 1-amino-9,10-anthraquinone 9-arylimines are the end products. Reactions with the anions of CH-acids containing an alkoxycarbonyl or cyano group occur with substitution in position 9 followed by intramolecular cyclization with the formation of 2-alkoxy-or 2-amino-7H-dibenzo[f, ij]isoquinolin-7-one derivatives, respectively.
- Gorelik,Titova,Gladysheva
-
p. 1147 - 1153
(2007/10/03)
-
- Non-reductive conversion of 1-nitro-9,10-anthraquinone to 1-amino-9,10-anthraquinones
-
Heating 1-nitro-9,10-anthraquinone 2 with ureas 4 in N,N,N',N'-tetramethylurea (TMU) at around 130 °C resulted in the displacement of the nitro group by the amino groups, leading to the corresponding aminoanthraquinones 5 in good yields.
- Suzuki,Kawakami,Maeda
-
p. 9217 - 9220
(2007/10/02)
-
- A facile method for preparing substituted 1-aminoanthraquinones
-
An efficient and simple preparation of α-substituted aminoanthraquinones using 2,2,-dialkoxyethylamines is described.
- Wormser,Sardessai,Abramson
-
p. 3211 - 3222
(2007/10/02)
-
- Synthesis of 1-aminoanthraquinone
-
1-Aminoanthraquinone (1-AAQ) is synthesized by the reaction of 2-chlorobenzyl chloride and xylene in the presence of a solid acid catalyst to yield 2-chloro dimethyldiphenylmethane, subsequent oxidation of the methyl groups, ring closure to form a 1-chloroanthraquinone carboxylic acid, replacement of the 1-chloro group with ammonia, and decarboxylation.
- -
-
-
- CHARACTERISTIC FEATURES OF THE REACTION OF 3(5)-AMINO-5(3)-METHYLPYRAZOLE WITH 1-NITROANTHRAQUINONE-2-CARBOXYLIC ACID
-
In the reaction of 3(5)-amino-5(3)-methylpyrazole with 1-nitroanthraquinone-2-carboxylic acid in sulfolane at 150 deg C, 2-methylpyrazolonaphthoquinazoline-5,10.13-trione is formed with an admixture of 1-aminoanthraquinone-2-carboxylic acid and 1-aminoanthraquinone.Under similar conditions, from 4-amino-1,5-dimethylpyrazole, only 1-(1,5-dimethyl-4-pyrazolylamino)anthraquinone-2-carboxylic acid is formed.
- Perevalov, V. P.,Baryshnenkova, L. I.,Tsoi, K. S.
-
p. 1004 - 1005
(2007/10/02)
-
- Pyrolysis of Aryl Azides. XI. Enhanced Neighbouring Group Effects of Carbonyl in a Locked Conformation
-
Rates of pyrolysis in nitrobenzene solution have been measured for 1-azido-9H-fluoren-9-one, 1-azido-9H-xanthen-9-one, 1-azidoacridin-9(10H)-one and 1-azidoanthracene-9,10-dione; relative to azidobenzene at 120 deg these were respectively 5.68, 1750, 5090 and 18400.The lack of neighbouring group participation for the first azide is related to the large distance between carbonyl oxygen and the inner azido nitrogen atom, and the data argue against a published proposal that the transition state is stabilized by electrostatic attraction.In the remaining azides, the 'locked conformation' leads to much larger neighbouring group assistance than is observed for freely rotating ortho groups such as benzoyl rel 79).Only the last azide yields an isoxazole on pyrolysis, the second and third ones providing the first reported examples of neighbouring-group-assisted pyrolysis in which no cyclic product is obtained.These results are interpreted in terms of an electrocyclic mechanism in which the transition state is early and N---O bond formation is less advanced than other changes in bonds.Much of the rate enhancement is attributed to an electron distribution which favours nitrogen loss. 1-Aminoanthracen-9(10H)-one, 1-amino-9H-fluoren-9-one and 1-amino-9H-xanthen-9-one do not yield the corresponding isoxazoles when oxidative cyclization is attempted.
- Dyall, Leonard K.,Ferguson, John A.
-
p. 1991 - 2002
(2007/10/02)
-
- Alkynes and Poly(ethylene glycol) Derivatives as Nucleophiles and Catalysts in Substitution Reactions of 1-Chloroanthraquinones
-
Two synthetically useful approaches to 1-substituted anthraquinone derivatives are reported.Application of these methods afforded the following 1-anthraquinyl ethers: n-propyl, n-butyl, n-octyl, n-nonyl, n-hexadecyl, isoamyl, allyl, 2-butenyl, (E)-2-hexenyl, (E)-2-tridecyl, benzyl, phenyl, 4-methylphenyl, 2-butynyl, 2-pentynyl, 2-hexynyl, 3-pentynyl, 3-hexynyl, 3-heptynyl, 3-nonynyl, 4-hexynyl, 4-heptynyl, 5-heptynyl, 5-octynyl, 5-nonynyl, 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, 2-ethoxy>ethyl, 2-(methylthio)ethyl, 2-(1-piperidino)ethyl, and 2-(1-morpholino)ethyl.The results of about 100 nucleophilic substitution reactions (a number were duplicates) are presented.Most of these reactions involve either a new approach, new products, or both.Includes are displacements of chloride by alkanols, alkenols, and alkynols.Of the three, only the latter afford acceptable yields of product, although lower yields are observed as the distance between hydroxyl and triple bond increases.Nucleophiles of the type RO(CH2CH2O)nOH proved remarkably effective.Alkynyl ethers and poly(oxyethylene) ethers also proved to be excellent leaving groups.Both alkynols and oligoethylene glycol monoethers were found to be catalysts for the conversion of 1-chloroanthraquinone into 1-anthraquinyl ethers.In an attempt to understand the mechanism of this reaction, solid-state structures of four anthraquinone derivatives have been obtained.These have poly(ethyleneoxy), morpholino, or alkynyl side arms.
- Fang, JunPing,Lu, Tianbao,Kim, Hyunsook,Delgado, Isaura,Geoffroy, Philippe,et al.
-
p. 7059 - 7065
(2007/10/02)
-
- Synthesis of 2,6-Dihydronaphthindol-6-ones
-
The reaction of 1-aminoanthraquinone with benzyl chloride in KOH-DMSO system afforded 3,11b-dibenzyl-2-phenyl-2,3,7,11b-tetrahydroanthraoxazin-7-one (5; 78percent yield), whose structure was determined by single-crystal X-ray diffraction.The reaction of compound 5 with aluminium chloride gave 1-phenyl-2,6-dihydronaphthindol-6-one (52percent yield) having strong fluorescence.
- Arai, Sadao,Yamauchi, Sigeaki,Yamagishi, Takamichi,Hida, Mitsuhiko
-
p. 324 - 326
(2007/10/02)
-
- REACTION OF 6-OXO-6H-ANTHRAISOXAZOLES WITH CYCLOHEXENE
-
The reaction of 6-oxo-6H-anthraisoxazoles with cyclohexene in the presence of aluminum chloride leads to the corresponding 1-cyclohexylamino-9,10-anthraquinones.
- Gornostaev, L. M.,Medvedeva, S. A.
-
p. 1547 - 1549
(2007/10/02)
-
- Selective Catalytic Reduction of Aromatic Nitro Compounds Affording Amines under CO/H2O Conditions Using Amine-added Ruthenium-Carbonyl Complexes
-
Remarkably high selectivities of nitro-group as well as high catalytic activities for the reduction of aromatic nitro compounds affording corresponding amines under CO/H2O conditions are exhibited by using amine (HNR2)-added Ru-carbonyl complexes; the reduction also proceeded without by-producing H2 which was formed by the Water-Gas Shift Reaction.
- Nomura, Kotohiro
-
p. 1679 - 1682
(2007/10/02)
-
- EQUILIBRIUM NH ACIDITY OF 4-SUBSTITUTED 1-AMINOANTHRAQUINONES IN DIMETHYL SULFOXIDE
-
The equilibrium acidity of 1-amino-4-R-anthraquinones (R = CH3O, H, Cl, Br, NO2) was determined by transmetallation in DMSO (the Na+ cation, 25 deg C).A linear correlation was established between the pK values of the 4-substituted 1-aminoanthraquinones and the ?p- constants of the substituents R.The conduction of the electronic effect of the substituents R is stronger in the aminoanthraquinones than in the anilines and is closer to the naphthylamines.A linear relation is observed between the conduction of the electronic effect of the substituent and the square of the coefficient in the HOMO for the carbon atom at the point of addiion of the substituent in the series of anions of NH acids of various structure types.The increase in the NH acidity with change in the structure type of the NH acid is not necessarily accompanied by a decrease in the conduction of the electronic effect of the substituents.
- Os'kina, I. A.,Vlasov, V. M.,Terekhova, M. I.,Petrov, E. S.
-
p. 2041 - 2044
(2007/10/02)
-
- Process for the preparation of 1-aminoanthraquinones
-
There is disclosed a process for the preparation of 1-aminoanthraquinones from 5-nitro-1,4,4a,9a-tetrahydroanthraquinones with a basic reducing agent, which process is carried out under pressure in the temperature range above 100° C. and in an aqueous-organic medium. The process affords very pure 1-aminoanthraquinone, which is, inter alia, an important intermediate.
- -
-
-
- REACTION OF 6H-6-OXOANTHRAISOXAZOLES WITH ALKYL PHENYL ETHERS AND DIMETHYLANILINE
-
The reactions of halogen-substituted 6H-6-oxoanthraisoxazoles with alkyl phenyl ethers or dimethylaniline in the presence of aluminum chloride lead to the formation of 1-amino-2-chloro-4-(4-alkoxyphenyl)anthraquinones or 1-amino-2,4-di(4-dimethylaminophenyl)anthraquinone and simultaneous reduction of the heterocycle.
- Gornostaev, L. M.,Es'kin, A. P.,El'tsov, A. V.
-
p. 200 - 202
(2007/10/02)
-
- TRANSFORMATIONS OF ANTHRAQUINONE-1-NITRO-2-CARBOXYLIC ACID DURING REDUCTION BY HYDROGEN ON A CATALYST.
-
The authors studied the catalytic reduction of anthraquinone-1-nitro-2-carboxylic acid by hydrogen under a pressure of 0. 1-5. 5 MPa and at temperatures of 20-100 degree C in different solvents. The concentration of the substrate was varied from 0. 05 to 0. 3 mole/dm**3. A 5% palladium on carbon was used in a 0. 1 dm**3 thermostated ideal mixing reactor. It was found that in the reaction of anthraquinone-1-nitro-2-carboxylic acid with catalytically activated hydrogen, several reactions proceed. Depending on the conditions of carrying out the process, the main product may be anthraquinone-1-amino-2-carboxylic acid (II) or 1-aminoanthraquinone. The characteristic feature of this process is decarboxylation of anthraquinone-9,10-dihydro-1-amino-2-carboxylic acid.
- Rogovik,Dzvinka,Vinyukova
-
p. 1252 - 1255
(2007/10/02)
-
- Method for purifying 1-aminoanthraquinone
-
A method for purifying 1-aminoanthraquinone which comprises previously subjecting a crude 1-aminoanthraquinone to a removal treatment of inorganic impurities so that their content is reduced to not more than 4 wt. % as converted to ash basis or to a removal treatment of iodine-consuming reductive inorganic impurities so that their content is reduced to not more than 2 wt. % as converted to consumed iodine basis, and then rectifying the 1-aminoanthraquinone.
- -
-
-
- SYNTHESIS OF AMINOANTHRAQUINONES BY HYDROGENATION OF THE CORRESPONDING NITRO DERIVATIVES.
-
In this work hydrogenation of nitroanthraquinones was studied in the presence of a palladium complex with an aminated chloromethylated copolymer of styrene with divinylbenzene (A), with palladium content of 1 mass %. Experimental data indicate that the rate of NAQ hydrogenation in ethanol is practically independent of the ratio. Thus, the influence of solvent adsorption on the hydrogenation of nitroanthraqinones to a first approximation can be disregarded. It is shown that the most suitable solvents for NAQ hydrogenation are alcohols and DMF. The reaction proceeds much more poorly in nonpolar aromatic hydrocarbons. A catalyst was also found which is capable of reducing all nitrogroups in nitroanthraquinones was obtained, substantially simplifying purification and isolation of 1-AAQ, since the separation and purification of aminoanthraquinones is substantially easier than nitroanthraquinones.
- Nasibulin,Klyuev
-
p. 2417 - 2420
(2007/10/02)
-
- Photographic products and processes
-
Photographic products and processes for the imagewise generation of a dye from a color shifted dye precursor of a preformed image dye, said precursor having at least one STR1 group, wherein R is hydrogen, alkyl, provided that the α-carbon does not have a hydrogen atom attached thereto, aryl such as phenyl or substituted phenyl, e.g. p-nitrophenyl, or heterocyclic such as pyridine; R1 -R6 are hydrogen, alkyl, preferably having from 1 to 6 carbon atoms, or aryl; n is 0 or 1; and T is a moiety containing a thiazolidin-2-yl group which upon silver-assisted cleavage of said thiazolidin-2-yl group results in the formation of a STR2 group, which may be protonated under the reaction conditions, followed by cleavage of said STR3 which cleavage is anchimerically assisted or accelerated by said STR4 to provide after protonation, an STR5 group in a dye chromophore. In a preferred embodiment the precursor is a substantially colorless compound.
- -
-
-
- Kinetics and product studies on Ullmann amination of 1-halogenoanthraquinones catalysed by copper(I)salts in acetonitrile solution
-
The kinetics and products of reactions of some primary amines (RNH2) with 1-halogenoanthraquininone (AQX) promoted by copper salts, particularly tetrakis(acetonitrile)copper(I) tetrafluoroborate, have been investigated in acetonitrile solution at 70 deg C.Provided that oxygen does not come into contact with solutions of the copper(I) salt and amine, the kinetics of the reactions have the simple form v = k, and the products consist almost entirely of the aminated anthraquinone, AQNHR, and dehalogenated material, AQH, their ratio being directly proportional to .The reaction rate is dependent on the identity of the departing halogen X, decreasing in the sequence I > Br > Cl, but the product ratio is little affected.N-Deuteration of the reactant amine gives rise to a small kinetic isotope effect, but the product ratio is unaffected.Conversely deutearation on the α-carbon atom of the amine has little kinetic effect but leads to a four-fold increase in the ratio of aminated to dehalogenated product.The observations are interpreted in terms of (i) formation of a copper(I)-amine complex, (II) activation of this species for attack on AQX by proton abstraction from an amine ligand by a free molecule (stepwise or concerted), and (iii) generation of an arylcopper(III) intermediate which is partitioned between formation of AQNHR by attack of an externel amine molecule and formation of AQH by an intramolecular process involving hydrogen transfer from the α-carbon atom in the amine ligand generated in (ii).Exposure of the initial copper(I)-amine complex to oxygen leads to a new complex, itself capable of reacting with AQX, which on prolonged incubation at 70 deg C in the presence of an excess of amine is transformed back to its original state.
- Bethell, Donald,Jenkins, Iwan L.,Quan, Peter M.
-
p. 1789 - 1796
(2007/10/02)
-
- Process for the preparation of monoaminoanthraquinones
-
The invention relates to a process for the preparation of monoaminoanthraquinones of the formula STR1 wherein R is a non-ionic substituent and n is 0, 1, 2 or 3, by reduction of corresponding mononitroanthraquinones, which process comprises reacting said mononitroanthraquinones with formaldehyde, in the presence of a base and a catalyst, in an aqueous alcoholic solution.
- -
-
-
- C-FORMYLATION OF α-PHENYLAMINOANTHRAQUINONES WITH FORMALDEHYDE. REACTION OF α-AMINOANTHRAQUINONES WITH FORMALDEHYDE IN SULFURIC ACID
-
The reaction of α-phenylaminoanthraquinones with formaldehyde in concentrated sulfuric acid leads to formylation at the para position of the phenyl group.The possibility of extending the reaction to related systems was demonstrated for the case of 6-phenylamino-N-methylanthrapyridone.It is suggested that the intermediate compounds in the C-formylation, N-methylation, and demethylation respectively of α-amino and α-methylaminoanthraquinones are 7H-7-oxoanthra-1,3-oxazinium cations.
- Kazankov, M. V.,Ginodman, L. G.,Mustafina, M. Ya.
-
p. 526 - 533
(2007/10/02)
-
- Process for producing aminoanthraquinone
-
A process for producing an aminoanthraquinone, which comprises feeding of a nitroanthraquinone and an alkali sulfide continuously into a reaction zone kept at a temperature of from 80° to 140° C., the alkali sulfide being used in an amount of 1.6 or more times the mole number of the nitro group, and withdrawing the reaction product continuously or intermittently from the reaction zone; and an aminoanthraquinone obtained by the above process which is one of the most important intermediates of anthraquinone dyes.
- -
-
-