Trimers oxidation

Soluble heptapnicanortricyclane anions [Pny] (Fig. 3a) and trishomocubane-shaped (ufosane-like) anions [Pnn] (Fig. 3d) are very common and known as in the binary solids for Pn = P, As, Sb (Table 2). Oxidative coupling of these monomers leads to the dimers [Pny-Pny]" and [Pnn-Pnn]" for Pn = P and As (Fig. 3b, e), which - as observed for the tetrel element clusters - have an external homoatomic bond, but in this case the structures of the monomeric units are fully retained upon dimerization. A trimeric oxidative coupling product of [Py] is the... 

In order to augment the upper bound for the Naa dissociation energy obtained in the studies outlined above, we have undertaken an experiment involving sodium trimer oxidation. The experiment involves the study of the reaction... 

D.-S. Yang, Coord. Chem. Rev., 2001, 214, 187. Describes the application of ZEKE photoelectron techniques to metal-containing molecules. Examples include metal dimer and trimer oxides, carbides, and nitrides. 

Chemical Properties. In addition to the reactions Hsted in Table 3, boron trifluoride reacts with alkali or alkaline-earth metal oxides, as well as other inorganic alkaline materials, at 450°C to yield the trimer trifluoroboroxine [13703-95-2] (BOF), MBF, and MF (29) where M is a univalent metal ion. The trimer is stable below — 135°C but disproportionates to B2O2 and BF at higher temperatures (30). 

The by-product of this process, pelargonic acid [112-05-0] is also an item of commerce. The usual source of sebacic acid [111-20-6] for nylon-6,10 [9008-66-6] is also from a natural product, ticinoleic acid [141-22-0] (12-hydroxyoleic acid), isolated from castor oil [8001-79-4]. The acid reacts with excess sodium or potassium hydroxide at high temperatures (250—275°C) to produce sebacic acid and 2-octanol [123-96-6] (166) by cleavage at the 9,10-unsaturated position. The manufacture of dodecanedioic acid [693-23-2] for nylon-6,12 begins with the catalytic trimerization of butadiene to make cyclododecatriene [4904-61-4] followed by reduction to cyclododecane [294-62-2] (see Butadiene). The cyclododecane is oxidatively cleaved to dodecanedioic acid in a process similar to that used in adipic acid production. 

The backbone of poly(phenylene oxide)s is cleaved under certain extreme reaction conditions. Lithium biphenyl reduces DMPPO to low molecular weight products in the dimer and trimer molecular weight range (20) and converts poly(2,6-diphenyl-l,4-phenylene oxide) to 3,5-diphenylphenol in 85% yield (21) (eq. 4). 

The sulfides are associated like the oxides, but to a lesser degree. They are crystalline, sharp-melting, soluble ia many organic solvents, and resistant to hydrolysis. Most are cycHc trimers (106). 

The polymer also can be made from trioxane (the trimer of formaldehyde), usually as a copolymer with ethylene oxide. The —CH2CH2— fragments in the copolymer chain prevent depolymerization acetal copolymer was developed by Celanese (10). 

This type of cement has been further improved by the substitution of -hexyl van ill ate [84375-71-3] and similar esters of vanillic acid [121 -34-6] and/or syringic acid [530-57 ] for eugenol (93—95). These substituted cements are strong, resistant to dissolution, and, unlike ZOE and EBA cements, do not inhibit the polymerization of resin-base materials. Noneugenol cements based on the acid—base reaction of zinc and similar oxides with carboxyhc acids have been investigated, and several promising types have been developed based on dimer and trimer acids (82). 

Calcium Chelates (Salicylates). Several successhil dental cements which use the formation of a calcium chelate system (96) were developed based on the reaction of calcium hydroxide [1305-62-0] and various phenohc esters of sahcyhc acid [69-72-7]. The calcium sahcylate [824-35-1] system offers certain advantages over the more widely used zinc oxide—eugenol system. These products are completely bland, antibacterial (97), facihtate the formation of reparative dentin, and do not retard the free-radical polymerization reaction of acryhc monomer systems. The principal deficiencies of this type of cement are its relatively high solubihty, relatively low strength, and low modulus. Less soluble and higher strength calcium-based cements based on dimer and trimer acid have been reported (82). 

Siace dimer acids, monomer acids, and trimer acids are unsaturated, they are susceptible to oxidative and thermal attack, and under certain conditions they are slightly corrosive to metals. Special precautions are necessary, therefore, to prevent product color development and equipment deterioration. Type 304 stainless steel is recommended for storage tanks for dimer acids. Eor heating coils and for agitators 316 stainless steel is preferred (heating coils with about 4s m (50 ft ) of heat transfer surface ia the form of a 5.1 cm schedule-10 U-bend scroU are recommended for a 37. 9-m (10,000-gal) tank. Dimer acid storage tanks should have an iaert gas blanket. 

Nylon 12 first beeame available on a semieommercial scale in 1963. The monomer, dodecanelactam, is prepared from butadiene by a multistaged reaction. In one proeess butadiene is treated with a Ziegler-type eatalyst system to yield the cyclic trimer, cyclododeca-1, 5, 9-triene. This may then be hydrogenated to give cyelododeeane, which is then subjeeted to direct air oxidation to give a mixture of cyclododecanol and cyclododecanone. Treatment of the mixture with... 

The dimer of 1-methyl- -pyrroline (39) was obtained by reduction of N-methylpyrrole with zinc and hydrochloric acid (132) and, together with the trimer, by mercuric acetate dehydrogenation of N-methylpyrrolidine (131). J -Pyrroline-N-oxides form dimers in a similar manner (302). Treatment of 1,2-dimethyl-zl -piperideine with formaldehyde, producing l-methyl-3-acetylpiperidine (603), serves as an example of a mixed aldol reaction (Scheme 18). 

LCo(H20)6] ion, and bidentate /V-donor ligands such as cn, bipy and phen form octahedral cationic complexes [Co(L-L)3] , which are much more stable to oxidation than is the hexaammine [Co(NH3)6l . Acac yields the orange [Co(acac)2(H20)2] which has the tram octahedral structure and can be dehydrated to [Co(acac)2l which attains octahedral coordination by forming the tetrameric species shown in Fig. 26.3. This is comparable with the trimeric [Ni(acac>2]3 (p. 1157), like which it shows evidence of weak ferromagnetic interactions at very low temperatures. fCo(edta)(H20)] is ostensibly analogous to the 7-coordinate Mn and complexes with the same stoichiometry, but in fact the cobalt is only 6-coordinate, 1 of the oxygen atoms of the cdta being too far away from the cobalt (272 compared to 223 pm for the other edta donor atoms) to be considered as coordinated. 

Figure 12.3 Clrromatogr-ams of an ignition-resistant high-impact polystyrene sample (a) Microcolumn SEC fi ace (b) capillary GC trace of peak x . Peak identification is as follows 1, ionol 2, benzophenone 3, styrene dimer 4, palmitic acid 5, stearic acid 6, styrene trimers 7, styrene trimer 8, styrene oligomer 9, Irganox 1076 and Irganox 168 10, styrene oligomer 11, nonabromodiphenyl oxide and 12, decabromodiphenyl oxide. Reprinted with permission from Ref. (12).

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