SYNTHESIS OF AZULENE-1-ALKANOIC ACIDS, AZULENE-1,3-DIALKANOIC ACIDS, AND RELATED COMPOUNDS . A 1,3-BRIDGED AZULENE
SYNTHESIS OF AZULENE-1-ALKANOIC ACIDS, AZULENE-1,3-DIALKANOIC ACIDS, AND RELATED COMPOUNDS . A 1,3-BRIDGED AZULENE
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DOI：
10.1021/jo01260a027
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发表时间：
1969-01-01
影响因子：
3.6
通讯作者：
BREAZEAL.RD
中科院分区：
文献类型：
--
作者：
ANDERSON, AG;BREAZEAL.RD
1, 3-Bis (2', 2'-(iicarboxyethyl) azulene (2), azulyl-1, 3-bis (propanoic acid)(3), 1, 3-bis (2'-carbethoxy-3'-oxo-butyl) azulene (4), 1, 3-bis (3'-oxobutyl) azulene (5), diethyl azulene-1, 3-dipropanoate (6), and l, 3-bis (3'-hy-droxypropyl) azulene (7) havebeen synthesized via nucleophilic displacement reactions on azulyl-1, 3-bis (methyl-trimethylammonium) diiodide (1). Vilsmeier acylation reactions and reduction of the carbonyl groups in the 1-acylazulene products to methylenes by either the hydride reduction-alkylideneazulenium salt-hydride reduction method or, in one step, by diborane have been used to prepare 1-ethylazulene, ethyl 5-(l-azulyl)-5-oxopentanoate (8a), ethyl 5-(l-azulyl) pentanoate (10a), l-(l'-oxo-4'-carbethoxybutyl)-3-(5'-chloropentyl> azulene (11a), azulene-1, 3-bis (hexanenitrile)(14a), ethyl 4-(l-azulyl)-4-oxobutanoate (8b), l-(4'-chlorobutyl)-3-(1'-oxo-3'-carbethoxypropyl) azulene(lib), azulene-1, 3-bis (pentanenitrile)(14b), 1, 3-bis (1'-oxo-3'-carbomethoxypropyl) azulene (16), N, N-diethyl-10-(l-azulyl) decanamide (21), pentylazulene (22), 1, 3-dipentyl-azulene (23), 1, 3-dipropionylazulene (24), and 1, 3-dipropylazulene (25). The principal maxima in the visible absorption spectra for the 1-alkyl-and 1, 3-dialkylazulenes are compared. The diborane reduction of the acyl-azulenes is discussed. A high-dilution Thorpe-Ziegler ring closure of 14a gave 1, 3-(5'-cyano-6'-oxoundeca-met, hylene) azulene (26), the first example of a 1, 3-bridged azulene. Attempts to form 1, 3-bridged products from 14b, 21, and 6 were unsuccessful.In the course of studies on azulene3 it was desired to prepare the derivatives given in the title, in part because certain of these might lead to 1, 3 bridging of the nonbenzenoid azulene structure and thus provide a novel example of this type of structure. The syntheses required the formation of a saturated methylene carbon attached to the ring and a suitable functional group at the other end of the chain. This paper describes the methods found to accomplish these objectives and the preparation of the first example of a 1, 3-bridged azulene. The direct introduction of a methylene carbon onto the 1 position of azulene had been found practical as a synthetic method only for aminomethylation4-6 and,
