1H- und 13C-NMR.-Spektren von 6-(p-X-Phenyl)fulvenen. Kurzmitteilung

¹H- and ¹³C-NMR.-spectra of 6-(p-X-phenyl)fulvenes The ¹H- and ¹³C-NMR.-spectra of a series of 6-(p-X-phenyl)fulvenes 3 , measured at 9.39 T (93.9 kgauss), have been analyzed. In these compounds, electronic effects due to the substituent X clearly exert changes in chemical shifts as well as in coupling constants in the 5-membered ring. Small changes in bond length are observed by comparison of the vicinal ¹H, ¹H-coupling constants, whereas changes in charge densities linearly influence the chemical shifts of C(5), C(2) and C(3).     

Novel Copolymers of Styrene. 10. Halo Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel electrophilic trisubstituted ethylene monomers, halo ring-substituted 2-cyano-3-phenyl-2-propenamides, RPhCH ? C(CN)CONH₂, where R is 2-bromo, 3-bromo, 2-fluoro, 3-fluoro, 2-iodo, 3-iodo, and 4-iodo were prepared and copolymerized with styrene. The monomers were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (7-19 wt%), which then decomposed in the 500–800°C range.     

Novel copolymers of styrene. 5. Alkyl and alkoxy ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, alkyl and alkoxy ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₃H₇ (where R is 2,3-dimethyl, 2,5-dimethyl, 2,6-dimethyl, 3,4-dimethyl, 2,3-dimethoxy, 2,4-dimethoxy, 2,5-dimethoxy, 2,6-dimethoxy 3,4-dimethoxy, 3,5-dimethoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (0.6–5.0% wt.), which then decomposed in the 500–800°C range.     

Biosynthesis of the cytochalasans. Part III. C-NMR. of cytochalasin B (phomin) and cytochalasin D. Incorporation of [1-13C]- and [2-13C]-sodium acetate

Sequential single frequency decoupling and partially relaxed Fourier transform (PRFT) are used to assign the natural abundance ¹³C-NMR. spectra of cytochalasin B (phomin) ( 1 ) and cytochalasin D ( 2 ). Cultures of Phoma spec. S 298 were fed [2-¹³C]-sodium acetate, and the distribution of this precursor in cytochalasin B (phomin) ( 1 ) was determined by ¹³C-NMR. spectroscopy. Likewise, the labelling patterns in cytochalasin D (zygosporin A) ( 2 ) from Zygos-posium masonii could be identified after incorporation of [2-¹³C]-sodium acetate and [l-¹³C]-sodium acetate. The results confirm previous proposals for the biogenesis of the cytochalasans from phenylalanine, methionine, and a C₁₈, or C₁₆, polyketide part.     

Novel Copolymers of Styrene. 9. Methyl and Methoxy Ring-Substituted 2-Cyano-3-phenyl 2-propenamides

Novel electrophilic trisubstituted ethylene monomers, methyl and methoxy ring- substituted 2-cyano-3-phenyl-2-propenamides, RPhCH=C(CN)CONH₂, where R is 2,3-dimethyl, 2,4-dimethyl, 2,5-dimethyl, 2-(3-methoxyphenoxy), 2-(4-methoxyphenoxy), 3-(4-methoxyphenoxy), 4-(4-methylphenoxy), 2,3-methylenedioxy were prepared and copolymerized with styrene. The monomers were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (5.8–33.8 wt%), which then decomposed in the 500–800°C range.     

Novel copolymers of styrene. 1. Alkyl ring-substituted propyl 2-cyano-3-phenyl-2-propenoates

Trisubstituted ethylenes, alkyl ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₃H₇ (where R is H, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-propyl, 4-i-propyl, 4-butyl, 4-i-butyl, 4-t-butyl) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H and ¹³C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 250–500°C range with residue (2–4% wt.), which then decomposed in the 500–800°C range.     

Novel copolymers of styrene. 8. Fluoro,methoxy, and methyl ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₃H₇ (where R is 2-fluoro-5-methoxy, 2-fluoro-6-methoxy, 3-fluoro-4-methoxy, 4-fluoro-3-methoxy, 5-fluoro-2-methoxy, 2-fluoro-6-methyl, 3-fluoro-2-methyl, 4-fluoro-2-methyl, 4-fluoro-3-methyl, 5-fluoro-2-methyl) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.4–3.0% wt.), which then decomposed in the 500–800°C range.     

Novel copolymers of styrene. 2. Oxy ring-substituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, oxy ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₃H₇ (where R is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy, 3-ethoxy, 4-ethoxy, 4-propoxy, 4-butoxy, 3-phenoxy, 4-phenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of oxy ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.2–3.6% wt.), which then decomposed in the 500–800°C range.     

Novel Copolymers of Trisubstituted Ethylenes and Styrene. 7. Dihalogen Ring-Substituted Ethyl 2-Cyano-1-oxo-3-phenyl-2-propenylcarbamates

Electrophilic trisubstituted ethylenes, dihalogen ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC₆H₃ CH = C(CN)CONHCO₂C₂H₅(where R is 2,3-diCl, 2,4-diCl, 2,6-diCl, 3,4-diCl, 3,5-diCl, and 2-Cl-6-F, were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and N-cyanoacetylurethane, and characterized by CHN analysis, IR, ¹H- and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H- and ¹³C-NMR. The order of relative reactivity (1/r ₁) for the monomers 2,4-diCl (4.4) > 2,6-diCl (3.6) > 2,3-diCl (3.4) = 3,4-diCl (3.4) > 2-Cl-6-F (2.7) > 3,5-diCl (2.0). High T _g of the copolymers in comparison with that of polystyrene indicates decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene structural unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in 270–420°C with residue (5–13% wt), which then decomposed in the 420–650°C range.     

Composition of Ni2+ cation solvation shell in NiCl2–methanol solution by multinuclear NMR

¹H-, ²H- and ¹³C-NMR spectra have been used to test the Ni²⁺ solvation shell composition in the 1.1 molal methanol solution of NiCl₂. It has been confirmed that Cl^? anion takes part in the nearest environment of Ni²⁺ cation at all the temperatures investigated. Using ²H-NMR allowed us to detect for the first time OD-signal of methanol in the primary solvation shell of Ni²⁺ cation. Both ²H- and ¹³C-NMR spectra show that the composition of the cation solvation shell becomes more complicated at temperatures lower than 220?K.     

The Conformation of 1,6-Diaza-2,7-cyclodecadione in Solution

From ¹H- and ¹³C-NMR. data, a crown conformation with trans amide bonds is deduced for 1,6-diaza-2,7-cyclodecadione ( 1 ) in solution. Compound 1 was obtained by reaction of 2-pyrrolidone with POCl₃.     

Novel Copolymers of Styrene. 11. Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel electrophilic trisubstituted ethylene monomers, halo ring-disubstituted 2-cyano-3-phenyl-2-propenamides, RPhCH = C(CN)CONH₂, where R is 2,3-difluoro, 2,4-difluoro, 2,5-difluoro, 2,6-difluoro, 3,4-difluoro, 3,5-difluoro, 2-chloro-4-fluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro were prepared and copolymerized with styrene. The monomers were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (10–14 wt%), which then decomposed in the 500–800°C range.     

Novel Copolymers of Trisubstituted Ethylenes and Styrene. 8. Fluoro Ring-Substituted Ethyl 2-Cyano-1-oxo-3-phenyl-2-propenylcarbamates

Electrophilic trisubstituted ethylenes, fluoro ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC₆H₃CH = C(CN)CONHCO₂C₂H₅(where R is 4-F-3-CH₃, 2-CF₃, 4-CF₃, 2,4-diF, 2,5-diF, 2,6-diF, 3,4-diF, and 3,5-diF), were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and N-cyanoacetylurethane, and characterized by CHN analysis, IR, ¹H- and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H- and ¹³C-NMR. The order of relative reactivity (1/r ₁) for the monomers 4-CF₃ (5.4) > 2,6-diF (2.0) > 2,4-diF (1.7) > 2,5-diF (1.0) > 2-CF₃ (0.8) > 3,4-diF (0.5) > 3,5-diF (0.4) > 4-F-3-CH₃ (0.3). High T _g of the copolymers in comparison with that of polystyrene indicates decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene structural unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in 270–420°C with residue (5–13% wt), which then decomposed in the 420–650°C range.     

Die Bromierung von «Push-Pull»-Olefinen. II. Die Struktur der Bromierungsprodukte

The Bromination of Push-Pull-Olefins. II. Structure Elucidation of the Bromination Products Bromination of 3-dialkylamino-acroleins 1a , b as well as of 4-dialkylamino-3-buten-2-ons 1c , d gives O-protonated produkts 2 with all-trans configuration of the (N? C? C? C? O)-skeleton. The structure of these hydrobromides 2 is confirmed by ¹H- as well as by ¹³C-NMR. evidence.     

Novel Copolymers of Styrene. 7. Chlorine Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel trisubstituted ethylenes, chlorine ring-substituted 2-cyano-3-phenyl-2-propenamides, RC₆H₃CH?C(CN)CONH₂ (where R is 2,3-dichloro, 2,4-dichloro, 2,6-dichloro, 3,4-dichloro, 2-chloro-5-nitro, 4-chloro-3-nitro, 5-chloro-2-nitro) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution in the presence of a radical initiation (AIBN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. Thus, the order of relative reactivity (1/r1) and the tendency toward alternation of monomer units in the copolymer for the monomers is 2-Cl-5-NO₂ (3.09) > 5-Cl-2-NO₂ (1.88) > 4-Cl-3-NO₂ (0.97) > 2,6-Cl₂ (0.93) > 3,4-Cl₂ (0.31) > 2,4-Cl₂ (0.30) > 2,3-Cl₂ (0.22). High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3.5–5.0 wt%), which then decomposed in the 500–800°C range.     

Characterization of tri-o-methylcellulose by one- and two-dimensional NMR methods

Tri-O-methylcellulose was prepared from partially O-methylated cellulose and its chemical shifts (¹H and ¹³C), and proton coupling constants were assigned using the following NMR methods: (1) One-dimensional ¹H and ¹³C spectra of the title compound were used to assign functional groups and to compare with literature data; (2) double quantum filtered proton–proton correlation spectroscopy (¹H, ¹H DQF-COSY) was used to assign the chemical shifts of the network of 7 protons in the anhydroglucose portion of the repeat unit; (3) the heteronuclear single-quantum coherence (HSQC) spectrum was used to establish connectivities between the bonded protons and carbons; (4) the heteronuclear multiple-bond correlation (HMBC) spectrum was used to connect the hydrogens of the methyl ethers to their respective sugar carbons; (5) the combination of HSQC and HMBC spectra was used to assign the ¹³C shifts of the methyl ethers; (6) all spectra were used in combination to verify the assigned chemical shifts; (7) first-order proton coupling constants data (J_H,H in Hz) were obtained from the resolution-enhanced proton spectra. The NMR spectra of tri-O-methylcellulose and other cellulose ethers do not resemble the spectra of similarly substituted cellobioses. Although the ¹H and ¹³C shifts and coupling constants of 2,3,6-tri-O-methylcellulose closely resemble those of methyl tetra-O-methyl-β-D -glucoside, there are differences with regard to the chemical shifts and the order of appearances of the resonating nuclei of the methyl ether appendages and the proton at position 4 in the pyranose ring. H4 in tri-O-methylcellulose is deshielded by the acetal system comprising the β-1→4 linkage, and it resonates downfield. H4 in the permethylated glucoside is not as deshielded by the equitorial O-methyl group at C4, and it resonates upfield. The order of appearance of the ¹H and ¹³C resonances in the spectra of the tri-O-methylcellulose repeat unit (from upfield to downfield) are H2 < H3 < H5 < H6a < H3a < H2a < pro R H6B < H4 < pro S H6A ≪ H1 and C6a < C3a < C2a < C6 < C5 < C4 < C2 < C3 ≪ C1, respectively. Close examination of the pyranose ring coupling constants of the repeat unit in tri-O-methylcellulose supports the ⁴C₁ arrangement of the glucopyranose ring. Examination of the proton coupling constants about the C5-C6 bond (J_5,6A and J_5,6B) in the nuclear Overhauser effect difference spectra revealed that the C6 O-methyl group is predominantly in the gauche gauche conformation about the C5-C6 bond for the polymer in solution. © 1999 John Wiley & Sons, Inc.* J Polym Sci A: Polym Chem 37: 4019–4032, 1999     

The trans-Influence in Platinum (II) Complexes. 1H- and 13C-NMR. and X-ray structural studies of tridentate Schiff's base complexes of platinum (II)

¹H- and ¹³C-NMR. data are reported for the complexes [Pt (1) L] and [Pt (2) L]; 1 = OC₆H₄CH ? NCH₂CH₂O, 2 = OC₆H₄CH ? NC₆H₄O; L = PR₃, AsR₃, C ? N (cyclohexyl), DMSO, pyridine, secondary amine. The molecular structures of [Pt (2) (NHEt₂)] (I) and [Pt (2) (PPh₃)] (II) have been determined by X-ray analysis. Relevant bond distances for I: Pt-N (amine) = 2.076 Å, Pt-N (imine) = 2.017 Å, Pt-O = 1.992 Å and 2.002 Å; for II: Pt-P = 2.248 Å, Pt-N = 2.064 Å, Pt-O = 1.964 and 2.005 Å. Both the solid and solution state data are interpreted in terms of differences in the trans influence of the ligand L. The question of metal-ligand d-p π back bonding to the imine is discussed.     

Novel copolymers of styrene. 9. Chloro and fluoro ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO₂C₃H₇ (where R is 2,5-dichloro, 2,6-dichloro, 3,4-dichloro, 2,3-difluoro, 2,4-difluoro, 2,5-difluoro, 2,6-difluoro) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.2–3.1% wt.), which then decomposed in the 500–800°C range.     

Hyperfine shifts of the 13C-NMR. in low spin iron(3) porphyrin complexes

The ¹³C-NMR. in Zn(II)(Porphin), Fe(III)(Porphin)(CN₂), Zn(II)(Tetraphenyl-porphin), and Fe(III)(Tetraphenylporphin)(CN₂) have been identified, and the ¹³C hyperfine shifts in the iron complexes evaluated. It was found that dipole-dipole coupling with the electron spin localized in the π-orbitals of the aromatic carbon atoms makes an important contribution, to the ¹³C hyperfine shifts. In a preliminary analysis the experimental spin density distribution obtained from the combined ¹H- and ¹³C-NMR.-data is compared with theoretical models of the iron porphyrin complexes.     

Novel copolymers of styrene. 12. Halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates

Electrophilic trisubstituted ethylenes, halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₄H₉ where R is 2-chloro-4-fluoro, 2-chloro-6-fluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro, 2-fluoro-5-iodo, 3-(3,4-dichlorophenoxy), 4-(2,4-dichlorophenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H and ¹³C-NMR.

Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.7–6.8% wt), which then decomposed in the 500–800°C range.