N-Alkylation of Aromatic Amines by Means of Alcohol. IV. Syntheses of N-Alkylanilines and Related Compounds

Miyano, Seiji; Nakao, Michiko

doi:10.1248/cpb.20.1328

Cited by 12 publications

(9 citation statements)

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“…Synthesis of 1,2,3,4-tetrahydroquinoxaline and 1,2,3,4,4a,5,10,10a-octahydrophenazine. [63] was heated in toluene at 110°C for 20 h under aerobic conditions, N-benzylideneaniline was formed in 92 % yield. [66] Other bases (NaOH, KOt-Bu, NaOt-Bu, K 2 CO 3 , K 2 CO 3 , CsOH and NEt 3 ) and solvents (THF, 1,4-dioxane and H 2 O) gave worse results.…”

Section: Synthesis Of Imines From Alcoholsmentioning

confidence: 99%

“…Later, the same authors studied the N-alkylation of aniline with a variety of primary aliphatic alcohols in the presence of sodium alkoxide to give N-alkylanilines in 20-72 % yields. [63] The protocol was extended to prepare tetrahydroquinoxalines (79) and octahydrophenazine (80) derivatives by reacting benzene-1,2-diamine 76 with ethane-1,2-diol (77) and cyclohexane-1,2-diol (78), respectively (Scheme 46). The use of sodium alkoxide not only promotes its dehydrogenation to the aldehyde, but also it reduces the intermediate imine by an MPV mechanism.…”

Section: Introductionmentioning

confidence: 99%

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Base‐Mediated Transition‐Metal‐Free Dehydrative C−C and C−N Bond‐Forming Reactions from Alcohols

Porcheddu

Chelucci

2019

The Chemical Record

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In recent years, there has been an increasing interest in using alcohols as alkylating agents for C−C and C−N bond‐forming processes employing mainly TM‐catalysts. Although BH‐catalysis looks like a green atom economy process since water is the only by‐product, it often suffers from one or more drawbacks, such as the use of expensive noble metal complexes, capricious ligands, and toxic organic solvents. Therefore, straightforward, efficient, atom economy and environmentally benign alternative protocols are desirable. This review aims to summarize the current knowledge within the published literature about dehydrative processes developed without TM‐catalysts. The most recent contributions to this topic have been reviewed keeping into account the new findings reported in this area. The features, strengths, and limitations of these alcohol‐based C−C and C−N bond‐forming processes has also been taken into account.

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Section: Synthesis Of Imines From Alcoholsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Base‐Mediated Transition‐Metal‐Free Dehydrative C−C and C−N Bond‐Forming Reactions from Alcohols

Porcheddu

Chelucci

2019

The Chemical Record

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“…In 1904, Nef first reported N ‐alkylation of amines or amides with alcohols under strongly basic conditions (Scheme a) . Following this original discovery, other alkali metal hydroxides or alkoxides were also successfully applied to N ‐alkylations of amines . Recently, base‐catalyzed direct alkylation of amines was also achievable with either catalytic amounts of aldehydes/alkyl halides or heteroarylamines/sulfonamides,, which avoided the utilization of harsh conditions and excess amounts of bases (Scheme b).…”

Section: Introductionmentioning

confidence: 99%

An Efficient Homogenized Ruthenium(II) Pincer Complex for N‐Monoalkylation of Amines with Alcohols

Yang

Wang

et al. 2017

Eur J Org Chem

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An ionic 2,6‐bis(imidazo[1,2‐α]pyridin‐2‐yl)pyridine‐based N^N^N pincer ruthenium(II) complex exhibited high efficiency in the C–N bond formation between amines and alcohols by the “borrowing hydrogen” (BH) or “hydrogen autotransfer” (HA) concept. The synthetic protocol selectively generated monoalkylated amines without formation of tertiary amines during the reaction. The unique selectivity enabled the formation of symmetrically and asymmetrically substituted diamines. This methodology features several advantages including a low catalyst loading (as low as 0.5 mol‐%), a short reaction time (as short as 2 h), and excellent N‐monoalkylation selectivity.

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“…Potassium hydroxide proved to be the optimized base, and only 5 mol % of KOH afforded the desired product 3a in 92% yield. “Extra” aldehyde 4a could be generated in the reaction conditions, , increasing from <0.1% in the starting material to 25% in the reaction mixture (Scheme ).…”

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confidence: 99%

Direct Alkylation of Amines with Alcohols Catalyzed by Base

Xiao

Yao

et al. 2015

Org. Lett.

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A base-catalyzed/promoted transition-metal-free direct alkylation of amines with alcohols has been developed, giving the desired amines in generally high yields from either aromatic or aliphatic alcohols. On the basis of the (1)H NMR and in situ IR (React-IR) monitoring experiments, isotope-labeling experiments, as well as control experiments, a novel "hemiaminal" model is proposed to understand the mechanism, which explains the formation of the "extra" aldehyde in the reaction.

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N-Alkylation of Aromatic Amines by Means of Alcohol. IV. Syntheses of N-Alkylanilines and Related Compounds

Cited by 12 publications

References 0 publications

Base‐Mediated Transition‐Metal‐Free Dehydrative C−C and C−N Bond‐Forming Reactions from Alcohols

Base‐Mediated Transition‐Metal‐Free Dehydrative C−C and C−N Bond‐Forming Reactions from Alcohols

An Efficient Homogenized Ruthenium(II) Pincer Complex for N‐Monoalkylation of Amines with Alcohols

Direct Alkylation of Amines with Alcohols Catalyzed by Base

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