CH393309A - Process for the preparation of stable compounds of vitamin A. - Google Patents
Process for the preparation of stable compounds of vitamin A.Info
- Publication number
- CH393309A CH393309A CH7822559A CH7822559A CH393309A CH 393309 A CH393309 A CH 393309A CH 7822559 A CH7822559 A CH 7822559A CH 7822559 A CH7822559 A CH 7822559A CH 393309 A CH393309 A CH 393309A
- Authority
- CH
- Switzerland
- Prior art keywords
- vitamin
- acid
- dependent
- nitro
- transesterification
- Prior art date
Links
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 title claims description 21
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 title claims description 18
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 title claims description 15
- 235000019155 vitamin A Nutrition 0.000 title claims description 15
- 239000011719 vitamin A Substances 0.000 title claims description 15
- 229940045997 vitamin a Drugs 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- -1 benzoic acid halide Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004347 all-trans-retinol derivatives Chemical class 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 5
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000019169 all-trans-retinol Nutrition 0.000 description 3
- 239000011717 all-trans-retinol Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N (R)-alpha-Tocopherol Natural products OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- NNOHXABAQAGKRZ-UHFFFAOYSA-N 3,5-dinitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC(C(Cl)=O)=CC([N+]([O-])=O)=C1 NNOHXABAQAGKRZ-UHFFFAOYSA-N 0.000 description 1
- NXTNASSYJUXJDV-UHFFFAOYSA-N 3-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(C(Cl)=O)=C1 NXTNASSYJUXJDV-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-M 4-chlorobenzoate Chemical compound [O-]C(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-M 0.000 description 1
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229960000342 retinol acetate Drugs 0.000 description 1
- QGNJRVVDBSJHIZ-QHLGVNSISA-N retinyl acetate Chemical compound CC(=O)OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C QGNJRVVDBSJHIZ-QHLGVNSISA-N 0.000 description 1
- 235000019173 retinyl acetate Nutrition 0.000 description 1
- 239000011770 retinyl acetate Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Saccharide Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung von stabilen Verbindungen von Vitamin A Bekanntlich ist Vitamin A gegenüber Sauerstoff äusserst empfindlich. So zersetzt es sich z. B. unter dem Einfluss von Luftsauerstoff beim Stehenlassen bereits innerhalb von wenigen Stunden. Auch die bisher bekannten Ester von Vitamin A weisen eine ähnlich hohe Unbeständigkeit auf. Durch Zugabe von Antioxydantien, z.
B. von a-Tocopherol, gelingt es zwar, die Stabilität des Vitamins A zu verbessern, doch ist der durch derartige Massnahmen erreichbare Effekt für viele Zwecke noch völlig ungenügend.
Es wurde nun überraschend gefunden, dass be stimmte Benzoesäureester des Vitamins A, selbst ohne Zusatz von Antioxydantien, eine erstaunlich hohe Stabilität besitzen. Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von sta bilen Verbindungen des Vitamins A, welches dadurch gekennzeichnet ist, dass man Vitamin A oder ein in der OH-Gruppe abgewandeltes Derivat desselben mit einer durch Halogenatome,
niedere Alkylgruppen oder niedere Alkoxygruppen mono- oder disubstituierten, oder in o- und/oder m-Stellung durch Nitrogruppen substituierten Benzoesäure oder einem funktionellen Derivat einer solchen Säure umsetzt.
Beispielsweise können diese genannten stabilen Ester durch Veresterung von Vitamin A mit einem reaktionsfähigen Derivat der genannten Säure ge wonnen werden. Als besonders geeignete reaktions- fähige Säurederivate haben sich die Säurehalogenide, insbesondere das Säurechlorid und die Säureanhydride erwiesen.
Werden die gewünschten Ester durch Umesterung gewonnen, so verwendet man zu diesem Zweck zweckmässig einen niederen Carbonsäureester des Vitamins A, z. B. Vitamin-A-Acetat, und erwärmt ihn mit einem niederalkoholischen Ester der ent sprechend substituierten Benzoesäure. Die Umeste- rungsreaktion wird mit Vorteil in Gegenwart von Umesterungskatalysatoren, z.
B. Alkalimetallhydro- xyden oder Alkalimetallalkoholaten unter kontinuier licher Entfernung des als Nebenprodukt gebildeten niederalkoholischen Esters der niederen Carbonsäure durchgeführt.
Beispiel <I>1</I> 8 g m-Nitro-benzoylchlorid werden in 70 ml Pyridin gelöst. Man kühlt die erhaltene Lösung auf + 10 ab, gibt 10 g Vitamin-A Alkohol zu und lässt die Reaktionsmischung 5 Stunden bei Zimmer temperatur stehen.
Hierauf giesst man die Lösung auf Eiswasser, extrahiert mit 250 ml Äther und wäscht die Ätherlösung zweimal mit je 200 ml Wasser, einmal mit 200 ml 3%iger Schwefelsäure, wieder mit Wasser, dann mit 200 ml 1%iger Natriumbicarbonatlösung und schliesslich nochmals mit Wasser.
Nach dem Trocknen des Äthers über Natriumsulfat und dem Abdampfen des Äthers erhält man 16,5 g eines gelben zähen Öls, das in 100 ml Petroläther (Siedebereich 60-90 ) gelöst wird. Nun wird von wenig Ungelöstem abfiltriert, worauf beim Stehenlassen bei 0 13 g Vit- amin-A-nitrobenzoat in orangeroten, derben Prismen auskristallisieren; Schmelzpunkt 78 . Absorptions- maximum bei 326 mu, E i = 1130 in Alkohol).
<I>Beispiel 2</I> 10 g Vitamin-A-Alkohol werden bei einer Tem peratur von + 10 zu einer Mischung von 8,4 g 3,5-Dinitro-benzoylchlorid mit 120 ml Pyridin ge geben. Die Reaktionsmischung wird anschliessend eine Stunde bei Raumtemperatur stehengelassen und wie in Beispiel 1 angegeben aufgearbeitet.
Man erhält 11,6 g Vitamin-A-3,5-dinitrobenzoat als kristallinen Rückstand, der aus Petroläther (Siedebereich 90 bis 110 ) umkristallisiert wird, wobei man rote Prismen erhält, die sich oberhalb 150 langsam zersetzen; Absorptionsmaximum bei 328 my, E i = 1020 (in Alkohol).
Beispiel <I>3</I> 6,1 g p-Chlor-benzoylchlorid werden in 80 ml Pyridin gelöst. Hierauf versetzt man die erhaltene Lösung bei 10 mit 10g Vitamin-A-Alkohol, lässt 5 Stunden bei Raumtemperatur stehen und arbeitet wie in Beispiel 1 angegeben auf.
Man erhält 14,7 g rohes Vitamin-A-p-chlorbenzoat, welches nach dem Umkristallisieren aus Aceton/Methanol farblose Blätt chen vom Schmelzpunkt 77-78 bildet; Absorp- tionsmaximum bei 327 my, E i = 1255 (in Alkohol).
Process for the preparation of stable compounds of vitamin A It is known that vitamin A is extremely sensitive to oxygen. So it decomposes z. B. under the influence of atmospheric oxygen when left standing within a few hours. The previously known esters of vitamin A also show a similarly high level of instability. By adding antioxidants, e.g.
B. from α-tocopherol, it is possible to improve the stability of vitamin A, but the effect that can be achieved by such measures is still completely inadequate for many purposes.
It has now been found, surprisingly, that certain benzoic acid esters of vitamin A, even without the addition of antioxidants, have an astonishingly high stability. The subject of the present patent is a process for the production of stable compounds of vitamin A, which is characterized in that vitamin A or a derivative thereof modified in the OH group with a halogen atom,
lower alkyl groups or lower alkoxy groups mono- or disubstituted, or benzoic acid substituted in the o- and / or m-position by nitro groups or a functional derivative of such an acid.
For example, these stable esters mentioned can be obtained by esterification of vitamin A with a reactive derivative of the acid mentioned. The acid halides, in particular the acid chloride and the acid anhydrides, have proven to be particularly suitable reactive acid derivatives.
If the desired esters are obtained by transesterification, it is expedient to use a lower carboxylic acid ester of vitamin A, e.g. B. vitamin A acetate, and heats it with a lower alcohol ester of the corresponding substituted benzoic acid. The transesterification reaction is advantageously carried out in the presence of transesterification catalysts, e.g.
B. alkali metal hydroxides or alkali metal alcoholates are carried out with continuous removal of the lower alcoholic ester of the lower carboxylic acid formed as a by-product.
Example <I> 1 </I> 8 g of m-nitro-benzoyl chloride are dissolved in 70 ml of pyridine. The resulting solution is cooled to +10, 10 g of vitamin A alcohol are added and the reaction mixture is left to stand for 5 hours at room temperature.
The solution is then poured onto ice water, extracted with 250 ml of ether and the ethereal solution is washed twice with 200 ml of water each time, once with 200 ml of 3% sulfuric acid, again with water, then with 200 ml of 1% sodium bicarbonate solution and finally again with water .
After drying the ether over sodium sulfate and evaporating the ether, 16.5 g of a yellow viscous oil are obtained, which is dissolved in 100 ml of petroleum ether (boiling range 60-90). A little undissolved material is then filtered off, whereupon 13 g of vitamin A-nitrobenzoate crystallize in orange-red, coarse prisms when left to stand at 0; Melting point 78. Absorption maximum at 326 mu, E i = 1130 in alcohol).
<I> Example 2 </I> 10 g of vitamin A alcohol are added at a temperature of + 10 to a mixture of 8.4 g of 3,5-dinitro-benzoyl chloride with 120 ml of pyridine. The reaction mixture is then left to stand for one hour at room temperature and worked up as indicated in Example 1.
11.6 g of vitamin A-3,5-dinitrobenzoate are obtained as a crystalline residue which is recrystallized from petroleum ether (boiling range 90 to 110), giving red prisms which slowly decompose above 150; Absorption maximum at 328 my, E i = 1020 (in alcohol).
Example <I> 3 </I> 6.1 g of p-chloro-benzoyl chloride are dissolved in 80 ml of pyridine. The solution obtained is then mixed with 10 g of vitamin A alcohol at 10, left to stand for 5 hours at room temperature and worked up as indicated in Example 1.
14.7 g of crude vitamin A p-chlorobenzoate are obtained, which after recrystallization from acetone / methanol forms colorless leaves with a melting point of 77-78; Absorption maximum at 327 my, E i = 1255 (in alcohol).
Claims (1)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH7822559A CH393309A (en) | 1959-09-15 | 1959-09-15 | Process for the preparation of stable compounds of vitamin A. |
| BE594982A BE594982A (en) | 1959-09-15 | 1960-09-13 | Method for stabilizing vitamin A |
| ES0261262A ES261262A1 (en) | 1959-09-15 | 1960-09-14 | PROCEDURE FOR THE STABILIZATION OF VITAMIN A |
| FR838514A FR653M (en) | 1959-09-15 | 1960-09-14 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH7822559A CH393309A (en) | 1959-09-15 | 1959-09-15 | Process for the preparation of stable compounds of vitamin A. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH393309A true CH393309A (en) | 1965-06-15 |
Family
ID=4536318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH7822559A CH393309A (en) | 1959-09-15 | 1959-09-15 | Process for the preparation of stable compounds of vitamin A. |
Country Status (4)
| Country | Link |
|---|---|
| BE (1) | BE594982A (en) |
| CH (1) | CH393309A (en) |
| ES (1) | ES261262A1 (en) |
| FR (1) | FR653M (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4200647A (en) * | 1977-12-21 | 1980-04-29 | Hoffmann-La Roche Inc. | Vitamin A compositions to treat rheumatic disease |
-
1959
- 1959-09-15 CH CH7822559A patent/CH393309A/en unknown
-
1960
- 1960-09-13 BE BE594982A patent/BE594982A/en unknown
- 1960-09-14 FR FR838514A patent/FR653M/fr active Active
- 1960-09-14 ES ES0261262A patent/ES261262A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR653M (en) | 1961-07-03 |
| BE594982A (en) | 1961-03-13 |
| ES261262A1 (en) | 1961-05-16 |
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