931-87-3 Usage
Uses
cis-Cyclooctene is used as a displaced ligand in chlorobis(cyclooctene)rhodium dimer and chlorobis(cyclooctene)iridium dimer in organometallic chemistry. It acts as a monomer used in synthetic chemistry. It is used to prepare 1-chloro-4-(trichloromethyl) cyclooctane by reaction with carbon tetrachloride using dichlorotris(triphenylphosphine) ruthenium(II) as a catalyst. Further, it is used to study the alkenes chemisorbed on silicon(100) by scanning tunneling microscopy.
Synthesis Reference(s)
Journal of the American Chemical Society, 102, p. 2693, 1980 DOI: 10.1021/ja00528a029The Journal of Organic Chemistry, 40, p. 2555, 1975 DOI: 10.1021/jo00905a040Tetrahedron Letters, 14, p. 2667, 1973
General Description
cis-Cyclooctene undergoes addition reaction with carbon tetrachloride catalyzed by dichlorotris(triphenylphosphine) ruthenium(II) to yield 1-chloro-4-(trichloromethyl) cyclooctane (1,4-adduct). It undergoes epoxidation catalyzed by molybdenum oxide nanoparticles incorporated in a mesoporous silica shell coated on dense silica-coated magnetite nanoparticles.
Purification Methods
The cis-isomer is freed from the trans-isomer by fractional distillation through a spinning-band column, followed by preparative gas chromatography on a Dowex 710-Chromosorb W GLC column. It is passed through a short alumina column immediately before use [Collman et al. J Am Chem Soc 108 2588 1986]. It has also been distilled in a dry N2 glove box from powdered fused NaOH through a Vigreux column (p 11), then passed through activated neutral alumina before use [Wong et al. J Am Chem Soc 109 4328 1987]. Alternatively it can be purified via the AgNO3 salt. This salt is obtained from crude cyclooctene (40 mL) by shaking at 70-80o with 50% w/w AgNO3 (2 x 15 mL) to remove cyclooctadienes (aqueous layer). Extraction is repeated at 40o (4 x 20 mL, of 50% AgNO3). Three layers are formed each time. The middle layer contains the AgNO3 adduct of cyclooctene which crystallises on cooling the layer to room temperature. The adduct (complex 2:1) is highly soluble in MeOH (at least 1g/mL) from which it crystallises in large flat needles when cooled at 0o. It is dried under slight vacuum for 1 week in the presence of CaCl2 and paraffin wax soaked in cyclooctene. It has m 51o and loses hydrocarbon on exposure to air. cis-Cyclooctene can be recovered by steam distillation of the salt, collected, dried (CaCl2) and distilled in vacuum. [Braude et al. J Chem Soc 4711 1957, AgNO3: Jones J Chem Soc 1808 1954, Cope & Estes J Am Chem Soc 72 1128 1950, Beilstein 5 I 35, 5 IV 263.] FLAMMABLE LIQUID.
Check Digit Verification of cas no
The CAS Registry Mumber 931-87-3 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 9,3 and 1 respectively; the second part has 2 digits, 8 and 7 respectively.
Calculate Digit Verification of CAS Registry Number 931-87:
(5*9)+(4*3)+(3*1)+(2*8)+(1*7)=83
83 % 10 = 3
So 931-87-3 is a valid CAS Registry Number.
InChI:InChI=1/C8H14/c1-2-4-6-8-7-5-3-1/h1-2H,3-8H2/b2-1-
931-87-3Relevant articles and documents
Cobalt Complexes of Bulky PNP Ligand: H2Activation and Catalytic Two-Electron Reactivity in Hydrogenation of Alkenes and Alkynes
Fayzullin, Robert R.,Gallagher, James M.,Khaskin, Eugene,Khusnutdinova, Julia R.,Lapointe, Sébastien,Osborne, James,Pandey, Dilip K.
supporting information, p. 3617 - 3626 (2021/11/16)
The reactivity of cobalt pincer complexes supported by the bulky tetramethylated PNP ligands Me4PNPR(R = iPr, tBu) has been investigated. In these ligands, the undesired H atom loss reactivity observed earlier in some classical CH2-arm PNP cobalt complexes is blocked, allowing them to be utilized for promoting two-electron catalytic transformations at the cobalt center. Accordingly, reaction of the formally CoIMe complex 3 with H2 under ambient pressure and temperature afforded the CoIII trihydride 4-H, in a reaction cascade reasoned to proceed by two-electron oxidative addition and reductive eliminations. This mechanistic proposal, alongside the observance of alkene insertion and ethane production upon sequential exposure of 3 to ethylene and H2, prompted an exploration into 3 as a catalyst for hydrogenation. Complex 4-H, formed in situ from 3 under H2, was found to be active in the catalytic hydrogenation of alkenes and alkynes. The proposed two-electron mechanism is reminiscent of the platinum group metals and demonstrates the utility of the bulky redox-innocent Me4PNPR ligand in the avoidance of one-electron reactivity, a concept that may show broad applicability in expanding the scope of earth-abundant first-row transition-metal catalysis.
Selective C-O Bond Reduction and Borylation of Aryl Ethers Catalyzed by a Rhodium-Aluminum Heterobimetallic Complex
Hara, Naofumi,Nakao, Yoshiaki,Saito, Teruhiko,Seki, Rin
supporting information, p. 6388 - 6394 (2021/05/31)
We report the catalytic reduction of a C-O bond and the borylation by a rhodium complex bearing an X-Type PAlP pincer ligand. We have revealed the reaction mechanism based on the characterization of the reaction intermediate and deuterium-labeling experiments. Notably, this novel catalytic system shows steric-hindrance-dependent chemoselectivity that is distinct from conventional Ni-based catalysts and suggests a new strategy for selective C-O bond activation by heterobimetallic catalysis.
Nickel-catalyzed deoxygenation of oxiranes: Conversion of epoxides to alkenes
Mori, Takamichi,Takeuchi, Yoshihito,Hojo, Makoto
supporting information, (2020/01/24)
Deoxygenation of epoxides takes place under the catalysis of nickel in the presence of diethylzinc as a deoxygenation agent to yield alkenes. Epoxides with a wide variety of substitution patterns are deoxygenated in this catalytic system to give terminal, 1,1-disubstituted, 1,2-disubstituted, trisubstituted, and tetrasubstituted alkenes in high yields. Reactions of 1,2-disubstituted epoxides we examined proceeded in an E-stereoselective manner. High compatibility with other functional groups through this transformation was also observed.