US20200283368A1 - New intermediates for the vitamin a synthesis - Google Patents
New intermediates for the vitamin a synthesis Download PDFInfo
- Publication number
- US20200283368A1 US20200283368A1 US16/645,614 US201816645614A US2020283368A1 US 20200283368 A1 US20200283368 A1 US 20200283368A1 US 201816645614 A US201816645614 A US 201816645614A US 2020283368 A1 US2020283368 A1 US 2020283368A1
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- United States
- Prior art keywords
- formula
- compound
- vitamin
- synthesis
- reaction
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- 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.)
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- MKRSCGLTQTWDQF-GZTJUZNOSA-N C=CC(C)(CC/C=C(\C)CCC1=C(C)CCCC1(C)C)OC(C)=O Chemical compound C=CC(C)(CC/C=C(\C)CCC1=C(C)CCCC1(C)C)OC(C)=O MKRSCGLTQTWDQF-GZTJUZNOSA-N 0.000 description 6
- CWGMQUUHSSQDKW-DKBAOEGPSA-N CC(=O)OC/C=C(\C)CC/C=C(\C)CCC1=C(C)CCCC1(C)C Chemical compound CC(=O)OC/C=C(\C)CC/C=C(\C)CCC1=C(C)CCCC1(C)C CWGMQUUHSSQDKW-DKBAOEGPSA-N 0.000 description 5
- YFEVBROYQHUOFN-MHWRWJLKSA-N C=CC(C)(O)CC/C=C(\C)CCC1=C(C)CCCC1(C)C Chemical compound C=CC(C)(O)CC/C=C(\C)CCC1=C(C)CCCC1(C)C YFEVBROYQHUOFN-MHWRWJLKSA-N 0.000 description 2
- JJTXQCMHUFFVOF-RIYZIHGNSA-N CC(=O)CC/C=C(\C)CCC1=C(C)CCCC1(C)C Chemical compound CC(=O)CC/C=C(\C)CCC1=C(C)CCCC1(C)C JJTXQCMHUFFVOF-RIYZIHGNSA-N 0.000 description 2
- YEMQBJJVHCHCKC-YTEIMQKESA-M C=CC(C)(CC/C=C(\C)CCC1=C(C)CCCC1(C)C)OC(C)=O.C=CC(C)(O)CC/C=C(\C)CCC1=C(C)CCCC1(C)C.CC(=O)CC/C=C(\C)CCC1=C(C)CCCC1(C)C.CC(=O)OC/C=C(\C)CC/C=C(\C)CCC1=C(C)CCCC1(C)C.I.II.I[IH]I.[V]I Chemical compound C=CC(C)(CC/C=C(\C)CCC1=C(C)CCCC1(C)C)OC(C)=O.C=CC(C)(O)CC/C=C(\C)CCC1=C(C)CCCC1(C)C.CC(=O)CC/C=C(\C)CCC1=C(C)CCCC1(C)C.CC(=O)OC/C=C(\C)CC/C=C(\C)CCC1=C(C)CCCC1(C)C.I.II.I[IH]I.[V]I YEMQBJJVHCHCKC-YTEIMQKESA-M 0.000 description 1
- VYWUQWUUEASMNG-AMULTCRRSA-N C=CC(C)(CC/C=C(\C)CCC1=C(C)CCCC1(C)C)OC(C)=O.CC(=O)OC/C=C(\C)CC/C=C(\C)CCC1=C(C)CCCC1(C)C Chemical compound C=CC(C)(CC/C=C(\C)CCC1=C(C)CCCC1(C)C)OC(C)=O.CC(=O)OC/C=C(\C)CC/C=C(\C)CCC1=C(C)CCCC1(C)C VYWUQWUUEASMNG-AMULTCRRSA-N 0.000 description 1
- QOLPKZFHRRDCIB-ZQLGXJRNSA-N C=CC(C)(CC/C=C(\C)CCC1=C(C)CCCC1(C)C)OC(C)=O.CC(=O)OC/C=C(\C)CC/C=C(\C)CCC1=C(C)CCCC1(C)C.I.II Chemical compound C=CC(C)(CC/C=C(\C)CCC1=C(C)CCCC1(C)C)OC(C)=O.CC(=O)OC/C=C(\C)CC/C=C(\C)CCC1=C(C)CCCC1(C)C.I.II QOLPKZFHRRDCIB-ZQLGXJRNSA-N 0.000 description 1
- HUYMQXPJHURUCH-UHFFFAOYSA-N CC(=O)CCC1=C(C)CCCC1(C)C.CC(=O)CCC=C(C)CCC1=C(C)CCCC1(C)C Chemical compound CC(=O)CCC1=C(C)CCCC1(C)C.CC(=O)CCC=C(C)CCC1=C(C)CCCC1(C)C HUYMQXPJHURUCH-UHFFFAOYSA-N 0.000 description 1
- QJJDNZGPQDGNDX-UHFFFAOYSA-N CC1(C)C(CCC(C)=O)=C(C)CCC1 Chemical compound CC1(C)C(CCC(C)=O)=C(C)CCC1 QJJDNZGPQDGNDX-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N CC1=C(/C=C/C(C)=C/C=C/C(C)=C/CO)C(C)(C)CCC1 Chemical compound CC1=C(/C=C/C(C)=C/C=C/C(C)=C/CO)C(C)(C)CCC1 FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B49/00—Grignard reactions
-
- 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
- C07C403/08—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 hydroxy groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
- C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Definitions
- the present invention relates to new compounds, to their synthesis and their use in organic synthesis, especially in the synthesis of vitamin A, Vitamin A acetate, or ⁇ -carotene and derivatives thereof, e.g. canthaxanthin, astaxanthin or zeaxanthin.
- the new compounds are useful as intermediates (building blocks) in the synthesis of vitamin A or ⁇ -carotene, preferably in the synthesis of vitamin A (or vitamin A acetate).
- Vitamin A plays a role in a variety of functions throughout the (human) body, such as e.g. vision process, gene transcription, immune function, bone metabolism, haematopoiesis, skin and cellular health and antioxidant function.
- the goal of the present invention was to find easily accessible compounds, which can then be used in an improved synthesis of vitamin A or its derivates, or ⁇ -carotene, preferably vitamin A (acetate).
- an embodiment of the present invention is the compound of formula (I)
- 6-Methyl-8-(2,6,6-trimethyl-1-cyclohexen-1-yl)-5-octen-2-one can be converted into ⁇ -cyclogeranyllinalool (compound of formula (IV)) by standard organic chemistry methods, e.g. by Grignard reaction.
- the present invention relates to a process to produce the compound of formula (II)
- Step (i) can be carried out according to standard organic chemistry methods, e.g. Grignard reaction.
- the compound of formula (IV) is acetylated. That can be done by commonly known compounds, such as for example acetic acid anhydride.
- step (ii) is carried out in presence of an tertiary amine, preferred triethylamine. It is very common and preferred that also at least one nucleophilic catalyst is used, such as for example dimethyl aminopyridine.
- step (ii) is carried out under an inert gas atmosphere.
- step (ii) is usually carried out at elevated temperatures, usually above 30° C., (in the range of 30-80° C.).
- step (iii) is carried out in an organic solvent.
- suitable solvents are ethers, e.g. THF, toluene, methyl-THF, methyl cyclopentyl ether, tert.-butyl methyl ether, tert.-butyl ethyl ether, tert.-amyl methyl ether or mixtures thereof.
- Most preferred solvents are are ethers, such as THF or 2-MeTHF.
- step (iii) is carried out in the presence of a catalyst such bis(acetonitrile)-dichloropalladium or bis(benzonitrile)-dichloropalladium.
- a catalyst such bis(acetonitrile)-dichloropalladium or bis(benzonitrile)-dichloropalladium.
- the product is then isolated and usually purified by commonly known methods.
- the compound of formula (I) is usually obtained in an overall yield (based on the compound of formula (II)) of more than 50%.
- the compounds of formula (I) and (II) according to the present invention can be used in organic synthesis.
- the new compounds are useful as intermediates (building blocks) in the synthesis of vitamin A or ⁇ -carotene or derivatives thereof, preferably vitamin A. Therefore, a further embodiment of the present invention relates to the use of compounds of formula (I) and (II) in organic synthesis. A preferred embodiment of the present invention relates to the use of compounds of formula (I) and (II) as intermediates (building blocks) in the synthesis of vitamin A or ⁇ -carotene, preferably vitamin A.
- the reaction mixture was cooled to room temperature, transferred into a separation funnel and diluted with 15 ml of diethyl ether.
- the organic layer was subsequently washed with semi-saturated NaHCO 3 solution (30 ml), water (30 ml) and brine (30 ml).
- the aqueous layers were re-extracted with diethyl ether (30 ml).
- the combined organic layers were dried over Na 2 SO 4 , filtered and concentrated under reduced pressure.
- the crude product was purified by column chromatography (SiO 2 , cyclohexane/diisopropyl ether 8:2). The purified product was obtained as colorless liquid in 81% yield.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the compound of formula (I). The invention further relates to the compound of formula (II). The invention further relates to the synthesis of these compounds as well as to their use in organic synthesis, especially in the synthesis of vitamin A or p-carotene and derivatives thereof, e.g. canthaxanthin, astaxanthin or zeaxanthin.
Description
- The present invention relates to new compounds, to their synthesis and their use in organic synthesis, especially in the synthesis of vitamin A, Vitamin A acetate, or β-carotene and derivatives thereof, e.g. canthaxanthin, astaxanthin or zeaxanthin.
- Especially to be mentioned is that the new compounds are useful as intermediates (building blocks) in the synthesis of vitamin A or β-carotene, preferably in the synthesis of vitamin A (or vitamin A acetate).
- Vitamin A or its derivatives such as Vitamin acetate
- is an important ingredient for many applications. Vitamin A plays a role in a variety of functions throughout the (human) body, such as e.g. vision process, gene transcription, immune function, bone metabolism, haematopoiesis, skin and cellular health and antioxidant function.
- Due to the importance of vitamin A (and its derivatives) and the complexity of the synthesis thereof, there is always a need for improved processes of production.
- The goal of the present invention was to find easily accessible compounds, which can then be used in an improved synthesis of vitamin A or its derivates, or β-carotene, preferably vitamin A (acetate).
- The aim was achieved by the compounds and the synthesis as disclosed and described below.
- Three new compounds, which are useful intermediates, have been found:
- ρ-Cyclogeranylgeranyl acetate (compound of formula (I))
- as well as β-cyclogeranyllinalyl acetate (compound of formula (II))
- which is a precursor compound for the compound of formula (I).
- Therefore, an embodiment of the present invention is the compound of formula (I)
- Therefore, another embodiment of the present invention is the compound of formula (II)
- The new synthesis uses 6-methyl-8-(2,6,6-trimethyl-1-cyclohexen-1-yl)-5-octen-2-one (compound of formula (III))
- as a starting material.
- 6-Methyl-8-(2,6,6-trimethyl-1-cyclohexen-1-yl)-5-octen-2-one (compound of formula (III)) was synthesized according to literature-known procedures, such as e.g. the following way
- 6-Methyl-8-(2,6,6-trimethyl-1-cyclohexen-1-yl)-5-octen-2-one can be converted into β-cyclogeranyllinalool (compound of formula (IV)) by standard organic chemistry methods, e.g. by Grignard reaction.
- The reaction scheme of the production of the compounds of formula (I) and (II) is the following:
- Therefore, the present invention relates to a process to produce the compound of formula (II)
- wherein the compound of formula (IV)
- is reacted with a compound (acetic acid anhydride or similar) to form the compound of formula (II).
- Step (i) can be carried out according to standard organic chemistry methods, e.g. Grignard reaction.
- The compound of formula (IV) is acetylated. That can be done by commonly known compounds, such as for example acetic acid anhydride.
- The reaction of step (ii) is carried out in presence of an tertiary amine, preferred triethylamine. It is very common and preferred that also at least one nucleophilic catalyst is used, such as for example dimethyl aminopyridine.
- Usually the reaction of step (ii) is carried out under an inert gas atmosphere.
- The reaction of step (ii) is usually carried out at elevated temperatures, usually above 30° C., (in the range of 30-80° C.).
- The product which is then obtained (compound of formula (II)) can be isolated and if needed further purified. The yields, which are obtained are usually above 80%.
- Step (iii):
- Compound of formula (I) is obtained by the reaction of the compound of formula (II). It is a rearrangement reaction. (step (iii)).
- Usually the reaction of step (iii) is carried out in an organic solvent. Suitable solvents are ethers, e.g. THF, toluene, methyl-THF, methyl cyclopentyl ether, tert.-butyl methyl ether, tert.-butyl ethyl ether, tert.-amyl methyl ether or mixtures thereof. Most preferred solvents are are ethers, such as THF or 2-MeTHF.
- Usually the reaction of step (iii) is carried out in the presence of a catalyst such bis(acetonitrile)-dichloropalladium or bis(benzonitrile)-dichloropalladium.
- The product is then isolated and usually purified by commonly known methods. The compound of formula (I) is usually obtained in an overall yield (based on the compound of formula (II)) of more than 50%.
- The compounds of formula (I) and (II) according to the present invention can be used in organic synthesis.
- Preferably the new compounds are useful as intermediates (building blocks) in the synthesis of vitamin A or β-carotene or derivatives thereof, preferably vitamin A. Therefore, a further embodiment of the present invention relates to the use of compounds of formula (I) and (II) in organic synthesis. A preferred embodiment of the present invention relates to the use of compounds of formula (I) and (II) as intermediates (building blocks) in the synthesis of vitamin A or β-carotene, preferably vitamin A.
- The following examples serve to illustrate the invention. The temperature is given in ° C. and all percentages are related to the weight.
- Under inert gas atmosphere, 22 mmol of (E)-6-methyl-8-(2,6,6-trimethylcyclohex-1-en-1-yl)oct-5-en-2-one (III) were dissolved in 22 ml of anhydrous THF. The solution was cooled to 0-5° C. with an ice-bath. Over 2 hours, 33 mmol vinyl magnesium bromide solution (1 M in THF) were added dropwise so that the temperature remains between 0-5° C. After complete addition, stirring was continued for 1 hour. After that the ice-bath was removed and the reaction was warmed to room temperature. After 1 hour at 24° C., sat. NH4Cl-solution (30 ml) was added dropwise over 10 min (exothermic). After stirring for another 30 min the mixture was diluted with methylene chloride (100 ml) and washed with brine (2×45 ml). The aqueous layers were re-extracted with methylene chloride (2×100 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatopgraphy (SiO2, cyclohexane/diisopropyl ether 8:2).
- Under inert gas atmosphere, 3.44 mmol β-cyclogeranyllinalool were dissolved in 6.9 ml of toluene. At room temperature, 8.61 mmol of triethylamine and 1.722 mmol of dimethyl aminopyridine (DMAP) were added. To the colorless solution were added 8.61 mmol of acetic acid anhydride. Then the reaction mixture was warmed to 50° C. and stirred for 2 hours.
- The reaction mixture was cooled to room temperature, transferred into a separation funnel and diluted with 15 ml of diethyl ether. The organic layer was subsequently washed with semi-saturated NaHCO3 solution (30 ml), water (30 ml) and brine (30 ml). The aqueous layers were re-extracted with diethyl ether (30 ml). The combined organic layers were dried over Na2SO4, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (SiO2, cyclohexane/diisopropyl ether 8:2). The purified product was obtained as colorless liquid in 81% yield.
- Under inert gas atmosphere, 0.05 mmol bis(acetonitrile)-dichloropalladium were dissolved in 1 ml of anhydrous THF. At room temperature, a solution of 1 mmol of β-cyclogeranyllinalool acetate in 4 ml of anhydrous THF was added within 20 min. After stirring for 4 hours at room temperature, the reaction was complete. The solvent was removed and the crude product was purified by column chromatography (SiO2, n-hexane/ethyl acetate 95:5). The purified product was obtained as yellow liquid in 50% yield.
Claims (8)
5. Use of the compound of formula (I) in organic synthesis.
6. Use according to claim 5 , wherein the vitamin A or β-carotene are produced (preferably vitamin A).
7. Use of the compound of formula (II) in organic synthesis.
8. Use according to claim 7 , wherein the vitamin A or β-carotene are produced (preferably vitamin A).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17192631.4 | 2017-09-22 | ||
EP17192631 | 2017-09-22 | ||
PCT/EP2018/074748 WO2019057600A1 (en) | 2017-09-22 | 2018-09-13 | New intermediates for the vitamin a synthesis |
Related Parent Applications (1)
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PCT/EP2018/074748 A-371-Of-International WO2019057600A1 (en) | 2017-09-22 | 2018-09-13 | New intermediates for the vitamin a synthesis |
Related Child Applications (1)
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US17/676,077 Continuation US11851404B2 (en) | 2017-09-22 | 2022-02-18 | Intermediates for the vitamin A synthesis |
Publications (1)
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US20200283368A1 true US20200283368A1 (en) | 2020-09-10 |
Family
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US16/645,614 Abandoned US20200283368A1 (en) | 2017-09-22 | 2018-09-13 | New intermediates for the vitamin a synthesis |
US17/676,077 Active US11851404B2 (en) | 2017-09-22 | 2022-02-18 | Intermediates for the vitamin A synthesis |
Family Applications After (1)
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US17/676,077 Active US11851404B2 (en) | 2017-09-22 | 2022-02-18 | Intermediates for the vitamin A synthesis |
Country Status (4)
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US (2) | US20200283368A1 (en) |
EP (2) | EP3684748A1 (en) |
CN (1) | CN111108086A (en) |
WO (1) | WO2019057600A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2021130059A1 (en) * | 2019-12-23 | 2021-07-01 | Dsm Ip Assets B.V. | Functionalisation of 1,3-alpha-dienes (ii) |
US20230192605A1 (en) * | 2020-03-31 | 2023-06-22 | Dsm Ip Assets B.V. | Process for production of intermediates |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3062875A (en) | 1962-11-06 | Displacement reactions of myrcene | ||
CH168135A (en) * | 1933-03-03 | 1934-03-31 | Chem Ind Basel | Process for the preparation of an unsaturated monocyclic primary diterpene alcohol of the type of vitamin A. |
US2369166A (en) * | 1942-03-03 | 1945-02-13 | Research Corp | Synthesis of vitamin a |
US2451739A (en) | 1945-10-18 | 1948-10-19 | Hoffmann La Roche | Process for the manufacture of pentaenes |
US3928400A (en) | 1972-11-02 | 1975-12-23 | Hoffmann La Roche | Process for producing vitamin A |
-
2018
- 2018-09-13 EP EP18765474.4A patent/EP3684748A1/en not_active Ceased
- 2018-09-13 EP EP23215700.8A patent/EP4324819A2/en active Pending
- 2018-09-13 US US16/645,614 patent/US20200283368A1/en not_active Abandoned
- 2018-09-13 CN CN201880061082.7A patent/CN111108086A/en active Pending
- 2018-09-13 WO PCT/EP2018/074748 patent/WO2019057600A1/en unknown
-
2022
- 2022-02-18 US US17/676,077 patent/US11851404B2/en active Active
Also Published As
Publication number | Publication date |
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WO2019057600A1 (en) | 2019-03-28 |
EP3684748A1 (en) | 2020-07-29 |
EP4324819A2 (en) | 2024-02-21 |
US20220169590A1 (en) | 2022-06-02 |
CN111108086A (en) | 2020-05-05 |
US11851404B2 (en) | 2023-12-26 |
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