cas 2571-54-2, 2,4,6-Trimethoxybenzonitrile

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Electrochemical Oxidative C?H Cyanation of Quinoxalin-2(1H)-ones with TMSCN
Both quinoxalin-2(1H)-ones and nitriles are valuable organic compounds, and it is an interesting task to introduce cyano into quinoxalin-2(1H)-ones. Herein a regioselective C?H cyanation of quinoxalin-2(1H)-ones was developed with a nucleophilic cyano source TMSCN under electrochemical oxidative conditions. This process allowed the synthesis of C3 cyanated quinoxalin-2(1H)-ones in moderate to excellent yields in the absence of transition-metal catalysts and organic hydroperoxides.
Li, Yifan,Liu, Ping,Sun, Peipei,Tong, Jinwen,Zhan, Yanling
p. 2193 - 2197
(2021)
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Site-Selective Electrochemical C-H Cyanation of Indoles
An electrochemical approach for the site-selective C-H cyanation of indoles employing readily available TMSCN as cyano source has been developed. The electrosynthesis relies on the tris(4-bromophenyl)amine as a redox catalyst, which achieves better yield and regioselectivity. A variety of C2- and C3-cyanated indoles were obtained in satisfactory yields. The reactions are conducted in a simple undivided cell at room temperature and obviate the need for transition-metal reagent and chemical oxidant.
Li, Laiqiang,Hou, Zhong-Wei,Li, Pinhua,Wang, Lei
supporting information
p. 5983 - 5987
(2021/08/16)

Copper-Catalyzed One-Pot Synthesis of Quinazolinones from 2-Nitrobenzaldehydes with Aldehydes: Application toward the Synthesis of Natural Products
A novel, efficient, and atom-economical approach for the construction of quinazolinones from 2-nitrobenzaldehydes has been unveiled via copper-catalyzed nitrile formation, hydrolysis, and reduction in one pot for the first time. In this reaction, urea is used as a source of nitrogen for nitrile formation, hydrazine hydrate is used for both the reduction of the nitro group and the hydrolysis of nitrile, and atmospheric oxygen is used as the sole oxidant. The method portrays a wide substrate scope with good functional group tolerances. Moreover, this method was applied for the synthesis of schizocommunin, tryptanthrin, phaitanthrin-A, phaitanthrin-B, and 8H-quinazolino[4,3-b]quinazolin-8-one.
Pal, Shantanu,Sahoo, Subrata
p. 18067 - 18080
(2021/12/06)

DIBENZOTHIOPHENE SALT AS ALKYNYLATING AND CYANATING AGENT
The present invention describes a new alkynylation and cyanation agent, as well as its preparation and use to introduce nitrile (cyano) or alkyne groups into chemical target molecules by means of an electrophilic reaction. To enable an electrophilic reaction, the chemical backbone of dibenzothiophene was used.
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(2021/08/27)

Conversions of aryl carboxylic acids into aryl nitriles using multiple types of Cu-mediated decarboxylative cyanation under aerobic conditions
Here, we used malononitrile or AMBN as a cyanating agent to develop efficient and practical protocols for Cu-mediated decarboxylative cyanations, under aerobic conditions, of aryl carboxylic acids bearing nitro and methoxyl substituents at the ortho position as well as of heteroaromatic carboxylic acids. These protocols involved economical methods to synthesize value-added aryl nitriles from simple and inexpensive raw materials. Further diversification of the 2-nitrobenzonitrile product was performed to highlight the practicality of the protocols. This journal is
Cai, Hu,Cao, Xihan,Fu, Zhengjiang,Guo, Shengmei,Wang, Shuiliang
supporting information
p. 8381 - 8385
(2020/11/05)

Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes
Photoexcited electron-hole pairs on a semiconductor surface can engage in redox reactions with two different substrates. Similar to conventional electrosynthesis, the primary redox intermediates afford only separate oxidized and reduced products or, more rarely, combine to one addition product. Here, we report that a stable organic semiconductor material, mesoporous graphitic carbon nitride (mpg-CN), can act as a visible-light photoredox catalyst to orchestrate oxidative and reductive interfacial electron transfers to two different substrates in a two- or three-component system for direct twofold carbon–hydrogen functionalization of arenes and heteroarenes. The mpg-CN catalyst tolerates reactive radicals and strong nucleophiles, is straightforwardly recoverable by simple centrifugation of reaction mixtures, and is reusable for at least four catalytic transformations with conserved activity.
Ghosh, Indrajit,Khamrai, Jagadish,Savateev, Aleksandr,Shlapakov, Nikita,Antonietti, Markus,K?nig, Burkhard
p. 360 - 366
(2019/08/15)

5-(Cyano)dibenzothiophenium Triflate: A Sulfur-Based Reagent for Electrophilic Cyanation and Cyanocyclizations
The synthesis of 5-(cyano)dibenzothiophenium triflate 9, prepared by activation of dibenzo[b,d]thiophene-5-oxide with Tf2O and subsequent reaction with TMSCN is reported, and its reactivity as electrophilic cyanation reagent evaluated. The scalable preparation, easy handling and broad substrate scope of the electrophilic cyanation promoted by 9, which includes amines, thiols, silyl enol ethers, alkenes, electron rich (hetero)arenes and polyaromatic hydrocarbons, illustrate the synthetic potential of this reagent. Importantly, Lewis acid activation of the reagent is not required for the transfer process. We additionally report herein biomimetic cyanocyclization cascade reactions, which are not promoted by typical electrophilic cyanation reagents, demonstrating the superior ability of 9 to trigger challenging transformations.
Li, Xiangdong,Golz, Christopher,Alcarazo, Manuel
supporting information
p. 9496 - 9500
(2019/06/27)

GaCl3-Catalyzed C-H Cyanation of Indoles with N-Cyanosuccinimide
An efficient GaCl3-catalyzed direct cyanation of indoles and pyrroles using bench-stable electrophilic cyanating agent N-cyanosuccinimide was achieved and afforded 3-cyanoindoles and 2-cyanopyrroles in good yields and excellent regioselectivities. Notably, this protocol exhibited high reactivity for unprotected indoles and was applicable to a broad range of indole and pyrrole substrates.
Wang, Xue,Makha, Mohamed,Chen, Shu-Wei,Zheng, Huaiji,Li, Yuehui
p. 6199 - 6206
(2019/05/24)

Dual Ligand-Enabled Nondirected C-H Cyanation of Arenes
Aromatic nitriles are key structural units in organic chemistry and, therefore, highly attractive targets for C-H activation. Herein, the development of an arene-limited, nondirected C-H cyanation based on the use of two cooperatively acting commercially available ligands is reported. The reaction enables the cyanation of arenes by C-H activation in the absence of directing groups and is therefore complementary to established approaches.
Chen, Hao,Mondal, Arup,Wedi, Philipp,Van Gemmeren, Manuel
p. 1979 - 1984
(2019/02/19)

Ligand-Promoted Non-Directed C?H Cyanation of Arenes
This article reports the first example of a 2-pyridone accelerated non-directed C?H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (kH/kD=4.40) indicates that the C?H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.
Liu, Luo-Yan,Yeung, Kap-Sun,Yu, Jin-Quan
supporting information
p. 2199 - 2202
(2019/01/24)

SUBSTITUTED IMIDAZOLIUM SULFURANES AND THEIR USE
The present invention refers to substituted imidazolium sulfuranes, the use thereof for the transfer of a -CN group or an alkyne group.
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(2017/01/26)

Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
p. 2794 - 2803
(2016/04/26)

Rhodium-Catalyzed Transnitrilation of Aryl Boronic Acids with Dimethylmalononitrile
An efficient transnitrilation of aryl boronic acids with dimethylmalononitrile (DMMN) is described. This rhodium-catalyzed electrophilic cyanation presents a novel approach to prepare aryl nitriles by using a carbon-bound cyanating reagent which undergoes cross-coupling with the aryl boronic acid. The reaction expands the degree of functional-group compatibility exhibited by the transnitrilation of aryl Grignard and aryllithium reagents. A variety of aryl boronic acid derivatives and dialkylmalononitriles were amenable to the transnitrilation.
Malapit, Christian A.,Reeves, Jonathan T.,Busacca, Carl A.,Howell, Amy R.,Senanayake, Chris H.
supporting information
p. 326 - 330
(2016/01/25)

Facile one-pot transformation of arenes into aromatic nitriles under metal-cyanide-free conditions
Electron-rich arenes bearing methyl or methoxy groups on the aromatic ring were treated with dichloromethyl methyl ether and ZnBr2, and then with molecular iodine and aq. ammonia to give the corresponding aromatic nitriles in good yields. Using this method, febuxostat was efficiently prepared from 4-bromophenol in four steps. The method can be used for the preparation of aromatic nitriles from arenes in one pot under metal-cyanide-free conditions. Various electron-rich arenes could be effectively converted into the corresponding aromatic nitriles in good yields, by treatment with ZnBr2 and dichloromethyl methyl ether, followed by reaction with molecular iodine and aq. ammonia.
Tamura, Toshiyuki,Moriyama, Katsuhiko,Togo, Hideo
p. 2023 - 2029
(2015/03/18)

Copper-mediated cyanation of indoles and electron-rich arenes using DMF as a single surrogate
The copper-mediated cyanation of indoles with DMF as a single surrogate has been realized. This approach could be applied for the cyanation of some electron-rich arenes and aryl aldehydes as well. Aryl aldehydes were demonstrated to be the key intermediates in the cascade process of cyanation of indoles and electron-rich arenes.
Zhang, Lianpeng,Lu, Ping,Wang, Yanguang
p. 8322 - 8329
(2015/08/03)

Electroorganic synthesis of nitriles via a halogen-free domino oxidation-reduction sequence
A direct electroorganic sequence yielding nitriles from oximes in undivided cells is reported. Despite the fact that intermediate nitrile oxides might be formed, the method is viable to prepare benzonitriles without substituents ortho to the aldoxime moiety. This constant current method is easy to perform for a broad scope of substrates and employs common electrodes, such as graphite and lead.
Hartmer, Marius F.,Waldvogel, Siegfried R.
supporting information
p. 16346 - 16348
(2015/11/16)

Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis
An electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides, by a transnitrilation with dimethylmalononitrile (DMMN) was developed. DMMN is a commercially available, bench-stable solid. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates. The transnitrilation of aryllithium species generated by directed ortho-lithiation enabled a net C-H cyanation. The intermediacy of a Thorpe-type imine adduct in the reaction was supported by isolation of the corresponding ketone from the quenched reaction. Computational studies supported the energetic favorability of retro-Thorpe fragmentation of the imine adduct. (Chemical Equation Presented).
Reeves, Jonathan T.,Malapit, Christian A.,Buono, Frederic G.,Sidhu, Kanwar P.,Marsini, Maurice A.,Sader, C. Avery,Fandrick, Keith R.,Busacca, Carl A.,Senanayake, Chris H.
supporting information
p. 9481 - 9488
(2015/08/11)

Dihalo(imidazolium)sulfuranes: A Versatile Platform for the Synthesis of New Electrophilic Group-Transfer Reagents
The syntheses of imidazolium thiocyanates and imidazolium thioalkynes from dihalo(imidazolium) sulfuranes are reported and their reactivities as CN+ and R-CC+ synthons evaluated, respectively. The easy and scalable preparation of these electrophilic reagents, their operationally simple handling, broad substrate scope, and functional group tolerance clearly illustrate the potential of these species to become a reference for the direct electrophilic cyanation and alkynylation of organic substrates.
Talavera, Garazi,Pe?a, Javier,Alcarazo, Manuel
supporting information
p. 8704 - 8707
(2015/07/27)

Acetonitrile as a cyanating reagent: Cu-catalyzed cyanation of arenes
A novel approach to the Cu-catalyzed cyanation of simple arenes using acetonitrile as an attractive cyano source has been documented. The C-H functionalization of arenes without directing groups involves a sequential iodination/cyanation to give the desired aromatic nitriles in good yields. A highly efficient Cu/TEMPO system for acetonitrile C-CN bond cleavage has been discovered. TEMPO is used as a cheap oxidant and enables the reaction to be catalytic in copper. Moreover, TEMPOCH2CN 6 has been identified as the active cyanating agent and shows high reactivity for forming the -CN moiety.
Zhu, Yamin,Zhao, Mengdi,Lu, Wenkui,Li, Linyi,Shen, Zengming
supporting information
p. 2602 - 2605
(2015/06/16)

Catalytic cyanation of aryl iodides using DMF and ammonium bicarbonate as the combined source of cyanide: A dual role of copper catalysts
Cu(ii)-catalyzed cyanation of aryl iodides has been developed using DMF and ammonium bicarbonate as the combined source of cyanide. It is assumed that copper is involved both in the generation of CN units from DMF-ammonia and in the cyanation of aryl halides. A range of electron-rich and fused (hetero)aryl iodides underwent cyanation resulting in moderate to good yields.
Pawar, Amit B.,Chang, Sukbok
supporting information
p. 448 - 450
(2014/01/06)

Copper- and silver-mediated cyanation of aryl iodides using ddq as cyanide source
A new copper and silver-mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, providing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles. A new copper and silver-mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved.
Zheng, Kui,Yu, Peng,Chen, Shuyou,Chen, Fen,Cheng, Jiang
supporting information
p. 449 - 452
(2013/08/25)

Copper-catalyzed cyanation of aryl iodide with the combined cyanide source of urea and DMSO
A simple copper-catalyzed cyanation of aryl iodide with the combination of urea and dimethyl sulfoxide as a cyanide source is achieved, providing nitriles in moderate to good yields. This new approach represents an exceedingly practical and safe method for the synthesis of aryl nitriles.
Zheng, Kui,Liu, Bin,Chen, Shuyou,Chen, Fan
supporting information
p. 5250 - 5252
(2013/09/02)

Copper-mediated cyanation of aryl halides by activation of benzyl cyanide as the cyanide source
Aryl nitriles were efficiently synthesized through copper-mediated cyanation of aryl halides using benzyl cyanide as the cyanide source. Aryl halides with various substituents on the aromatic ring afforded the corresponding aryl nitriles in 32-97 % yields (25 examples). This reaction could also be carried on a gram scale by using commercially available reagents. Additionally, a C-H bond oxidation and a C-CN cleavage are proposed to be involved in this cascade process. An efficient, copper-mediated cascade synthesis of aryl nitriles from aryl halides using benzyl cyanide as the cyanide source is described. Compared with traditional copper-mediated cyanation reactions, this approach effectively avoided the use of toxic MCN and low soluble reagents. Furthermore, C-H oxidation and C-CN cleavage are proposed to be involved in this cascade process. Copyright
Wen, Qiaodong,Jin, Jisong,Mei, Yuncai,Lu, Ping,Wang, Yanguang
p. 4032 - 4036
(2013/07/11)

Palladium-catalyzed cyanation of aryl halides with CuSCN
A palladium-catalyzed cyanation of aryl halides and borons has been developed by employing cuprous thiocyanate as a safe cyanide source. This protocol avoids the use of a highly toxic cyanide source, providing aromatic nitriles in moderate to good yields with good functional tolerance.
Zhang, Guo-Ying,Yu, Jin-Tao,Hu, Mao-Lin,Cheng, Jiang
p. 2710 - 2714
(2013/05/08)

Practical one-pot conversion of aryl bromides and β-bromostyrenes into aromatic nitriles and cinnamonitriles
Various aryl bromides were efficiently converted into the corresponding aromatic nitriles in good yields by the treatment with Mg turnings and subsequently DMF, followed by treatment with molecular iodine and aq NH 3. The same treatment of aryl bromides, which are weakly reactive to Mg turnings, with iPrMgCl·LiCl and subsequently DMF, followed by the treatment with molecular iodine and aq NH3 also afforded the corresponding aromatic nitriles in good yields. On the other hand, when N-formylpiperidine was used instead of DMF, p-substituted β-bromostyrenes were converted into the corresponding p-substituted cinnamonitriles, i.e., α,β-unsaturated nitriles, in good to moderate yields by the same procedure. The reactions were carried out by means of a simple experimental procedure and did not require any toxic metal cyanides or expensive rare metals. Therefore, the present reactions are practical and environmentally benign one-pot methods for the preparation of aromatic nitriles, cinnamonitriles, and aliphatic nitriles from aryl bromides, β-bromostyrenes, and alkyl bromides, respectively, through the formation of Grignard reagents and their DMF or N-formylpiperidine adducts.
Ishii, Genki,Harigae, Ryo,Moriyama, Katsuhiko,Togo, Hideo
p. 1462 - 1469
(2013/02/25)

Practical one-pot transformation of electron-rich aromatics into aromatic nitriles with molecular iodine and aq NH3 using Vilsmeier-Haack reaction
Various electron-rich aromatics could be efficiently transformed into the corresponding aromatic nitriles in good to moderate yields by treatment with DMF and POCl3, followed by the reaction with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH) in aq NH3. Some of less reactive aromatics, such as anisole, 1,2-dimethoxybenzene, 1,4-dimethoxybenzene, and mesityrene, could be also transformed into the corresponding aromatic nitriles in good to moderate yields using N-methylformanilide and O(POCl 2)2, followed by the reaction with molecular iodine in aq NH3. Moreover, propiophenone derivatives could be successfully transformed into the corresponding β-chlorocinnamonitriles by the reaction with DMF and POCl3, followed by the reaction with molecular iodine and aq NH3. These reactions are novel metal-free one-pot methods for the preparation of aromatic nitriles from electron-rich aromatics and β-chlorocinnamonitriles from propiophenones.
Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
experimental part
p. 4588 - 4595
(2012/07/27)

Copper-mediated sequential cyanation of aryl C-B and arene C-H bonds using ammonium iodide and DMF
The cyanation of aromatic boronic acids, boronate esters, and borate salts was developed under copper-mediated oxidative conditions using ammonium iodide and DMF as the source of nitrogen and carbon atom of the cyano unit, respectively. The procedure was successfully extended to the cyanation of electron-rich benzenes, and regioselective introduction of a cyano group at the arene C-H bonds was also achieved. The observation that the reaction proceeds via a two-step process, initial iodination and then cyanation, led us to propose that ammonium iodide plays a dual role to provide iodide and nitrogen atom of the cyano moiety.
Kim, Jinho,Choi, Jiho,Shin, Kwangmin,Chang, Sukbok
supporting information; experimental part
p. 2528 - 2531
(2012/04/04)

Pd(OAc)2-catalyzed alkoxylation of arylnitriles via sp 2 C-H bond activation using cyano as the directing group
A Pd(OAc)2-catalyzed ortho-alkoxylation of arylnitrile was described. Using cyano as a directing group, the aromatic C-H bond can be functionalized efficiently to generate ortho-alkoxylated arylnitrile derivatives with moderate yields. The opti
Li, Wu,Sun, Peipei
p. 8362 - 8366
(2013/01/15)

Transformation of aromatic bromides into aromatic nitriles via formations of grignard reagents and their DMF adducts
Various aromatic bromides were efficiently transformed into the corresponding aromatic nitriles in good yields via the formations of Grignard reagents and subsequently N,N-dimethyl formamide (DMF) adducts, followed by treatment with molecular iodine (I2) in aq NH3 at room temperature. The present reaction is an easy and practical method for the preparation of aromatic nitriles from aromatic bromides with less toxic reagents, such as Mg, DMF, I2, and aq NH3.
Ishii, Genki,Moriyama, Katsuhiko,Togo, Hideo
experimental part
p. 2404 - 2406
(2011/05/16)

One-pot conversion of aromatic bromides and aromatics into aromatic nitriles via aryllithiums and their DMF adduct
Various aromatic bromides and iodides were smoothly converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH3. The same treatment of typical aromatics and heteroaromatics with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH3 also provided the corresponding aromatic nitriles in good yields. Moreover, the same treatment of aromatic bromides and aromatics with half amount of DIH (1,3-diiodo-5,5- dimethylhydantoin) instead of molecular iodine worked effectively to give the corresponding aromatic nitriles, respectively, in good yields. These reactions are novel and environmentally benign one-pot methods for the preparation of aromatic nitriles from aromatic bromides and aromatics, respectively, through the formation of aryllithiums and their DMF adducts.
Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
experimental part
p. 958 - 964
(2011/03/19)

CYTOKINE INHIBITORS
The present invention provides compounds represented by general formula (I): wherein, R1; R2, R3, L and T are as defined in the specification, in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, and their pharmaceutically acceptable salts, pharmaceutically acceptable solvates, and prodrugs thereof. The invention also relates to processes for the manufacture of compounds of formula (I) and pharmaceutical compositions containing them. The compounds and the pharmaceutical compositions of the present invention are useful in the treatment of a condition or disorder mediated by one or more cytokines selected from Tumor Necrosis Factor-alpha (TNF-oc) and interleukins such as IL-1, IL-6, and IL-8. The present invention further provides a method of treatment of inflammatory disorders by administering a therapeutically effective amount of the said compound of formula (I) or its pharmaceutical composition, to a mammal in need thereof.
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(2011/10/13)

Iron-mediated cyanation of methoxybenzene, indole, and 2-arylpyridine C-H bonds
An iron-mediated direct cyanation of indole and 2-arylpyridine C-H bonds is described. Notably, trimethoxybenzene reacted smoothly under the procedure, forming a C-CN bond via C-H bond cleavage without chelation assistance. Georg Thieme Verlag Stuttgart · New York.
Zhang, Guangyou,Lv, Guanglei,Pan, Changduo,Cheng, Jiang,Chen, Fan
supporting information; experimental part
p. 2991 - 2994
(2012/01/07)

Lewis acid catalyzed direct cyanation of indoles and pyrroles with N-cyano-N-phenyl-p-toluenesulfonamide (NCTS)
BF3?OEt2-catalyzed direct cyanation of indoles and pyrroles using a less toxic, bench-stable, and easily handled electrophilic cyanating agent N-cyano-N-phenyl-para-toluenesulfonamide (NCTS) affords 3-cyanoindoles and 2-cyanopyrroles in good yields with excellent regioselectivity. The substrate scope is broad with respect to indoles and pyrroles.
Yang, Yang,Zhang, Yan,Wang, Jianbo
supporting information; experimental part
p. 5608 - 5611
(2011/12/03)

Copper-mediated cyanation of aryl halide with the combined cyanide source
A simple copper-mediated cyanation of aryl halide with the combination of ammonium bicarbonate and N,N-dimethylformamide as a cyanide source is achieved, providing nitriles in moderate to good yields. This new approach represents an exceedingly practical and safe method for the synthesis of aryl nitriles.
Zhang, Guoying,Ren, Xinyi,Chen, Jianbin,Hu, Maolin,Cheng, Jiang
supporting information; experimental part
p. 5004 - 5007
(2011/11/12)

One-pot conversion of aromatic bromides and aromatics into aromatic nitriles
Various aromatic bromides and iodides were smoothly converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with butyllithium and subsequently DMF, followed by treatment with molecular iodine in aqueous ammonia. The
Ushijima, Sousuke,Togo, Hideo
experimental part
p. 1562 - 1566
(2010/09/05)

Metal-free one-pot conversion of electron-rich aromatics into aromatic nitriles
Various electron-rich aromatics could be smoothly converted into the corresponding aromatic nitriles in good to moderate yields by treatment of electron-rich aromatics with POCl3 and DMF, followed by treatment with molecular iodine in aqueous ammonia. The present reaction is a novel metal-free one-pot method for the preparation of aromatic nitriles from electron-rich aromatics.
Ushijima, Sousuke,Togo, Hideo
experimental part
p. 1067 - 1070
(2010/06/14)

Palladium-catalyzed direct cyanation of indoles with K4[Fe(CN) 6]
"Chemical equation presented" Direct cyanation of Indole derivatives has been achieved with nontoxic K4[Fe(CN)6] as cyanating agent through Pd-catalyzed C-H bond activation.
Yan, Guobing,Kuang, Chunxiang,Zhang, Yan,Wang, Jianbo
scheme or table
p. 1052 - 1055
(2010/06/13)

Direct transformation of methyl arenes to aryl nitriles at room temperature
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Zhou, Wang,Zhang, Liangren,Jiao, Ning
supporting information; experimental part
p. 7094 - 7097
(2009/12/28)

Convenient conversion of aldoximes into nitriles with N-chlorosuccinimide and pyridine
Benzaldehyde oximes substituted with electron-donating groups are dehydrated to the corresponding benzonitriles by N-chlorosuccinimide/pyridine in acetonitrile. Benzaldehyde oxime itself and alkanal oximes afford the corresponding aldehydes. Thieme Stuttgart.
Gucma, Miroslaw,Golebiewski, W. Marek
scheme or table
p. 1997 - 1999
(2009/04/03)

Efficient and Rapid One-pot Conversions of Aldehydes into Nitriles and Ketones into Amides Using Silica Chloride under Microwave Irradiation
Under solvent free conditions, several aldehydes and ketones were efficiently and rapidly converted into the corresponding nitriles and amides respectively by treatment with hydroxylamine hydrochloride under microwave irradiation using silica chloride as catalyst. The yields of the products were very high and the time required for their preparation was very short compared to conventional heating experiments.
Srinivas,Mahender,Das, Biswanath
p. 738 - 739
(2007/10/03)

Highly convenient and efficient one-pot conversions of aldehydes into nitriles and ketones into amides using HY-zeolite
One-pot conversions of aldehydes into nitriles and ketones into amides have been carried out conveniently and efficiently using HY-zeolite as catalyst. Both microwave irradiation and conventional methods have been studied.
Srinivas,Reddy, E. Bolla,Das, Biswanath
p. 625 - 627
(2007/10/03)

Chemistry of 2,4,6-trinitrobenzonitrile 1. Nitro group substitution in 2,4,6-trinitrobenzonitrile under the action of anionic nucleophiles. Factors favoring substitution of the ortho-nitro group
The direction of the nitro group substitution (the ratio of the ortho/para substitution) in 2,4,6-trinitrobenzonitrile under the action of anionic nucleophiles (MeO-, RS-, and N3-) as well as of HCl was studied.
Dalinger,Cherkasova,Vorob'ev,Aleksandrov,Popova,Shevelev
p. 2401 - 2405
(2007/10/03)

A simple and highly efficient one-pot chemoselective synthesis of nitriles from aldehydes: Mechanistic insight and selectivity control through modulation of electronic and steric factors
Aldehydes are converted into nitriles in a one-pot reaction by treatment with H2NOH·HCl in dipolar aprotic solvents under heating. Amongst various solvents NMP offers the best results. No competitive ether cleavage (e.g. methoxy, benzyloxy) or aromatic nucleophilic substitution (e.g. nitro or chloro) takes place for substrates beating such functionalities. Electronic and steric factors around the aldehyde carbon affect the rate of nitrile formation. Excellent to moderate selectivity is observed during intermolecular competition between pair of aldehydes with varying electronic and steric requirements.
Chakraborti,Kaur,Roy
p. 1000 - 1006
(2007/10/03)

Exploitation of aldoxime esters as radical precursors in preparative and EPR spectroscopic roles
Photolyses of aldoxime esters, containing a considerable range of alkyl groups, lead to cleavage of their N-O bonds and formation of aryliminyl and alkyl radicals. The process was found to be favoured by 4-methoxyacetophenone as a photosensitiser and by methoxy substituents in the aryl rings. 4-Nitro- and pentafluoro-substitutions of the aryl rings were, on the other hand, deleterious. The intermediate iminyl radicals, together with primary, secondary and tertiary alkyl radicals were characterised by 9 GHz EPR spectroscopy. Cyclopropyl, CF3, and CCl3 radicals were probably also formed, but were too reactive for direct EPR spectroscopic detection. Photosensitised reaction of benzophenone oxime O-nonanoyl ester produced the diphenylmethaniminoxyl, as well as the expected n-octyl and iminyl radicals. This indicated that O-C bond scission accompanied O-N scission for this ketoxime ester. At higher temperatures the C-centred radicals added to the starting oxime esters to produce alkoxyaminyl radicals that were also spectroscopically detected in some cases. No evidence for abstraction of the iminyl hydrogen by tertbutoxyl radicals was obtained. Instead, the t-BuO radicals added to the C=N double bonds of the oxime esters. Similarly, chlorine abstraction from alkylbenzohydroximoyl chlorides by trimethyltin radicals did not take place. Preparative scale experiments with oxime esters containing suitably unsaturated alkyl groups showed that good yields of cyclised products could be obtained in the presence of the photosensitiser. This process constitutes a general method by which carboxylic acids or acid chlorides can be converted into alkyl radicals and hence to cyclised derivatives.
McCarroll, Andrew J.,Walton, John C.
p. 2399 - 2409
(2007/10/03)

Photolytic and radical induced decompositions of O-alkyl aldoxime ethers
Direct photolytic radical induced homolyses of O-alkyl arylaldoxime ethers (ArCH=NOR) were studied by EPR spectroscopy and by end product analyses. Initiating radicals (X·), including t-BuO·, t-BuS· , alkyl and Me3Sn·, added rapidly to the C=N double bond to give adduct oxyaminyl radicals (ArCHXN·OR) that could be observed and characterised by EPR spectroscopy. For O-alkyl arylaldoxime ethers containing H-atoms attached to the carbon adjacent to the ether oxygen (OR = OCHR12), t-BuO· radicals also abstracted this hydrogen to yield oxyalky radicals that underwent rapid β-scission to afford iminyl radicals (ArCHN·) and an aldehyde or ketone (R12CO). judged by the relative importance of ROH and ArCN amongst the products, abstraction of the iminyl hydrogen atom also took place to yield oximidoyl radicals (ArC·=NOR), although this could not be confirmed by EPR spectroscopic observation of these radicals. Thus, homolysis induced by t-BuO· radicals took place comparatively unselectively. Addition of the t-BuO· radical to the C=N double bond of oxime ethers was very fast, the rate constant being comparable to that for addition of the same radical to nitrones. Direct and photosensitised UV photolysis of O-alkyl arylaldoxime ethers gave alkoxyl and aryliminyl radicals in very low yields. Although traces of 2-methyl-tetrahydrofuran were detected from cyclisation of the pent-4-enyloxyl radical generated by direct photolysis of O-pent-4-enyl benzaldoxime, yields were too low for preparative purposes.
McCarroll, Andrew J.,Walton, John C.
p. 1868 - 1875
(2007/10/03)

One-pot synthesis of nitriles from aldehydes under microwave irradiation: Influence of the medium and mode of microwave irradiation on product formation
Chemoselective transformation of aldehyde to nitrile takes place in a one-pot reaction by treatment with H2NOHHCl in N- methyl-2-pyrrolidinone (NMP) under microwave irradiation using convection mode.
Chakraborti, Asit K.,Kaur, Gurmeet
p. 13265 - 13268
(2007/10/03)

Microwave promoted rapid dehydration of aldoximes to nitriles on a solid support
Aldoximes undergo rapid dehydration with H2SO4/SiO2 solid support, under microwave irradiation in dry media to afford nitriles in high yields.
Kumar, H.M. Sampath,Mohanty, Pradyumna K.,Kumar, M. Suresh,Yadav
p. 1327 - 1333
(2007/10/03)

Polyhalogenoaromatic Compounds. Part 50. Reactions of 4-Benzyloxytetrahalogenopyridines with Nucleophiles
Reaction of 4-benzyloxy-3,5-dichloro-2,6-difluoro- (1; R = CH2Ph) and 4-benzyloxytetrachloropyridine (2; R = CH2Ph) with various nucleophiles (N,N-dimethylhydrazine, piperidine, N,N,N',N'-tetramethylethane-1,2-diamine, triphenylphosphine) occurs unexpectedly at the benzylic methylene group with alkyl-oxygen cleavage to give the corresponding benzylammonium (4) or triphenylphosphonium salt (9) respectively.The molecular structure of the salt derived from 4-benzyloxytetrachloropyridine and N,N-dimethylhydrazine was confirmed by an X-ray study.Preliminary experiments of ut ilising the benzyl cleavage for the preparation of various benzyl derivatives (PhCH2X; X = Cl,Br,I,CN,N3) are described.
Julia, Louis,Suschitzky, H.,Barnes, John C.,Tomlin, Clive D.S.
p. 2507 - 2511
(2007/10/02)