Preparation method of 3-butene-1-ol and derivative 4-bromo-1-butene thereof

Abstract

The invention discloses a preparation method of 3-butene-1-ol and a derivative 4-bromine-1-butene thereof, and provides a brand-new synthesis method for new heterocyclic derivative drugs and pesticide intermediates. The synthesis method comprises the following steps: by taking 1, 4-butanediol as a raw material, firstly reacting with sulfonyl chloride to synthesize 1, 4-butanediol monosulfonate (I), then carrying out elimination reaction under the action of alkali to obtain 3-butene-1-ol (II), then reacting with sulfonyl chloride to synthesize corresponding active ester (III), and finally carrying out substitution reaction with NaBr to prepare the intermediate 4-Br-1-butene IV. The method has the advantages of cheap and easily available raw materials, unharsh reaction conditions, low equipment requirements, simple process operation and low process cost, and has important significance for research and development of preparation methods and amplified production of 3-butene-1-ol and derivatives thereof 4-Br-1-butene.

Description

Technical Field

[0001] The invention relates to the technical field of fine chemicals, and in particular to a method for preparing 3-butene-1-ol and its derivative 4-bromo-1-butene. Background Art

[0002] 3-Butene-1-ol molecules contain double bonds and hydroxyl groups, which can undergo a variety of chemical reactions such as esterification, addition, oxidation and reduction. They are widely used in petrochemicals, agrochemical products, pharmaceutical synthesis and other fields. They are important intermediates for the synthesis of heterocyclic derivatives and new drugs, and their market demand is very large. 4-Br-1-butene is a derivative of 3-butene-1-ol and a brominated olefin. It can be used not only as a reagent but also as a drug intermediate in organic synthesis. Therefore, the development of the synthesis method of 3-butene-1-ol intermediates and their derivatives 4-Br-1-butene intermediates is worthy of research by synthesis workers.

[0003] The synthetic methods of 3-butene-1-ol reported so far mainly include:

[0004] (1) Patent CN108715573, in which the author uses ethylene oxide and vinyl chloride as raw materials and ether as solvent. Vinyl chloride first reacts with magnesium metal to form a Grignard reagent, and then reacts with ethylene oxide ether solution to synthesize the target product. This method uses explosive ether solvent and involves the preparation of Grignard reagent. Industrial production is very dangerous. In addition, ethylene oxide and vinyl chloride are gases, and the equipment requirements are relatively high. The reaction formula is as follows:

[0005]

[0006] (2) Patent JP2017014133, in which the author uses 1,4-butanediol as raw material, and synthesizes the target product under high temperature and high pressure conditions of 300-375°C under the action of a catalyst. In order to avoid the dangers of conventional high temperature and high pressure reactions, this method uses fluid chemical synthesis technology, but the cost of the flow pipeline reactor is higher than that of the traditional reactor. The reaction formula is as follows:

[0007]

[0008] (3) Patent CN111704524, in which the author uses allyl bromide, zinc powder, and formaldehyde as raw materials and ethyl acetate as solvent to synthesize 3-butene-1-ol under the catalysis of copper salt. This method uses easily explosive zinc powder, which has a high risk factor, and the price of the raw material allyl bromide is relatively high, and the process cost is high. The reaction formula is as follows:

[0009]

[0010] The main methods for synthesizing 4-bromo-1-butene reported so far are:

[0011] (1) Patent US5208244A, in which the author uses 3-butyne-1-ol as raw material, ether as solvent, and phosphorus tribromide as bromination reagent to synthesize 4-bromo-n-butyne. In the document Journal of the American Chemical Society, 1988, vol. 110, p. 5383, the author uses diisobutylaluminum hydride as a reducing agent to reduce the acetylenic bond to a double bond to obtain 4-bromo-1-butene. This scheme uses explosive and dangerous solvent ether and expensive raw material 3-butyne-1-ol and reducing agent diisobutylaluminum hydride, and the yield of the bromination reaction is only 27%. The process cost is high, which is not conducive to commercial production. The reaction formula is as follows:

[0012]

[0013] (2) Patent JP5979791B2, the author of the patent, using hydroxymethylcyclopropane as raw material, under the action of equimolar ionic liquid 1-ethyl-3-methylimidazolium bromide, passing hydrogen bromide gas to react, NMR monitoring reaction 4-bromo-1-butene conversion rate is only 20%, bromomethylcyclopropane conversion rate is 51%, cyclobutyl bromide conversion rate is 24%. This method has low product conversion rate, and the price of ionic liquid is relatively high, which is not conducive to commercial scale-up production. Its reaction formula is as follows:

[0014]

[0015] (3) The Journal of Chemical Research, Miniprint, 1992, #9, p. 2409–2446 reported that 4-bromo-1-butene was synthesized by using 1,4-dibromobutane as raw material and HMPA as solvent at 200-210°C. The solvent HMPA in this scheme is a potential carcinogen, and the reaction needs to be carried out at high temperature, which places high demands on equipment. The reaction formula is as follows:

[0016]

[0017] In order to solve the problem of industrial production, the present application studies the synthesis method of 3-butene-1-ol and its derivative 4-bromo-1-butene, and provides a new synthesis method with cheap and readily available raw materials and simple process, which is suitable for industrial production. Summary of the invention

[0018] In order to solve the technical and industrial production problems, the present invention provides a preparation method of 3-butene-1-ol and its derivative 4-X-1-butene (X=Br, I), specifically, 1,4-butanediol is used as a raw material, first reacted with R1-sulfonyl chloride to synthesize 1,4-butanediol mono R1-sulfonate, then an elimination reaction is carried out under the action of a base to obtain 3-butene-1-ol, then reacted with sulfonyl chloride to generate active R2-sulfonate, and finally an SN2 substitution reaction is carried out with NaBr to obtain 4-Br-1-butene.

[0019] In this scheme, the chemical structural formulas of 3-butene-1-ol and 4-bromo-1-butene are as shown in (II) and (IV) below:

[0020]

[0021] The synthesis route is shown in the following reaction flow:

[0022]

[0023] In order to achieve the above technical objectives, the technical solution adopted by the present invention is:

[0024] The preparation method of 3-butene-1-ol comprises: taking 1,4-butanediol as a raw material, first reacting it with R1-sulfonyl chloride to synthesize 1,4-butanediol mono R1-sulfonate (I), and then performing an elimination reaction under the action of a base to obtain 3-butene-1-ol (II).

[0025] As a preferred implementation option, preferably, the preparation method of 3-butene-1-ol in this scheme comprises the following steps:

[0026] Step 1), in the presence of a base, 1,4-butanediol is used as a raw material, and it is first reacted with R1-sulfonyl chloride to synthesize 1,4-butanediol mono R1-sulfonate (Ⅰ);

[0027] Step 2), under the action of a base, 1,4-butanediol mono R1-sulfonate undergoes an elimination reaction to obtain 3-butene-1-ol (II).

[0028] As a preferred implementation option, preferably, in step 2) of this scheme, a solvent is used when the 1,4-butanediol mono R1-sulfonate undergoes an elimination reaction, and the solvent is one of DMSO, THF, and DMF.

[0029] As a preferred implementation option, preferably, in step 1) and / or step 2) of this scheme, the base is one of sodium hydride, potassium hydride, potassium tert-butoxide, and sodium tert-butoxide.

[0030] As a preferred implementation option, preferably, in step 2) of this scheme, the reaction temperature of the elimination reaction is -5 to 30°C, and the reaction time is 5 to 25 hours.

[0031] Based on the above, this solution further proposes a method for preparing 4-bromo-1-butene, a derivative of 3-butene-1-ol, characterized in that: it uses the preparation method described in any one of claims 2 to 5, and further includes:

[0032] Step 3), under alkaline conditions, reacting 3-butene-1-ol with R2-sulfonyl chloride to obtain active R2-sulfonate (III);

[0033] Step 4), the active R2-sulfonate is reacted with the nucleophilic reagent NaBr to undergo SN2 substitution reaction to obtain 4-bromo-1-butene (IV).

[0034] As a preferred implementation option, preferably, in step 3) of this scheme, a reaction solvent is used when 3-butene-1-ol is reacted with R2-sulfonyl chloride to obtain active R2-sulfonate, which is one of dichloromethane, tetrahydrofuran and DMF.

[0035] As a preferred implementation option, preferably, in step 3) of this scheme, the alkaline condition is constructed by sodium hydride, triethylamine, and DIEA, and the reaction temperature is -5 to 35°C, and the reaction time is 2 to 20 hours.

[0036] As a preferred implementation option, preferably, in step 4) of this scheme, when the active R2-sulfonate is subjected to an SN2 substitution reaction with a nucleophilic reagent NaBr to obtain 4-bromo-1-butene, a solvent is used, which is one of acetone, 2-butanone, and DMF, the reaction temperature of the substitution reaction is 25-75°C, and the reaction time is 2 to 24 hours.

[0037] Based on the above, this scheme further proposes a method for preparing 3-butene-1-ol and its derivative 4-bromo-1-butene, which includes the preparation method described above.

[0038] By adopting the above technical scheme, the present invention has the following beneficial effects compared with the prior art: the scheme provides a method for preparing 3-butene-1-ol and its derivative 4-bromo-1-butene, which provides a new synthesis method for heterocyclic derivative new drugs and pesticide intermediates; specifically, it relates to a method of using 1,4-butanediol as a raw material, first reacting with sulfonyl chloride to synthesize 1,4-butanediol monosulfonate (I), then undergoing an elimination reaction under the action of a base to obtain 3-butene-1-ol (II), then reacting with sulfonyl chloride to synthesize the corresponding active ester (III), and finally undergoing a substitution reaction with NaBr to prepare the intermediate 4-Br-1-butene IV. The synthetic method has cheap and easy-to-obtain raw materials, undemanding reaction conditions, low equipment requirements, simple process operation, and low process cost, and is of great significance for the research and development of a preparation method for 3-butene-1-ol and its derivative 4-Br-1-butene and scaled-up production. DETAILED DESCRIPTION

[0039] The present invention will be further described in detail below in conjunction with the embodiments. It is particularly noted that the following embodiments are only used to illustrate the present invention, but are not intended to limit the scope of the present invention. Similarly, the following embodiments are only partial embodiments of the present invention rather than all embodiments, and all other embodiments obtained by those of ordinary skill in the art without creative work are within the scope of protection of the present invention.

[0040] This embodiment proposes a method for preparing 3-butene-1-ol and its derivative 4-Br-1-butene, and its chemical structural formula is shown in (II) and (IV) below:

[0041]

[0042] The synthesis route is shown in the following reaction flow:

[0043]

[0044] The preparation method comprises: using 1,4-butanediol as a raw material, first reacting with sulfonyl chloride to synthesize 1,4-butanediol monosulfonate (I), then performing an elimination reaction under the action of a base to obtain an intermediate 3-butene-1-ol (II), then reacting with sulfonyl chloride to synthesize a corresponding active ester intermediate (III), and finally performing a substitution reaction with NaBr to prepare an intermediate 4-Br-1-butene (IV).

[0045] In order to facilitate the elaboration of this solution, the following is an implementation description of the solution in combination with multiple embodiments:

[0046] The terms are as follows:

[0047] DMF N,N-Dimethylformamide THF Tetrahydrofuran <![CDATA[ 1 H-NMR]]> H NMR DIEA N,N-Diisopropylethylamine NaBr Sodium bromide HMPA Hexamethylphosphoric acid triamide DMSO Dimethyl sulfoxide d-DMSO Deuterated dimethyl sulfoxide

[0048] Example 1

[0049] The preparation method of 3-butene-1-ol and its derivative 4-Br-1-butene in this embodiment comprises:

[0050] 1,4-Butanediol (40g, 0.44mol, 4.0eq) was dissolved in dichloromethane (200mL), triethylamine (11.67g, 0.116mol, 1.05eq) was added, the temperature was controlled at -5 to 5°C, p-toluenesulfonyl chloride (20.97g, 0.11mol, 1.0eq) was slowly added in batches, after the addition was completed, the mixture was stirred for 1 to 3 hours at a temperature of 100°C, water (200g) was added to quench the reaction, the mixture was allowed to stand to separate the lower organic layer, dichloromethane (120mL*2) was added to the aqueous phase and extracted twice, the organic phases were combined, washed twice with water (200mL*2), the organic phase was dried over anhydrous sodium sulfate, and dried under reduced pressure at 30 to 60°C to obtain 21.5g of 1,4-butanediol monosulfonate, i.e., intermediate I (measured yield 80%).

[0051] The obtained product was subjected to hydrogen nuclear magnetic resonance spectroscopy, and the result was:

[0052] 1 HNMR(CDCl3)δ7.80(m,2H),7.35(d,J=8.4Hz,2H),4.07(t,J=6.4Hz,2H),3.6 3(t,J=6.4Hz,2H),2.46-2.45(m,3H),1.75-1.71(m,2H),1.63-1.55(m,2H).

[0053] Take intermediate I (i.e. 150 g, 0.613 mol, 1.0 eq of 1,4-butanediol monosulfonate) and dissolve it in DMSO (1500 mL), cool to -5°C, control the temperature at -5 to 10°C, slowly add potassium tert-butoxide (144.6 g, 1.287 mol, 2.1 eq) in batches, stir at 10 to 25°C for 11 h, add saturated ammonium chloride (3000 mL) to quench the reaction, add ethyl acetate (750 mL*3) and extract 3 times, combine the organic phases, wash once with water (1500 mL), dry over anhydrous sodium sulfate, first concentrate most of the ethyl acetate under reduced pressure at 20 to 30°C, and then obtain 33.15 g of intermediate II (3-butene-1-ol) by distillation, with a yield of 75%, a purity of 98.7%, and an appearance of light yellow to colorless liquid. 1H NMR(d-DMSO)δ8.51(s,3H),1.33(s,3H),0.89(m,2H),0.51~0.56(m,2H).

[0054] Take intermediate II (i.e. 32 g, 0.44 mol, 1.0 eq of 3-butene-1-ol) and dissolve it in dichloromethane (160 mL), add triethylamine (51.1 g, 0.506 mol, 1.15 eq), control the temperature at 0-10°C, add p-toluenesulfonyl chloride (92.27 g, 0.29 mol, 1.1 eq) in batches, stir at room temperature (20-30°C) for 10 h, add water (320 mL), extract and separate the liquids, extract the aqueous phase with dichloromethane (100 mL*2) twice, combine the organic phases, wash once with saturated sodium bicarbonate solution (500 mL), wash once with water (160 mL), dry over anhydrous sodium sulfate, concentrate at 30-55°C, and obtain 98 g of intermediate III (yield 98.4%) by column chromatography, i.e. active R2-sulfonate.

[0055] The obtained product was subjected to hydrogen nuclear magnetic resonance spectroscopy, and the result was:

[0056] 1H NMR (CDCl3, 400MHz): δ7.80-7.77(m,2H),7.35-7.33(m,2H),5.67(ddt,J=17.0,10.5, 6.5Hz, 1H), 5.11-5.03 (m, 2H), 4.07 (t, 2H), 2.44 (s, 3H), 2.40 (dt, J = 6.5, 1.5Hz, 2H).

[0057] Take compound III (i.e., active R2-sulfonate 46g, 0.20mol, 1.0eq) and dissolve it in acetone (230mL), add sodium bromide (26.75g, 0.26mol, 1.3eq), heat up and reflux with stirring to react for 5h, return to room temperature (15-25°C), add methyl tert-butyl ether (250mL) and water (200mL), extract and separate the liquids, extract the aqueous phase with methyl tert-butyl ether (150mL) once, combine the organic phases, wash twice with water (150mL*2), dry the organic layer over anhydrous sodium sulfate, and distill under reduced pressure to obtain 24.3g of intermediate IV4-bromo-1-butene (yield 90%), purity 99.1%, appearance: colorless to light brown liquid.

[0058] The obtained product was subjected to hydrogen nuclear magnetic resonance spectroscopy, and the result was:

[0059] 1H NMR(d-DMSO)δ8.51(s,3H),1.33(s,3H),0.89(m,2H),0.51~0.56(m,2H).

[0060] Example 2

[0061] The preparation method of 3-butene-1-ol and its derivative 4-Br-1-butene in this embodiment comprises:

[0062] 1,4-Butanediol (30 g, 0.33 mol, 3.0 eq) was dissolved in dichloromethane (200 mL), triethylamine (11.67 g, 0.116 mol, 1.05 eq) was added, the temperature was controlled at -5 to 5°C, p-toluenesulfonyl chloride (20.97 g, 0.11 mol, 1.0 eq) was added slowly in batches, after the addition was completed, the mixture was stirred for 2 hours at the temperature, water (200 g) was added to quench the reaction, the lower organic layer was separated after standing, dichloromethane (120 mL*2) was added to the aqueous phase and extracted twice, the organic phases were combined, washed twice with water (200 mL*2), the organic phase was dried over anhydrous sodium sulfate, and dried under reduced pressure at 30 to 60°C to obtain 18.6 g of intermediate I (yield 69%), i.e., 1,4-butanediol monosulfonate.

[0063] Take intermediate I (i.e. 150 g, 0.613 mol, 1.0 eq of 1,4-butanediol monosulfonate) and dissolve it in DMSO (1500 mL), cool to -5°C, control the temperature at -5 to 10°C, slowly add NaH (49.15 g, 1.287 mol, 2.1 eq, 60%) in batches, stir at 10 to 25°C for 12 h, add saturated ammonium chloride (3000 mL) to quench the reaction, add ethyl acetate (750 mL*3) and extract 3 times, combine the organic phases, wash once with water (1500 mL), dry over anhydrous sodium sulfate, first concentrate most of the ethyl acetate under reduced pressure at 20 to 30°C, and then obtain 32.4 g of intermediate II (3-butene-1-ol) by distillation, with a yield of 73.3%, a purity of 98.2%, and an appearance of light yellow to colorless liquid.

[0064] Intermediate II (i.e. 3-butene-1-ol 16g, 0.22mol, 1.0eq) was dissolved in tetrahydrofuran (75mL), triethylamine (25.6g, 0.253mol, 1.15eq) was added, the temperature was controlled at 0-5°C, p-toluenesulfonyl chloride (446.2g, 0.145mol, 1.1eq) was added in batches, after the addition was completed, it was stirred at room temperature (20-30°C) for 14h, water (160mL) was added, and the liquid was extracted. The aqueous phase was extracted twice with dichloromethane (50mL*2), the organic phases were combined, washed once with saturated sodium bicarbonate solution (250mL), washed once with water (80mL), dried over anhydrous sodium sulfate, concentrated at 30-55°C, and column chromatography was performed to obtain 44g of intermediate III (yield 88.3%), i.e. active R2-sulfonate.

[0065] Take compound III (i.e., active R2-sulfonate 46.2g, 0.20mol, 1.0eq) and dissolve it in 2-butanone (230mL), add sodium bromide (26.75g, 0.26mol, 1.3eq), heat to 65-70℃ for reaction for 2.5h, return to room temperature (15-25℃), add methyl tert-butyl ether (250mL) and water (200mL), extract and separate the liquids, extract the aqueous phase with methyl tert-butyl ether (150mL) once, combine the organic phases, wash twice with water (150mL*2), dry the organic phase over anhydrous sodium sulfate, and distill under reduced pressure to obtain 19.4g of intermediate IV, i.e., 4-bromo-1-butene (yield 90%), with a purity of 98.5%, and an appearance of colorless liquid.

[0066] Example 3

[0067] The preparation method of 3-butene-1-ol and its derivative 4-Br-1-butene in this embodiment comprises:

[0068] 1,4-Butanediol (50g, 0.55mol, 5.0eq) was dissolved in dichloromethane (200mL), triethylamine (11.67g, 0.116mol, 1.05eq) was added, the temperature was controlled at -5 to 5°C, p-toluenesulfonyl chloride (20.97g, 0.11mol, 1.0eq) was added slowly in batches, after the addition was completed, the mixture was stirred for 2 hours at the temperature, water (200g) was added to quench the reaction, the lower organic layer was separated after standing, dichloromethane (120mL*2) was added to the aqueous phase and extracted twice, the organic phases were combined, washed twice with water (200mL*2), the organic phase was dried over anhydrous sodium sulfate, and dried under reduced pressure at 30 to 60°C to obtain 21.8g of intermediate I (yield 81%), i.e., 1,4-butanediol monosulfonate.

[0069] Take intermediate I (i.e. 150 g, 0.613 mol, 1.0 eq of 1,4-butanediol monosulfonate) and dissolve it in DMSO (1500 mL), cool to -5°C, control the temperature at -5 to 10°C, slowly add sodium tert-butoxide (123.7 g, 1.287 mol, 2.1 eq) in batches, stir at 10 to 25°C for 14 h, add saturated ammonium chloride (3000 mL) to quench the reaction, add ethyl acetate (750 mL*3) and extract 3 times, combine the organic phases, wash once with water (1500 mL), dry over anhydrous sodium sulfate, first concentrate most of the ethyl acetate under reduced pressure at 20 to 30°C, and then obtain 28.1 g of intermediate II (3-butene-1-ol) by distillation, with a yield of 63.57%, a purity of 96.9%, and an appearance of yellow to colorless liquid.

[0070] Take intermediate II (i.e. 16 g, 0.22 mol, 1.0 eq of 3-butene-1-ol) and dissolve it in DMF (50 mL), add triethylamine (25.6 g, 0.253 mol, 1.15 eq), control the temperature at 0-5°C, add p-toluenesulfonyl chloride (446.2 g, 0.145 mol, 1.1 eq) in batches, stir at room temperature (20-30°C) for 14 h, add water (160 mL), extract and separate the liquids, extract the aqueous phase with dichloromethane (50 mL*2) twice, combine the organic phases, wash once with saturated sodium bicarbonate solution (250 mL), wash once with water (80 mL), dry over anhydrous sodium sulfate, concentrate at 30-55°C, and purify by column chromatography to obtain 30 g of intermediate III (yield 60.20%), i.e. active R2-sulfonate.

[0071] Take compound III (i.e., active R2-sulfonate 46g, 0.20mol, 1.0eq) and dissolve it in DMF (200mL), add sodium bromide (26.75g, 0.26mol, 1.3eq), heat to 65-70℃ for 4h, return to room temperature (15-25℃), add methyl tert-butyl ether (250mL) and water (200mL), extract and separate the liquids, extract the aqueous phase with methyl tert-butyl ether (150mL) once, combine the organic phases, wash 3 times with saturated sodium chloride aqueous solution (150mL*3), dry the organic phase over anhydrous sodium sulfate, and distill under reduced pressure to obtain 16g of intermediate IV 4-bromo-1-butene, with a yield of 92%, a purity of 99.2%, and an appearance of colorless liquid.

[0072] The above descriptions are only some embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Any equivalent device or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing 3-butene-1-ol, characterized in that: It includes: 1,4-butanediol is used as a raw material, which is first reacted with R1-sulfonyl chloride to synthesize 1,4-butanediol mono-R1-sulfonate, and then an elimination reaction is carried out under the action of a base to obtain 3-butene-1-ol.

2. The method for preparing 3-butene-1-ol according to claim 1, characterized in that: It includes the following steps: Step 1), under the action of a base, using 1,4-butanediol as a raw material, first reacting it with R1-sulfonyl chloride to synthesize 1,4-butanediol mono-R1-sulfonate; Step 2), under the action of a base, 1,4-butanediol mono-R1-sulfonate undergoes an elimination reaction to obtain 3-butene-1-ol.

3. The method for preparing 3-butene-1-ol according to claim 2, characterized in that: In step 2), a solvent is used when the 1,4-butanediol mono-R1-sulfonate undergoes an elimination reaction, and the solvent is one of DMSO, THF, and DMF.

4. The method for preparing 3-butene-1-ol according to claim 2, characterized in that: In step 1) and / or step 2), the base is one of sodium hydride, potassium hydride, potassium tert-butoxide and sodium tert-butoxide.

5. The method for preparing 3-butene-1-ol according to any one of claims 2 to 4, characterized in that: In step 2), the reaction temperature of the elimination reaction is -5 to 30° C., and the reaction time is 5 to 25 hours.

6. A method for preparing 4-bromo-1-butene, a derivative of 3-butene-1-ol, characterized in that: The invention is applied with the preparation method according to any one of claims 2 to 5, which further comprises: Step 3), under alkaline conditions, reacting 3-butene-1-ol with R2-sulfonyl chloride to obtain active R2-sulfonate; Step 4), the active R2-sulfonate is reacted with the nucleophilic reagent NaBr to undergo SN2 substitution reaction to obtain 4-bromo-1-butene.

7. The method for preparing 4-bromo-1-butene based on a derivative of 3-butene-1-ol according to claim 6, characterized in that: In step 3), when 3-butene-1-ol is reacted with R2-sulfonyl chloride to obtain active R2-sulfonate, a reaction solvent is used, which is one of dichloromethane, tetrahydrofuran and DMF.

8. The method for preparing 4-bromo-1-butene based on a derivative of 3-butene-1-ol according to claim 6, characterized in that: In step 3), the alkaline condition is composed of sodium hydride, triethylamine and DIEA, and the reaction temperature is -5 to 35° C. and the reaction time is 2 to 20 hours.

9. The method for preparing 4-bromo-1-butene based on a derivative of 3-butene-1-ol according to claim 6, characterized in that: In step 4), when the active R2-sulfonate is subjected to SN2 substitution reaction with the nucleophilic reagent NaBr to obtain 4-bromo-1-butene, a solvent is used, which is one of acetone, 2-butanone, and DMF. The reaction temperature of the substitution reaction is 25-75° C., and the reaction time is 2 to 24 hours.

10. A method for preparing 3-butene-1-ol and its derivative 4-bromo-1-butene, characterized in that: It comprises the preparation method according to any one of claims 6 to 9.

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