N 5-acetal

However, it is to be expected that the rotation of the dimethylamino groups out of the plane should diminish their donor capacity. This is supported by the observation that the C=C barriers are lower in acceptor-substituted 1-dimethylamino-1-methyl-thioethenes (ketene N,5-acetals, 26) than in the l,l-bis(dimethylamino)ethenes (24) with the same acceptor combination (Table 6), in spite of the fact that dimethylamino groups in general are much better donors than methylthio groups33. However, the situation is not quite simple, since in a crystallographic study the ketene A S-acetal 26a was found to have the dimethylamino group twisted 25° out of the plane with a C1=C2 bond twist of ca 20°67. 

A few asymmetric 1,1-enediamines, i.e. with different a-amino substituents, have been prepared from ketene A S-acetals and amines5,51,52,79,80. For example, the primary 1,1-enediamines 45 are obtained by treating ketene N,5-acetals 44 with ammonia... 

Ethyl acetate. Use 58 g. (73-5 ml.) of absolute ethyl alcohol, 225 g. of glacial acetic acid and 3 g. of concentrated sulphuric acid. Reflux for 6-12 hours. Work up as for n-propyl acetate. B.p. 76- 77°. Yield 32 g. Much ethyl acetate is lost in the washing process. A better yield may be obtained, and most of the excess of acetic acid may be recovered, by distilhng the reaction mixture through an efficient fractionating column and proceeding as for methyl acetate. 

Hydrolysis (or saponification) of n-butyl acetate. Boil 4-5 g. of n-butyl acetate (Section 111,95) with 50 ml. of 10 per cent, sodium hydroxide solution under reflux until the odour of the ester can no longer be detected (about 1 hour). Set the condenser for downward distiUation and coUect the first 10 ml. of distillate. Saturate it with potassium carbonate, aUow to stand for 5 minutes, and withdraw all the Uquid into a small pipette or dropper pipette. AUow the lower layer of carbonate solution to run slowly into a test-tube, and place the upper layer into a small test-tube or weighing bottle. Dry the alcohol with about one quarter of its buUr of anhydrous potassium carbonate. Remove the alcohol with a dropper pipette and divide it into two parts use one portion for the determination of the b.p. by the Siwoloboff method (Section 11,12) and convert the other portion into the 3 5-dinitrobenzoate (Section III, 27) and determine the m.p. 

Furthermore, the catalytic allylation of malonate with optically active (S)-( )-3-acetoxy-l-phenyl-1-butene (4) yields the (S)-( )-malonates 7 and 8 in a ratio of 92 8. Thus overall retention is observed in the catalytic reaction[23]. The intermediate complex 6 is formed by inversion. Then in the catalytic reaction of (5 )-(Z)-3-acetoxy-l-phenyl-l-butene (9) with malonate, the oxidative addition generates the complex 10, which has the sterically disfavored anti form. Then the n-a ir rearrangement (rotation) of the complex 10 moves the Pd from front to the rear side to give the favored syn complex 6, which has the same configuration as that from the (5 )-( )-acetate 4. Finally the (S)-( )-mal-onates 7 and 8 are obtained in a ratio of 90 10. Thus the reaction of (Z)-acetate 9 proceeds by inversion, n-a-ir rearrangement and inversion of configuration accompanied by Z to isomerization[24]. 

Tnfluoroacetylketene 0,0- and 5,5-acetals readily react with various amines to give the corresponding 0,N-, S,N- and N,N-acetals [96] (equation 82). 

The whole is slowly heated to 85°C and stirred at this temperature for 45 minutes. The reaction mixture is cooled and the precipitated product is filtered off. It is washed successively with water and ethanol, dried and crystallized from a mixture of acetic acid and methanol, yielding methyl N-[5(6)-benzoyl-2-benzimidazolyl] carbamate MP 288.5°C. 

A yellow crystalline precipitate was immediately formed, which, after crystallization from acetic acid, melted at 182°C and consisted of N-(5-nitro-2-furfurylidene)-3-amino-5-methyl-mercaptomethyl-2-oxazolidinone. 

N,O-acetal intermediate 172, y,<5-unsaturated amide 171. It is important to note that there is a correspondence between the stereochemistry at C-41 of the allylic alcohol substrate 173 and at C-37 of the amide product 171. Provided that the configuration of the hydroxyl-bearing carbon in 173 can be established as shown, then the subsequent suprafacial [3,3] sigmatropic rearrangement would ensure the stereospecific introduction of the C-37 side chain during the course of the Eschenmoser-Claisen rearrangement, stereochemistry is transferred from C-41 to C-37. Ketone 174, a potential intermediate for a synthesis of 173, could conceivably be fashioned in short order from epoxide 175. 

Engel et al.92) have estimated the nucleation parameter for H(Pro-Pro-Gly) OH by computing AG° and AS° with Eq. (5) and reported melting temperatures Tm and AH0 values determined calorimetrically. Utilizing the chain length dependence, they obtained the following parameters (in diluted acetic acid at 25 °C n = 5, 10, 14.15) ... 

Comparing equations 13.8 and 13.9, it is seen that the adiabatic saturation temperature i > equal to the wet-bulb temperature when s = h/hDpA. This is the case for most water vapour systems and accurately so when Jf = 0.047. The ratio (h/hopAs) = b is sometimes known as the psychrometric ratio and, as indicated, b is approximately unity for the air-water system. For most systems involving air and an organic liquid, b = 1.3 - 2.5 and the wet-bulb temperature is higher than the adiabatic saturation temperature. This was confirmed in 1932 by SHERWOOD and COMINGS 2 who worked with water, ethanol, n-propanol, n-butanol, benzene, toluene, carbon tetrachloride, and n-propyl acetate, and found that the wet-bulb temperature was always higher than the adiabatic saturation temperature except in the case of water. 

Because esters 745 a, b of imidazole-acetic acid are unstable when stored for long periods, owing to intramolecular catalysis by the imidazole moiety, the esters should be converted into their salts or free acids and stored as such. Only tert-butyl imidazole-(4,5)acetates derived from tert-butyl 4-chloroacetoacetate seem to be stable [232, 233]. N-alkyl-substituted amidines give rise to a mixture of alkyl N-alkylimidazole-4- and 5-acetates [232, 233]. 

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