Benzene with unsaturated amines

Lithium aluminum hydride reduced )J-azidoethylbenzene to j8-aminoethyl-benzene in 89% yield [600], The azido group was also reduced with aluminum amalgam (yields 71-86%) [149], with titanium trichloride (yields 54-83%) [601], with vanadous chloride (yields 70-95%) [217] Procedure 40, p. 215), with hydrogen sulfide (yield 90%) [247], with sodium hydrosulfite (yield 90%) [259], with hydrogen bromide in acetic acid (yields 84-97%) [232], and with 1,3-propanedithiol (yields 84-100%) [602]. Unsaturated azides were reduced to unsaturated amines with aluminum amalgam [149] and with 1,3-propane-dithiol [602]. 

The structure of the pyridazine-based antidepressant agent minaprine (34-6) departs markedly from both the older tricyclic drugs and the more recent selective serotonin re-uptake inhibitors. There is evidence that the compound acts via a dopa-mimetic route. Friedel-Crafts acylation of benzene with itaconic anhydride (34-1) leads to the keto-acid (34-2). Condensation with hydrazine leads to the formation of the hydrazine and hydrazide bonds the double bond shifts into the ring to give the fully unsaturated pyridazinone (34-3) this is then converted to the chloride (34-4) in the usual way. The displacement of halogen by the amine on 3-(A -morpho-lino)propylamine (34-5) affords (34-6) [36]. 

In addition to alkenes, functionalized alkenes can also be used as alkylating agents. Koltunov, Walspurger, and Sommer, have reported the alkylation of benzene with a,/3-unsaturated carboxamides in the presence of excess aluminum chloride [Eq. (5.72)]. The reaction takes place under mild conditions and gives the products in near-quantitative yields. Results with ortlro-dichlorobenzene and triflic acid are usually inferior. Triflic acid, however, can catalyze similar reactions of cyclic and open-chain unsaturated amines with benzene to give phenylalkylamines in excellent yields.180 The transformations are interpreted by invoking the involvement of dica-tionic intermediates 39 and 40. 

It is obvious here to think of an interaction of the Debye type of the appreciable moment of the nitro or carbonyl group with the readily polarizable unsaturated C — C bond in the unsaturated hydrocarbons or with the likewise readily polarizable free electron pair in the amines, etc. Actually the stability increases with increasing polarizability, compare for example, the heat of formation of j-trinitrobenzene with, respectively, benzene, naphthalene and anthracene AH 0.6, 3.4 and 4.4 kcal. In the series mono-, di- and tri-nitro-benzene with acenaphthene AH also increases with increasing number of partial moments, namely AH — o, 1.35 and 2.45 kcal. Nevertheless this explanation is inadequate, nitromethane with a moment [x = 3.54 D gives very much less stable compounds than nitrobenzene with (X = 4,22 D, while nitrosobenzene with [x =3.2 D gives stronger colour effects than nitrobenzene. 

Enamines and metalloenamines provide a valuable alternative to the use of eno-lates for the selective alkylation of aldehydes and ketones. Enamines are a,p-unsaturated amines and are obtained simply by reaction of an aldehyde or ketone with a secondary amine in the presence of a dehydrating agent, or by heating in benzene or toluene solution in the presence of toluene-/7-sulfonic acid (TsOH) as a catalyst, with azeotropic removal of water (1.31). Pyrrolidine and morpholine are common secondary amines useful for forming enamines. All of the steps of the reaction are reversible and enamines are readily hydrolysed by water to reform the carbonyl compound. All reactions of enamines must therefore be conducted under anhydrous conditions, but once the reaction has been effected, the modified carbonyl compound is liberated easily from the product by addition of dilute aqueous acid to the reaction mixture. 

The rate of reaction of ozone with amine was determined during the ozonization of rubber solution, where the reaction between ozone and rubber also proceeded concurrently. The extent of the reaction of rubber with ozone was calculated from the change in unsaturation of the rubber determined by the Wijs reagent. For example, SBR (Japan Synthetic Rubber, JSR 1502), purified by precipitation with acetone from benzene solution, was dissolved in carbon tetrachloride to give a 5% rubber solution. The rubber solution (20 ml.) was added with 80 ml. of carbon tetrachloride containing 1 X 10 3 mole of amine derivatives. Oxygen, containing 0.89% ozone, was introduced into the solution at 30°C. for 3 minutes at the rate of 550-560 ml./min. Under these conditions, all... 

The literature up to 1988 has been reviewed . Dienamines are usually prepared from a,j8-unsaturated aldehydes or ketones under conditions analogous to those used for preparation of the simple enamines . Reaction of secondary amines with a,)S-unsaturated ketones in the presence of p-toluenesulphonic acid is slower than that with the corresponding saturated ketones. Pyrrolidine is more reactive than morpholine. In some cases, satisfactory yields may be obtained when the water formed is removed by azeotropic distillation using a solvent such as benzene or toluene, but better results are obtained when the condensate is passed over a molecular sieve. The pyrrolidine dienamines of certain A -3-oxosteroids may be prepared by simply mixing the ketone with a secondary amine in hot methanol. Compounds with 17- or 20-oxo group are unreactive. ... 

In connection with a study of a number of anticancer compounds which, presumably also act as inhibitors of free-radical polymerization, eight classes of compounds were studied as to their inhibitory properties. The classes studied were unsaturated hydrocarbons, phenolic compounds, quinones, amines, stable free-radicals, sulfiir compounds, carbonyl compounds, and metallic salts. The most effective inhibitors, of those evaluated, were cupric acetate and cupric resinate, followed by /runs-1,3,5-hexatriene, hydroquinone, benzoquinone, and diphenylamine as modest inhibitors. Among the low-activity inhibitors were 2,2-diphenyl-1-picrylhydrazyl, benzene thiol, and crotonaldehyde [70]. 

Table 5,3 Examples of QSAR models for estimating toxicity to fish of non-polar non-specific toxicants (e.g. alkanes, alkenes, saturated and unsaturated halogenated aliphatic hydrocarbons, basic ethers, cyclic ethers, ketones, amides, secondary and tertiary aliphatic and aromatic amines, alkylbenzenes, halogenated benzenes, piperazines, pyrimidines, polychlorinated hydrocarbon pesticides) log LC50 correlations with various parameters. 

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