undecane

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

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-(2-fluorobenzyloxy)benzoic acid (P2, 5.5 g, 22.3 mmol) was suspended in thionyl chloride (16.5 mL) and heated to 65° C. and held for 3 hours during which time the reactor was kept under a slow sweep of nitrogen. The mixture was then concentrated to a thick oil under hi vac to remove all traces of residual thionyl chloride. The residue was then diluted in CH2Cl2 (20 mL) and cooled to 0° C. In a separate flask, a solution of diaza(1,3)bicycle[5.4.0]undecane (DBU, 8.0 mL, 8.15 g, 53.52 mmol) and N-methoxy-N-methyl amine hydrochloride (2.61 g, 26.76 mmol) in CH2Cl2 (20 mL) was made and slowly added to the solution at 0° C. After warming to 20-25° C., the mixture was washed with 1 M HCl and then with a saturated NaHCO3 solution. After drying over Na2SO4, the solution was concentrated to a thick residue. The mixture was then purified by flash column chromatography eluting with 0→100% EtOAc/hexanes (gradient). Concentration of the fractions containing the title compound gave an oil that crystallized upon standing (6.0 g, 93% yield). The mixture was then concentrated to a thick oil under hi vac to remove all traces of residual thionyl chloride The residue was then diluted in CH2Cl2 (20 mL) cooled to 0° C slowly added to the solution at 0° C After warming to 20-25° C. the mixture was washed with 1 M HCl After drying over Na2SO4 the solution was concentrated to a thick residue The mixture was then purified by flash column chromatography eluting with 0→100% EtOAc/hexanes (gradient) Concentration of the fractions containing the title compound gave an oil that crystallized

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

Procedure: D,L-2-aza-2'-hydroxy-5,6-benzotricyclo[6.3.01,8.04,11 ] undecane (2.68 g; 11.7 mmoles) is refluxed under argon in a mixture of acetic acid (67 ml) and 47% hydrobromic acid (677 ml) for 30 hours. The mixture is evaporated to dryness. The residue is dissolved in hot methanol and evaporated onto 15 g silica gel which is then placed on top of 80 g silica gel. Elution with chloroform:methanol:ammonium hydroxide (100:15:1 v:v:v) yields D,L-2-aza-2'-hydroxy-5,6-benzotricyclo[6.3.01,8.04,11 ] undecane hydrobromide: 2.23 g, 89%; melting point: 284°-286° C. The mixture is evaporated to dryness The residue is dissolved in hot methanol evaporated onto 15 g silica gel which Elution with chloroform:methanol:ammonium hydroxide (100:15:1 v:v:v)

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

Procedure: To a mixture of 307 mg (purity: 98.0%; 1.82 mmol) of 4-hydroxy-3,6-dichloropyridazine and 828 mg (5.53 mmol) of 2-cyclopropyl-6-methylphenol were added undecane (2.76 g) and 322 mg (5.46 mmol) of 95% potassium hydroxide at room temperature. The resultant mixture was heated to 180° C. while stirring, and stirred at that temperature for 4 hours. Then, the resultant reaction mixture was cooled to room temperature, and a 1 N aqueous hydrochloric acid solution and methanol were added to the reaction mixture to obtain a uniform solution. The obtained solution was quantitatively determined by an HPLC internal standard analysis method, which showed that 340 mg of 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (yield: 68%) and 1.8 mg of 3-chloro-6-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (yield: 0.4%) were obtained. stirred at that temperature for 4 hours Then, the resultant reaction mixture to obtain a uniform solution

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

Procedure: Black-colored colorant particles having a polystyrene core and a polypyrrole shell were produced and the surfaces thereof were hydrophobized in the same manner as in Example 10 except that the dodecyl methacrylate used for the hydrophobization was replaced by octyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.). The resultant is subjected to a centrifugation and a solvent substitution, to thereby obtain an undecane dispersion [12A] of black-colored colorant particles having a polystyrene core and a polypyrrole shell. The particle concentration of the undecane dispersion [12A] was adjusted to 20% by mass, to thereby obtain a black ink [12B] as an ink for an EW element.

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4.806 g of para-chlorobenzotrifluoride, 0.4991 g of cuprous chloride, 3.103 g of potassium fluoride, 13 g of ammonia, 17.9241 g of methanol, and 0.1961 g of n-undecane was heated at 200° C for 5 hrs in an 80 ml Hastelloy shaker tube. After cooling and venting the ammonia, the product mixture was removed. Most of the methanol and para-chlorobenzotrifluoride were distilled out of the product mixture. The remaining solution was diluted with diethyl ether and extracted with 0.5 M KOH to remove copper and ammonium salts as well as potassium fluoride. The ether layer was dried over CaSO4. Vacuum distillation of the ether layer gave 0.55 g of para-aminobenzotrifluoride. After cooling the product mixture was removed Most of the methanol and para-chlorobenzotrifluoride were distilled out of the product mixture The remaining solution was diluted with diethyl ether extracted with 0.5 M KOH to remove copper and ammonium salts as well as potassium fluoride The ether layer was dried over CaSO4 Vacuum distillation of the ether layer

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4.806 g of para-chlorobenzotrifluoride, 0.4991 g of cuprous chloride, 3.103 g of potassium fluoride, 13 g of ammonia, 17.9241 g of methanol, and 0.1961 g of n-undecane was heated at 200° C for 5 hrs in an 80 ml Hastelloy shaker tube. After cooling and venting the ammonia, the product mixture was removed. Most of the methanol and para-chlorobenzotrifluoride were distilled out of the product mixture. The remaining solution was diluted with diethyl ether and extracted with 0.5 M KOH to remove copper and ammonium salts as well as potassium fluoride. The ether layer was dried over CaSO4. Vacuum distillation of the ether layer gave 0.55 g of para-aminobenzotrifluoride. After cooling the product mixture was removed Most of the methanol and para-chlorobenzotrifluoride were distilled out of the product mixture The remaining solution was diluted with diethyl ether extracted with 0.5 M KOH to remove copper and ammonium salts as well as potassium fluoride The ether layer was dried over CaSO4 Vacuum distillation of the ether layer

Conditions: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1.80 M t-BuLi in pentane (0.78 mL, 1.40 mmol) was added at −40° C. to 5.0 mL of a THF solution of 4-methoxyphenylboronic acid pinacol ester (351.2 mg, 1.5 mmol). The reaction mixture was stirred at −40° C. for 30 minutes, and then stirred at 0° C. for 30 minutes. The solvent was removed at 0° C. under reduced pressure. White crystals of the residual lithium t-butyl borate were dissolved in 2.4 mL THF at 0° C. To the resulting solution of lithium t-butyl borate were added undecane (66.2 mg, 0.42 mmol), bromocycloheptane (178.2 mg, 1.01 mmol), a 0.10 M THF solution of magnesium bromide MgBr2 (2.00 mL, 0.20 mmol), and a THF solution (0.60 ml, 0.030 mmol, 3.00 mol %) of an iron chloride.1,2-bis(bis(3,5-trimethylsilylphenyl)phosphino)benzene complex (FeCl2.[3,5-(t-Bu)2]-DPPBz complex). The coupling reaction was performed at 40° C. for 3 hours. The resulting reaction mixture was cooled to 0° C., and 2.0 mL of a saturated aqueous solution of ammonium chloride was subsequently added thereto. The aqueous layer was extracted five times with diethylether. The combined organic extract was filtered using a Florisil pad (100-200 mesh, Nacalai Tesque, Inc.). After thin-layer chromatography (hexane), (4-methoxyphenyl)cycloheptane was obtained as a colorless liquid (0.199 g, yield 97%). stirred at 0° C. for 30 minutes The solvent was removed at 0° C. under reduced pressure White crystals of the residual lithium t-butyl borate were dissolved in 2.4 mL THF at 0° C The coupling reaction was performed at 40° C. for 3 hours The resulting reaction mixture was cooled to 0° C. The aqueous layer was extracted five times with diethylether The combined organic extract was filtered

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

Procedure: The following were charged into the aqueous phase: undecane, N-oxide, hexane (same quantities as above) and a supplementary amount of acetic acid (0.6 g). The mixture was then heated for 1 hour and the procedure was thereafter as before. Nine conversions were performed in this manner on the same catalytic lower layer. The yields of citral are given in the following table: The following were charged into the aqueous phase The mixture was then heated for 1 hour

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-(2-fluorobenzyloxy)benzoic acid (P2, 5.5 g, 22.3 mmol) was suspended in thionyl chloride (16.5 mL) and heated to 65° C. and held for 3 hours during which time the reactor was kept under a slow sweep of nitrogen. The mixture was then concentrated to a thick oil under hi vac to remove all traces of residual thionyl chloride. The residue was then diluted in CH2Cl2 (20 mL) and cooled to 0° C. In a separate flask, a solution of diaza(1,3)bicycle[5.4.0]undecane (DBU, 8.0 mL, 8.15 g, 53.52 mmol) and N-methoxy-N-methyl amine hydrochloride (2.61 g, 26.76 mmol) in CH2Cl2 (20 mL) was made and slowly added to the solution at 0° C. After warming to 20-25° C., the mixture was washed with 1 M HCl and then with a saturated NaHCO3 solution. After drying over Na2SO4, the solution was concentrated to a thick residue. The mixture was then purified by flash column chromatography eluting with 0→100% EtOAc/hexanes (gradient). Concentration of the fractions containing the title compound gave an oil that crystallized upon standing (6.0 g, 93% yield). The mixture was then concentrated to a thick oil under hi vac to remove all traces of residual thionyl chloride The residue was then diluted in CH2Cl2 (20 mL) cooled to 0° C slowly added to the solution at 0° C After warming to 20-25° C. the mixture was washed with 1 M HCl After drying over Na2SO4 the solution was concentrated to a thick residue The mixture was then purified by flash column chromatography eluting with 0→100% EtOAc/hexanes (gradient) Concentration of the fractions containing the title compound gave an oil that crystallized

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

Procedure: D,L-2-aza-2'-hydroxy-5,6-benzotricyclo[6.3.01,8.04,11 ] undecane (2.68 g; 11.7 mmoles) is refluxed under argon in a mixture of acetic acid (67 ml) and 47% hydrobromic acid (677 ml) for 30 hours. The mixture is evaporated to dryness. The residue is dissolved in hot methanol and evaporated onto 15 g silica gel which is then placed on top of 80 g silica gel. Elution with chloroform:methanol:ammonium hydroxide (100:15:1 v:v:v) yields D,L-2-aza-2'-hydroxy-5,6-benzotricyclo[6.3.01,8.04,11 ] undecane hydrobromide: 2.23 g, 89%; melting point: 284°-286° C. The mixture is evaporated to dryness The residue is dissolved in hot methanol evaporated onto 15 g silica gel which Elution with chloroform:methanol:ammonium hydroxide (100:15:1 v:v:v)

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

Procedure: D,L-2-aza-2'-hydroxy-5,6-benzotricyclo[6.3.01,8.04,11 ] undecane (2.68 g; 11.7 mmoles) is refluxed under argon in a mixture of acetic acid (67 ml) and 47% hydrobromic acid (677 ml) for 30 hours. The mixture is evaporated to dryness. The residue is dissolved in hot methanol and evaporated onto 15 g silica gel which is then placed on top of 80 g silica gel. Elution with chloroform:methanol:ammonium hydroxide (100:15:1 v:v:v) yields D,L-2-aza-2'-hydroxy-5,6-benzotricyclo[6.3.01,8.04,11 ] undecane hydrobromide: 2.23 g, 89%; melting point: 284°-286° C. The mixture is evaporated to dryness The residue is dissolved in hot methanol evaporated onto 15 g silica gel which Elution with chloroform:methanol:ammonium hydroxide (100:15:1 v:v:v)