3-z-butyl

To a solution of 0.30 mol of ethyllithium (note 1) in about 270 ml of diethyl ether (see Chapter II, Exp. 1) v/as added 0.30 mol of methoxyallene at -20°C (see Chapter IV, Exp. 4) at a rate such that the temperature could be kept between -15 and -2Q°C. Fifteen minutes later a mixture of 0.27 mol of >z-butyl bromide and 100 ml of pure, dry HMPT ivas added in 5 min with efficient cooling, so that the temperature of the reaction mixture remained below 0°C. The cooling bath was then removed and the temperature was allowed to rise. After 4 h the brown reaction mixture was poured into 200 ml of ice-water. The aqueous layer was extracted twice with diethyl ether. The combined solutions were washed with concentrated ammonium chloride solution (which had been made slightly alkaline by addition of a few millilitres of aqueous ammonia, note 2) and dried over potassium carbonate. After addition of a small amount (2-5 ml) of... 

The introduction of a methyl into the head group at the Cl -position and in particular the R-isomer (237) resulted in 4-fold higher affinity than AEA, while the S- isomer (238) had 2-fold lower affinity than AEA [48, 157], the R-isomer (237) was also resistant to enzymatic hydrolysis [157]. However, introduction of larger alkyl groups into the CT position such as the z-butyl analogue (239) leads to a large drop in activity [155]. Methylation of the C2 position also leads to improved affinity compared to AEA. In particular, the R-isomer (240) has 4-fold enhanced affinity this derivative is also stable to enzymatic hydrolysis by FAAH [48] (see Table 6.20). 

Large macrocyclic phthalocyanines can be obtained from the condensation reactions of 2,5-diamino-l,3,4-thiadiazole <2006SC1801,2006MI837,20010L2153>. Diaminothiadiazole reacts with 5- z/-butyl-l,3-diiminoisoindoline in 2-ethoxy-ethanol at 135 °C for 24 h to give macrocycles 107 and 108 in 54% and 15% yields, respectively <20010L2153>. 

Dinuclear palladium complexes catalyze m-hydroarylation of alkynes with arenes.56 The reaction of 3-hexyne with benzene in the presence of a dinulear palladium complex Pd2R2(M-OH)(//-dpfam) [dpfam = j/V,Ar -bis[2-(diphenyl-phosphino)phenyl]formamidinate, R=/>-Tol] and tri(/z-butyl)borane at 100 °C for 4h affords ( )-3-phenyl-3-hexene quantitatively (Equation (53)). The hydroarylation of 3-hexyne with monosubstituted benzenes ( )-3-aryl-3-hexenes with a 2 1 ratio of the meta- and ra -isomers. This regioselectivity is different from that of the hydroarylation of diphenylacetylene catalyzed by Rh4(GO)12.57... 

A solution of 14.8 g. (0.20 mole) of Z-butyl alcohol in 125 ml. of benzene (Note 1) is placed in a 500-ml. three-necked flask equipped with a stirrer, a thermometer, and an addition funnel, and 26.0 g. (0.40 mole) of sodium cyanate (Note 2) is added. The suspension is stirred as slowly as possible (ca. 120 r.p.m. Note 3) while 48.0 g. (31.2 ml., 0.42 mole) of trifluoroacetic acid is added dropwise at a rapid rate. The temperature slowly rises to about 37° after three-quarters of the trifluoroacetic acid has been added (ca. 7 minutes). At this point (Note 4) the mixture is cooled to 33-35° by brief immersion in an ice-water bath, then the addition is continued. When the addition of the acid is completed (10-12 minutes total time), the temperature slowly... 

Under drastic thermal conditions, the iminosilane-LiF adduct 82 eliminates LiF and the iminosilane intermediate 83 rearranges intramolecularly by C-H bond insertion affording 2,2,4,4-tetra-/i /Z-butyl-l,3-diaza-2,4-disilabicy-clo[3.3.0]octane 84 in 87% yield (Equation 6) <1996JOM203>. 

R = cycZo-CsHg 3 R = cycZo-CeHii 4 R = cycZo-C7Hi3 5 R = norbornyl 6 R = Z-butyl 7 R = Z-octyl... 

Thus, as shown in Scheme 6, sodium hydroxide mediated hydrolysis of 27 and chain extention by activation with A T -carbonyldiimidazole followed by reaction with the magnesium salt of potassium z-butyl malonate and acidification followed by... 

A third route developed by this group started with the commercially available alcohol 32," a compound which has also been the subject of considerable process development due to its use as a common intermediate in the synthesis of several HMGR inhibitors.Conversion of 32 to the 4-halo or 4-nitrobenzenesulfonate 33 followed by displacement with sodium cyanide provided 34 in 90% yield, which is the z-butyl-ester analog of 29. It was noted that this procedure was most scaleable employing the 4-chlorobenzenesulfonate 33a due to the instability of the 4-bromo and 4-nitro-analogs to aqueous hydrolysis. Ra-Ni reduction as before provided the fully elaborated side-chain 35 as the f-butyl ester (Scheme 8). 

C2HBr302, is used as a polymerization catalyst. Tfibromo-Z -butyl alcohol [76-08-1], C4H7Br30, is a modifier in the polymerization of vinyl chloride. 

ASTM standard /z-Butyl D 304-85 Isobutyl D 1719-86. fftf-Butyl D 1007-85 Specification method... 

A mechanism involving an azatropilium cation has been discussed112 as a possibility for the observed ring contraction of 3,6- and 2,5-di-z-butyl-3//-azepines when these compounds are treated successively with bromine and aqueous K2CO3. 

ACETONYLATION O-z-Butyl-O-isopropenyl peroxy carbonate. 3-Chloro-2-(trimethylsilyloxy)-1 -propene. 

The API bumetanide reacts under acidic conditions to the convert the secondary amine into the corresponding primary amine (Fig. 41) (62). The mechanism is analogous to the Hofmann-Martius reaction resulting in the debutylated amine and z-butyl chloride (the chloride presumably comes from HC1) (63). 

This reaction gives two products 21 and 22 but neither contains the /-butyl group. Both contain instead the z-butyl group. The intermediate complex rearranges by hydride shift 19 into the t-butyl cation 20 as the primary cation 17 is too unstable. 

Selective ring opening of benzofuran with lithium, in the presence of a catalytic amount of 4,4 -di( z/-butyl)diphenyl (TDBB), forms the (Z)-dilithiated species 72, which upon addition of a ketone or aldehyde forms 2//-chromenes (Scheme 24) <2001EJ02809>. 

Later, Butler and Hendry294 repeated this work, measuring the rates of bromination of some 2-substituted thiophenes (the same derivatives used by Marino85 plus 2-ethyl, 2-Z-butyl, and 2-phenyl) in 85% aqueous acetic acid and in the presence of lithium bromide. The p value obtained was identical (—10.0), showing that it is not affected at all by passing from anhydrous to aqueous acetic acid. 

In connection with the above characteristic features of metallocene methy-laluminoxane catalysts, it must be emphasised that alternative, potentially cheaper alkylaluminoxanes, such as ethyl or z-butyl derivatives, which are more soluble in aliphatic hydrocarbons than methylaluminoxane, or other alkylaluminium compounds used as activators for metallocene procatalysts, show inferior activity. 

A. t-Butyl S-methylthiolcarbonate. In a 5-1. round-bottomed flask, fitted with mechanical stirrer, reflux condenser, and dropping funnel are placed 430 ml. (422 g., 5.33 moles) of pyridine, 508 ml. (395 g., 5.33 moles) of Z-butyl alcohol, and 1.61. of chloro-... 

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