From active hydrogen compounds

Tomono. T., Hasegawa. E., and Tsuchida, E., Polyamine polymers from active hydrogen compounds, formaldehyde and aminc.s, J. Polym. Sei. Polym. Chem. Pd., 12,953, 1974. 

Reaction with active-hydrogen compounds [1, 96, before references]. Hauser11 reports that n-butyllithium can afford dilithio salts from active-hydrogen compounds when use of potassium amide in liquid ammonia is ineffective. Thus acetanilide (1) reacts with n-butyllithium in THF or ether to form a dilithio derivative formulated as (2). This disalt on alkylation with benzyl chloride gives (3). 

The growing vinyl fluoride free radical is not resonance stabilized. Therefore it is quite reactive and capable of abstracting a hydrogen atom from active hydrogen compounds such as isopropanol or acetonitrile with consequent chain termination by a ehain-transfer mechanism. In the case of a solvent such as dimethyl sulfoxide, such processes do not take place. As a result, the precipitating polymer has difficulties finding appropriate radieals for termination reactions. As in other examples of the gel or TrommsdorfF effect, an acceleration in rate is observed because the free radical propagation is not terminated while the viscosity of the product increases and the rate of the transfer of the released heat to the outside is severely limited. 

Free radical initiators or active hydrogen compounds such as amines or alcohols are not very effective initiators for the polymerization of lactones. Polyesters of low molecular weight are produced by these techniques. For example, copolymerization of various lactones in the presence of water at 200 °C proceeded via a hydrolysis followed by the polycondensation reaction of the hydroxy acid, giving low molecular weight products [67-69]. Low molecular weight (=10,000) tri-block copolymer (CL-b-EO-b-CL) has been prepared from e-CL and poly(ethylene glycol) (Mn=10 3) by carrying out the polymerization at 165 °C for several hours in the absence of catalysts [70]. 

Interfacial polymerizations rely on reactions of diacid chlorides and active hydrogen compounds. Other examples include production of a polyurethane from a diamine and a bischloroformate ... 

Some of the most familiar reactions falling into the polycondensation class are those leading to polyamides derived from dicarboxylic acids and diamines, polyesters from glycols and dicarboxylic acids, polyurethanes from polyols and polyisocyanates, and polyureas from diamines and diisocyanates. Similar polymer formations utilizing bifunctional acid chlorides with polyols or polyamines also fall into this class. The condensations of aldehydes or ketones with a variety of active hydrogen compounds such as phenols and diamines are in this group. Some of the less familar polycondensation reactions include the formation of polyethers from bifunctional halogen compounds and the sodium salts of bis-phenols, and the addition of bis-thiols to diolefins under certain conditions. 

The effect of the solvent on the kinetics of organic reactions has been studied in detail for the reactions of a host of model compounds, and for some polymerizations. Several generalizations are readily apparent. The most powerful solvents, i.e, those giving the fastest reaction rate, are often those which may be considered to function as mild catalysts themselves. The dipoles in h hly polar solvents such as dimethyl formamide or dimethyl sulphoxide may actually function as weak acids or bases, catalysing the reactions. In contrast, solvents of intermediate polarity may complex the active hydrogen compound to such an extent (at least at low to moderate temperatures) that they shield it from reaction, thus retarding the reaction. Solvents of very low polarity may permit faster reactions in these cases. For example, the reaction between... 

Reaction of 1,3-dienes tith active hydrogen compounds. The catalyst resulting from the combination of nickel bromide and a dialkoxyphenylphosphine effects condensation of 1,3-dienes with active hydrogen compounds to give butenyl and octadienyl adducts.1 Thus the reaction of morpholine (1, 0.05 mole) with butadiene (0.15 mole) in the presence of nickel bromide (1 mmole) and diisopropoxyphenylphosphine (1.1 mmole) at 100° for 30 min. gives a 79% conversion to the adducts (2), (3), (4), and (5). 

Furthermore although there is no definite evidence, the oxidative additions of active hydrogen compounds, such as alcohols, water, hydrogen cyanide, and active methylene compounds, are reasonably predictable from their reactivity. Some reactions involving these compounds can be explained by oxidative addition with splitting of bonds to hydrogen. Several examples of this type are surveyed later. 

The polymerization of ethylene oxide and propylene oxide with various active hydrogen compounds is the primary thrust of the present chapter. However, other epoxy compounds also undergo this type of reaction as is detailed in the chapter Polymerization of Epoxides and Cyclic Ethers of this series [5]. An example of the polycondensation of a complex glycidyl ether with a polyol, taken from the patent literature, is cited here for reference only. 

Active hydrogen compounds such as alcohols, thiols, amides, urethans, and sulfonamides can be alkylated by N-vinyl-amides, -urethans, or -sulfonamides in high yields. A one-step conversion of ar. nitro compounds to isocyanates has been reported Aliphatic isothiocyanates can be prepared from amines and carbon disulfide with dicyclohexylcarbodiimide under remarkably mild conditions... 

Recently, Bayliss et al. [132] described the synthesis of anthracene-9-carbonyl chloride and its aplications as a label for fluorescence and UV absorbance detection of hydroxy compounds. The preparation and properties of esters of short-chain alcohols, diols, trichothecene mycotoxins and sterols were investigated. Anthracene-9-carbonyl chloride was prepared from commercial anthracene-9-carboxylic acid. Derivatization was carried out in acetonitrile free from water or active hydrogen compounds. The reaction rate was dejjendent on the structure of the alcohol. The derivatization of diethylene glycol was complete at ambient temp>erature within 10 min (0.25 M reagent) or 30 min (0.1 M reagent) without a catalyst, but required 1 h for diolesteroL testosterone and the trichothecene T-2 toxin. For sterically hindered alcohols such as t-butanol and 17a-methyl-testosterone, more than 10 h, or refluxing for 1 h, was needed to complete the reaction. The derivatives had absorption maxima at 250 run. Both normal and reversed phase HPLC were applied to the separation of the derivatives. 

Recently Saunders (39) conducted a detailed study of emulsion latices made from methyl ethyl ketoxime-blocked lEM (lEM-MEKO). Compositions investigated were styrene/-butyl acrylate/IEM-MEKO, styrene/butyl aerylate/IEM-MEKO latex formulated with active hydrogen compounds and styrene/butyl acrylate/IEM-MEKO copolymerized with vinyl acids or hydroxy monomers. The effect of urethane catalysts on the deblocking/curing reaction was also studied. 

Condensations in which the active hydrogen compound is a )3-keto ester or a )S-diketone often )deld products that result from one molecule of aldehyde or ketone and two molecules of the active methylene component. For example. 

The hexamethyldisiloxane is separated from other silanized active hydrogen compounds and determined by gas chromatography. 

Propylene oxide is obtained from the ring closure of alkali of 1-chloro-2-propanol or 2-chloro-l-propanol under alkaline conditions. By ring-opening polymerization, polymer is obtained when reacting with active hydrogen compounds like alcohol, fatty... 

A recent patent application disclosed a method for making polyurethanes made from nitrite esters and di/poly-isocyanates with the help of UV-irradiation for use as coatings. The application disclosed polymerizable and curable compositions and processes of polymerizing and curing polyurethanes involving an isocyante compound and a nitrite ester compound. Irradiation of the nitrite ester compound with UV generates an active hydrogen compound by the Barton nitrite photolysis reaction that reacts with an isocyanate compound to produce and/or crosslink a polyurethane. 

Platinum-carbon/sodium hydride Sodium hydride as hydrogen generator Reduction of active hydrogen compounds Sec. alcohols from ketones Replacement of chlorine by hydrogen... 

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