Alloc group amines

Allylamines are difficult to cleave with Pd catalysts. Therefore, amines are protected as carbamates, but not as allylamines. Also, allyl ethers used for the protection of alcohols cannot be cleaved smoothly, hence alcohols are protected as carbonates. In other words, amines and alcohols are protected by an allyloxycarbonyl (AOC or Alloc) group. 

Pd(Ph3P)4, RS02Na, CH2CI2 or THF/MeOH, 70-99% yield. These conditions were shown to be superior to the use of sodium 2-ethylhexanoate. Methallyl, allyl, crotyl, and cinnamyl ethers, the Alloc group, and allyl-amines are all efficiently cleaved by this method. ... 

Pd(Ph3P)4 and Bu3SnH convert the Alloc group to other amine derivatives when electrophiles such as (B0C)20, AcCl, TsCl, or succinic anhydride are added. Hydrolysis of the stannyl carbamate with acetic acid gives the free amine. 

Alloc-protected amines to directly convert them to new amine derivatives. Albericio and Barany have also used a mixture of DMSO, THF, 0.1 N HCl, and A-methyhnorpholine (2 2 1 0.1) to deprotect Alloc from resin-bound peptides that also contain base-sensitive Fmoc groups.f i ... 

The conversion of the BOC group to other carbamates is achieved by heating the alcohol, Ti(0-/-Pr)4 in toluene. Teoc-, Cbz-, and Alloc-pro-tected primary amines have been prepared in this fashion. The reaction is selective for a primary BOC derivative. ... 

In the Colour Index both conventional sulphur dyes and their leuco counterparts are allocated the same Cl constitution number a different number is given to the related solubilised version. Thus, for example, Cl Sulphur Black 1 and Cl Leuco Sulphur Black 1 have the reference Cl 53185 whereas Cl Solubilised Sulphur Black 1 appears under Cl 53186. Because of the complexity of the final products, sulphur dyes are classified according to the chemical structure of the organic starting material that predominates in the manufacturing process. Typical intermediates include aromatic amines, with or without nitro and phenolic groups, and diphenylamine derivatives. 

The alloc protective group is cleaved by palladium providing a secondary amine, which is alkylated by (Z)-2-iodo-2-butenyl tosylate to give the corresponding vinyl iodide in 96 % yield. The latter vinyl... 

When the N-alloc protecting group of primary amines such as benzylamine is cleaved rapidly imder these standard conditions in quantitative yields, the use of a 40-fold excess of diethylamine as the 7t-allyl scavenger or a five-fold excess of diethylamine in a butyronitrile/water system is necessary for the quantitative deprotection of aUoc derivatives of secondary amines. 

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