WO2020212166A1 - Novel enol-acetates(ii) - Google Patents

Novel enol-acetates(ii) Download PDF

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Publication number
WO2020212166A1
WO2020212166A1 PCT/EP2020/059482 EP2020059482W WO2020212166A1 WO 2020212166 A1 WO2020212166 A1 WO 2020212166A1 EP 2020059482 W EP2020059482 W EP 2020059482W WO 2020212166 A1 WO2020212166 A1 WO 2020212166A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl group
formula
carried out
process according
cor
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/EP2020/059482
Other languages
English (en)
French (fr)
Inventor
Werner Bonrath
Marc-André Mueller
Bettina Wuestenberg
Florian ZIEGLER
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.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
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 DSM IP Assets BV filed Critical DSM IP Assets BV
Priority to JP2021556335A priority Critical patent/JP2022528612A/ja
Priority to CN202080028196.9A priority patent/CN113710653A/zh
Priority to EP20714641.6A priority patent/EP3956305A1/en
Priority to US17/603,488 priority patent/US20220220071A1/en
Priority to BR112021020443A priority patent/BR112021020443A2/pt
Publication of WO2020212166A1 publication Critical patent/WO2020212166A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups

Definitions

  • the present invention relates to new specific enol acetates as well as to their production.
  • Enol acetates are important intermediates in various organic syntheses.
  • R is -COR’, wherein R’ is a C 1 -C 16 alkyl group (preferably a C-i, C 2 or C- 15 -alkyl group).
  • R is -COR’, wherein R’ is a C 1 -C 16 alkyl group (preferably a Ci, C 2 or C 15 - alkyl group). Therefore, the present invention relates to compounds of formula (I)
  • R is -COR’, wherein R’ is a C1 -C16 alkyl group (preferably a Ci, C2 or C15- alkyl group).
  • the present invention relates to the compounds of formula (la)
  • R is -COR’, wherein R’ is a C1 -C16 alkyl group (preferably a Ci, C2 or C15- alkyl group).
  • R is -COR’, wherein R’ is a C1 -C16 alkyl group (preferably a Ci, C2 or C15- alkyl group).
  • the enol acetate according to the present invention are produced by an enol- acetate formation of the compound of formula (II)
  • Compound of formula (II) has two isomers (among others) of the following formula (I la) and (lib):
  • R is a C 1 -C 16 alkyl group (preferably a C-i, C 2 or Cis-alkyl group).
  • the process of the present invention can be carried out in the presence of a transition metal catalyst. Especially in the presence of a Cu catalyst. Especially a Cu(ll) catalyst. Very suitable is Cu(Ac) 2 as a catalyst.
  • the present invention relates to a process (P) for the production of the compounds of formula (I)
  • R is -COR’, wherein R’ is a C 1 -C 16 alkyl group (preferably a C-i, C 2 or C 15 - alkyl group) by acetylation of a compound of formula (II)
  • R is a C1-C16 alkyl group (preferably a C-i, C2 or Cis-alkyl group).
  • the process according to the present invention can be carried out in the presence of at least one transition metal catalyst; especially in the presence of a Cu catalyst.
  • a Cu catalyst Especially a Cu(ll) catalyst.
  • Very suitable is Cu(Ac)2 as a catalyst.
  • the amount of the catalyst used in the process according to the present invention can vary.
  • the amount of the catalyst usually goes from 0.001 mol-equivalent up to 0.01 mol-equivalent (in relation to compound of formula (II)).
  • the process according to the present invention is usually carried out in the presence of at least one organic acid or in the presence of a base. Especially in the presence of p-toluenesulfonic acid.
  • the amount of the acid or of the base can vary. It goes usually from 0.005 mol- equivalent up to 0.1 mol-equivalent (in relation to compound of formula (II)).
  • the reaction is can be carried out in an inert solvent or the reaction can be carried out without a solvent. Preferably no solvent is used.
  • the process according to the present is usually carried out at elevated temperatures. Usually the process according to the present invention is carried out at a temperature of from 0°C - 100 °C, preferably from 5°C - 90°C. As stated above the process according to the present invention is one important step in the synthesis of vitamin A (and/or its derivatives).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/EP2020/059482 2019-04-15 2020-04-03 Novel enol-acetates(ii) Ceased WO2020212166A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2021556335A JP2022528612A (ja) 2019-04-15 2020-04-03 新規なエノールアセテート（ｉｉ）
CN202080028196.9A CN113710653A (zh) 2019-04-15 2020-04-03 新的烯醇乙酸酯(ii)
EP20714641.6A EP3956305A1 (en) 2019-04-15 2020-04-03 Novel enol-acetates(ii)
US17/603,488 US20220220071A1 (en) 2019-04-15 2020-04-03 Novel enol-acetates(ii)
BR112021020443A BR112021020443A2 (pt) 2019-04-15 2020-04-03 Enol-acetatos(ii)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19169208.6 2019-04-15
EP19169208 2019-04-15

Publications (1)

Publication Number Publication Date
WO2020212166A1 true WO2020212166A1 (en) 2020-10-22

Family

ID=66182396

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/059482 Ceased WO2020212166A1 (en) 2019-04-15 2020-04-03 Novel enol-acetates(ii)

Country Status (6)

Country Link
US (1) US20220220071A1 (https=)
EP (1) EP3956305A1 (https=)
JP (1) JP2022528612A (https=)
CN (1) CN113710653A (https=)
BR (1) BR112021020443A2 (https=)
WO (1) WO2020212166A1 (https=)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1031561A1 (en) * 1999-02-22 2000-08-30 F. Hoffmann-La Roche Ag Manufacture of cycloalkenylpolyene esters

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10359433A1 (de) * 2003-12-17 2005-07-21 Basf Ag Verfahren zur Herstellung von Vitamin A-Acetat
JP6064264B2 (ja) * 2011-12-27 2017-01-25 ディーエスエム アイピー アセッツ ビー．ブイ． ビタミンａ中間体の触媒合成
CN102603588A (zh) * 2012-03-13 2012-07-25 浙江工业大学 一种维生素a衍生物的制备方法
EP3684748A1 (en) * 2017-09-22 2020-07-29 DSM IP Assets B.V. New intermediates for the vitamin a synthesis
FR3085037B1 (fr) * 2018-08-20 2020-09-25 Adisseo France Sas Procede de synthese de la vitamine a

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1031561A1 (en) * 1999-02-22 2000-08-30 F. Hoffmann-La Roche Ag Manufacture of cycloalkenylpolyene esters

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
C. FEHR, ET AL.: "The synthesis of (Z)-trisubstituted allylic alcohols by the selective 1,4-hydrogenation of dienol esters: improved synthesis of (-)-beta-santalol", CHEMISTRY - A EUROPEAN JOURNAL, vol. 17, no. 4, 7 December 2010 (2010-12-07), Wiley-VCH Verlag, Weinhem, DE, pages 1257 - 1260, XP055007610, ISSN: 0947-6539, DOI: 10.1002/chem.201002729 *
D. FAVARA, ET AL.: "A facile synthesis of trans (+)-4-carboxymethyl-3-ethylazetidin-2-one and its conversion into natural PS-5", TETRAHEDRON LETTERS, vol. 23, no. 30, July 1982 (1982-07-01), Elsevier Science Publishers, Oxford, GB, pages 3105 - 3108, XP055393165, ISSN: 0040-4039, DOI: 10.1016/S0040-4039(00)87545-0 *
W.J. BAILEY, ET AL.: "Pyrolysis of esters. V. Mechanism of 1,4-elimination", JOURNAL OF ORGANIC CHEMISTRY, vol. 21, no. 3, 1 March 1956 (1956-03-01), American Chemical Society, Washington, DC, US, pages 328 - 331, XP055701508, ISSN: 0022-3263, DOI: 10.1021/jo01109a017 *

Also Published As

Publication number Publication date
US20220220071A1 (en) 2022-07-14
BR112021020443A2 (pt) 2022-03-03
CN113710653A (zh) 2021-11-26
EP3956305A1 (en) 2022-02-23
JP2022528612A (ja) 2022-06-15

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