4- Methyl-3-decen

Methyl-3-decen-5-ol is prepared by Grignard reaction of pentyl magnesium bromide and 2-methyl-2-pentenal [14a]. 

It is interesting to note that the add moiety of aplysflla-mides A and B is 3-methyl-decen-2-oic add, which can be found hydroxylated at position 8 or 9 in irdniasulfonic acids (see above). 

In contrast to oxidation in water, it has been found that 1-alkenes are directly oxidized with molecular oxygen in anhydrous, aprotic solvents, when a catalyst system of PdCl2(MeCN)2 and CuCl is used together with HMPA. In the absence of HMPA, no reaction takes place(100]. In the oxidation of 1-decene, the Oj uptake correlates with the amount of 2-decanone formed, and up to 0.5 mol of O2 is consumed for the production of 1 mol of the ketone. This result shows that both O atoms of molecular oxygen are incorporated into the product, and a bimetallic Pd(II) hydroperoxide coupled with a Cu salt is involved in oxidation of this type, and that the well known redox catalysis of PdXi and CuX is not always operalive[10 ]. The oxidation under anhydrous conditions is unique in terms of the regioselective formation of aldehyde 59 from X-allyl-A -methylbenzamide (58), whereas the use of aqueous DME results in the predominant formation of the methyl ketone 60. Similar results are obtained with allylic acetates and allylic carbonates[102]. The complete reversal of the regioselectivity in PdCli-catalyzed oxidation of alkenes is remarkable. 

Entsprechend wird endo-5-Hydroxy-3-methyl-endo-tricyclo[5.2.1,02 6]decen-(3) (89% d.Th. F 79,4-79,9°) erhalten. 

So erhalt man z. B. aus 1-Jod-decan in DMF/TEAPan Quecksilber lediglich bei-1,1 V [vs. Cd(FIg)/CdCl2/NaCl] ausschlieBlich Didecyl-quecksilber ansonsten werden wech-selnde Gemische von Decan, Decen-(1), Decanol-(l) sowic /V-Methyl-N-decyl-formamid (bei — 1,9 V 40%d-Th.) erhalten7. Zur Reduktion von 3-Brom-1-phenyl-propan zu Propyl- benzol s. S. 619. 

Zur Reduktion von 3,7-Dioxo-6/3-methyl-2-(2-carboxy-athyl)-bicyclo[4.4.0]decen-( 1) s.S. 764. 

Acetylene Compounds. V. Dehydro Matricaria Ester (Methyl n-decene-triynoate) from the Essential Oil of Artemisia vulgaris L. Acta Chem. Scand. 4, 1567 (1950). 

The Michael reaction of nitromethane with methyl vinyl ketone and l-decene-3-one followed by reductive cyclization gives two isomeric pyrrolizidines, depending on reduction conditions (Eq. 10.74).117... 

Materials. 5-Methyl-1,4-hexadiene was obtained by the codimerization of isoprene and ethylene with a catalyst (18) consisting of iron octanoate, triethylaluminum and 2,2 -bi-pyridyl. The product mixture which contained principally 5-methyl-1,4-hexadiene and 4-methy1-1,4-hexadiene was fractionated through a Podbielniack column to yield high purity (>99%) 5-methylxhexadiene, b.p. 92.80C,njj 1.4250 (Lit. (19) b.p. 88-89°C, np 1.4249). 1-Hexene (99.9% purity), 1-decene (99.6% purity), 4-methyl-1-hexene (99.5% purity) and 5-methyl-l-hexene (99.7% purity) were obtained from Chemical Samples Co. 6-TiCl3 AA (Stauffer Chemical Co.j contains 0.33 mole AICI3 per mole of TiClj). Diethylaluminum Chloride was obtained from Texas Alkyls (1.5 M in hexane). 

More substituted and unactivated dienophiles such as 3-acetoxy-2-methyl-cyclopentenone, did not react with 112 even in the presence of BF3 etherate. 4-Acetylspiro[2.1.2.3]decen-9-one (128) could also be isolated under these con-... 

Cyclic stannanes can be generated by reaction of stannylenes with alkynes112. For example, bis[bis(trimethylsilyl)methyl]tin reacts with cyclooctyne to provide A1,18-9,10-(distanna-9,9,10,10-tetrakis[bis(trimethylsilyl)methyl])bicyclo[6,2,0]-decene, 69. This reaction is a typical oxidative addition on stannylenes. 

As already mentioned, and as illustrated in Table 6.6, an important prerequisite for efficient cationic (ebthi)Zr-catalyzed hydrogenation is that the alkene should not be able to polymerize in a facile manner. Whereas with 1-decene as the substrate, only 28% of the hydrogenation product is obtained (Table 6.6, entry 1 the remainder of the product is the derived polymer), 2-methyl-l-pentene affords 97% of the hydrogenation adduct... 

Polymers Catalytic reactions involving C=C bonds are widely used for the conversion of unsaturated fatty compounds to prepare useful monomers for polymer synthesis. Catalytic C-C coupling reactions of unsaturated fatty compounds have been reviewed by Biermann and Metzger [51]. Metathesis reactions involving unsaturated fatty compounds to prepare co-unsaturated fatty acid esters have been applied by Warwel et al. [52], Ethenolysis of methyl oleate catalyzed by ruthenium carbenes developed by Grubb yields 1-decene and methyl 9-decenoate (Scheme 3.6), which can be very useful to prepare monomers for polyolefins, polyesters, polyethers and polyamide such as Nylon 11. 

Larvae of the tenebrionid beetle Hypophloeus versipellis were shown to possess an unpaired defensive gland reservoir with an opening situated at the anterior border of the ninth tergite [ 126]. The secretion contains methyl- 1,4-ben-zoquinone 7, ethyl-1,4-benzoquinone 8, ethylhydroquinone, and acetophenone as well as 6-methyl-1,4-naphthoquinone 177,6-ethyl-1,4-naphthoquinone 178, and 6-propyl-1,4-naphthoquinones 179. Several alkenes (probably 1-alkenes) like 1-tridecene, 1-tetradecene, 1-pentadecene (main constituent), 1-hexa-decene, and 1-heptadecene may function as solvents for the solid biologically active compounds. 

Similar results were obtained in the biphasic Wacker oxidation of 1-decene, catalyzed by PdS04, CUSO4 and a heteropolyacid H9PV6M06O40 in the presence of chemically modified p-cyclodextrins (methyl, methoxy, hydroxypropyl derivatives). The reactions yielded 2-decanone in rather high yield (up to 58 %) accompanied by extensive isomerization of 1-decene to internal decenes. Nevertheless, these latter apparently did not react, since the ratio of 2-decanone among the oxodecenes exceeded 99 % (Scheme 10.12). 

In order to explain the structures of the decenes by the action of 75% sulfuric acid on 3-methyl-2-butanol (methylisopropylcarbinol), it is necessary to assume the intermediate formation of 2-methyl-2-butene and 2-methyl-l-butene in the ratio of 3 to 1 ... 

The influence of the sensitivity of the assessors on AEDA has been studied [11], with the result that the differences in the FD factors determined by a group of six panellists amount to not more than two dilution steps (e.g. 64 and 256), implying that the key odorants in a given extract will undoubtedly be detected. However, to avoid falsification of the result by anosmia, AEDA of a sample should be independently performed by at least two assessors. As detailed in [6], odour threshold values of odorants can be determined by AEDA using a sensory internal standard, e.g. ( )-2-decenal. However, as shown in Table 16.6 these odour threshold values may vary by several orders of magnitude [8] owing to different properties of the stationary phases. Consequently, such effects will also influence the results of dilution experiments. Indeed, different FD factors were determined for 2-methyl-3-furanthiol on the stationary phases SE-54 and FFAP 2 and 2 , respectively. In contrast, 5-ethyl-3-hydroxy-4-methyl-2(5H)-furanone showed higher FD factors on FFAP than on SE-54 2 and 2, respectively. Consequently, FD factors should be determined on suitable GC capillaries [8]. However, the best method to overcome the limitations of GC-O and the dilution experiment is a sensory study of aroma models (Sect. 16.6.3). 

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