1-methylcyclopenta-1,3-diene

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

Procedure: 33.4 g (417 mmol) of freshly distilled methylcyclopentadiene are added dropwise to a suspension of 10 g (417 mmol) of sodium hydride in 250 ml of absolute diethyl ether at RT over a period of one hour. 76.1 g of (3-chloropropyl)dimethoxy-methylsilane are subsequently added dropwise over a period of 30 minutes. The solution becomes warm during this process. After taking off the solvent, the mixture is fractionally distilled in an oil pump vacuum to give 78.9 g of (3-methylcyclopentadienylpropyl)dimethoxy-methylsilane (yield: 89%). The solution becomes warm during this process the mixture is fractionally distilled in an oil pump vacuum

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

Procedure: In the same manner as in Example 2, a Diels-Alder reaction was carried out on isobutylene and cyclopentadiene in order to synthesize 5,5-dimethyl-2-norbornene, and the latter was then reacted with methylcyclopentadiene to produce a 1:1:1 adduct of methylcyclopentadiene, cyclopentadiene and isobutylene. That is to say, 225 g of isobutylene and 260 g of cyclopentadiene were placed in a 1000-ml autoclave, and heating was gradually accomplished so that its temperature might become 25° to 120° C. and a reaction was performed at 120° C. for 8 hours, so that 118 g of 5,5-dimethyl-2-norbornene were obtained. Then, 115 g of the latter compound were similarly reacted with 201 g of methylcyclopentadiene at 120° C. for 10 hours. Then, 97 g of a fraction having a boiling point 97° C./1 mmHg were obtained. According to the measurement by a mass spectrometer, it was found that a molecular weight of the fraction was 202. Further, IR analysis indicated that characteristic absorptions of olefins appeared at 3020 cm-1 and 1670 cm-1. From these results, it was elucidated that the fraction was the 1:1 adduct of 5,5-dimethyl-2-norbornene and methylcyclopentadiene, i.e., the 1:1:1 adduct of methylcyclopentadiene, cyclopentadiene and isobutylene. In the same manner as in Example 2, a Diels-Alder reaction

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

Procedure: At 170° C., 156 g of propylene were reacted with 243 g of dimethyldicyclopentadiene for 20 hours, and by vacuum distillation 93 g of dimethylnorbornene were obtained. Then, 91 g of the thus prepared dimethylnorbornene were reacted with 135 g of dimethyldicyclopentadiene at 165° C. for 20 hours, and for the resultant reaction liquid, vacuum distillation was carried out to obtain 73 g of a 1:1 adduct of dimethylnorbornene and methylcyclopentadiene, i.e., a 2:1 adduct of methylcyclopentadiene and propylene at a boiling point of 97° C./2 mmHg. by vacuum distillation 93 g of dimethylnorbornene were obtained for the resultant reaction liquid, vacuum distillation

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

Procedure: To 130 ml of dehydrated methanol, 22.6 g (283 mmol) of methylcyclopentadiene and 8.50 ml (116 mmol) of acetone were added, then 14.5 ml (174 mmol) of pyrrolidine was dropwise added at 0° C., and the mixture was reacted at room temperature for one night. Then, 10 ml (180 mmol) of acetic acid was added at 0° C. The mixture was diluted with ether and water and then subjected to extraction. Then, the organic phase was separated, washed with water and dried over anhydrous magnesium sulfate to obtain 12.9 g of a brown liquid. The analyzed values are given below. the mixture was reacted at room temperature for one night subjected to extraction Then, the organic phase was separated washed with water dried over anhydrous magnesium sulfate

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

Procedure: To 130 ml of dehydrated methanol, 22.6 g (283 mmol) of methylcyclopentadiene and 8.50 ml (116 mmol) of acetone were added, then 14.5 ml (174 mmol) of pyrrolidine was dropwise added at 0° C., and the mixture was reacted at room temperature for one night. Then, 10 ml (180 mmol) of acetic acid was added at 0° C. The mixture was diluted with ether and water and then subjected to extraction. Then, the organic phase was separated, washed with water and dried over anhydrous magnesium sulfate to obtain 12.9 g of a brown liquid. The analyzed values are given below. the mixture was reacted at room temperature for one night subjected to extraction Then, the organic phase was separated washed with water dried over anhydrous magnesium sulfate

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 150 ml of methylcyclopentadiene dimer was fractionally distilled from 100 ml of mineral oil and at 62° C. and collected at 0° C. 500 mmol of methyl lithium (1.4 M; diethylether) were added, dropwise, to a mixture of 500 mmol of freshly distilled methylcyclopentadiene and 137 ml of dry acetone at 0° C. The solution was stirred for 1 hour at 25° C. 8 g (85% yield) of 3,6,6,-trimethylfulvene were recovered from the organic layer by vacuum distillation after an extraction with 100 ml of saturated, aqueous NH4Cl and drying over MgSO4. 150 ml of methylcyclopentadiene dimer was fractionally distilled from 100 ml of mineral oil and at 62° C. collected at 0° C

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

Procedure: The synthetic procedure according to Example 1 step A, is followed but the methylcyclopentadiene is replaced by 1,3-dimethylcyclopentadiene.

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

Procedure: The synthetic procedure according to Example 1 step A, is followed but the methylcyclopentadiene is replaced by 1,3-dimethylcyclopentadiene.

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

Procedure: A 1 liter flask was charged with 400 mL methanol, methylcyclopentadiene (120.0 mL, 1.21 mol), acetone (200 mL, 2.72 mol), and pyrrolidine (40.0 mL, 0.464 mol). After stirring the orange solution for 71 hours, 50 mL of acetic acid were added, followed by 1200 mL H2O and 200 mL diethyl ether. The organic layer was isolated and the aqueous layer was extracted with diethyl ether (5×100 mL). The combined organic layers were extracted with H2O (3×30 mL) and 10% aqueous NaOH (3×30 mL). The organic layer was dried over MgSO4, filtered and rotavapped to give 158.8 grams of a red-orange oil that was subjected to Kugelrohr distillation under high vacuum. The first 15 grams of material that distilled at room temperature was discarded and the product was obtained from the second fraction that distilled at 50° C.: 136.58 grams (94.0%). The organic layer was isolated the aqueous layer was extracted with diethyl ether (5×100 mL) The combined organic layers were extracted with H2O (3×30 mL) and 10% aqueous NaOH (3×30 mL) The organic layer was dried over MgSO4 filtered

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

Procedure: A 1 liter flask was charged with 400 mL methanol, methylcyclopentadiene (120.0 mL, 1.21 mol), acetone (200 mL, 2.72 mol), and pyrrolidine (40.0 mL, 0.464 mol). After stirring the orange solution for 71 hours, 50 mL of acetic acid were added, followed by 1200 mL H2O and 200 mL diethyl ether. The organic layer was isolated and the aqueous layer was extracted with diethyl ether (5×100 mL). The combined organic layers were extracted with H2O (3×30 mL) and 10% aqueous NaOH (3×30 mL). The organic layer was dried over MgSO4, filtered and rotavapped to give 158.8 grams of a red-orange oil that was subjected to Kugelrohr distillation under high vacuum. The first 15 grams of material that distilled at room temperature was discarded and the product was obtained from the second fraction that distilled at 50° C.: 136.58 grams (94.0%). The organic layer was isolated the aqueous layer was extracted with diethyl ether (5×100 mL) The combined organic layers were extracted with H2O (3×30 mL) and 10% aqueous NaOH (3×30 mL) The organic layer was dried over MgSO4 filtered

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

Procedure: Methylcyclopentadiene (8.01 g: 100 mmol) was dissolved in methyl ethyl ketone (10 mL), to which acrylic acid (7.93 g: 110 mmol) was added dropwise at 0° C. over 1 hour. The thus-obtained mixture was stirred at room temperature for 3 hours. Light components, such as the solvent and unreacted acrylic acid, were then distilled off under reduced pressure from the reaction mixture, whereby methyl-5-norbornene-2-carboxylic acid (14.9 g: 98 mmol) was obtained. was added dropwise at 0° C. over 1 hour Light components, such as the solvent and unreacted acrylic acid, were then distilled off under reduced pressure from the reaction mixture

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 150 ml of methylcyclopentadiene dimer was fractionally distilled from 100 ml of mineral oil and at 62° C. and collected at 0° C. 500 mmol of methyl lithium (1.4M; diethylether) were added, dropwise, to a mixture of 500 mmol of freshly distilled methylcyclopentadiene and 137 ml of dry acetone at 0° C. The solution was stirred for 1 hour at 25° C. 8 g (85% yield) of 3,6,6-trimethylfulvene were recovered from the organic layer by vacuum distillation after an extraction with 100 ml of saturated, aqueous NH4Cl and drying over MgSO4. 150 ml of methylcyclopentadiene dimer was fractionally distilled from 100 ml of mineral oil and at 62° C. collected at 0° C