Tetramethylene diamine

From DMT and 1,4-tetramethylene diamine, a dimethylesterdiamide unit (T4T-dimethyl) is prepared as described above for T6T-dimethyl (Example 22a). The T4T-dimethyl has a Tm of265° C and a AHm of 152 J/g. 

The clear mixture was cooled to 0 °C, and freshly distilled tetramethylene diamine (1 mL) was added. The system was stirred for 10 minutes after the addition. 

To illustrate the transitions occurring in the glassy state, the temperature dependencies of the dynamic mechanical loss tangent at 1 Hz of the DGEBA/HMDA, DGEBA/tetramethylene diamine and DEBA/dodecamethyl-ene diamine systems [65] are shown in Fig. 93. They clearly exhibit two transitions ... 

Fig. 93 Loss tangent versus temperature for DGEBA/HMDA (circles with bottom side black), DGEBA/tetramethylene diamine (circles with right side black) and DGEBA/dodeca-methylene diamine ( ) systems (from [65])...

FIGURE 5.27 Bidentate diamine ligands (a) trimethylenediamine(tm) (b) tetramethylene-diamine(tmd) (c) tra i-l,2-cyclopentanediarnine(cptm) (d) 2,4-pentanediamine(ptm). 

Reaction of (69) with the tetramethylene diamine at temperatures below 50 °C affords the azepinopyridine derivative (70). A complex reaction mechanism has been proposed, involving the intermediate formation of the pyridone (71), which undergoes a Smiles type rearrangement to give the final product <95J1IC477>. 

Polyacrylamide gels are prepared by copolymerisation of acrylamide monomer (CH2=CHCO NH2) with a cross linking agent, usually N, N-methylene bisacrylamide, CH2(NHCOCH = CH2)2, in the presence of a catalyst accelerator-chain initiator mixture. This mixture may consist of freshly prepared ammonium persulphate as catalyst (0.1 to 0.3% w/v) together with about the same concentration of a suitable base, for example, dimethylamino propionitrile (DMAP) or N, N, N, N tetramethylene diamine (TEMED) as initiator. TEMED is most frequently used and proportional increases in its concentration speed up the rate of gel polymerisation. Photochemical polymerisation may be brought about by riboflavin in the presence of UV radiation. Gelation is due to vinyl polymerisation as shown below ... 

Proceeding from the above considerations it should be assumed that trans-piperylene behaves in polymerization according to the curve for the s-cis-conformation in Fig. 4, whereas the behavior of eis-piperylene corresponds to the curve of the s-frans-conformation. The available literature data reviewed in detail in Ref. [67] (see also Refs. [49, 68]) confirm this assumption. Moreover, this assumption is in an agreement with the fact that in isoprene polymerization the monomer form complexed with tetramethylene diamine is less reactive than the non-solvated form [69]. 

Polyamines are low-molecular-weight molecules which are found in both prokaryotes and eukaryotes, and which fulfil essential needs for growth, division and differentiation. The most common poly amines are putrescine (1,4-diaminobutane tetramethylene-diamine), spermidine (N-(3-aminopropyl)-l,4-butane diamine) and spermine (N,N -bis(3-aminopropyl)-1,4-butane diamine). Cadaverine (1,5-diaminopentane) is also found in some micro-organisms (1,2). Most prokaryotes do not contain spermine but all cells contain putrescine and spermidine, in most cases in millimolar concentrations. 

Primary aliphatic diamines are very important intermediates in polymer industry. Tetramethylene diamine is a monomer for polyamide 4,6. Hexame-thylene diamine is used in two main industrial productions. Copolymerisation with adipic add gives rise to nylon 6,6. Reaction with phosgene leads to isocyanates which are monomers for painting industry. Methylpenta-methylene diamine is a monomer for thermoplastics (DU PONT s DYTEK). 

Tetramethylene Diamine, NH2(CH2)4NH2, usually called putrescine, is formed in the decay of animal matter. It melts at 27°-28°, and boils at 158°. 

Yet, omithin can also be decomposed in another manner and thus give putrescin or tetramethylene-diamine ... 

Tetramethylene diamine Diethyl oxalate Tetramethylene diamine Adipic acid... 

Tetramethylene diamine Isophthalic acid Hexamethylene diamine Isophthalic acid Hexamethylene diamine Terephthalic acid Bis(4-aminophenyl)methane Dodecanedioic acid... 

Tetramethylene diamine and diethyl oxalate were prepol5onerized in a 50/50 phenol/trichlorobenzene mixture at 140°C. The prepolymer, after purification, was subjected to solid-phase polymerization under nitrogen at 250 300°C to form poly(tetramethylene oxalamide) or nylon-4,2 [78], The polymer exhibited rjuih as high as 2.7 dl/g as measured from a 0.5% solution of polymer in 96% sulfuric acid. Interestingly, the polymer was soluble in trifluoroacetic acid, dichloroacetic acid, and 96% sulfuric acid, but not in 90% formic acid. It had a melt temperature of 388-392°C and heat of fusion of 148-154 J/g (35-37 cal/g). 

Poly(tetramethylene adipamide) or nylon-4,6 is prepared from tetramethylene diamine and adipic acid by polymerization in an organic solvent or by melt polymerization followed by solid-state polymerization [79,80]. The polymer melts at 295°C, about 30°C above nylon-6,6. It is more sensitive to degradation and branching. The volatility of tetramethylene diamine also makes it difficult to control the balance of end groups during polymerization. Excess diamine is added to compensate the losses. Values of M as high as 32,900 have been reported. 

A dual initiator was employed by Cramail etal to synthesize block copolymer of St and chloroethyl vinyl ether (CEVE) via anionic-to-cationic transformation. The anionic living polymerization of St was initiated by lithiopropionaldehyde diethyl acetal in the presence of tetramethylene diamine. The resulted polymer with acetal functionality was converted into the corresponding a-iodo-ether with trimethylsilyl iodide (TMSI),... 

The polymer has good heat stability and the strength is unaffected by heating up to 185°C for 5 h. The polyamide melts at 370°C. When hexamethylene diamine is replaced with tetramethylene diamine, the melting point rises to 430°C. The condensation product from isophthalic acid and tetramethylene diamine melts at 250°C. 

Figure 1 The polymerization reaction of acrylamide. The structure of acrylamide, A/,A/ -methylenebisacrylamide (Bis) and of a representative segment of cross-linked polyacrylamide are shown. Initiators, designated by /, shown are peroxidisulfate, riboflavin, and A/,A/,A/, A/ -tetramethylene diamine (TEMED). Light is designated as hv. (Reprinted with permission from Chrambach A and Rodbard D (1971) The polymerization reaction of acrylamide. Science 172 440-451.)...

Reaction of trimeric chloride with tetramethylene diamine gives (7.373a) while reaction with spermine produces the double spiran (7.373b) [28,29]. 

The second method is based on the formation of carbanions on the carrier and there are three reaction steps. The initial step is the reaction of 5-butyllithium with cis-1,4-polybutadiene in dry cyclohexane. The presence of tetramethylene diamine (TMDA) favors the formation of carbanions in allyl positions of the polymer matrix. The second step is the exchange between Ti(OBu)4 and the polymer lithiated compound with the formation of Ti—C bonds in the polymer backbone. Ti(IV) atoms bound to the polymer are reduced to Ti(III). Acetylene is then polymerized to produce a dark blue copolymer with a conductivity of 1.4 x 10 S/cm on doping by Ij. 

Polymers were obtained by radical copolymerization in aqueous media of acrylamide and the corresponding ionic acrylic comonomers (AMPS or MSA). By using a redox system (potassium persulfate, N,iV,iV, j V, tetramethylene diamine) the polymerization can be performed at a temperature lower than 35° [17-18] which avoids branching the latter may occur at a reaction temperature higher than 60°. Polymers are recovered from the reaction medium by precipitation in ethanol. 

Putreacine, H2N.CHg.CH2.CH2.CH2.1 2> tetramethylene diamine, is derived from the diamino acid ornithine, by decarboxylation. 

Synthesis of (—)-0-methyl metazocine (39). To a cooled solution (—78 °C) of amine 37 (40 mg, 0.16 mmol) in THF (1 mL) was added diisopropyl amine (0.005 mL, 0.03 mmol), tetramethylene-diamine (0.010 mL, 0.066 mmol), and -BuLi (0.026 mL, 1.3 M in hexane). The reaction mixture was warmed to room temperature and stirred for 8 hours in an argon atmosphere. The solution was quenched with water, dried over Na2S04, and concentrated under vacuum. Flash column chromatography (5-10% MeOH in CH2CI2) provided 39 mg (98%) of the product 39. [a]D = —76.4 (c=1.3,EtOH). 

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