M-amino-styrene

A major advance was accomplished with the introduction of hydrazine derivatives by Che, in particular, M-amino phthalimide [38]. Although initial work had relied on PhI(OAc)2 as the oxidant, the same group later discovered that a tricomponent system consisting of 2-iodoanisole (49), wCPBA, and the A -amino phthalimide could be employed for an in situ preparation of the required imino-iodane [39]. It is important to note that the final iminoiodane contains a 2-methoxyphenyl substituent, which is in line with the observation from Zhdankin on enhanced solubility of derivatives of the type 42. Under these conditions, a series of styrenes 48 could be submitted to intermolecular aziridination and provided products 50 under mild conditions and in good to excellent yields. 

To prepare the diborane in tetrahydrofuran, add 0.3 M NaBH4 (or LiBH4) and 0.4 M BF3 in total 200 ml tetrahydrofuran and keep dry in refrigerator, or generate the diborane in the reaction flask as follows To a well-stirred suspension of 3.4 g NaBH4 in 150 ml tetrahydrofuran and 0.3M of the styrene or propenylbenzene, add over one hour at room temperature, 15.1 ml BF3 in ether in 20 ml tetrahydrofuran (keep temperature at room temperature) let stand one hour at room temperature and decompose the excess hydride with water then add the NaOH and chloramine (or hydroxyl-amino-O-sulfonic acid) and proceed as above to get the amine. 

A 2-cyclohexenone derivative can be transformed into the corresponding epoxy tosyl-hydrazone by sequential treatment with peracid and tosylhydrazine. The elimination of nitrogen and p-toluenesulfinate and fragmentation after rearrangement to the 3-tosylazo allylic alcohol may occur under mild conditions. Carbonyl compounds with 5,6-triple bonds are formed in high yields (J. Schreiber, 1967 M. Tanabe, 1967). If one applies this reaction to a 9,10-epoxy-1-decalone, a ten-membered 5-cyclodecyn-l-one ring is formed (D. Felix, 1971). This product is an important intermediate in the perfume industry and has been used on a large scale. For this purpose Eschenmoser developed a synthesis in which the readily removed styrene was split off instead of a sulfmic acid. Thus a l-amino-2-phenylaziridine hydrazone was used instead of a tosylhydrazone (D. Felix, 1968). ... 

Nitrate ISEs have been formulated using amino acid betaines with the general formula (CH2=CHCH2)3N+CHRCOOH CT within styrene-butadiene membranes. These have been shown to give a Nernstian response from 10 10 7 M with selectivity over chloride (selectivity coefficient 0.0034), representing a significant improvement on commercial sensors with response times <1 min [23]. 

Some novel water soluble macromonomers, 24, have been synthesized by the oxyanionic polymerization [149] of 2-(dimethylamino)ethyl, 2-(diisopropyl-amino)ethyl, and 2-(JV-morpholino)ethyl methacrylate, and conducted to dispersion copolymerization of styrene in alcohol media [150]. Sufobetaine-based macromonomer was prepared by the polymer reaction of 24 (R=CH3) with propane sultone, and was found to be useful in the dispersion polymerization of styrene even at high electrolyte levels (up to 1 M NaCl). Ito et al. [151] synthesized new PEO macromonomers with a cationic charge at the co-end, 25, and examined the influence of the charge on the particles size in dispersion copolymerization with styrene in alcohol media. 

A significant number of works are concerned with the development of new membranes for the separation of mixtures of aromatic/alicyclic hydrocarbons [10,11,77-109]. For example, the following works can be mentioned. A mixture of cellulose ester and polyphosphonate ester (50 wt%) was used for benzene/cyclohexane separation [113]. High values of the separation factor and flux were achieved (up to 2 kg/m h). In order to achieve better fluxes and separation factors the attention was shifted to the modification of polymers by grafting technique. Grafted membranes were made of polyvinylidene fluoride with 4-vinyl pyridine or acrylic acid by irradiation [83]. 2-Hydroxy-3-(diethyl-amino) propyl methacrylate-styrene copolymer membranes with cyanuric chloride were prepared, which exhibited a superior separation factor /3p= 190 for a feed aromatic component concentration of 20 wt%. Graft copolymer membranes based on 2-hydroxyethyl methylacrylate-methylacrylate with thickness 10 pm were prepared [85]. The membranes yielded a flux of 0.7 kg/m h (for feed with 50 wt% of benzene) and excellent selectivity. Benzene concentration in permeate was about 100 wt%. A membrane based on polyvinyl alcohol and polyallyl amine was prepared [87]. For a feed containing 10 wt% of benzene the blend membrane yielded a flux of 1-3 kg/m h and a separation factor of 62. 

Ersoz M, Vura US, Okdan A, Pehlivan E, and Yildiz S. Transport studies of amino acids through a liquid membrane system containing carboxylated poly (styrene) carrier. J Mem Sci, 1995 104(3) 263-269. 

A soln. of N -cyano-N-(2-cyanoethyl)acetamidine in abs. tetrahydrofuran added dropwise to a vigorously stirred refluxing soln. of Na-N-methylanilide (prepared from Na, N-methylaniline, and monomeric stabilized styrene) in the same solvent, and stirring continued 2 hrs. at room temp. 4-amino-2-methyl-l,6 dihydro-5-pyrimidinecarbonitrile. Y 77%. A. Edenhofer, H. Spiegelberg, and W. E. Ober-hansli, Helv. 58, 1230 (1975) s. a. M.S. Newman et al., J. Org. Chem. 40, 2863 (1975) 4-aminoimidazoles with ethanolic Na-ethoxide (s. Synth. Meth. 18, 819) cf. A. Edenhofer, Helv. 58, 2192 (1975). 

Active esters of N-blocked amino acids bound to poly-4-hydro3g -3-nitro-styrene when stirred for several hours with amino p tide esters in dimethylformamide (D.M. F.) at room temperature give hi yields of blocked peptides. Preferential removal of the a-amino blocking group followed by coupling with pol3rmeric active esters of N-blocked amino acids allows the stepwise synthesis of peptides with predetermined sequence. Bradykinin was synthesized by this technique (Fridkin et al., and Patchornik et al.. 1966) as shown in the scheme. 

UPRs are composed not only of UPs and a crosslinking monomer, usually styrene they contain, moreover, initiators (hardeners), curing promoters (accelerators) and polymerization inhibitors, hi the systems with benzoyl peroxide as the initiator, tertiary aromatic amines, e.g. N,N-dimethylaniline or Ar,M-dimethyl-p-toluidine, are applied as the promoters. Some amino-glycols were built into the UP molecules, thus increasing the reactivity [170]. The best results were achieved when using 3,6-diaza-3,6-diphenyloctane-l,8-diol (Scheme 25) ... 

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