Reaction with diethylamino

It must be considered that silyl triflates are not stable in THF for an extended time, because they can initiate the cationic ring-opening polymerization (ROP) of cyclic ethers. Therefore, the silyl triflate (in diethyl ether) is added in drops to the (aminosilyl)lithium compound dissolved in THF. The reaction proceeds very quickly, and ROP of THF is not observed under these conditions. The trisilanes la - Ic can be converted by reaction with triflic acid into the silyl bis (triflates) 2a - 2c. These compounds are precursors for further chain elongation. The reaction with (diethylamino)-diphenylsilyllithium leads to the pentasilanes 3a - 3c. The reaction of bis(diethylamino)phenylsilyl-lithium [9] with silyl triflates proceeds analogously. The formation of the disilane 4 is shown in Scheme 2 as an example. Conversion with triflic acid and chain elongation with LiSiPh2(NEt2) leads to the branched tetrasilane 6. 

Kang, J., Kim, J. H., Jang, G. S. A Shapiro reaction with [(diethylamino)sulfonyl]hydrazones. Bull. Korean Chem. Soc. 1992, 13,192-199. 

Halide derivatives may be fluorides, chlorides, or bromides. Fluorides are best prepared by the reaction of hydroxy groups with (diethylamino)sulfur trilluoride ( DAST M. Sharma, 1977) or of glycosyl thioethers with DAST/NBS (K.C. Nicolaou, 1990 B). The other halides are usually only introduced at the glycosidic position, where treatment with hydrogen chloride... 

When the 2-hydroxy group of a monosaccharide reacts with (diethylamino)sulfur trifluoride (DAST), quantitative and stereoselective rearrangements are observed (K.C Nico-laou, 1986). This reaction may simultaneously introduce fluorine to C-1 and a new oxygen, sulfur, or nitrogen residue to C-2 with inversion of configuration. 

Dimroth rearrangement, 5, 438 Imidazolium chloride, 4-chloromethyl-reaction with poly(vinyl alcohol), 1, 306 Imidazolium chloride, 2,4,5-tri(diethylamino)-reduction, 5, 415 Imidazolium complexes, 7, 746... 

The enamino ketone (49) was reported to give no identifiable products on reaction with N,N-dimethyl carbamoyl chloride 63). However, reaction of (49) with N,N-diethyl carbamoyl chloride in refluxing chlorobenzene gave the N-(3-diethyl-amino-5,5-dimethylcyclohex-2-en-1 -ylidene)pyrrolidinium salt, isolated as the perchlorate. The latter must have been formed as outlined in Scheme I, involving initial O carbamoylation followed by an addition-elimination reaction to give 138 cation which can react with diethylamino anion by a further addition-elimination displacement to give the product 46). 

E. Miscellaneous Reactions.—Desulphurization of S-labelled benzyl trisulphide (119) with triphenylphosphine leads to predominant removal of the central sulphur atom, while reaction with tris(diethylamino)-... 

Heating pyridine-2,3-dicarboxylic acid anhydride with l-ethyl-2-methylindole has been claimed to yield solely the pyridine-2-carboxylic acid, albeit in low yield. This then clearly reacts with Af,A/-diethyl-3-toluidine in acetic anhydride to give the 7-azaphthalide. This is surprising in view of a later report70 in which a one-pot process has been described. Heating pyridine-2,3-dicarboxylic anhydride, prepared in situ, with the indole and subsequent reaction with 3-/V,/V-diethylamino-phenetol under identical conditions to those used in Scheme 8 (but without intermediate isolations) produced a 20 1 mixture of the 4- and 7-azaisomers 16 and 17. It appears that in the previous report the major intermediate isomer, the pyridine-3-carboxylic acid, has not been isolated. 

VUIb is formed by dimerization of the diazasilaindane, Vb, and subsequent reaction of the cyclic dimer, Vllb, with bis(phenylamino)-dimethylsilane, VIb, as it was shown in separate experiments starting from Vb and VIb. It was subsequently found that VUIb is formed in fairly good yield whenever o-phenylenediamine is brought into reaction with difunctional silanes, such as dichlorodimethylsilane, bis(diethylamino)dimethylsilane and hexamethyl-cyclotrisilazane. 

Lidocaine Lidocaine, 2-(diethylamino)-A-(2,6-dimethylphenyl)acetamide (2.2.2), is synthesized from 2,6-dimethylaniline upon reaction with chloroacetic acid chloride, which gives a-chloro-2,6-dimethylacetanilide (2.1.1), and its subsequent reaction with diethy-lamine [11]. 

Quinacrine Quinacrine, 6-chloro-9-(4-diethylamino-l-methylbntylamino)-2-methoxy-acridine (37.1.4.3), is synthesized from 6,9-dichloro-2-methoxyacridine (37.1.4.2) and aforementioned 4-diethylamino-l-methylbutylamine (37.1.1.2). The 6,9-dichloro-2-methoxyacridine (37.1.4.2) necessary for the synthesis is made in two stages. The initial reaction of 2,4-dichlorobenzoic acid and p-anizidine in the presence of copper dnst and potassium carbonate gives 2-(4-methoxyanilino)-4-chlorobenzoic acid (37.1.4.1), which upon reaction with phosphorus oxychloride turns into the necessary 6,9-dichloro-2-methoxyacridine (37.1.4.2) [33-38]. 

The a-pyrone (635) undergoes an exothermic Diels-Alder reaction with 1-diethylamino-1-propyne to afford the cycloadduct (636) (77JOC2930). Only a single regioisomer is produced, which is in line with the expected polarization of these reagents (Scheme 144). A Diels-Alder reaction of the same a-pyrone with 1-dibenzylamino-l-propyne affords an aniline derivative which has been employed in a chiral synthesis of the aromatic portion of the ionophore antibiotic lasalocid (80JA6178). 

---