Chemistry Reference
In-Depth Information
generated BocNMeCH
2
CH
2
NMeCO
2
C
6
H
2
(CHO)
3
, then the addition of diethyl mal-
onate, followed by reduction (DIBALH) gave BocNMeCH
2
CH
2
NMeCO
2
C
6
H
2
[CH
ΒΌ
C(CH
2
OH)
2
]
3
[128].
3.5 1 ! 3 ADAMANTANE-BRANCHED MONOMERS
Photolysis of 1-nitroadamantane in (COCl)
2
, followed by treatment with MeOH
afforded (ca. 25%) 1-nitro-3,5,7-tris(methoxycarbonyl)adamantane [129], which
was catalytically reduced to give the 1-amino-3,5,7-tris(methoxycarbonyl)adaman-
tane in low overall yields [130]; notably, this is a rigid analog to the above Behera's
amine [32]. Similarly, 1-bromoadamantane gave (24%) 1-bromo-3,5,7-tris(methox-
ycarbonyl)adamantane under similar conditions, then reduction (LAH, 95%) gave the
1-bromo-3,5,7-tris(hydroxymethyl)adamantane, which was transformed (Tf
2
O/pyr,
AcSK/18crown6, KOH) to 1-bromo-3,5,7-tris(mercaptomethyl)adamantane [131]. A
related series of 1
3 monomers was prepared by using 1-(4-bromo/iodophenyl)-
3,5,7-tris(hydroxymethyl)adamantane [131]. Alternatively, when 1,3,5,7-tetraphe-
nyladamantane was oxidized and esterified 1,3,5,7-tetrakis(methoxycarbonyl)ada-
mantane was isolated [132], it was selectively saponified (90%) to the monoacid,
then subjected to the Curtius reaction [133] to give 1-amino-3,5,7-tris(methox-
ycarbonyl)adamantane in 83% yield [134]. The synthesis of the related 1-amino-
3,5,7-tris(3-propionic acid)adamantane, from adamantane has been reported [135].
The related 1-amido-3,5,7-tricarboxyadamantane and 1-carboxy-3,5,7-amidoada-
mantane have been isolated from a mixture of products when 1,3,5,7-tris(chlor-
ocarbonyl)adamantane was treated with aminofluorescein [136]. Tetrakis(4-iodo-
phenyl)adamantane [137], prepared from tetraphenyladamantane with [bis(trifluoro-
acetoxy)iodo]benzene and iodine in CCl
4
or CHCl
3
[138], was treated with t-BuLi,
followed by CO
2
, hydrolysis, and CH
2
N
2
generated in low yield (6-10%) the 1-(4-
iodophenyl)-3,5,7-tris(4-methoxycarbonylphenyl)adamantane [139]; whereas,
1-(4-ethynylphenyl)-3,5,7-tris(4-cyanophenyl)adamantane was generated from
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