Compartmentalization of Incompatible Polymers within Metal-Organic Frameworks towards Homogenization of Heterogeneous Hybrid Catalysts for Tandem Reactions.

New catalytic systems that contain incompatible catalytic sites were constructed by the in situ polymerization of acidic and basic polymers into metal-organic frameworks, which resulted in highly porous, recyclable, and durable catalytic composites with excellent compartmentalization, so that opposing agents were spatially isolated. These synthesized hybrid catalysts exhibited excellent catalytic activity for one-pot "wolf and lamb" reactions (deacetalization/Knoevenagel or Henry), which was attributed to their unique characteristic of having a locally homogeneous, but globally heterogeneous, structure.

Synthesis, antifungal activity, and QSAR study of novel trichodermin derivatives.

In an attempt to discover more potential antifungal agents, in this study, 21 novel trichodermin derivatives containing conjugated oxime ester (5a-5u) were designed and synthesized and were screened for in vitro antifungal activity. The bioassay tests showed that some of them exhibited good inhibitory activity against the tested pathogenic fungi. Compound 5a exhibited better activity against Pyricularia oryzae and Sclerotonia sclerotiorum than trichodermin, and compound 5j showed particular activity against P.oryzae and Botrytis cinerea. The quantitative structure-activity relationship (QSAR) indicated that log P and hardness were two critical parameters for the biological activities. The result suggested that these would be potential lead compounds for the development of fungicides with further structure modification.

Synthesis and biological evaluation of novel trichodermin derivatives as antifungal agents.

To discover more potential antifungal agents, 17 novel trichodermin derivatives were designed and synthesized by modification of 3 and 4a. The structures of all the synthesized compounds were confirmed by (1)H NMR, ESI-MS and HRMS. Their antifungal activities against Ustilaginoidea oryzae and Pyricularia oryzae were evaluated. Most of the target compounds showed potent inhibitory activity, in which 4g showed superior inhibitory effects than 4a and commercial fungicide prochloraz. Furthermore, 4h demonstrated comparable inhibitory activity to 4a. Moreover, 4i and 4l exhibited excellent inhibitory activity for Pyricularia oryzae. Additionally, compound 9 was found to be more active against all tested fungal strains than 3, with EC50 values of 0.47 and 3.71 mg L(-1), respectively.

(1'S,4'S)-5-(2,5-Dimethyl-phen-yl)-4'-meth-oxy-6-oxa-3-aza-spiro-[bicyclo-[3.1.0]hexane-2,1'-cyclo-hexa-n]-4-one.

In the title compound, C18H23NO3, the cyclo-hexane ring has a chair conformation. The oxirane plane (OCC) makes a dihedral angle of 76.15 (13)° with that of the pyrrolidine ring to which it is fused. The mean plane of the cyclo-hexane ring and the benzene ring are almost normal to the pyrrolidine ring, with dihedral angles of 88.47 (8) and 77.85 (8)°, respectively. In the crystal, mol-ecules are linked via pairs of N-H⋯O hydrogen bonds, forming inversion dimers. These dimers are linked via pairs of C-H⋯O hydrogen bonds, forming chains along the a-axis direction.

3-(2,5-Di-methyl-phen-yl)-8-meth-oxy-2-oxo-1-aza-spiro-[4.5]dec-3-en-4-yl 3-(2-bromo-4-fluoro-phen-yl)acrylate.

In the title compound, C27H27BrFNO4, which is an inhibitor of acetyl-CoA carboxyl-ase, the cyclo-hexane ring displays a chair comformation with the spiro-C and meth-oxy-bearing C atoms deviating by 0.681 (7) and -0.655 (1) Å, resppectively, from the mean plane formed by the other four C atoms of the spiro-C6 ring. The mean planes of the cyclo-hexane and 2-bromo-4-fluoro-phenyl rings are nearly perpendicular to that of the pyrrolidine ring, making dihedral angles 89.75 (6) and 87.60 (9)°, respectively. In the crystal, mol-ecules are linked via pairs of N-H⋯O hydrogen bonds, forming inversion dimers.

3-tert-Butyl-2-oxo-1-oxaspiro-[4.5]dec-3-en-4-yl 4-chloro-benzoate.

The title tetronic acid derivative, C(20)H(23)ClO(4), which is a spiro-diclofen analogue, has two crystallographically independent mol-ecules in the asymmetric unit (Z' = 2). The cyclo-hexane rings in the respective mol-ecules A and B adopt chair conformations [four C atoms are planar with mean deviations of 0.013 (2) and 0.001 (2) Å, and the flap positions deviate by 0.653 (4) and -0.663 (3) Š(mol-ecule A) and 0.642 (4) and -0.643 (5) Š(mol-ecule B) from the plane]. The furan ring makes dihedral angles of 86.9 (1) (mol-ecule A) and 85.4 (1)° (mol-ecule B) with the respective benzene rings.

8-{[(E)-3-(2-Chloro-phen-yl)acrylo-yloxy]imino}-12,13-ep-oxy-trichethec-9-en-4-yl (E)-3-(2-chloro-phen-yl)acrylate.

In the title compound, C(33)H(31)Cl(2)NO(6), the five-membered ring displays an envelope conformation, whereas the two six-membered rings both exhibit a chair conformation. As for the seven-membered ring, the dihedral angle between the mean planes formed by the four C atoms of the envelope unit and the three C and one O atoms of the six-membered chair is 69.08 (4)°, and these two mean planes are nearly perpendicular to the ep-oxy ring, making dihedral angles of 87.53 (4) and 88.67 (4)°, respectively.

3-Mesityl-2-oxo-1-oxaspiro-[4.4]non-3-en-4-yl benzoate.

In the title compound, C(24)H(24)O(4), a derivative of the potent insecticide and miticide spiro-mesifen, one cyclo-pentane C atom is disordered over two positions with occupancies of 0.574 (12) and 0.426 (12), resulting in respective envelope and twisted conformations for the cyclo-pentane ring. The atom at the flap position is 0.620 (5) Šout of the mean plane formed by the other four atoms of the envelope form. The furan ring makes dihedral angles of 68.26 (3) and 69.38 (2)°, respectively, with the 2,4,6-trimethyl-phenyl and benzene rings. The dihedral angle between the two benzene rings is 62.27 (3)°.

Trichodermin (12,13-ep-oxy-trichethec-9-en-4ß-yl 4-fluoro-benzoate).

IN THE TITLE TRICHODERMIN COMPOUND (SYSTEMATIC NAME: 12,13-ep-oxy-trichothec-9-en-4ß-yl 4-fluoro-benzoate), C(22)H(25)FO(4), the five-membered ring displays an envelope conformation, whereas the two six-membered rings show the different conformations, viz. chair and half-chair. As for the seven-membered ring, the dihedral angle between the mean planes formed by the four C atoms of the envelope unit and the three C and one O atoms of the six-membered chair is 68.67 (2)°; these two mean planes are nearly perpendicular to the ep-oxy ring with angles of 87.97 (2)and 88.14 (2)°, respectively.

2,7-Dichloro-4-(chloro-acet-yl)fluorene.

There are two mol-ecules in the asymmetric unit of the title compound, C(15)H(9)Cl(3)O. The fluorene rings of the two mol-ecules are both coplanar within 066 (3) Å. In the crystal, C-H⋯O and C-H⋯Cl hydrogen bonds link the mol-ecules into sheets running parallel to (100).

Trichodermol (4α-hydr-oxy-12,13-epoxy-trichothec-9-ene).

In the title compound, C(15)H(22)O(3), the five-membered ring displays an envelope conformation, whereas the two six-membered rings show different conformations, viz. chair and half-chair. In the crystal, mol-ecules are linked through inter-molecular O-H⋯O hydrogen bonds, forming chains running along the b axis.

3-(2,4-Dichloro-phen-yl)-2-oxo-1-oxa-spiro-[4.5]dec-3-en-4-yl 4-chloro-benzoate.

In the title spiro-diclofen derivative, C(22)H(17)Cl(3)O(4), the cyclo-hexane ring adopts a chair conformation [four C atoms are planar with a mean deviation of 0.018 Šand the two C atoms at the flap positions deviate by 0.613 (4) and -0.668 (5) Šfrom the plane]. The dihedral angles between the furan ring and the two benzene rings are 55.78 (3) and 49.92 (3)°. Weak inter-molecular C-H⋯Cl inter-actions are observed in the crystal structure.

3-(2,4-Dichloro-phen-yl)-2-oxo-1-oxaspiro-[4.5]dec-3-en-4-yl acetate.

In the title compound, C(17)H(16)Cl(2)O(4), the cyclo-hexyl ring displays a chair conformation [the four C atoms are planar with a mean deviation of 0.001 (2) Šand the two C atoms at the flap positions deviate by 0.625 (2) and -0.680 (2) Šfrom the plane]. The furan ring is planar with a mean deviation of 0.004 (2) Šand forms a dihedral angle of 46.73 (2)° with the benzene ring.

Dihalogenated trichodermin (4ß-acet-oxy-9,10-dibromo-12,13-epoxy-tri-chothec).

In the title dihalogenated trichodermin mol-ecule, C(17)H(24)Br(2)O(4) (systematic name: 9,10-dibromo-12,13-epoxy-trichothec-9-en-4ß-yl acetate), the five-membered ring displays an envelope conformation, whereas the two six-membered rings show the same conformation, viz. chair. As for the seven-membered ring, the dihedral angle between the mean planes formed by the four C atoms of the envelope unit and the three C and one O atoms of the six-membered chair is 69.08 (4)°; these two mean planes are nearly perpendicular to the ep-oxy ring with angles of 87.53 (4) and 88.67 (4)°, respectively.

3-Mesityl-2-oxo-1-oxaspiro-[4.4]non-3-en-4-yl 4-chloro-benzoate.

The title compound, C(24)H(23)ClO(4), is a potent insecticide and miticide. The five-membered cyclo-pentane ring displays an envelope conformation with the atom at the flap position 0.611 (2) Šout of the mean plane formed by the other four atoms. The furan ring makes dihedral angles of 71.3 (2) and 81.9 (2)°, respectively, with the 2,4,6-trimethyl-phenyl and 4-chloro-phenyl rings. The dihedral angle between the two benzene rings is 76.6 (1)°. In the crystal, mol-ecules are linked through weak inter-molecular C-H⋯O hydrogen bonds, forming chains running along the c axis.

4-Hydr-oxy-3-mesityl-1-oxaspiro-[4.4]non-3-en-2-one.

In the title compound, C(17)H(20)O(3), the five-membered cyclo-pentyl ring displays an envelope conformation, with the atom at the flap position 0.538 (3) Šout of the mean plane formed by the other four atoms. The dihedral angle between the benzene and furan rings is 63.34 (15)°. In the crystal structure, mol-ecules are linked through inter-molecular O-H⋯O hydrogen bonds, forming a zigzag chain along [101].

Pyridine Alkaloids in the Venom of Imported Fire Ants.

Venomous imported fire ants cause significant medical problems. Alkaloids are an important component of imported fire ant venom. Piperidine and piperideine alkaloids have been identified in fire ant venom. In this study, we studied the venom alkaloids of the red imported fire ant, Solenopsis invicta Buren, the black imported fire ant, Solenopsis richteri Forel, and the hybrid, S. invicta × S. richteri. Pyridine alkaloids were detected the first time in fire ants using solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (SPME-GC-MS). The thermal desorption process was manipulated to facilitate the isolation and identification of pyridine alkaloids that were coeluted with piperidine or piperideine alkaloids in GC. After SPME extraction of ant venom, we conducted a series of consecutive GC-MS injections, each with a partial desorption. Hidden pyridine alkaloid peaks were revealed after the overlapping piperidine or piperidiene alkaloid peaks had been desorbed. Using this approach, 10 2-methyl-6-alkyl (or alkenyl)pyridines (1-10) were found the first time in the venom of imported fire ants. Structures of three pyridine alkaloids were confirmed by synthesis, including 2-methyl-6-undecylpyridine (1), 2-methyl-6-tridecylpyridine (7), and 2-methyl-6-pentadecylpyridine (10). We also developed a silica gel column chromatography method to separate the pyridine alkaloids from other alkaloids. Using column chromatography and GC-MS with single ion monitoring at 107 m/z, five pyridine alkaloids were quantified for both workers and female alates of S. invicta and S. richteri.

2-(4-Chloro-phen-yl)-3-methyl-N-(5-methyl-thia-zol-2-yl)butanamide.

In the title compound, C(15)H(17)ClN(2)OS, the thia-zole ring, which is essentially planar with a maximum deviation of 0.044 (3) Å, makes a dihedral angle of 54.76 (8)° with the benzene ring. In the crystal, adjacent molecules related by twofold rotation symmetry are linked by pairs of N-H⋯N hydrogen bonds.

3-Mesityl-2-oxo-1-oxaspiro-[4.4]non-3-en-4-yl 2-(4-chloro-phen-yl)-3-methyl-butyrate.

In the title compound, C(28)H(31)ClO(4), the five-membered cyclo-pentyl ring displays an envelope conformation with the atom at the flap position 0.519 (3) Šout of the mean plane formed by the other four atoms. The furan ring makes dihedral angles of 72.9 (1) and 82.4 (1)°, respectively, with the trimethyl- and chloro-phenyl rings. The dihedral angle between the two benzene rings is 15.3 (1)°. In the crystal, mol-ecules are linked through inter-molecular C-H⋯Cl hydrogen bonds, forming a chain running along the b axis.

A Copper-Catalyzed Tandem Cyclization Reaction of Aminoalkynes with Alkynes for the Construction of Tetrahydropyrrolo[1,2-a]quinolines Scaffold.

A synthetic method for diversely substituted tetrahydropyrrolo[1,2-a]quinolines was developed via CuCl-catalyzed cascade transformation of internal aminoalkynes with alkynes under microwave- irradiation.