The Alkylation of Amines with t-Acetylenic Chlorides. Preparation of Sterically Hindered Amines<sup>1</sup>

Hennion, G. F.; Hanzel, Robert S.

doi:10.1021/ja01503a040

Cited by 63 publications

(22 citation statements)

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“…-Thermal rearrangements. The N- ( 1', 1 '-dimethylally1)anilines rearrange in MBO at 200-260" with the exception of the p-cyano compound 10 in a clean reaction to give the corresponding 2-(3'-methyl-2'-butenyl)anilines [22][23][24][25][26] (Table 2 and 3). The amount of splitting into the anilines is < 4 % (10 gives -40% splitting).…”

Section: Discussionmentioning

confidence: 99%

“…Der pK,-Wert von protoniertem N-Allylanilin (1) betragt 4,17 (25") [77], derjenige von protoniertern Propylphenylather -6,40 (0") [78]. [24]. 27,9 g NMR.…”

Section: Schlussbemerkungunclassified

“…H), 4,46 (s, HN), 2,33 (s, H-C(3')), 1,63 (3, 6H, H$-C(l')). -MS.: 184 (M', 36), 169 (loo), 118 (99), 67 (34), 41 (22).C12Hl2N2(184,24) Ber.C 78,23 H 6,57 N 15,20% Gef. C 7832 H 6,46 N 14,91% H), 3,69 (s, 6H, 2H3C-C(1')).…”

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confidence: 99%

“…ten Formen 5-11 wurden aus den entsprechenden 2'-Propinyl-Verbindungen erhalten, die ihrerseits nach einer allgemeinen, von Hennion et al beschriebenen Methode[24] [25] durch Umsetzung der Aniline mit 3-Chlor-3-methyl-1-butin[26] in Gegenwart von Triathylamin, Kupfer (I)-chlorid und Kupferpulver hergestellt wurden(Schema 4)4). Bei dieser N-Alkylierung traten als einzige Nebenprod~kte~) ' ) Die Menge an diesen Anilinen im Hydriergemisch wurde nur diinnschichtchromatographisch bestimmt: unter gleichen Hydrierbedingungen war die Spaltungsrate fur die 2'-Propinyl-Verbindung mit R=H am kleinsten und fur diejenige mit R=CN am grossten.…”

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Untersuchungen über aromatische Amino‐Claisen‐Umlagerungen

Jolidon

Hansen

1977

Helvetica Chimica Acta

104

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Investigations on Aromatic Amino‐Claisen Rearrangements The thermal and acid catalysed rearrangement of p‐substituted N‐(1′,1′‐dimethylallyl)anilines (p‐substituent=H (5), CH3 (6), iso‐C3H7 (7), Cl (8), OCH3 (9), CN (10)), of N‐(1′,1′‐dimethylallyl)‐2,6‐dimethylaniline (11), of o‐substituted N‐(1′‐methylallyl)anilines (o‐substituent=H (12), CH3 (13), t‐C4H9 (14), of (E)‐ and (Z)‐N‐(2′‐butenyl)aniline ((E)‐ and (Z)‐16), of N‐(3′‐methyl‐2′‐butenylaniline (17) and of N‐allyl‐(1) and N‐allyl‐N‐methylaniline (15) was investigated (cf. Scheme 3). The thermal transformations were normally conducted in 3‐methyl‐2‐butanol (MBO), the acid catalysed rearrangements in 2N‐0,1N sulfuric acid. ‐ Thermal rearrangements. The N‐(1′,1′‐dimethylallyl)anilines rearrange in MBO at 200‐260° with the exception of the p‐cyano compound 10 in a clean reaction to give the corresponding 2‐(3′‐methyl‐2′‐butenyl)anilines 22–26 (Table 2 and 3). The amount of splitting into the anilines is <4% (10 gives ≃ 40% splitting). The secondary kinetic deuterium isotope effect (SKIDI) of the rearrangement of 5 and its 2′,3′,3′‐d3‐isomer 5 amounts to 0.89±0.09 at 260° (Table 4). This indicates that the partial formation of the new s̀‐bond C(2), C(3′) occurs already in the transition state, as is known from other established [3,3]‐sigmatropic rearrangements. The rearrangement of the N‐(1′‐methylallyl)anilines 12–14 in MBO takes place at 290–310° to give (E)/(Z)‐mixtures of the corresponding 2‐(2′‐Butenyl)anilines ((E)‐ and (Z)‐30,‐31, and ‐32) besides the parent anilines (5–23%). Since a dependence is observed between the (E)/(Z)‐ratio and the bulkiness of the o‐substituent (H: (E)‐30/(Z)‐30=4,9; t‐C4H9: (E)‐32/(Z)‐32=35.5; cf. Table 6), it can be concluded, that the thermal amino‐Claisen rearrangement occurs preferentially via a chair‐like transition state (Scheme 22). Methyl substitution at C(3′) in the allyl chain hinders the thermal amino‐Claisen‐rearrangement almost completely, since heating of (E)‐and (Z)‐16, in MBO at 335° leads to the formation of the expected 2‐(1′‐methyl‐allyl) aniline (33) to an extent of only 12 and 5%, respectively (Scheme 9). The main reaction (≃60%) represents the splitting into aniline. This is the only observable reaction in the case of 17. The inversion of the allyl chain in 16 ‐ (E)‐ and (Z)‐30 cannot be detected ‐ indicated that 33 is also formed in a [3, 3]‐sigmatropic process. This is also true for the thermal transformation of N‐allyl‐(1) and N‐allyl‐N‐methylaniline (15) into 2 and 34, respectively, since the thermal rearrangement of 2′, 3′, 3′‐d3‐1 yields 1′, 1′, 2′‐d3‐2 exclusively (Table 8). These reaction are accompanied to an appreciable extent by homolysis of the N, C (1′) bond: compound 1 yields up to 40% of aniline and 15 even 60% of N‐methylaniline ((Scheme 10 and 11). The activation parameters were determined for the thermal rearrangements of 1, 5, 12 and 15 in MBO (Table 22). All rearrangements show little solvent dependence (Table 5, 7 and 9). The observed ΔH≠ values are in the range of 34‐40 kcal/mol and ...

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Section: Discussionmentioning

confidence: 99%

“…Der pK,-Wert von protoniertem N-Allylanilin (1) betragt 4,17 (25") [77], derjenige von protoniertern Propylphenylather -6,40 (0") [78]. [24]. 27,9 g NMR.…”

Section: Schlussbemerkungunclassified

mentioning

confidence: 99%

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Untersuchungen über aromatische Amino‐Claisen‐Umlagerungen

Jolidon

Hansen

1977

Helvetica Chimica Acta

104

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“…To avoid allene formation, Brinkmeyer and Macdonald found that in the treatment of propargylic acetates with organocuprates, blocking the terminal position of the acetylene with a bulky group afforded the desired acetylenic products in good yield 10. In 1960, Hennion and Hanzel reported a copper‐catalyzed route towards propargylic amines starting from tertiary propargylic chlorides 11. Only with weakly nucleophilic amines (i.e.…”

Section: Catalyzed Propargylic Substitutionsmentioning

confidence: 91%

Catalyzed Propargylic Substitution

2009

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Besides being a versatile entity for further chemical transformations, the propargylic subunit is also part of various natural products, fine chemicals, and synthetic pharmaceuticals. Propargylic substitution reactions, however, are rather unexplored. An overview of this emerging field is presented. We especially focus on experimental results that deal with catalyzed substitutions of propargylic alcohols and their derivatives. Finally, some enantioselective propargylic substitution methods are discussed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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tert ‐Butyl‐ tert ‐Octylamine

Corey

Gross

2003

Organic Syntheses

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tert ‐Butyl‐ tert ‐octylamine intermediate: 29.7 g of nitroso‐tert‐octane intermediate: N‐tert‐butyl‐N‐tert‐octyl‐O‐tert‐butylhydroxylamine intermediate: N‐tert‐octyl‐O‐tert‐butylhydroxylamine product: tert‐butyl‐tert‐octylamine

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The Alkylation of Amines with t-Acetylenic Chlorides. Preparation of Sterically Hindered Amines¹

Cited by 63 publications

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Untersuchungen über aromatische Amino‐Claisen‐Umlagerungen

Untersuchungen über aromatische Amino‐Claisen‐Umlagerungen

Catalyzed Propargylic Substitution

tert ‐Butyl‐ tert ‐Octylamine

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The Alkylation of Amines with t-Acetylenic Chlorides. Preparation of Sterically Hindered Amines1

Cited by 63 publications

References 0 publications

Untersuchungen über aromatische Amino‐Claisen‐Umlagerungen

Untersuchungen über aromatische Amino‐Claisen‐Umlagerungen

Catalyzed Propargylic Substitution

tert ‐Butyl‐ tert ‐Octylamine

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The Alkylation of Amines with t-Acetylenic Chlorides. Preparation of Sterically Hindered Amines¹