Benzotrichloride

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: There were mixed together 23.0 grams (1.0 mole) of sodium metal along with 90 cc. of xylene and 80 cc. of tetrahydrofurane and the mixture placed under a nitrogen atmosphere. There were then added over a 35 minute period 138.10 grams (1.0 mole) of diethyl phosphite using external cooling to control the reaction exotherm and maintain the temperature at 60° to 65° C. After addition was complete the mixture was heated to 100° C. and maintained there for about 1 hour until there was no more sodium. The mixture was cooled to 60° C. and there was started the addition of 64.5 grams (0.33 mole) of benzotrichloride (α,α,α-trichlorotoluene). The exothermic reaction was cooled to maintain the temperature at 60° to 65° C. during the 25 minute addition period. The mixture was heated at 70° to 75° C. for 7 hours and the sodium chloride filtered off. The product in the pot was then subjected to distillation, terminal conditions being a pot temperature of 205° C., distillate temperature 125° C. and pressure 4 mm. The solid residue in the pot was hexaethyl phenyl methane triphosphonate. This product was hydrolyzed and the hydrolysis product purified as in Example 1 to obtain phenyl methane triphosphonic acid. external cooling maintain the temperature at 60° to 65° C After addition maintained there for about 1 hour until there The mixture was cooled to 60° C. The exothermic reaction was cooled to maintain the temperature at 60° to 65° C. during the 25 minute addition period The mixture was heated at 70° to 75° C. for 7 hours the sodium chloride filtered off The product in the pot was then subjected to distillation, terminal conditions a pot temperature of 205° C., distillate temperature 125° C. and pressure 4 mm the hydrolysis product purified as in Example 1

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: N,N'-Bis(4-n-octylcarbamylphenyl)benzamidine (4) was prepared from 4-amino-N-n-octylbenzamide and α,α,α-trichlorotoluene; pale-yellow oil: 1H-NMR (CDCl3) 7.7-6.9 (m, 14H), 6.2 (br t, 2H, J=6 Hz), 3.3 (br q, 4H, J=6 Hz), 1.7-0.7 (m, 30H); IR (CHCl3) 3430, 1640, 1590; MS (m/e) 582 (M+), 335 (base).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: N,N'-Bis[4-(2-ethylhexyl)oxycarbonylphenyl]benzamidine (3) was prepared from 2-ethylhexyl 4-aminobenzoate and α,α,α-trichlorotoluene; viscous, gold oil: 1H-NMR (CDCl3) 7.9-6.8 (m, 14H), 4.1 (d, 4H, J=4 Hz), 1.9-0.8 (m, 30H); IR (Neat) 3330, 1710, 1585; MS (m/e) 584 (M+), 336 (base).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: N,N'-Bis[4-(2-ethylhexyl)oxycarbonylphenyl]benzamidine (3) was prepared from 2-ethylhexyl 4-aminobenzoate and α,α,α-trichlorotoluene; viscous, gold oil: 1H-NMR (CDCl3) 7.9-6.8 (m, 14H), 4.1 (d, 4H, J=4 Hz), 1.9-0.8 (m, 30H); IR (Neat) 3330, 1710, 1585; MS (m/e) 584 (M+), 336 (base).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: N,N'-Bis(4-methoxycarbonylphenyl)benzamidine (1) was prepared from methyl 4-aminobenzoate and α,α,α-trichlorotoluene; pale-yellow crystals: mp 180°-182° C. 1H-NMR (CDCl3) 8.0-7.0 (m, 14H), 3.8 (s, 6H); IR (CDCl3) 3330, 1705, 1585; MS (m/e) 388 (M+), 238 (base).

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of ethyl 4-aminobenzoate (165.0 g; 1.0 mole) in xylene (465 mL) was added α,α,α-trichlorotoluene (100.7 g; 0.52 mole). The mixture was allowed to reflux for 18 h, then was cooled to 0° C. and filtered. The resultant precipitate was washed with ice-cold xylene (2×70 mL), triturated with hot toluene and dried to yield the salt (89.8 g; 39.7%) as white crystals: mp 214.0°-215.5° C. 1H-NMR (CDCl3) 8.0-6.9 (m, 14H), 4.3 (q, 4H, J=7 Hz), 1.4 (t, 6H, J=7 Hz); IR (CHCl3) 1715, 1600; MS (m/e) 416 (M+ -HCl), 252 (base). to reflux for 18 h filtered The resultant precipitate was washed with ice-cold xylene (2×70 mL) triturated with hot toluene dried to yield the salt (89.8 g; 39.7%) as white crystals

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 375.9 g (1.67 mol) of 3-bromotetrafluoropropionic acid, 10 g of ferric chloride, and 488.7 g (2.50 mol) of benzotrichloride was refluxed for 1.5 h, then crude product was removed, bp about 60°. Redistillation gave 287.9 g (71%) of 3-bromotetrafluoropropionyl chloride, bp 67°-68°. IR (CCl4): 5.53 (C=O). ##STR44## was refluxed for 1.5 h crude product was removed Redistillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 375.9 g (1.67 mol) of 3-bromotetrafluoropropionic acid, 10 g of ferric chloride, and 488.7 g (2.50 mol) of benzotrichloride was refluxed for 1.5 h, then crude product was removed, bp about 60°. Redistillation gave 287.9 g (71%) of 3-bromotetrafluoropropionyl chloride, bp 67°-68°. IR (CCl4): 5.53 (C=O). ##STR44## was refluxed for 1.5 h crude product was removed Redistillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 19.5 g (0.1 mole) of benzotrichloride, 18 g (0.2 mole) of butanethiol and 0.2 g of copper-I bromide were heated to the reflux temperature, while stirring, and were left to react until the evolution of hydrogen chloride had ended (duration: 6 hours). The mixture was then subjected to fractional distillation to give 11.9 g (74%) of benzal chloride at a boiling point of 102°-106° C./30 mbar. were left The mixture was then subjected to fractional distillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 19.5 g (0.1 mole) of benzotrichloride, 18 g (0.2 mole) of butanethiol and 0.2 g of copper-I bromide were heated to the reflux temperature, while stirring, and were left to react until the evolution of hydrogen chloride had ended (duration: 6 hours). The mixture was then subjected to fractional distillation to give 11.9 g (74%) of benzal chloride at a boiling point of 102°-106° C./30 mbar. were left The mixture was then subjected to fractional distillation

反応条件: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In the apparatus described in Example 13, 5.9 g of 2,5-diaminohydroquinone hydrochloride (28 m moles) were placed and at 180° C, 7.6 g of benzotrichloride (39 m moles) were added drop by drop. After 3 hours of heating at 190° C, the mixture was cooled and ground with mortar and pestle. The reaction product was extracted twice with 150 ml of xylene and passed through an aluminum oxide column heated at 125° C. The product was 4.5 g of crude XXII (74% of the theory). After two recrystallizations from xylene the melting point was 319°-323° C. were placed and at 180° C the mixture was cooled The reaction product was extracted twice with 150 ml of xylene heated at 125° C After two recrystallizations from xylene the melting point was 319°-323° C.

反応条件: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In the apparatus described in Example 13, 5.9 g of 2,5-diaminohydroquinone hydrochloride (28 m moles) were placed and at 180° C, 7.6 g of benzotrichloride (39 m moles) were added drop by drop. After 3 hours of heating at 190° C, the mixture was cooled and ground with mortar and pestle. The reaction product was extracted twice with 150 ml of xylene and passed through an aluminum oxide column heated at 125° C. The product was 4.5 g of crude XXII (74% of the theory). After two recrystallizations from xylene the melting point was 319°-323° C. were placed and at 180° C the mixture was cooled The reaction product was extracted twice with 150 ml of xylene heated at 125° C After two recrystallizations from xylene the melting point was 319°-323° C.