T-Amyl chloride

The specific rates of hydrolysis of five organic halides in three water-based liquid mixtures near their respective equilibrium consolute points have been observed to be suppressed. The systems studied included t-amyl chloride in isobutyric acid water (upper consolute temperature), and 3-chloro-3-methylpentane in 2-butoxyethanol water (lower consolute temperature). The slowing effect occurred within a few tenths of a degree on either side of the consolute temperature. 

The interaction of (10) with vinylmagnesiiim chloride yields, after hydrolysis of the ketal group, 46% of the 3a-vinyl-l7-ketone (11b) and 7% of the 3j5-vinyl-17-ketone (12b). Ethynylation of (10) with potassium acetylide in dimethylformamide or with acetylene and potassium t-amyloxide in t-amyl alcohol-ether gives only the 3a-ethynyl derivative (11c) in 63% and 74% yields, respectively. ... 

Complexes of other metals are also capable of catalyzing useful carbonylation reactions under phase transfer conditions. For example, certain palladium(o) catalysts, like Co2(C0)g, can catalyze the carbonylation of benzylic halides to carboxylic acids. When applied to vinylic dibromides, unsaturated diacids or diynes were obtained, using Pd(diphos)2[diphos l,2-bis(diphenylphosphino)ethane] as the metal catalyst, benzyltriethylammonium chloride as the phase transfer agent, and t-amyl alcohol or benzene as the organic phase(18),... 

Tertiary alkyl halides undergo a series of reactions when treated with hydrogen fluoride. f-Amyl chloride by means of reactions catalyzed by hydrogen fluoride yielded a series of teritary chlorides including f-butyl chloride (Simons et al., 35). t-Butyl chloride gives the same series of... 

The 3-acylbenzo[6]thiophenes, separated from the mixture obtained on acylation of benzo[6]thiophene (Section 3.14.2.4), are readily reduced to 3-alkylbenzo[6]thiophenes. 3-Benzo[6 ]thienyllithium can be prepared from 3-bromobenzo[6]thiophene at -70 °C (68JCS2733) and this may serve as a source of 3-acylbenzo[Z>]thiophenes. In certain instances, Friedel-Crafts alkylation gives the 3-substituted benzo[6]thiophenes nearly exclusively. For example, 3-t-amylbenzo[6]thiophene was the exclusive product of alkylation of benzo[6 Jthiophene with t-amyl alcohol in the presence of tin(IV) chloride <70AHC(11)177). 

Electron withdrawing groups on the alkene considerably retard the epoxidation. For example, acrylic esters and acrylonitrile are not reactive, while allyl chloride is about one tenth as reactive as propylene towards TBHP/MoVI.240 The epoxidation of alkenes is completely stereoselective eri-alkenes are exclusively transformed into ds-epoxides and (runs-alkenes into trans-epoxides. Oxygen addition to the double bond preferentially occurs from the less shielded face of the substrate, e.g. in the selective epoxidation of terpenes by r-pentyl hydroperoxide (t-amyl hydroperoxide, TAHP) (equations 67 and 68).225... 

Sodium borohydride-Palladium chloride. Sodium borohydride-Rhodium(lII) chloride. Sodium borohydride-Tin(II) chloride. Sodium cyanoborohydride. Sodium 9-cyano-9-hydrido-9-borabicyclo[3.3.1]nonane. Sodium dithionite. Sodium hydride-Sodium t-amyl oxide-Zinc chloride. Sodium trimethoxyborohydride. Tetra-/i-butylammonium borohydride. Tetra-n-butylammonium cyanoborohydride. Tetra-n-butylammonium octahydrotriborate. Tri-n-butyltin hydride. Triethoxy silane. Triisobutylaluminum-Bis(N-methyl-salicyclaldimine)nickel. Zinc borohydride. REDUCTIVE CYCLIZATION Cobaloximc(I). 

Amination. The conversion of aryl chlorides to amines is catalyzed by Ni(OAc)2-2,2-bipyridine and sodium t-amylate/NaOH in THF. 

Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride 2,2 -Azobis (2-methylpropane) 2,2 -Azobis (2-methylpropionamide) dihydrate 2,2 -Azobis [N-(2-propenyl)-2-methylpropionamide] 2,2 -Azobis [2-(3,4,5,6-tetrahydropyrimidin-2-yI) propane] dihydrochloride 2,2 -Azobis (2,4,4-trimethylpentane) n-Butyl-4,4-bis (t-butylperoxy) valerate t-Butyl hydroperoxide t-Butyl peroxycrotonate t-Butyl peroxyneoheptanoate Cerium Cumene hydroperoxide Cumyl peroxyneodecanoate o-Cumylperoxyneoheptanoate 1 -[(1 -Cyano-1 -methylethyl) azo] formamide Decanoyl chloride Decanoyl peroxide Di-t-amyl peroxide 2,2-Di (t-butylperoxy) butane Dicetyl peroxydicarbonate Dicyclohexyl peroxydicarbonate Dimethyl 2,2 -azobis (2-methylpropionate) 2,5-Dimethyl-2,5-di (benzoylperoxy) hexane 2,5-Dimethylhexane-2,5-dihydro peroxide Dimyristyl peroxydicarbonate Di-n-propyl peroxydicarbonate Ethyidibutylperoxybutyrate 3,3,6,6,9,9-Hexamethyl 1,2,4,5-tetraoxa cyclononane Lauroyl chloride Pelargonyl peroxide, 2-Phenylazo-4-methoxy-2,4-dimethylvaleronitrile Phosphine Potassium persulfate Sodium persulfate Succinic acid peroxide... 

N-lsopropyl-N -phenyl-p-phenylenediamine I-Limonene Methylal Salicylic acid Sorbitol 1,3,5-Trihydroxybenzene resin mfg., alkyd Linseed acid resin mfg., artificial Benzyl chloride Maleic acid resin mfg., epoxy ester Linseed acid resin mfg., food-contact 2,6-Xylenol resin mfg., oil-soluble p-t-Amyl phenol... 

Further studies of complex reducing agents based on sodium hydride have shown that a mixture of sodium hydride, sodium t-amylate, and zinc chloride (ZnCRA) gives regioselective 1,2-reduction of a, 8-enones to allylic alcohols, in contrast to the 1,4-reduction preference shown by the earlier developed NiCRA (3,135). The activity is enhanced by the addition of MgBr2. 

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