Three bis(dithiocarbamate) derivatives of glycerol were obtained in 30−95% yields by reaction of a dithiocarbamic acid salt with 1,3-dichloro-1,3-dideoxyglycerol. The in vitro antifungal activity of the new compounds was evaluated against Alternaria brassicae, Pseudocercosporella herpotrichoides, Septoria nodorum, and Phytophtora cinnamomi. Some of the compounds displayed greater activity than commercial fungicides. Bis(N,N-diethyldithiocarbamoyl)-1,3-dideoxyglycerol (4) was found to maintain its pesticidal activity up to 24 days in open field tests against A. brassicae. Keywords: Fungicides; bis(1,3-dithiocarbamoyl)-1,3-dideoxyglycerol; in vitro antifungal activity; in vivo antifungal activity; open field test

Novel carbamic esters possessing a carbohydrate moiety derived from glycerol or D-glucose with two N,N-diethyldithiocarbamoyl groups and a series of bisdithiocarbamic esters having a ketone or an alkyl ester have been synthesized. The in vitro activity of these new compounds was evaluated against Fusarium oxysporum f. sp. lini. Some of the compounds [bis[1,3-S-(N,N-diethyldithiocarbamoyl)]-1, 3-dideoxyglycerol) and diethyl N,N'-(1,3-dideoxyglycer-1, 3-diyl)bis(dithiocarbamate)] were more active for inhibiting vegetative mycelium growth than, respectively, the commercial N, N-diethyldithiocarbamic acid sodium salt and Maneb. The structure activity of these new compounds is discussed.

Following a new four-step route, we prepared a family of "extended" glucidoamphiphiles from Dglucose, D-galactose, and xylitol in which the n-dodecyl chain is attached to the glucidic moiety by the linkage Z = O-Et-O-Et-O-(α-PP-O-) n , where -O-(α-PP-O-) n is a poly-(α-propyloxy) commercial oligomeric mixture (with average length n = 6, 10, and 14). This amphiphilic behavior study showed that (i) the glucose derivative exhibits water solubility and hydrophilic-lipophilic balance values that are close to those found for the glucose compound with Z = -O-(α-PP-O-) n (without the Et-O-Et group), (ii) all these compounds are more strongly hydrophilic than the corresponding glucidic derivatives with Z = O, (iii) the increase of the poly-(α-propyloxy) chain length from ñ = 6 to ñ = 14 tends to reduce the hydrophilicity slightly.In a companion paper (1) comparing of the surfactant properties of 3-O-n-dodecyl-D-glucopyranose (23) and its "extended" homolog 3-O-n-dodecyl-O-(α-PP-O-) n -D-glucopyranose (8) in which (α-PP-O-) n = poly-(α-propyloxy) with ñ = 6, we showed that compound 8 exhibited a 100-fold increase in water solubility and a four-unit increase in hydrophiliclipophilic balance (HLB) with respect to compound 23. These results stimulated us to prepare and study the properties of the structural analogs of 8 with different glucidic moieties and of variable poly-(α-propyloxy) length. Before proceeding further, we tried to analyze the reasons for the low overall yield (10%) encountered in the synthesis of the "extended" species 8 along a six-step route (Scheme 1). This was obviously a consequence of the key step e, which required an activated substrate with a leaving group (OMs) linked to a primary carbon to introduce the glucose derivative 6. In the starting oligomeric mixture, 1, there was a secondary carbon at one of the extremities and a primary carbon at the other. Therefore, we first protected this position regiospecifically by a trityl group (step a). Subsequently, the alkyl chain, R, was introduced at the terminal secondary carbon with n-dodecyl bromide (step b). To obtain the activated intermediate, 5, the trityl group was then removed (step c) to introduce the mesylate group (step d), which was substituted by 1,2:5,6-di-O-isopropylidene-α-D-glucopyranose (6). Final desacetalation (step f ) produced the expected compound 8.In the present paper, we describe an alternative four-step route to attain slightly different "extended" glucidoamphiphiles such as compound 18 (Scheme 2), in which a diethyloxy group is introduced between the glucidic moiety and the poly-(α-propyloxy) spacer arm. This strategy is applied in preparing the corresponding D-glucose, D-galactose, and DL-xylitol derivatives with poly-(α-propyloxy) oligomers having an average degree of condensation, ñ, ranging from 6 to 14. This new "extended" glucidoamphiphile family includes enough members that some conclusions can be drawn on the influence of the di-ethyloxy group, the poly-(α-propyloxy) oligomer chain length, and the glucidic moiety on the ...

We prepared a new nonionic surfactant, 8, in which the n-dodecyl chain is attached at the C-3 carbon of the D-glucose-based glucopyranose moiety by the linkage Z = -O-(α-PP-O) n with -O-(α-PP-O) n being a commercial poly-(αpropyloxy) oligomeric mixture (with average ñ = 6). This amphiphilic behavior study showed that, when compared to the reference compound 3-O-dodecyl-D-glucopyranose (Z = O), compound 8 exhibits (i) a water solubility that is 100-fold higher, (ii) a hydrophilic-lipophilic balance value increase from 8.5 to 12.6 units, and (iii) a slighly lower critical micelle concentration. SCHEME 2 a, Trityl (Tr) chloride (1.5 equiv), pyridine, reflux, 3 h (95%) 9; b, n-C 12 H 25 -Br (1.1 equiv), KOH (2.2 equiv), 4:1 toluene/dimethylsulfoxide (DMSO), room temperature (RT) 72 h (60%) 9; c, 4:1 AcOH/H 2 O, 100°C, 1 h 30 min (93%) 9; d, mesyl (Ms) chloride (1.1 equiv), 1:1 toluene/triethylamine, RT 72 h (60%); e, 6 (1.6 equiv), KOH (3.2 equiv), 4:1 toluene/DMSO, RT 72 h (52%); f, 9:1 CF 3 COOH/H 2 O, RT 30 min, twice (58%).