Tertiary amines table

In summary, the reaction of osmium tetroxide with alkenes is a reliable and selective transformation. Chiral diamines and cinchona alkakoid are most frequently used as chiral auxiliaries. Complexes derived from osmium tetroxide with diamines do not undergo catalytic turnover, whereas dihydroquinidine and dihydroquinine derivatives have been found to be very effective catalysts for the oxidation of a variety of alkenes. OsC>4 can be used catalytically in the presence of a secondary oxygen donor (e.g., H202, TBHP, A -methylmorpholine-/V-oxide, sodium periodate, 02, sodium hypochlorite, potassium ferricyanide). Furthermore, a remarkable rate enhancement occurs with the addition of a nucleophilic ligand such as pyridine or a tertiary amine. Table 4-11 lists the preferred chiral ligands for the dihydroxylation of a variety of olefins.61 Table 4-12 lists the recommended ligands for each class of olefins. 

Most local anesthetic agents consist of a lipophilic group (eg, an aromatic ring) connected by an intermediate chain via an ester or amide to an ionizable group (eg, a tertiary amine) (Table 26-1). In addition to the general physical properties of the molecules, specific stereochemical configurations are associated with differences in the potency of stereoisomers (eg, levobupivacaine, ropivacaine). Because ester links are more prone to hydrolysis than amide links, esters usually have a shorter duration of action. 

Alternatively, TbrlonAI-30 and AI-50 are amenable to aqueous systems when formulated with a tertiary amine Table 12.4 [27]. Due to the very low degree of imidization compared to AI-10 or polyamide-imides produced in the isocyanate process, these polymers can form stable, low-viscosity solutions in water at low to moderate polymer sohds. Generally the polymer sohds are 5 to 15%, depending on the polyamide-imide used, and provide solutions with a viscosity in the range of 50 to 2000 cP. 

A butadiene-modified clay was prepared to produce PS, HIPS, ABS terpolymer, PMMA, polypropylene, and polyethylene nanocomposites by melt- or solution blending [73, 74]. The butadiene surfactant was obtained from the reaction of vinylbenzyl chloride-grafted polybutadiene with a tertiary amine (Table 3.6). All the composites were immiscible microcomposites. 

The antistatic agents recommended for PO fibers are quaternary ammonium salts of fatty acids, alkano-lamines, alkanolamides, polyglycolesters, alkoxylated triglicerides, and ethoxylated tertiary amines (Table 2). The quaternary ammonium compounds and nonionic surfactants dominate this field because of their higher oil solubility and hygroscopicity. 

The melting points of the derivatives of a number of tertiary amines, both aliphatic and aromatic, are coUeoted in Table IV,100C. 

Tertiary Aliphatic and Aromatic Amines, Table IV, lOOC. 

Many perfluoroaUphatic ethers and tertiary amines have been prepared by electrochemical fluorination (1 6), direct fluorination using elemental fluorine (7—9), or, in a few cases, by fluorination using cobalt trifluoride (10). Examples of lower molecular weight materials are shown in Table 1. In addition to these, there are three commercial classes of perfluoropolyethers prepared by anionic polymerization of hexafluoropropene oxide [428-59-1] (11,12), photooxidation of hexafluoropropene [116-15-4] or tetrafluoroethene [116-14-3] (13,14), or by anionic ring-opening polymeriza tion of tetrafluorooxetane [765-63-9] followed by direct fluorination (15). 

In addition to the stmctuies in Tables 30—33, commeicial quatemaiy surfactants include a variety of modifications, prepared, eg, by quatemization of simple tertiary amines ... 

Table 1. Tertiary Amine Catalysts for Flexible Foams...

Calorimetry has been used to measure the rate of reaction for several tertiary amines with benzoyl peroxide [48]. The relative rate results are in line with the predictions from general organic chemistry. The rates given in Table 4, see also Scheme 7, are based on A/,A/-dimethylaniline = 1.00. 

The activation energy of substitution of an unactivated aromatic halide (e.g., fiuorobenzene and 2-chloronaphthalene ) is over 30 kcal while that of activated compounds is 5-20 kcal. For the tabulated reactions (Tables II-VIII) with alkoxide and with primary, secondary, or tertiary amines, resonance activation (cf. 278 and 279) by ortho or para nitrogens is found to be greater than inductive activation (cf. 251). This relation is qualitatively demonstrated in... 

Qiu et al. [11] reported that the aromatic tertiary amine with an electron-rich group on the N atom would favor nucleophilic displacement and thus increase the rate of decomposition of diacyl peroxide with the result of increasing the rate of polymerization (Table 1). They also pointed out that in the MMA polymerization using organic peroxide initiator alone the order of the rate of polymerization Rp is as follows ... 

Table 2 MMA Polymerization Initiated by BPO-Aromatic Tertiary Amine Systems...

Several articles [7,8] have reported that a persulfate-amine system, particularly persulfate-triethanol amine and persulfate-tetramethylethylenediamine (TMEDA) can be used as redox initiators in aqueous solution polymerization of vinyl monomers. Recently, we studied the effect of various amines on the AAM aqueous solution polymerization and found that not only tertiary amine but also secondary and even primary aliphatic amine and their polyamines can promote the vinyl polymerization as shown in Table 6 [40-42]. 

The spin adducts of free radicals and MNP or DMPO were observed by means of an ESR spectrometer. The data of hyperfine splitting constants were compiled in Tables 9 and 10 [40-42,44,45]. ESR studies on the initial free radicals revealed that the monoalkylamino radical RHN-, dialkylamino radical R2N-, and aminomethyl radical -CH2N< or aminoethylidene radical >N( CHCH3) were obtained from the corresponding primary, secondary, and cyclic tertiary amine. In case of a tertiary diamine such as TMEDA, formation of... 

Table 1). Further determinants of blocking potency are the membrane potential and the state in which the sodium channel is in (resting, activated, inactivated). The tertiary amine group can be protonated giving most local... 

Ketenes react with tertiary allylic amines in the presence of Lewis acids to give zwitterionic intermediates which undergo [3,3]-sigmatropic rearrangement [119]. Photolysis of chromium carbene complexes in the presence of tertiary amines results in similar chemistry [120]. Cyclic (Table 21) and strained allylic amines (Eq. 34) work best, while acylic amines are less reactive (Eq. 35). 

Table 2. Dibromination of Phenol with NBS in the Presence of Primary, Secondary, and Tertiary Amines )...

This procedure, which is based on the work of Ishii and co-workers, affords a mild and general method for converting a wide variety of esters to primary, secondary, and tertiary amides (Table 1). While the preparation of the tertiary amide, N,N-dimethylcyclohexanecarboxamide, described here is carried out in benzene, aluminum amides derived from ammonia and a variety of primary amines have been prepared by reaction with trimethylaluminum in dichloromethane and utilized for aminolysis in this solvent. Although 1 equivalent of the dimethylaluminum amides from amines was generally sufficient for high conversion within 5-48 hours, best results were obtained when 2 equivalents of the aluminum reagent from ammonia was used. Diethyl-aluminum amides can also effect aminolysis, but with considerably slower rates. 

For larger cryptands [6] (Cox et al., 1978), the protonation/deprotonation kinetics have also been measured. Table 4 lists the kinetic and the equilibrium data for such cryptands. When compared to the neutralization of protonated tertiary amines by OH, the reaction of the second smallest protonated cryptand [2.1.1] H is 10 to 10 times slower (Cox et al., 1978), indicating a strong shielding and possibly an i -orientation of the proton. For the [2.2.1] cryptand, no k and k-i values could be calculated, probably due to a fast pre-equilibrium between in,in- and m,OMt-conformations. 

Rosenblatt etal have examined the effect of structure and isotopic substitution upon the permanganate oxidation of some alky famines (Table 4). The isotope effect of 1.84 is considered to be sufficiently low to be compatible with aminium radical-cation formation, and it is felt that, while C-H cleavage is significant for oxidation of primary amines, the dominant mode of oxidation of tertiary amines is electron-transfer, e.g. 

---