2765-29-9

Usage

Chemical Properties

CLEAR SLIGHTLY YELLOW LIQUID

Purification Methods

Purify the triene by fractional distillation, preferably in a vacuum under N2, and it forms an insoluble AgNO3 complex. [IR: Breil et al. Makromol Chemie 69 28 1963, Beilstein 5 IV 1114.]

InChI:InChI=1/C12H18/c1-2-4-6-8-10-12-11-9-7-5-3-1/h1-2,7-10H,3-6,11-12H2/b2-1-,9-7+,10-8+

Upstream product

• 106-99-0 buta-1,3-diene 
• 706-31-0 (1E,5E,9Z)-cyclododeca-1,5,9-triene 
• 548757-71-7 cis-,cis-,cis-C₁₂H₁₈Ni 
• 51097-60-0 (Z)-oct-4-enedial 
• 15546-42-6 [1,1'-(butane-1,4-diyl)bis(triphenylphosphonium)] dibromide 
• 101-02-0 triphenyl phosphite 
• 548757-70-6 [Ni(1,5,9-cyclododecatriene)] 
• 3194-55-6 1,2,5,6,9,10-Hexabrom-cyclododecan 
• 4526-07-2 1,4-bis(trimethylsilyl)-1,3-butadiyne 
• 57776-89-3 trans-,trans-,cis-C₁₂H₁₈NiP(C₆H₅)3 
• 37249-40-4 trans-,trans-,cis-C₁₂H₁₈NiP(C₆H₁₁-cyclo)3 
• 119449-01-3 (E,E)-2,5-Dibrom-cyclododeca-1,5-dien-9-in 

Downstream Products

• 60323-50-4 1,5,9-cyclododecatriyne 
• 706-31-0 (1E,5E,9Z)-cyclododeca-1,5,9-triene 
• 676-22-2 (1E,5E,9E)-cyclododeca-1,5,9-triene 

Relevant academic research and scientific papers

Titanium-catalyzed [4+2] and [6+2] cycloadditions of 1,4-bis(trimethylsilyl)buta-1,3-diyne

The (C2H5)2AlCl/TiCl4 catalyst induces the [4+2] cycloaddition of butadiene or the [6+2] cycloaddition of 1,3,5-cycloheptatriene (CHT) to individual acetylenic moieties of 1,4-bis(trimethylsilyl)buta-1,3-diyne (BSD). Heating of the 2:1 butadiene adduct, bis(2-trimethylsilylcyclohexa-1,4-dien-1-yl), to 250°C yields 2,2′-bis(trimethylsilyl)biphenyl. The 1:1 adduct of BSD with CHT, 7-trimethylsilyl-8-trimethylsilylethynylbicyclo[4.2.1]nona-2,4-diene, is obtained as virtually the only product if the initial molar ratio CHT:BD equal to 1.86 is used.

THERMAL CONVERSION OF 1,5,9-TRIYNES. CYCLOADDITIONS OR SIGMATROPIC SHIFTS?

The gas phase pyrolyses of variously labeled 1,5,9-decatriynes (1) and 1,5,9-cyclododecatriynes (2) were investigated to determine possible modes of thermal isomerizations.Conditions included temperatures in the range 400-600 deg C, pressures of 40 -10E-4 Torr, and contact times of ca 1 ms to 15 s.The labeling patterns in 1 and 2 were chosen such as to be able to distinguish direct intramolecular cycloadditions of the alkyne units to form an aromatic ring (perhaps with subsequent rearrangements), and sigmatropic shifts of the 1,5-diyne moieties.Methods for synthesizing the isotopically (particularly (13)C) labeled triynes were devised and implemented.The route to 5,6-(13)C2-1,5,9-decatriyne (1c) made use of a new procedure for the synthesis of symmetrically disubstituted alkynes involving coupling between two equivalents of an alkyl copper reagent and diiodoacetylene-(13)C2.The synthesis of 1,10-(13)C2-1,5,9-cyclododecatriyne (2b) was accomplished starting with K(13)CN, elaboration to labeled diethyl succinate, a crucial bis-Wittig condensation to labeled 1,5,9-cyclododecatriene 10, and bromination-dehydrobromination of the latter (NaOH-ethylene glycol).Products from the pyrolysis of unlabeled 1a included dicyclobutabenzene, naphtalene and 3,4-dimethylidene-1-(but-3-ynyl)cyclobutene.Pyrolysis of 1b gave 3,6-dideuteriodicyclobutabenzene and partially deuterated naphthalene, that of 1c produced 1,2-(13)C2-dicyclobutabenzene and 9,10-(13)C2-naphthalene.While the pyrolysis of 2a resulted in hexamethylidenecyclohexane (hexaradialene), 2b furnished 1,4-(13)C2-hexaradialene.The results rule out the occurence of cycloadditions of the alkyne units, but are consistent with the intervention of a series sigmatropic shifts which connect starting materials with products.