Colchicum ukaisnei of Jordanian origin has yielded three new alkaloids, (-) jerusalemine [1], (-)-salimine [2], and (-)-suhailamine [3], besides the known alkaloid (-) androbiphenyline. Colchicum deraisnei Boiss. (Liliaceae) is native to the Middle East and has not been previously investigated for its alkaloidal content. The tubers of this plant were collected in Al-Salt near Amman, defatted, and subjected to cold MeOH extraction. Extensive chromatography of the extracts furnished three levorotatory dibenzocycloheptylamine alkaloids (1-3). The eims of jerusalemine [1] showed the molecular ion peak at m/z 345 (80%). Hrms afforded the exact mass at m/z 345.1582 (calcd for C19H23NO5, 345.1576). The base peak was present at m/z 314 (C17H18O5, hrms 314.1227, calcd 314.1154) due to the facile loss of the methylamine residue. The uv spectrum of 1 showed maxima at 212 and 267 nm typical for the dibenzocycloheptadiene chromophore (3,4). A broad absorption band at 3280 cm-1 and another band at 3515 cm-1 in the ir spectrum corresponded to the presence of NH and phenolic hydroxyl groups. The 400 MHz ¹H-nmr spectrum of 1 included three aromatic singlets, each integrating for one proton, indicating the absence of any neighboring protons in ortho or meta positions. Moreover, three 3H singlets were present for the three OMe protons at δ 3.91, 3.87, and 3.50. A sharp 3H singlet at δ 2.40 was due to the N-methyl protons. In order to confirm the positions of these signals, a series of nOe experiments were performed. Irradiation of the aromatic singlet at δ 6.55 (H-4) produced an nOe enhancement for the singlet at δ 3.91 (3-OMe) and for the multiplet at δ 2.45 (H-5a). On the other hand, the 3-OMe (δ 3.91) showed reciprocating nOe with H-4 (δ 6.55). Irradiation of the upfield methoxyl group at δ 3.50 (1-OMe) did not show any enhancement of other methoxyl groups, indicating the presence of a hydroxyl group rather than a methoxyl group at C-2. The methoxyl singlet at δ 3.87 (9-OMe) showed mutual nOe interactions with the aromatic singlet at δ 7.05 (H-8). In view of the nOe interactions between H-7 and H-8 on the one hand, and between H-8 and the 9-OMe on the other hand, as well as the lack of any coupling of H-8 and H-11 with any other proton, the second hydroxyl group was placed at C-10. Interestingly, H-7 resonated at δ 3.41 as a doublet of doublets with coupling constants 12.0 and 6.4 Hz, the larger coupling constant corresponding to a diaxial relationship with the C-6β proton. This larger coupling constant also reflects a boat conformation for ring B of jerusalemine [1], which is also in accord with the X-ray data recorded in the literature for the structurally related N-acetylcolchinol (5). The detailed ¹H-nmr data of (-)-jerusalemine [1] are indicated around expression 1. The GASPE spectrum of jerusalemine [1] indicated the presence of nineteen carbon atoms, of which there were three methoxyl, three aromatic methine, two methylene, and one N-methyl carbons. The ¹³C-nmr assignments were determined with the help of an HMQC (6) experiment (see Experimental). The second new alkaloid, (-)-salimine [2], showed a molecular ion peak in eims at m/z 415.1623 (100%) corresponding to the molecular formula, C21H25NO8 (calcd 415.1631). Like (-)-jerusalemine [1], the 400 MHz ¹H-nmr spectrum of salimine [2] showed three aromatic singlets each integrating for one proton. Four aromatic methoxyls were also present, in addition to the acetyl methyl signal at δ 2.04. The most salient features of the ¹H-nmr spectrum of compound 2 were the lack of coupling of the aromatic protons and the presence of a downfield singlet at δ 10.82 for the carboxyl proton. COSY-45 and nOe experiments were performed to confirm the structure. Weak interactions were seen in the COSY spectrum between H-4 and 3-OMe, between H-11 and 1-OMe, between H-8 and 9-OMe, between H-8 and H-7β, and between the C-5 and C-6 protons. The aromatic singlet at δ 6.55 (H-4) showed reciprocating nOe's with the methoxyl singlet at δ 3.89 (3-OMe). Similarly, irradiation at the sterically hindered methoxyl singlet at δ 3.55 (1-OMe) gave an nOe at the methoxyl singlet at δ 3.92 (2-OMe), as well as at H-11 (δ 7.96). Irradiation of the aromatic one-proton singlet at δ 6.90 (H-8) produced nOe enhancement of both the broad doublet centered at δ 5.75 (-NH) and of the multiplet at δ 4.80 (H-7β). The ¹H-nmr chemical shift data are summarized around expression 2. Again, as in 1, ring B in 2 appeared to be mainly in a boat-like conformation, because nOe interactions were seen between H-4 and H-5a, on the one hand, as well as between H-8 and H-7 on the other hand. An nOe interaction was also seen between H-8 and the NH proton. The ¹³C-nmr data has been assigned using GASPE and HMQC experiments (Experimental). The uv spectrum of the third alkaloid, (-)-suhailamine [3] along with ms and ¹H-nmr data indicated that it contains the dibenzocycloheptadiene skeleton. The eims showed a molecular ion peak at m/z 399.1680 (15%, calcd for C21H25NO7, 399.1682) and the base peak at m/z 312. The ¹H-nmr spectrum of (-)-suhailamine [3] (400 MHz, CDCl3) showed the presence of four aromatic protons and four methoxyl singlets (3 × OMe, 1 × COOMe) in addition to the acetyl methyl group at δ 2.05. The ¹H-nmr spectrum contained a downfield doublet at δ 7.42 for H-11 (J = 8.4 Hz) and a doublet of doublets at δ 6.84 for H-10 (J10,11 = 8.4 Hz, J10,8 = 2.8 Hz). Another doublet appeared at δ 6.80 for H-8 (J8,10 = 2.8 Hz). The mol wt of suhailamine [3] is 16 mu less than that of salimine [2]. Moreover, the downfield proton at δ 10.82 for the carboxyl proton characterized in the spectrum of 2 is absent in the spectrum of suhailamine [3]. Extensive spectral studies (COSY-45, nOe, GASPE, and HMQC) resulted in unambiguous assignment of the ¹H-nmr data, which are presented around structure 3. In order to confirm the positions of the methoxyls and the aromatic protons, a series of ¹H-nmr nOe experiments were performed. The methoxyl singlet at δ 3.89 (3-OMe) produced reciprocating nOe with the aromatic singlet at δ 6.55 (H-4), which in turn showed nOe of the multiplet centered at δ 2.45 (H-5a). On the other hand, irradiation of the methoxyl singlet at δ 3.92 (2-OMe) affected the nOe of the upfield methoxyl at δ 3.52 (1-OMe). Interestingly, irradiation of the aromatic doublet centered at δ 6.80 (J = 2.8, H-8) resulted in an nOe of both the multiplet centered at δ 4.78 (H-7) and of the methoxyl at δ 3.85 (-COOMe). The latter in turn gave an nOe of the doublet of doublets at δ 6.84 (H-10). Furthermore, irradiation of the downfield ortho coupled proton at δ 7.42 (H-11) produced an nOe of the doublet of doublets at δ 6.84 (H-10). This resulted in the assignment of the carbomethoxy group at C-9. It is notable that H-11 appeared at δ 7.42 in 3 with a meta-disposed CO2Me group, while H-11 in 2, which has the COOH group in an ortho position, is present further downfield (δ 7.96) as expected. The downfield shift of this proton in 1, 2, and 3 is probably due to its location in the paramagnetic zone of ring A. The ¹³C-nmr spectrum (GASPE) of compound 3 was assigned with the help of HMQC data (see Experimental). The negative optical rotation of 1, 2, and 3 established that they have the same 7S configuration as other structurally related colchicine-type compounds (4). With the characterization of (-)-jerusalemine [1], (-)-salimine [2], and (-)-suhailamine [3], it is possible to delineate the outlines of possible catabolic routes to the colchicine-type alkaloids (1). For (-)-jerusalemine [1], the presence of a peroxidase enzyme system in the plant may facilitate the decarbonylation of the tropolone ring of (-)-2-demethyldemecolcine [4], with accompanying oxidation resulting ultimately in the formation of (-)-jerusalemine [1] as shown in Scheme 1 (7). On the other hand, (-)-salimine [2] and (-)-suhailamine [3] may arise from (-)-colchicine by enzymatic peroxidation of ring C followed by hydroxylation and methylation (7).