Secondary amines compounds

Based on comparisons with imipramine and amitriptyline, desipramine and nortriptyline (secondary amine compounds) are comparable in efficacy with their tertiary amine parent compounds and clearly superior to placebo (Table 7-5). Clinically, they are often preferred to the tertiary amine compounds because of their less... 

When C1207 reacted with NC13, primary and secondary amine compounds belonging to the class of perchloric acid amides were produced ... 

The reaction sequence 73a -> 77 (Scheme 2) was claimed as a new route to imminium salts, and the first entry into transannular reactions of secondary amines. Compounds 76a (R = COPh) and 76b (R = CH2Ph), can also... 

Isocyanates also react with primary and secondary amine compounds. Tertiary amines cannot react with isocyanates because they do not contain active hydrogen atoms, but they are powerful catalysts for many other isocyanate reactions. Diamines are frequently used as chain extenders and curing agents in PU manufacture. The addition of a diamine to the reaction mixture increases the overall reactivity during polymerization. The reaction between an isocyanate group and an amine results in the formation of a urea bond. The polyurea segments present in the finished PU serve to increase the potential for both covalent and hydrogen bond crosslinks within the polymer. 

Certain secondary amine compounds are commonly used for chemical derivation of isocyanates which, like phosgene, form substituted urea compounds amenable to chromatographic determination. One of the most common of these reagents is 1—(2—pyridyl)-piperazine (PYP) PYP reacts on a one-to-one basis with isocyanate compounds yielding a stable urea derivative which can be quantified specifically and sensitively with reversed phase, high performance liquid chromatography (HPLC) and ultraviolet absorbance detection. 

Mecamylamine. This secondary amine compound merits a mention because it is the most used antagonist in behavioral studies, thanks to its ability to cross the blood-brain barrier [for a review, see Young et al. (289)]. 

This section contains the carbon-13 NMR chemical shifts of several types of secondary amine compounds (R — NH— R"). The secondary amine groups exert a moderately strong deshielding effect on adjacent aliphatic carbons. Aliphatic additivity constants for the secondary amine groups are ... 

Am. Compounds I, II, III, and IV are the primary amines. Compounds V, VI, and VII are secondary amines. Compound VIII is a tertiary amine. 

Optically active (+)-methyl-2-thienylmethanol has been obtained through reduction of 2-acetylthiophen with a lithium aluminium hydride-quinine complex. The 2-thienyl analogues of ephedrine and 0-ephedrine have been synthesized from 2-propionylthiophen via the a-bromo-derivative and the methylamino-ketone, followed by borohydride reduction. The amines were resolved into optical antipodes. Through the Claisen condensation between 2-acetylthiophen and ethyl formate, followed by the reaction with secondary amines, compounds of type (164) were obtained. 

The commercially available and easily handled crystalline solid W,N -carbonyl-diimidazole (CDI) is utilized as a starting reagent for the general synthesis of unsymmetrical tetrasubstituted ureas. The intermediate carbamoyl imidazole 1017 is first obtained by reaction of CDI with a secondary amine. Compound 1017 is then converted into the more reactive and resonance-stabilized imidazolinium salt 1018 by N-alkylation of the imidazole moiety. Addition of a different secondary amine to 1018 furnishes N,N,N, N -unsymmetrical tetrasubstituted ureas 1019 in high yield (72-99%). 

Dimethyl Sulphate Method for hydroxy compounds and for primary and secondary amines, acid amides, etc. The substance is dissolved or suspended in water, a small excess (above the theoretical) of sodium hydroxide added and then the theoretical quantity of dimethyl sulphate, the mixture being finally shaken without external warming. Methylation is usually rapid, the dimethyl sulphate being converted to methyl hydrogen sulphate... 

Diasomethane Method. Diazomethane readily methylates phenolic hydroxy-compounds, primary and secondary amines, and carboxylic acids,... 

The Mannich Reaction involves the condensation of formaldehyde with ammonia or a primary or secondary amine and with a third compound containing a reactive methylene group these compounds are most frequently those in which the methylene group is activated by a neighbouring keto group. Thus when acetophenone is boiled in ethanolic solution with paraformaldehyde and dimethylamine hydrochloride, condensation occurs readily with the formation of... 

Water, alcohols and hydroxy compounds generally, and also primary and secondary amines, give the hydrocarbon corresponding to the Grignard reagent,... 

The nitroso compound (diphenyinitrosamine) of the purely aromatic secondary amine diphenylamine is a crystalline solid, and therefore provides an interesting preparation eminently suitable for students ... 

Method 2. Place a 3 0 g. sample of the mixture of amines in a flask, add 6g. (4-5 ml.) of benzenesulphonyl chloride (or 6 g. of p-toluenesulphonyl chloride) and 100 ml. of a 5 per cent, solution of sodium hydroxide. Stopper the flask and shake vigorously until the odour of the acid chloride has disappeared open the flask occasionally to release the pressure developed by the heat of the reaction. AUow the mixture to cool, and dissolve any insoluble material in 60-75 ml. of ether. If a solid insoluble in both the aqueous and ether layer appears at this point (it is probably the sparingly soluble salt of a primary amine, e.g., a long chain compound of the type CjH5(CH2) NHj), add 25 ml. of water and shake if it does not dissolve, filter it off. Separate the ether and aqueous layers. The ether layer will contain the unchanged tertiary amine and the sulphonamide of the secondary amine. Acidify the alkaline aqueous layer with dilute hydrochloric acid, filter off the sulphonamide of the primary amine, and recrystaUise it from dilute alcohol. Extract the ether layer with sufficient 5 per cent, hydrochloric acid to remove all the tertiary amine present. Evaporate the ether to obtain the sulphonamide of the secondary amine recrystaUise it from alcohol or dilute alcohol. FinaUy, render the hydrochloric acid extract alkaline by the addition of dilute sodium hydroxide solution, and isolate the tertiary amine. 

DinitrophenyI derivatives. The halogen atom in 2 4-di-nitrochlorobenzene is reactive and coloured crystalline compounds (usually yellow or red) are formed with primary and with secondary amines ... 

Knoevenagel reaction. The condensation of an aldehyde with an active methylene compound (usually malonic acid or its derivatives) in the presence of a base is generally called the Knoevenagel reaction. Knoevenagel found that condensations between aldehydes and malonic acid are effectively catalysed by ammonia and by primary and secondary amines in alcoholic solution of the organic amines piperidine was regarded as the best catalyst. 

Compounds containing one or more —NH— groups, e.g., ammonia, primary and secondary amines, hydrazines, hydroxylamines and amides. 

Dilute sodium hydroxide solution. Carboxylic acids (RCOOH), sulphonic acids (RSO3H), phenols (ArOH), thiophenols (ArSH), mer-captans (RSH), imides (RCONHCOR), aryl sulphonamides (AxSOjNHj), arylsulphonyl derivatives of primary amines (AxSOjNHR), oximes (RCH=NOH), primary and secondary nitro compounds (RCH=NOOH and RjC=NOOH-oci forms), and some enols (e.g., of 1 3-diketones... 

Sulphones, sul-phonamides of secondary amines, sulphides, sul. phates and other sulphur compounds... 

Acetyl chloride test (for primary and secondary amines). In a semi-micro test-tube (75 x 10 mm.) treat 0-5 ml. (or 0-5 g.) of the compound with acetyl chloride drop by drop. Note whether reaction occurs. If no solid separates, pour the contents of the tube into 3 ml. of water and neutralise the aqueous layer with solid sodium bicarbonate. Observe whether a product different from the original compound is produced. 

Reduction of a nitrosamine to a secondary amine. Proceed as for a nitro compound. Determine the solubility of the residue after evaporation of the ether and also its behaviour towards benzenesulphonyl (or p-toluenesulphonyl) chloride. 

Primary and secondary amines also react with epoxides (or in situ produced episulfides )r aziridines)to /J-hydroxyamines (or /J-mercaptoamines or 1,2-diamines). The Michael type iddition of amines to activated C—C double bonds is also a useful synthetic reaction. Rnally unines react readily with. carbonyl compounds to form imines and enamines and with carbo-tylic acid chlorides or esters to give amides which can be reduced to amines with LiAlH (p. Ilf.). All these reactions are often applied in synthesis to produce polycyclic alkaloids with itrogen bridgeheads (J.W. Huffman, 1967) G. Stork, 1963 S.S. Klioze, 1975). 

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