- Rapid and Simple Access to α-(Hetero)arylacetonitriles from Gem-Difluoroalkenes
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A scalable cyanation of gem-difluoroalkenes to (hetero)arylacetonitrile derivatives was developed. This strategy features mild reaction conditions, excellent yields, wide substrate scope, and broad functional group tolerance. Significantly, in this reacti
- Hu, Dandan,Liu, Jiayue,Ren, Hongjun,Song, Jinyu,Zhang, Jun-Qi,Zhu, Guorong
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supporting information
p. 786 - 790
(2022/01/28)
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- Assembly of α-(Hetero)aryl Nitriles via Copper-Catalyzed Coupling Reactions with (Hetero)aryl Chlorides and Bromides
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α-(Hetero)aryl nitriles are important structural motifs for pharmaceutical design. The known methods for direct synthesis of these compounds via coupling with (hetero)aryl halides suffer from narrow reaction scope. Herein, we report that the combination of copper salts and oxalic diamides enables the coupling of a variety of (hetero)aryl halides (Cl, Br) and ethyl cyanoacetate under mild conditions, affording α-(hetero)arylacetonitriles via one-pot decarboxylation. Additionally, the CuBr/oxalic diamide catalyzed coupling of (hetero)aryl bromides with α-alkyl-substituted ethyl cyanoacetates proceeds smoothly at 60 °C, leading to the formation of α-alkyl (hetero)arylacetonitriles after decarboxylation. The method features a general substrate scope and is compatible with various functionalities and heteroaryls.
- Chen, Ying,Xu, Lanting,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 7082 - 7086
(2021/02/26)
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- Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
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Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.
- Dong, Yanan,Li, Yuehui,Yang, Peiju,Zhao, Shizhen
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- Combretastatin A4 analogue containing cyanoethylene joining chain and application in preparing antitumor drugs
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The invention a Combretastatin A4 analogue containing a cyanoethylene joining chain and an application in preparing antitumor drugs, which relates to the field of a medicinal compound. A structural formula (I-IV) is shown as the specification, an anticancer candidate compound which has strong inhibitory activity against cancer cells and is not toxic to normal cells is currently lacked, for the reason, the method prepares 19 I-IV series compounds, and the para and meta positions of the B ring (benzene ring) introduce various alkyl groups, alkoxy groups or amino substituents or replace the B ring (benzene ring) with various heterocyclic rings. In the I-series compound, when the para position of the B ring (benzene ring) is substituted with an ethyl group, an isopropyl group, a dimethylaminogroup or a diethylamino group, the proliferation resistance of the cancer cells is very strong, and toxicity is weak for the L-02 normal cells, a selective anticancer activity coefficient (an IC50 value ratio of L-02 normal cells to cancer cells) can even exceed 10,000, and the four compounds have the potential to be developed into safe and highly effective anticancer drugs.
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- Synthesis and pharmacological evaluation of 2,3-diphenyl acrylonitriles-bearing halogen as selective anticancer agents
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Eighteen novel 2,3-diphenyl acrylonitrile derivatives bearing halogens were designed, synthesized, and evaluated for biological activity. Preliminary in vitro results indicated that the majority of the compounds with a para-substituted halogen had considerable antiproliferative activity against five human cancer cell lines, including MGC-803, AGS, and BEL-7402, with IC50 values in the range of 0.46–100?μm. No significant toxic effects on the non-cancerous human liver cell line L-02 were observed. The selective inhibitory activities against cancer cells were significantly better than that of the control lead compound CA-4 and CA-4P. Particularly, potent activities were found for the derivatives of 3-(4-halogen phenyl)-2-(3,4,5-trimethoxyphenyl)acrylonitrile, such as 5c (4-fluoro), 5f (4-bromo), 5h (4-chloro), and 5k (4-trifluoro- methyl), for AGS with IC50 values of 0.75?±?0.24, 0.68?±?0.21, 0.41?±?0.05, and 1.49?±?0.92?μm, respectively. The antiproliferative effects of 5f were attributed to cell-cycle arrest in the G2/M phase, induction of cellular apoptosis, suppression of cell migration, and inhibition of cell colony formation in AGS cells.
- Li, Jia-Jun,Ma, Jun,Xin, Ya-Bing,Quan, Zhe-Shan,Tian, Yu-Shun
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p. 1419 - 1428
(2018/06/06)
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- Preparation and uses of combretastatin A4 analogs containing cyano and halogen
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The present invention provides preparation and uses of combretastatin A4 analogs containing cyano and halogen, and relates to the field of medicinal compounds, wherein the structure of the combretastatin A4 analog is represented by the following formula defined in the specification. In the prior art, the selective anticancer activity compounds with characteristics of strong inhibition activity oncancer cells and no toxicity to normal cells are necessary to the generation of novel anticancer drugs while the compounds are absent. According to the present invention, based on the requirements inthe prior art, 11 series I combretastatin A4 analogs with fluorine, chlorine, bromine or trifluoromethyl at the ortho position, meta position or para position of the B ring, and 7 series II analogs are synthesized; in the series I compounds, when the para position of the B ring is substituted by fluorine, chlorine, bromine or trifluoromethyl, the good selective anticancer activity can be achieved,and the toxicity to L-02 normal cells is weak; when the para position is substituted by fluorine, chlorine or bromine, a ratio of the IC50 value in AGS cancer cells to the IC50 value in L-02 normal cells is greater than 100; when the para position is substituted by trifluoromethyl, a ratio of the IC50 value in MGC-803 cancer cells to the IC50 value in L-02 normal cells is greater than 100; and the selective anticancer activity of the four compounds is good.
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- Synthesis and characterisation of (Z)-styrylbenzene derivatives as potential selective anticancer agents
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To identify anticancer agents with high potency and low toxicity, a series of (Z)-styrylbenzene derivatives were synthesised and evaluated for anticancer activities using a panel of nine cancer cell lines and two noncancerous cell lines. Most derivatives exhibited significant anti-proliferative activities against five cancer cell lines, including MGC-803 and BEL-7402. (Z)-3-(p-Tolyl)-2-(3,4,5-trimethoxyphenyl)acrylonitrile (6h) showed a strong inhibitory effect on MGC-803 cells (IC50 50 50 value of 6h in L-02 cells was 10,000-fold higher than in MGC-803 cells. Compound 6h inhibited proliferation of BEL-7402 cells by arresting at the G2/M phase through up-regulation of cyclin B1 expression, down-regulation of cyclin A and D1 expression, and induction of apoptosis. In addition, 6h inhibited the migration of BEL-7402 cells and the formation of cell colonies.
- Xin, Ya-Bing,Li, Jia-Jun,Zhang, Hong-Jian,Ma, Jun,Liu, Xin,Gong, Guo-Hua,Tian, Yu-Shun
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p. 1554 - 1564
(2018/10/02)
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- Copper-Catalyzed Cyanation of N-Tosylhydrazones with Thiocyanate Salt as the "cN" Source
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A novel protocol for the synthesis of α-aryl nitriles has been successfully achieved via a copper-catalyzed cyanation of N-tosylhydrazones employing thiocyanate as the source of cyanide. The features of this method include a convenient operation, readily available substrates, low-toxicity thiocyanate salts, and a broad substrate scope.
- Huang, Yubing,Yu, Yue,Zhu, Zhongzhi,Zhu, Chuanle,Cen, Jinghe,Li, Xianwei,Wu, Wanqing,Jiang, Huanfeng
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p. 7621 - 7627
(2017/07/26)
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- One-Pot Preparation of C1-Homologated Aliphatic Nitriles from Aldehydes through a Wittig Reaction under Metal-Cyanide-Free Conditions
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A one-pot protocol to obtain C1-homologated aliphatic nitriles was achieved by treating aromatic and aliphatic aldehydes with the (methoxymethyl)triphenylphosphonium ylide followed by hydrolysis of the resulting methyl vinyl ethers with pTsOH (Ts = para-toluenesulfonyl) and treatment with molecular iodine and aqueous ammonia under metal cyanide free conditions. Neopentyl-type nitriles, which could not be obtained by conventional methods that involved conversion of the neopentyl alcohol into a tosylate and treatment with metal cyanide, were successfully obtained by using the present method.
- Ezawa, Masatoshi,Togo, Hideo
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p. 2379 - 2384
(2017/05/01)
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- I2-Mediated oxidative bicyclization of 4-pentenamines to prolinol carbamates with CO2 incorporating oxyamination of the C=C bond
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A metal-free oxyamination reaction of alkenes with ambient CO2 is reported. In the presence of I2 and DBU, CO2 is applied in situ as a protecting group to regulate the nucleophilicity of the amino group and facilitate the bicyclization of 4-pentenamines with high chemoselectivity. Moreover, this reaction provided a feasible approach to prepare prolinol carbamates with good tolerance of functional groups and high efficiency under mild conditions.
- Wang, Sheng,Zhang, Xiaowei,Cao, Chengyao,Chen, Chao,Xi, Chanjuan
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supporting information
p. 4515 - 4519
(2017/10/13)
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- Preparation of novel magnetic dicationic ionic liquid polymeric phase transfer catalyst and their application in nucleophilic substitution reactions of benzyl halides in water
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PEG-based magnetic dicationic ionic liquid was successfully prepared and evaluated as phase-transfer catalyst for nucleophilic substitution reactions of benzyl halides for the synthesis of benzyl azides and cyanides from good to excellent yields at 90 °C in water. The reactions occur in water and furnish the corresponding benzyl derivatives in high yields. No evidence for the formation of by-product for example benzyl alcohol of the reaction was observed and the products were obtained in pure form without further purification.
- Godajdar, Bijan Mombani,Ansari, Bita
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- The Concise Synthesis of Unsymmetric Triarylacetonitriles via Pd-Catalyzed Sequential Arylation: A New Synthetic Approach to Tri- and Tetraarylmethanes
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The selective synthesis of multiarylated acetonitriles via sequential palladium-catalyzed arylations of chloroacetonitrile is reported. The three aryl groups are installed via a Pd-catalyzed Suzuki-Miyaura cross coupling reaction followed by back-to-back C-H arylations to afford triarylacetonitriles in three steps with no over-arylation at any step. The triarylacetonitrile products can be converted into highly functionalized species including tetraarylmethanes. This new strategy provides rapid access to a variety of unsymmetrical tri- and tetraarylmethane derivatives from simple, readily available starting materials. (Chemical Presented)
- Nambo, Masakazu,Yar, Muhammad,Smith, Joel D.,Crudden, Cathleen M.
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supporting information
p. 50 - 53
(2015/07/28)
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- Two-step cyanomethylation protocol: Convenient access to functionalized aryl- and heteroarylacetonitriles
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A two-step protocol has been developed for the introduction of cyanomethylene groups to metalated aromatics through the intermediacy of substituted isoxazoles. A palladium-mediated cross-coupling reaction was used to introduce the isoxazole unit, followed by release of the cyanomethylene function under thermal or microwave-assisted conditions. The intermediate isoxazoles were shown to be amenable to further functionalization prior to deprotection of the sensitive cyanomethylene motif, allowing access to a wide range of aryl- and heteroaryl-substituted acetonitrile building blocks.
- Lindsay-Scott, Peter J.,Clarke, Aimee,Richardson, Jeffery
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p. 476 - 479
(2015/03/05)
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- Ionic liquid-induced conversion of methoxymethyl-protected alcohols into nitriles and iodides using [Hmim][NO3]
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This Letter reports a one-pot efficient conversion of methoxymethyl-ethers into their corresponding nitriles and iodides using the ionic liquid, 1-methyl-3H-imidazolium nitrate ([Hmim][NO3]) under microwave irradiation. A variety of products were prepared in high yields using this method.
- Noei, Jalil,Mirjafari, Arsalan
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supporting information
p. 4424 - 4426
(2014/08/05)
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- A heterogeneous palladium catalyst hybridised with a titanium dioxide photocatalyst for direct C-C bond formation between an aromatic ring and acetonitrile
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A palladium catalyst hybridised with a titanium dioxide photocatalyst can promote cyanomethylation of an aromatic ring by using acetonitrile, where the photocatalyst activates acetonitrile to form a cyanomethyl radical before the C-C bond formation using the palladium catalyst.
- Yoshida, Hisao,Fujimura, Yuki,Yuzawa, Hayato,Kumagai, Jun,Yoshida, Tomoko
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supporting information
p. 3793 - 3795
(2013/05/22)
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- Copper-catalyzed cyanation of benzyl chlorides with non-toxic K 4[Fe(CN)6]
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Copper-based catalysts were firstly introduced into the cyanation of benzyl chlorides with non-toxic K4[Fe(CN)6]. The presented method avoids the use of extremely poisonous alkali cyanides and precious palladium catalysts. No other reagent apart from CuI, K4[Fe(CN) 6] and toluene was used in the cyanation, showing that the presented protocol is simple and practical. A series of benzyl chlorides were smoothly cyanated in up to 85% yield under the optimal conditions.
- Ren, Yunlai,Dong, Chuanhua,Zhao, Shuang,Sun, Yanpei,Wang, Jianji,Ma, Junying,Hou, Chaodong
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supporting information; experimental part
p. 2825 - 2827
(2012/07/17)
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- Calixarene ionic liquids: Excellent phase transfer catalysts for nucleophilic substitution reaction in water
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The first examples of calixarene ionic liquids 3 and 6 with 3D-shaped cavities were obtained in high yields by reacting calix[4]arene or thiacalix[4]arene with 1,6-dibromohexane and then refluxing in 1-methylimidazole. The experiments of phase transfer catalysis in water suggested that they possessed excellent catalytic properties of aromatic nucleophilic substitution reaction and benzyl nucleophilic substitution. The optimized yields of product in catalytic reaction were as high as approximate 97% under mild reaction conditions. The cavities of calixarene skeleton played the crucial roles in catalysis and the stable cone conformation was favorable for catalysis.
- Yang, Fafu,Guo, Hongyu,Jiao, Ziyu,Li, Congcong,Ye, Jinqi
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experimental part
p. 327 - 332
(2012/08/08)
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- Pd-catalyzed cyanation of benzyl chlorides with nontoxic K 4[Fe(CN)6]
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Non-toxic K4[Fe(CN)6] was demonstrated to be effective as a green cyanating agent for the cyanation of alkyl halides using PPh3/Pd(OAc)2 as a catalyst system. The presented method allowed a series of benzyl chlorides to be smoothly cyanated in up to 88% yield. In order to avoid or suppress the deactivation of the catalyst, the reaction was required to be performed in a stringent inert ambiance.
- Ren, Yunlai,Yan, Mengjie,Zhao, Shuang,Sun, Yanpei,Wang, Jianji,Yin, Weiping,Liu, Zhifei
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scheme or table
p. 5107 - 5109
(2011/10/05)
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- Synthesis of α-Aryl nitriles through palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates
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Worth its salt: The palladium-catalyzed decarboxylative coupling of the cyanoacetate salt as well as its mono- and disubstituted derivatives with aryl chlorides, bromides, and triflates is described (see scheme). This reaction is potentially useful for the preparation of a diverse array of α-aryl nitriles and has good functional group tolerance. S-Phos=2-(2,6- dimethoxybiphenyl)dicyclohexylphosphine), Xant-Phos=4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene. Copyright
- Shang, Rui,Ji, Dong-Sheng,Chu, Ling,Fu, Yao,Liu, Lei
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supporting information; experimental part
p. 4470 - 4474
(2011/06/24)
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- Palladium-catalyzed cyanomethylation of aryl halides through domino Suzuki coupling-isoxazole fragmentation
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A one-pot protocol for the cyanomethylation of aryl halides through a palladium-catalyzed reaction with isoxazole-4-boronic acid pinacol ester was developed. Mechanistically, the reaction proceeds through (1) Suzuki coupling, (2) base-induced fragmentation, and (3) deformylation as shown by characterization of all postulated intermediates. Under optimized conditions (PdCl2dppf, KF, DMSO/H2O, 130 °C) a broad spectrum of aryl bromides could be converted into arylacetonitriles with up to 88% yield.
- Velcicky, Juraj,Soicke, Arne,Steiner, Roland,Schmalz, Hans-Guenther
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supporting information; experimental part
p. 6948 - 6951
(2011/06/19)
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- Novel lariat calix[4]-1,3-aza-crowns with two branched chains-the excellent phase transfer catalysts for nucleophilic substitution reaction
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By reacting calix[4]-1,3-diethoxylaminoethyl derivative (2) with phenyl isothiocyanate, novel dendritic calix[4]-arene derivative (3) with two different branched chains was synthesized in a yield of 78%. By reacting compound 2 with 1,6-diisocyanatohexane or N,N'-bis(2-chloracetamide)ethylene in a ''1 + 1'' intermolecular addition mode, novel lariat calix[4]-1,3-aza-crowns (4 and 5, respectively) with two branched ethoxyl chains were prepared in reasonable yields. The composition, structures, and conformations of all new compounds were confirmed by elemental analyses, IR, ESI-MS, 1H NMR, and so forth. The liquid-liquid extraction experiments showed that all new hosts possessed good extraction abilities towards soft and hard metal cations. The liquid membrane transport experiments suggested that they had good transport abilities for K+ and Ag+. The experiments of phase transfer catalysis indicated that they possessed excellent catalytic properties of aromatic nucleophilic substitution reaction and benzyl nucleophilic substitution. The optimum yields of products in catalytic reaction were as high as approximately 100%.
- Yang, Fafu,Wang, Yanhua,Guo, Hongyu,Xie, Jianwei,Liu, Zhiqiang
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experimental part
p. 622 - 627
(2010/08/22)
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- Microwave-promoted, one-pot conversion of alkoxymethylated protected alcohols into their corresponding nitriles, bromides, and iodides using [bmim][InCl4] as a green catalyst
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The Lewis acid room temperature ionic liquid, [bmim][InCl4], was found to be an efficient and green catalyst for the highly chemoselective and one-pot conversion of MOM- or EOM-ethers into their corresponding nitriles, bromides, and iodides under microwave irradiation. The procedures are simple, rapid, and high yielding. The catalyst exhibited a remarkable reactivity and is reusable.
- Mirjafari, Arsalan,Mohammadpoor-Baltork, Iraj,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Khosropour, Ahmad Reza
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supporting information; experimental part
p. 3274 - 3276
(2010/07/18)
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- Versatile and fluoride-free cyanation of alkyl halides and sulfonates with trimethylsilyl cyanide
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Cyanation of biphenyl-4-ylmethyl methanesulfonate with trimethylsilyl cyanide using fluoride-free inorganic salts, such as Cs2CO 3, K2CO3, and LiOH·H2O, as additives in MeCN quantitatively gave biphenyl-4-ylacetonitrile. This methodology was applied to various alkyl halides to give the corresponding nitrile compounds in good to excellent yields. Of note, 4-(hydroxymethyl) benzyliodide O-protected by the silyl group was converted into phenylacetonitrile derivative in 99% yield without desilylation. Georg Thieme Verlag Stuttgart.
- Yabe, Osamu,Mizufune, Hideya,Ikemoto, Tomomi
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experimental part
p. 1291 - 1294
(2009/10/23)
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- o-iodoxybenzoic acid- and tetraethylammonium bromide-mediated oxidative transformation of primary carboxamides to one-carbon dehomologated nitriles
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A clean and efficient method for the oxidative transformations of primary carboxamides to one-carbon dehomologated nitriles using the combination of o-iodoxybenzoic acid and tetraethylammonium bromide has been developed. This method exhibits a broad scope and is expected to be of great utility in organic synthesis.
- Bhalerao, Dinesh S.,Mahajan, Ulhas S.,Chaudhari, Kiran H.,Akamanchi, Krishnacharya G.
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p. 662 - 665
(2007/10/03)
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- Cyanation of alcohols with diethyl cyanophosphonate and 2,6-dimethyl-1,4-benzoquinone by a new type of oxidation-reduction condensation
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Cyanation of various alcohols by a new type of oxidation-reduction condensation is described. Primary alkyl diphenylphosphinites, 2,6-dimethyl-1,4-benzoquinone (DMBQ), and diethyl cyanophosphonate gave the corresponding nitriles in high yields. During the above experiment on cyanation of 4-phenylbutan-2-ol, the unexpected formation of a mixture of nitrile and isocyanide was observed. After careful examination of the reaction conditions, selective synthesis of isocyanides from secondary alcohols was successfully accomplished by the use of zinc oxide (ZnO) as an additive. Reaction of tertiary alcohols provided the corresponding isocyanides exclusively in the absence of an additive. Cyanation of optically active alcohols was tried in order to clarify the stereochemistry of this reaction, and the reaction was thus proved to proceed with the inversion of configuration.
- Masutani, Kouta,Minowa, Tomofumi,Hagiwara, Yoshiaki,Mukaiyama, Teruaki
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p. 1106 - 1117
(2007/10/03)
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- Preparation of nitriles from primary alcohols by a new type of oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone and diethyl cyanophosphonate
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Cyanation of alkoxydiphenylphosphines, in situ prepared from nBuLi and various primary alcohols, with 2,6-dimethyl-1,4- benzoquinone (DMBQ) and diethyl cyanophosphonate provided the corresponding nitriles in high yields.
- Mukaiyama, Teruaki,Masutani, Kouta,Hagiwara, Yoshiaki
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p. 1192 - 1193
(2007/10/03)
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- Thermal Isomerizations of Substituted Benzyl Isocyanides: Relative Rates Controlled Entirely by Differences in Entropies of Activation
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The absolute and relative rates of thermal rearrangments of substituted benzyl isocyanides were obtained at the temperatures between 170 and 230 °C. The relative rates are independent of temperature and exhibit excellent Hammett correlations (p+ = -0.24). The temperature studies yielded activation parameters (ΔHY? and ΔSY?) and their differential counterparts (ΔΔHY-H? and ΔΔSY-H?). The differential terms were plotted against σ+. The secondary α-deuterium kinetic isotope effects (kD/kH = 1.11) were measured at several temperatures. The rate data can be rationalized with the cyclic TS. The substituent effects on the rates are due to the entropic contributions.
- Kim, Sung Soo,Choi, Won Jung,Zhu, Yu,Kim, Jin Hyun
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p. 1185 - 1189
(2007/10/03)
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- Using secondary α deuterium kinetic isotope effects to determine the symmetry of S(N)2 transition states
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The secondary α deuterium and heavy atom kinetic isotope effects found for two different S(N)2 reactions suggest that the magnitude of secondary α deuterium kinetic isotope effects can be determined by the length of only the shorter (stronger) reacting bond in an unsymmetrical S(N)2 transition state rather than by the usual nucleophile-leaving group distance. Although this means the interpretation of these isotope effects is more complex than has been recognized, the results suggest that they can be used to determine whether an S(N)2 transition state is symmetrical or unsymmetrical.
- Westaway, Kenneth Charles,Van Pham, Thuy,Fang, Yao-Ren
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p. 3670 - 3676
(2007/10/03)
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- Facile synthesis of nitriles from primary nitro compounds via nitrolic acids and their esters
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The reactions of alkane- and arylalkanenitrolic acids esters Bu3SnH in the presence of a catalytic amount of AIBN in refluxing benzene afforded the corresponding nitriles in excellent yields.
- Chang, Rae Kyu,Kim, Kyongtae
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p. 7791 - 7794
(2007/10/03)
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- Degradation of 3-aryl-2-hydroxyiminopropionic acids into arylacetonitriles using 1,1'-carbonyldiimidazole or 2,2'-oxalyldi(o-sulfobenzimide)
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1,1'-Carbonyldiimidazole (1) is a useful reagent for the preparation of arylacetonitriles (9) from 3-aryl-2-hydroxyiminopropionic acids (8), and 2,2'-oxalyldi (o-sulfobenzimide) (2) can also be used for this purpose under essentially neutral conditions.
- Kitagawa,Kawaguchi,Inoue,Katayama
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p. 3030 - 3033
(2007/10/02)
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- A Facile Synthesis of Nitriles from 1-Nitro-1-alkenes by Electroreduction
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Electroreduction of 1-nitro-1-alkenes in the presence of titanium(IV) chloride affords nitriles in good yields.This procedure provides a facile transformation of aldehydes to one-carbon elongated nitriles since the 1-nitro-1-alkenes are best prepared from aldehydes and nitromethane.
- Sera, Akira,Tani, Hiroyuki,Nishiguchi, Ikuzo,Hirashima, Tsuneaki
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p. 631 - 633
(2007/10/02)
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- Nickel-Catalyzed Synthesis of Arylacetonitriles from Arylzinc Chlorides and Bromoacetonitrile
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Arylacetonitriles are synthesised by coupling arylzinc chlorides with bromoacetonitrile using Ni(acac)2/P(c-C6H11)(C6H5)2 as catalyst.The arylacetonitriles are reduced in situ with LiAlH4/AlCl3 to give the corresponding 2-aryl-1-aminoethanes.
- Frejd, Torbjoern,Klingstedt, Tomas
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- PALLADIUM CATALYZED REACTION OF ARYL BROMIDES WITH CYANOMETHYLTRIBUTYLTIN. AROMATIC CYANOMETHYLATION
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Palladium catalyzed reaction of aryl bromides with cyanomethyltributyltin gave arylacetonitriles in moderate yields.Aryl bromides having strong electron-withdrawing groups (such as acyl, cyano, nitro, etc.) cannot be applied to the reaction.
- Kosugi, Masanori,Ishiguro, Masahiro,Negishi, Yoshikazu,Sano, Hiroshi,Migita, Toshihiko
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p. 1511 - 1512
(2007/10/02)
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- Reaction of Aryl Aldehydes with Thiocyanates in the Presence of Tributylphosphine
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Aryl aldehydes react with methyl thiocyanate in the presence of tributylphosphine to afford S-methyl thiobenzoates and arylacetonitriles in good yields.This is a novel disproportionation reaction involving carbon-carbon bond formation.These compounds thus obtained are easily converted into deoxybenzoins using sodium hydride.On the other hand, p-dialkylaminobenzaldehydes react with methyl thiocyanate under the same conditions to furnish both the corresponding trans-dicyanostilbenes and succinonitriles in moderate yields.Finally, the reaction was carried out with aryl thiocyanates resulting in the formation of addition products.
- Yokoyama, Masataka,Ohteki, Hiroko,Kurauchi, Masahiko,Hoshi, Kazuko,Yanagisawa, Eizaburo,et al.
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p. 2635 - 2640
(2007/10/02)
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- Photochemical Aromatic Cyanomethylation: Aromatic Substitution by Way of Radical Cations
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Photolysis at 254 nm of chloroacetonitrile in the presence of aromatic hydrocarbons led to ring cyanomethylation.In addition radical coupling products were found, especially with toluene where 3-phenylpropionitrile, succinonitrile, and bibenzyl accompanied the tolylacetonitriles.These same byproducts were obtained from toluene and chloroacetonitrile upon thermolysis with peroxide initiators, but no nuclear cyanomethylation was observed.The mechanism for aromatic cyanomethylation involves initial excitation of the aromatic hydrocarbons, followed by an electron transfer (probably by way of an exiplex) to chloroacetonitrile, which was found to quench aromatic fluorescence at high rates.Direct spectral evidence for the resulting radical cation with p-dimethoxybenzen was obtained by using flash laser spectroscopy.Loss of a chloride ion from the resulting radical anion produces a cyanomethyl radical in close proximity to an aromatic radical cation.Coupling leads to the aromatic substitution products whereas radicals escaping from the cage account for the observed byproducts.
- Kurz, M. E.,Lapin, S. C.,Miriam, K.,Hagen, T. J.,Qian, X. Q.
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p. 2728 - 2733
(2007/10/02)
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- Sonochemical Switching of Reaction Pathways in Solid-Liquid Two-phase Reactions
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Ultrasonic irradiation of a mixture of benzyl bromide, potassium cyanide, and alumina in an aromatic solvent yields benzyl cyanide, whereas mechanical agitation gives the Friedel-Crafts type product; sonication changes the main reaction pathway from aromatic electrophilic to aliphatic nucleophilic substitution.
- Ando, Takashi,Sumi, Shinjiro,Kawate, Takehiko,Ichihara, Junko,Hanafusa, Terukiyo
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p. 439 - 440
(2007/10/02)
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- A SIMPLE ONE-POT CONVERSION OF ARYL HALIDES INTO ARYLACETONITRILES
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When heated in hexamethylphosphoric triamide in the presence of copper(I) iodide, aryl iodides and bromides react with cyanoacetate anion to form arylcyanoacetates, which lose the ester group on hydrolysis, giving the corresponding arylacetonitriles in good to moderate yields.
- Suzuki, Hitomi,Kobayashi, Tsutomu,Yoshida, Yoshiki,Osuka, Atsuhiro
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p. 193 - 194
(2007/10/02)
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- A NOVEL DISPROPORTIONATION REACTION OF AROMATIC ALDEHYDES INVOLVING C-C BOND FORMATION
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The reaction of aromatic aldehydes with methyl thiocyanate in the presence of tributylphosphine afforded both S-methyl thiobenzoates and phenylacetonitriles via a novel disproportionation pathway involving carbon-carbon bond formation.
- Kurauchi, Masahiko,Imamoto, Tsuneo,Yokoyama, Masataka
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p. 4985 - 4986
(2007/10/02)
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- Photochemical Aromatic Cyanomethylation
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Cyanomethylation is accomplished by the photolysis of chloroacetonitrile in the presence of aromatics by way of electron transfer followed by radical coupling.
- Lapin, Stephen,Kurz, Michael E.
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p. 817 - 818
(2007/10/02)
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