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The crystal structures of (5R)-(10-methyl-1-oxa-4-thiaspiro[4.5]dec-9-en-9-yl)phenyl(S)-methanol, C 16 H 20 O 2 S, (1), and 1(S)-[(5R)-10-methyl-1-oxa-4-thiaspiro[4.5]dec-9-en-9-yl)ethyl 4-methoxybenzoate, C 19 H 24 O 4 S, (2), are composed of independent molecules separated by normal van der Waals distances. The molecular dimensions in both structures are normal. The hydroxyl and heterocyclic ring O atoms exhibit a short intermolecular hydrogen bond of the order of 2.814 (4) A in (1) forming a chain of molecules along the c axis.

Copolymerizations of ethylene with 1-decene were carried out with a series of stereospecific metallocene compounds, C/sub 2/H/sub 4/[Ind]/sub 2/Zr(NMe/sub 2/)/sub 2/ (1), C/sub 2/H/sub 4/[Ind]/sub 2/Hf(NMe/sub 2/)/sub 2/ (2), (CH/sub 3/)/sub 2/Si(1-C/sub 5/H/sub 2/-2-CH/sub 3/-4-/sup t/C/sub 4/H/sub 9/)/sub 2/Zr(NMe/sub 2/)/sub 2/ (3), C/sub 2/H/sub 4/(Fluo)(Cp)Zr(NMe/sub 2/)/sub 2/ (4), (CH/sub 3/)/sub 2/C(Fluo)(Cp)Zr(NMe/sub 2/)/sub 2/ (5) (Cp = /spl eta//sup 5/-cyclopen-tadienyl, Ind = /spl eta//sup 5/-indenyl Fluo = /spl eta//sup 5/-fluorenyl), combined with Al(i-Bu)/sub 3//[CPh/sub 3/][B(C/sub 6/F/sub 5/)/sub 4/] cocatalyst. The copolymerization rate decreased in the order of 3 > 1 > 2 /spl sim/ 4 > 5 and the 1-decene reactivity decreased in the order of 2 > 5 > 1 /spl sim/ 4 > 3. The reactivity product of ethylene and 1-decene (r/sub E/ /spl times/ r/sub D/) was below 1 except 3 catalyst, corresponding to random copolymer structures with an alternating character. The melting point, crystallinity, intrinsic viscosity and density of the 1-decene/ethylene copolymers decreased markedly with an increase in the 1-decene content, regardless of the type of catalytic system.

We have described an efficient gold-catalyzed double cyclization of 1,5-enynes to afford a range of heterobicyclic compounds, including oxabicylclo[3.2.1]octenes, azabicyclo[3.2.1]octenes, oxaspiro[5.4]decene, azaspiro[5.4]decene, oxaspiro[5.5]undecene, oxabicyclo[4.3.0]nonene, azabicyclo[4.3.0]nonene, and oxabicyclo[4.4.0]decene. The mechanism of this reaction is proposed to involve a chemoselective gold-based alkyne activation, carbocyclization, intramolecular nucleophilic addition, followed by protodemetalation. The most notable aspect of this process is the efficient and diastereospecific interception of the reactive intermediate of the initial 6-endo-dig (or 5-endo-dig) cyclization with either oxygen- or nitrogen-based nucleophiles.

Copolymerizations of ethylene with 1-decene were carried out with a series of stereospecific metallocene compounds, rac–(EBI)Zr(NMe2)2 [ 1, EBI = ethylene–1,2–bis( 1–indenyl)], rac–(EBI)Hf(NMe2 (2), rac–Me2Si( 1–C5H2–2–Me–4– t Bu)2Zr(NMe2)2 (3), ethylidene(cyclopentadienyl)(9-fluorenyl)ZrMe2 [4, Et(Flu)(Cp)ZrMe2] and isopropylidene(cyclopentadienyl)(9–fluorenyl)ZrMe2 [5, iPr(Flu)(Cp)ZrMe2], combined with Al(i–Bu)3/[CPh3] [B(C6F5)4] cocatalyst. All catalyst systems showed very high copolymerization rates and the 1–decene reactivity decreased in the order of 2 > 5 > 1∼ 4 > 3. The reactivity product of ethylene and 1–decene (r E x r D) was below 1 except 3 catalyst, corresponding to random copolymer structures with an alternating character. The melting point (Tm), crystallinity (XC), intrinsic viscosity ([η] and density of the 1–decene/ethylene copolymers decreased markedly with an increase in the 1–decene content, regardless of the type of catalytic system.

The title compound, 2,4-dimethyl-9-oxabicyclo[5.3.0]-dec-5-ene-1,3-diol deuterochloroform solvate, C 11 H 18 O 3 .CDCl 3 , has a seven-membered and a five-membered ring which are trans-fused and are affected by angle strain. There are three types of intermolecular hydrogen bonding present in the structure, namely, O-H...OH [O...O 2.774 (2) A], O-H...O [O...O 2.837 (2) A] and C-D...OH [C...O 3.043 (2) A].

Oligomers of higher olefins like 1-decene, known as polyalphaolefins (PAO), are used as base oils for lubricants and stand out due to a high stability combined with extraordinary greasing properties. Ionic liquids have properties that are variable in a wide range (polarity, acidity) and are employed both as solvents and catalysts. They are very well suited for biphasic catalysis and are preferentially used to recycle a catalyst. In this thesis there are various possibilities shown to oligomerise 1-decene with ionic liquids. In order to use the polyalphaolefins as base oils for engine oils, a product distribution comprised of trimers as the principal component was desired. This distribution was reached using systems consisting of boron trifluoride and tetrafluoroborates. In this work there is shown that boron trifluoride can be immobilised and recycled in ionic liquids. Further on there is explained how to control the product distribution from geometric to Poisson-like by solubility properties of the ionic liquid. The use of tensid-like tetrafluoroborates here very likely results in polyalphaolefins of higher quality.

A water-soluble phosphonate-functionalized phosphine ligand Na 2 [Ph 2 P(CH 2 ) 12 PO 3 ] ( 8 ), was prepared in eight steps from cyclododecanone. Phosphine 8 reacts with [Rh(COD)Cl] 2 in methanol to give the new complex Na 2 [Rh(COD)(Ph 2 P(CH 2 ) 12 PO 3 )Cl] ( 9 ). Complex 9 is inactive in the catalytic hydrogenation of 1-hexene and cyclohexene due to the decomposition of 9 to rhodium metal in the presence of hydrogen gas. Hydrogenation of decene using [Rh(COD) 2 ]BF 4 and 3 equiv. of 8 in an aqueous emulsion was achieved using 1 atm H 2 . 31 P NMR studies on 8 suggest a lack of well-defined aggregation in water, which has been ascribed to the steric bulk of the diphenylphosphino group.

[CuI(C 14 H 24 N 4 ]I cristallise dans P2 1 /c avec a=9,277, b=18,200, c=11,749 A, β=92,925 o , Z=4; affinement jusqu'a R=0,0349. La sphere de coordination du Cu 2+ a une geometrie pyramidale carree deformee avec quatre liaisons equatoriales Cu−N, dont les longueurs sont comprises entre 2,016 et 2,064' A, et une liaison axiale Cu−I de 2,788 A. Les confirmations des trois cycles chelate peuvent etre decrites en tant que demi-chaise, chaise tordue. Les deux groupes amino forment des liaisons hydrogene avec les ions iodure

Recent advances in the total synthesis of xanthanolide/dinorxanthanolide sesquiterpenoids are described. This family of natural products can be divided into two structural classes according to the stereochemistry at C8 of the basic carbon framework, the oxabicyclo[5.3.0]decene core, i.e., the cis- and trans-fused γ-butyrolactone series. This article reviews the successful total syntheses of the five natural products, 8-epi-xanthatin (1) and sundiversifolide (2) (the cis-series), and 11α,13-dihydroxanthatin (3), xanthatin (4) and diversifolide (5) (the trans-series).

Publisher Summary The chapter discusses the general physical and spectroscopic properties of polycyclic compounds including their molecular structure, reactions, synthesis, and spectroscopy and spectrometry. General chemical reactions of these compounds provide information on several processes like hydrogenolysis, the metal–halogen treatment process, reaction with helium tritide ions, and acetolysis. The bicyclo butane group is discussed, explaining the synthesis and reactions of butanes. The general properties and reactions of bicyclo pentanes are also outlined. Details on the synthesis, structure and spectra, and chemical reactions of bicyclo hexanes are presented and the synthesis, structure, and reactions of bicyclo heptanes are summarized. The chapter also discusses bicyclo octanes, bicyclo nonanes, bicyclo decene, bicyclo tridecane, bicyclo alkanes, bicyclo hexanes and heptanes, bicyclo hexenes and heptanes, bicyclo octanes and nonanes, bicyclo octane, bicyclo nonane, decane, and undecane, and bicyclo decanes.

Bis [bis(trimethylsilyl) methyl]tin (1a) reacts with cyclooctyne (5) to provide Δ 1,8 -9,10-distanna-9,9,10,10-tetrakis [bis(trimethylsilyl) methyl] bicyclo [6.2.0] decene (6). Compound 6 reacts with m-chloroperbenzoic acid (MCPBA) in toluene to provide [Sn 2 (CH(Si(CH 3 ) 3 ) 2 ) 4 (C 8 H 12 )(O)] (7) in 79% yield and with iodine (1 equiv) to cleave the tin-tin bond and provide the air-sensitive adduct [Sn 2 (CH(Si(CH 3 ) 3 ) 2 ) 4 (C 8 H 12 )(I) 2 ] (8) in 79% yield. Treatment of 6 with 2 equiv of iodine in the presence of moisture produces the hydroxy-bridged ditin cation [Sn 2 (CH(Si(CH 3 ) 3 ) 2 ) 4 (C 8 H 12 )(OH)] [I 3 ]

A divergent synthetic approach to the construction of dimethylsilyl linked dihydroxybenzyl alcohol based dendrimers via acid–base hydrolytic chemistry of bis(dimethylamino)dimethylsilane with 3,5-dihydroxybenzyl alcohol, is reported. The peripheral OH groups lead to significant aggregation that was studied using FT-IR and UV-Vis spectroscopies, light scattering and transmission electron microscopy. Different generations of dendrimers could be easily functionalized at the periphery with phosphorus donor groups that were subsequently bound to RhCl(1,5-C8H12). Such organometallic dendrimers were found to be active and recoverable catalysts for hydrogenation of decene. The catalytic efficiency was found to be dependent on the number of generations and reaction time. An uncontrolled reaction of Me2Si(NMe2)2 with 3,5-dihydroxybenzyl alcohol in a multi-step addition process or one-pot reaction, led to the formation of hyperbranched polymers in which the build-up of the polymeric backbone was found to be dependent on the preferential reactivity and sterics at the benzylic center, as observed during dendrimer construction.

The crystal structure of the title molecule has been determined by single crystal X-ray diffraction method. The molecule crystallizes in the orthorhombic space group Pbca with unit-cell dimensions a = 21.872(8), b = 11.815(6), c = 10.785(6) A, and Z = 8. The structure has been solved by MULTAN and refined by least-squares calculations to R = 7.62% for 2088 reflections measured by a diffractometer. The molecule has the exo configuration. The central cyclobutane ring is nearly planar. The two five-membered rings are of the envelope conformation. The dihedral angle between the cyclobutane ring and the terminal five-membered ring is 75.5° and that between the cyclobutane ring and the other five-membered ring is 62.2°.

The reaction of bromine trifluoride with octafluoronaphthalene has been investigated, from which was obtained decafluoro-1,2-benzocyclohexa-1,4-diene, 2-bromo-undecafluorotetralin and a mixture of dibromotetradecafluorobicylo [4,4,0] decene isomers. Dehalogenation and reduction gave decafluoro-1,2-benzocyclohexa-1,3-diene in addition to the 1,4-diene and 2 H -undecafluorotetralin, a similar mixture being obtained from the dibromo decene. The reactions of the dienes and bromofluorotetralin with methoxide ion have also been studied.

A four-step synthesis of 1-decene-2-13C starting with 1-bronooctane (57% overall yield) is described.

Compounds with a conjugated oxo-ene-oxo system were tested for inhibition of blood platelet aggregation. All compounds with this structure in trans configuration were effective inhibitors of aggregation induced by thrombin and by arachidonic acid. While the oxo-trans-ene-oxo system is prerequisite for such activity, other structural features of the compounds may be varied without loss of activity. Inhibition is exemplified by 9,12-dioxo-trans-10- and 10,13-dioxo-trans-11-octadecenoic acids and their methyl esters, by 11,14-dioxo-trans-12- eicosenoic acid, by 4,7-dioxo-trans-5- decene and by trans- dibenzoylethylene . The half-inhibition concentrations are in the order of 2-6 microM, with complete inhibition at 8-20 microM. According to experiments with the inhibiting 9,12-dioxo-trans-10-octadecenoic acid, the normal oxygenation of exogenous arachidonic acid by platelets is not affected but the thrombin-induced internal release of this acid seems to be abolished by the inhibitor. The inhibition of aggregation in the presence of exogenous arachidonic acid and its products suggests that the inhibitor also interferes with other events leading to aggregation. By implication from other properties of the oxo-trans-ene-oxo system, reaction with SH groups may be a mechanism for inhibition.

Exchange of Carbonyl Group Sites in Tetracarbonyl(η-(Z)-cycloalkene)iron Complexes via Non-Berry Pseudorotation The tetracarbonyliron complexes of cyclobutene, cyclopentene, 4,4-dimethyl-cyclopentene, 2,5-dihydrofurane, cyclohexen, (Z)-cyclohepten, -octene, -nonene, and -decene were prepared by thermal or photochemical reaction of the corresponding olefins with nonacarbonyldiiron and pentacarbonyliron, respectively. The low-temperature behaviour of the mostly new complexes which can be stored over a longer period only below 250 K and which exhibit four C,O-stretching frequencies in the IR. spectra (cf. Table 2), indicative for a trigonal bipyramidal structure with the olefin ligand in an equatorial position, was studied in CCl2F2 by 13C-NMR. spectroscopy between 200 and 115 K. In this temperature range all complexed olefin ligands with the exception of (Z)-cyclooctene (cf. [11]) show an averaged Cs-symmetry on the NMR. time scale. About 115 K the tetracarbonyliron group gives rise to three 13C-signals in a ratio of 1:1:2 for the complexes of (Z)-cycloheptene, (Z)-cyclodecene and 2,5-dihydrofurane (Cf. Table 3). This is an agreement with the fixed equatorial position of the non-rotating olefin ligands. The complexes of cyclooctene and cyclononene give only two 13C-signals in a ratio of 1:1 for the carbonyl groups. The temperature dependence of the signals indicates that in these cases the two axial carbonyl groups exhibit accidentally the same chemical shift. In all cases a complete line shape analysis of the 13C-signals of the carbonyl groups could only be accomplished by using two exchange constants (cf. Tables 4 and 5 as well as Fig. 2–5 and Fig. 8). The same is true for the cyclobutene complex, but only one exchange constant could be determined (at 120 K: two 13C-signals in a ratio of 1:3 with the beginning of a further coalescence). The cyclopentene and cyclohexene complexes showed only one 13C-signal even at 115 K. The observed temperature-dependent line shapes of the 13C-signals can be interpreted in terms of a Non-Berry pseudorotation mechanism involving a three site exchange with each of the two diastereotopic axial carbonyl groups and the two equatorial carbonyl groups (for activation parameters see Table 4). The differences in the activation parameters can be explained on steric grounds by assuming a transition state (cf. Fig. 8) similar to the C3b-structure of tetracarbonyliron which lies about 27 kJmol−1 above its C2v-structure (cf. [30]) comparable with the ground state of our complexes with weak dπ(Fe),pπ(Olefin) back bonding. The transition state model implies that the reorganization process involving the axial carbonyl group in exo-position possesses the higher exchange barrier (cf. Fig. 8).

1. The reaction of dichloro- and diiodogermulenes with 2,2,6,6-tetramethyl-4-thiacyclo-heptyne gave 80–85% yields of the Δ−1.7-2,2,6,6-tetramethyl-8,8,9,9-tetrachloro- and Δ−1.7-2,2, 6,6-tetramethyl-8,8,9,9-tetraiodo-4-thia-8,9-digermabicyclo[5.2.0]nonenes, which are the first examples of a new class of heterocyclic compounds- the 1,2-digermacyclobut-3-enes. 2. The 1,1,2,2-tetrachloro(iodo)-1,2-digermacyclobut-3-enes obtained are thermally stable to 200–230°C they do not react with O2 MeOH, or HClAgF. They react comparatively readily with sulfur (with the formation of the corresponding 1-thia-2,5-digermacyclopent-3-enes) and SbCl5 (giving Δ−1.7-2,2,6,6-tetramethyl-9-oxa-4-thia-8,8,10,10-tetrachloro-8,10-digermabicyclo[5.3.0]decene after partial hydrolysis).

The strain energy of cycloalkatrienes with seven to ten carbon atoms in the ring is calculated as a function of various geometrical parameters. The most stable conformations are the boat for 1,3,5,cycloheptatriene and 1,3,5,cyclooctatriene, the all- cis C 2 for 1,3,6,cyclooctatriene, the boat-chair for 1,3,5, cyclononatriene, the all- cis crown for 1,4,7,cyclononatriene, a cis-trans-cis form for 1,3,5,cyclodecatriene, a cis-cis-trans and a trans-cis-cis conformer for 1,3,7, and 1,4,8,cyclodecatriene respectively. Some interconversion barriers are also discussed and compared with available experimental data. Fair agreement is generally found.

This article demonstrates how gas-liquid chromatography can be used for a quantitative analysis of the alkylate without removal of the unreacted starting materials (phenol and olefins). The cation exchange resin KU-2 was used as a catalyst to obtain an alkylate. The reaction was carried out in a single-pass flow unit at 130/sup 0/C with a 1:1 mole ratio of phenol to 1-decene and a space velocity of 0.5h/sup -1/. The alkylate obtained was distilled in a column with an efficiency of 25 theoretical plates, obtaining mono- and diisodecylphenol fractions. The compounds obtained were used in making artificial mixtures, in selecting the conditions for optimal separation of these mixtures, and in determining the detector sensitivity coefficients for these compounds. The analyses were performed in a Khrom-4 chromatograph. Relative correction factors are determined for the components of different chemical types (decenes, phenol, numberisodecyl phenyl ethers, monoisodecylphenols, diisodecylphenols). It is found that the relative error at a confidence level of 0.95 is no greater than 5%. Includes a table.

Polymerizations of decene-1 were carried out from 0° to 70° at A/T = 167 and [M] = 0.75 M initiated by 0.17, 0.34, and 0.69 mM of Ti contained in the MgCl2/ethylbenzoate/p-cresol/AlEt3/TiCl4-AlEt3/methyl-p-toluate catalyst. The rate of polymerization is directly proportional to the catalyst concentration. About 12% of the Ti in the catalyst is initially active at 50°; they are 1.4%, 8.8%, and 9.4% at 0°, 25°, and 70°, respectively. The changes of Rp with temperature parallels the variations in the active site concentration. The decline of Rp with time has second-order plots with slopes which are inversely proportional to the catalyst concentration, but the rate constants for these deactivations are nearly the same for decene and propylene polymerizations. These results strongly support a mechanism of deactivation involving two adjacent sites in the catalyst particle surfaces. The rate constants of propagation and of chain transfer to AlEt3, the energetics for these processes, and MW and MW distribution data have been obtained.

Epoxydation selective de cyclopentene, cyclohexene, methylcyclohexene, styrene, methylstyrene, octene et decene

Oligomerisation des decenes de Fischer-Tropsch et des decenes Synthol amorcee par BF 3 : etude de la distribution en oligomeres, de leur degre de ramification et de leur viscosite en fonction de la temperature et du degre d'avancement de la reaction. Comparaison avec des produits obtenus avec le decene-1 comme compose modele

The synthesis and base-induced cage opening of 5-fucctionalized homocubyl alcohols 22 (R is some protective group) is described. In a first approach, the synthesis of 22 has been attempted starting from tricyclic enol 14 and involving the Favorskii cage contraction of l,3-bishomocubanones 24 . Unexpectedly, 4-methoxypentacyclo [5.3.0.0 2,5 .0 3,9 .0 4,8 ]decan-6-ones 24b and 29 undergo a facile add-catalyzed cage fragmentation to give tricyclo[5.3.0.0 2,5 ]decene diones 28a and b , respectively. The Favorskii cage contraction of 24 to homocubane carboxylic add 25c has been accomplished for the MEM-protected 24c , albeit in low yield. With silver cations under basic conditions, 24b and c undergo an unusual oxidative cage fission reaction leading to tetracyclo[4.3.0.0 2,4 .0 3,8 ]nonan-5-one 7-carboxylic acids 40 and 41 . An efficient route to 4-bromohomocubyl acetate 48 has finally been accomplished starting from 4,5-dibromo-l,3-bishomocubanone 43 . Base-induced homoketonization of 48 is essentially directed by the 5-bromine atom and a regioapedfic cleavage of the central C 4 –C 5 bond is observed, producing, in a stereospecific manner, 10-oxapeatacyclo [5.3.0.0 2,6 .0 3,9 .0 4,8 ]decane 51 .

A crystal structure determination of the title complex has been carried out. Cell dimensions are a= 19.523(11), b= 8.491 (7). c= 18.792(11)A, α= 79.6(1), β= 115.6(1), and γ= 96.4(1)°. The crystals are triclinic, space group P, wiith Z= 4. The two molecules in the asymmetric unit have similar geometries. The zinc atoms have five-co-ordinate square-pyramidal environments, being bonded to an axial [2.628(4), 2.620(3)A] and an equatorial [2.540(4),2.558(4)A] iodine atom and to three equatorial nitrogen atoms [Zn-N(pyridine) 2.103(17),2.101 (19)A;Zn-N 2.235(15)—2.280(15)A]. The sulphur atoms of the macrocycle are not bonded to the metal primarily because the four carbon atoms between them cannot an pproximately planar girdle.

The rearrangement and elimination reaction observed in the mass spectra of stereoisomeric hydroxy, acetoxy and oxo derivatives of tricyclo [5.2.1.02,6] decanes and -decenes strongly depends on the orientation of the substituents. In contrast to that the fragmentation of stereoisomeric hydrocarbons is mainly influenced by the strain energy of the compounds. A new type of a dyotropic rearrangement leads to drastic differences in the mass spectra of the stereoisomers.

Etude experimentale de la reaction d'oligomerisation du decene-1 en presence du systeme catalytique BF 3 -silice-eau, avec possibilite de recuperation et de recyclage de BF 3

The reaction of N-acetyl derivatives of N,N′-trimethylene- and N,N′-tetramethylene-o-phenylenediamines with ethylene oxide gave the corresponding N-(β-hydroxyethyl)-N′-acetyl derivatives, the cyclization of which in refluxing hydrobromic acid leads to benzo[f]-1,5-diazabicyclo[3.2.2]nonene and benzo[g]-1,6-diazabicyclo[4.2.2.]decene.

Decene-1 was polymerized with the CW catalyst and fractionated by precipitation technique. Light-scattering and viscometric measurements on these fractions established the relationship [η] = 5.19 × 10−3M. The unperturbed mean square end-to-end distance is (〈R〉/M)1/2 = (6.17 ± 0.34) × 10−9. Light-scattering data is consistent with a relatively stiff molecule with length of L = 1.75 × 10−5 cm for poly(decene-1) with MW = 397,000. Its mean square radius of gyration 〈R〉 is 2.79 × 10−11 cm.2 The ratio of L2/〈R〉 = 11 is close to the theoretical ratio of 12 for this kind of macromolecule.

Preparation de copolymeres avec des α-olefines C 10 , C 12 et C 16 par copolymerisation Ziegler-Natta. Composition analysee par spectroscopie RMN du carbone 13

Decene-l was polymerized with the MgCl2/ethylebenzoate/p-cresol/AIEt3/TiCl4-AlEt3/methyl-p-toluate catalyst at 50° using an A/T ratio of 167 and a range of monomer concentration. The concentration of the two kinds of active sites are [Ti] = 12% and [Ti] = 4% of the total titanium. The rate constants of propagation are 24 M−1 s−1. Chain transfers to AIEt3, monomer, and by β-hydride elimination have rate constant values of 1.7 × 10−3 M−1 s−1, 1.34 × 10−2 M−1 s−1, and 1.7 × 10−2 s−1, respectively. Poly(decene-l) have relatively narrow MW which are unchanged during the course of a polymerization. Therefore, the active site concentrations in the CW catalyst for propylene and decene polymerization are identical and their rate constant values agree within a factor of 2. However, the rate of decene polymerization depends on fractional order of monomer concentration and decreases with the increase of activator concentration. Furthermore, the formation of metal polymer bonds has a rate independent of these concentrations. These kinetic behaviors are a manifestation of absorption processes of these species which are not seen in propylene polymerizations.

Determination d'une methode de localisation des doubles et triples liaisons dans les alcenes, alcynes, dienes, acides gras, esters gras et acetates d'alcenyles

A precise method for the determinations of Ti+2, Ti+3 and Ti+4 was developed. The CW-procatalyst before activation contains mostly Ti+4 ions with 6% Ti+3 and 4% Ti+2 ions. Activation with AlEt3 alone at room temperature reduced all the titaniums to lower valence states consisting of 71% Ti+3 and 29% Ti+2. Reduction is incomplete when methyl-p-toluate was present as external Lewis base during activation: at 25°C the distribution of Ti+4 : Ti+3 : Ti+2 is 36% : 25% : 38%; the distribution at 50°C is 37% : 22% : 40%. Aging of the activated catalyst caused little or no changes in the distribution of [Ti+n]; whereas the catalytic activity decays rapidly with aging. The aged catalysts have polymerization activity comparable to the decreased activity of the catalyst during a polymerization. The [Ti+n] was determined for the CW-catalyst during the course of a decene polymerization; they were found to be Ti+4 : Ti+3 : Ti+2 = 30% : 27% : 43%, which did not change with polymerization time. These results suggest that the reducibility of Ti+4 species by AlEt3 or 3AlEt3/MPT to different valence states is predicated by their structures. These species do not undergo further changes in their oxidation states during either aging or polymerization. Their decays probably involve nonreductive metathesis reactions like those known for zirconium alkyls. Possible structures for the stereospecific and nonspecific sites are proposed.

The decomposition of 1-decanol and decanal in the presence of hydrogen by using Ni- and H-ZSM-5 embedded within a silica binder was investigated. Temperatures and pressures for the decanol decomposition ranged from 572 to 666 K and 0.57 to 1.45 MPa, whereas for decanal the ranges were 622 to 722 K and 0.58 to 1.22 MPa. Decanol was converted to decene through the intermediate didecyl ether. Decanal was convered to nonane by the elimination of carbon monoxide; to a β-hydroxy carbonyl compound, an aldo, which subsequently dehydrated to yield C20 aldehyde. The aldehyde, subsequently, was converted to hydrocarbons. All of the above are acid-catalyzed reactions. A side reaction catalyzed by the reactor walls which occurred with both compounds was the hydrogenation of decanal or dehydrogenation of decanol.

1-Decene ozonide (1) was isolated by column chromatography of the mixed products of ozonation of 1-decene (2) in several nonpolar solvents. 1-Methoxy- (3) and 1-tertiary butoxynonane-1-hydroperoxide (4) were similarly obtained. The thin-layer chromatographic separation of these products from each other and from other ozonation products was examined. Compounds 3 and 4 were smoothly oxidized to di-(1-alkoxyalkyl)peroxides by Ce(IV). The stoichiometry of this reaction, examined by isothermal calorimetry, was 1:1. Compounds 1,3, and 4 were oxidized by CF3CO3H and by other oxidizing agents to nonanoic acid with chain degradation loss of 2–30%.

The preparations of Δ8-hexahydro-1,4,8-pyrimidazole, Δ9-1,5,9-triazabicyclo(4.4.0)decene, and Δ9-1,4,9-triazabicyclo(5.3.0)decene from the corresponding 2-(ω-hydroxyalkylamino)-Δ2-1,3-diazacycloalkenes by chlorination and dehydrohalogenation are described. The nitro derivatives of these bicyclic compounds are more stable towards refluxing ethanol than 1-nitro-2,3,5,6-tetrahydro-1-imidaz(1,2-a)imidazole.

Thermal and photochemical syntheses of aryl derivatives with highly aliphatic chains were examined and the following results were obtained.1) The thermal reaction of decene-mercuric acetate adduct with benzene affords 1-phenyl-2-decene (yield 18.7%) as the main product, while the photochemical reaction affords 1-phenyl-1-decene (3.6%), 1-phenyl-2-decene (11.3%), 1-phenyl-3-decene (2.6%) and 1-phenyl-4-decene (1.6%).2) The thermal reaction of decene-mercuric acetate adduct with toluene affords 1- (2-methylphenyl) -2-decene (18.0%) and 1- (4-methyl-phenyl) -2-decene (23.5%) as main products, while the photochemical reaction gives 1- (3-methylphenyl) -decane (22.8%) and 1- (4-methylphenyl) -decane (31.3%).3) These products would be formed through heterolytic cleavage of aryl- (acetoxymercury) -decane with demercuration in the thermal process, while through homolytic cleavage in the photochemical process.

When straight-chain mono-olefins, from pentene to decene, are subjected to the Koch carboxylic acid synthesis by the addition of CO and H2O or CH3OH in the presence of strongly acidic catalysts, not only the expected secondary acids, but also mixtures of a specific type of tertiary acids or their methyl esters are formed. When the catalysts contain boron trifluoride, the secondary acids are formed in ratios of isomers which are, within the scope of this investigation, independent of the experimental conditions and which agree well with the values calculated from the isomer equilibria of the corresponding n-olefins. Using concentrated sulfuric acid as catalyst, a larger proportion of tertiary acids is obtained than with BF3-catalysis, and amongst the secondary acids, those isomers predominate in which the COOH group is situated near the centre of the molecule.

Mass spectra of cis - and trans -2-decene were obtained at 15, 20, 23 and 26 eV by electron impact and 950 A (13.0 eV), 826 A (15.0 eV) and 584 A (21.2 eV) by photoionization using synchrotron radiation. The spectral differences are discussed primarily in terms of energy transfer function differences.