Amination, butane diol

For highly polar polymers, Hs < —Hw, and the equilibrium concentration is a decreasing function of temperature. This is often found in the most hydrophilic networks, based, for example, on the aromatic amine -aliphatic diepoxide of diglycidyl ether of butane diol (DGEBD) type (Tcharkhtchi et al., 2000), or on particular polyimides (Hilaire and Verdu, 1993). 

The vapor phase reaction of butane diol with methyl amine at 300°C in the presence of a Cr-ZSM-5 catalyst gave a 65% yield of N-methyl pyrrolidine, 42 (Eqn. 22.41). Tetrahydrofuran was also converted to 42 in 98% yield under these conditions. 5... 

Waterborne polyurethane resins are produced from maleinised monoglyceride (MMG) of sunflower oil, hydroxy-terminated polybutadiene, toluene diisocyanate and ethylene diamine. The carboxylic acid groups of MMG are neutralised by triethyl amine, making the resin water dispersible. The monoalkylated castor oil (MCO) or dehydrated castor oil (DCO) is treated with a polyether glycol at 120°C, followed by the addition of IPDI and DBTDL. To obtain a series of aqueous polyurethanes, butane diol and dimethylol propionic acids (DMPA) are added and the mixture heated to 70°C for two hours to produce a NCO-terminated pre-polymer which forms salt with triethylamine, giving a water-soluble polymer. The reaction mixture is dispersed in water and a chain extender, ethylene diamine, is added. Two aqueous polyurethanes, MCPU and DCPU, are finally obtained from MCO and DCO, respectively. 

Table 10.6 Comparison of some stoichiometric, fully cured epoxide-amine networks Tg, glass transition temperature [Ar], aromatic group concentration F, flex parameter (see text) n, crosslink density and [OH], hydroxyl concentration. Note DGEBD = diglycidyl ether of butane diol DGEBA = diglycidyl ether of bisphenol A (i = degree of polymerization) and TGAP = triglycidyl derivative of p-aminophenol ...

The second option involves the incorporation of either chiral amines or chiral alcohols into the heteroatom-carbene side chain (R ), which represents the most versatile approach to diastereoselective benzannulation. The optically pure (2R,3R)-butane-2,3-diol was used to tether the biscarbene complex 37. The double intramolecular benzannulation reaction with diphenylbutadiyne allowed introduction of an additional stereogenic element in terms of an axis... 

When either an alcohol or an amine function is present in the alkene, the possibility for lactone or lactam formation exists. Cobalt or rhodium catalysts convert 2,2-dimethyl-3-buten-l-ol to 2,3,3-trimethyl- y-butyrolactone, with minor amounts of the 8-lactone being formed (equation 51).2 In this case, isomerization of the double bond is not possible. The reaction of allyl alcohols catalyzed by cobalt or rhodium is carried out under reaction conditions that are severe, so isomerization to propanal occurs rapidly. Running the reaction in acetonitrile provides a 60% yield of lactone, while a rhodium carbonyl catalyst in the presence of an amine gives butane-1,4-diol in 60-70% (equation 52).8 A mild method of converting allyl and homoallyl alcohols to lactones utilizes the palladium chloride/copper chloride catalyst system (Table 6).79,82 83... 

Ritter et al. [147-155] have been studying side chain poiyrotaxanes. They synthesized side chain poiyrotaxanes by amide coupling of polymer-carrying carboxylic acid moieties with various semirotaxanes of methylated /l-CD(s) and an axle bearing an amine group at one end [147-154]. These works have been reviewed in an excellent review by Raymo and Stoddard [78]. Ritter et al. [155] reported recently a new type of side chain polyrotaxane. They polymerized inclusion complexes of di(meth)acrylates of butan-l,4-diol and hexan-l,6-diol with a-CD and with methylated /1-CD using a redox initiator system in aqueous media, and characterized the polyrotaxane structure by IR and glass-transition temperature measurements. 

A second type of derivative of phosphorus-containing aldehydes and ketones was prepared from a Mannich-type condensation of a phosphorus-containing carbonyl compound, such as 3-(diethyl phosphono)butanal with diethyl phosphonate and diethanol amine, to form a phosphorus-rich diol, l-((diethyl)phosphono]-l-CN,N-di(hyroxyethyl)amino]-3-C(diethyl)phosphono] butane as shown In Eq. 2 of Fig. 2. Examples of the preparation of such diols are shown as Ex 3 and 4 of Table 3. 

BUTANE-l,2-DIOL (584-03-2) C4H10O2 CH3CHjCH(0H)CH20H Combustible liquid (flash point 194°F/90°C Fire Rating 2). Incompatible with strong oxidizers, strong acids, caustics, aliphatic amines, isocyanates. On small fires, use dry chemical powder (such as Purple-K-Powder), alcohol-resistant foam, water spray, or COj extinguishers. 

BUTANE-1,2-DIOL (584-03-2) Combustible liquid (flash point 194°F/90°C). Incompatible with strong oxidizers, strong acids, caustics, aliphatic amines, isocyanates. 

Synthetic routes are usually quite complex. For example, the manufacture of N-methyl-2-pyrrolidone involves the reaction of acetylene with formaldehyde. The resulting but-2-ine-1,4-diol is hydrated to butane-1,4-diol and then dehydrated to Y-butyrolactone then reacted with monomethyl amine to give the final product. Strict process control is essential to obtain very high purity. 

Polyurethanes (PUs), one of the most commonly used polymers for various blood-contacting biomedical applications, are generally prepared by the polycondensation reactions of diisocyanates with diols or amines [35, 36]. Reactions of diisocyanates with diols result in the formation of urethane linkages while diisocyanates reactions with amines result in urea linkages. Both aliphatic, as well as aromatic diisocyanate monomers, are commonly used for preparing polyurethane biomaterials. Examples include 1,4-butane diisocyanate (BDI), 1,6-hexamethylene diisocyanate (HDI), 4,4-dicyclohexylmethane diisocyanate (HMDI), and 4,4-diphenylmethane diisocyanate (MDl) [37]. Commonly used diols (or termed as polyols) for preparing polyurethanes includes poly ethers, polycaprolactone, and polyesters with molecular weights up to 5000 Da. 

Condensation of 2-acetylthiophen with glyoxylic acid in the presence of a secondary amine gave compounds of the type (164a). Products from the reductive electrochemical dimerization of 2-acetyIthiophens, such as 2,3-di-(2-thienyl)butane-2,3-diol, have been isolated and identified. ... 

---