1,3,5,7-Octatetrayne → HCID 15510876, 화합물

HRID 1063886노트

반응식

HRID 1063886 반응식
[Si:1]([C:8]#[C:9][C:10]#[C:11][C:12]#[C:13][C:14]#[CH:15])([CH2:6][CH3:7])([CH2:4][CH3:5])[CH2:2][CH3:3].[CH:16]#[C:17][C:18]#[C:19][C:20]#[C:21][C:22]#[CH:23]>>[Si:1]([C:8]#[C:9][C:10]#[C:11][C:12]#[C:13][C:14]#[CH:15])([CH2:6][CH3:7])([CH2:4][CH3:5])[CH2:2][CH3:3].[Si:1]([C:8]#[C:9][C:10]#[C:11][C:12]#[C:13][C:14]#[C:15][C:16]#[C:17][C:18]#[C:19][C:20]#[C:21][C:22]#[C:23][Si:1]([CH2:6][CH3:7])([CH2:4][CH3:5])[CH2:2][CH3:3])([CH2:6][CH3:7])([CH2:4][CH3:5])[CH2:2][CH3:3]

참가 물질

4

반응물 2

HCID 1386801,3,5,7-OctatetrayneHCID 15510876HCID 15510876, 화합물

생성물 2

HCID 15510876HCID 15510876, 화합물HCID 131718670HCID 131718670, 화합물

실험 절차

Acetylenic derivatives having the general formula H—(C≡C)m—H can be formed by the procedure disclosed in Eastmond et al., “Silylation as a Protective Method for Terminal Alkynes in Oxidative Couplings—A General Synthesis of the Parent Polyynes,” Tetrahedron, 1972, 28, 4601, incorporated herein by reference, and can be converted into dilithio salts by reacting with n-butyllithium. Synthesis of the lower polyyne series H—(C≡C)m—H (n=2, 3, 4 and 5) is known to be based upon low temperature sodamide dehydrohalogenation of α,ω-bis(chloromethyl)alkynes, ClCH2—(C≡C)m−l—CH2Cl in liquid ammonia, a technique which provided a convenient route to diacetylene but which proved increasingly troublesome for tri- and tetraacetylene. Pentaacetylene, the highest member of the series was obtained in ca. 1% yield from the precursor, ClCH2-(C≡C)4—CH2Cl. Polyynes in the series H—(C≡C)m—H (n═4, 5, 6, 7, 8, 9, 10 and 12) are known to have been prepared in solution by sequences involving Cu-catalyses oxidative couplings (Hay technique) of silyl-protected terminal alkynes, partial cleavage (desilylation) of the products by alkali, recoupling and complete desilylation. Thus using conditions established in a model coupling Et3Si—C≡C—H (I)→Et3Si—(C≡C)2—SiEt3 (II), coupling of the silyldiyne Et3Si—(C≡C)2—H (III) gives Et3S—(C≡C)4—SiEt3 (IV) which upon controlled cleavage yields a chromatographically separable mixture of Et3S—(C≡C)4—SiEt3 (IV), Et3Si—(C≡C)4—H (V) and H—(C≡C)4—H (VI). Coupling of Et3Si—(C≡C)4—H (V) in turn gives Et3Si—(C≡C)8—SiEt3 (VII) which upon cleavage yields Et3Si—(C≡C)8—H (VIII) and H—(C≡C)8—H (IX) and coupling of Et3Si—(C≡C)8—H (VIII) gives the bissilylhexadecaacetylene Et3Si—(C≡C)16—SiEt3 (X).

후처리

  1. customyields

출처 및 근거

ORD 기록
ord-7aca4e6ab9f3400fb40bfa5d7b90d67b
출처 데이터셋
uspto-grants-2005_11
특허 번호
US06967233B2

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