Residues of chlorinated pesticides in mother\u27s milk and child\u27s serum

Uzorci mlijeka i seruma 27 hospitaliziranih dojilja iz Bjelovara i Zaboka s okolnim mjestima analizirani su na ostatke kloriranih insekticida aldrina, dieldrina, endrina, heptaklora, heptaklor epoksida, lindana i ostalih stereoizomera heksaklorcikloheksana, pp-\u27DDT-a i metabolita (pp-\u27DDE i pp-\u27DDD) i op-\u27DDT. Posebno je još analizirano 18 seruma majki i isto toliko seruma njihove djece koji su svi iz Zagreba. U uzorcima smo dokazali prisutnost samo Gama-HCH (Lindan). Alfa-HCH, pp-\u27DDE, op-\u27DDT, pp-\u27DDD i pp-\u27DDT. Koncentracije nađenih insekticida mnogo su veće u mlijeku dojilja nego u serumima. U serumima djece bilo je manje samo pp-\u27DDE i pp-\u27DDT nego u serumima njihovih majki. Uzorci seruma dojilja iz Zaboka i okolnih mjesta, hospitaliziranih u Zaboku i serumi dojilja iz Bjelovara hospitaliziranih u Zagrebu (N = 27) sadržavaju više navedenih insekticida nego uzorci seruma dojilja s područja Zagreba (N = 18).Milk samples obtained from 27 hospitalized lactating women and an equal number of sera from the same women were examined for residues of chlorinated hydrocarbon insecticides: aldrin, dieldrin, endrin, heptachlor, heptachlorepoxide, lindan and other steroisomers of hexachlorcyclohexane, pp\u27DDT and its metabolites (pp\u27-DDE, pp\u27-DDD) and op\u27-DDT. Additional 18 samples of mother\u27s sera and an equal number of their children\u27s sera were examined separately. The aim was to find out whether there is a correlation between the pesticide residues in mother\u27s serum and mother\u27s milk and in the serum of the mother and her child. The insecticides were determined according to the procedure used by the US Food and Drug Administration (4). Chlorinated hydrocarbon insecticides in the serum were examined with the method described by Wyllie and coworkers (5). In all samples only the presence of a-HCH, y-HCH, pp\u27-DDE, op\u27-DDT, pp\u27-DDD and pp\u27-DDT could be demonstrated. The concentration ratio between mother\u27s milk and serum was between 4 and 11. The concentration ratio between mother\u27s and child\u27s serum was below 1 except for pp\u27-DDE and pp\u27-DDT

<i>peri</i>-Substituted Phosphino-Phosphonium Salts: Synthesis and Reactivity

The clean reaction of 5-lithio-6-(diisopropylphosphino)­acenaphthene with dichlorophosphines RPCl₂ gives the <i>peri</i>-substituted phosphino-phosphonium salts [Acenap­(P<i>i</i>Pr₂)­(PR)]⁺Cl^– (<b>2</b>, R = Ph; <b>3</b>, R = Fc; <b>4</b>, R = NMe₂; <b>5</b>, R = <i>i</i>Pr; Acenap = acenaphthene-5,6-diyl). Their ionic structure is maintained in solution and in the solid state. The reduction of <b>2</b> and <b>3</b> with LiAlH₄ led to the formation of mixed tertiary/secondary chelating bis­(phosphines) Acenap­(P<i>i</i>Pr₂)­(PRH) (<b>6</b> and <b>7</b>), which were subsequently reacted with PtCl₂(cod) to give the complexes [(<b>6</b>)/(<b>7</b>)­PtCl₂] (<b>8</b> and <b>9</b>). Reaction of <b>2</b> and <b>3</b> with a large excess of MeOTf at elevated temperature gave the chiral 1,2-diphosphoniums [Acenap­(P<i>i</i>Pr₂)­(PRMe)]²⁺([TfO]⁻)₂ (<b>10</b> and <b>11</b>), which were reduced with LiAlH₄ to the heteroleptic bis­(phosphines) Acenap­(P<i>i</i>Pr₂)­(PRMe) (<b>12</b> and <b>13</b>); these were then reacted with [(nor)­Mo­(CO)₄] to give the complexes [(<b>12</b>)/(<b>13</b>)­Mo­(CO)₄] (<b>14</b> and <b>15</b>). The heteroleptic bis­(phosphines) <b>6</b>, <b>7</b>, <b>12</b>, and <b>13</b> display large through-space couplings (formally ⁴<i>J</i>_PP = 163–199 Hz), comparable in magnitude to ¹<i>J</i>_PP couplings observed in phosphino-phosphonium salts <b>2</b>–<b>5</b> (303–412 Hz). Single-crystal X-ray structures of <b>2</b>, <b>3</b>, <b>7</b>–<b>9</b>, <b>14</b>, and <b>15</b> are reported

<i>peri</i>-Substituted Phosphino-Phosphonium Salts: Synthesis and Reactivity

The clean reaction of 5-lithio-6-(diisopropylphosphino)­acenaphthene with dichlorophosphines RPCl₂ gives the <i>peri</i>-substituted phosphino-phosphonium salts [Acenap­(P<i>i</i>Pr₂)­(PR)]⁺Cl^– (<b>2</b>, R = Ph; <b>3</b>, R = Fc; <b>4</b>, R = NMe₂; <b>5</b>, R = <i>i</i>Pr; Acenap = acenaphthene-5,6-diyl). Their ionic structure is maintained in solution and in the solid state. The reduction of <b>2</b> and <b>3</b> with LiAlH₄ led to the formation of mixed tertiary/secondary chelating bis­(phosphines) Acenap­(P<i>i</i>Pr₂)­(PRH) (<b>6</b> and <b>7</b>), which were subsequently reacted with PtCl₂(cod) to give the complexes [(<b>6</b>)/(<b>7</b>)­PtCl₂] (<b>8</b> and <b>9</b>). Reaction of <b>2</b> and <b>3</b> with a large excess of MeOTf at elevated temperature gave the chiral 1,2-diphosphoniums [Acenap­(P<i>i</i>Pr₂)­(PRMe)]²⁺([TfO]⁻)₂ (<b>10</b> and <b>11</b>), which were reduced with LiAlH₄ to the heteroleptic bis­(phosphines) Acenap­(P<i>i</i>Pr₂)­(PRMe) (<b>12</b> and <b>13</b>); these were then reacted with [(nor)­Mo­(CO)₄] to give the complexes [(<b>12</b>)/(<b>13</b>)­Mo­(CO)₄] (<b>14</b> and <b>15</b>). The heteroleptic bis­(phosphines) <b>6</b>, <b>7</b>, <b>12</b>, and <b>13</b> display large through-space couplings (formally ⁴<i>J</i>_PP = 163–199 Hz), comparable in magnitude to ¹<i>J</i>_PP couplings observed in phosphino-phosphonium salts <b>2</b>–<b>5</b> (303–412 Hz). Single-crystal X-ray structures of <b>2</b>, <b>3</b>, <b>7</b>–<b>9</b>, <b>14</b>, and <b>15</b> are reported

Synthetic and Structural Study of the Coordination Chemistry of a <i>peri</i>-Backbone-Supported Phosphino-Phosphonium Salt

Coordination chemistry of an acenaphthene <i>peri</i>-backbone-supported phosphino-phosphonium chloride (<b>1</b>) was investigated, revealing three distinct modes of reactivity. The reaction of <b>1</b> with Mo­(CO)₄(nor) gives the Mo(0) complex [(<b>1</b>)­Mo­(CO)₄Cl] (<b>2</b>), in which the ligand <b>1</b> exhibits monodentate coordination through the phosphine donor and the P–P bond is retained. PtCl₂(cod) reacts with the chloride and triflate salts of <b>1</b> to form a mononuclear complex [(<b>1</b>Cl)­PtCl₂] (<b>3</b>) and a binuclear complex [((<b>1</b>Cl)­PtCl)₂]­[2TfO] (<b>4</b>), respectively. In both of these complexes, the platinum center adds across the P–P bond, and subsequent chloride transfer to the phosphenium center results in phosphine-chlorophosphine bidentate coordination. [((<b>1</b>)­PdCl)₂] (<b>5</b>) was isolated from the reaction of <b>1</b> and Pd₂(dba)₃ (dba = dibenzylideneacetone). Oxidative addition to palladium(0) results in a heteroleptic phosphine bridging phosphide coordination to the Pd­(II) center. In addition, reaction of <b>1</b> with BH₃·SMe₂ leads to the bis­(borane) adduct of the corresponding mixed tertiary/secondary phosphine (<b>6</b>), with BH₃ acting as both a reducing agent and a Lewis acid. The new compounds were fully characterized, including X-ray diffraction. The ligand properties of <b>1</b> and related bonding issues are discussed with help of DFT computations

Synthetic, Structural, NMR, and Computational Study of a Geminally Bis(<i>peri</i>-substituted) Tridentate Phosphine and Its Chalcogenides and Transition-Metal Complexes

Coupling of two acenaphthene backbones through a phosphorus atom in a geminal fashion gives the first geminally bis­(<i>peri</i>-substituted) tridentate phosphine <b>1</b>. The rigid nature of the aromatic backbone and overall crowding of the molecule result in a rather inflexible ligand, with the three phosphorus atoms forming a relatively compact triangular cluster. Phosphine <b>1</b> displays restricted dynamics on an NMR time scale, which leads to the anisochronicity of all three phosphorus nuclei at low temperatures. Strained bis- and tris­(sulfides) <b>2</b> and <b>3</b> and the bis­(selenide) <b>4</b> have been isolated from the reaction of <b>1</b> with sulfur and selenium, respectively. These chalcogeno derivatives display pronounced in-plane and out-of-plane distortions of the aromatic backbones, indicating the limits of their angular distortions. In addition, we report metal complexes with tetrahedral [(<b>1</b>)­Cu­(MeCN)]­[BF₄] (<b>5</b>), square planar [(<b>1</b>)­PtCl]­[Cl] (<b>6</b>), trigonal bipyramidal [(<b>1</b>)­FeCl₂] (<b>7</b>), and octahedral <i>fac</i>-[(<b>1</b>)­Mo­(CO)₃] (<b>8</b>) geometries. In all of these complexes the tris­(phosphine) backbone is distorted, however to a significantly smaller extent than that in the mentioned chalcogenides <b>2</b>–<b>4</b>. Complexes <b>5</b> and <b>8</b> show fluxionality in ³¹P and ¹H NMR. All new compounds <b>1</b>–<b>8</b> were fully characterized, and their crystal structures are reported. Conclusions from dynamic NMR observations were augmented by DFT calculations

Synthetic, Structural, NMR, and Computational Study of a Geminally Bis(<i>peri</i>-substituted) Tridentate Phosphine and Its Chalcogenides and Transition-Metal Complexes

Coupling of two acenaphthene backbones through a phosphorus atom in a geminal fashion gives the first geminally bis­(<i>peri</i>-substituted) tridentate phosphine <b>1</b>. The rigid nature of the aromatic backbone and overall crowding of the molecule result in a rather inflexible ligand, with the three phosphorus atoms forming a relatively compact triangular cluster. Phosphine <b>1</b> displays restricted dynamics on an NMR time scale, which leads to the anisochronicity of all three phosphorus nuclei at low temperatures. Strained bis- and tris­(sulfides) <b>2</b> and <b>3</b> and the bis­(selenide) <b>4</b> have been isolated from the reaction of <b>1</b> with sulfur and selenium, respectively. These chalcogeno derivatives display pronounced in-plane and out-of-plane distortions of the aromatic backbones, indicating the limits of their angular distortions. In addition, we report metal complexes with tetrahedral [(<b>1</b>)­Cu­(MeCN)]­[BF₄] (<b>5</b>), square planar [(<b>1</b>)­PtCl]­[Cl] (<b>6</b>), trigonal bipyramidal [(<b>1</b>)­FeCl₂] (<b>7</b>), and octahedral <i>fac</i>-[(<b>1</b>)­Mo­(CO)₃] (<b>8</b>) geometries. In all of these complexes the tris­(phosphine) backbone is distorted, however to a significantly smaller extent than that in the mentioned chalcogenides <b>2</b>–<b>4</b>. Complexes <b>5</b> and <b>8</b> show fluxionality in ³¹P and ¹H NMR. All new compounds <b>1</b>–<b>8</b> were fully characterized, and their crystal structures are reported. Conclusions from dynamic NMR observations were augmented by DFT calculations

Sterically Encumbered Tin and Phosphorus <i>peri-</i>Substituted Acenaphthenes

A group of sterically encumbered <i>peri</i>-substituted acenaphthenes have been prepared, containing tin moieties at the 5,6-positions in <b>1</b>–<b>3</b> ([Acenap­(SnR₃)₂], Acenap = acenaphthene-5,6-diyl; R₃ = Ph₃ (<b>1</b>), Me₃ (<b>2</b>); [(Acenap)₂(SnMe₂)₂] (<b>3</b>)) and phosphorus functional groups at the proximal <i>peri</i>-positions in <b>4</b> and <b>5</b> ([Acenap­(PR₂)­(P^<i>i</i>Pr₂)] R₂ = Ph₂ (<b>4</b>), Ph­(^<i>i</i>Pr) (<b>5</b>)). Bis­(stannane) structures <b>1</b>–<b>3</b> are dominated by repulsive interactions between the bulky tin groups, leading to <i>peri</i>-distances approaching the sum of van der Waals radii. Conversely, the <i>quasi</i>-linear C_Ph-P···P three-body fragments found in bis­(phosphine) <b>4</b> suggest the presence of a lp­(P)−σ*­(P–C) donor–acceptor 3c-4e type interaction, supported by a notably short intramolecular P···P distance and notably large <i>J</i>_PP through-space coupling (180 Hz). Severely strained bis­(sulfides) <b>4-S</b> and <b>5-S</b>, experiencing pronounced in-plane and out-of-plane displacements of the exocyclic <i>peri</i>-bonds, have also been isolated following treatment of <b>4</b> and <b>5</b> with sulfur. The resulting nonbonded intramolecular P···P distances, ∼4.05 Å and ∼12% longer than twice the van der Waals radii of P (3.60 Å), are among the largest ever reported <i>peri</i>-separations, independent of the heteroatoms involved, and comparable to the distance found in <b>1</b> containing the larger Sn atoms (4.07 Å). In addition we report two metal complexes with square planar [(<b>4</b>)­PtCl₂] (<b>4-Pt</b>) and octahedral <i>cis</i>-[(<b>4</b>)­Mo­(CO)₄] (<b>4-Mo</b>) geometries. In both complexes the bis­(phosphine) backbone is distorted, but notably less so than in bis­(sulfide) <b>4-S</b>. All compounds were fully characterized, and except for bis­(phosphine) <b>5</b>, crystal structures were determined