Tert-Butyl cyanide

Trimethylacetic acid may be made by the hydrolysis of tert-butyl cyanide with weak hydrochloric acid at ioo0.1 It is also obtained by oxidation of trimethylpyroracemic acid with silver oxide or potassium dichromate and sulfuric acid,2 by oxidation of tertf-butylethylene with permanganate solution,3 or by oxidation of dimethyl 2,2-propanol with chromic acid.4 Schroeter reports the formation of trimethylacetic acid by rearrangement of the oxime of trimethylacetophenone to give the anilide of trimethylacetic acid, which can be hydrolyzed to give the acid.5... 

Kinetically stabilized azetes also show a high tendency for cycloaddition with a variety of other reagents. Cycloaddition of 96 with singlet oxygen produced an isolable dioxetan adduct 97, which decomposes at 25"C into tert-butyl cyanide and a 1,2-dione. 

Bromo-l-propanamine hydrobro- tert-Butyl cyanide 4275 Calcium catbimide 1696... 

The reaction of tert butyl chloride with cyanide ion proceeds by elimination rather than substitu tion... 

An efficient stereoselective Strecker synthesis of phenylglycine has been achieved using the tert-butyl ester tm-leucine as the chiral auxiliary. Its benzaldimine reacts with hydrogen cyanide in hexane at — 23 °C to furnish the ( )-diastereomer with the excellent diastereoselectivity of >98 254. 

The silver cyanide-catalyzed reaction of difunctional nucleophiles with tert-butyl isocyanide has been described in earlier sections on azoles (see Scheme 105 in Section IV,D,6). An example of the use of this simple approach... 

Reported are extremely violent to expl reactions when vinyl cyanide is in contact with acids, bases, bromine, polymerization initiators (such as azoisobutyronitrile, dibenzoyl peroxide or di-tert-butyl peroxide),... 

H. Berger (Koninklijke/Shell Laboratorium, Amsterdam) Concerning the effect of cyanides on metal catalysis (deactivation and formation of oxygenated products), what are your arguments against the explanation that the metal ion becomes completely inactive, while the products arise from a mechanism analogous to that proposed by Berger [Rec. Trav. Chim. 82, 733 (1963)] for the oxidation in tert-butyl alcohol with excess mercaptan relative to base, Did you check that no hydrolysis of disulfide occurs in the presence of cyanide ... 

Cis 4-formyl-(3-lactams like 183, Scheme 56, overcome a ring expansion to the corresponding y-lactams 184 when treated with tert-butyl dimethylsilyl cyanide and 10 mol% iodine at room temperature [140, 141]. The parent trans (3-lactams remain unchanged under the same conditions. A mechanism has been postulated that implies cationic intermediates in which iodine acts as a Lewis acid. 

A novel asymmetric synthesis of a-amino acids via electrophilic amination has been demonstrated by Zheng and Armstrong and co-workers.94 No +NHBoc was observed when lithium tert-butyl-A-tosyloxycarbamate (LiBTOC) was reacted with zinc and lithium enolates of 48. Transmetallation of the lithium enolate with copper cyanide was necessary to generate a reactive amide cuprate, which then added efficiently to the electrophile. The electrophilic amination of chiral cuprates with LiBTOC provided an expedient approach to a-amino acids with predictable absolute configuration in high enantiomeric purity and good yield (Scheme 24.23). 

We present at the end of this section, several isolated examples of trinuclear cyanide-bridged complexes that do not fall within the two major classes of compounds. The first group of such complexes is based on a triangular cluster core. For example, Evans et al., (127) obtained [(Cp )2Sm CNR)( j,-CN)]3 (R = hexyl, tert-butyl) [Fig. 19(a)] from a reductive cleavage of the isocyanide CNR ligand by Cp 2Sm (thf)2. Moreover, the same group later demonstrated the preparation of such trinuclear complexes by isocyanide cleavage with Cp 3Sm ... 

Selenium dioxide oxidations may be accomplished by heating with neat substrates [5f9], but more often, they are carried out in solvents such as water, tert-butyl alcohol, ethanol, dioxane, acetic acid, and acetic anhydride. The solvent used often affects the outcome of the reaction. The use of acetic acid or acetic anhydride favors oxidation to acetates (and thence to alcohols), whereas in water or dioxane, carbonyl compounds are usually formed. An unpleasant feature of oxidations with selenium dioxide is the formation of red colloidal selenium, which cannot always be separated by distillation but can be removed by treatment of the product with potassium cyanide [522], mercury [523], or deactivated Raney nickel [524]. 

This reaction has been extended to a considerable number of monophenylcyclopropanes with low oxidation potentials < 1.4 V), other electron acceptors and nucleophiles (water, cyanide, ethanol, isopropyl alcohol, tert-butyl alcohol). anti-Markovnikov products analogous to 6 are generally formed as the main product however, frequently in moderate to low isolated yields.The nucleophilic substitution step [e.g. 4(4-) - 7] occurs for all mentioned nucleophiles with > 99% inversion of configuration at carbon and the rate is remarkably insensitive... 

Butyl chlorocartxxiate 1077-8 Butyl cyanide (n) 6405 But cyanide (tert) 6246... 

The chlorine groups in 4-chloro-1,10-phenanthroline and 4,7-dichloro-1,10-phenanthroline are replaced by cyano groups on fusion with potassium cyanide while 2-cyano- and 5-cyano-1,10-phenanthrolines have been obtained from 2-chloro and 5-bromo-1,10-phenanthrolines, respectively, by reaction with cuprous cyanide. 2-Chloro-1,10-phenanthroline (69) reacts with the sodium salt of tert-butyl cyanoacetate to give the intermediate 105, which with cold hydrochloric acid affords 2-cyanomethyl-1,10-phenanthroline (106). 2-Chloro-1,10-phenanthroline also participates in the Ullmann reaction to afford 2,2 -bi-( 1,10-phenanthroline) (107). 5,5 -Bi-(l,10-phenanthroline) was also prepared, but by a different route starting from 8,8 -diamino-6,6 -biquinoline. 

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