4- cyano-1-methoxy

Substituted benzyl fluorides react with sodium bcnzenethiolate yielding substituted (ben-zylsulfanyl)benzenes.1 The reactions were studied kinetically and found to be of the SN2 type.1 As expected, from the chloro-, cyano-, methoxy-, and methylbenzyl fluorides tested, 4-(fluoro-methyl)benzonitrile is the most reactive derivative. 

NitroBIPS having in the 5 -position (4 -X-benzoyloxy)-benzylidenamino substituents (128), where X is cyano, methoxy, and n-hexoxy, form amorphous films exhibiting birefringence when colored. The bulk materials exhibit quasi-liquid crystalline properties, intermediate between supercooled liquids and mesophases, which are attributed to the interactions between small ordered domains of the spiropyran molecules.149... 

Pentacoordinated hydrosilanes react with excess aryl isocyanates to give isocyanurates. Carboxylic acids are directly reduced to aldehydes in a one-pot process through the thermal decomposition of pentacoordinated silyl carboxylates (eq 4). The aldehydes are extracted from the crude product mixture by distillation, or separated from the trisiloxane by column chromatography over FlorisU. The reaction is selective, since fluoro, nitro, cyano, methoxy and heteroaryl substituents do not react with the silane. The present method also permits the reduction of Q , -unsaturated acids. The efficiency follows the order (2) > (1) > (3). 

A soln. of 1.42 g. dimethyl acetylenedicarboxylate in acetonitrile added with stirring and ice-cooling to a soln. of 2.26 g. isoquinolinium cyano(methoxy-carbonyl)methylid in the same solvent, the ice-cooled mixture allowed to stand overnight, then coned, under reduced pressure below 40° -> 2.75 g. trimethyl 3-cyano-3,10b-dihydropyrrolo[2,l-a]isoquinoline-l,2,3-tricarboxylate. T. Kutsuma, K. Fujiyama, and Y. Kobayashi, Chem. Pharm. Bull. 20, 1809 (1972). 

Treatment of quinoline with cyanogen bromide, the von Braun reaction (17), in methanol with sodium bicarbonate produces a high yield of l-cyano-2-methoxy-l,2-dihydroquinoline [880-95-5] (5) (18). Compound (5) is quantitatively converted to 3-bromoquinoline [5332-24-1], through the intermediate (6) [66438-70-8]. These conversions are accompHshed by sequential treatment with bromine in methanol, sodium carbonate, or concentrated hydrochloric acid in methanol. Similar conditions provide high yields of 3-bromomethylquinoHnes. 

Pyridazine 1-oxides substituted at position 3 or positions 3 and 6 afford the corresponding 5-nitro derivatives. A methyl group at position 6 (a with respect to the iV-oxide group) is frequently converted into the cyano group, and a methoxy group at position 6 is demethy-lated by benzoyl chloride/silver nitrate. For example, 3-substituted 6-methylpyridazine 1-oxides give the 5-nitro derivatives (96) and the 6-cyano-5-nitro derivatives (97), whereas... 

Pyridinium methiodide, 3-cyano-hydrogen-deuterium exchange, 2, 287 Pyridinium methiodide, 3-methyl-hydrogen-deuterium exchange, 2, 287 Pyridinium methosulfate, l-methoxy-3-methyl-reactions... 

Pyridinium salts, 3-carbamoyl-l-methoxy-covalent amination, 2, 239 Pyridinium salts, cetyl-in electrophotography, 1, 391 Pyridinium salts, 3-chloro-l-methyl-covalent amination, 2, 239 Pyridinium salts, N-cyano-reactions... 

Like the Cope rearrangement, the Claisen rearrangement is sensitive to substituents on the reacting system. Cyano groups promote the rearrangement by a factor of 10 at positions 2 and 4 and have smaller effects at the other positions, as shown below. Data are also available for methoxy groups at positions 2, 4, 5, and 6. ... 

The stabilizing role of other functional groups can also be described in resonance terms. Both electron-attracting groups such as carbonyl and cyano and electron-donating groups such as methoxy and dimethylamino have a stabilizing etfect on a radical intermediate at an adjacent carbon. The resonance structures which depict these interactions indicate delocalization of the unpaired electron onto the adjacent substituents ... 

Methoxy-D-Homo-estra-l,3,5(10)-trien-17a-one (96)" (/) Acetic acid (6.4 ml) is added to a stirred solution of estrone methyl ether (93 1.1 g) in ethanol (35 ml) containing potassium cyanide (6 g) at 0°. After being stirred for 1 hr at 0° and 2.5 hr at room temperature, the reactants dissolve and potassium acetate preciptates. Water (65 ml) is added to the reaction mixture and the precipitated solid is collected by filtration. The crude product is dissolved in ethyl acetate and the ethyl acetate solution is washed with water, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. Recrystallization of a portion of the crude product from cyclohexane-acetone gives 3-methoxy-17a-cyano-estra-l, 3,5(10)-trien-17j5-ol (94a) as needles mp 158.5°. 

A solution of the crude cyanohydrin (94a ca. 1 g) in pyridine (15 ml) and acetic anhydride (15 ml) is allowed to stand at room temperature for 52 hr. The solvents are evaporated under reduced pressure below 60°. The residue is dissolved in ether, and the ether solution is washed successively with 5 % hydrochloric acid, water and saturated salt solution. The solvent is evaporated under reduced pressure to give a crystalline residue. Recrystallization of the crude product from cyclohexane-acetone gives 3-methoxy-17a-cyano-estra-l,3,5(10)-trien-17i5-ol acetate (94b 0.9 g), mp 130-132°, as large prisms. 

Methoxy-17a-cyano-estra-l,3,5(10)-trien-17/8-ol acetate, 388 3-Methoxyestra-2,5(10)-dien-17-one, 68 3-Methoxyestra-2,5( 10)-dien-17-one 17-ethylene ketal, 367, 371 3-Methoxyestra-3,5( 10)-dien-17-one 17-ethylene ketal, 369... 

The relative electron-donating ability of rings can be estimated by the change in the infrared stretching frequencies of attached amino, carbonyl, cyano, or methoxy groups, but the quantitative relation to chemical reactivity does not appear to be defined at... 

BRP2307177). The bromine atom of 203 was also replaced by a methoxy and a cyano groups with NaOMe in the presence of Cu(I)I and with Cu(I)CN to give compounds 205 and 206, respectively. The nitrile group of 206 was converted into a methoxycarbonyl group to give compound 207. 

Reaction of 5-cyano-6-methoxy-l,2,3,4-tetrahydropyridin-2-ones 387 with 1,3-propanediamine in boiling A/, A -dimethylacetamide gave 9-cyano-l,2,3,4,7,8-hexahydro-6//-pyrido-[l,2-n]pyrimidin-6-ones 388 either via route a or via route b (95H(41)2173). 

The 2-cyano-6-methoxy-naphthalene is in turn converted by successive reactions into ... 

Miscellaneous Identified Inhibitors. 3-Acetyl-6-methoxy-benzaldehyde is present in the leaves of the desert shrub Encelia farinosa. It is apparently leached from the leaves and washed into the soil by rain. Concentrations of approximately 0.5 mg. per gram of dried leaf material have been measured. In sand culture studies, growth of tomato seedlings was inhibited by 50 p.p.m. while 115 p.p.m. reduced growth by 50% (53). A concentration of 250 p.p.m. killed the test plants within one day. The structure was confirmed by synthesis, and the synthetic material was shown to be as active as the natural product (54). Derivatives were also prepared in which a cyano, nitro, or amino group was substituted for the aldehyde moiety. The amino derivative was reported to be the most highly toxic. 

Abietylamine, dehydro-, A tnfluoro- [Acetamide, 2,2,2-trifluoro-/V-[ [1,2,3,4,4a, 9,10,1 Oa-octahydro-l, 4a-dtmethyl-7-(l-methylethyl)-l -phenanthrenyl ] -methyl]-, [17 (la,4ad,10aa))-, 125 Acetamides, A-arylalkyl-, 7 Acetanilide, 2,2,2-tnfluoro- [Acetamide, 2,2,2-tnfluoroTV-phenyl-], 122 Acetic acid, cyano-, methyl ester, 63 Acetic acid, methoxy-, 70 Acetic acid, phenoxy-, 68 Acetic acid, phenyl- [Benzeneacetic acid],... 

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