dichloromethylbenzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:62.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: There were charged into the reaction vessel 23.0 grams (1.0 mole) of sodium metal along with 90 cc. of xylene and 80 cc. of tetrahydrofurane. The vessel was placed under a nitrogen blanket and 138.10 grams (1.0 mole) of diethyl phosphite added over a 35 minute period. An exothermic reaction ensued which was maintained at 62° C. by external cooling. After addition was complete the mixture was heated to 100° C. and held there until all of the sodium metal was gone. The mixture was cooled to 60° to 70° C. and 80.50 grams (0.5 mole) of benzal chloride were added gradually over a 25 minute period. An exothermic reaction ensued which was maintained at 60° to 70° C. by external cooling. The mixture was then heated for 4 hours at 70° to 75° C., cooled to 60° C. The liquid material was separated from the solid and the solid boiled 8 times with 100 cc. of benzene to extract the organic material. The eluate product was then distilled, terminal conditions being a pot temperature of 201° C., distillate temperature 125° C. and pressure 6 mm. The solid residue of 70 grams was tetraethyl phenyl methane diphosphonate. This product was hydrolyzed and the hydrolysis product purified as in Example 1 to obtain phenyl methane diphosphonic acid. added over a 35 minute period An exothermic reaction After addition was heated to 100° C. The mixture was cooled to 60° to 70° C. An exothermic reaction was maintained at 60° to 70° C. by external cooling The mixture was then heated for 4 hours at 70° to 75° C. cooled to 60° C The liquid material was separated from the solid of benzene to extract the organic material The eluate product was then distilled a pot temperature of 201° C., distillate temperature 125° C. and pressure 6 mm the hydrolysis product purified as in Example 1

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

Procedure: 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

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

Procedure: 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

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

Procedure: To a cold (-78°), stirred solution containing 664 mg of ethyl 5-chloro-3-thiophenylindole-2-carboxylate from Preparation 5 in 3.5 mL of dry tetrahydrofuran, under argon, was added 3.5 mL of a 0.62 M solution of potassium hexamethylsilamide in toluene. The reaction mixture was stirred at -78° for 1 h and at 0° for 1 h then recooled to -78°. 0.75 mL of g chlorobenzyl chloride, 1.0 mL of hexamethylphosphoric triamide and 20 mg of tetra-n-butylammonium bromide were then added. The resultant mixture was allowed to warm to room temperature and stirred for 18 h. Saturated aqueous ammonium chloride and ether were added. The ether layer was separated, washed with water, 10% aqueous cupric sulfate, water and brine and dried over MgSO4. The reaction mixture was stirred at -78° for 1 h and at 0° for 1 h then recooled to -78° stirred for 18 h The ether layer was separated washed with water, 10% aqueous cupric sulfate, water and brine dried over MgSO4

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

Procedure: To a cold (-78°), stirred solution containing 664 mg of ethyl 5-chloro-3-thiophenylindole-2-carboxylate from Preparation 5 in 3.5 mL of dry tetrahydrofuran, under argon, was added 3.5 mL of a 0.62 M solution of potassium hexamethylsilamide in toluene. The reaction mixture was stirred at -78° for 1 h and at 0° for 1 h then recooled to -78°. 0.75 mL of g chlorobenzyl chloride, 1.0 mL of hexamethylphosphoric triamide and 20 mg of tetra-n-butylammonium bromide were then added. The resultant mixture was allowed to warm to room temperature and stirred for 18 h. Saturated aqueous ammonium chloride and ether were added. The ether layer was separated, washed with water, 10% aqueous cupric sulfate, water and brine and dried over MgSO4. The reaction mixture was stirred at -78° for 1 h and at 0° for 1 h then recooled to -78° stirred for 18 h The ether layer was separated washed with water, 10% aqueous cupric sulfate, water and brine dried over MgSO4

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

Procedure: Furthermore, it is known from Liebig's Annalen der Chemie, Volume 626, pages 26 to 34 (1959) to react benzaldehyde with triphenylphosphine dichloride to give benzal chloride, but the yield is only 59%. When cyclohexanone is reacted with triphenylphosphine dichloride in the presence of an equimolar amount of triethylamine it is not the corresponding geminal dihalide which is obtained but 1-chlorocyclohex-1-ene in 45% yield (loc. cit., page 33).

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: JP79125629 (1979) discloses a method for preparing α,α,α′,α′-tetrachloro-p-xylene by reacting 4-methyl benzaldehyde with PCl5, forming an intermediate product 4-methyl, 1-(dichloromethyl)benzene, and conducting a photochlorination reaction. This prior art method has the following reaction formula: The abovementioned reaction is a two-step reaction. Even though the first step reaction has a yield of 96.5%, the second step reaction has a very low yield. The product mixture is very difficult to be purified.

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

Procedure: Inside a nitrogen purged glove box, to a solution of 4-bromophenol (12.0 grams, 69.4 millimoles, 2.5 equivalents) dissolved in anhydrous 1-methyl-2-pyrrolidinone (100 milliliters), was added 95% sodium hydride (1.82 grams, 72.1 millimoles, 2.6 equivalents) in small portions over a 30 minute period. The reaction was stirred for an additional 90 minutes at room temperature. α,α-dichlorotoluene (4.13 milliliters, 27.7 millimoles, 1.0 equivalent) was added and the reaction was heated to 70° C. overnight. The reaction was quenched addition to water (200 milliliters). The aqueous phase was extracted with a 1:1 mixture of diethyl ether and ethyl acetate (3×120 mL). The combined organic phases were then washed with de-ionized water (5×100 milliliters), brine (1×100 milliliters) and dried over magnesium sulfate. After filtration and concentration on the rotary evaporator, the residue was taken up in diethyl ether (60 milliliters) and filtered through a plug of basic alumina. The product was fully eluted with additional diethyl ether (700 milliliters) and concentrated on the rotary evaporator. Further drying under high vacuum for several days yielded the product quantitatively in form of a yellow oil that crystallizes over time to give an off-white solid (12.0 grams, 27.7 millimoles, 100%). m.p.: 50.8; 1H-NMR (400 MHz, CDCl3) δ 7.59-7.51 (m, 2H), 7.44-7.37 (m, 3H), 7.37-7.29 (m, 4H), 6.93-6.82 (m, 4H), 6.59 (s, 1H); 13C-NMR (101 MHz, CDCl3) δ 155.07, 136.58, 132.59, 129.65, 128.86, 126.78, 119.60, 115.42, 100.77; FTIR: 605, 658, 674, 694, 741, 792, 816, 848, 886, 928, 984, 1031, 1060, 1100, 1115, 1167, 1178, 1210, 1242, 1280, 1304, 1363, 1449, 1483, 1584, 1689, 3033, 3065 cm−1; UV/Vis 223 (shoulder), 237, 278 nm; GC/MS/EI+: 432, 434, 436 [M+] (2×Br isotope pattern); 261, 263 [Br—C6H4—O—CHPh]+ (1×Br isotope pattern); 182 [C6H4—O—CHPh]+; HRMS (ESL): calc. for C19H13Br2O2− [M+Na]+ 430.9288, found 430.9287. the reaction was heated to 70° C. overnight The reaction was quenched addition to water (200 milliliters) The aqueous phase was extracted with a 1:1 mixture of diethyl ether and ethyl acetate (3×120 mL) The combined organic phases were then washed with de-ionized water (5×100 milliliters), brine (1×100 milliliters) dried over magnesium sulfate After filtration and concentration on the rotary evaporator filtered through a plug of basic alumina The product was fully eluted with additional diethyl ether (700 milliliters) concentrated on the rotary evaporator Further drying under high vacuum for several days yielded the product quantitatively in form of a yellow oil that crystallizes over time

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

Procedure: Inside a nitrogen purged glove box, to a solution of 4-bromophenol (12.0 grams, 69.4 millimoles, 2.5 equivalents) dissolved in anhydrous 1-methyl-2-pyrrolidinone (100 milliliters), was added 95% sodium hydride (1.82 grams, 72.1 millimoles, 2.6 equivalents) in small portions over a 30 minute period. The reaction was stirred for an additional 90 minutes at room temperature. α,α-Dichlorotoluene (4.13 milliliters, 27.7 millimoles, 1.0 equivalent) was added and the reaction was heated to 70° C. overnight. The reaction was quenched by addition to water (200 milliliters). The aqueous phase was extracted with a 1:1 mixture of diethyl ether and ethyl acetate (3×120 milliliters). The combined organic phases were then washed with de-ionized water (5×100 milliliters), brine (1×100 milliliters) and dried over magnesium sulfate. After filtration and concentration on the rotary evaporator, the residue was taken up in diethyl ether (60 milliliters) and filtered through a plug of basic alumina. The product was fully eluted with additional diethyl ether (700 milliliters) and concentrated on the rotary evaporator. Further drying under high vacuum for several days yielded the product quantitatively in form of a yellow oil that crystallizes over time to give an off-white solid (12.0 grams, 27.7 millimoles, 100%). m.p.: 50.8° C.; 1H-NMR (400 MHz, CDCl3) δ 7.59-7.51 (m, 2H), 7.44-7.37 (m, 3H), 7.37-7.29 (m, 4H), 6.93-6.82 (m, 4H), 6.59 (s, 1H); 13C-NMR (101 MHz, CDCl3) δ 155.07, 136.58, 132.59, 129.65, 128.86, 126.78, 119.60, 115.42, 100.77; FTIR: 605, 658, 674, 694, 741, 792, 816, 848, 886, 928, 984, 1031, 1060, 1100, 1115, 1167, 1178, 1210, 1242, 1280, 1304, 1363, 1449, 1483, 1584, 1689, 3033, 3065 cm−1; UV/Vis 223 (shoulder), 237, 278 nm; GC/MS/EI+: 432, 434, 436 [M+] (2×Br isotope pattern); 261, 263 [Br—C6H4—O—CHPh]+ (1×Br isotope pattern); 182 [C6H4—O—CHPh]•+ HRMS (EST): calc. for C19H13Br2O2 [M+Na]+ 430.9288. found 430.9287. the reaction was heated to 70° C. overnight The reaction was quenched by addition to water (200 milliliters) The aqueous phase was extracted with a 1:1 mixture of diethyl ether and ethyl acetate (3×120 milliliters) The combined organic phases were then washed with de-ionized water (5×100 milliliters), brine (1×100 milliliters) dried over magnesium sulfate After filtration and concentration on the rotary evaporator filtered through a plug of basic alumina The product was fully eluted with additional diethyl ether (700 milliliters) concentrated on the rotary evaporator Further drying under high vacuum for several days yielded the product quantitatively in form of a yellow oil that crystallizes over time

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

Procedure: The so-produced nonenyl chloride (112 g; 700 mmol) was added to an equimolar amount of the 2,4-hexadiene in a 100 mL round-bottomed flask equipped with a magnetic stir bar and a reflux condenser, along with 6 g of α,α-dichlorotoluene. This solution was subsurface-sparged with nitrogen for 10 minutes. The catalyst of Example 1 (1.15 g; 1.4 mmol) was added and the reaction flask was placed in an 85° C. oil bath for 15 hours. The reaction was terminated by cooling to room temperature, followed by the addition of 300 ml of hexanes and filtering three times through 75 g of silica gel. Hexanes were removed under reduced pressure and the remaining liquid was vacuum distilled through a 2 cm×30 cm packed bed column to yield 12 g of 8-nonen-1-yl chloride (Bpt1.5 36-40° C.), 46.3 g of 8-decen-1-yl chloride (Bpt1.5 56-60° C.), 15.3 g of 8,10-dodecadien-1-yl chloride (Bpt1.5 90-91 C.), and 30.4 g of 76% purity 1,16-dichloro-8-hexadecene and high boilers that remained in the distillation pot. This solution was subsurface-sparged with nitrogen for 10 minutes was placed in an 85° C. for 15 hours The reaction was terminated followed by the addition of 300 ml of hexanes filtering three times through 75 g of silica gel Hexanes were removed under reduced pressure distilled through a 2 cm×30 cm