Applications alcohol-ammonia reactions

Alkoxylation of MHal is performed by KOR, NaOR, or LiOR or by ammonia in solution in alcohol (formally ammonium alkoxide). Reaction with NaOR is accompanied by formation of NaCl, which is almost completely insoluble in organic solvents and is, therefore, used in the synthesis of soluble metal alkoxides. One of the first examples of application of such reactions has not lost its importance as a method of synthesis to this day ... 

MC15 with alcohols in the presence of ammonia (method 5) and the alcohol interchange of M(OPr )5 (method 6). Mehrotra proposed later the application of esters in the alcohol interchange reaction for Nb(OEt)5 [223],... 

The loss of resonance energy involved in the reduction of an aromatic ring makes this a difficult process. If the reaction is carried out using hydrogen and a catalyst, high pressure and temperature are required. However, reduction can be achieved by the stepwise addition of electrons using sodium or lithium in liquid ammonia, followed by protonation from an alcohol. This reaction, which has had wide application in the laboratory, is known as the Birch reduction. It is commonly used... 

Application of this method is limited by high stability (and presumably low solubility in alcohols) of the complexes of chlorides with ammonia, such as LnCl3 3NH3. Interaction of MHalnwith ammonium alkoxides cannot lead to compounds with higher basicity, such as Th(OR)4 (its alcohol solution is alkaline). Such alkoxides are synthesized by reaction of ThCl4 withNaOR. 

Metal-ammonia reduction of ketones. Swiss chemists have reported a detailed study of the mechanism of this reaction, using for the most part (-l-)- 3,3-D2] camphor as substrate. The conclusions drawn have some useful practical applications. The choice of metal (Li, Na, or K) has little effect on the course of reduction to the thermodynamically more stable diastereoisomeric alcohol. The most important conclusion is that pinacol reduction can be suppressed completely in Na-NH3 reductions by use of ammonium chloride as the proton source, a finding first reported by Murphy and Sullivan.2 This salt also partially suppresses pinacol formation in Li-NHj reductions. It also suppresses reduction of enolates, and thus should decrease racemization in reduction of chiral ketones. 

Summary ADN can be prepared directly form ammonium carbamate by first, reacting the carbamate with nitronium tetrafluoroborate in the presence of acetonitrile to form an intermediate, the free acid of ADN, which need not be isolated. This intermediate is then treated with an alcoholic solution of ammonia in the presence of ether. The ADN, is then recovered by evaporation of the reaction mixture, followed by treatment with a solvent mixture, to remove impurities. The product is recovered by evaporation, and then reciystallized from butanol to form high purity ADN. Commercial Industrial note For related, or similar information, see Application No. 539,647, June 18th, 1990, by SRI International, to Jeffrey C. Bottaro, Mountain View, CA, Robert J. Schmitt, Redwood City, CA, Paul E. Penwell, Menlo Park, CA, and David S. Ross, Palo Alto, CA. Part or parts of this laboratory process may be protected by international, and/or commercial/industrial processes. Before using this process to legally manufacture the mentioned explosive, with intent to sell, consult any protected commercial or industrial processes related to, similar to, or additional to, the process discussed in this procedure. This process may be used to legally prepare the mentioned explosive for laboratory, educational, or research purposes. 

The reduction of benzoic acids affords the dienolate (77) which may be alkylated in situ by a variety of electrophiles to afford 1-substituted derivatives. Clearly, the addition of alcohol must be avoided or limited to small quantities. It may also be necessary to remove the ammonia before adding the electrophile. The vast majority of applications have been based on reactions with alkyl halides to form (78), but additions of (77) to formaldehyde, epoxides and a,p-unsaturated esters to form the range of adducts (79) to (81) have also been reported (Scheme 14). 

A wide variety of a. -unsaturated ketones have been reduced to saturated ketones, usually in good yield, by metal solutions, mainly in liquid ammonia.The reduction is applicable to compounds with any degree of substitution on the double bond. Although only 2 equiv. of these metals are required for the conversion of an enone to a saturated ketone, it is often convenient to employ the metal in excess. A suspension of lithium bronze (Li4NH3) in ether allows the employment of the metal in stoichiometric amounts. Proton donors are often employed to reduce competing side reactions, such as dimerization. The presence of proton donors in the medium may lead to the conversion of an a,p-unsaturated ketone to the saturated alcohol, but at least 4 equiv. of metal must obviously be present for this type of reduction to take place. 

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