O-prop-2-enylhydroxylamine;hydrochloride

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 0.19 Gram of 2-propionyl-5-[2-(4-trifluoromethylphenylthio)ethyl]cyclohexane-1,3-dione was dissolved in 5 ml of ethanol, and 0.07 g of allyloxyamine hydrochloride and 0.06 g of triethylamine were added to the resulting solution which was then stirred overnight at room temperature. The reaction solution was poured into water, acidified and extracted with chloroform. After removing chloroform, the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1) to obtain 0.13 g of 2-(1-allyloxyaminopropylidene)-5-[2-(4-trifluoromethylphenylthio)ethyl]cyclohexane-1,3-dione. extracted with chloroform After removing chloroform the residue was purified by thin layer chromatography (eluent, hexane:ethyl acetate=5:1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Chloro-4-hydroxyphenyl)glyoxylic acid (2 g.) and O-allylhydroxylamine hydrochloride (1.1 g.) were reacted according to a similar manner to that of Preparation (5-2)(a) to give oil of 2-allyloxyimino-2-(3-chloro-4-hydroxyphenyl)acetic acid (syn isomer) (2.5 g.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Chloro-4-hydroxyphenyl)glyoxylic acid (2 g.) and O-allylhydroxylamine hydrochloride (1.1 g.) were reacted according to a similar manner to that of Preparation (5-2)(a) to give oil of 2-allyloxyimino-2-(3-chloro-4-hydroxyphenyl)acetic acid (syn isomer) (2.5 g.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Hydroxyphenyl)glyoxylic acid (2.0 g.) and O-allylhydroxylamine hydrochloride (1.7 g.) were reacted according to a similar manner to that of Preparation (5-2)(a) to give oil of 2-allyloxyimino-2-(3-hydroxyphenyl)acetic acid (syn isomer) (2.7 g.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Hydroxyphenyl)glyoxylic acid (2.0 g.) and O-allylhydroxylamine hydrochloride (1.7 g.) were reacted according to a similar manner to that of Preparation (5-2)(a) to give oil of 2-allyloxyimino-2-(3-hydroxyphenyl)acetic acid (syn isomer) (2.7 g.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Chloro-4-hydroxyphenyl)glyoxylic acid (2 g.) and O-allylhydroxylamine hydrochloride (1.1 g.) were reacted according to a similar manner to that of Preparation 5-2) (a) to give oil of 2-allyloxyimino-2-(3-chloro-4-hydroxyphenyl)acetic acid (syn isomer) (2.5 g.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Hydroxyphenyl)glyoxylic acid (2.0 g.) and O-allylhydroxylamine hydrochloride (1.7 g.) were reacted according to a similar manner to that of Preparation 5-2) (a) to give oil of 2-allyloxyimino-2-(3-hydroxyphenyl)acetic acid (syn isomer) (2.7 g.).

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4,6-dichloro-2,5-diformamidopyrimidine (3.75 g, 16 mmol), O-allylhydroxylamine hydrochloride (1.8 g, 16.4 mmol) and triethylamine (9.1 ml, 66 mmol) in dioxan (80 ml) was stirred at 100° C. for 6 hours. The cooled reaction mixture was filtered and evaporated to dryness under reduced pressure. The residue was on silica gel (eluted with chloroform chromatographed methanol, 10:1) and the product recrystallised from chloroform-methanol affording the title compound (2.1 g, 48%), m.p. 170°-181° C. IR: υmax (KBr) 3240, 1705, 1650, 1590, 1570, 1495, 1465, 1420 cm-1. 1H NMR: δH [(CD3)2SO] 4.37 (2H, d, J=6 Hz, CH2ON), 5.28 (2H, m, CH=CH2), 6.00 (1H, m, CH=CH2), 8.17 (1H, s, CHO), 9.30 (1H, s, CHO), 9.45 (1H, br.s, NH), 10.87 (2H, br.s, 2×NH). Found: C, 39.64; H, 3.49; N, 25.34%, M+ 271.0469. C9H10ClN5O3 requires C, 39.79; H, 3.71; N, 25.78%, M+ 271.0469. The cooled reaction mixture was filtered evaporated to dryness under reduced pressure the product recrystallised from chloroform-methanol affording the title compound (2.1 g, 48%), m.p. 170°-181° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Chloro-4-hydroxyphenyl)glyoxylic acid (2 g.) and O-allylhydroxylamine hydrochloride (1.1 g.) were reacted according to a similar manner to that of Preparation (5-2)(a) to give oil of 2-allyloxyimino-2-(3-chloro-4-hydroxyphenyl)acetic acid (syn isomer) (2.5 g.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Chloro-4-hydroxyphenyl)glyoxylic acid (2 g.) and O-allylhydroxylamine hydrochloride (1.1 g.) were reacted according to a similar manner to that of Preparation (5-2)(a) to give oil of 2-allyloxyimino-2-(3-chloro-4-hydroxyphenyl)acetic acid (syn isomer) (2.5 g.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(3-Hydroxyphenyl)glyoxylic acid (2.0 g.) and O-allylhydroxylamine hydrochloride (1.7 g.) were reacted according to a similar manner to that of Preparation (5-2)(a) to give oil of 2-allyloxyimino-2-(3-hydroxyphenyl)acetic acid (syn isomer) (2.7 g.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Triethylamine (1.2 g) was added to a solution of 2-butyryl-5,5-dimethyl -3-hydroxy-4-phenyl cyclohex-2-ene-1-one (2.8 g) and O-allylhydroxylamine hydrochloride (1.2 g) in ethanol (50 ml). After stirring at ambient temperature overnight, the ethanol was evaporated in vacuo, water was added to the residue and the aqueous solution extracted with methylene chloride. After drying the organic extracts over anhydrous magnesium sulphate, the methylene chloride was evaporated in vacuo. The residue was chromatographed on a silica gel column using 5% (v/v) diethyl ether-methylene chloride as eluant to give the title compound (2.1 g) as a viscous, colourless oil. the ethanol was evaporated in vacuo, water was added to the residue the aqueous solution extracted with methylene chloride After drying the organic extracts over anhydrous magnesium sulphate the methylene chloride was evaporated in vacuo The residue was chromatographed on a silica gel column