- Electrochemical strategies for: N -cyanation of secondary amines and α C -cyanation of tertiary amines under transition metal-free conditions
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Transition metal-free electrochemical approaches for the N-cyanation of secondary amines and the α C-cyanation of tertiary amines have been well established, with products being obtained in moderate to good yields and with good functional group tolerance under ambient conditions. The synthetic application of the protocols has been highlighted through scale-up experiments in a galvanostatic mode. Preliminary mechanistic investigation has confirmed that TBAB played a critical role in N-cyanation transformation and has indicated that the transformation might proceed via a free radical process. This journal is
- Cai, Hu,Fu, Yaping,Fu, Zhengjiang,Guo, Shengmei,Hao, Guangguo,Yi, Xuezheng,Yin, Jian,Zhong, Tingting
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supporting information
p. 9422 - 9427
(2021/12/09)
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- Preparation method of diallylamine and hydrochloride thereof
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The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of diallylamine and hydrochloride thereof. The preparation method comprises the following steps: inputting ammonia water into a reaction kettle, adding a catalyst, dropwise adding 3-chloropropene at a constant temperature and a constant pressure, heating the mixture to 50-55 DEG C after dropwise addition, keeping the temperature for 1 hour, and reducing the temperature to 35-40 DEG C to obtain slurry; extracting the slurry to a distilling kettle, adding sodium hydroxide and a byproduct ammonium chloride into the distilling kettle to react, absorbing generated ammonia water with water and reusing the same, neutralizing the same, starting distillation till a water phase is obtained, adding caustic soda flakes to dehydrate, cyclically using the dehydrated alkaline liquor t o obtain a diallylamine coarse product; and inputting the coarse product into a rectifying kettle, taking a small amount of precomponent first, then receiving diallylamine, and returning the precomponent to a reaction kettle to be used. The diallylamine and hydrochloride thereof are prepared by adopting an amination process, so that the method is safe and is guaranteed, and meanwhile, excessive ammonia water and alkaline water are fully recycled, so that the preparation method is low in energy consumption and little in pollution, and the three wastes can be recycled.
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Paragraph 0047; 0048; 0049
(2019/03/08)
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- N-Cyanation of Secondary Amines Using Trichloroacetonitrile
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A one-pot N-cyanation of secondary amines has been developed using trichloroacetonitrile as an inexpensive cyano source. A diverse range of cyclic and acyclic secondary amines can be readily transformed into the corresponding cyanamides in good isolated yields, with the method successfully utilized in the final synthetic step of a biologically active rolipram-derived cyanamide. This approach exhibits distinct selectivity when compared to the use of highly toxic cyanogen bromide.
- Ayres, James N.,Ling, Kenneth B.,Morrill, Louis C.
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p. 5528 - 5531
(2016/11/17)
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- A copper-mediated oxidative N-cyanation reaction
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Copper-promoted N-cyanation of aliphatic sec-amine by CuCN is achieved via oxidative coupling. This procedure employs O2 as a clean oxidant. Notably, sulfoximines and 1,1,3,3-tetramethylguanidine also worked well in this procedure. Thus, it represents a key progress in the C-N bond formation reaction as well as in the cyanation reaction. This journal is the Partner Organisations 2014.
- Teng, Fan,Yu, Jin-Tao,Jiang, Yan,Yang, Haitao,Cheng, Jiang
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supporting information
p. 8412 - 8415
(2014/07/22)
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- Phenyl chloro(thionoformate): A new dealkylating agent of tertiary amines
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Phenyl chloro(thionoformate) reacts rapidly with unhindered tertiary aliphatic amines at 20° to give a thiocarbamate and an alkyl chloride. Dialkylcyclohexylamines react surprisingly rapidly to form predominantly cyclohexene. The thiocarbamates are converted into the secondary amine salt by treatment with dimethyl sulfate, followed by hydrolysis with water. Rates of reaction and alkyl group cleavage selectivity in amines were found to be superior or comparable to those previously reported with chloroformates.
- Milan, David S.,Prager, Rolf H.
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p. 841 - 849
(2007/10/03)
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- Palladium(0)-catalyzed allylation of highly acidic and non-nucleophilic arenesulfonamides, sulfamide, and cyanamide. I.
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Arenesulfonamides, sulfamide, and cyanamide are efficiently allylated using allylic carbonates under Pd(0)-catalysis. N-Arenesulfonyl-2,5- dihydropyrroles are obtained by ruthenium-mediated ring closing metathesis of the corresponding N-diallylated compounds. A stereochemical study of the reactions of ethyl cis-(5-methyl-2-cyclohexenyl) carbonate with 2,4,6- triisopropylphenylsulfonamide was performed, clean overall retention of configuration being found with bidentate phosphines.
- Cerezo, Silvia,Cortes, Jordi,Moreno-Manas, Marcial,Pleixats, Roser,Roglans, Anna
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p. 14869 - 14884
(2007/10/03)
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- SYNTHESIS OF ALKYL N-CYANO-N-SUBSTITUTED CARBAMATES AND N,N-DISUBSTITUTED CYANAMIDES
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The reaction of S,S' methyl cyanodithioimidocarbonate with potassium hydroxide in alkyl or benzyl alcohol furnished the O-alkyl and benzyl O-potassium cyanoimidocarbonates (1-5).The reaction of the potassium salts (1, 3, or 4) with 10 percent excess of alkyl, allyl or benzyl halides afforded the unknown titled carbamates (6-17).The reaction of 2 with 10 percent excess benzyl bromide or 5 with 10 percent excess methyl iodide gave the same product, N-benzyl-N-methyl cyanamide (18).The reaction of 2 with 10 percent and 55 percent excess allyl bromide afforded N-allyl-N-methyl cyanamide (19) and N,N-diallyl cyanamide (20), respectively.The reaction of 3 with 28 percent excess of allyl iodide furnished N-allyl-N-propyl cyanamide (21). Possible mechanisms and supporting NMR, IR and mass spectra data are discussed.
- Suba, Lydia,Schafer, Tann,Ruminski, Peter G.,D'Amico John J.
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p. 219 - 226
(2007/10/02)
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- Process for preparation of di-substituted cyanamides using quaternary salt catalysis
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An improved process for the di-substitution of cyanamide is disclosed which comprises reacting a compound having the formula in which R1 is a member selected from the group consisting of C1 -C6 alkyl, C2 -C6 alkenyl, C2 -C6 alkynyl, C7 -C10 phenylalkyl, and C7 -C10 halophenylalkyl, and X is halogen, with cyanamide in the presence of an aqueous solution of an alkali metal or alkaline earth metal hydroxide and a catalytic amount of a catalyst having the formula in which R2, R3, R4, and R5 are independently C1 -C25 alkyl, M is selected from the group consisting of nitrogen, phosphorus, and arsenic, and Y is halogen.
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