Synthesis of 2-and 6-thienylazulenes by palladium-catalyzed direct arylation of 2-and 6-haloazulenes with thiophene derivatives

Preparation of 2- and 6-thienylazulene derivatives was established by the palladium-catalyzed direct cross-coupling reaction of 2- and 6-haloazulenes with the corresponding thiophene derivatives in good yield. Several thienylazulene derivatives were also used in the reaction with 2-chloroazulene derivatives in the presence of the palladium-catalyst to afford the thiophene derivatives with two azulene functions in good yield.ArticleORGANIC & BIOMOLECULAR CHEMISTRY. 23(66):10191-10197 (2015)journal articl

Synthesis of 1-azulenyl ketones by Bronsted acid mediated hydration of 1-azulenylalkynes

Preparation of 1-azulenyl ketones was achieved by metal-free hydration of 1-azulenylalkynes using trifluoroacetic acid as a Bronsted acid in good to excellent yields. The reaction was accomplished at a relatively low temperature with complete regio-selectivity and compatibility of several functional groups.ArticleRSC ADVANCES. 90(1):78303-78306 (2016)journal articl

Synthesis of 1,2 '-Biazulenes by Palladium-Catalyzed Unusual Homocoupling Reaction of 1-Haloazulenes in the Presence of Ferrocene

The synthesis of 1,2-biazulenes was established by palladium-catalyzed homocoupling reactions of the corresponding 1-haloazulenes in the presence of ferrocene. The optical properties of the novel 1,2-biazulenes were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behaviors of 1,2-biazulenes were also examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV).ArticleSYNTHESIS. 89(11):2438-2448 (2016)journal articl

Synthesis of 2-Aminofurans by Sequential [2+2] Cycloaddition-Nucleophilic Addition of 2-Propyn-1-ols with Tetracyanoethylene and Amine-Induced Transformation into 6-Aminopentafulvenes

Synthesis of 2-aminofuran derivatives with an azulene or N,N-dimethylanilino substituent was established by the formal [2+2] cycloaddition-retroelectrocyclization of 3-(1-azulenyl or N,N-dimethylanilino)-2-propyn-1-ols with tetracyanoethylene, followed by intramolecular nucleophilic addition to the initially formed tetracyanobutadiene moiety of the internal hydroxyl group that come from 2-propyn-1-ol. The reaction proceeds under mild conditions with short reaction period. The products of the reaction are readily available through a simple purification procedure. 2-Aminofuran derivatives obtained by this reaction could be converted into 6-aminofulvene derivatives upon reaction with various amines. The structures of 2-aminofuran and 6-aminopentafulvene with a N,N-dimethylanilino substituent were confirmed by single-crystal X-ray structural analysis.ArticleCHEMISTRY-A EUROPEAN JOURNAL. 23(21):5126-5136 (2017)journal articl

Synthesis of 2-amino- and 2-arylazoazulenes via nucleophilic aromatic substitution of 2-chloroazulenes with amines and arylhydrazines

The SNAr reaction of 2-chloroazulene derivative 1 with ethoxycarbonyl groups at the 1,3-positions of the azulene ring with several amines afforded the corresponding 2-aminoazulenes 3-9 in excellent yields. 2-Chloroazulene (2) without the electron-withdrawing groups reacted with highly nucleophilic cyclic amines (i.e., morpholine, piperidine and pyrrolidine) under the high-temperature conditions in a sealed tube to produce the corresponding 2-aminoazulenes 10-12 in good yields. 2-Aminoazulenes 10-14 without the electron-withdrawing groups were also obtained in good yields by the treatment of compounds 3-7 with 100% H3PO4, but in the cases of the reaction of 8 and 9 with a secondary amine function, the decomposition of the products resulted. The synthesis of 2-arylazoazulenes 15-18 was also established via the SNAr reaction of 1 with arylhydrazines. The optical and electrochemical properties of the 2-arylazoazulene derivatives were examined by UV/Vis spectroscopy, theoretical calculations and voltammetric experiments.ArticleORGANIC & BIOMOLECULAR CHEMISTRY. 94(10):3917-3923 (2017)journal articl

Molecular Transformation of 2-Methylazulenes: An Efficient and Practical Synthesis of 2-Formyl- and 2-Ethynylazulenes

First published: 09 Jan 20182-Formylazulene derivatives have been obtained in good yields by the reactions of 2-methylazulenes with N,N-dimethylformamide dimethyl acetal, followed by oxidative cleavage of the intermediately formed enamines with NaIO4. Vilsmeier formylation of 1-phenyl-3-methylazulenes also afforded the corresponding 2-formylazulenes in moderate yields. The treatment of a 2-methylazulene derivative bearing a formyl group at the 1-position with sodium methoxide led, through a self-condensation reaction, to a trans-1-(azulen-1-yl)-2-(azulen-2-yl)ethylene derivative, the structure of which was verified by single-crystal X-ray diffraction analysis. The 2-formylazulenes obtained were transformed into 2-ethynylazulenes in good yields by a modified Seyferth-Gilbert reaction. The reactivity of a 1-iodoazulene bearing a 2-formyl function in palladium-catalyzed cross-coupling reactions has also been examined.ArticleEUROPEAN JOURNAL OF ORGANIC CHEMISTRY. 2018(9):1145-1157 (2018)journal articl

3D船舶モデルデータのVR・AR・3D画面への表示

発表要旨, 第48回 CG・可視化研究会(CAVE研究会, 2011年9月28日, 埼玉工業大学

Renal Function after Nephrectomy Influences the Risk of Cardiovascular Events

We retrospectively analyzed the factors related to postoperative cardiovascular (CV) events in patients undergoing partial nephrectomy (PN) or radical nephrectomy (RN) for clinical T1 renal cell carcinoma (RCC). We identified 570 patients who underwent PN or RN for T1 renal cell carcinoma between January 1998 and December 2009 at our institution and related hospitals. We determined the cumulative incidence rate of CV events and overall survival (OS) using Kaplan-Meier survival curves with a log-rank test, and we evaluated the risk for an increase in CV events and OS using Cox proportional hazard regression. Of the 570 patients, 171 underwent PN and 399 underwent RN. The type of surgery was not significantly related with CV events. The only factor that significantly increased the risk of CV events in both the univariate (HR 2.67, p=0.006) and multivariate analyses (HR 2.14, p=0.044) was a postoperative estimated glomerular filtration rate (eGFR) <45 ml/min/1.73 m2. Postoperative eGFR was also a significant risk factor for OS in the univariate analysis (HR 2.38, p=0.0104), but not in the multivariate model. Postoperative renal function was a significant independent predictor of the incidence of subsequent CV events

Acute adrenal crisis after orthopedic surgery for pathologic fracture

BACKGROUND: Adrenal crisis after surgical procedure is a rare but potentially catastrophic life-threatening event. Its manifestations, such as hypotension, tachycardia, hypoxia, and fever mimic the other more common postoperative complications. Clinical outcome is dependent upon early recognition of the condition and proper management with exogenous steroid administration. CASE PRESENTATION: We report a 75-year-old man who presented with shock immediately after surgery for a femoral fracture from lung cancer metastasis. Anemia and severe hyponatremia were detected. Despite adequate fluid resuscitation, nonspecific symptoms including hypotension, tachycardia, hypoxia, fever and confusion occurred. Emergent CT revealed enlarged bilateral adrenal glands. Under the diagnosis of adrenal crisis due to metastatic infiltration of adrenal glands, the patient was treated with appropriate steroid replacement resulting in rapid improvement and recovery. CONCLUSION: We describe a case of adrenal crisis caused by the lack of adrenal reserve based on metastatic involvement and surgical stress, the first published case of adrenal crisis after surgery for a pathologic fracture from lung cancer metastasis. Surgeons treating pathologic fractures should be aware of this complication and familiar with its appropriate therapy because of increasing opportunity to care patients with metastatic bone tumors due to recent advances in cancer treatment