- NaOH-promoted one-pot aryl isothiocyanate synthesis under mild benchtop conditions
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In this work, we have established a green synthesis of aryl isothiocyanates promoted by the low-cost and readily available NaOH from aryl amines and carbon disulfide in a one-pot procedure. The developed protocol features no extra desulfurating reagents and mild benchtop conditions, in which NaOH serves as both the base and the desulfurating reagent to decompose the dithiocarbamate intermediate. Fourteen examples of aryl amines bearing electronic neutral, rich and poor substituents, as well as benzylamine, have proved to be compatible substrates in the developed method to furnish the corresponding isothiocyanates. The reaction has been performed on a gram scale to further demonstrate its synthetic utility. Compared to the reported base-promoted synthesis of aryl isothiocyanates that requires the use of special equipment, such as the ball mill or the microwave reactor, the simplicity in operation and scalability enables this method to efficiently access a variety of aryl isothiocyanates.
- Li, Hang,Liu, Xinyun,Yin, Xiaogang
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supporting information
p. 839 - 844
(2021/05/27)
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- 4-Dimethylaminopyridine-catalyzed synthesis of isothiocyanates from amines and carbon disulfide
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Isothiocyanates were synthesized by reactions between primary amines and CS2 in the presence of 4-dimethylaminopyridine as a catalyst and tert-butyl hydroperoxide as an oxidant. Various aryl, benzyl, alkyl, and hydroxyl amines were transformed into the corresponding isothiocyanates in 41–82% yields.
- Rong, Hao-Jie,Chen, Tao,Xu, Ze-Gang,Su, Tian-Duo,Shang, Yu,Wang, Yong-Qiang,Yang, Cui-Feng
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- Synthesis of thiocarbamoyl fluorides and isothiocyanates using amines with CF3SO2Cl
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A practical and efficient method to synthesize thiocarbamyl fluorides and isothiocyanates from amines with trifluoromethanesulfonyl chloride was developed. In the presence of the reducing agent triphenylphosphine and sodium iodide, thiocarbamyl fluorides and isothiocyanates were synthesized from secondary/primary amine in moderate to excellent yields, respectively. A broad scope of substrates and good functional group compatibility were observed.
- Jiang, Lvqi,Yi, Wenbin,Wei, Jingjing,Liang, Shuaishuai
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p. 12374 - 12381
(2020/11/10)
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- Direct, Microwave-Assisted Synthesis of Isothiocyanates
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A microwave-assisted desulfuration of readily available dithiocarbamates, formed in situ from primary amines, leading to target isothiocyanates has been developed. This efficient protocol provides a rapid, environmentally benign route to aliphatic and aromatic isothiocyanates.
- Janczewski, ?ukasz,Gajda, Anna,Gajda, Tadeusz
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supporting information
p. 2528 - 2532
(2019/04/03)
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- Synthesis of thiocarbamoyl fluorides and isothiocyanates using CF3SiMe3 and elemental sulfur or AgSCF3 and KBr with amines
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Reactions of thiocarbonyl fluoride derived from cheap, readily available, and widely used CF3SiMe3, elemental sulfur, and KF with secondary amines and primary amines at room temperature in THF provided a wide variety of thiocarbamoyl fluorides and isothiocyanates in moderate to excellent yields, respectively. The two reactions show broad substrate scope and good functional group tolerance. Moreover, AgSCF3 reacts with secondary/primary amines under KBr at room temperature, affording quantitative thiocarbamoyl fluorides/isothiocyanates, which feature late-stage application.
- Zhen, Long,Fan, Hui,Wang, Xiaoji,Jiang, Liqin
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supporting information
p. 2106 - 2110
(2019/03/26)
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- Synthesis methods for isothiocyanate derivative
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The invention discloses synthesis methods for an isothiocyanate derivative. The first synthesis method includes reacting raw materials, including primary amine, trifluoromethyltrimethylsilane, potassium fluoride and sulfur, with an organic solvent at the room temperature to obtain the isothiocyanate derivative. The synthetic isothiocyanate derivative has the advantages of simple operation, safety,high efficiency, non-toxicity, low raw material price, mild condition, high yield, wide application range of substrates, high compatibility of functional groups and the like. The second synthesis method includes reacting raw materials, including the primary amine, silver trifluoromethane and potassium bromide, with the organic solvent at the room temperature to obtain the isothiocyanate derivative. The isothiocyanate derivative has the advantages of simple operation, safety, high efficiency, easy availability of the raw materials, nearly quantitative yield, wide application range of the substrates, applicability to selective post-modification of drugs or complex compounds, and the like.
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Paragraph 0033; 0034; 0035; 0036; 0073; 0074; 0075; 0076
(2019/05/22)
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- Na2S2O8-mediated efficient synthesis of isothiocyanates from primary amines in water
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We have developed two green, practical, and efficient procedures, including a one-pot one, to synthesize isothiocyanates from amines and carbon disulfide via desulfurization with sodium persulfate. Water is used as the solvent. Basic conditions are necessary for good chemoselectivity for isothiocyanates. Structurally diverse linear and branched alkyl amines and aryl amines are readily converted to isothiocyanates by the two procedures in satisfactory yields. Halogens, benzylic C-H bonds, methylthio, nitro, ester, alkenyl, electron-rich or -deficient (hetero)aryls, acetylenyl, and even phenolic and alcoholic hydroxyls are well tolerated. The one-pot procedure in water can also be used to realize the preparation of chiral isothiocyanates from chiral amines, and the modification of bioactive structures with free amino groups. In large-scale preparation, simple and practical purification procedures independent of column chromatography are developed.
- Fu, Zhicheng,Yuan, Wenhao,Chen, Ning,Yang, Zhanhui,Xu, Jiaxi
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supporting information
p. 4484 - 4491
(2018/10/17)
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- Reaction of Thiocarbonyl Fluoride Generated from Difluorocarbene with Amines
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The reaction of thiocarbonyl fluoride, generated from difluorocarbene, with various amines under mild conditions is described. Secondary amines, primary amines, and o-phenylenediamines are converted to thiocarbamoyl fluorides, isothiocyanates, and difluoromethylthiolated heterocycles, respectively. Thiocarbamoyl fluorides were further transformed into trifluoromethylated amines by using a one-pot process. Thiocarbonyl fluoride is generated in situ and is rapidly fully converted in one pot under mild conditions; therefore, no special safety precautions are needed.
- Yu, Jiao,Lin, Jin-Hong,Xiao, Ji-Chang
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supporting information
p. 16669 - 16673
(2017/12/07)
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- Isothiocyanation of amines using the Langlois reagent
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The Langlois reagent was found to be effective for the isothiocyanation of primary amines in the presence of copper iodide and diethyl phosphonate.
- Liao, Yan-Yan,Deng, Jian-Chao,Ke, Yan-Ping,Zhong, Xiao-Lin,Xu, Li,Tang, Ri-Yuan,Zheng, Wenxu
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supporting information
p. 6073 - 6076
(2017/07/10)
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- NOVEL BENZIMIDAZOLE BASED EGFR INHIBITORS
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The present invention disclosed a novel EGFR inhibitor compound of formula (I), process for preparation thereof and methods of treating abnormal cell growth in mammals by administering the compounds of formula (I). Wherein, R= -H, 3-CH3, 4-NO2, 4-Cl, 2-CH3, 4-CH3, 4-Br, 4-F R1= -H, -4-OCH3, -4-NO2,-2-NO2, -4-Cl, -2,4,6-CH3, -4-CH3, -2-F,4-Br, -4-CF3, -4-S-CH3, -4-Cl,-3-CF3, -3-S-CH3, -3,5-CF3, -2-S-CH3, -3-CF3,-4-OCF3, -Si-(CH3)3, -Si-(C2H5)3, (CH3)2-Si- C2H5.
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Page/Page column 12
(2016/06/15)
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- Synthesis and coordination properties of nitrogen(I)-based ligands
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Chemical Equation Reprentation Cive me four: In contrast to typical imines, the central nitrogen atom in cyclopropenyl-derived carbeneimines (see example; C gray, N blue) can donate up to four electrons to form coordination complexes.
- Bruns, Hans,Patil, Mahendra,Carreras, Javier,Vazquez, Arcadio,Thiel, Walter,Goddard, Richard,Alcarazo, Manuel
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supporting information; experimental part
p. 3680 - 3683
(2010/08/07)
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- Sterically bulky thioureas as air- and moisture-stable ligands for pd-catalyzed heck reactions of aryl halides
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We demonstrate that sterically bulky N,N′-disubstituted cyclic thiourea-Pd(0) complexes are air- and moisture-stable and highly active catalysts for palladium-catalyzed Heck reaction of aryl iodides and bromides with olefins (TONs up to 500 000 for the reaction of Phl and methyl acrylate). Even activated aryl chlorides can undergo complete conversion in Bu 4NBr in the presence of 1 mol % Pd catalyst.
- Yang, Dan,Chen, Ying-Chun,Zhu, Nian-Yong
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p. 1577 - 1580
(2007/10/03)
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- Synthesis of unsymmetrical sulfides derived from tetrazole-5-thiols
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A series of unsymmetrical sulfides derived from I-substituted tetrazole-5-thiols was prepared by fusion of the corresponding 1-R-tetrazole-5-thiol sodium salt with 1-R′-5-halotetrazole. The structure was confirmed by 1H NMR and 13C NMR spectra. The target compounds were prepared in 50-80% yields.
- Hrabalek,Pus,Baranek,Kunes,Palat
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p. 183 - 189
(2007/10/03)
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- Synthesis of new heterocyclic systems: Spirothiadiazolepyrazolo[1,5,4- ef][1,5]benzodiazepines
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New derivatives spiro type of pyrazolo-1,5-benzodiazepines have been synthesized by 1,3-dipolar cycloaddition of nitrile imines with pyrazolo[1,5,4-ef][1,5]benzodiazepin-6-thione. When the nitrile oxide was used the corresponding pyrazolobenzodiazepin-6-o
- Rakib, El Mostapha,Benchidmi, Mohammed,Essassi, El Mokhtar,Bouadili, Abdelaziz El,Khouili, Mostafa,Barbe, Jean M.,Pujol, M. Dolors
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p. 571 - 577
(2007/10/03)
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- Thiazolo[4,5-d]pyrimidine thiones and -ones as corticotropin-releasing hormone (CRH-R1) receptor antagonists
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A series of thiazolo[4,5-d]pyrimidine thiones and -ones was prepared and discovered to have good binding affinity to the CRH-R1 receptor, thus showing promise as a new class of potential anxiolytics and/or antidepressants.
- Beck, James P.,Curry, Matt A.,Chorvat, Robert J.,Fitzgerald, Larry W.,Gilligan, Paul J.,Zaczek, Robert,Trainor, George L.
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p. 1185 - 1188
(2007/10/03)
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- A facile one-pot preparation of isothiocyanates from aldoximes
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Isothiocyanates 2a-l were prepared in excellent yields in a one-pot reaction from aldoxime derivatives 1a-l by successive treatment of aldoxime with N-chlorosuccinimide (NCS), thiourea, and triethylamine. The use of HCl/DMF/Oxone system in the reaction instead of NCS was equally effective.
- Kim, Jae Nyoung,Jung, Keum Shin,Lee, Hong Jung,Son, Ji Suk
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p. 1597 - 1598
(2007/10/03)
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- Cycloaddition and Oxidation Reactions of a Stable Thioaldehyde, (2,4,6-Tri-t-butyl)thiobenzaldehyde
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The title thioaldehyde 1 undergoes [4 + 2] cycloaddition with 2,3-dimethyl-1,3-butadiene at 160°C and [3 + 2] cycloadditions with diphenylnitrilimine and mesitonitrile oxide at room temperature. The intermediary cycloadduct with mesitonitrile oxide undergoes cycloreversion to give 2,4,6-tri-t-butylbenzaldehyde and mesityl isothiocyanate as the final products. Oxidation of 1 with m-chloroperbenzoic acid (mCPBA) and dimethyldioxirane (9) gives a mixture of (E)- and (Z)-isomers of the corresponding S-oxides (sulfines), the former and the latter being kinetically and thermodynamically controlled products, respectively. Although both (E)- and (Z)-sulfines are not further oxidized by mCPBA, the (Z)-sulfine is oxidized with 9 to give 7-oxa-8-thia-2,4,6-tri-t-butylbicyclo[4.3.0]nona-2,4,9-triene 8,8-dioxide and 6,8-di-t-butyl-3,4-dihydro-4,4-dimethyl-1H-2-benzothiopyran 2,2-dioxide, both of which are intramolecular cyclization products of an intermediary thioaldehyde dioxide (sulfene).
- Watanabe, Soichiro,Yamamoto, Toshio,Kawashima, Takayuki,Inamoto, Naoki,Okazaki, Renji
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p. 719 - 724
(2007/10/03)
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- SYNTHESIS, STRUCTURE, AND REACTIVITY OF 1,4,2-OXATELLURAZOLE: A NOVEL TELLURIUM-CONTAINING HETEROCYCLE
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A novel tellurium containing heterocycle, 1,4,2-oxatellurazole, was characterized by X-ray crystallographic analysis which showed a remarkably small C-Te-C bond angle (79.4 deg), and its 1,3-dipolar cycloreversion is discussed.
- Minoura, Mao,Kawashima, Takayuki,Okazaki, Renji
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p. 403 - 404
(2007/10/02)
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- Structure and Thermolysis of a 1,4,2-Oxatellurazole, a Novel Tellurium Containing Heterocycle
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A novel tellurium containing heterocycle, 1,4,2-oxatellurazole, was characterized by X-ray crystallographic analysis which showed a remarkably small C-Te-C bond angle (79.4 deg), and its thermolysis afforded the corresponding ketone and isonitrile derived from an intermediary isotellurocyanate in a manner of 1,3-dipolar cycloreversion.
- Minoura, Mao,Kawashima, Takayuki,Okazaki, Renji
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p. 1691 - 1692
(2007/10/02)
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- A convenient synthesis of isothiocyanates from nitrile oxides
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Isothiocyanats were prepared in quantitative yields from the reaction of nitrile oxides with thiourea in tetrahydrofuran at room temperature in short time.
- Kim, Jae Nyoung,Ryu, Eung K.
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p. 8283 - 8284
(2007/10/02)
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- Thioketones and Enethiolates by 1,3-Anionic Cycloreversion of Dithiolane Derivatives
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The reactive (ar)aliphatic thioketones 3a-c are generated by cycloreversion of the anions 2 of 1,3-dithiolane-4,5-dicarboxylates 1 and are trapped by mesitonitrile oxide (5) in a 1,3-dipolar cycloaddition to give 7.From the fragmentation of anions 12 of 1,3-dithiolane 1,1-dioxides 11, thiobenzophenone (3d) and thiocamphor (3e) are isolated, wheras thioketones 3a,c with α-hydrogen are deprotonated in situ to provide enethiolates 13.Anions 13 add nitrile oxide 5 to yield thiohydroximates 8.
- Schaumann, Ernst,Ruehter, Gerd
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p. 1159 - 1164
(2007/10/02)
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- Heterodiene and Heteroene Activity of Benzoyl Isothiocyanates towards Electron-Rich Alkynes. Synthesis and Crystal Structure of Regioisomeric 1,3-Oxazine-thiones.
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The reactions of benzoyl isothiocyanate (2a-c) with 1-diethylaminopropyne (1) lead to mixtures of regioisomeric 1,3-oxazinethiones (4) - (6) in variable ratios depending on the substituent ( H, p-NO2, p-OMe ) in the phenyl ring of (2) and the solvent polarity.Benzoyl isocyanate (3) and (1) give exclusively the 1,3-oxazine-4-one (7).The 1,3-oxazinethiones (4) - (6) are interpreted to arise from three concurrent processes, a (4+2) and a (2+2)-cycloaddition as well as a 1,2-addition, which involve the alkyne triple bond and different sites of the isothiocyanate.From benzoyl isothiocyanate (2a) and ethoxyacetylene, the only product isolated is the formal (4+2)-cycloadduct 1,3-oxazine-2-thione derivative (16a).The structures of three selected oxazinethiones were established by X-ray crystallography.
- Kniezo, Ladislav,Kristian, Pavol,Dondoni, Alessandro,Pedrini, Paola,Andreetti, Giovanni Dario,Ugozzoli, Franco
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p. 537 - 578
(2007/10/02)
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- Nouvelles syntheses de systemes biheterocycliques II. Cycloaddition dipolare-1,3 et condensation de carbene sur des triazepines-1,2,4
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The condensation of mesitonitrile and dichlorocarbene in aqueous medium to 1,2,4-triazepines has been studied.In all cases this cycloaddition is peri and regiospecific.Compounds with the unknown ring systems isoxazolo-1,2,4-triazepine and azirino-1,2,4-triazepine have been synthesized.The structural elucidation of these products was accomplished by spectral evidences.
- Hasnaoui, A.,Messaoudi, M. El,Lavergne, J.-P.
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p. 129 - 131
(2007/10/02)
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- FRAGMENTATION OF 1,3-DITHIOLANE-DERIVED SULFUR YLIDES. A CONVENIENT THIOALDEHYDE SYNTHESIS
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S-Ylides 10, which are generated by regiospecific deprotonation of 1,3-dithiolanium salts 9 with electron-withdrawing groups in the 4,5 positions, fragment under mild conditions to generate thioaldehydes 12.
- Schaumann, Ernst,Ruhter, Gerd
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p. 5265 - 5268
(2007/10/02)
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- Reactions of Metal and Metalloid Compounds with Polyfunctional Molecules, XXXVII. New Syntheses of Cyclic N-Silylureas and -thioureas
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N,N'-Diorganylureas react with silicon tetrachloride to give the 1,3,5-triaza-2-silacyclohexan-4,6-diones 1-4, in case of N,N'-dicyclohexylurea to give dicyclohexylcarbodiimide.By reacting bis(diethylamino)dimethylsilane with N,N'-diorganylureas and thioureas, resp., one obtains 1,3,5-triaza-2,4-disilacyclohexan-6-ones 6, 10, 13-15, 1-oxa-3,5-diaza-6-silacyclohexan-4-ones 5, 9, 1,3,5-triaza-2-silacyclohexan-4,6-diones 7, 11, 1,3-dioxa-5-aza-2,6-trisilacyclohexanes 8, 12, 1,3,5-triaza-2,4-disilacyclohexan-6-thiones 16-25 or the organylamino-diethylamino-dimethylsilanes 26-28.The compounds were characterized analytically and spectroscopically. - Keywords: N-Silylated Ureas and Thioureas, Silicon Tetrachloride, Bis(dimethylamino)dimethylsilane
- Maringgele, Walter
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- Dediazoniation of Arenediazonium Ions. Part XIX. Effect of Thiocyanate Ion in the Reactions of 2,4,6-Trimethylbenzenediazonium Tetrafluoroborate in 2,2,2-trifluoroethanol
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The dediazoniation of 2,4,6-trimethylbenzenediazonium tetrafluoroborate (1) in 2,2,2-trifluoroethanol (TFE) was studied in the presence of potassium thiocyanate.The effect of added salt on the dediazoniation rate, the Nα-Nβ rearrangement (Eqn. 2), the exchange of the 15N-labelled diazo group with molecular nitrogen (Eqn. 3), and the reaction products was determinated.With 0.3M KSCN a dediazoniation-rate increase of 16.5percent was achieved, and the amounts of rearranged and exchanged product were reduced to 88percent and 70percent, respectively, of the values found in pure TFE.The dediazoniation products formed are ArF (3), ArOCH2CF3 (4), ArSCN (5), ArNCS (6) and traces of 5,7-dimethylindazole (7).All the data are in agreement with, and support the previously proposed mechanism (Eqn. 1) of heterolytic dediazoniation of arenediazonium salts.
- Szele, Ivanka,Zollinger, Heinrich,Deshpande, Ashok D.
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p. 2721 - 2727
(2007/10/02)
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