Amides, preparation tables

More recently, the same group has used a simpler and more easily prepared chiral ammonium phase-transfer catalyst 99 derived from BINOL in asymmetric Darzens reactions with a-halo amides 97 to generate glycidic tertiary amides 98 (Table 1.13). Unfortunately the selectivities were only moderate to low [48]. As mentioned in Section 1.2.3.1, tertiary amides can be converted to ketones. 

The mechanism of the aminolysis and the electronic effects of substituents at C-2 or C-4 on the kinetics of amide bond formation have been studied. In some cases, ring opening with amines occurs with partial isomerization of the exocyclic double bond. However, with more hindered compounds, such as unsaturated oxazolones derived from ketones, ring opening is stereospecific.Ring opening using diamines has also been described. Selected examples of dehydroamino acid amides prepared by aminolysis of unsaturated 5(4//)-oxazolones are shown in Table 7.40 (Fig. 7.51). 

Table 108 Chromium(rV) Alkoxides and Amides Preparation and Properties...

Cyano acyl halides, preparation, 547 preparations listed in table 61, 554 Cyano aldehydes, hydrolysis, 414 preparations listed in table 73, 621 Cyano amides, preparation, 570... 

For bis-ort/ o-snbstituted anilides with a high rotational barrier, such as amide 42, pure enantiomers (M)-(-)-42 and (P)-(+)-42 can be prepared (Table 12.1). If the intramolecular Mizoroki-Heck reaction of 42 is faster than the rate of racemization by rotation about the N—Ar bond, then reaction of a single enantiomer with an achiral palladium catalyst would produce an enantioenriched product. By employing room-temperature Mizoroki-Heck... 

Amides prepared by conventional methods are listed in Tables XI-14 and XI-27. 

To shed further light on the possible opportunity to use NVP, we prepared a poly(AA-co-IA-co-NVP) material with a 7 3 1 ratio, respectively, and ev uated the FS, CS, DTS, fracture toughness (FT), working (WT) and setting (ST) times of the possible new matrix resin. Elemental analysis showed the synthesized copolymer as having 1.34 % N (theory, 1.39 % N). The IR spectra of the copolymer showed bands at 1717 and 1651 cm indicative, respectively, of carboxylic acid and cyclic amide groups (Table 1). The and C NMR spectra, with bands at 8.32 and 12.10-12.25 and 172.0 and 176.0 ppm (Table 1), also supported the copolymer structure(s). An... 

Strain. By these criteria, methyl methanesulfonate, A -acetoxyfluorenylacet-amide, captan, and others are preferential inhibitors of the pol Ai strain (Tables 7 and 8). On the other hand, streptomycin and chloramphenicol, although they induce lethality in both indicator strains, do not preferentially kill the pol Ar strain (SI = 1.12 and 1.02, respectively). It should be noted that this procedure is compatible with metabolic activation. Thus, the precarcinogens 2-aminofluorene and cyclophosphamide, which require metabolic activation by hepatic enzymes, do not preferentially inhibit the pol Ai strain in the absence of rat liver microsomes, but do so in the presence of this preparation (Tables 7 and 8). This procedure has the added advantage that results obtained by this modified pol Ai assay are expressed quantitatively, rather than as differences in the diameters of the zones of growth inhibition. As will be seen below, this modified procedure greatly increases the usefulness of the pol A assay (Table 9). 

One of the virtues of the Fischer indole synthesis is that it can frequently be used to prepare indoles having functionalized substituents. This versatility extends beyond the range of very stable substituents such as alkoxy and halogens and includes esters, amides and hydroxy substituents. Table 7.3 gives some examples. These include cases of introduction of 3-acetic acid, 3-acetamide, 3-(2-aminoethyl)- and 3-(2-hydroxyethyl)- side-chains, all of which are of special importance in the preparation of biologically active indole derivatives. Entry 11 is an efficient synthesis of the non-steroidal anti-inflammatory drug indomethacin. A noteworthy feature of the reaction is the... 

Section 20 18 Nitnles are prepared by nucleophilic substitution (8 2) of alkyl halides with cyanide ion by converting aldehydes or ketones to cyanohydrins (Table 20 6) or by dehydration of amides... 

Amide-Based Sulfonic Acids. The most important amide-based sulfonic acids are the alkenylarnidoalkanesulfoiiic acids. These materials have been extensively described ia the Hterature. A variety of examples are given ia Table 5. Acrylarnidoalkanesulfoiiic acids are typically prepared usiag technology originally disclosed by Lubrizol Corporation ia 1970 (80). The chemistry iavolves an initial reaction of an olefin, which contains at least one aHyhc proton, with an acyl hydrogen sulfate source, to produce a sulfonated intermediate. This intermediate subsequendy reacts with water, acrylonitrile, and sulfuric acid. 

The A -fluoroamide reactants were initially prepared by fluorination of amides with fluoroxytnfluoromethane [63 Current methods involve the direct fluorination of amide reagents with elemental fluorine under a variety of conditions [48. 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 76, 81. 82] (Tables 3a and 3b)... 

Nitrogen forms binary compounds with almost all elements of the periodic table and for many elements several stoichiometries are observed, e.g. MnN, Mn Ns, Mn3N2, MniN, Mn4N and Mn tN (9.2 < jc < 25.3). Nitrides are frequently classified into 4 groups salt-like , covalent, diamond-like and metallic (or interstitial ). The remarks on p. 64 concerning the limitations of such classifications are relevant here. The two main methods of preparation are by direct reaction of the metal with Ni or NH3 (often at high temperatures) and the thermal decomposition of metal amides, e.g. ... 

TABLE XXVn. l-Methyl-l,6-dihydropyrazolo[3,4-c]pyridin-7-ones Prepared by Cyclization of Vicinal 4-(Alkyn- l-yl)pyrazole-5-carboxylic Acid Amides [90IZV2089]. 

By this procedure, the following amides (Table 16.2) may be prepared from the indicated starting materials in the approximate yields given. 

As an alternative, tin enolates are very useful in these additions. Usually they are prepared in situ from the amide using tin(II) trifluoromethanesulfonate and a base. They are subsequently reacted with an enone, catalyzed by a Lewis acid47-48 (see Table 3). With triinethylsilyl trifluoromethanesulfonate as a catalyst, in the presence of proline derived diamines anti-adducts are formed exclusively49 (see Section 1.5.2.4.3.1.). 

The last method for the preparation of 2-quinolones described in this chapter relies on a intramolecular Heck cyclization starting from heteroaryl-amides (Table 2) [57]. These are synthesized either from commercially available pyrrole- and thiophene-2-carboxylic acids (a, Table 2) or thiophene-and furan-3-carboxylic acids (b, Table 2) in three steps. The Heck cyclization is conventionally performed with W,Ar-dimethylacetamide (DMA) as solvent, KOAc as base and Pd(PPh3)4 as catalyst for 24 h at 120 °C resulting in the coupled products in 56-89% yields. As discussed in Sect. 3.4, transition metal-catalyzed reactions often benefit from microwave irradiation [58-61], and so is the case also for this intramolecular reaction. In fact, derivatives with an aryl iodide were successfully coupled by conventional methods, whereas the heteroarylbromides 18 and 19, shown in Table 2, could only be coupled in satisfying yields by using MAOS (Table 2). 

This procedure, which is based on the work of Ishii and co-workers, affords a mild and general method for converting a wide variety of esters to primary, secondary, and tertiary amides (Table 1). While the preparation of the tertiary amide, N,N-dimethylcyclohexanecarboxamide, described here is carried out in benzene, aluminum amides derived from ammonia and a variety of primary amines have been prepared by reaction with trimethylaluminum in dichloromethane and utilized for aminolysis in this solvent. Although 1 equivalent of the dimethylaluminum amides from amines was generally sufficient for high conversion within 5-48 hours, best results were obtained when 2 equivalents of the aluminum reagent from ammonia was used. Diethyl-aluminum amides can also effect aminolysis, but with considerably slower rates. 

Activated NHS esters of carboxylic acids are prepared by reacting the acid with NHS in the presence of DCC (Table 4, Figure 16). A-Hydroxysuccinimide esters are stable when kept under anhydrous and slightly acidic conditions, and they react rapidly with amino groups to form an amide in high yield. 

Table 3.3 Preparation of Weinreb amides from esters.

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