WO2000053553A1 - Verfahren zur herstellung von cyclobutanon - Google Patents

Verfahren zur herstellung von cyclobutanon Download PDF

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Publication number
WO2000053553A1
WO2000053553A1 PCT/EP2000/001707 EP0001707W WO0053553A1 WO 2000053553 A1 WO2000053553 A1 WO 2000053553A1 EP 0001707 W EP0001707 W EP 0001707W WO 0053553 A1 WO0053553 A1 WO 0053553A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyclobutanone
acids
cyclobutanol
acid
hypochlorite
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/EP2000/001707
Other languages
German (de)
English (en)
French (fr)
Inventor
Hans-Joachim Knops
Bernd Gallenkamp
Lubbertus Mulder
Stefan Antons
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DE50006027T priority Critical patent/DE50006027D1/de
Priority to AT00907651T priority patent/ATE257141T1/de
Priority to IL14478000A priority patent/IL144780A0/xx
Priority to EP00907651A priority patent/EP1161408B1/de
Priority to JP2000603995A priority patent/JP2002539098A/ja
Priority to KR1020017011427A priority patent/KR20010102539A/ko
Priority to AU29166/00A priority patent/AU2916600A/en
Priority to US09/936,121 priority patent/US6476274B1/en
Publication of WO2000053553A1 publication Critical patent/WO2000053553A1/de
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring

Definitions

  • the invention relates to a new process for the preparation of cyclobutanone.
  • cyclobutanone can be obtained by oxidation of cyclobutanol.
  • customary organic oxidizing agents such as various dialkyldioxiranes, chloral, tert-butyl hydroperoxide or optionally substituted perbenzoic acids; or transition or noble metal catalysts, including their oxides and oxide complexes (see, e.g., React. Funct. Polym., 29 (2), 101-14, 1996; Can. J. Chem., 62 (9), 1835- 9, 1984; Org. Synth., 60, 20-5, 1981; and
  • the systems chromium-VI-oxide / oxalic acid and ruthenium oxide / sodium periodate are at most suitable for implementation on an industrial scale. But these also have the general disadvantage of the high cost of the catalyst system (here ruthenium oxide) or the large amounts of waste, including disposal (here chromium and iodine).
  • cyclobutanone can be obtained in a simple manner in very good yields and in high purity by the process according to the invention, without the cyclobutane ring being expanded and opened in a BAYER-VILLIGER oxidation to give butyrolactone as the main reaction.
  • the implementation according to the invention thus has the advantage of simple, inexpensive and environmentally friendly access to cyclobutanone, in particular on an industrial scale.
  • Cyclobutanol as a starting material is a generally known compound of organic chemistry and is obtainable in a generally known manner, e.g. by reaction / ring expansion of cyclopropylcarbinol with concentrated hydrochloric acid (see e.g. Org. Synth. 60, 20-25, 1981).
  • hypochlorite Sodium, potassium and calcium hypochlorite are preferably mentioned as alkali and alkaline earth hypochlorite.
  • the hypochlorites are usually called aqueous
  • Preferred organic acids are alkanoic acids, in particular C1-C4-
  • Alkanoic acids such as acetic acid in question
  • Mineral acids in particular hydrochloric acid, are preferred as inorganic acids.
  • the chlorine / glacial acetic acid system is particularly advantageous.
  • the reaction temperatures can be varied within a wide range during the oxidation. Generally one works between -20 ° C and + 30 ° C, preferably between -20 ° C and + 20 ° C, particularly preferably between -10 ° C and + 10 ° C. Working up is carried out in the customary manner, the pH being kept in the slightly basic range, if appropriate by adding alkali metal carbonate or alkali metal bicarbonate, such as, in particular, potassium or sodium bicarbonate (see also the preparation examples).
  • alkali metal carbonate or alkali metal bicarbonate such as, in particular, potassium or sodium bicarbonate (see also the preparation examples).
  • the preparation of the starting material cyclobutanol from cyclopropylcarbinol in the presence of acids, in particular concentrated mineral acids, and the subsequent oxidation to cyclobutanone can be carried out in a “one-pot reaction”, ie in situ without isolation of the intermediate product and without Change of solvent (see also the manufacturing examples).
  • cyclobutanol from cyclopropylcarbinol is known per se. It is usually carried out in water as a solvent in the presence of acids, especially mineral acids such as concentrated hydrochloric acids. Typical reaction temperatures are in the range of 20 ° C to 120 ° C; as a rule, the reaction is carried out under reflux conditions.
  • the cyclobutanone to be produced by the process according to the invention is a generally interesting, central intermediate.
  • the mixture is extracted with 2 ⁇ 30 1 and 2 ⁇ 16 1 methylene chloride, the aqueous phase becoming clear.
  • the organic phase is stirred into 60 l of water and 6.9 kg of sodium bicarbonate are slowly added (foaming! With stirring, the pH being 6.
  • the aqueous phase is separated off, 30 l of water are added to the organic phase and 2.3 kg of sodium bicarbonate are again added with stirring, the pH value 8 being reached.
  • the organic phase is separated off and concentrated in the kettle at 40 ° C. and 550 to 600 mbar.
  • the residue (18.2 kg) is finely distilled in the distillation laboratory.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/EP2000/001707 1999-03-10 2000-03-01 Verfahren zur herstellung von cyclobutanon Ceased WO2000053553A1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE50006027T DE50006027D1 (de) 1999-03-10 2000-03-01 Verfahren zur herstellung von cyclobutanon
AT00907651T ATE257141T1 (de) 1999-03-10 2000-03-01 Verfahren zur herstellung von cyclobutanon
IL14478000A IL144780A0 (en) 1999-03-10 2000-03-01 Method of producing cyclobutanone
EP00907651A EP1161408B1 (de) 1999-03-10 2000-03-01 Verfahren zur herstellung von cyclobutanon
JP2000603995A JP2002539098A (ja) 1999-03-10 2000-03-01 シクロブタノンを製造する方法
KR1020017011427A KR20010102539A (ko) 1999-03-10 2000-03-01 시클로부탄온의 제조 방법
AU29166/00A AU2916600A (en) 1999-03-10 2000-03-01 Method of producing cyclobutanone
US09/936,121 US6476274B1 (en) 1999-03-10 2000-03-01 Method of producing cyclobutanone

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19910464.6 1999-03-10
DE19910464A DE19910464A1 (de) 1999-03-10 1999-03-10 Verfahren zur Herstellung von Cyclobutanon

Publications (1)

Publication Number Publication Date
WO2000053553A1 true WO2000053553A1 (de) 2000-09-14

Family

ID=7900330

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/001707 Ceased WO2000053553A1 (de) 1999-03-10 2000-03-01 Verfahren zur herstellung von cyclobutanon

Country Status (9)

Country Link
US (1) US6476274B1 (enExample)
EP (1) EP1161408B1 (enExample)
JP (1) JP2002539098A (enExample)
KR (1) KR20010102539A (enExample)
AT (1) ATE257141T1 (enExample)
AU (1) AU2916600A (enExample)
DE (2) DE19910464A1 (enExample)
IL (1) IL144780A0 (enExample)
WO (1) WO2000053553A1 (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006512086A (ja) * 2002-09-20 2006-04-13 ダイヴァーサ コーポレイション スタチンおよびスタチン中間体の合成のための酵素化学的方法
US8546118B2 (en) 2006-03-07 2013-10-01 Verenium Corporation Aldolases, nucleic acids encoding them and methods for making and using them
CN111138252A (zh) * 2019-12-26 2020-05-12 海门华祥医药科技有限公司 一种环丁酮的合成方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1477469B1 (de) * 2003-05-10 2005-07-27 Degussa AG Salzfreies Verfahren zur Herstellung von Cyclobutanon
US6958421B2 (en) 2003-06-13 2005-10-25 Degussa Ag Salt-free preparation of cyclobutanone
DE102007011288A1 (de) 2007-03-08 2008-09-11 Evonik Degussa Gmbh Verfahren zur Stabilisierung von Cyclobutanonderivaten
EP2634253B1 (en) 2010-10-27 2016-05-11 Jichi Medical University Adeno-associated virus virions for transferring genes into neural cells
CN103449994A (zh) * 2013-09-09 2013-12-18 成都红胜科技发展有限公司 一种环丁酮的纯化工艺
CN104892385B (zh) * 2014-03-05 2016-08-24 淄博职业学院 一种环丁酮的纯化工艺
CN110294717B (zh) * 2018-03-21 2021-01-19 湖南加法检测有限公司 农药全组分中2,2-二取代环丁酮杂质及其衍生物、制备方法与应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANON.: "A process for making diketone from diol", RESEARCH DISCLOSURE, no. 380, 1995, Emsworth, GB, pages 816 - 820, XP000549835 *
COLEMAN, K. ET AL: "Selective Catalytic Oxidation of Alcohols by a Ruthenium-Copper Bifunctional System Using Molecular Oxygen", EUR. J. INORG. CHEM., vol. 11, 1998, Weinheim, DE, pages 1673 - 1675, XP000909457 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006512086A (ja) * 2002-09-20 2006-04-13 ダイヴァーサ コーポレイション スタチンおよびスタチン中間体の合成のための酵素化学的方法
US8148324B2 (en) 2002-09-20 2012-04-03 Verenium Corporation Chemoenzymatic methods for the synthesis of statins and statin intermediates
US8546118B2 (en) 2006-03-07 2013-10-01 Verenium Corporation Aldolases, nucleic acids encoding them and methods for making and using them
US9290755B2 (en) 2006-03-07 2016-03-22 Basf Enzymes Llc Aldolases, nucleic acids encoding them and methods for making and using them
US9719079B2 (en) 2006-03-07 2017-08-01 Basf Enzymes Llc Aldolases, nucleic acids encoding them and methods for making and using them
CN111138252A (zh) * 2019-12-26 2020-05-12 海门华祥医药科技有限公司 一种环丁酮的合成方法

Also Published As

Publication number Publication date
ATE257141T1 (de) 2004-01-15
DE50006027D1 (de) 2004-05-19
US6476274B1 (en) 2002-11-05
AU2916600A (en) 2000-09-28
JP2002539098A (ja) 2002-11-19
DE19910464A1 (de) 2000-09-14
EP1161408A1 (de) 2001-12-12
KR20010102539A (ko) 2001-11-15
EP1161408B1 (de) 2004-01-02
IL144780A0 (en) 2002-06-30

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