Diethylamine, reaction with halides

An efficient resolntion of the racemic lithinm tert-bntylphosphine-borane complex 203 dnring deprotonation by n-BnLi/(—)-sparteine (11) and alkylation was reported by Liv-inghonse and Wolfe (eqnation 47) . One of the epimers 204/cp/-204 on warming to 0 °C crystallizes during a dynamic thermodynamic resolntion, and reaction with alkyl halides fnmishes the alkylation prodncts 205 with high ee values. Applying dihalides, essentially enantiomerically pure diphosphines snch as 206, besides few of the mcio-diastereomer, were obtained. Borane is removed by treatment with diethylamine to yield the free tertiary phosphines 207. 

Acyl halides and alkynes also give lactones upon reaction with Ni(CO)4 in an aqueous acetone medium. The result in this system is typically a 3,y-unsaturated lactone, formed together with some product derived from condensation with molecules of solvent (equation 18). Lactones are also formed in low yield as byproducts from the reactions of acylnickel carbonyl anions (derived from addition of RLi to Ni(CO)4) with terminal alkynes at -30 A single example of y-aminolactone formation is reported from 2-butyne, CO and diethylamine, catalyzed by (Et2NH)2NiBr2. ... 

Apart from the problem of polyalkylation when an amine reacts with an alkyl halide, there is another potential problem. Speculate on potential side reactions that might occur when diethylamine reacts with 2-bromopentane in ethanol solvent. 

Allylic halides can be useful synthetic precursors, as seen for reactions with ammonia. The reaction of 1.35 with diethylamine to give ethyl 4-(NJ4-diethyl-amino)but-2-enoate, 1.36. In this case the yield of 1J6 is moderate rather than high, but generally better than the identical reaction with ammonia (vide supra). A... 

Bromo-, 3-chloro-, 3-fluoro- and 3-iodo-oxetanes have all been prepared in good yield by the reaction of 3-oxetanyl tosylate with alkali metal halides in hot triethylene glycol (equation 70). Substitution reactions of the halogen atom have not been reported, except for the reaction of 3-iodooxetane with diethylamine. A low yield of 2-diethylaminooxetane was obtained from this reaction at 200 °C, but its chemical properties are not known (73JOC2061). 

Uses. There may be some captive use of carbonyl sulfide for production of certain thiocarbamate herbicides (qv). One patent (38) describes the reaction of diethylamine with carbonyl sulfide to form a thiocarbamate salt which is then alkylated with 4-chlorobenzyl halide to produce 5- (4- chi o r o b enzyl) A/, A/-diethyl thiocarbamate [28249-77-6], ie, benthiocarb [28249-77-6]. Carbonyl sulfide is also reported to be useful for the preparation of aliphatic polyureas. In these preparations, potassium thiocyanate and sulfuric acid are used to first generate carbonyl sulfide, COS, which then reacts with a diamine ... 

Elementary analyses and molecular-weight determinations have indicated simply the loss of the elements of hydrogen bromide in the reaction of the O-acetylglycosyl halides with diethylamine. That this loss occurs with the creation of a double bond and the retention of the ring structure... 

Urethanes. Methyl carbamates (1) can be prepared from primary or secondary amines, alkyl halides, and carbon dioxide in a reaction promoted by copper(I) /-butoxide (equation I). The ligand t-butyl isocyanide can be replaced with tri-n-butylphosphine. Copper(I) f-butoxide is more effective than other copper salts. In the case of diethylamine, the intermediates a and b were isolated and b was converted to the methyl carbamate in 86% yield. 

The reaction of allylic halides with diethylamine to give the allylamine is catalyzed by a mixture of Pd(acac)2 and PPhs 17) ... 

The reaction to produce LSD from the acid chloride is then a very simple one. A very standard and time tested procedure would be to mix about 1.5 ml of diethylamine into 50 ml of chloroform for this one half gram example recipe. Then slowly and with stirring the approximately one half gram of lysergic acid halide obtained from the preceeding recipe should be added in small portions to the diethylamine in chloroform. It would be best if the Lysergic acid halide was in solution when it is added to the reaction mixture. We know it dissolves into naptha or hexane, so that is one solvent choice. It probably dissolves into chloroform as well. Once all the lysergic acid... 

Heating A, Af -diphenylurea with amines (butylamine, cyclohexylamine, benzylamine, 2,6-diethylaniline or morpholine) in DMF in the presence of triethylamine yields unsym-metrical ureas, e.g. PhNHCONHBu from butylamine . High yields of isocyanates RNCO are obtained in the reactions of primary aliphatic amines, carbon dioxide and triethylamine with phosphorus oxychloride . Treatment of secondary amines with butylUthium, followed by carbon monoxide at —78 °C under atmospheric pressure, sulphur and an alkyl halide affords 5-alkyl thiocarbamates, e.g. Et2NC(0)SCH2Ph from diethylamine and benzyl bromide. The key step in the sequence is the generation of the lithium thiocarbamate shown in equation 112 . 

The preparation of tertiary amines from alkyl halides and a secondary amine, or a primary amine in which both TV-hydre en atoms are to be replaced by identical alkyl groups, can be carried out with favourable yields in many cases, as evidenced by preparations of diethyl-n-hexadecylamine (from diethylamine) and of dimethyl-n-docosylamine (from dimethylamine) . Alkyl sulphonates have similarly been used, and the reaction extended to the preparation of cyclic tertiary amines from primary amines and appropriate terminal di-sulphonates (reaction 38) . Satisfactory conditions have been reported... 

Oxidative addition of alkenyl halides, triflates, and other esters to zerovalent palladium compounds has been long known as a viable route to palladium(ii)-alkenyl complexes. Stereospecific coupling reactions involving mono- and (E)- or (Z)-dihalo-alkenes with palladium-copper catalysis under modified Sonogashira conditions are quite versatile and useful. These proceed through oxidative addition of the alkenyl halide via palladium(ii) alkenyl complexes, followed by coupling with a nucleophile (usually an alkynylcopper reagent obtained in situ with co-catalytic copper(i) from terminal alkynes in the presence of, in this case, a base like piperidine instead of diethylamine). ... 

Full details of the Ni - and Pd -catalysed telomerization reactions of butadiene with phenylhydrazones (see Volume 6, p. 388) have now been published. Reaction of butadiene with diethylamine gives (49 Z = NEta) in the presence of allyl M halides. The catalytic activity increases in the series M = Ni < M = Ptsimilar reactions of butadiene, especially virith cyclic secondary amines (e.g. morpholine). For M = Pd addition of AcOH improves the yield of (49 Z = NEta) whilst for M = Pt no telomers are formed in the absence of Al(OR)3 (R = Pr or Bu ) co-catalysts. The reaction of butadiene with acetic acid to give (49 Z = OAc) is also catalysed by [M(cod)2] although with the catalyst M = Pd l-vinylhex-5-enyl acetate is a by-product (20%). Reactions of butadiene with acetaldehyde and phenyl isocyanate in the presence of [Pd(cod)t]-2PPh3 give (50 and (51), respectively, ... 

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