Diterpenoids. XXVI. A new diterpenoid acid from the oleoresin of Callitris columellaris

Abstract

A new diterpenoid acid, labda-8(17), 13(16),14-trien-19-oic acid, has been isolated from the oleoresin of Callitris columellaris.Further1 investigation of the oleoresin of white cypress pine, Callitris coluwzellaris, has revealed the presence of sandaracopimaric acid ( 1 ) . 2 cis-communic acid (3), transcommunic acid (5),Vsopimaric acid (7). 7-0x0-4-epidehydroabietic acid (9), and a new acid. labda-8(17),13(16),14-trien-19-oic acid (11).$ The conjugated diene acids (11) and (5) constitute a major portion of fresh (soft. sticky) resin (c. 27% and c. 18% respectively) but only trace amounts are present in old (hard, brittle) resin which contains c. 45% polymeric material.

Terpenoid Compositions of Resins from Callitris Species (Cupressaceae)

“…The mass spectra of the communic acids (XIII-XV) and sandaracopimaric acid (XVI) match those of the respective standards (Figure 2e–h and Figure S1ee–hh). The communic acids have been characterized for resin from C. columellaris [21]. Ozic acid (XVII, 4- epi -communic acid, assumed 12E-isomer) was a dominant component in two samples, and its mass spectra (Figure 2i and Figure S1ii) were interpreted by comparison with literature data [37,38] and the GC retention indices versus those of the communic acids.…”

“…Mass spectra of the terpenoids listed in Table 2, analyzed as the natural products, methylated and/or silylated derivatives: ( a ) methyl abieta-6,8,11,13-tetraene-19-oate (VIII), ( b ) methyl abieta-8,11,13,15-tetraen-19-oate (IX, [33]), ( c ) methyl callitrisate (methyl abieta-8,11,13-trien-19-oate, X), ( d ) methyl 4- epi -pimarate (XII, [34]), ( e ) methyl iso -communate (XIII), ( f ) methyl 12Z-communate (XIV), ( g ) methyl 12E-communate (XV), ( h ) methyl sandaracopimarate (XVI), ( i ) methyl 12E-ozate (XVII), ( j ) methyl 7-oxocallitrisate (XXI, [21]), ( k ) methyl lambertianate (XXII), ( l ) methyl 2α-hydroxycallitrisate (XXIII), ( m ) methyl 12-hydroxycallitrisate (XXIV, [35]), ( n ) methyl 7β-hydroxycallitrisate (XXV), ( o ) methyl 7α-hydroxycallitrisate (XXVI, [23]), ( p ) callitrisol-TMS (V), ( q ) ferruginol-TMS (VI), ( r ) sandaracopimaradien-3β-ol (VII), ( s ) methyl 12-hydroxycallitrisate-TMS (XXIV), ( t ) methyl 7β-hydroxycallitrisate-TMS (XXV), ( u ) methyl 7α-hydroxycallitrisate-TMS (XXVI), ( v ) 12-hydroxycallitrisol-diTMS (XVIII), ( w ) hinokiol-diTMS (XIX), and ( x ) 3β,18-dihydroxypimaradiene-diTMS (XX).…”

“…Callitrisic acid was isolated from Callitris columellaris wood and its structure was determined by correlation with known compounds and synthesis [20]. Additional resin acids, including 7-oxocallitrisic acid, were also reported [21]. Callitrisic acid has a restricted distribution in the extant plant kingdom, mainly in Callitris species and isolated reports for Juniperus , Calceolaria , Rabdosia , and Illicium species, the latter three belonging to Angiosperms [15,22,23,24].…”

Natural Resins of Art and Archaeology Their Sources, Chemistry, and Identification

“…Resin from the Australian cypress pines, Callitris spp., was in commerce in the last century under the name of Australian sandarac. One of these, C. colunlellaris F. MUller, has been studied chenlically [26,27]. It contains inter alia cis-and trans-communic acids and a related acid with the conjugated diene side-chain as in (XVIIb).…”

“…Studies inConservation, 22 (1977),[12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] Natural resins of art and archaeology. Their sources, chemistry, and identification…”