2,3-Decadien

Decadien 4-Aminomethyl- -Dihydrooxalat E16d, 1197 (lmin-Spaltung)... 

Decadien 4-(Methylamino-methyl)- E16d, 1197 (Imin-Spaltung/N-Methylierung)... 

One of the butadiene dimeri2ation products, COD, is commercially manufactured and used as an intermediate in a process called FEAST to produce linear a,C0-dienes (153). COD or cyclooctene [931-87-3], obtained from partial hydrogenation, is metathesi2ed with ethylene to produce 1,5-hexadiene [592-42-7] or 1,9-decadiene [1647-16-1], respectively. Many variations to make other diolefins have been demonstrated. Huls AG also metathesi2ed cyclooctene with itself to produce an elastomer useful in mbber blending (154). The cycHc cis,trans,trans-tn.en.e described above can be hydrogenated and oxidi2ed to manufacture dodecanedioic acid [693-23-2]. The product was used in the past for the production of the specialty nylon-6,12, Qiana (155,156). 

The electrochemical conversions of conjugated dienes iato alkadienedioic acid have been known for some time. Butadiene has been converted iato diethyl-3,7-decadiene-l,10,dioate by electrolysis ia a methanol—water solvent (67). An improvement described ia the patent Hterature (68) uses an anhydrous aprotic solvent and an electrolyte along with essentially equimolar amounts of carbon dioxide and butadiene a mixture of decadienedioic acids is formed. This material can be hydrogenated to give sebacic acid. 

Named bombykol, the sex pheromone secreted by the female silkworm moth has the formula C16H280 and the systematic name (10 ,12Z)-10,12-hexa-decadien-l-oJ. Draw bombykol showing correct geometry for the two double bonds. 

Figure 8.3 Wagener s ADMET of 1,9-decadiene using Schrock s [W] catalyst.

Kinetic studies using 1,9-decadiene and 1,5-hexadiene in comparison widi catalyst 14 and catalyst 12 demonstrate an order-of-magnitude difference in their rates of polymerization, widi 14 being the faster of the two.12 Furdier, this study shows diat different products are produced when die two catalysts are reacted widi 1,5-hexadiene. Catalyst 14 generates principally lineal" polymer with the small amount of cyclics normally observed in step condensation chemistry, while 12 produces only small amounts of linear oligomers widi die major product being cyclics such as 1,5-cyclooctadiene.12 Catalyst 12, a late transition metal benzylidene (carbene), has vastly different steric and electronic factors compared to catalyst 14, an early transition metal alkylidene. Since die results were observed after extended reaction time periods and no catalyst quenching or kinetic product isolation was performed, this anomaly is attributed to mechanistic differences between diese two catalysts under identical reaction conditions. 

The following steps are performed in an argon atmosphere glovebox. In a 50-mL round-bottom flask equipped with a Teflon magnetic stirbar, 2.03 g (14.7 mmol) of previously distilled and degassed 1,9-decadiene (9) (Aldrich) and 27.6 mg (3.61 x 10 2 mmol) of Schrock s catalyst (14) (400 1) are combined. In a matter of seconds, the catalyst is dissolved into the monomer and a vigorous evolution of ethylene is observed. The flask is sealed with a Teflon vacuum adapter and removed from the box. The polymerization vessel is immediately connected to the vacuum line, placed into an oil bath, and stirred at 30°C. Intermittent vacuum... 

Figure 8.8 ADMET polymerization of (a) 1,9-decadiene and (b) 6-methyl-1,10-undecadiene.

ADMET polymers are easily characterized using common analysis techniques, including nuclear magnetic resonance ( H and 13C NMR), infrared (IR) spectra, elemental analysis, gel permeation chromatography (GPC), vapor pressure osmometry (VPO), membrane osmometry (MO), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The preparation of poly(l-octenylene) (10) via the metathesis of 1,9-decadiene (9) is an excellent model polymerization to study ADMET, since the monomer is readily available and the polymer is well known.21 The NMR characterization data (Fig. 8.9) for the hydrogenated versions of poly(l-octenylene) illustrate the clean and selective nature of ADMET. 

Model systems indicate that aldehydes may also be produced by the action of polyphenoloxidases on amino acids in the presence of catechin, all of which are present in coffee beans at some stage between green and roasted. For example, valine yields isobutanal, leucine yields isopentanal, and isoleucine yields 2-methyl-butanal.14 Some of these aldehydes probably undergo condensation reactions in the acidic medium of the roasted bean when moisture is present.15 Some dienals in green coffee beans have recently been identified as (E,E)-2,4- and (E,Z)-2,4-nonadienal and (E,E)-2,4- and (E,Z)-2,4-decadienal.18... 

Studies related to Naturally Occurring Acetylene Compounds. VII. The Synthesis of two Stereoisomers of Methyl n-Decadiene-2,8-diyn-4,6-oates the Configuration of Matricaria Ester. Acta Chem. Scand. 5, 1244 (1951). 

Matricaria Ester (n-Decadiene-2,8-diyne-4,6-oic Acid Methyl Ester). Acta Chem. Scand. 4, 416 (1950). 

Figure 8 The air-stable 77-conjugated organoboron segmented block copolymer (8) obtained by the hydroboration polymerization of allyl-telechelic polyisobutylene, 1,9-decadiene, and tripylborane. (Adapted from ref. 28.)...

Detailed investigation of T. rotula and other diatom species revealed that 2,4-decadienal (24) and 2,4,7-decatrienal (27) represent only members of a structurally diverse class of oc, 3,y,6-unsaturated aldehydes found in several... 

The effects of decadienal (24) as well as of diatom extracts are not restricted to the reduction of copepod success. Low, micromolar concentrations of this compound also inhibits fertilization, embryogenesis, and hatching success in polychaetes and echinoderms. Crude diatom extracts as well as purified aldehydes inhibited these processes in a dose-dependent manner [80]. 

Evidence for a methylene-metal-initiating species was provided by detection of propylene early in the course of metathesis of 2,8-decadiene with Me4Sn/WCl6, in addition to normal metathesis products ... 

Proper deuterium-labeling experiments involving (CD3)4Sn and [1,1,1,-10,10,10-D6]-2,8-decadiene confirmed that propylene is indeed the first-formed olefin, and its structure indicated that the methylidene and ethyl-idene moieties originated from Me4Sn and 2,8-decadiene, respectively. 

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