Methylamine di

The parent drug of this series, promazine (24), was prepared originally as an antihistamine. Following the identification of the more potent chloro analog as an antipsychotic, it too came into use for that indication. The drug is prepared by straightforward alkylation of phenothiazine with w-C3-chloropropyl)di-methylamine by means of sodium hydride in xylene. ... 

The product can also be prepared from benzaldehyde, di-methylamine, and potassium cyanide in cold acetic acid and aqueous ethanol.5... 

Diamino-substituted complexes of type 37 were first obtained by Fischer et al. [12] in two steps via the 1,2-addition-elimination product 34 from di-methylamine and 35 (Scheme 6). The (3-aminoallenylidene)chromium complexes 36, which can be prepared either from 33 [47,48] or directly from 35 [33], can also be transformed to l,3-bis(dialkylamino)-substituted complexes of type 37 (e.g., R2=z Pr) by treatment with dimethylamine in excellent yields [33]. Although the complex 37 is accessible by further reaction of the complex 34 with dimethylamine, and 34 itself stems from the reaction of 35 with dimethylamine, the direct transformation of 33 to 37 could not be achieved [12]. In spite of this, heterocyclic carbene complexes with two nitrogens were obtained by reactions of alkynylcarbene complexes 35 with hydrazine [49] and 1,3-diamines [50]. 

Amine Methylamine (primary) Di methylamine (secondary) Tri methylamine (tertiary)... 

The amino interchange reaction is another method commonly used for preparing phosphinous amides [67] (Scheme 9). The low boiling points of di-methylamine and diethylamine allow their displacement from Ar,AT-dimethyl and AT,iV-diethyl phosphinous amides, respectively, by other less volatile amines, leading to new members of the same class. High reaction temperatures are nevertheless required. 

In Fig. 31.8 we determine the DMSO/methylenedichloride ratio of the di-methylamine-N02 substituted compound approximately at 1.6, where the computed ratio from Table 31.2 is 42.38/26.07 or 1.63. 

The first bipolar axis (DMSO/ethanol) accounts for the contrast between compounds with NO2 substitutions and those without. Compounds with a NO2 substituent systematically obtain higher scores on this bipolar axis than others. The second bipolar axis (methylenedichloride/ethanol) seems to produce an order of the substituents according to their electronic properties. To emphasize this point we have reproduced the log double-centered biplot again in Fig. 31.10. The dashed line near the middle separates the class of NO2 substituted chalcones from the other compounds. Further, we have joined substituents by line segments according to the sequence CF3, F, H, methyl, ethyl, I -propyl, t-butyl, methoxy, phenyl and di-methylamine. The electronic properties of these substituents vary progressively from electron acceptors to electron donors [ 11 ] in accordance with their scores on the second bipolar axis. 

Formal isomerization of the double bond of testosterone to the 1-position and methylation at the 2-position provides yet another anabolic/androgenic agent. Mannich condensation of the fully saturated androstane derivative 93 with formaldehyde and di-methylamine gives aminoketone 94. A/B-trans steroids normally enolize preferentially toward the 2-position, explaining the regiospecificity of this reaction. Catalytic reduction at elevated temperature affords the 2a-methyl isomer 95. It is not at all unlikely that the reaction proceeds via the 2-methylene intermediate. The observed stereochemistry is no doubt attributable to the fact that the product represents the more stable equatorial isomer. The initial product would be expected to be the p-isomer but this would experience a severe 1,3-diaxial non-bonded interaction and epimerize via the enol. Bromination of the ketone proceeds largely at the tertiary carbon adjacent to the carbonyl (96). Dehydrohalogenation... 

Auch der thermische Zerfall der Diamidoborazide (18, 19) liefert grofiten-teils undefinierte Produkte zur vollstandigen Zersetzung muB 18 Stunden auf Temperaturen oberhalb 270 °C erhitzt werden. Beim Zerfall von Bis(dimethylamido)borazid entsteht auBer N2 pro Mol Azid 1 Mol Di-methylamin, beim Zerfall von Bis(diathylamido)borazid findet man da-gegen 30 % der nach der Disproportionierungsgleichung... 

Acetylgramine. This substance is active (IV. in mice) at doses of 5 mg per kg and less, making it quite potent. It potentiates response to DMPP (l,l-Dimethyl-4-phenylpiperazinium iodide) and blocks response to acetylcholine and adrenalin. Reflux a mixture of 15 g of 5-aeetylindole or analog (in equimolar amount), 7.55 g of 37% aqueous formaldehyde, 17 g of 25% aqueous di-methylamine, 25 ml of acetic acid, and 250 ml of methanol for 3 hours. Concentrate in vacuo to 20% of original volume, treat with 100 ml of water, wash with chloroform, chill in freezer, and make basic with 20% NaOH. Filter off the crystalline precipitate and wash with cold (near freezing) water to get a little over 17 g of the title product. Recrystallize from benzene to purify. It is unknown to me if this is active orally. 

In addition to the protected pyrroles mentioned above, the 1-azafulvene dimer formed by Mannich reaction of pyrrole-2-carboxaldehyde with di-methylamine has also been successfully lithiated adjacent to both pyrrole nitrogens (Scheme 10). Reaction with electrophiles and subsequent hydrolysis leads to 5-substituted pyrrole-2-carboxaldehydes in good yield [88TL777 92JOM(423)173]. 

In the names of amines, the general use of suffixes and prefixes is not always observed. Normally, the suffix -amine would be added to the name of the parent hydride and engender names such as methanamine (CH3-NH2). Further substitution on the nitrogen atom would then be indicated by prefixes, leading to names that appear very cumbersome, such as A -methylmethanamine for (CH3)2NH and N,N-dimethylmethanamine for (CH3)3N. The traditional names of methylamine, di-methylamine and trimethylamine are much simpler. In these names, the term amine is not a suffix. It is, in fact, the name of the parent hydride, NH3, which now serves as the basis of substitutive names. Names such as diethylamine and tributylamine are representative of the preferred nomenclature. Diamines are named accordingly, as with ethane-1,2-diamine for H2N-CH2-CH2-NH2 and propane-1,3-diamine for H2N-[CH2]3-NH2. There are allowed alternatives for these last two compounds ethylenediamine and propane-1,3-diyldiamine. 

Reaction of rra s-Ar,A -dimethyl-2-phenylcyclopropylamine with di-methylamine in methanol to give the open-chain enamine 1-dimethylamino-3-phenyl-l-propene [178]. 

These devices showed EL enhancements to ammonia, methylamine, di-methylamine, trimethylamine, and sulfur dioxide that increased in magnitude with concentration until saturation was reached [14]. The LEDs with larger active layers produced the greatest change in EL intensity with exposure to sulfur dioxide and the amines. Intensity changes were attributed principally to surface recombination velocity effects, as the significant forward biases employed should eliminate the depletion width. 

N-(Thexyl dimethylsilyl)dimethylamine (N-[2,3-dimethyl-2-butyl]dimethylsilyl di-methylamine) [81484-86-8] M 187.4, b 156-160°/720mm. Dissolve in hexane, filter, evaporate and distil. Colourless oil extremely sensitive to humidity. It is best to store small quatities in sealed ampoules after distillation. For estimation of purity crush an ampoule in excess 0.1N HC1 and titrate the excess acid with 0.1M NaOH using methyl red as indicator. [HCA 67 2128 1984]. 

The analysis of polymeric and gaseous products of the reaction of PMMA and di-methylamine at low dimethylamine levels shows that there was a clean reaction that produced 1 eq of anhydride (NOT Amide) per 1 eq of dimethylamine and per 1 eq of MMA. Note that this is in most close agreement with pathway 2a- 3a (Figure 2) in which most of the MMA carbonyls have been converted to COOH or alkylammonium COO salts followed by closure to anhydride. This shows that direct acyl addition (2c— 3c) to form amide, or reaction of carboxylate with adjacent ester (2b- 3b) to form anhydride (which liberates MeOH after proton transfer, and requires only 0.5 eq. dimethylamine per MMA group) are not the predominant pathways under these conditions. The Flory limit effect is consistent with random initial MAA formation, which after cyclization to anhydride (Figure 2) eventually leads to some groups trapped between rings which remain in the uncyclized acid form. 

To 200 ml. of glacial acetic acid in a 1-1. round-bottomed flask is added slowly, with cooling in an ice bath, 151 ml. (54 g. of di-methylamine, 1.2 mole) of 40% aqueous dimethylamine solution, followed by 90 ml. (36 g. of formaldehyde, 1.2 mole) of 37% aqueous formaldehyde (formalin) solution. The flask is removed from the ice bath and equipped with a reflux condenser, through which 82 g. (90 ml., 1 mole) of 2-methylfuran (Note 1) is added all at once. Upon gentle swirling of the flask, an exothermic reaction may set in spontaneously if it does not, the flask is heated on a steam bath until reaction commences. In any event, the spontaneous reaction is allowed to proceed without further external heating. When it ceases, the reaction mixture is heated on a steam bath for another 20 minutes, cooled, and without delay poured into a cold solution of 250 g. of sodium hydroxide (Note 2) in 800 ml. of water. 

The parallelism in reactions with HMPT and mixtures of phosphorus pentoxide and amines can best be realized by looking at the mechanism of HMPT reactions [1 5 ]. In the reaction of p-methoxy-benzylalcohol with HMPT which produce the corresponding N,N-dimethylbenzyl amine--p-methoxybenzyl phosphate was identified in the XP NMR spectrum of the reaction mixture. Since pyrophosphate was also observed during the reaction of the benzyl alcohol with HMPT, the intermediate formation of the metaphosphate anion can be assumed. Addition of the benzyl alcohol to that anion then produce the benzyl phosphate. Phosphate ions are known to be good leaving groups so that a benzylamine can easily be produced from the phosphate by reaction with di-methylamine released from the dimethylammonium ion. The phosphoric acid produced during the reaction is believed to react with HMPT, so that more dihydro-gen-bis(dimethylammonium) pyrophosphate is formed. 

Those amines and acids with a disagreeable odor, such as 1,4-butanediamine, di-methylamine, butyric acids, and valeric acids, should be neutralized and the resulting salt solutions flushed down the drain, diluted with at least 1,000 volumes of water. 

The reagent is prepared from (R,R)-( + )-diethyl tartrate by reaction with di-methylamine followed by methylation (dimethyl sulfate and 2,2-dimethoxypro-pane). 

Figure 11. Alternative reducing agents for reductive alkylation (1) di-methylamine borane (II) trimethylamine borane (27)...

Oxidation of phenylacetylene with oxygen in the presence of cupric acetate and di-methylamine is claimed to give a mixture constituting of 58 % dimethylamino phenylacetylene and of 42% 1,4 diphenylbutanediyne. Hydrazine purportedly increases the ynamine/diyne ratio 169). The patent claims isolation of pure phenylynamines despite aqueous work-up. Unfortunately, to our knowledge, there are no reported attempts to duplicate this potentially useful approach. 

The thermal degradation of arecaidine methyl betaine (167) and the subsequent work-up with hydrochloric acid gave a mixture of 5-di-methylamino-l,3-pentadiene (159), m-2-pentenal (170), and di-methylamine. The 1,2-diene (168) and the enamine (169) are assumed as the unisolated intermediates.131... 

Among the diamines suitable for the manuf of such explosives may be mentioned phenyl-ene-di(methylamine) and phenylene-ditoluidine... 

Druey et have performed reactions of 4-methyl-3,6-dichloro-pyridazine with ammonia and other nucleophiles, but did not establish their structures. Later studies revealed that treatment of the mentioned pyridazine with anhydrous ammonia in methanol at 120° afforded a mixture of aminochloro-4-methylpyridazines in the ratio of about 1 10, the isomer 73a (X = NH2, R = Me) predominating. Also modified reaction conditions have led to a mixture of both isomers, where the isomer 73a was prevailing, and when di-methylamine has been used only isomer 73a (R=Me, X = NMe2) was isolated. From the reaction with hydrazine hydrate the isomer 74a (R=Me, X = NHNH2) is claimed to be the main product. 

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