Aliphatic amines chlorination

The novel chlorinated fluorescein succinimidyl esters 52 and 53 are considerably stable if properly stored. They exhibit intermediate reactivity toward amines, with high selectivity toward aliphatic amines. Their reaction rate with aromatic amines, alcohols, phenols, and histidine is relatively low. 

The fate of dissolved amines during disinfection of water by chlorination was determined by membrane injection MS. Aliphatic amines undergo TV-chlorination to exhaustion of the N-H atoms by one of the tentatively proposed paths shown in reaction 28. Aromatic amines undergo mainly ring substitution however, the possible intervention of N-C1 intermediates is not excluded. At pH 10.6 aniline chlorination is much slower than that of n-butylamine383. 

In the oxidation of aliphatic amines by aqueous chlorine, the key rate-limiting step is the transfer of chlorine from HOCl to the amino group N with probable involvement in the transition state of water molecules. 

TEES is capable of treating several classes of organic compounds, including aliphatics, aromatics, chlorinated aliphatics and aromatics, polycyclic aromatics, cyanides, amines, phenolics, organic acids, and ketones. 

In sulfamation, also termed IV-sulfonation, compounds of the general structure I NSC H are formed as well as their corresponding salts, acid halides, and esters. The reagents are sulfamic acid (amido—sulfuric acid), SO3—pyridine complex, S03—tertiary amine complexes, aliphatic amine—S03 adducts, and chlorine isocyanate—S03 complexes (3). 

Coordination Compounds. Palladium forms numerous complexes with ammonia and with simple amines. Examples are [Pd(NH3)4]2+ [15974-14-8], [PdCl(dien)]+ [17549-31-4], cis-[PdCL (NH3)2] [15684-18-1], and trans-[PdC (NH3)2] [13782-33-7]. Monoammine complexes such as [PdCl3 (NH3)] [15691-32-4] are stable but less common. Examples of aromatic amine complexes include trans- [PdCf (pyr)2] [14052-12-1], [PdCl2(bipy)] [14871-92-2], and nucleosides such as [PdCl(dien)(guanosine)]+ [73601-42-0] (193). Complexes of Pd(IV) such as [PdCl2(NH3)4]2+ [70491-81-5] and [PdCl4(bipy)] [57209-01-5] may be prepared by chlorine oxidation of the corresponding Pd(2+). The aromatic amine Pd(IV) complexes are more stable than ammine and aliphatic amine species, which are reduced to Pd(II) in water or thermally (194). 

The capture of 4,6-dichloro-2-(methylthio)pyrimidine (8) was performed in DMF with diisopropylethylamine (DIPEA, Huenig s base) as a base and tetrabutylammonium bromide as a catalyst at 90°. The substitution of the remaining chlorine atom on the polymer-bound scaffold requires harsher conditions. Thus the immobilized 6-chlorothiomethylpyrimidine (9) could be substituted with aliphatic amines in neat amine at 140°. The coupling with anilines could be afforded consistently only by using KO Bu as base and [18]crown-6. Also, the use of Pd catalysts gave positive results, but failures were observed occasionally. Finally, the substitution of the thiomethyl group in resin-bound 2-(methylthio)pyrimidine-4,6-diamines... 

Viton/butyl Acetone, toluene, aromatics, aliphatic hydrocarbons, chlorinated solvents, ketones, amines, aldehydes... 

Isocyanates and amines react together to form ureas. Primary aliphatic amines react very quickly at temperatures down to ambient, whereas secondary aliphatic and primary aromatic amines react less quickly. The reaction rate of secondary aromatic amines is the slowest. The speed of the reaction can further be modified by the addition of substitutes near the amine group. The control of the speed can either be electronic, as illustrated by the effect of the chlorine in the MOCA ring, or by stereo chemical influences where the groups next to the amine group have a very strong hindrance to the curing. This is... 

Reinhoudt et al. have chosen tetraether derivatives of calix[4]arenes fixed in the cone-conformation as such a molecular skeleton.280 Bis-melamine derivatives 135 are easily prepared in a huge diversity (different residues Y, R1, R2) from 1,3-diamino calix[4]arenes by reaction with cyanurchloride, followed by stepwise substitution of the remaining chlorine atoms by ammonia and an aliphatic amine. 

Azonation of tertiary aliphatic amines has received some attention in recent years. Amine oxide formation was established long ago (1). Oxidation of alkyl groups was reported by Henbest and Stratford (2), Shulman (3), and Bailey et al. (4, 5). Formation of amine hydrochlorides was established when chlorinated solvents were used (2-5). De-alkylated products were formed (2, 4, 5), and amides were found by the same authors (2-5). 

Iron(III) complexes of reduced hemes have been claimed to stabilize the dxzAyz) Axy) ground state much more readily than iron porphyrinates. However, in some cases this may be more a result of the choice of axial ligands than to the electronic nature of the reduced heme ligand. It is now clear that iron(III) chlorins, when bound to imidazole,dimethylphenylphosphine or aliphatic amine ligands, have the same electronic ground state as iron(III) porphyrins, that is, dxy) dxzAyzf whereas when bound to cyanide a somewhat different... 

The use of a base, especially an aliphatic amine, may lead to the introduction of dialkylamino groups into the purine. However hypoxanthin-l-ol was chlorinated with phosphoryl chloride in the presence of triethylamine to give 2,6-dichloropurine (5) in good yield. 

Mechanistic studies of the chemical oxidation of aliphatic amines have been reviewed extensively by Chow et al. [22]. Many studies of the mechanism of oxidation of amines have been performed with chlorine dioxide or ferricyanide as oxidants, because they have absorption bands with maxima at 357 and 420 nm, respectively. Changes in the absorbance at these wavelengths for the respective oxidants can be conveniently used to follow the kinetics of the reactions. On the basis of these studies, the electron-transfer mechanism shown in Scheme 1 has been proposed for amine oxidation. 

The nucleophilic substitution of the reactive chlorine atoms in hexa- and dichloride clathrochelates by a series of aliphatic amines is very sensitive to the effects of the medium (primary, the solvent employed), and the trend of the reaction is determined to a great extent by the donor properties of the amines and the steric accessibility of the nucleophilic centre. The subsequent substitution reaction course and feasible reaction products in the case of hexachloride precursors are presented in Scheme 24. The stepwise-formed clathrochelate complexes are denoted according to the degree of the substitution of chlorine atoms by amine groups ... 

Different chlorine-substituted fragments in partially substituted complexes have similar reactivities, and the direction of the reaction is not determined by the electron density on the carbon atoms (i.e., their electrophilic properties) but by more specific effects an intramolecular activation via hydrogen bonds in the case of sterically unhindered primary amines and sterical hindrances in the case of secondary and sterically hindered primary amines. The reaction with sterically unhindered primary amines occurs via the route An through the substitution of a halogen atom from an already monofunctionalized fragment. In the case of secondary and sterically hindered primary aliphatic amines, the reaction proceeds via the route Bn with sterically controlled substitution. 

The conversion of a wide variety of P, S, and N organic compounds over H-mordenite and HZSM-5 catalysts has been described. The reaction of nitric oxide and chlorine near to equilibrium over H-mordenite was studied by use of a pressure-jump method. The preparation of aliphatic amines from the reaction of Ci—C3 alcohols and ethers with ammonia over HZSM-5, HZSM-11, and HZSM-21 has been described. The proportion of secondary and tertiary amines decreased as the size of alcohol or ether reactant increased. Chang and Silvestri showed that methanethiol is converted over HZSM-5 to hydrocarbons in a broadly similar way to methanol. However, a higher temperature (755 K) is required and even so 27.2 % total carbon remains unconverted as (CH3)2S. Propane is the major paraffin and the aromatics are largely C9. 

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