71138-64-2

Usage

InChI:InChI=1/C12H24/c1-4-6-7-8-9-10-11-12(3)5-2/h3-11H2,1-2H3

Upstream product

• 872-05-9 1-Decene 
• 557-18-6 diethylmagnesium 
• 96-10-6 diethylaluminium chloride 
• 5732-02-5 3-methylene-1-undecene 
• 85058-00-0 1-Brommethylsulfonyl-1-ethylnonan 
• 97-93-8 triethylaluminum 
• 764-93-2 1-decyne 
• 629-27-6 1-Iodooctane 
• 85057-95-0 2-<(1-Ethylnonyl)sulfonyl>-1-phenyl-1-ethanon 
• 17049-49-9 octylmagnesium bromide 
• 74-85-1 ethene 
• 85057-92-7 2-Nonylsulfonyl-1-phenyl-1-ethanon 

Downstream Products

• 2216-87-7 undecan-3-one 
• 17312-57-1 3-methyldodecane 

Relevant academic research and scientific papers

Elongation and branching of a-olefins by two ethylene molecules

a-Olefins are important starting materials for the production of plastics, pharmaceuticals, and fine and bulk chemicals. However, the selective synthesis of a-olefins from ethylene, a highly abundant and inexpensive feedstock, is restricted, and thus a broadly applicable selective a-olefin synthesis using ethylene is highly desirable. Here, we report the catalytic reaction of an a-olefin with two ethylene molecules. The first ethylene molecule forms a 4-ethyl branch and the second a new terminal carbon-carbon double bond (C2 elongation). The key to this reaction is the development of a highly active and stable molecular titanium catalyst that undergoes extremely fast b-hydride elimination and transfer.

Copper-Catalyzed Regioselective Hydroalkylation of 1,3-Dienes with Alkyl Fluorides and Grignard Reagents

Copper complexes generated in situ from CuCl2, alkyl Grignard reagents, and 1,3-dienes play important roles as catalytic active species for the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides through C-F bond cleavage. The alkyl group is introduced to an internal carbon atom of the 1,3-diene regioselectively, thus giving rise to the branched terminal alkene product. Making the switch: A copper-hydride species, generated by the treatment of a copper salt with alkyl Grignard reagents, catalyzes the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides and Grignard reagents. The alkyl group of the alkyl fluoride is selectively introduced to an internal carbon atom of the 1,3-diene and the Grignard reagent acts as hydride source to give the branched terminal alkene, even in the presence of alkenes and alkynes.

Iron-catalyzed alkenylation of Grignard reagents by enol phosphates

Stereoselective preparation of trisubstituted olefins can be easily performed from an Z/E-mixture of enol phosphates by reacting only the E-isomer with a Grignard reagent in the presence of Fe(acac)3. This procedure combines a kinetic differentiation and a stereoselective reaction. The coupling is very chemoselective in the presence of an alkyl chloride, an ester, a ketone or a nitrile. Georg Thieme Verlag Stuttgart.

Conversions of 1-decene under the action of complex zirconium-containing catalysts

A study has been made of the bulk conversion of 1-decene on complex catalysts containing Zr(OC3H7)4 and Zr(OCO-iso-C3H7)4 and Al(C2H5)3, (C2H5)2AlCl or (C2H5)1·5AlCl1·5 at temperatures of 80-110°C. It has been established that the total conversion of 1-decene under the action of the given catalysts depends on the nature of the organoaluminium cocatalyst and decreases in the order (C2H5)1·5AlCl1·5 > (C2H5)2AlCl > Al(C2H5)3. The main products of conversions of 1-decene are 2-ethyl-1-decene, dimers and trimers of 1-decene, and also 2-decene. The yield of 2-ethyl-1-decene increases with an increasing Al/Zr molar ratio and reaches 20 mole/mole zirconium compound in the catalyst. The probable mechanism of the conversions occurring is proposed.

Multiple mechanistic pathways for zirconium-catalyzed carboalumination of alkynes. Requirements for cyclic carbometalation processes involving C-H activation

The reactions of internal and terminal alkynes with organoalanes containing Et, n-Pr, and i-Bu groups in the presence of Cp2ZrCl2 and MeZrCp2Cl were investigated with the goal of clarifying mechanistic details of some representative cases. Three fundamentally different processes, i.e., (i) C-M bond addition without C-H activation in the alkyl group, (ii) cyclic C-M bond addition via C-H activation, and (iii) hydrometalation, have been observed, and the courses of these reactions significantly depend on (i) the nature and number of alkyl groups in organoalanes, (ii) their amounts, and (iii) solvents. The reaction of alkynes with Et3Al in the presence of 0.1 equiv of Cp2ZrCl2 in nonpolar solvents, e.g., hexanes, proceeds via C-H activation to give the corresponding aluminacyclopentenes. Investigation of the reaction of 5-decyne with 1-3 equiv of Et3Al and 1 equiv of Cp2ZrCl2, which gave mono-, di-, or trideuterated (Z)-5-ethyl-5-decene as shown, together with the previously reported structural study on the reaction of Et3Al with Cp2ZrCl2 leading to the formation of well-characterized bimetallic species 9, 10, and 11, supports a catalytic cycle involving bimetallic species 10 and 18. In summary, this process requires a zirconocene derivative containing one Zr-bound Et group which is linked to Et3Al (but not to Et2AlCl) through a Cl bridge, i.e., 18, to produce 10 via β C-H activation. In sharp contrast, the reaction of Et2AlCl-Cp2ZrCl2 as well as of (n-Pr)2AlCl-Cp2ZrCl2 does not involve any C-H activation processes. It proceeds well in chlorinated hydrocarbon solvents, e.g., (CH2Cl)2, but it is extremely sluggish in nonpolar solvents, e.g., hexanes. The reaction may well involve direct C-Al bond addition to alkynes, as suggested earlier for Zr-catalyzed Me-Al bond addition to alkynes, but a few other alternatives cannot be ruled out on the basis of the currently available data. The reaction of alkynes with (n-Pr)3Al-Cp2ZrCl2 in nonpolar solvents proceeds partially via C-H activation and partially via hydrometalation. In contrast with the C-H activation process observed with Et3Al, that with (n-Pr)3Al is totally dominated by dimerization of alkynes to give aluminacyclopentadienes rather than aluminacyclopentenes, reflecting a previously established generalization that propene can be much more readily displaced from Zr by alkynes than ethylene. Hydrometalation is the exclusive process with (i-Bu)3Al-Cp2ZrCl2. This hydrometalation reaction, however, reveals a few interesting complications. Alkyl-substituted internal alkynes give double bond migrated products in addition to the expected hydrometalation products. With terminal alkynes the reaction produces the expected hydrometalation products and the 1,1-dimetalloalkanes in comparable yields. Various other related reactions involving other alkynes, e.g., PhC≡CPh, n-OctC≡CH, and PhC≡CH, and other reagents, e.g., Et3Al-MeZrCp2Cl, Et2AlCl-MeZrCp2Cl, and (n-Pr)3Al-MeZrCp2Cl, were also studied.

Convenient Synthesis of Diene-Zirconocenes and Regioselective Partial Reduction of the More Highly Substituted Double Bonds of Conjugated Dienes via Complexation with Zirconocenes and Protonolysis

Conjugated dienes can be initially converted to their zirconocene complexes most conveniently by their reaction with (C5H5)2ZrCl2 and freshly ground Mg; the resultant complexes can then be protonolysed with 3 mol dm-3 HCl to give regioselectively monoenes corresponding to partial hydrogenation of the more highly substituted double bond.

New Synthetic Methods, 7. - β-Ketosulfones, Useful Ethylenediide Equivalents for the Preparation of Olefins and the Synthesis of 6-Nonen-1-ol, the Sex Attractant of the Mediterranean Fruit Fly (Ceratitus capitata)

β-Ketosulfones, which form dianions (α and γ position), are alkylated in both positions.Brominating cleavage gives α-bromosulfones which, by Ramberg-Baecklund rearrangement, form olefins.The synthesis of 6-nonen-1-ol, starting from 2-(methylsulfonyl)cyclohexanone, is described.