DE1212960B - Process for the preparation of secondary-tertiary alkenediols - Google Patents
Process for the preparation of secondary-tertiary alkenediolsInfo
- Publication number
- DE1212960B DE1212960B DEB67489A DEB0067489A DE1212960B DE 1212960 B DE1212960 B DE 1212960B DE B67489 A DEB67489 A DE B67489A DE B0067489 A DEB0067489 A DE B0067489A DE 1212960 B DE1212960 B DE 1212960B
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- general formula
- formula
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- hal
- radical
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 7
- -1 alkenyl radical Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 230000003533 narcotic effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical class II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 231100000636 lethal dose Toxicity 0.000 description 2
- 239000011981 lindlar catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- ZBFFNPODXBJBPW-UHFFFAOYSA-N 1-hydroxy-1-phenylpropan-2-one Chemical compound CC(=O)C(O)C1=CC=CC=C1 ZBFFNPODXBJBPW-UHFFFAOYSA-N 0.000 description 1
- WLVPRARCUSRDNI-UHFFFAOYSA-N 2-hydroxy-1-phenyl-1-propanone Chemical compound CC(O)C(=O)C1=CC=CC=C1 WLVPRARCUSRDNI-UHFFFAOYSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002149 estolides Chemical class 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/045—Hydroxy compounds, e.g. alcohols; Salts thereof, e.g. alcoholates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epidemiology (AREA)
- Pharmacology & Pharmacy (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicinal Preparation (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. CL:Int. CL:
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:
C 07cC 07c
Deutsche Kl.: 12 ο-19/03 German class: 12 ο -19/03
1212 960
B67489IVb/12o
30. Mai 1962
24. März 19661212 960
B67489IVb / 12o
May 30, 1962
March 24, 1966
Die Erfindung betrifft Verfahren zur Herstellung sekundär-tertiärer Alkendiole der allgemeinen Formel The invention relates to processes for the preparation of secondary-tertiary alkeniols of the general formula
RiRi
R2-CH-C —R3 OH OHR 2 -CH-C-R 3 OH OH
worin Ri einen Alkyl-, Alkenyl-, Cycloalkyl-, Ar- ίο alkyl- oder einen Arylrest, R2 einen Alkyl-, Aralkyl- oder einen Arylrest und R3 einen Alkenylrest mit endständiger Doppelbindung mit 2 bis 4 Kohlenstoffatomen bedeutet, das dadurch gekennzeichnet ist, daß in an sich bekannter Weisewherein Ri is an alkyl, alkenyl, cycloalkyl, Ar ίο alkyl or an aryl radical, R2 is an alkyl, aralkyl or an aryl radical and R3 an alkenyl radical with a terminal double bond with 2 to 4 carbon atoms means that is characterized in that in a manner known per se
a) a-Hydroxyketone der allgemeinen Formela) a-hydroxyketones of the general formula
Ri R2-CH-C Ri R 2 -CH-C
IIII
OH OOH O
mit metallorganischen Verbindungen der Formelwith organometallic compounds of the formula
Hai — Me — R3 IIIShark - Me - R 3 III
oder a-Hydroxyketone der allgemeinen Formelor α-hydroxyketones of the general formula
R2-CH-C-R3 OH OR 2 -CH-CR 3 OH O
IVIV
mit metallorganischen Verbindungen der Formel Hal — Me-Ri Vwith organometallic compounds of the formula Hal - Me-Ri V
worin den Resten Ri bis R3 die oben angegebene Bedeutung zukommt, Hai ein Halogenatom und Me ein Metallatom bedeutet, umgesetzt werden oder daßin which the radicals Ri to R3 have the meaning given above, Hai a halogen atom and Me a metal atom means to be reacted or that
b) Alkindiole der allgemeinen Formelb) alkynediols of the general formula
RiRi
R2 CH C R4 OH OHR2 CH C R4 OH OH
VIVI
worin den Resten Ri und R2 die oben angegebene Bedeutung zukommt und R4 einen Alkinylrest mit 2 bis 4 Kohlenstoffatomen mit endständiger Dreifachbindung bedeutet, partiell hydriert werden.in which the radicals Ri and R 2 have the meaning given above and R4 is an alkynyl radical having 2 to 4 carbon atoms with a terminal triple bond, are partially hydrogenated.
Diese Reaktionen nach a) werden vorteilhaft unter den für Umsetzungen nach Grignard üblichen Verfahren zur Herstellung sekundärtertiärer Alkendiole These reactions according to a) are advantageous among those customary for reactions according to Grignard Process for the production of secondary tertiary alkeniols
Anmelder:Applicant:
C. H. Boehringer Sohn, Ingelheim/RheinC. H. Boehringer Sohn, Ingelheim / Rhine
Als Erfinder benannt:Named as inventor:
Dr. Herbert Koppe,Dr. Herbert Koppe,
Dr. Karl Zeile, Ingelheim/RheinDr. Karlzeile, Ingelheim / Rhine
Bedingungen durchgeführt, d. h. unter Verwendung von wasserfreien organischen Lösungsmitteln, wie Diäthyläther oder Tetrahydrofuran. Zur Herstellung der metallorganischen Verbindungen III bzw. V wird vorzugsweise Magnesium verwendet. Auch Zink und Aluminium sind brauchbar.Conditions carried out, d. H. using anhydrous organic solvents such as Diethyl ether or tetrahydrofuran. For the preparation of the organometallic compounds III and V magnesium is preferably used. Zinc and aluminum can also be used.
Die als Ausgangsverbindungen verwendeten a-Hydroxyketone II bzw. IV werden gleichfalls nach an sich bekannten Verfahren in hier nicht beanspruchter Weise hergestellt.The α-hydroxyketones II and IV used as starting compounds are also used according to an known methods produced in a manner not claimed here.
Bei der Herstellung von Verbindungen der Formel I, worin Ri und R3 identisch sind, ist es nicht notwendig, die a-Hydroxyketone zu isolieren. Es können vielmehr a-Hydroxycarbonsäurederivate in einem Einstufenverfahren einer doppelten Umsetzung nach Grignard mit der metallorganischen Verbindung unterworfen werden. Besonders geeignet sind hierfür a-Hydroxycarbonsäureester oder Estolide.In the preparation of compounds of the formula I in which Ri and R3 are identical, it is not necessary to isolate the α-hydroxyketones. Rather, α-hydroxycarboxylic acid derivatives can be used in a one-step process subjected to a double reaction according to Grignard with the organometallic compound will. Α-Hydroxycarboxylic acid esters or estolides are particularly suitable for this.
Diese partielle Hydrierung nach b) wird vorteilhaft katalytisch unter Verwendung von desaktivierten Katalysatoren (vgl. H. L i η d 1 a r , HeIv., 35, S. 446ff. [1952], und D. J. C r a m et al., J. Am. Chem. Soc, 78, S. 2518 ff. [1956]) durchgeführt. Als Reaktionsmedium sind organische Lösungsmittel, beispielsweise niedrigmolekulare Alkanole, geeignet. Die Hydrierung erfolgt vorzugsweise bei Raumtemperatur unter Normaldruck. Jedoch ist es auch möglich, bei höheren Temperaturen unter Druck zu arbeiten.This partial hydrogenation according to b) is advantageously catalytically using deactivated Catalysts (cf. H. L i η d 1 a r, HeIv., 35, p. 446ff. [1952], and D.J. C ram et al., J. Am. Chem. Soc, 78, pp. 2518 ff. [1956]). Organic solvents are used as the reaction medium, for example low molecular weight alkanols, suitable. The hydrogenation is preferably carried out at room temperature under normal pressure. However, it is also possible to work under pressure at higher temperatures.
Alkindiole der Formel VI sind gleichfalls neu und können beispielsweise nach den in der, deutschen Patentschrift 1 178 839 und der Patentanmeldung B 67488 IVb/12o des gleichen Erfinders mit dem Titel »Verfahren zur Herstellung neuer Propargyldiole« beschriebenen Verfahren hergestellt werden.Alkynediols of the formula VI are also new and can, for example, according to the, German Patent specification 1 178 839 and patent application B 67488 IVb / 12o by the same inventor with the title "Process for the production of new propargyl diols" described processes are produced.
Die neuen Verbindungen sind wertvolle Pharmazeutika mit sedativer Wirkung. Gegenüber bekannten, ähnlich gebauten Verbindungen zeichnen sie sichThe new compounds are valuable pharmaceuticals with a sedative effect. Compared to known, They are distinguished by similarly built connections
609 539/427609 539/427
insbesondere durch bessere Wirksamkeit bei ausgezeichneter Verträglichkeit aus-.in particular through better effectiveness with excellent tolerance.
VergleichsversucheComparative experiments
Die folgenden Substanzen wurden bezüglich ihrer narkotischen Wirksamkeit und Toxizität vergleichend untersucht:The following substances were compared for their narcotic efficacy and toxicity examined:
CH3 CH 3
C-CH2-CH = CH2 C-CH 2 -CH = CH 2
OHOH
Beispiel 1 a der deutschen Auslegeschrift 1095 271OH OH
Example 1 a of the German Auslegeschrift 1095 271
H3C CH3 H 3 C CH 3
C —
OHC -
OH
C-C-
OHOH
CH2 — CH = CH2 CH 2 - CH = CH 2
C. CH3-CHC. CH 3 -CH
CH = CH2 CH = CH 2
OH OHOH OH
Beispiel 2 der vorliegenden Erfindung.Example 2 of the present invention.
Die Substanzen wurden mit Olivenöl und Gummiarabikum in Wasser emulgiert und an Mäusen per os geprüft. Eine narkotische Wirkung wurde angenommen, wenn die Tiere die Rückenlage beibehielten. Die Berechnung der mittleren narkotischen (ND50) und letalen Dosis (LDso) erfolgte nach der Methode von L i t c h f i e 1 d und W i 1 c ο χ ο η . Die Ergebnisse sind in der folgenden Tabelle zusammengestellt :The substances were emulsified in water with olive oil and gum arabic and administered per os on mice checked. A narcotic effect was assumed if the animals remained supine. The calculation of the mean narcotic (ND50) and lethal dose (LDso) was carried out according to the method from L i t c h f i e 1 d and W i 1 c ο χ ο η. The results are compiled in the following table :
mg/kgND00
mg / kg
mg/kgLD 50
mg / kg
B
CA.
B.
C.
1050
640860
1050
640
1050
1800860
1050
1800
Beispiel 1 der deutschen Auslegeschrift 1 073 477Example 1 of the German Auslegeschrift 1 073 477
Der Tabelle ist zu entnehmen, daß die nach den Verfahren der vorliegenden Erfindung hergestellte Verbindung C den bekannten, zum Vergleich herangezogenen Verbindungen A und B sowohl hinsichtlich der narkotischen Wirkung als auch hinsichtlich der Toxizität deutlich überlegen ist. Die Substanzen A und B weisen erst im Bereich der letalen Dosis eine narkotische Wirkung auf.It can be seen from the table that that prepared by the methods of the present invention Compound C the known, used for comparison compounds A and B both in terms of the narcotic effect as well as in terms of toxicity is clearly superior. The substances A and B only show a narcotic effect in the lethal dose range.
Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
Beispiel 1
4-Methyl-4,5-dihydroxy-5-phenyl-penten-(l)example 1
4-methyl-4,5-dihydroxy-5-phenyl-pentene- (l)
Zu einer Grignard-Mischung aus 24,3 g (1 Mol) Magnesium, 400 ml absolutem Äther, 121 g (1 Mol) Allylbromid und einigen Jodkristallen wird eine Lösung von 60 g (0,4 Mol) Phenylacetylcarbinol in 100 ml absolutem Äther so langsam zugegeben, daß die Reaktionsmischung unter Rückfluß siedet. Nach beendeter Zugabe des Hydroxyketone wird noch 2 Stunden unter Rückfluß erhitzt, dann abgekühlt, in Eis eingerührt, mit verdünnter Salzsäure schwach angesäuert, die wäßrige Phase abgetrennt, mit Äther nochmals extrahiert, die vereinigten Ätherlösungen mit Wasser gewaschen und über Magnesiumsulfat getrocknet. Nach Abdestillieren des Äthers wird das Glykol im Vakuum fraktioniert. Kp.0,01118 bis 12O0C, Ausbeute 52% der Theorie.A solution of 60 g (0.4 mol) of phenylacetylcarbinol in 100 ml of absolute ether is added to a Grignard mixture of 24.3 g (1 mol) of magnesium, 400 ml of absolute ether, 121 g (1 mol) of allyl bromide and some iodine crystals slowly added so that the reaction mixture boils under reflux. When the addition of the hydroxyketone is complete, the mixture is refluxed for a further 2 hours, then cooled, stirred into ice, weakly acidified with dilute hydrochloric acid, the aqueous phase separated off, extracted again with ether, the combined ethereal solutions washed with water and dried over magnesium sulfate. After the ether has been distilled off, the glycol is fractionated in vacuo. Bp 0.01118 to 12O 0 C, yield 52% of theory.
Beispiel 2
3-Phenyl-3,4-dihydroxy-penten-(l)Example 2
3-phenyl-3,4-dihydroxy-pentene- (l)
37,4g(0,213 Mol) 3-Phenyl-3,4-dihydroxy-pentin-(l) werden in 100 ml. Äthanol gelöst, 5 g Lindlar-Katalysator und 1,5 g Chinolin zugegeben und bei Raumtemperatur und Normaldruck unter Schütteln hydriert. Nach etwa 100 Minuten ist die Wasserstoffaufnahme beendet. Nach Abfiltrieren des Katalysators wird das Äthanol abdestilliert und der Rückstand im Vakuum fraktioniert. Kp.o,o2 83 bis 85°C, Ausbeute 87% der Theorie.37.4 g (0.213 mol) of 3-phenyl-3,4-dihydroxypentyn- (l) are dissolved in 100 ml of ethanol, 5 g of Lindlar catalyst and 1.5 g of quinoline are added and the mixture is hydrogenated with shaking at room temperature and normal pressure . The uptake of hydrogen has ended after about 100 minutes. After filtering off the catalyst, the ethanol is distilled off and the residue is fractionated in vacuo. Kp.o, O 2 83 to 85 ° C, yield 87% of theory.
Beispiel 3
4-Phenyl-4,5-dihydroxy-hexen-(l)Example 3
4-phenyl-4,5-dihydroxy-hexene- (l)
Zu einer Grignard-Lösung aus 39 g (1,6 Mol) Magnesium, 700 ml absolutem Äther, 193,5 g (1,6 Mol) Allylbromid und einem Jodkristall werden 100 g (0,66 Mol) a-Hydroxypropiophenon, in 150 ml absolutem Äther gelöst, bei 20 bis 30° C langsam zugegeben und 12 Stunden bei etwa 20°C gerührt. Anschließend wird das Reaktionsgemisch in Eis eingerührt, mit verdünnter Salzsäure leicht angesäuert und die wäßrige Schicht abgetrennt. Die wäßrige Phase wird dreimal mit Äther ausgeschüttelt, die vereinigten Ätherextrakte mit Wasser gewaschen, über Magnesiumsulfat getrocknet und der Äther abdestilliert. Der Rückstand wird im Vakuum fraktioniert. Kp.0,01 88 bis 92°C, Ausbeute 57,5% der Theorie.To a Grignard solution of 39 g (1.6 mol) of magnesium, 700 ml of absolute ether, 193.5 g (1.6 mol) allyl bromide and an iodine crystal are 100 g (0.66 mol) α-hydroxypropiophenone, in 150 ml dissolved in absolute ether, added slowly at 20 to 30 ° C and stirred for 12 hours at about 20 ° C. The reaction mixture is then stirred into ice and slightly acidified with dilute hydrochloric acid and the aqueous layer separated. The aqueous phase is extracted three times with ether, the combined ether extracts washed with water, dried over magnesium sulfate and the ether distilled off. The residue is fractionated in vacuo. Bp 0.01 88 to 92 ° C, yield 57.5% of the Theory.
2-Methyl-4-(2'-methylallyl)-4,5-dihydroxyhexen-(l) 2-methyl-4- (2'-methylallyl) -4,5-dihydroxyhexene (l)
Zu der Grignard-Verbindung aus 12,15 g (0,5 Mol) Magnesium, 200 ml absolutem Äther, einigen Jodkristallen und 45 g (0,5MoI) 2-Methyl-allylchlorid werden 14,4 g (0,1 Mol) Laktid, in 150 ml Tetrahydrofuran gelöst, so langsam zugegeben, daß das Reaktionsgemisch unter Rückfluß siedet. Nach beendeter Zugabe wird noch 2 Stunden im Wasserbad erwärmt. Nach dem Erkalten wird das Reaktionsgemisch auf Eis gegossen, mit verdünnter Salzsäure leicht angesäuert und etwas Benzol zugegeben. Die wäßrige Phase wird abgetrennt, dreimal mit je 100 ml Äther extrahiert, die vereinigten organischen Phasen mit Wasser gewaschen, über Magnesiumsulfat getrocknet und die Lösungsmittel abdestilliert. Der verbleibende Rückstand wird im Vakuum fraktioniert. Kp.0,1 73 bis 74°C, Ausbeute 40% der Theorie.About the Grignard compound of 12.15 g (0.5 mol) of magnesium, 200 ml of absolute ether, a few iodine crystals and 45 g (0.5 mol) of 2-methyl-allyl chloride 14.4 g (0.1 mol) of lactide, dissolved in 150 ml of tetrahydrofuran, are added so slowly that the The reaction mixture boils under reflux. When the addition is complete, it is continued for 2 hours in the water bath warmed up. After cooling, the reaction mixture is poured onto ice with dilute hydrochloric acid slightly acidified and added a little benzene. The aqueous phase is separated off, three times with 100 ml each time Ether extracted, the combined organic phases washed with water, dried over magnesium sulfate and the solvents are distilled off. The remaining residue is fractionated in vacuo. Bp 0.173 to 74 ° C, yield 40% of theory.
Beispiel 5
3-Methyl-3,4-dihydroxy-4-phenyl-buten-(l)Example 5
3-methyl-3,4-dihydroxy-4-phenyl-butene (l)
, 35,2 g (0,2 Mol) S-MethyM^-dihydroxy^-phenylbutin-(l) werden in 150 ml Äthanol gelöst, 4,1 g Lindlar-Katalysator zugegeben und bei Normaldruck, 35.2 g (0.2 mol) S-MethyM ^ -dihydroxy ^ -phenylbutin- (l) are dissolved in 150 ml of ethanol, 4.1 g of Lindlar catalyst are added and at normal pressure
ι ziz youι ziz you
und Raumtemperatur hydriert. Nach 65 Minuten ist die Wasserstoffaufnahme beendet. Nach Abtrennen des Katalysators wird das Lösungsmittel abdestilliert und der Rückstand im Vakuum fraktioniert. Die geruch- und farblose viskose Flüssigkeit hat Kp.o,i 93 bis 93,5°G, Ausbeute 59% der Theorie.hydrogenated and room temperature. The uptake of hydrogen has ended after 65 minutes. After detaching of the catalyst, the solvent is distilled off and the residue is fractionated in vacuo. the odorless and colorless viscous liquid has a boiling point of 93 to 93.5 ° G, yield 59% of theory.
Claims (2)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB67489A DE1212960B (en) | 1962-05-30 | 1962-05-30 | Process for the preparation of secondary-tertiary alkenediols |
| CH1454166A CH430690A (en) | 1962-05-30 | 1963-05-21 | Process for the production of new secondary-tertiary alkenediols |
| FR936142A FR2638M (en) | 1962-05-30 | 1963-05-27 | New alkenediols. |
| GB21694/63A GB986720A (en) | 1962-05-30 | 1963-05-30 | Substituted alkene diols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB67489A DE1212960B (en) | 1962-05-30 | 1962-05-30 | Process for the preparation of secondary-tertiary alkenediols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1212960B true DE1212960B (en) | 1966-03-24 |
Family
ID=6975537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB67489A Pending DE1212960B (en) | 1962-05-30 | 1962-05-30 | Process for the preparation of secondary-tertiary alkenediols |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH430690A (en) |
| DE (1) | DE1212960B (en) |
| FR (1) | FR2638M (en) |
| GB (1) | GB986720A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1073477B (en) * | 1960-01-21 | Lovens kemiske Fabrik ved A. Kongsted, Kopenhagen | Process for the production of 2-phenyl- and 2-p-chlorophenyl- 3-methyl-2,3-dihydroxy-hexene- (5) effective as sedatives | |
| DE1095271B (en) * | 1958-07-04 | 1960-12-22 | Geigy Ag J R | Process for the production of new, therapeutically effective glycols |
-
1962
- 1962-05-30 DE DEB67489A patent/DE1212960B/en active Pending
-
1963
- 1963-05-21 CH CH1454166A patent/CH430690A/en unknown
- 1963-05-27 FR FR936142A patent/FR2638M/en not_active Expired
- 1963-05-30 GB GB21694/63A patent/GB986720A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1073477B (en) * | 1960-01-21 | Lovens kemiske Fabrik ved A. Kongsted, Kopenhagen | Process for the production of 2-phenyl- and 2-p-chlorophenyl- 3-methyl-2,3-dihydroxy-hexene- (5) effective as sedatives | |
| DE1095271B (en) * | 1958-07-04 | 1960-12-22 | Geigy Ag J R | Process for the production of new, therapeutically effective glycols |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2638M (en) | 1964-07-06 |
| CH430690A (en) | 1967-02-28 |
| GB986720A (en) | 1965-03-24 |
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