WO2013035674A1 - Procédé de fabrication d'une 2-halo-1-(1-halocyclopropyl)éthanone - Google Patents

Procédé de fabrication d'une 2-halo-1-(1-halocyclopropyl)éthanone Download PDF

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Publication number
WO2013035674A1
WO2013035674A1 PCT/JP2012/072377 JP2012072377W WO2013035674A1 WO 2013035674 A1 WO2013035674 A1 WO 2013035674A1 JP 2012072377 W JP2012072377 W JP 2012072377W WO 2013035674 A1 WO2013035674 A1 WO 2013035674A1
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Prior art keywords
ethanone
aliphatic alcohol
compound
halocyclopropyl
formula
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PCT/JP2012/072377
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English (en)
Japanese (ja)
Inventor
久 菅野
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株式会社クレハ
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Publication of WO2013035674A1 publication Critical patent/WO2013035674A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to a novel process for producing 2-halo-1- (1-halocyclopropyl) ethanone used as an intermediate for agricultural chemicals and the like.
  • Patent Document 1 describes a method for producing these intermediates by reacting a chlorinating agent or brominating agent with 1- (1-halocyclopropyl) ethanone in the presence of a diluent. . Specifically, a method for producing the above intermediate by chlorination or bromination of 1- (1-halocyclopropyl) ethanone in dichloromethane using sulfuryl chloride or sulfuryl bromide is described. Yes.
  • Japanese Patent Publication Japanese Unexamined Patent Publication No. 64-22857” (published on January 25, 1989) Japanese Patent Publication “JP-A-8-277240 (published on Oct. 22, 1996)”
  • the method for producing the intermediate described in Patent Document 1 requires a long reaction time because of poor reactivity. Further, when the reaction is performed for a long time, unnecessary chlorination or bromination occurs, and a non-negligible by-product can be produced. For example, when chlorination is carried out, the main product, 2-chloro-1- (1-chlorocyclopropyl) ethanone, remains even when 1- (1-chlorocyclopropyl) ethanone as the raw material remains. As a result, chlorination further proceeds and a by-product 1- (1-chlorocyclopropyl) -2,2-dichloroethanone is produced in a considerable amount.
  • the present invention has been made in view of such problems and requirements.
  • the object of the present invention is to produce 2-halo-1- (1-halocyclopropyl) ethanone in a shorter reaction time and with higher selectivity. It is to provide a method of manufacturing.
  • the inventor has conducted various studies to solve these problems, and as a result, in the production of 2-halo-1- (1-halocyclopropyl) ethanone, the reaction system can be shortened by coexisting an aliphatic alcohol. It has been found that the conversion rate can be increased even with the reaction time, and the production of 1- (1-halocyclopropyl) -2,2-dihaloethanone as a by-product can be suppressed, and the present invention has been completed.
  • X 1 is the same as X 1 in formula (I)
  • a sulfuryl halide In the presence of an aliphatic alcohol, the compound is reacted with a sulfuryl halide to be halogenated, whereby a method for producing 2-halo-1- (1-halocyclopropyl) ethanone is provided.
  • the halogenation of 1- (1-halocyclopropyl) ethanone is carried out in the presence of an aliphatic alcohol. It is possible to produce 2-halo-1- (1-halocyclopropyl) ethanone with a shorter reaction time than in the past and with high selectivity.
  • X 1 is the same as X 1 in formula (I))
  • 2-halo-1- (1-halocyclopropyl) ethanone represented by the general formula (I) (hereinafter referred to as compound (I)) is a target product in the present invention. Can be used as a body.
  • X 1 and X 2 are the same or different halogen atoms.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • X 1 and X 2 are preferably bromine atoms or chlorine atoms, and X 1 and X 2 are both Particularly preferred is a chlorine atom.
  • compound (II) 1- (1-halocyclopropyl) ethanone represented by general formula (II) (hereinafter referred to as compound (II)) is a raw material for producing compound (I).
  • X 1 in compound (II) is the same halogen atom as the halogen atom represented by X 1 in compound (I).
  • compound (II) is a well-known compound, and what was manufactured using the prior art can be used.
  • the aliphatic alcohol is not particularly limited as long as it can synthesize compound (I) from compound (II) in a shorter reaction time and with high selectivity.
  • Such an aliphatic alcohol may be either a saturated aliphatic alcohol or an unsaturated aliphatic alcohol, and examples thereof include saturated or unsaturated aliphatic alcohols having 1 to 10 carbon atoms. Examples of more suitable aliphatic alcohols include saturated aliphatic alcohols having 1 to 4 carbon atoms.
  • methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like are preferable, and methanol and ethanol are particularly preferable.
  • the sulfuryl halide is a compound represented by the general formula: SO 2 X 2 X 3 .
  • X 2 are the same halogen atom and X 2 in the compound (I), X 3 is the same or as X 2 is a different halogen atom. Of these it is preferred and X 2 and X 3 are identical halogen atoms.
  • the plurality of halogen atoms contained in the halogenated sulfuryl are preferably the same halogen atoms.
  • the halogenated sulfuryl include sulfuryl fluoride, sulfuryl chloride, sulfuryl bromide, and sulfuryl iodide.
  • halogen atoms contained are different from each other, such as sulfuryl chlorofluoride.
  • a method for isolating a compound halogenated by a desired halogen atom when X 2 and X 3 are halogenated using a sulfuryl halide which is a halogen atom different from each other a method such as distillation is used. Can do.
  • This reaction can be advantageously performed in a solvent inert to the reaction.
  • the solvent used in this reaction is not particularly limited, but a solvent that does not react with sulfuryl halide is preferable.
  • Specific examples of the solvent include, for example, halogenated hydrocarbons such as dichloromethane, trichloromethane and dichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as petroleum ether, hexane and methylcyclohexane. Among them, halogenated hydrocarbons are preferable. Moreover, you may use these solvents in mixture of 2 or more types.
  • the amount of the sulfuryl halide used relative to compound (II) is, for example, 0.5 to 10 times mol, preferably 0.8 to 5 times mol.
  • the amount of the aliphatic alcohol used relative to compound (II) is, for example, 0.01 to 20 times mol, preferably 0.1 to 20 times mol, more preferably 0.5 to 10 times mol. .
  • the reaction temperature and reaction time can be appropriately set depending on the type of solvent and aliphatic alcohol used.
  • the reaction temperature is preferably ⁇ 100 ° C. to 100 ° C., more preferably 0 ° C. to 80 ° C.
  • the reaction time is preferably 0.01 to 48 hours, more preferably 0.1 to 24 hours, and further preferably 0.1 to 12 hours.
  • reaction time When the reaction time is increased, the produced compound (I) is further halogenated with sulfuryl halide, and 1- (1-halocyclopropyl) -2 represented by the following general formula (III), which is a byproduct. , 2-dihaloethanone (hereinafter referred to as compound (III)) is produced. Therefore, it is preferable that the reaction time is shorter.
  • X 1 and X 2 are the same as X 1 and X 2 in General Formula (I), respectively, and X 3 is the same as X 3 in the sulfuryl halide.
  • Example 1 In a 100 ml three-necked flask, 1- (1-chlorocyclopropyl) ethanone (compound (V)) (5 g) and 2 equivalents of methanol to compound (V) were dissolved in dichloromethane (20 ml). Next, under cooling with ice water (reaction temperature 20 ° C.), sulfuryl chloride (11.38 g) was added dropwise over 10 minutes. After completion of the dropwise addition, in order to calculate the conversion rate and the selectivity due to the difference in reaction time, the reaction solution was collected after 0.25 hours and 1 hour and analyzed. Specifically, the collected reaction solution was dissolved in deuterated chloroform, and a 1 H-NMR spectrum was measured. And the ratio of compound (IV), (V) and (VI) was computed from the integrated value. The results are shown in Table 1.
  • Example 2 Synthesis of 2-chloro-1- (1-chlorocyclopropyl) ethanone and the same procedure as in Example 1 except that the reaction was performed using 1 equivalent of ethanol with respect to compound (V) instead of methanol. Analysis was carried out. The results are shown in Table 1.
  • the conversion rate (%) represents the ratio of the reacted compound (V) in the starting compound (V). Therefore, when the value of conversion rate is high, it shows that many reaction products are produced
  • the selectivity (%) represents the ratio of the compound (IV) in the reaction product.
  • the amount of aliphatic alcohol is the amount used relative to the amount of compound (V) used in the reaction.
  • the conversion rate was low in the short-time reaction (for example, 4% conversion rate in the 1-hour reaction). That is, almost no compound (IV) is produced, indicating that the reactivity is poor. Further, it was shown that the selectivity is about 77% although the conversion rate is increased to 99% or more by carrying out the reaction for a long time (68 hours). That is, it is shown that the ratio of the compound (VI) as a by-product is increased while the ratio of the reaction product is increased by performing the reaction for a long time.
  • the present invention can be suitably used for production of industrially important agricultural chemicals and intermediates thereof.

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

Abstract

La présente invention concerne un procédé de fabrication d'une 2-halo-1-(1-halocyclopropyl)éthanone représentée par la formule générale (I), dans lequel un composé représenté par la formule générale (II) est halogéné en étant mis à réagir avec un halogénure de sulfuryle en présence d'un alcool aliphatique. (Dans les formules, X1 et X2, identiques ou différents, représentent chacun un atome d'halogène).
PCT/JP2012/072377 2011-09-09 2012-09-03 Procédé de fabrication d'une 2-halo-1-(1-halocyclopropyl)éthanone WO2013035674A1 (fr)

Applications Claiming Priority (2)

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JP2011-197688 2011-09-09
JP2011197688 2011-09-09

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104292089A (zh) * 2014-09-30 2015-01-21 大连九信生物化工科技有限公司 一种1-氯-1’-氯乙酰基环丙烷的合成工艺
CN104447262A (zh) * 2014-12-17 2015-03-25 上海生农生化制品有限公司 一锅法合成1-氯-1-氯乙酰基-环丙烷的方法
CN107602365A (zh) * 2017-09-27 2018-01-19 长治市晋宁化工有限公司 一种2‑氯‑1‑(1‑氯环丙基)乙酮的制备方法
WO2018060093A1 (fr) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Dérivés d'imidazole à substitution en position 1 et 5 en tant que fongicides pour la protection des cultures agricoles
CN108586220A (zh) * 2018-06-27 2018-09-28 安徽国星生物化学有限公司 一种2-氯-1-(1-氯环丙基)乙酮的合成方法
CN111675608A (zh) * 2020-05-26 2020-09-18 安徽久易农业股份有限公司 一种生产1-氯-1’-氯乙酰基-环丙烷的工艺
CN116178122A (zh) * 2023-02-28 2023-05-30 山东京博农化科技股份有限公司 一种1-氯-1-氯乙酰基环丙烷的合成方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310702A (en) * 1980-07-28 1982-01-12 Allied Corporation Selective monochlorination of ketones and aromatic alcohols
JPS63222140A (ja) * 1987-03-10 1988-09-16 Mitsui Petrochem Ind Ltd クロルジアセチルの製法
JPS6422857A (en) * 1987-06-24 1989-01-25 Bayer Ag Azolylmethyl-cyclopropyl derivative
JPH05286902A (ja) * 1992-04-10 1993-11-02 Sumitomo Pharmaceut Co Ltd α−クロロ−β−ケトエステル誘導体の製造方法
JPH069480A (ja) * 1992-03-05 1994-01-18 Bayer Ag １−フルオロシクロプロピルメチルケトンの製造方法
JPH08277240A (ja) * 1995-03-31 1996-10-22 Basf Ag α−クロルアルキルアリールケトンの製法
JPH09255653A (ja) * 1996-03-28 1997-09-30 Sumitomo Seika Chem Co Ltd α−ハロアセトフェノン誘導体の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310702A (en) * 1980-07-28 1982-01-12 Allied Corporation Selective monochlorination of ketones and aromatic alcohols
JPS63222140A (ja) * 1987-03-10 1988-09-16 Mitsui Petrochem Ind Ltd クロルジアセチルの製法
JPS6422857A (en) * 1987-06-24 1989-01-25 Bayer Ag Azolylmethyl-cyclopropyl derivative
JPH069480A (ja) * 1992-03-05 1994-01-18 Bayer Ag １−フルオロシクロプロピルメチルケトンの製造方法
JPH05286902A (ja) * 1992-04-10 1993-11-02 Sumitomo Pharmaceut Co Ltd α−クロロ−β−ケトエステル誘導体の製造方法
JPH08277240A (ja) * 1995-03-31 1996-10-22 Basf Ag α−クロルアルキルアリールケトンの製法
JPH09255653A (ja) * 1996-03-28 1997-09-30 Sumitomo Seika Chem Co Ltd α−ハロアセトフェノン誘導体の製造方法

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104292089A (zh) * 2014-09-30 2015-01-21 大连九信生物化工科技有限公司 一种1-氯-1’-氯乙酰基环丙烷的合成工艺
CN104292089B (zh) * 2014-09-30 2016-01-13 大连九信生物化工科技有限公司 一种1-氯-1’-氯乙酰基环丙烷的合成工艺
CN104447262A (zh) * 2014-12-17 2015-03-25 上海生农生化制品有限公司 一锅法合成1-氯-1-氯乙酰基-环丙烷的方法
CN104447262B (zh) * 2014-12-17 2021-05-11 上海生农生化制品股份有限公司 一锅法合成1-氯-1-氯乙酰基-环丙烷的方法
WO2018060093A1 (fr) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Dérivés d'imidazole à substitution en position 1 et 5 en tant que fongicides pour la protection des cultures agricoles
CN107602365A (zh) * 2017-09-27 2018-01-19 长治市晋宁化工有限公司 一种2‑氯‑1‑(1‑氯环丙基)乙酮的制备方法
CN108586220A (zh) * 2018-06-27 2018-09-28 安徽国星生物化学有限公司 一种2-氯-1-(1-氯环丙基)乙酮的合成方法
CN111675608A (zh) * 2020-05-26 2020-09-18 安徽久易农业股份有限公司 一种生产1-氯-1’-氯乙酰基-环丙烷的工艺
CN111675608B (zh) * 2020-05-26 2023-12-15 安徽久易农业股份有限公司 一种生产1-氯-1’-氯乙酰基-环丙烷的工艺
CN116178122A (zh) * 2023-02-28 2023-05-30 山东京博农化科技股份有限公司 一种1-氯-1-氯乙酰基环丙烷的合成方法

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