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WO2021033200A1 - Procédé de préparation de sultones - Google Patents

Procédé de préparation de sultones Download PDF

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Publication number
WO2021033200A1
WO2021033200A1 PCT/IN2020/050717 IN2020050717W WO2021033200A1 WO 2021033200 A1 WO2021033200 A1 WO 2021033200A1 IN 2020050717 W IN2020050717 W IN 2020050717W WO 2021033200 A1 WO2021033200 A1 WO 2021033200A1
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WO
WIPO (PCT)
Prior art keywords
formula
mixture
acid
preparation
sultone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IN2020/050717
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English (en)
Inventor
Jaya Shanmuga PRAKASH
Sekhar THURAKA
Mariano Philips
Arumugam NAGAPPAN
Kapil Kumar
Anurag Jain
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SRF Ltd
Original Assignee
SRF Ltd
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Filing date
Publication date
Application filed by SRF Ltd filed Critical SRF Ltd
Publication of WO2021033200A1 publication Critical patent/WO2021033200A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings

Definitions

  • the present invention provides a simple and safe process for preparation of sultones.
  • Sultones such as 1,3-propanesultone and 1,4-butanesultone are widely used as electroplating intermediates, pharmaceutical intermediates, photosensitive material, lithium batteries, and other household chemicals.
  • the market for sultone is expanding owing to their applications as lithium battery electrolyte.
  • European Journal of Organic Chemistry, Volume 586, issue 1, 1954 discloses a process for preparation of 1, 4-butane sultone by reacting tetrahydrofuran and acetyl chloride in presence of zinc chloride to form 4-chloro-butylacetate, followed by reaction with sodium sulphite, then neutralisation with acid and distillation of sultone at high temperature of 175-185°C. It also involves distillation step for isolation of 1,4-butane sultone.
  • CN106397392A provides a process for preparation of 1,4-butane sultone using 3- buten-l-ol and sodium sulphite. This process involves four steps for preparation of 1,4-butane sultone. It suggests vacuum dehydration in presence of a solvent at high temperature range of 150-200°C to form 1,4-butane sultone.
  • the ethanol used in the process is highly flammable and unsafe to use at this high temperature. It involves multiple drawbacks such as high temperature range, tedious operation, excess solvent and safety hazard. Thus, there remains an urgent need to develop a simple, efficient and industrially viable process for preparation of sultones.
  • the present invention provides a process for preparation of sultones of formula I,
  • n is 1-3 comprising the steps of: a) reacting haloalkyl acetate and alkali metal sulphite in water to obtain a mixture; b) adding an alcohol to the reaction mixture of step a); c) neutralizing the reaction mixture of step b) to obtain hydroxyalkyl sulphonic acid; d) dehydrating hydroxyalkyl sulphonic acid at a temperature of 75-115°C to obtain sultone of formula I.
  • the present invention provides a process for preparation of sultone of formula I having purity greater than 99.0% comprising, the steps of dehydrating crude hydroxyalkyl sulphonic acid at temperature of 75-115°C to obtain sultone of formula I.
  • the main object of present invention is to provide a simple and industrially applicable process for preparation of sultones of formula I.
  • Sultones have high boiling point and are usually separated from the crude mixture by distillations that leads to the decomposition and formation of sulphur dioxide. This affects the overall yield of the process and pose safety concerns during industrial scale ups.
  • the present inventors improved the process for preparation of sultone by dehydrating crude hydroxyalkyl sulphonic acid at temperature below 100°C. Surprisingly, this step has increased the yield of present invention up to 90%.
  • the present invention avoids use of distillation and high temperature for preparation of sultone.
  • alkali metal sulphite is selected from sodium sulphite and potassium sulphite.
  • dehydration refers to removal of water from 4-hydroxyalkyl sulphonic acid to aid its cyclization to sultone.
  • the step of dehydration of hydroxyalkyl sulphonic acid to isolate sultone is carried out at a temperature of 75-115°C.
  • the step of dehydration is carried out at atmospheric or reduced pressure.
  • the reduced pressure is in the range of 1-100 torr and preferably 10-50 torr, more preferably 10-30 torr.
  • the step of dehydration may be carried out in presence or absence of solvent.
  • the step of dehydration of hydroxyalkyl sulphonic acid at atmospheric pressure is carried out in presence of a solvent by azeotropically removing water with the solvent.
  • the solvents may be selected from a group consisting of toluene, heptane, octane, xylene, chlorobenzene, or like or a mixture thereof.
  • the step of dehydration of hydroxyalkyl sulphonic acid is carried out at a reduced pressure in absence of a solvent.
  • alkyl refers to propyl, butyl and pentyl and “halo” refers to chloro, bromo and iodo.
  • haloalkyl acetate may be selected from a group consisting of 4- chlorobutylacetate, 5-chloropentylacetate, 3-chloropropylacetate, 4- bromobutylacetate, 5-bromopentylacetate, 3-bromopropylacetate.
  • the preferred haloalkyl acetate for present invention are chloroalkyl acetate selected from the group consisting of 4-chlorobutylacetate, 5-chloropentylacetate, 3-chloropropylacetate .
  • the present invention provides a process for preparation of sultone of formula I having purity greater than 99.0%, comprising the steps of: a) dehydrating hydroxy alkyl sulphonic acid at a temperature of 75-115°C under reduced pressure in absence of solvent to obtain sultone of formula I; and b) isolating sultone of formula I.
  • the present invention provides a process for preparation of sultone of formula I having purity greater than 99.0% comprising, the step of dehydrating hydroxy alkyl sulphonic acid at a temperature of 75-115°C at an atmospheric pressure in presence of a solvent, by azeotropically removing water to obtain sultone of formula I.
  • the present invention provides a process for preparation of 1,4-butane sultone comprising dehydrating 4-hydroxybutane sulphonic acid under reduced pressure in absence of a solvent.
  • the present invention provides a process for preparation of 1,4-butane sultone comprising dehydrating 4-hydroxybutane sulphonic acid at an atmospheric pressure in toluene, by azetropically removing water from the mixture.
  • the present invention provides a process for preparation of sultones of formula I, comprising the steps of: a) reacting haloalkyl acetate and alkali metal sulphite in water to obtain a mixture; b) adding an alcohol to the reaction mixture of step a); c) neutralizing the reaction mixture of step b) to obtain hydroxyalkyl sulphonic acid; d) dehydrating hydroxyalkyl sulphonic acid at a temperature of 75-115°C to obtain sultone of formula I.
  • the molar ratio of alkali metal sulphite to haloalkyl acetate is in the range of 1-1.5.
  • the alcohol is selected from a group consisting of methanol, ethanol, and propanol or like.
  • the step of dehydration is carried out without purifying hydroxyalkyl sulphonic acid.
  • the step of neutralization is carried out in presence of an acid selected from a group consisting of sulphuric acid, hydrochloric acid or phosphoric acid or like.
  • the acid may be used in anhydrous or aqueous form.
  • the preferred acid is anhydrous hydrochloric acid.
  • haloalkyl acetate and alkali metal sulphite were reacted in presence of water to obtain a mixture containing hydroxyalkyl sulphonic acid.
  • the mixture obtained was diluted with an alcohol and neutralized using anhydrous hydrochloric acid.
  • the neutralised mixture was filtered and filtrate was concentrated to obtain crude hydroxyalkyl sulphonic acid.
  • the crude hydroxyalkyl sulphonic acid was dehydrated at a temperature of 75- 115°C under reduced pressure of 10-30 torr.
  • haloalkyl acetate and alkali metal sulphite were reacted in presence of water to obtain a mixture containing hydroxyalkyl sulphonic acid.
  • the mixture obtained was diluted with an alcohol and neutralized using anhydrous hydrochloric acid.
  • the neutralised mixture was filtered and filtrate was concentrated to obtain crude hydroxyalkyl sulphonic acid.
  • the crude hydroxyalkyl sulphonic acid was dehydrated at a temperature of 75-115°C in a solvent such as toluene by azeotropically removing water at atmospheric pressure.
  • sultone is isolated by solvent extraction.
  • the solvent for extraction is selected from a group consisting of dichloromethane, methanol, ethyl acetate, pentane, hexane, heptane, xylene, chlorobenzene, ethylbenzene, chloroform, toluene or like.
  • the yield of sultone of formula I is in the range of 75%-95%.
  • the sultone for present invention is obtained with a purity of 99.0% to 99.9%.
  • the present invention provides a process for preparation of 1,4-butane sultone, comprising the steps of: a) reacting 4-chlorobutyl acetate and alkali metal sulphite in water to obtain a reaction mixture; b) adding methanol to the reaction mixture of step a); c) neutralizing the reaction mixture of step b) using anhydrous hydrochloric acid to obtaining crude 4-hydroxybutane sulphonic acid; d) dehydrating crude 4-hydroxybutane sulphonic acid at 75-115°C at a reduced pressure of 10-30 torr to obtain 1,4-butane sultone to isolate 1,4-butane sultone of purity more than 99.0%.
  • the present invention provides a process for preparation of 1,4-butane sultone, comprising the steps of: a) reacting 4-chlorobutyl acetate and alkali metal sulphite in water to obtain a reaction mixture; b) adding methanol to the reaction mixture of step a); c) neutralizing the reaction mixture of step b) using anhydrous hydrochloric acid to obtain crude 4-hydroxybutane sulphonic acid; d) azeotropically removing water from a solution of 4-hydroxybutane sulphonic acid and toluene at 75-90°C to obtain 1,4-butane sultone;
  • the side product acetic acid may be recovered from the reaction mixture.
  • the solvents used in the present invention may be recycled and acetic acid formed can be recovered.
  • the haloalkyl acetate used as raw material has purity greater than 95%.
  • haloalkyl acetate used in present invention may be prepared by any method known in the literature or can be obtained commercially.
  • 4-chlorobutylacetate may be prepared using tetrahydrofuran and acetyl chloride.
  • the alkali metal sulphite, solvents and acid used for present invention are obtained commercially.
  • the product may be isolated by any method known in the art, for example, chemical separation, extraction, acid-base neutralization, distillation, evaporation, column chromatography and filtration or a mixture thereof.
  • TLC thin layer chromatography
  • HPLC high pressure liquid chromatography
  • UPLC ultra-pressure liquid chromatography
  • GC Gas chromatography
  • LC liquid chromatography
  • any of the words “comprising”, “comprises” and includes mean “including without limitation” and shall not be construed to limit any general statement that it follows to the specific or similar items or matters immediately following it.
  • Embodiments of the invention are not mutually exclusive, but may be implemented in various combinations.
  • the described embodiments of the invention and the disclosed examples are given for the purpose of illustration rather than limitation of the invention as set forth in the appended claims.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'objet principal de la présente invention est de fournir un procédé économique et applicable industriellement pour la préparation de sultones de formule (I). Dans la formule, n est 1 à 3. Les sultones, tels que la 1,3-propanesultone et la 1,4-butanesultone, sont largement utilisées en tant qu'intermédiaires d'électrodéposition, intermédiaires pharmaceutiques, matériau photosensible, électrolytes pour batteries au lithium et autres produits chimiques ménagers.
PCT/IN2020/050717 2019-08-21 2020-08-17 Procédé de préparation de sultones Ceased WO2021033200A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN201911033684 2019-08-21
IN201911033684 2019-08-21

Publications (1)

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WO2021033200A1 true WO2021033200A1 (fr) 2021-02-25

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PCT/IN2020/050717 Ceased WO2021033200A1 (fr) 2019-08-21 2020-08-17 Procédé de préparation de sultones

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114292257A (zh) * 2021-12-27 2022-04-08 湖北吉和昌化工科技有限公司 一种1,4-丁烷磺内酯的合成方法
CN118373800A (zh) * 2024-02-29 2024-07-23 九江德思光电材料有限公司 1,3-丙烷磺酸内酯的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3115501A (en) * 1961-05-05 1963-12-24 Shell Oil Co Sultone manufacture

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3115501A (en) * 1961-05-05 1963-12-24 Shell Oil Co Sultone manufacture

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. WILLEMS: "The Aliphatic Hydroxysulphonic Acids and Their Internal Esters: The Sultones Part II. The Sultones", BULL. SOC. CHIM. BELG., vol. 64, no. 11-12, 1955, pages 747 - 771, XP055066010, DOI: 10.1002/bscb.19550641111 *
WILLIAM E. TRUCE ET AL.: "The Chemistry of Sultones. I. Friedel-Crafts Reactions of Sultones", J. AM. CHEM. SOC., vol. 76, no. 21, 1954, pages 5357 - 5360, XP002396754, DOI: 10.1021/ja01650a032 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114292257A (zh) * 2021-12-27 2022-04-08 湖北吉和昌化工科技有限公司 一种1,4-丁烷磺内酯的合成方法
CN114292257B (zh) * 2021-12-27 2023-10-27 湖北吉和昌化工科技有限公司 一种1,4-丁烷磺内酯的合成方法
CN118373800A (zh) * 2024-02-29 2024-07-23 九江德思光电材料有限公司 1,3-丙烷磺酸内酯的制备方法

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