Amines tosylates

By treatment with aliphatic primary or secondary amines, tosyl groups on cellulose (a low-substituted cellulose, such as methylcellulose, was employed) may be replaced by substituted amino groups. The products obtained are insoluble in water but dissolve readily in dilute acid. 

Condensation of 5,6-methylenedioxyindole (661) with hexane-2,5-dione gave the carbazole 662 which was formylated and condensed with amino acetal. The resulting Schiff base 663 was reduced with sodium borohydride in methanol to give an amine. Tosylation followed by reaction with 6 N hydrochloric acid in dioxane at room temperature gave 8,9-methylenedioxyellipticine (660 Scheme 45). The overall yield was low. 

ICI 194008. The benzaldehyde imine route to the amine tosylate precursor. Bench development and readiness for scale-up (5, page 22)... 

The reaction of the vinylcyclopropanedicarboxylate 301 with amines affords an allylic amine via the 7r-allylpalladium complex 302[50]. Similarly, three-membered ring A -tosyl-2-(l,3-butadienyl)aziridine (303) and the four-mem-bered ring azetidine 304 can be rearranged to the five- and six-membered ring unsaturated cyclic amines[183]. 

Dialkylation of an amine or sulfonamide with a 1,3-dihalide provides a further route to azetidines <79CRV33l, 64HC( 19-2)88 5). Examples of this approach are the formation of N-tosylazetidine from tosylamide and l-bromo-3-chloropropane and the formation of N-alkylazetidinyl esters (36). The latter reaction works well except for R=Me the former provides a useful route to azetidine since the tosyl group can be removed by reductive methods. 

Tosylates are generally formed from an amine and tosyl chloride in an inert solvent such as CH2CI2 with an acid scavenger such as pyridine or triethylamine. 

Synthesis of the title compound is representative of a number of syntheses of nonaromatic nitrogen heterocycles via Pd(Ill-catalyzed amination of olefins. These tosylated enamines are not readily available by standard synthetic methods, and show potential for further functionalization of the heterocycle. The saturated amine can be synthesized from the title compound by hydrogenation of the double bond followed by photolytic deprotection. ... 

The primary amine of an amino acid as its tosylate salt can be protected by coordination with a crown ether. The protection scheme was sufficient to allow the HOBt/DDC coupling of amino acids. The crown is removed by treatment with diisopropylethylamine or KCl solution. 

Electrolysis, Me4N Cl , 5°, 65-98% yield. " Acylation of a tosylated amine with BOC or benzoyl reduces the potential required for electrolytic cleavage so that these aryltosyl groups can be selectively removed in the presence of a simple tosylamide. °... 

The Jackson modification involves cyclisation of iV-tosylated amine 12 and provides a complementary method to the classical Pomeranz-Fritsch reaction for entry into the fully unsaturated ring system 13. Amine 12 can be prepared from either the Pomeranz-Fritsch-Bobbitt imine 10 or reaction of benzylhalide 14 and the corresponding sodium anion 15. ... 

Tosylation of secondary amine 48 gave desired precursor 49 which was cyclised under prolonged acidic conditions to yield a mixture of linear and angular fully unsaturated isoquinolines 50 and 51. ... 

The key intermediate, normeperidine (81), is obtained by a scheme closely akin to that used for the parent molecule, Thus, alkylation of phenylacetonitrile with the tosyl analog of the bischloroethyl amine (78) leads to the substituted piperidine... 

Two closely related indoles fused to an additional saturated ring have been described as CNS agents. The first of these is obtained in straightforward manner by Fischer indole condensation of functionalized cyclohexanone 0 with phenyl hydrazine (19). The product, cyclindole (21) shows antidepressant activity. The fluorinated analogue flucindole (26) can be prepared by the same scheme. An alternate route starting from a somewhat more readily available intermediate involves as the first step Fischer condensation of substituted phenyl hydrazine with 4-hydroxycyclohexanone (23). The resulting alcohol (24) is then converted to its tosylate (25). Displacement by means of dimethyl amine leads to the antipsychotic agent flucindole (26). ... 

Bis(3-methylsulfonyloxypropyl) amine HCI Improsulfan tosylate Bismuth oxide... 

In a similar manner, bromination, dehydrobromination and amination of l-tosyl-l//-l-benz-azepin-3(2/7)-one yields the 2-amino-3//-l-benzazepin-3-one 10, which condenses with ben-zene-1,2-diamine to give 6//-l-benzazepino[2,3-6]quinoxaline (11).27... 

Aus Sulfonamiden erhalt man auf analoge Weise Amine und Sulfinsauren, wobei bei Di-tosyl-aminen nur eine S—N-Bindung gespalten wird5,6 ... 

The inertia of (TMS)3SiH toward azides allows this functionality to be used as a radical acceptor. An example is given in Reaction (52) where the amine product was tosylated before work-up. 

Aziridines have been opened by organometallic reagents to give amines. Although less reactive than epoxides, it is also possible to open aziridines with organometallic reagents. Isopropylmagnesium chloride reacts with A-tosyl 2-... 

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