Preparation method of 3-methyl-3-butene-1-ol

Abstract

The invention provides a preparation method for 3-methyl-3-butene-1-ol. The preparation method comprises the following steps: in the presence of ultrasonic waves, carrying out an addition reaction on acetone and formaldehyde in an alkali solution to obtain 4-hydroxy-2-butanone; taking 4-hydroxy-2-butanone and isobutene to react in the presence of a strong acidic cationic resin catalyst to obtain an intermediate 1; taking the intermediate 1 and a methylenation reagent to react to obtain an intermediate 2; and carrying out a deprotection reaction on the intermediate 2 in the presence of a deprotection catalyst to obtain the product. The method is simple in process, low in cost, few in byproducts, good in selectivity and high in yield.

Description

technical field

[0001] The invention belongs to the field of synthesis of unsaturated alcohols, in particular to a preparation method of 3-methyl-3-buten-1-ol. Background technique

[0002] 3-Methyl-3-buten-1-ol is an important organic intermediate, which can be isomerized to synthesize 3-methyl-2-buten-1-ol under catalyst and certain temperature and pressure conditions , as a raw material for pyrethroids; in addition, the alcohol can be used as an initiator for the synthesis of polyether, under the action of a basic catalyst, to form a polymerization-initiating active species, thereby triggering the ring-opening polymerization of alkylene oxide to synthesize unsaturated polyether , the synthesized unsaturated polyether can be used as raw material for synthesizing ether type polycarboxylate water reducer.

[0003] The preparation method of 3-methyl-3-buten-1-ol is usually based on the Prins condensation reaction method, which is divided into the Prins thermal condensation r...

Examples

Embodiment 1

[0032] Add 1 mol of formaldehyde, 1 mol of acetone, and 0.01 mol of NaOH (prepared into a 0.1 mol / L aqueous solution) into a single-necked flask with mechanical stirring, and then place the flask in a constant temperature ultrasonic instrument with a frequency of 18KHz and power 150w, 120min at 20°C. After the reaction, the system was neutralized to neutral, transferred to a vacuum rectification device for vacuum distillation, and the fraction with a boiling point of 70-71°C (1.6KPa) was collected, which was 4-hydroxy-2-butanone.

[0033] Add 4-hydroxy-2-butanone, 2 mol of isobutene, 20 g of NKC-9 sulfonic acid resin, and 200 mL of n-hexane into a three-necked flask equipped with mechanical stirring, reflux condensing device, and thermometer. The temperature of the system is controlled at 50°C and the reaction time for 4h. After the reaction, the catalyst was recovered by filtration, and the filtrate was neutralized with sodium carbonate to neutrality, then transferred to rec...

Embodiment 2

[0039] Add 1 mol of formaldehyde, 3 mol of acetone, and 0.02 mol of KOH (prepared into a 0.5 mol / L aqueous solution) into a single-necked flask with mechanical stirring, and then place the flask in a constant temperature ultrasonic instrument with a frequency of 60KHz and power 480w, 30°C for 15min. After the reaction, the system was neutralized to neutral, transferred to a vacuum rectification device for vacuum distillation, and the fraction with a boiling point of 70-71°C (1.6KPa) was collected, which was 4-hydroxy-2-butanone.

[0040] Add 4-hydroxy-2-butanone, 1.1 mol of isobutene, 50 g of Amberlyst15 sulfonic acid resin, and 500 mL of n-hexane into a three-necked flask equipped with mechanical stirring, reflux condensing device, and thermometer. The temperature of the system is controlled at 60°C, and the reaction time is 6h. After the reaction, the catalyst was recovered by filtration, and the filtrate was neutralized with sodium carbonate to neutrality, then transferred...

Embodiment 3

[0045] 1mol formaldehyde, 4mol acetone, 0.10mol Na 2 CO 3 (prepared as a 1mol / L aqueous solution), added to a single-necked flask with mechanical stirring, and then placed the flask in a constant temperature ultrasonic instrument with a frequency of 45KHz and a power of 360w, and reacted at 25°C for 60min. After the reaction, the system was neutralized to neutral, transferred to a vacuum rectification device for vacuum distillation, and the fraction with a boiling point of 70-71°C (1.6KPa) was collected, which was 4-hydroxy-2-butanone.

[0046] Add 4-hydroxy-2-butanone, 3mol of isobutene, 70g of 001×7(732) hydrogen sulfonic acid resin, and 500mL of cyclohexane into a three-necked flask equipped with mechanical stirring, reflux condensing device, and thermometer to control the temperature of the system The temperature is 80°C and the reaction time is 8h. After the reaction, the catalyst was recovered by filtration, and the filtrate was neutralized with sodium carbonate to neu...

technical field

[0001] The invention belongs to the field of synthesis of unsaturated alcohols, in particular to a preparation method of 3-methyl-3-buten-1-ol. Background technique

[0002] 3-Methyl-3-buten-1-ol is an important organic intermediate, which can be isomerized to synthesize 3-methyl-2-buten-1-ol under catalyst and certain temperature and pressure conditions , as a raw material for pyrethroids; in addition, the alcohol can be used as an initiator for the synthesis of polyether, under the action of a basic catalyst, to form a polymerization-initiating active species, thereby triggering the ring-opening polymerization of alkylene oxide to synthesize unsaturated polyether , the synthesized unsaturated polyether can be used as raw material for synthesizing ether type polycarboxylate water reducer.

[0003] The preparation method of 3-methyl-3-buten-1-ol is usually based on the Prins condensation reaction method, which is divided into the Prins thermal condensation r...

Examples

Embodiment 1

[0032] Add 1 mol of formaldehyde, 1 mol of acetone, and 0.01 mol of NaOH (prepared into a 0.1 mol / L aqueous solution) into a single-necked flask with mechanical stirring, and then place the flask in a constant temperature ultrasonic instrument with a frequency of 18KHz and power 150w, 120min at 20°C. After the reaction, the system was neutralized to neutral, transferred to a vacuum rectification device for vacuum distillation, and the fraction with a boiling point of 70-71°C (1.6KPa) was collected, which was 4-hydroxy-2-butanone.

[0033] Add 4-hydroxy-2-butanone, 2 mol of isobutene, 20 g of NKC-9 sulfonic acid resin, and 200 mL of n-hexane into a three-necked flask equipped with mechanical stirring, reflux condensing device, and thermometer. The temperature of the system is controlled at 50°C and the reaction time for 4h. After the reaction, the catalyst was recovered by filtration, and the filtrate was neutralized with sodium carbonate to neutrality, then transferred to rec...

Embodiment 2

[0039] Add 1 mol of formaldehyde, 3 mol of acetone, and 0.02 mol of KOH (prepared into a 0.5 mol / L aqueous solution) into a single-necked flask with mechanical stirring, and then place the flask in a constant temperature ultrasonic instrument with a frequency of 60KHz and power 480w, 30°C for 15min. After the reaction, the system was neutralized to neutral, transferred to a vacuum rectification device for vacuum distillation, and the fraction with a boiling point of 70-71°C (1.6KPa) was collected, which was 4-hydroxy-2-butanone.

[0040] Add 4-hydroxy-2-butanone, 1.1 mol of isobutene, 50 g of Amberlyst15 sulfonic acid resin, and 500 mL of n-hexane into a three-necked flask equipped with mechanical stirring, reflux condensing device, and thermometer. The temperature of the system is controlled at 60°C, and the reaction time is 6h. After the reaction, the catalyst was recovered by filtration, and the filtrate was neutralized with sodium carbonate to neutrality, then transferred...

Embodiment 3

[0045] 1mol formaldehyde, 4mol acetone, 0.10mol Na 2 CO 3 (prepared as a 1mol / L aqueous solution), added to a single-necked flask with mechanical stirring, and then placed the flask in a constant temperature ultrasonic instrument with a frequency of 45KHz and a power of 360w, and reacted at 25°C for 60min. After the reaction, the system was neutralized to neutral, transferred to a vacuum rectification device for vacuum distillation, and the fraction with a boiling point of 70-71°C (1.6KPa) was collected, which was 4-hydroxy-2-butanone.

[0046] Add 4-hydroxy-2-butanone, 3mol of isobutene, 70g of 001×7(732) hydrogen sulfonic acid resin, and 500mL of cyclohexane into a three-necked flask equipped with mechanical stirring, reflux condensing device, and thermometer to control the temperature of the system The temperature is 80°C and the reaction time is 8h. After the reaction, the catalyst was recovered by filtration, and the filtrate was neutralized with sodium carbonate to neu...

Images