Bromobutyl

Bromobutyl Rubber Compounding and Applications, Exxon Chemical Co. 

Halobutyls. Chloro- and bromobutyls are commercially the most important butyl mbber derivatives. The halogenation reaction is carried out in hydrocarbon solution using elemental chlorine or bromine (equimolar ratio with enchained isoprene). The halogenation is fast, and proceeds mainly by an ionic mechanism. The stmctures that may form include the following ... 

Halobutyl Cures. Halogenated butyls cure faster in sulfur-accelerator systems than butyl bromobutyl is generally faster than chlorobutyl. Zinc oxide-based cure systems result in C—C bonds formed by alkylation through dehydrohalogenation of the halobutyl to form a zinc chloride catalyst (94,95). Cure rate is increased by stearic acid, but there is a competitive reaction of substitution at the halogen site. Because of this, stearic acid can reduce the overall state of cure (number of cross-links). Water is a strong retarder because it forms complexes with the reactive intermediates. Amine cure may be represented as follows ... 

Whereas polyisobutylene and butyl mbber exhibit chain cleavage on free-radical attack, halobutyls, particulady bromobutyl and CDB, are capable of being cross-linked with organic peroxides. The best cure rate and optimal properties are achieved using a suitable co-agent, such as y -phenjiene bismaleimide. This cure is used where high temperature and steam resistance is required. 

The intramolecular cyclization of l-(4-bromobutyl)-3-methoxycarbonyl-l,4,5, 6-tetrahydropyridine (140) and l-(3-bromopropyl)-3-methoxycarbonyl-l,4,5,6-tetrahydropyridine (143) (89T5269) resulted in the synthesis of quinolizidine ring system 141 and indolizidine ring system 144 in 43% and 72% yields along with the reduced tetrahydropyridines 142 and 145 in 21% and 8% yields, respectively. All the cyclized products appeared to be (ran.s-fused indolizidines or quinolizidines. The (ran.s -fused simple indolizidines are known to be some 2.4 kcal mol more stable than the d.s-fused isomers (68TL6191). In the and-isomer the methoxycarbonyl substituent occupies an equatorial position. 

The synthetic utility of radical cyclization was used as the key step in a four-step synthesis of the natural product (d,0-epilupinine (134b, a quinolizidine alkaloid) (75CB1043) from methyl nicotinate (146). Thus, l-(4-bromobutyl)-3-methoxycarbonyl-l,4,5,6-tetrahydropyridine (140), obtained from methyl nicotinate (146), was cyclized to 141 (43%), which on reduction with LiAlH4 in THF provided 134b in 95% yield (89T5269). 

Perhydropyrido[l,2-a]pyrimidin-2-one was A -alkylated with 1,4-dibro-mobutane to yield a 1-(4-bromobutyl) derivative (94MIP6). 6-Methyl-4-oxo-4/f-],6,7,8,9,9a-hexahydro-4//-pyrido[],2-a]pyrimidine-3-carboxylate 138 was alkylated with alkyl chlorides 139 to give 1-substituted derivatives 140 (97MIP2). 

Phthalimidobutyl)-2,3,4,4u,5,6-hexahydro-l//-pyrazino[l,2-u]quino-line was obtained in the reaction of 2,3,4,4u,5,6-hexahydro-l//-pyrazino[l,2-u]quinoline and A-(4-bromobutyl)phthalimide in boiling MeCN in the presence of K2CO3 (97MIP12). 2,3,4,4u,6,7-He-xahydro-l//-pyrazino[l,2-ujquinolines were N-alkylated with 3-dimethylaminomethyl-l//-pyrrolo[2,3-6]pyridine and a mixture of l//-pyrrolo[2,3-6]pyridine and 37% aqueous H2CO in aqueous AcOH in the presence of NaOAc (96USP5576319). 3-[3-Substituted 2-propen-l-yl]-2,3,4,4u, 5,6-hexahydro-l//-pyrazino[l,2-u]qui-... 

In a particular application involving a typical O type mount, the nitrile rubber (NR) compound causes a resonance frequency of 28 Hz, whereas resonance was previously tolerable only well below 20 Hz. In this case, a blend of NR and bromobutyl rubber is more suitable. A comparison is shown in Table 3. 

Similarly, in the case of a cup type mount, an initial attempt to restrict resonance amplification featured the use of white factice in a NR formulation. However, the successful formulation was a blend of predominantly bromobutyl with NR, as shown in Table 6. 

Figure 5 Dependence of particle size of dispersed bromobutyl rubber on the DMAE concentration. Source Ref. 53.

Bromide appears to be useful in this regard. Table II summarizes our homopolymerization experiments on (2-bromoethyl)oxirane, (3-bromopropyl)oxirane and (4-bromobutyl)oxirane (3a-c) (10-12). 

The bromine atom of 4-aryl-2-(4-bromobutyl)-2,3,5,6,7,8-hexahydro-177- ancj -perhydropyrido[l,2-c]pyrimidine-l,3-diones was displaced with 4-substituted piperazines <2002FES959, 2004APH139, 2004PHA99>. Heating 3-hydroxymethyl derivatives of epimeric 6-methyl-l,3,4,6,7,llb-hexahydro-277-pyrimido[6,l-,2]isoquinolin-2-ones 152 resulted in the formation of the 3-unsubstituted derivatives 153 by loss of CH20 (Equation 26) <1997LA1165>. 

Butyl rubber is not compatible with natural rubber, SBR, nitrile rubber or with any other elastomer having an appreciable degree of unsaturation modified butyls (chlorobutyl and bromobutyl) are compatible with such elastomers and used as liners in tubeless tyres to improve air retention. 

Chlorobutyl (CIIR) and bromobutyl (BIIR) are modified types containing 1.2% wt of chlorine or bromine, the isoprene unit being the site of halogenation. Introduction of the halogen gives greater cure flexibility, and enhanced cure compatibility in blends with other diene rubbers. It also confers increased adhesion to other rubbers and metals. 

Resin cures utilise the same resins that are used for butyl rubber, but more resin (ca. 10-12 phr) and a halogen donor (10 phr), typically bromobutyl, or polychloroprene, are required. Although heat stability is slightly improved by resin curing when compared to sulphur cures, the effect is not as marked as in the resin curing of butyl. 

Narrowly distributed Pl-ft-PS-i-PI triblock copolymer chains with both of their ends capped with bromobutyl groups were prepared by sequential addition of living anionic polymerization and terminated by excess of 1,4-dibromobutane (PS block Mw = 3.5 x 103 g/mol PI blocks Mw = 3.1 x 103 g/mol Mw/Mn = 1.12 The degree of end-functionalization was 92% characterized by HNMR). Figure 6 shows the SEC profile of such prepared triblock copolymer chains. The small but a detectable amount ( 5%) of Pl-i-PS-i-PI dimers, PI-Z>-PS-Z>-PI-c-PI-Z>-PS-Z>-PI, is presumably formed via the Wurtz-type coupling reaction. 

Halobutyl Bromobutyl Bromoiso- butene- isoprene BIIR Polyhalo- genated(iso butylene- co-isoprene) CA 0.93 40-90 20 850 200... 

However, in many cases the structure of the drug does not match the structure of the reactive groups on the polymeric carrier. In this case, the structure of at least one reactant has to be modified before conjugation. Derivatives of 5-fluorouracil, namely l-(3-bromopropionyl)-5-fluorouracil, 1-chlorocarbonyl-5-fluorouracil, and l-(4-bromobutyl)-5-fluorouracil were synthesized to permit the drug attachment to poly(L-cysteine) [146] (Fig. 6). 

To this category belong homopolymers of polyisobutylene, copolymers of isobutylene and isoprene (butyl rubber), chlorobutyl, and bromobutyl. All these have been produced commercially for decades. 

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