Chemical Constituents from the Leaves of Magnolia Denudata

Abstract

20 compounds were isolated from the leaves of Magnolia denudata including 16 lignans, which belong to 6 structural types. Except for (7R, 8S, 1′S) -δ^8′ - 1′, 4′ - dihydro - 5′- methoxy - 3, 4 -methylenedioxy - 4′ - oxo -7.O.2′, 8.1′ - neolignan (6), magliflonenone (9), 2,5′ - diene-2′, 8′- epoxy - 5′ - methoxy - 8 - methyl - 4′ - oxo - 3,4-methylenedioxy - spiro (5,5) - undecane (10), veraguensin (16) and β-sitosterol (20), the other 15 compounds were obtained from this species for the first time. The absolute configurations of 3 compounds (1,4,10) were determined by CD spectroscopy for the first time. The anti-inflammatory activities of compounds 1, 2 and 16 were assessed and 2 was shown to have significant inhibition effect on mice hind-paw edema induced by carrageenan.     

宝藿甙-Ⅰ,Ⅵ,Ⅶ和宝藿素的分离和结构研究

自宝兴淫羊藿(Epimedium davidii Franch)中分离出8个黄酮类化合物,根据理化数据、光谱分析(UV,IR,¹HNMR,¹³CNMR,MS)和水解实验证明,其中E₃,E₁₃和E₈分别为已知成分淫羊藿甙、淫羊藿素和苜蓿素。E₁,E₁₁、E₁₆和E₁₅是新黄酮类化合物,并证明结构,分别命名为宝藿甙-Ⅰ(baohuoside Ⅰ),宝藿甙-Ⅵ(baohuoside Ⅵ),宝藿甙-Ⅶ(baohuo side Ⅶ)和宝藿素(baohuosu)。E¹⁷的结构待定。     

Addition von β-Dicarbonylverbindungen an 2-Acetyl-p-benzochinon, 3. Mitt.1): Untersuchung der Umsetzung mit α-Hydroxymethylencycloalkanonen

Addition of β-Dicarbonyl Compounds to 2-Acetyl-p-benzoquinone, III¹⁾: The reaction of α-hydroxymethylenecyclopentanone 2 with acetylquinone 1 yields the spiro-compound 3 . α-Hydroxymethylenecyclohexanone 7 gives the dibenzopyran 8 and the spiro-compound 9 as by-product. Compounds 3, 8 , and 9 are labile, rearrangement to 6 and 11 is examined by NMR spectroscopy. Acetylation of 6 and 11 yields 5 and 12 . With hydrochloric acid the spiro-compounds 6, 11 are rearranged to 16 and 17 , respectively.     

Cholinesterase and BACE1 inhibitory diterpenoids from <Emphasis Type="Italic">Aralia cordata</Emphasis>

Fourteen diterpenes were isolated from the n-hexane fraction of the roots of Aralia cordata (syn. = A. continentalis). Through spectroscopy, the chemical structures were determined as: ent-pimara-8(14),15-diene-19-oic acid (1); ent-kaur-16-en-19-oic-acid (2); 18-nor-ent-pimara-8(14),15-diene-4β-ol (3); 18-nor-ent-kaur-16-ene-4β-ol (4); ent-pimara-8(14),15-diene-19-ol (5); 7α-hydroxy-ent-pimara-8(14),15-diene-19-oic acid (6); 7β-hydroxy-ent-pimara-8(14),15-diene-19-oic acid (7); ent-pimar-15-en-8α,19-diol (8); 7-oxo-ent-pimara-8(14),15-diene-19-oic acid (9); 16α-hydroxy-17-isovaleroyloxy-ent-kauran-19-oic acid (10); 17-hydroxy-ent-kaur-15-en-19-oic acid (11); 15α,16α-epoxy-17-hydroxy-ent-kauran-19-oic acid (12); 16α,17-dihydroxy-ent-kauran-19-oic acid (13); and 16α-methoxy-17-hydroxy-ent-kauran-19-oic acid (14). Compounds 4, 5, 8, 12, and 14 were first isolated from this plant. The anti-Alzheimer and antioxidant effects of ent-pimarane-type diterpenes 1, 3, 5, 8, and 9, as well as ent-kaurane-type diterpenes 2, 4, and 10∼13, were evaluated via β-site amyloid precursor protein cleaving enzyme 1 (BACE1), acetylcholinesterase (AChE), butyrylcholinesterase (BChE), peroxynitrite (ONOO⁻), and nitric oxide (NO·) assays. Of the compounds tested, 8 exerted the most effective BChE inhibition with an IC₅₀ value of 7.58 μM, followed by 3, 13, 11, 2, and 10. Compounds 9∼11 exhibited good BACE1 inhibitory activities with IC₅₀ values of 18.58∼24.10 μM. However, 11 showed marginal AChE inhibitory effect, and all compounds tested showed no scavenging activities on ONOO⁻ and NO· at a concentration of 100 μM.     

Substituierte 2-Aminonicotinonitrile

Substituted 2-Aminonicotinonitriles Aminolysis of the cyanoketene-O,N-acetal 1 Z/E with the amines 2a,b leads to the E-configurated cyanoketeneaminals 3a,b . Compounds 3a,b are reacted with 1,3-biselectrophiles 4, 6a,b, 9 HCl, 12, 13, 15a,b, 17 , and 19 to yield the N²-substituted 2-aminonicotinonitriles 5, 7, 8, 10, 11, 14, 16 , and 20 . Reaction of some 2-aminonicotinonitriles with an α-phenylethyl substituent in position 2 ( 14b, 16a, 8a, 20b, 5 and 8b ) with PPA leads to the primary 2-aminonicotinonitriles 21a-f .     

Synthesis and characterization of a new labeled gastrin ligand, 125I-BH-[Leu15]-gastrin-(5-17), on binding to canine fundic mucosal cells and Jurkat cells

In the course of our study concerning gastrin and cholecystokinin (CCK) receptors, we have synthesized and characterized a new labeled gastrin ligand, ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) [(3-[¹²⁵I]iodo-4-hydroxyphenyl)-propionyl-[Leu¹⁵]-gastrin-(5-17)]. Binding of ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) to isolated canine fundic mucosal cells was specific, saturable and of high affinity. ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) and ¹²⁵I-BH-CCK-8 [(3-[¹²⁵I]iodo-4-hydroxyphenyl)-propionyl-CCK-8] interact with isolated canine fundic mucosal cells with small differences in maximal binding capacities and affinities, 3800 ± 900 binding sites/cell (Kd = 0.52 ± 0.23 nM) and 6200 ± 1100 binding sites/cell (K_d= 0.31 ± 0.18 nM), respectively. The relative order of potencies for gastrin and CCK analogs in displacing ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) binding correlated well with those obtained using ¹²⁵I-BH-CCK-8. Selective CCK/gastrin antagonists L-364,718 (MK-329) and L-365,260 also inhibited ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) binding. These results indicate that ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) binds to gastrin receptors in isolated canine fundic mucosal cells. We have also characterized ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) binding to the human Jurkat lymphoblastic cell line (Jurkat cells) known to express the CCK-B/gastrin receptor. Saturation experiments have shown that both ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) and ¹²⁵I-BH-CCK-8 interact with a single class of high-affinity binding sites in the Jurkat cell line. Binding characteristics of ¹²⁵I-BH-[Leu¹⁵]-Gastrin-(5-17) and ¹²⁵I-BH-CCK-8 were estimated to be about 2500 ± 400 binding sites/cell (Kd= 0.19 ± 0.09 nM) and 2400 ± 350 binding sites/cell (Kd= 0.06 ± 0.02 nM), respectively. Furthermore, the apparent affinities of CCK analogs and selective antagonists MK-329 and L-365,260 for the sites labeled by both probes were identical. The biological activity of cold ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) and [Leu¹⁵]-gastrin-(5-17) was demonstrated by their ability to increase intracellular calcium concentration in Jurkat cells. All these experiments showed that ¹²⁵I-BH-[Leu¹⁵]-gastrin-(5-17) provides a convenient ligand for gastrin receptor binding studies. © Munksgaard 1994.     

Synthesis and assay of tyrosinated analogs of a crustacean pigment-dispersing neuropeptide hormone

In an effort to obtain biologically active tyrosine analogs of the octadecapeptide pigment-dispersing hormone (β-PDH) of the fiddler crab Uca pugilator, we have synthesized [Tyr¹⁵]- and [Nle¹⁸]-β-PDH, as well as eight tyrosine analogs of [Nle¹⁵]-β-PDH by the solid-phase method. Each analog was purified to homogeneity by gel filtration, ion-exchange chromatography, and partition chromatography. When tested for melanophore pigment-dispersing activity in destalked Uca, [Nle¹⁵, Tyr¹⁶]-β-PDH and [Nle¹⁵]-β-PDH were found to be 31-fold and 16-fold more potent, respectively, than β-PDH. Somewhat reduced potency was displayed by [N-Tyr,Nle¹⁵]-β-PDH (81%) and [Nle¹⁵, Tyr¹⁷]-β-PDH (26%). All other analogs, including [Nle¹⁵, Tyr¹⁹]-β-PDH and the four derivatives of [Nle¹⁵]-β-PDH obtained through substitution for nonpolar amino acid residues at positions 4, 5, 8, and 11 in the primary structure, showed marked decrease in biological activity (0.01 to 2% potency).     

消旋17-苯-18,19,20-失三碳前列腺素F2α甲酯及其15-差向异构体的合成

从中间体(4)出发,经醛(5),与鏻叶立德(3)或2-酮-4-苯丁烷磷酸酯(11)钠缩合成(6),再钠硼氢还原得3′α-醇(7A)及其差向异构体(7B),经硅胶柱色谱分开,分别经二异丁基铝氢还原,与溴化5-三苯鏻戊酸之Wittig试剂缩合,得17-苯-18,19,20-失三碳前列腺素F_2α(9A)及其15-差向异构体(9B),再用重氮甲烷甲酯化,分别得相应的17-苯-18,19,20-失三碳前列腺素F_2α甲酯(10A)及其15-差向异构体(10B)。     

Rearranged Abietane Diterpenoids from Clerodendrum Mandarinorum

Abstract

Five new abietane derivatives which have a commonly rearranged abietane skeleton contained a 17(15 → 16),18(4 → 3)-diabeo-abietane framework, mandarones D–H, were isolated from the stem of Clerodendrum mandarinorum Diels (Verbenaceae). The structures were characterized as (16S)-12,16-epoxy-11-hydroxy-17(15 → 16),18(4 → 3)-diabeo-abieta-3,5,8,11,13-pentaene-7-one (mandarone D, 1), 12,16-epoxy-11,14-dihydroxy-17(15 → 16),18(4 → 3)-diabeo-abieta-3,5,8,11,13,15-hexaene-7-one (mandarone E, 2), 12,16-epoxy-6,11,14-trihydroxy-17(15 → 16),18(4 → 3)-diabeo-abieta-3,5,8,11,13,15-hexaene-7-one (mandarone F, 3), 12,16-epoxy-11,14-dihydroxy-6-methoxy-17(15 → 16),18(4 → 3)-diabeo-abieta-3,5,8,11,13,15-hexaene-2,7-dione (mandarone G, 4) and 12,16-epoxy-11,14-dihydroxy-17(15 → 16),18(4 → 3)-diabeo-abieta-3,5,8,11,13,15-hexaene-1,7-dione (mandarone H, 5) respectively, mainly based on the spectral analysis and by comparison with those of closely related compounds.     

Synthesis of stable isotope‐labeled epothilone D using a degradation–reconstruction approach

The stabilization of microtubules using epothilones represents a novel mechanism of action to treat Alzheimer's disease. Epothilone D is one such microtubule‐stabilizing drug that has been investigated by Bristol‐Myers Squibb. An important step in the development process was the synthesis of a stable isotope‐labeled analog for use in bioanalytical assays to accurately quantify the concentration of the drug in biological samples. A novel synthetic route to stable isotope‐labeled epothilone D is described. The synthetic route was based on a strategy to degrade epothilone B and then use that key intermediate to reconstruct stable isotope‐labeled epothilone D. Epothilone B was treated with potassium osmate and sodium periodate. The thiazole moiety in epothilone B was efficiently cleaved to give (1S,3S,7S,10R,11S,12S,16R)‐3‐acetyl‐7,11‐dihydroxy‐8,8,10,12,16‐pentamethyl‐4,17‐dioxabicyclo[14.1.0]heptadecane‐5,9‐dione. The epoxide in the macrocyclic ring of that intermediate was cleanly removed by treatment with tungsten hexachloride and n‐butyllithium to give the corresponding olefin (4S,7R,8S,9S,16S,Z)‐16‐acetyl‐4,8‐dihydroxy‐5,5,7,9,13‐pentamethyloxacyclohexadec‐13‐ene‐2,6‐dione. Bis(triethylsilyl) protection produced (4S,7R,8S,9S,16S,Z)‐16‐acetyl‐5,5,7,9,13‐pentamethyl‐4,8‐bis(triethylsilyloxy)‐oxacyclohexadec‐13‐ene‐2,6‐dione. This intermediate was coupled to a stable isotope‐labeled thiazole using a Wittig reaction as the key step to provide ¹³C₅, ¹⁵N‐labeled epothilone D. In summary, the synthesis was completed in nine total steps, only six of which involved isotopically labeled reagents. A total of 168 mg of ¹³C₅, ¹⁵N‐labeled epothilone D was prepared in an 8% overall yield from ¹³C₂, ¹⁵N‐labeled thioacetamide and ¹³C₃‐labeled ethyl bromopyruvate.     

Untersuchungen an 1.4-Naphthochionen, 15. Mitt. Reaktion von 2- und 3-Chlor/Bromjuglonderivaten mit methanolischer Lauge (Teil 1: Monomere Produkte)

1.4-Naphthoquinones, XV: Reaction of 2- and 3-Chloro- or Bromojuglone Derivatives with OH? in Methanol (Part 1: Monomeric Compounds) The 2- and 3-chloro- or bromojuglone derivatives 1–4 do not react regiospecific ally with sodium hydroxide in methanol to yield the analogous hydroxyjuglone derivatives 5 or 6 . Rather, mixtures of 5 and 6 are obtained via the methoxy derivatives 7 and 8 . The corresponding reactions of the 2.3-dichloro- and dibromojuglone derivatives 14 and 15 always lead to the same mixtures of 16a/b and 17a/b . The structures of these products were established by halogen elimination with Bu₃SnH which leads to the known compounds 7 and 8 .     

Synthese und Eigenschaften fluoreszierender Estradiol-Derivate

Syntheses and Properties of Fluorescent Estradiol Derivatives 5-[4- (3β,17β-Dihydroxyestran-7α-yl) -1-oxobutylamino]-2- (6-hydroxy-3-oxo-3H-xanthen-9-yl) benzoic acid ( 3 ) is prepared by linking fluoresceinamine to 4-(3β,17β-dihydroxyestran-7α-yl)butanoic acid ( 1 ) with the aid of dicyclohexylcarbodiimide. 7α-(4-aminobutyl)-3β,17β-estradiol ( 2 ) reacts with fluorescamine to the pyrrolinone derivative 4 , and with fluorescein isothiocyanate to 5-[4-(3β,17β-dihydroxyestran-7α-yl)butylaminothioxomethylamino]-2-(6-hyddroxy-3-oxo-3H-xanthen-9-yl)benzoic acid ( 5 ). The conjugate compounds are determined by fluorometry in concentrations below 1 nmol/ml. The binding activity for the cytosol estrogen receptor is analysed by competition against [³H]-estradiol; 50% displacement of [³H]-estradiol is achieved by 3 at a concentration of 5 × 10^?7mol/l, by 4 at a concentration of 1 × 10^?6mol/l and by 5 at a concentration of 1,8 × 10^?7mol/l.     

青心酮防治ApoE(-/-)小鼠主动脉粥样硬化斑块形成与脂氧素的关系

目的观察青心酮防治ApoE(-/-)小鼠主动脉粥样硬化(AS)病变形成与脂氧素的关系。方法取8只8周龄C57BL/6小鼠作空白对照组;取24只8周龄的ApoE(-/-)小鼠,♂,随机分成3组(每组8只):动脉硬化组(乙醇20 mg kg 1 d 1);青心酮组(青心酮20 mg kg 1 d 1);辛伐他汀组(辛伐他汀20 mg kg 1 d 1)。所有小鼠均以"西方类型膳食"饲养至16周。取血检测脂氧素、血脂和15-脂氧合酶蛋白的含量等;取主动脉根部行HE染色观察ApoE(-/-)主动脉粥样硬化病变情况;电镜观察斑块内皮细胞变化。Western blotting法测定血清中15-LO水平。结果青心酮组脂氧素增加,血脂含量降低,AS病灶形成减少,斑块内皮细胞损伤减轻,15-脂氧合酶含量减少。结论青心酮防治ApoE(-/-)小鼠AS病变,可能与其增加15-脂氧合酶途径产物——脂氧素有关。     

Synthese von 2,2a,3,4-Tetrahydro[1,2-d]benz[b]-1,4-oxazin-2,4-dionen, 2. Mitt.

Synthesis of 2,2a,3,4,-Tetrahydro[1,2d]benz[b]-1,4-oxazine-2,4-diones, II The diasteromeric 3-amino-β-lactams 7 and 8 were obtained from the azides 5 and 6 and the phthalimido derivatives 9 and 12 . Compound 9 was synthesized directly from 2 by means of phthalimidoacetyl chloride/triethylamine, whereas 12 is accessible from 11 only by the Mitsunobu reaction. Acylation of 7 or 8 (to 13 or 14 ) is followed by hydrolysis of the ester function (to 15 or 16 ) and debenzylation to yield 17 or 18 which are lactonized to 19 or 20 by the action of DCC.     

Zur Tautomerie von O-Acyl- und O-Alkylidenpropandinitril-Gruppen in Trihalotropolonen und Dithiotropolonen

Tautomerism of O-Acyl and O-Alkylidenpropanedinitrile Groups in Trihalotropolones and Dithiotropolones The thallium(I)-trihalotropolonates 4 react with benzoyl chloride ( 5 ) or (1-chlorobenzylidene)propanedinitrile ( 7 ) to form the O-benzoyl-trihalotropolones 6 or the O-(benzylidenepropanedinitrile)trihalotropolones 8. Both of them show a rapid migration of the O-substituents between the oxygen atoms with very similar ΔG^# and k₂₅ values obtained from NMR spectra. Alkylation of sodium dithiotropolonate ( 10 ) gives rise to the thermolabile dithiotropolone ethers 12 , which decompose on heating before undergoing a thio-Claisen rearrangement. O-Thiobenzoyl-tropolone ( 18 ) has been prepared from tropolone ( 13 ) and thiobenzoyl chloride ( 15 ) or from sodium tropolonate ( 19 ) and dithiobenzoic acid anhydride ( 20 ). 18 too shows a rapid migration of the thiobenzoyl group.     

Conformational behaviour of a synthetic peptide of the C-terminus of villin that interacts with actin: an NMR,CD and simulated annealing study

The solution structure of a synthetic 22-amino acid peptide (P1) corresponding to the extreme C-terminal end and one of the F-actin binding sites of villin has been determined by ¹H NMR and CD spectroscopy. The structure of this peptide was compared to that of a peptide in which lysine to glutamic acid substitutions were introduced at positions 17 and 19 (P11), abolishing F-actin binding. Both peptides are largely unstructured in aqueous solution. Changes observed in the NMR and CD spectra of both peptides are consistent with α-helix formation in trifluoroethanol/water mixtures. A set of 189 interproton distances derived from nuclear Overhauser enhancement (NOE) measurements, 17 φ-angle constraints obtained from ³J_nhα coupling constants, as well as about 10 N···O distance restraints deduced from amide proton exchange kinetics with deuterium, were used for the structure determination. The three-dimensional structure of P1 and P11 is characterized by two helical regions, one extending from residues 2 to 5 and a second covering residues 7 to 17. The central fragment, ranging from Leu-7 to Leu-15, is more stable. The C-terminal residues are less structured, particularly within peptide P11. The significance of these structural results is discussed in relation to the biological activity of villin. © Munksgaard 1995.     

Structural comparison of alanine-substituted analogues of the calcitonin gene-related peptide 8-37 Importance of the C-terminal segment for antagonistic activity

Replacement of specific residues of the antagonistic fragment human calcitonin gene-related peptide 8–37 (hCGRP 8–37) by alanine residues produces good antagonists to CGRP1 receptors when the replacement is made at positions 17 and 20 but a poor antagonist when the replacement is made at position 21. The solution structures of hCGRP 8-37 and of the three alanine analogues have been determined by two-dimensional ¹H NMR spectroscopy and molecular modeling. Following the complete assignment of the NMR spectra, a comparison of the chemical shifts and of the temperature dependence of the amide chemical shifts showed that these parameters differed for [Ala¹⁷]-hCGRP 8–37 and [Ala²⁰]-hCGRP 8–37 relative to hCGRP 8–37 in the N-terminal and central segments but not in the C-terminal segment (residues 31–37). In the case of [Ala²¹]-hCGRP 8–37, differences were observed all along the chain. Molecular modeling calculations were performed by distance geometry, simulated annealing and energy minimization using NOE distance constraints. Molecular models showed a structural homology between [Ala¹⁷]-hCGRP 8–37, [Ala²⁰]-hCGRP 8–37 and hCGRP 8–37 in the C-terminal segment Asn³¹-Phe³⁷ as well as hydrogen bonding between Val²⁸ and Asn³¹. These structural similarities are not observed with [Ala²¹]-hCGRP 8–37. Therefore, the structure of the C-terminal segment of hCGRP 8–37 appears to be critical for antagonistic activity at CGRP1 receptors.     

Potential anti-inflammatory activity and ulcerogenicity study of some novel pyrimido[4′,5′:4,5]pyrimido[1,6-<Emphasis Type="Italic">a</Emphasis>]azepine derivatives

A series of novel tricyclic pyrimido[4′,5′:4,5]pyrimido[1,6-a]azepine derivatives were synthesized using the starting compound 3-amino-1-oxo-2-phenyl-5-(pyrrolidin-1-yl)-1,2,4a,5,6,7,8,9-octahydropyrimido[1,6-a]azepine-4-carbonitrile 4. This series includes the 3-aryl derivatives 6a, b, the 3-cycloaminoalkyl derivatives 8a–f, the 3-mercaptomethyl derivatives 10 and 11a, b, the 2-cycloaminomethyl derivatives 13a–c, the 1-cycloamino derivatives 15a–c and the 1-amino derivative 16. The structures of the newly synthesized compounds were elucidated by IR, ¹H NMR, ¹³C NMR, mass spectroscopy and elemental analyses. The anti-inflammatory activity of all newly synthesized compounds was evaluated using the carrageenan-induced paw oedema test in rats using diclofenac sodium as the reference drug. Ulcer indices for the most active compounds were calculated. The 3-mercaptomethylacetic acid derivative 10 was the most active compound, showing activity comparable to diclofenac sodium with minimal ulcerogenic effect while the rest of the tested compound exhibited moderate anti-inflammatory activity.     

Synthese und Alkylierung von 10H-Pyrimido[5,4-b][1,4]benzothiazinen

Synthesis and Alkylation of 10H-Pyrimido[5,4-b][1,4]benzothiazines 10H-Pyrimido[5,4-b][1,4]benzothiazines 8 were prepared by condensation of barbituric acids 5 with 2-aminothiophenol (7) in DMSO via the ylide 6 . Compound 8 was characterized as a 1,5-dihydro system similar to the thia-isoalloxazines 1b . The structures of the alkyl derivatives isolated from a complex mixture were established by UV/VIS, ¹H-NMR, IR and ESR spectroscopy. They are discussed with regard to the alkylation of pyrimidobenzothiazines which carry substituents at N-10.     

Heterosubstituierte Fulvene, 11. Mitt. Cyanvinyl-fulvene und Cyan-azavinyl-fulvene

Heterosubstituted Fulvenes, XI: (Cyanovinyl)fulvenes and (Cyanoazavinyl)fulvenes The (cyanovinyl)cyclopentadienes 1 condense with amide acetales to form the (cyanovinyl)-fulvenes 5a - e , the (cyanoazavinyl)cyclopentadienes 7 give the (cyanoazavinyl)fulvenes 8a - b . The sodium or thallium salts of 1 react with sulfur containing derivatives of carbonic acid to yield the (cyanovinyl)fulvenes 10a - d and 11a - b . According to ¹H-NMR spectra the cyanovinyl or cyanoazavinyl groups occupy position 2 of the fulvene ring with the exception of 11a/1 . The δG value for rotation around the C(6)-N bond has been determined for some fulvenes on the basis of the coalescence temperature. Compound 8a reacts with thallium acetate to form 15 , which is converted to the 3-iodofulvene 16 by potassium iodide.