CN102690175A - Preparation method of 3-methoxybenzyl chloride - Google Patents
Preparation method of 3-methoxybenzyl chloride Download PDFInfo
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Abstract
The invention discloses a preparation method of 3-methoxybenzyl chloride, which changes the traditional technical route. The preparation method comprises the following steps: methylating 3-hydroxybenzaldehyde to obtain 3-methoxybenzaldehyde, reducing with potassium borohydride to obtain 3-methoxybenzaldehyde, and chlorinating with hydrochloric acid to obtain the 3-methoxybenzyl chloride. The preparation method has the advantages of cheap and accessible raw materials, simple technical route and high safety, is simple to operate, lowers the cost, and solves the problem pf three-waste pollution; and the prepared methoxybenzyl chloride has the advantages of high content, controllable structural property and high purity (higher than 99%).
Description
Technical field
The present invention relates to a kind of preparation method of 3-methoxybenzyl chlorine, belong to the Chemicals preparation field.
Background technology
3-methoxybenzyl chlorine, another name: 3-methoxyl group benzyl chloride, 3-methoxy benzyl chlorine, 3-methoxy benzyl chlorine, meta-methoxy benzyl chloride, meta-methoxy benzyl chlorine; Molecular formula CH
3OC
6H
4CH
2Cl, CAS:824-98-6, molecular weight 156.61,124 ℃ of boiling points.Can be as a kind of medicine intermediate, be the important intermediate of synthetic anti-painstaking effort tubing drug salts acid clonidine, also can utilize the character of its benzyl chloride base to be used as other purposes.
At present, the main method of production 3-methoxybenzyl chlorine is:
The 3-methoxybenzaldehyde obtains 3-anisole methyl alcohol through the Raney's nickel reduction, prepares 3-methoxybenzyl chlorine with thionyl chloride through catalytic chlorination again.The used raw material of this technology has: 3-methoxybenzaldehyde, thionyl chloride, Raney's nickel, DMF, used solvent has: ethanol, toluene.Yet the catalyzer Raney's nickel is prone to inactivation in this technology, and service efficiency is low, and costs an arm and a leg.If use hydrogen to be reductive agent, there is substantial risk, be unfavorable for suitability for industrialized production.In addition, used solvent toluene toxicity is bigger, contaminate environment.Cause 3-methoxybenzaldehyde price higher.
Summary of the invention
In order to address the above problem, the present invention has designed a kind of preparation method of 3-methoxybenzyl chlorine, and this method has changed traditional operational path, through the 3-hydroxy benzaldehyde is obtained the 3-methoxybenzaldehyde through methylating; With potassium borohydride reduction to 3-anisole methyl alcohol, obtain 3-methoxyl group benzyl chloride with chlorination of hydrochloric acid then again, low in raw material cost is easy to get; Operational path is simple, and is easy and simple to handle, reduced cost; Significantly improve yield, solved the three-waste pollution problem, and method safety.
Technical scheme of the present invention is:
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) be the water dissolution that adds 1-10 times of 3-hydroxy benzaldehyde quality in the m-hydroxybenzaldehyde to the 3-hydroxy benzaldehyde; Under 10-50 ℃, in this solution, drip the sodium hydroxide of 0.25-0.7 times of 3-hydroxy benzaldehyde quality again, sodium hydroxide is diluted with water to concentration 10mol/L; And in 30-180 minute, dropwise; Drip the methyl-sulfate of 0.9-2 times of 3-hydroxy benzaldehyde quality between controlling 5-50 ℃, between 0.5-6 hour, dropwise, continue reaction 2-36 hour; Use adjusting PH with base=9-10 again, reacted 0.5-2 hour, add the methyl chloride solvent of 0.5-3 times of 3-hydroxy benzaldehyde quality again; Extracting and demixing, water layer merge organic layer with the methyl chloride SX of 0.5-1 times of 3-hydroxy benzaldehyde quality; Water washing with 0.5-1 times of 3-hydroxy benzaldehyde quality; Layering, normal pressure or negative pressure solvent evaporated obtain the 3-methoxybenzaldehyde;
Wherein, the add-on of described sodium hydroxide is preferably 0.5 times of 3-hydroxy benzaldehyde quality; The add-on of described methyl-sulfate is preferably 1.5 times of 3-hydroxy benzaldehyde quality.
(2) the 3-methoxybenzaldehyde that in step (1), obtains adds the water of 1-10 times of 3-methoxybenzaldehyde quality, adds the reductive agent of 0.05-1 times of 3-methoxybenzaldehyde quality under 25-60 ℃ in batches, adds continued reaction 1-10 hour; Regulate pH to acid with hydrochloric acid again; Layering, 3-anisole methyl alcohol, water layer is with twice of the methyl chloride SX of 0.5-1 times of 3-methoxybenzaldehyde quality; Normal pressure or negative pressure solvent evaporated get 3-anisole methyl alcohol, merge 3-anisole methyl alcohol;
Wherein, the add-on of described reductive agent is preferably 0.5 times of 3-methoxybenzaldehyde quality.
(3) secondary solvent that adds 0.5-5 times of 3-anisole methanol quality in the 3-anisole methyl alcohol that in step (2), obtains; The massfraction that adds 2-10 times of 3-anisole methanol quality again is the hydrochloric acid of 28-36.5%; Reacted 4-48 hour down at 25-55 ℃; Layering, water layer merges organic layer with the secondary solvent extraction of 0.2-1.5 times of 3-anisole methanol quality;
Wherein, the add-on of described hydrochloric acid is preferably 0.5 times of 3-anisole methanol quality.
(4) with organic phase washing twice in the step (3), the consumption of each water is the twice of organic phase weight; Wash twice with cleaning composition again, the 1-5 that each consumption is an organic phase weight doubly; Wash once with saturated nacl aqueous solution, consumption is 1-5 a times of organic phase weight again, and layering gets organic layer and distills out secondary solvent with micro-vacuum, goes out the colourless transparent liquid product with molecular distillation again;
Wherein, the add-on of described cleaning composition is preferably 3 times that wash organic phase weight; The add-on of described saturated nacl aqueous solution is preferably 3 times of washing organic phase weight.
Reaction equation is following:
In the above-mentioned steps: described reductive agent is POTASSIUM BOROHYDRIDE 97MIN, Peng Qinghuana or both mixtures;
Described methyl chloride solvent is one or more any mixture in methylene dichloride, trichloromethane, the tetrachloromethane;
Described secondary solvent is a hexanaphthene;
Described cleaning composition is for to comprise that the sodium hydrogencarbonate of 1-20% and the iron ion of 1-50% remove agent by percentage to the quality, and all the other are water; Wherein, to remove agent be Hydrocerol A, Trisodium Citrate, sodium ethylene diamine tetracetate or YD 30 to described iron ion.
The 3-hydroxy benzaldehyde that the present invention uses is technical grade.
The invention has the advantages that: utilize the 3-hydroxy benzaldehyde to prepare 3-methoxyl group benzyl chloride, through the 3-hydroxy benzaldehyde is obtained the 3-methoxybenzaldehyde through methylating, again with potassium borohydride reduction to 3-anisole methyl alcohol; Obtain 3-methoxyl group benzyl chloride with chlorination of hydrochloric acid then, low in raw material cost is easy to get, and operational path is simple; Easy and simple to handle; Reduce cost, solved the three-waste pollution problem, and method safety; The 3-methoxyl group benzyl chloride content of preparation is high, and textural property is controlled, and purity reaches more than 99 ﹪.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for explanation and explains the present invention, and be not used in qualification the present invention.
Embodiment 1
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) 80g 3-hydroxy benzaldehyde adds the 240g water dissolution, and 25 ℃ drip 28.8g sodium hydroxide (being diluted with water to concentration 10mol/L) down; Dripped off in about 30 minutes; Control 15-20 ℃ and drip 91.2g methyl-sulfate (add-on is the quality of 1.14 times of 3-hydroxy benzaldehydes) down, dripped off in about 60 minutes, continue reaction 180 minutes; Hydro-oxidation sodium is regulated pH to 9, stirs 30 minutes; Add the 100g methylene dichloride, stirred 15 minutes, layering, water layer merges organic layer with the 60g dichloromethane extraction, with the 100g washing, layering, solvent evaporated gets the 3-methoxybenzaldehyde.
(2) the 3-methoxybenzaldehyde of 80g adds 240g water, adds the 9.4g POTASSIUM BOROHYDRIDE 97MIN under 35-40 ℃ in batches, adds to continue reaction 2～3 hours.Reaction finishes, and dripping hydrochloric acid transfers PH to acid, and layering gets 3-anisole methyl alcohol, and water layer reclaims solvent and gets 3-anisole methyl alcohol with 50g * 2 time dichloromethane extraction, merges 3-anisole methyl alcohol.
(3) the 3-anisole methyl alcohol of 80g adds the 70g hexanaphthene, stirs, and adds massfraction and be 36.5% hydrochloric acid 360g, in 38-42 ℃ of reaction 12 hours, and layering, water layer is with the extraction of 40g hexanaphthene, the merging organic layer.
(4) organic layer that step (3) is obtained is used 150g water at every turn, washes 2 times, uses the saturated NaHCO of 150g more at every turn
3+ 200 gram EDTA two sodium solutions are washed 2 times, use 150g saturated nacl aqueous solution (normal temperature) to wash once then, leave standstill, and divide earlier and remove free-water, leave standstill more than 60 minutes again, divide and remove residual moisture.At-0.10Mpa vacuum tightness recover solvent, bullion, under-0.099Mpa vacuum tightness, tell front-end volatiles earlier, begin to collect 3-methoxybenzyl chlorine products again, product content >=99%.
Embodiment 2
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) 80g 3-hydroxy benzaldehyde; Add 400g water, 25 ℃ drip 28.8g Pottasium Hydroxide (being diluted with water to concentration 10mol/L) down, dripped off in about 30 minutes; Drip 91.2g methyl-sulfate (add-on is the quality of 1.14 times of 3-hydroxy benzaldehydes) under controlling 20-30 ℃ dripped off in about 60 minutes; Continue reaction 180 minutes, hydro-oxidation potassium is regulated pH to 10, stirs 30 minutes; Add the 100g ethylene dichloride, stirred 15 minutes, layering, water layer merges organic layer with the extraction of 60g ethylene dichloride, with the 100g washing, layering, solvent evaporated gets the 3-methoxybenzaldehyde.
(2) the 3-methoxybenzaldehyde of 80g adds 240g water, adds the 9.4g Peng Qinghuana under 30-35 ℃ in batches, adds to continue reaction 2～3 hours.React and finish, dripping hydrochloric acid transfers PH to acid, and layering gets 3-anisole methyl alcohol, and water layer reclaims solvent and gets 3-anisole methyl alcohol with 50g * 2 time ethylene dichloride extraction, merges 3-anisole methyl alcohol.
(3) the 3-anisole methyl alcohol of 80g adds the 70g hexanaphthene, stirs, and adds the hydrochloric acid 360g of massfraction 37%, in 35-48 ℃ of reaction 12 hours, and layering, water layer merges organic layer with the extraction of 40g hexanaphthene.
(4) organic layer that step (3) is obtained is used 150g water at every turn, washes 2 times, uses the saturated NaHCO of 150g more at every turn
3+ 200 gram sodium citrate solns are washed 2 times, wash once with the 150g saturated nacl aqueous solution then, leave standstill, and divide earlier and remove free-water, leave standstill more than 60 minutes again, divide and remove residual moisture.At-0.10Mpa vacuum tightness recover solvent, bullion, under-0.099Mpa vacuum tightness, tell front-end volatiles earlier again, begin to collect 3-methoxybenzyl chlorine products again, product content >=99%.
Embodiment 3
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) 80g 3-hydroxy benzaldehyde adds 640 water, and 25 ℃ drip 20g sodium hydroxide (being diluted with water to concentration 10mol/L) down; Dripped off in about 30 minutes; Control 15-20 ℃ and drip 72g methyl-sulfate (add-on is the quality of 0.9 times of 3-hydroxy benzaldehyde) down, dripped off in about 60 minutes, continue reaction 180 minutes; Hydro-oxidation sodium is regulated pH to 9, stirs 30 minutes; Add the 100g trichloromethane, stirred 15 minutes, layering, water layer merges organic layer with the 60g chloroform extraction, with the 100g washing, layering, solvent evaporated gets the 3-methoxybenzaldehyde.
(2) the 3-methoxybenzaldehyde of 80g adds 240g water, adds the 9.4g POTASSIUM BOROHYDRIDE 97MIN under 35-40 ℃ in batches, adds to continue reaction 2-3 hour.React and finish, dripping hydrochloric acid transfers PH to acid, and layering gets 3-anisole methyl alcohol, and water layer reclaims solvent and gets 3-anisole methyl alcohol with 50g * 2 time chloroform extraction, merges 3-anisole methyl alcohol.
(3) the 3-anisole methyl alcohol of 80g adds the 70g hexanaphthene, stirs, and adds massfraction and be 36.5% hydrochloric acid 360g, in 38-42 ℃ of reaction 12 hours, and layering, water layer is with the extraction of 40g hexanaphthene, the merging organic layer.
(4) organic layer that step (3) is obtained is used 150g water at every turn, washes 2 times, uses the saturated NaHCO of 150g more at every turn
3+ 200 gram EDTA two sodium solutions are washed 2 times, wash once with the 150g saturated nacl aqueous solution then, leave standstill, and divide earlier and remove free-water, leave standstill more than 60 minutes again, divide and remove residual moisture.At-0.10Mpa vacuum tightness recover solvent, bullion, under-0.099Mpa vacuum tightness, tell front-end volatiles earlier again, begin to collect 3-methoxybenzyl chlorine products again, product content >=99%.
Embodiment 4
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) 80g 3-hydroxy benzaldehyde adds 800g water, and 25 ℃ drip 28.8g sodium hydroxide (being diluted with water to concentration 10mol/L) down; Dripped off in about 30 minutes; Control 25-35 ℃ and drip 91.2g methyl-sulfate (add-on is the quality of 1.14 times of 3-hydroxy benzaldehydes) down, dripped off in about 60 minutes, continue reaction 180 minutes; Hydro-oxidation sodium is regulated pH to 10, stirs 30 minutes; Add the 100g ethylene dichloride, stirred 15 minutes, layering, water layer merges organic layer with the 60g dichloromethane extraction, with the 100g washing, layering, solvent evaporated gets the 3-methoxybenzaldehyde.
(2) the 3-methoxybenzaldehyde of 80g adds 240g water, adds the 9.4g POTASSIUM BOROHYDRIDE 97MIN under 38-50 ℃ in batches, adds to continue reaction 2-3 hour.React and finish, dripping hydrochloric acid transfers PH to acid, and layering gets 3-anisole methyl alcohol, and water layer reclaims solvent and gets 3-anisole methyl alcohol with 50g * 2 time ethylene dichloride extraction, merges 3-anisole methyl alcohol.
(3) the 3-anisole methyl alcohol of 80g adds the 70g hexanaphthene, stirs, and adds the hydrochloric acid 360g of massfraction 36.5%, in 45-55 ℃ of reaction 12 hours, and layering, water layer merges organic layer with the extraction of 40g hexanaphthene.
(4) organic layer that step (3) is obtained is used 150g water at every turn, washes 2 times, washes 2 times with the saturated NaHCO3+200 gram of 150g EDTA two sodium solutions more at every turn; Wash once with the 150g saturated nacl aqueous solution then, leave standstill, divide earlier and remove free-water; Leave standstill again more than 60 minutes, divide and remove residual moisture.At-0.10Mpa vacuum tightness recover solvent, bullion, under-0.099Mpa vacuum tightness, tell front-end volatiles earlier again, begin to collect 3-methoxybenzyl chlorine products again, product content >=99%.
Embodiment 5
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) 80g 3-hydroxy benzaldehyde adds 240g water, and 25 ℃ drip 28.8g Pottasium Hydroxide (being diluted with water to concentration 10mol/L) down; Dripped off in about 30 minutes; Control 25-35 ℃ and drip 91.2g methyl-sulfate (add-on is the quality of 1.14 times of 3-hydroxy benzaldehydes) down, dripped off in about 60 minutes, continue reaction 180 minutes; Hydro-oxidation sodium is regulated pH to 9, stirs 30 minutes; Add the 100g methylene dichloride, stirred 15 minutes, layering, water layer merges organic layer with the 60g dichloromethane extraction, with the 100g washing, layering, solvent evaporated gets the 3-methoxybenzaldehyde.
(2) the 3-methoxybenzaldehyde of 80g adds 240g water, adds the 9.4g POTASSIUM BOROHYDRIDE 97MIN under 35-40 ℃ in batches, adds to continue reaction 2-3 hour.React and finish, dripping hydrochloric acid transfers PH to acid, and layering gets 3-anisole methyl alcohol, and water layer reclaims solvent and gets 3-anisole methyl alcohol with 50g * 2 time dichloromethane extraction, merges 3-anisole methyl alcohol.
(3) the 3-anisole methyl alcohol of 80g adds the 70g hexanaphthene, stirs, and adds the hydrochloric acid 480g of massfraction 20%, in 30-35 ℃ of reaction 12 hours, and layering, water layer merges organic layer with the extraction of 40g hexanaphthene.
(4) organic layer that step (3) is obtained is used 150g water at every turn, washes 2 times, uses the saturated NaHCO of 150g more at every turn
3+ 400 gram sodium citrate solns are washed 2 times, wash once with the 150g saturated nacl aqueous solution then, leave standstill, and divide earlier and remove free-water, leave standstill more than 60 minutes again, divide and remove residual moisture.At-0.10Mpa vacuum tightness recover solvent, bullion, under-0.099Mpa vacuum tightness, tell front-end volatiles earlier again, begin to collect 3-methoxybenzyl chlorine products again, product content >=99%.
Embodiment 6
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) 80g 3-hydroxy benzaldehyde adds 240g water, 25 ℃ of following Dropwise 5 6g sodium hydroxide (being diluted with water to concentration 10mol/L); Dripped off in about 30 minutes; Control 15-20 ℃ and drip 160g methyl-sulfate (add-on is the quality of 2 times of 3-hydroxy benzaldehydes) down, dripped off in about 60 minutes, continue reaction 180 minutes; Hydro-oxidation sodium is regulated pH to 10, stirs 30 minutes; Add the 100g methylene dichloride, stirred 15 minutes, layering, water layer merges organic layer with the 60g dichloromethane extraction, with the 100g washing, layering, solvent evaporated gets the 3-methoxybenzaldehyde.
(2) the 3-methoxybenzaldehyde of 80g adds 240g water, adds the 9.4g POTASSIUM BOROHYDRIDE 97MIN under 35-40 ℃ in batches, adds to continue reaction 2-3 hour.React and finish, dripping hydrochloric acid transfers PH to acid, and layering gets 3-anisole methyl alcohol, and water layer reclaims solvent and gets 3-anisole methyl alcohol with 50g * 2 time dichloromethane extraction, merges 3-anisole methyl alcohol.
(3) the 3-anisole methyl alcohol of 80g adds the 70g hexanaphthene, stirs, and adds the hydrochloric acid 360g of massfraction 36.5%, in 38-42 ℃ of reaction 12 hours, and layering, water layer merges organic layer with the extraction of 40g hexanaphthene.
(4) organic layer that step (3) is obtained is used 150g water at every turn, washes 2 times, washes 2 times with the saturated NaHCO3+200 gram of 150g edta solution more at every turn; Wash once with the 150g saturated nacl aqueous solution then, leave standstill, divide earlier and remove free-water; Leave standstill again more than 60 minutes, divide and remove residual moisture.At-0.10Mpa vacuum tightness recover solvent, bullion, under-0.099Mpa vacuum tightness, tell front-end volatiles earlier again, begin to collect 3-methoxybenzyl chlorine products again, product content >=99%.
Embodiment 7
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) 80g 3-hydroxy benzaldehyde adds 80g water, and 10 ℃ drip 20g sodium hydroxide (being diluted with water to concentration 10mol/L) down; Dripped off in about 30 minutes, and controlled 5 ℃ and drip the 72g methyl-sulfate down, dripped off in about 30 minutes; Continue reaction 2 hours, hydro-oxidation sodium is regulated pH to 9, stirs 30 minutes; Add the 40g methylene dichloride, stirred 15 minutes, layering, water layer merges organic layer with the 40g dichloromethane extraction, with the 40g washing, layering, solvent evaporated gets the 3-methoxybenzaldehyde.
(2) the 3-methoxybenzaldehyde of 80g adds 80g water, adds the 4g POTASSIUM BOROHYDRIDE 97MIN under 25 ℃ in batches, adds to continue reaction 1 hour.React and finish, dripping hydrochloric acid transfers PH to acid, and layering gets 3-anisole methyl alcohol, and water layer reclaims solvent and gets 3-anisole methyl alcohol with 40g * 2 time dichloromethane extraction, merges 3-anisole methyl alcohol.
(3) the 3-anisole methyl alcohol of 80g adds the 40g hexanaphthene, stirs, and adds the hydrochloric acid 160g of massfraction 28%, in 25 ℃ of reactions 4 hours, and layering, water layer merges organic layer with the extraction of 40g hexanaphthene.
(4) organic layer that step (3) is obtained is used 80g water at every turn, washes 2 times, washes 2 times with the saturated NaHCO3+46 gram of 34g edta solution more at every turn; Wash once with the 80g saturated nacl aqueous solution then, leave standstill, divide earlier and remove free-water; Leave standstill again more than 60 minutes, divide and remove residual moisture.At-0.10Mpa vacuum tightness recover solvent, bullion, under-0.099Mpa vacuum tightness, tell front-end volatiles earlier again, begin to collect 3-methoxybenzyl chlorine products again, product content >=99%.
Embodiment 8
A kind of preparation method of 3-methoxybenzyl chlorine specifically may further comprise the steps:
(1) 80g 3-hydroxy benzaldehyde adds 800g water, 50 ℃ of following Dropwise 5 6g sodium hydroxide (being diluted with water to concentration 10mol/L); Dripped off in about 3 hours, and controlled 50 ℃ and drip the 160g methyl-sulfate down, dripped off in about 6 hours; Continue reaction 36 hours, hydro-oxidation sodium is regulated pH to 10, stirs 2 hours; Add the 240g methylene dichloride, stirred 15 minutes, layering, water layer merges organic layer with the 80g dichloromethane extraction, with the 80g washing, layering, solvent evaporated gets the 3-methoxybenzaldehyde.
(2) the 3-methoxybenzaldehyde of 80g adds 800g water, adds the 80g POTASSIUM BOROHYDRIDE 97MIN under 60 ℃ in batches, adds to continue reaction 10 hours.React and finish, dripping hydrochloric acid transfers PH to acid, and layering gets 3-anisole methyl alcohol, and water layer reclaims solvent and gets 3-anisole methyl alcohol with 80g * 2 time dichloromethane extraction, merges 3-anisole methyl alcohol.
(3) the 3-anisole methyl alcohol of 80g adds the 400g hexanaphthene, stirs, and adds the hydrochloric acid 800g of massfraction 36.5%, in 55 ℃ of reactions 48 o'clock, and layering, water layer merges organic layer with the extraction of 120g hexanaphthene.
(4) organic layer that step (3) is obtained is used 400g water at every turn, washes 2 times, washes 2 times with the saturated NaHCO3+240 gram of 160g edta solution more at every turn; Wash once with the 400g saturated nacl aqueous solution then, leave standstill, divide earlier and remove free-water; Leave standstill again more than 60 minutes, divide and remove residual moisture.At-0.10Mpa vacuum tightness recover solvent, bullion, under-0.099Mpa vacuum tightness, tell front-end volatiles earlier again, begin to collect 3-methoxybenzyl chlorine products again, product content >=99%.The physical and chemical index parameter of the 3-methoxyl group benzyl chloride that embodiment 1-8 makes sees the following form.
The physical and chemical index parameter list of 3-methoxyl group benzyl chloride
| Sequence number | Outward appearance | Content % | Specific density |
| 1 | Colourless transparent liquid | 99.46 | 1.15 |
| 2 | Colourless transparent liquid | 99.36 | 1.14 |
| 3 | Colourless transparent liquid | 99.21 | 1.15 |
| 4 | Colourless transparent liquid | 99.18 | 1.15 |
| 5 | Colourless transparent liquid | 99.08 | 1.16 |
| 6 | Colourless transparent liquid | 99.23 | 1.15 |
| 7 | Colourless transparent liquid | 99.33 | 1.16 |
| 8 | Colourless transparent liquid | 99.13 | 1.15 |
Wherein, the outward appearance in the 3-methoxyl group benzyl chloride is to measure through appearance method; Content is through measuring with chromatography of gases; Specific density is to measure through densometer.
Except as otherwise noted, the percentage ratio that is adopted among the present invention is weight percentage.
What should explain at last is: the above is merely the preferred embodiments of the present invention; Be not limited to the present invention; Although the present invention has been carried out detailed explanation with reference to previous embodiment; For a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a 3-methoxybenzyl chlorine is characterized in that, specifically may further comprise the steps:
(1) is to be dissolved in water in the m-hydroxybenzaldehyde to the 3-hydroxy benzaldehyde, in this solution, drips the sodium hydroxide of 0.25-0.7 times of 3-hydroxy benzaldehyde quality again, drip the methyl-sulfate of 0.9-2 times of 3-hydroxy benzaldehyde quality again; And with adjusting PH with base=9-10; Add the extraction agent extraction again, washing, layering; Solvent evaporated obtains the 3-methoxybenzaldehyde;
(2) the 3-methoxybenzaldehyde that in step (1), obtains adds water, and adds the reductive agent of 0.05-1 times of 3-methoxybenzaldehyde quality, and is extremely acid with acid for adjusting pH after reaction is accomplished; Layering; Water layer extracts with extraction agent, and solvent evaporated obtains 3-anisole methyl alcohol;
(3) add secondary solvent in the 3-anisole methyl alcohol that in step (2), obtains, add the hydrochloric acid of 2-10 times of 3-anisole methanol quality again, layering, water layer extracts with secondary solvent, merges organic layer;
(4) with organic phase washing in the step (3), wash with cleaning composition then, wash with saturated nacl aqueous solution again, layering, organic layer, steam secondary solvent, steam again product.
2. preparation method according to claim 1 is characterized in that: described reductive agent is POTASSIUM BOROHYDRIDE 97MIN, Peng Qinghuana or both mixtures.
3. preparation method according to claim 1 is characterized in that: described extraction agent is the methyl chloride solvent.
4. preparation method according to claim 3 is characterized in that: described methyl chloride solvent is one or more any mixture in methylene dichloride, trichloromethane, the tetrachloromethane.
5. preparation method according to claim 1 is characterized in that: described secondary solvent is a hexanaphthene.
6. preparation method according to claim 1 is characterized in that: described cleaning composition is for to comprise that the sodium hydrogencarbonate of 1-20% and the iron ion of 1-50% remove agent by percentage to the quality, and all the other are water.
7. preparation method according to claim 1 is characterized in that: it is Hydrocerol A, Trisodium Citrate, sodium ethylene diamine tetracetate or YD 30 that described iron ion removes agent.
8. preparation method according to claim 1 is characterized in that: the add-on of the middle sodium hydroxide of said step (1) is 0.5 times of 3-hydroxy benzaldehyde quality; The add-on of methyl-sulfate is 1.5 times of 3-hydroxy benzaldehyde quality.
9. preparation method according to claim 1 is characterized in that: the add-on of the middle reductive agent of said step (2) is 0.5 times of 3-methoxybenzaldehyde quality.
10. preparation method according to claim 1 is characterized in that: the add-on of the middle hydrochloric acid of said step (3) is 0.5 times of 3-anisole methanol quality.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483166A (en) * | 2013-09-16 | 2014-01-01 | 台州职业技术学院 | Method for preparing m-anisaldehyde |
| CN114736098A (en) * | 2021-12-07 | 2022-07-12 | 上海泰坦科技股份有限公司 | Chloro compound and preparation method thereof |
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| CN103483166B (en) * | 2013-09-16 | 2015-06-24 | 台州职业技术学院 | Method for preparing m-anisaldehyde |
| CN114736098A (en) * | 2021-12-07 | 2022-07-12 | 上海泰坦科技股份有限公司 | Chloro compound and preparation method thereof |
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