Acetaldehyde, ammonia reaction preparation

Variations on this theme include the use of acrolein/ammonia (72GEP2224160) and acrolein/acetaldehyde/ammonia (64BRP963887,69BRP1141526). Ketones can also be utilized. For example, 2,6-dimethylpyridine is obtained in 36% yield from combination of for-malin/acetone/ammonia (71GEP2064397) (Scheme 3). This general reaction has recently been extended to include the preparation of 2,6-disubstituted (78BEP858390) and 2,3-disubstituted (78GEP2712694) pyridines from aromatic or heteroaromatic ketones/aliphatic aldehydes and ammonia. 

Strecker, A. The preparation of a new material by the reaction of acetaldehyde-ammonia imine and hydrogen cyanide. Liebigs Ann. Chem. 

When 2,7-dimethyloxepin is treated with potassium in liquid ammonia at — 70 C, a mixture of oct-4-en-2-one (1) and octa-4,6-dien-2-one (2) in a ratio of 75 20 is obtained.203 The major product can be separated by preparative gas chromatography in 23% yield. The analogous reaction of 3-benzoxepin gives, in 30% yield, a mixture of (2-cthylphenyl)acetaldehyde (3) and (2-ethynylphenyl)acetaldehyde (4) that resists separation.203 The Latter product can be formed exclusively in 17% yield when 3-benzoxepin is treated with sodium amide in tetra-hydrofuran at 33 C for 210 minutes.203... 

Taurine is generally prepared from ox bile1 or the large muscle of the abalone.2 It has been synthesized from isethionic add through chloroethanesulfonic acid followed by the action of aqueous ammonia 3 from ethyleneimine and sulfur dioxide 4 from 2-mercaptothiazoline by oxidation with bromine water 5 from bromoethylamine and ammonium sulfite 6 and from acetaldehyde by a complex set of reactions involving sulfonation, formation of the aldehyde ammonia and the imido sulfonic add and finally reduction.7 The method given in the procedure has recently appeared in the literature.8 9... 

Seventeen grams of acetaldehyde are dissolved in 20ml of water and added dropwise to a suspension of 40g of sodium bisulfite in 30ml of water. The reaction mixture is kept cold in an ice bath to prevent loss of the aldehyde by volatilization much heat Is liberated by the formation of the bisulfite addition compound. The temperature of the solution is adjusted to 50°C and 17ml of 20% aqueous ammonia are added. The latter is prepared from 13ml of the... 

Reaction CXLIV. Action of Ammonia on Aldehydes.—The simplest case is the formation of an aldehyde ammonia by the action of dry ammonia gas on the aldehyde in dry ethereal solution. Acetaldehyde and several of the aliphatic aldehydes react after this fashion. (See Preparation 440.)... 

In 1958, Ikekawa10 synthesized 2,7-naphthyridine and various substituted derivatives. His approach involved the reaction of 4-methylnicotinic acid with formaldehyde to afford the lactone 99 (R = H). The reaction of 99 with ammonia in methanol yields the amide (100) which, on oxidation with chromium trioxide, afforded 2,7-naphthyridin-l-one (101). This substance was converted into 2,7-naphthyridine (102, R = H) by consecutive treatment with phosphorus oxychloride, hydrazine, and copper sulfate. The 3-methyl derivative was similarly prepared starting with acetaldehyde. 

The iV-alkylation was considered to occur by the reaction of the carbonyl compounds, formed by the dehydrogenation of alcohols over the catalyst, with the hydrogenation products of pyridine,25 as suggested by Schwoegler and Adkins, who obtained good yields of /V-alkylpiperidines by the reaction of piperidine with alcohols.26 Maruoka et al. obtained a higher maximal yield of the iV-ethylated product in ethanol over Raney Co than over Raney Ni in the hydrogenation of 5-ethyl-2-methylpyridine (eq. 12.16),23 an alkylated pyridine prepared industrially by the reaction of acetaldehyde with ammonia. 

Aryl-substituted ketones react directly with elemental sulfur in hexa-methylphosphorus triamide with formation of l,2-dithiole-3-thiones.46,47 Aryl-substituted acetaldehydes can condense likewise with carbon disulfide to give the analogous 4-aryl-substituted l,2-dithiole-3-thiones.48 The same reaction was observed with aryl-substituted acetic acid esters, in which a methylthio group is incorporated into the reaction product (26).49 Thioketones and enthioles react analogously. 50,51 The parent l,2-dithiole-3-thione (27) has been prepared from the tetra-methyl acetal of malondialdehyde and phosphorus pentasulfide.52 In the presence of ammonia the reaction of cyclohexanone or cycloheptanone with carbon disulfide and sulfur gives as by-products the condensed 1,2-dithiole-3-thiones 28a and 28b, respectively.53... 

Problem 9.9. The reaction of methanal (formaldehyde, H2C=0) with ammonia (NH3) is used to prepare l,3,5,8-tetrazatricyclo-[3.3.1.1 ]decane (hexamethylenetetramine) (Thble 9.4). Write a plausible series of reactions between these reagents that would have the desired product as the outcome. Account for the different result to produce the trimer (shown below) with ethanal (acetaldehyde) and ammonia. 

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