Amino Salts

Volatile corrosion Organic amino salts From solution Adsorbed, non-... 

At the end of the 1970s, OCPs were found in the waters of Belorussia s rivers the Dnepr, Western Dvina, Pripyati, and Nemana. Of the 960 analyzed samples, 82.7% contained DDT, and 81.6% contained HCH. Concentrations of the herbicide 2,4-D (amino salt) in drainage runoffs reached 1400 mkg/l (standards in those years were 200 mkg/l, and today are 2 mkg/l) [3]. 

On April 25, 1972, a field from the Banner of Communism Collective Farm in the Bratsk Region was treated with polychlorpinen. Thirty-three female collective farm workers, working in this field from May 5-21, did not complain about conditions. On May 22, two to three hours after a wind carried over amino salt 2,4-D from a neighboring field that had been sprayed at the time, all 33 displayed symptoms of acute poisoning (the concentration of polychlorpinen in the air over the field was only 0.03-0.001 mg/m3 two days after the poisoning). 

The starting benzothiazole carboxylic ester 387 was subjected to a Anamination by using mesityl hydroxylamine to give an A -amino salt 388, which was treated with a tertiary amine to give the deprotonated intermediate 389. This species when reacted with phenylisocyanate yielded the final product 390 in moderate yield <2001JOC8528>. 

Acidic drugs are usually converted to their metallic or amino salts, whilst the salts of organic acids are normally used for basic drugs (Table 3.1). 

The N-amination of 3-aminopyridazines occurs next to the amino function (75JHC107 81T1787), while 3-methylpyridazine and its 6-methoxy derivative followed the trend of N-alkylation being aminated at N-2 (72CPB1814). 3-Methoxypyridazine gave the 1-amino salt as expected (71CPB2106). 

Dipolar cycloaddition of iV-imines, derived from the mono-7V-amino salt of 2-phenyl-quinoxaline, with dimethyl acetylenedicarboxylate results in formation of a tricyclic heterocyclic ring system with bridgehead nitrogen. 

Benzamidinc combines with 2-amino-3-phenacyl-l,3,4-oxadiazolium bromides to give l-acylamino-2-benzimidoylamino-4-arylimidazolcs. Yields arc only moderate (14-43%), but the reaction works for a variety of 4-arylimidazoles f22. Reactions of /V-methyl-JV-(JV -phenylbenzimidoyl)amino-acetonitrile (13) under acidic conditions lead to imidazolium salts which have amino (14) or amido (15) groups in the 4-position (Scheme 2.2.6). The 4-amino salt (14) undergoes Dimroth rcaaangement to the 4-phenylaminoimidazole (16) direct conversion of (13) into (16) also occurs in warm alkali [8]. A Claisen rearrangement of the adduct (17), which forms from interaction of an arylamidoxime and a propiolate ester, provides a method... 

O-Mesitylenesulfonylhydroxylamine (MSH) reacts with thietane to give the 5-amino salt 81. " An attempt to prepare a sulfilimine by treatment of 81 with a basic ion exchange resin was not successful.Chloramine-T gives the N-(p-tolylsulfonyl)sulfilimine 82. Several substituted thietanes yield the A -tosyl-sulfilimines in 56-100% yields. ... 

Attempts to prepare the tosyl derivative of the sulfilimine 198 from the 5-amino salt 81 resulted in cleavage of the S-N bond to give ammonia and thietane. ... 

Four-Membered Sulfur Heterocydes TABLE 7. THIETANE SULFILIMINES AND 5-AMINO SALTS... 

The treatment of salts 109 with aromatic amines gave 3-arylimino isothiazoles 360 (59-84%) and 361 (31-58%), which can be rearranged to 3-amino salts 362,363 by protonation (76CB659, 80CB2490, Scheme 121). 

N-Amination of heterocycles disclosed useful synthons, the N-amino-heterocycles. Several pyridazines were transformed by hydroxylamine-O-sulfonic acid into the corresponding 1-aminopyridazinium derivatives.295 Substituted pyridazines, like 3-methyl-, or 3-methyl-6-methoxypyridazine were aminated only at N2,295 but 3-methoxypyridazine gives the 1-amino derivative.280 O-Mesitylenesulfonylhydroxylamine is an efficient reagent for N-amination, and 3-aminopyridazines give the corresponding N-amino salts in high yields.296... 

A-Aminopyridinium salts (14), and their derivatives substituted at the exocyclic amino group, can also be prepared by rearrangement reactions. Thus, the diazepinone 22 and diazepinium betaine 23 are converted into the A-amino salts (26) by concentrated acids.44-47 This rearrangement... 

Isoquinoline V-imines also have been made only by deprotonation of V-aminoisoquinolinium salts. Just as for the corresponding pyridinium derivatives (see Section II,A,1), the salts 43 can be produced by amination of isoquinoline with hydroxylamine-O-sulfonic acid75 or from V-(2,4-di-nitrophenyl) isoquinolinium chloride (44), 30 31 76 Substituted quaternary amino salts (46) are obtained by cyclization of 2-(2,4-dinitroanilino)-o-styrylaldehyde hydrazones (45) with ethanolic hydrochloric acid, and deprotonation to V-imines is easily effected by alkali. On liberation from the salts by alkali, unsubstituted isoquinoline V-imines dimerize to give... 

Two syntheses of benzocinnoline Ar-imines have been described recently.78 They can be prepared from benzocinnoline and hydroxy lamine-O-sulfonic acid or by diazotization of 2,2 -diaminobiphenyl with pentyl nitrite or JV-nitrosodiphenylamine. Diazotization of the diamine presumably proceeds via the triazepine 48, which is isomeric with unsubstituted benzocinnoline iV-imine. Benzocinnoline iV-imine itself, the only unsubstituted iV-imine so far isolated, was prepared from benzocinnoline and hydroxylamine-O-sulfonic acid. Under similar conditions, quaternary IV-amino salts were isolated from the other iV-heterocycles. The unsubstituted Ar-imine can be converted easily into the acyl, sulfonyl, and 2,4-dinitrophenyl derivatives (Scheme 3). 

Amination of allosecurinine (32) and securinine (33) with 0-mesitylenesulpho-nylhydroxylamine has been shown to give the N-amino-salts (34) and (37), respectively (Scheme 3). The stereochemistry of (34) and (37) is assigned on the basis of the observed rearrangements of the corresponding ylides (35) and (38) into compounds (36) and (39), respectively. These reactions may be envisaged to proceed by a [2,3] sigmatropic shift mechanism. The stereochemistry of the amination reaction parallels that of the quaternization of the two alkaloids with methyl iodide. 

The synthesis of these cations was recently included in a broader review <9lCHE92l>. In addition to the procedures covered in the first edition, the parent cation (123) has been reported to be formed in excellent overall yield from 2-vinyloxypyridine (Scheme 25) <86CHE1132>. The 3-amino salt... 

Bands at 1600 cm are attributed to the formation of primary amines by network scission at high temperature [12]. In our case, the ongoing cure of residual reactive amines should rather lead to a decrease in primary amine concentration. Therefore, the band must have another origin, such as the protonation of primary and secondary amines to form amino salts or the formation of carboxyl... 

Recent results, which have been confirmed by MS, indicate that DMN does occur in certain food products at the 5-10 pg kg level. Investigations undertaken on the occurrence of nitrosamines (DMNA, DENA) in meat and meat products have assessed concentration levels of 10pgkg , although large amounts can be found as a result of various transformation processes (in fried bacon or smoked meat). A precursor of DMNA is the amino acid glycine. It may also originate from quaternary amino salts such as choline, acetylocholine, and betaine, which are common in meat. 

Phenazinium, 3-((7-((4-aminophenyl)amino)-5-phenylphenazinium-3-yl)amino)-5-phenyl-7-((5-phenyl-7-(phenylamino)phenazinium-3-yl)-amino)-, salt with chromic acid... 

Laus and his colleagues are responsible for a valuable and extensive series of studies of imidazolium derivatives that includes the crystallographic characterisation of a series of N-hydroxy, alkoxy and amino salts. Among these, a pairwise conparison may be made between [(RO)2im][PF0] [93] data collected at 233 K] R = Me (syn form) (mpt. 83-84°C U l 466 kJ... 

A series of lithium salts of protected primary amino acids (105, n = 0-2) catalyse asymmetric Michael addition of malonates to 2-cyclohexen-l-one. The -amino salt (n = 1) gave higher ee than either the y- or the a-. A mechanistic study using DPT has been carried out to identify how the -amino salt better coordinates the imine intermediate and maximizes ee. 

And again, from the figure, it is evident that the polymerization leads to asymmetric polymer chain formation from the amino salt of Bu-l-acid. Further, in order to confirm the demonstration, a series of polymers obtained from monomer salts of a-phenyl ethyl amine having various optical rotations was prepared. As a result (see Figure 5) the optical rotation proved to be proportional to that of the a-phenyl ethyl amine employed in the... 

Fig. 6. CD Spectra of optically active (bu-l-acid) polymer and its amino salt.

Furthermore, the results of copolymerizations conducted with styrene and monomeric amino salt mixtures are shown in Table V. 

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