3- Dimethylamino-4-hydroxy

Preparation by reaction of potassium hydroxide with2-acetyl-3-dimethylamino-5-hydroxy-5-methyl-2-cyclo-hexenone in ethanol at 40° (41%) [2712], Yellow oil [2712] m.p. -5° [2712] ... 

The positive effect of the electron-withdrawing substituent in the ortho position also allowed the use of the corresponding bromide in place of the iodide with comparable yields although for a longer time. Too-bulky groups such as t-butyl led to the exclusive formation of the hexahydromethanobiphenylene compound shown in Sect. 4.1, Eq. 33. Groups that interfere with palladium in arylnorbornylpalladium complexes, such as mono- and dimethylamino, hydroxy and acetoxy, inhibited the reaction. 

A A Dimethylamino)phenol. 3-Hydroxy-A7,A7-dimethylariiline (14) forms white needles and is soluble in alkaU, mineral acid, ethanol, diethyl ether, acetone, and benzene and practically insoluble in water. 

A A Dimethylamino)phenol. 4-Hydroxy-Ai,A/-dimethylaniline (20) forms large rhombic crystals from diethyl ether—hexane or diethyl ether—ligroin. It forms a salt with sulfuric acid, mp 208—210°C (187). 

Oxidation of thiophene with peracid under carefully controlled conditions gives a mixture of thiophene sulfoxide and 2-hydroxythiophene sulfoxide. These compounds are trapped by addition to benzoquinone to give ultimately naphthoquinone (225) and its 5-hydroxy derivative (226) (76ACS(B)353). The further oxidation of the sulfoxide yields the sulfone, which may function as a diene or dienophile in the Diels-Alder reaction (Scheme 88). An azulene synthesis involves the addition of 6-(A,A-dimethylamino)fulvene (227) to a thiophene sulfone (77TL639, 77JA4199). 

Benzo[0 furan, 7-dimethylamino-2,3-dihydro-3-hydroxy-2-methyl-, methiodide H NMR, 4, 548 <71JOC1805>... 

Bipyrimidin-4(3H)-one, 2 -(dimethylamino)-6-hydroxy-synthesis, 3, 114 l,r Bipyrrole, octaphenyl-photochromic compound, 1, 386 Bipyrroles... 

Isoquinoline, l-(dimethylamino)-methylation, 2, 179 Isoquinoline, halo-lithium derivatives, 2, 363 Isoquinoline, 3-halo-nucleophilic substitution, 2, 59 Isoquinoline, l-halo-3-hydroxy-synthesis... 

Direct bromination readily yields the 6-bromo derivative (111), just as with uracil. Analogous chlorination and iodination requires the presence of alkalies and even then proceeds in low yield. The 6-chloro derivative (113) was also obtained by partial hydrolysis of the postulated 3,5,6-trichloro-l,2,4-triazine (e.g.. Section II,B,6). The 6-bromo derivative (5-bromo-6-azauracil) served as the starting substance for several other derivatives. It was converted to the amino derivative (114) by ammonium acetate which, by means of sodium nitrite in hydrochloric acid, yielded a mixture of 6-chloro and 6-hydroxy derivatives. A modified Schiemann reaction was not suitable for preparing the 6-fluoro derivative. The 6-hydroxy derivative (115) (an isomer of cyanuric acid and the most acidic substance of this group, pKa — 2.95) was more conveniently prepared by alkaline hydrolysis of the 6-amino derivative. Further the bromo derivative was reacted with ethanolamine to prepare the 6-(2-hydroxyethyl) derivative however, this could not be converted to the corresponding 2-chloroethyl derivative. Similarly, the dimethylamino, morpholino, and hydrazino derivatives were prepared from the 6-bromo com-pound. ... 

Reaction of 2-amino-4/f-pyrido[l,2-n]pyrimidin-4-ones 143 with HNMei -HCl and paraformaldehyde in Dowtherm A afforded a mixture of 3-(A,A-dimethylamino)methyl derivatives 144 and bis-compounds 145 (93FES1225). Mannich reaction of 9-hydroxy-2-methyl-4//-pyri-dor],2-nlpyrimidin-4-one (146) yielded 8-aminomethyl derivatives 147 (94KFZ(10)23). 

R = R = H, R = -0CH2CH20H), and the hydroxy group then was acylated with 2-(dimethylamino)acetic acid in CH2CI2 in the presence of 1,3-dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine at room temperature (94EUP626378, 95USP5378720). 

Chemical Name 4-(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,6,10,12,12a-penta-hydroxy-N-[ [4-(2-hydroxyethyl)-1 -piperazinyl] methyl] -6-methyl-1,11-dioxo-2-naphtha-cenecarboxamide... 

The 4-hydroxy-2-methylindole (MP 112°C to 115°C from benzene/ethyl acetate), used as starting material, may be obtained by hydrogenation of 4-banzyloxy-2-dimethylamino-methylindole (MP 117°C to 120°C from benzene) in the presence of a palladium catalyst (5% on aluminum oxide). 

Dry hydrogen chloride gas was passed into the ether solution until precipitation was completed. The solid was removed by filtration and was recrystallized from a mixture of methanol and ethyl acetate. The a-dl-1,2-diphenyl-2-hydroxy-3-methyl-4-dimethylamino-butane hydrochloride thus obtained melted at about 231° to 232°C. 

Durch Reduktion der aus einem Propargylalkohol, Dimethylamino-methanol und Me-thyljodid erhaltenen quartaren Ammonium-Salze mit Natrium-bis-[2-methoxy-athoxy]-dihydrido-aluminat werden ebenfalls a-Hydroxy-allene erhalten z.B.1... 

Hydroxy-4-[6-methoxy-naphthyl-(2)J-l-trimethyIammoniono-pcntin-(2)-jodid 292 g (1,29 Mol) rohes 3-Hydroxy-3-[6-methoxy-naphthyl-(2)]-butin-(l) werden in 4 / abs. 1,4-Dioxan gelost und unter Riihren mit 25 g (0,126 Mol) Kupfer(I)-chlorid und 152 g (2,34 Mol) Dimethylamino-methanol versetzt. Man riihrt 45 Min. bei 25°, gibt Wasser zu, extrahiert mit Dichlormethan und engt ein. Der Ruckstand wird in 5/ Dichlormethan mit 220 g( 1,55 Mol) Methyljodid 18 Stdn. bei 5°geriihrtundmit 10/ Diathylather versetzt Aus-beute 290 g (53% d.Th.) F 114-117°. 

Dihydroxy-1,4-bis- [dim ethyl-amino-meihyl]-benzol6 3-Hydroxy-2-dimethylamino-methyl-naphlhalin6... 

Besonders ausgepragt ist die selektive Reduzierbarkeit von Dioxo-steroiden mit Na-triumboranat7 (weiteres s. S. 329, 331 f.), wahrend symmetrische Diketone nur als Mono-(2-dimethylamino-athoxyimine) selektiv zu Hydroxy-ketonen reduziert werden8. Benzil kann mit Triathyl-siliciumhydrid durch Zinkchlorid katalysiert selektiv zu Benzoin reduziert werden9 ... 

Bis-[ ( benzo-1,3-oxazol) -yl-(2)-thio]- 343 Bis-[1,4- (bzw. 3,4]-dihydro-naphthy[-(2)-oxy]- 588 Bis-[dimethylamino]- 345 Bis-[4-dimethyIamino-phenyl]- 346 Bis-[4-hydroxy-phenyl]-(2-carboxy-phenyl)- 167 Bis-[4-methoxy-phenyl]-dideutero- 346 Bis-[4-methyl-phenyl]-Bis-f 2-methyl-thiiranyl-(2)]- 570 Bis-[naphthyl-(2)-oxy]- 588 Bis-[naphthyl-(2)-thio]-... 

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