WO2020212167A1 - Novel enol-acetates - Google Patents

Novel enol-acetates Download PDF

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Publication number
WO2020212167A1
WO2020212167A1 PCT/EP2020/059483 EP2020059483W WO2020212167A1 WO 2020212167 A1 WO2020212167 A1 WO 2020212167A1 EP 2020059483 W EP2020059483 W EP 2020059483W WO 2020212167 A1 WO2020212167 A1 WO 2020212167A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl group
formula
compounds
cor
carried out
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/EP2020/059483
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 BR112021020436A priority Critical patent/BR112021020436A2/pt
Priority to JP2021556321A priority patent/JP2022528611A/ja
Priority to EP20714642.4A priority patent/EP3956306A1/en
Priority to CN202080028200.1A priority patent/CN113661160A/zh
Priority to US17/603,122 priority patent/US20220194897A1/en
Publication of WO2020212167A1 publication Critical patent/WO2020212167A1/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.
  • R is -COR’, wherein R’ is a C1-C16 alkyl group. There are two isomers (compound of formula (la) and (lb))
  • R is -COR’, wherein R’ is a Ci-Ciealkyl group.
  • R is -COR’, wherein R’ is a C 1 -C 16 alkyl group (preferably a Ci, C 2 or C 15 - alkyl group).
  • the present invention relates to the compounds of formula (la)
  • 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 the compounds of formula (lb)
  • 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 the compounds of formula (la’)
  • R is -COR’, wherein R’ is a C 1 -C 16 alkyl group (preferably a Ci, C 2 or C 15 - alkyl group).
  • R is -COR’, wherein R’ is a Ci-Ciealkyl group (preferably a Ci, C2 or C 15 - alkyl group).
  • R is -COR’, wherein R’ is a C1 -C16 alkyl group (preferably a C-i, 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 compounds of formula (III)
  • R’ is a C 1 -C 16 alkyl group (preferably a C-i,
  • 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. Due to the C-C double bonds, the compounds of formula (I) as well as the compounds of formula (II) can have several stereochemical isomers, which are not all implicitly drawn in this application, but which are also covered by the present invention.
  • the present invention relates to a process (P) for the production of the compounds of formula (I)
  • R is -COR’, wherein R’ is a C1-C16 alkyl group(preferably a Ci, C2 or Cis-alkyl group)
  • R’ is a Ci-Ciealkyl group (preferably a C-i,
  • 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 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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/EP2020/059483 2019-04-15 2020-04-03 Novel enol-acetates Ceased WO2020212167A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR112021020436A BR112021020436A2 (pt) 2019-04-15 2020-04-03 Acetatos de enol
JP2021556321A JP2022528611A (ja) 2019-04-15 2020-04-03 新規なエノールアセテート
EP20714642.4A EP3956306A1 (en) 2019-04-15 2020-04-03 Novel enol-acetates
CN202080028200.1A CN113661160A (zh) 2019-04-15 2020-04-03 新的烯醇乙酸酯
US17/603,122 US20220194897A1 (en) 2019-04-15 2020-04-03 Novel enol-acetates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19169207 2019-04-15
EP19169207.8 2019-04-15

Publications (1)

Publication Number Publication Date
WO2020212167A1 true WO2020212167A1 (en) 2020-10-22

Family

ID=66182395

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/059483 Ceased WO2020212167A1 (en) 2019-04-15 2020-04-03 Novel enol-acetates

Country Status (6)

Country Link
US (1) US20220194897A1 (https=)
EP (1) EP3956306A1 (https=)
JP (1) JP2022528611A (https=)
CN (1) CN113661160A (https=)
BR (1) BR112021020436A2 (https=)
WO (1) WO2020212167A1 (https=)

Citations (2)

* 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
WO2020038858A1 (fr) * 2018-08-20 2020-02-27 Adisseo France S.A.S. Procédé de synthèse de la vitamine a

Family Cites Families (3)

* 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
EP2723713B1 (en) * 2011-06-22 2018-04-11 DSM IP Assets B.V. Method for making new intermediates for the vitamin a and -carotene synthesis
EP3684748A1 (en) * 2017-09-22 2020-07-29 DSM IP Assets B.V. New intermediates for the vitamin a synthesis

Patent Citations (2)

* 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
WO2020038858A1 (fr) * 2018-08-20 2020-02-27 Adisseo France S.A.S. Procédé de synthèse de la vitamine a

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, 24 January 2011 (2011-01-24), 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
JP2022528611A (ja) 2022-06-15
CN113661160A (zh) 2021-11-16
EP3956306A1 (en) 2022-02-23
BR112021020436A2 (pt) 2021-12-14
US20220194897A1 (en) 2022-06-23

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