DE1057115B - Process for the preparation of alpha-haloacetal peroxides - Google Patents
Process for the preparation of alpha-haloacetal peroxidesInfo
- Publication number
- DE1057115B DE1057115B DEF23557A DEF0023557A DE1057115B DE 1057115 B DE1057115 B DE 1057115B DE F23557 A DEF23557 A DE F23557A DE F0023557 A DEF0023557 A DE F0023557A DE 1057115 B DE1057115 B DE 1057115B
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- formula
- radicals
- aryl
- haloacetal
- 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 4
- 150000002978 peroxides Chemical class 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 150000002432 hydroperoxides Chemical class 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- -1 peroxide acetals Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- GUGRBFQNXVKOGR-UHFFFAOYSA-N butyl hypochlorite Chemical group CCCCOCl GUGRBFQNXVKOGR-UHFFFAOYSA-N 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- ZLGLOFIIXBAXCI-UHFFFAOYSA-N 2,3-dihydro-1H-indene hydrogen peroxide Chemical compound OO.C1=CC=C2CCCC2=C1 ZLGLOFIIXBAXCI-UHFFFAOYSA-N 0.000 description 1
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 description 1
- JSZPBTUOIOMFMS-UHFFFAOYSA-N 2-hydroperoxyoxolane Chemical compound OOC1CCCO1 JSZPBTUOIOMFMS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- USHDBZLNUZHGOP-UHFFFAOYSA-N pentyl hypochlorite Chemical group CCCCCOCl USHDBZLNUZHGOP-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
BUNDESREBUNDESRE
DEUTSCHESGERMAN
Es ist bekannt, daß man Peroxyacetale erhält, wenn man Hydroperoxyde an Vinyläther in Gegenwart von Schwefelsäure als Katalysator anlagert.It is known that peroxyacetals are obtained when hydroperoxides on vinyl ethers in the presence of Adds sulfuric acid as a catalyst.
Es wurde nun gefunden, daß man eine neue Gruppe halogenhaltiger Peroxydacetale der allgemeinen FormelIt has now been found that a new group of halogen-containing peroxide acetals of the general formula can be obtained
H YH Y
,OR,, OR,
0OR3 0OR 3
erhalten kann, wenn man Vinyläther der allgemeinen Formelcan be obtained when using vinyl ethers of the general formula
H YH Y
Rj — C = C —Rj - C = C -
mit Hydroperoxyden der allgemeinen Formelwith hydroperoxides of the general formula
R3OOHR 3 OOH
in Gegenwart von Hypohalogeniten der allgemeinen Formelin the presence of hypohalites of the general formula
R4OX
umsetzt.R 4 OX
implements.
In diesen allgemeinen Formeln bedeuten R1 und R2 gleiche oder verschiedene geradkettige oder verzweigte, gegebenenfalls ungesättigte Alkyl-, halogen- und bzw. oder acrylsubstituierte Alkyl-, Aryl- und sauerstoffheterocyclische Reste. R1 kann auch Wasserstoff sein.In these general formulas, R 1 and R 2 denote identical or different straight-chain or branched, optionally unsaturated alkyl, halogen and / or acrylic-substituted alkyl, aryl and oxygen-heterocyclic radicals. R 1 can also be hydrogen.
Dabei sollen unter Alkylresten auch cycloaliphatische und kondensiert cycloaliphatische Reste und unter substituierten Alkylresten auch solche, die Halogen oder aromatische Reste tragen, verstanden werden.The alkyl radicals should also include cycloaliphatic and condensed cycloaliphatic radicals and substituted alkyl radicals also include those which carry halogen or aromatic radicals.
Als Beispiele seien für Alkylreste dre Reste Methyl, Äthyl, Propyl, Butyl, Isopropyl, Isobutyl, 2-Äthyltexyl, Cyclohexyl, Methylcyclohexyl und der Irtdanrest, für substituierte Alkylreste die Reste /3-Chloräthyl, Phenylethyl, Phenylisopropyl, Diphenylmethyl, für Arylreste die Reste Phenyl und Naphthyl und für Heterocyclen die Reste Tetrahydrofurfuryl und Tetrahydropyranyl genannt.Examples of alkyl radicals are three methyl, Ethyl, propyl, butyl, isopropyl, isobutyl, 2-ethyltexyl, Cyclohexyl, methylcyclohexyl and the Irtdane radical, for substituted alkyl radicals the radicals / 3-chloroethyl, Phenylethyl, phenylisopropyl, diphenylmethyl, for aryl radicals the radicals phenyl and naphthyl and for Heterocycles called the radicals tetrahydrofurfuryl and tetrahydropyranyl.
Der Rest R3 bedeutet einen Alkylrest, acryl-,
halogen- und bzw. oder alkoxy- und bzw. oder Verfahren zur Herstellung
von ce-HalogenacetalperoxydenThe radical R 3 denotes an alkyl radical, acrylic, halogen and / or alkoxy and / or processes for production
of ce-haloacetal peroxides
Anmelder:Applicant:
Farbwerke Hoechst AktiengesellschaftFarbwerke Hoechst Aktiengesellschaft
vormals Meister Lucius & Brüning,formerly Master Lucius & Brüning,
Frankfurt/M., Brüningstr. 45Frankfurt / M., Brüningstr. 45
Dr. Klaus Weißermel und Dr. Michael Lederer,Dr. Klaus Weißermel and Dr. Michael Lederer,
Frankfurt/M.-Unterliederbadi,
sind als Erfinder genannt wordenFrankfurt / M.-Unterliederbadi,
have been named as inventors
cycloalkylsubstituierten Alkylrest oder einen sauers5 stoffheterocyclischen Rest.cycloalkyl-substituted alkyl radical or an acidic5 material heterocyclic radical.
Als Beispiele seien folgend« Hydroperoxyde genannt: tertiär-Butylhydroperoxyd, tertiär-Amylhydroperoxyd, Indanhydroperoxyd, Cumolhydroperoxyd, T«trahydroniaphthalinhydroperoxyd, p-Menthamhydroperoxyd, Tetrahydrofuranhydroperoxyd.The following are examples of hydroperoxides: tertiary butyl hydroperoxide, tertiary amyl hydroperoxide, Indane hydroperoxide, cumene hydroperoxide, trahydroniaphthalene hydroperoxide, p-mentham hydroperoxide, Tetrahydrofuran hydroperoxide.
Weiterhin bedeutet Y Wasserstoff oder gesättigte aliphatische Reste, wie Methyl-, Äthyl-, Propylreste.Y also denotes hydrogen or saturated aliphatic radicals, such as methyl, ethyl or propyl radicals.
Ferner bedeuten in der FormelAlso in the formula
R4OXR 4 OX
X Chlor oder Brom und R4 geradkettige verzweigte Alkylreste oder alkylsubstituierte Cycloalkylreste, vorzugsweise solche Reste, bei denen die Hypohalogenitgruppe an ein tertiäres Kohlenstoffatom gebunden ist.X is chlorine or bromine and R 4 straight-chain branched alkyl radicals or alkyl-substituted cycloalkyl radicals, preferably those radicals in which the hypohalite group is bonded to a tertiary carbon atom.
Als Hypohalogenite seien z. B. tertiär-Butylhypochlorit und tertiär-Amylhypochlorit angeführt.As hypohalites are z. B. tertiary butyl hypochlorite and tertiary amyl hypochlorite are listed.
Die Umsetzung von Vinyläthern mit organischem Hydroperoxyd und organischen Hypohalogeniten zu a-Halogenacetalperoxyden verläuft nach folgender Gleichung:The implementation of vinyl ethers with organic hydroperoxide and organic hypohalites too a-Halogenacetalperoxden proceeds according to the following Equation:
H YH Y
I 1I 1
R1-C = C-OR2 + R3OOH + R4-OX H YR 1 -C = C-OR 2 + R 3 OOH + R 4 -OX HY
I 1 /OR»I 1 / OR »
R1-C-C^ + R4OHR 1 -CC ^ + R 4 OH
0OR,0OR,
Dabei ist es zweckmäßig, den Vinyläther in geringem Überschuß und das Hydroperoxyd und das Hypohalogenit in äquimolekularen Mengen einzusetzen. Auch die Anwendung einer geringen Menge einesIt is advisable to use a slight excess of the vinyl ether and the hydroperoxide and the hypohalite use in equimolecular amounts. Even applying a small amount of one
909 510/490909 510/490
1<O571 <O57
säurebindenden Mittels, wie Natriumbicarbonat, hat einen günstigen Einfluß auf den Verlauf der Reaktion. Man kann in Abwesenheit von Lösungsmitteln bei Temperaturen von —60 bis +70° C arbeiten. Wendet man tiefere Temperaturen als —60° C an, so verläuft die Reaktion im allgemeinen zu Langsam. Will man bei Temperaturen oberhalb 70° C arbeiten, so ist die Reaktion auf sehr beständige Reaktionsteilnehmer eingeschränkt. Man kann auch inerte Verdünnungsmittel, die unter den Reaktionsbedingungen flüssig sind, wie Kohlenwasserstoffe und Äther, z. B. Pentan, Cyclohexan, Diäthyläther, Dioxan, bei der Reaktion anwenden, wodurch auch die Abführung der Reaktionswärme erleichtert wird. Zweckmäßig gibt man das Hypohalogenit unter Rühren und Feuchtigkeitsaus-Schluß langsam in das Gemisch der Reaktionsteilnehmer Vinyläther und Hydroperoxyd, das noch Natriumbicarbonat und gegebenenfalls ein Verdünnungsmittel enthält. Nach der meistens sehr rasch verlaufenden Umsetzung wird die Aufarbeitung und Abtrennung der Reaktionsprodukte nach den üblichen organischpräparativen Methoden vorgenommen, z. B. durch Destillation bzw. Extraktion und anschließende Fraktionierung. acid binding agents, such as sodium bicarbonate, have a beneficial effect on the course of the reaction. You can work in the absence of solvents at temperatures from -60 to + 70 ° C. Turns if temperatures lower than -60 ° C. are used, the reaction generally proceeds too slowly. Do you want work at temperatures above 70 ° C, the reaction is limited to very stable reactants. You can also use inert diluents that are liquid under the reaction conditions, such as Hydrocarbons and ethers, e.g. B. pentane, cyclohexane, diethyl ether, dioxane, use in the reaction, which also facilitates the dissipation of the heat of reaction. This is expediently given Hypohalite slowly into the mixture of the reactants with stirring and exclusion of moisture Vinyl ether and hydroperoxide, the sodium bicarbonate and optionally a diluent contains. After the reaction, which usually takes place very quickly, work-up and separation take place the reaction products made by the customary organic preparative methods, for. B. by Distillation or extraction and subsequent fractionation.
Man erhält nach diesem Einstufenverfahren neue Peroxydverbindungen, die sich als Polymerisationsund Härtungskatalysatoren, z. B. für Vinylverbindungen ύη3 ungesättigte Polyesterharze sehr gut eignen.This one-step process gives new peroxide compounds which can be used as polymerisation s and curing catalysts, e.g. B. very well suited for vinyl compounds gen ύη3 unsaturated polyester resins.
In einem mit Rückflußkühler, Rührwerk und Tropftrichter versehenen Reaktionsgefäß werden unter Feuchtigkeitsausschluß 72 g Vinyläthyläther mit 50 ecm absolutem Diäthyläther und 5 g Natriumbicarbonat vermischt und auf —10° C gekühlt. Man fügt 60 g tertiär-Butylhydroperoxyd, gelöst in 50 ecm absolutem Diäthyläther, hinzu und tropft dann bei —20 bis —25° C unter Rühren 73 g tertiär-Butylhypochlorit zu. Nach kurzer Zeit ist die Reaktion beendet. Man setzt noch 100 ecm Äther zu, wäscht mit wäßriger Sodalösung und Wasser und trocknet den Ätherauszug über Natriumsulfat.In a reaction vessel equipped with a reflux condenser, stirrer and dropping funnel, under Exclusion of moisture 72 g of vinyl ethyl ether with 50 ecm of absolute diethyl ether and 5 g of sodium bicarbonate mixed and cooled to -10 ° C. 60 g of tertiary butyl hydroperoxide, dissolved in 50 ecm absolute, are added Diethyl ether, added and then 73 g of tertiary butyl hypochlorite are added dropwise at -20 to -25 ° C. with stirring to. The reaction ends after a short time. A further 100 ecm of ether is added, and it is washed with aqueous solution Soda solution and water and dry the ether extract over sodium sulfate.
Man destilliert das Reaktionsprodukt im Vakuum und erhält 80 g Chloracetaldehydacetalperoxyd der FormelThe reaction product is distilled in vacuo and 80 g of chloroacetaldehyde acetal peroxide are obtained formula
OC2H5 OC 2 H 5
Cl-CH2-CHCl-CH 2 -CH
O —O-C(CH3)3 O-OC (CH 3 ) 3
vom Siedepunkt Kp.45 = 51°C und dem Brechungsindex ng = 1,4225.with a boiling point of bp 45 = 51 ° C and a refractive index ng = 1.4225.
In der gleichen Vorrichtung wie im Beispiel 1 werden 100 g Vinylisobutyläther mit 50 ecm absolutem Diäthyläther und 5 g Natriumbicarbonat vermischt, bei —10° C mit 60 g tertiär-Butylhydroperoxyd, gelöst in 50 ecm absolutem Diäthyläther, versetzt und bei —20 bis —25° C mit 73 g tertiär-Butylhypochlorit umgesetzt.In the same device as in Example 1, 100 g of vinyl isobutyl ether with 50 ecm absolute Diethyl ether and 5 g of sodium bicarbonate mixed, dissolved at -10 ° C with 60 g of tertiary butyl hydroperoxide in 50 ecm of absolute diethyl ether, added and at -20 to -25 ° C with 73 g of tertiary butyl hypochlorite implemented.
Man verdünnt mit 100 ecm Diäthyläther, wäscht die Lösung mit Sodalösurtg und Wasser, trocknet sie über Natriumsulfat und destilliert sie im Vakuum.It is diluted with 100 ecm of diethyl ether, the solution is washed with soda solution and water, and it is dried over sodium sulfate and distilled it in vacuo.
Man erhält 91 g Chloracetaldehyd-isobutylacetaltertiär-butylperoxyd
der Formel
H91 g of chloroacetaldehyde isobutyl acetal tertiary butyl peroxide of the formula are obtained
H
Cl — CH2 — C — O — O — C(CH3)3 Cl - CH 2 - C - O - O - C (CH 3 ) 3
O · C4H9 O • C 4 H 9
vom Siedepunkt Kp.001 = 31 bis 33° C und dem Brechungsindex wf? = 1,4240.from the boiling point bp. 001 = 31 to 33 ° C and the refractive index wf? = 1.4240.
Zu dem Gemisch aus 85 g Dihydropyran, 50 ecm absolutem Diäthyläther und 5 g NaHCO3 werden bei —10° C 60 g tertiär-Butylhydroperoxyd, gelöst in 50 ecm absolutem Äther, hinzugefügt. Dann setzt man, wie in den Beispielen 1 und 2, bei —27 bis — 34 C 66 g tertiär-Butylhypochlorit zu. Die ätherische Lösung wird mit Sodalösung und Wasser gewaschen und über Kaliumcarbonat getrocknet.To the mixture of 85 g of dihydropyran, 50 ecm of absolute diethyl ether and 5 g of NaHCO 3 , 60 g of tertiary butyl hydroperoxide dissolved in 50 ecm of absolute ether are added at -10 ° C. Then, as in Examples 1 and 2, 66 g of tert-butyl hypochlorite are added at -27 to -34 C. The ethereal solution is washed with soda solution and water and dried over potassium carbonate.
Man destilliert die Lösung im Vakuum und erhält 45,8 g des Chloracetalperoxydes der FormelThe solution is distilled in vacuo and 45.8 g of the chloroacetal peroxide of the formula are obtained
H2 H 2
H2C'H 2 C '
H2C,H 2 C,
ClCl
O-O-C(CH3)8 OOC (CH 3 ) 8
vom Siedepunkt Kp.OiO1 = 48 bis 49° C und dem Brechungsindex nf = 1,4585.from the boiling point bp. OiO1 = 48 to 49 ° C and the refractive index nf = 1.4585.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF23557A DE1057115B (en) | 1957-07-23 | 1957-07-23 | Process for the preparation of alpha-haloacetal peroxides |
| DEF24280A DE1063167B (en) | 1957-07-23 | 1957-10-30 | Process for the preparation of alpha-haloacetal hydroperoxides and bis (alpha-halogel) peroxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF23557A DE1057115B (en) | 1957-07-23 | 1957-07-23 | Process for the preparation of alpha-haloacetal peroxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1057115B true DE1057115B (en) | 1959-05-14 |
Family
ID=7090889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF23557A Pending DE1057115B (en) | 1957-07-23 | 1957-07-23 | Process for the preparation of alpha-haloacetal peroxides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1057115B (en) |
-
1957
- 1957-07-23 DE DEF23557A patent/DE1057115B/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1057115B (en) | Process for the preparation of alpha-haloacetal peroxides | |
| DE962073C (en) | Process for the production of 1,2-epoxycyclooctane | |
| DE1079635B (en) | Process for the production of halogen-containing organic peroxides | |
| DE1063167B (en) | Process for the preparation of alpha-haloacetal hydroperoxides and bis (alpha-halogel) peroxides | |
| DE1046054B (en) | Process for the production of organic peroxides | |
| EP0011208A1 (en) | Process for the preparation of 3-phenoxybenzaldehydes | |
| DE964595C (en) | Process for the preparation of substituted 3,4-epoxycyclohexanecarboxylic acid-3,4'-epoxycyclohexylmethyl esters | |
| EP0000535A1 (en) | Process for the preparation of vinyl oxiranes substituted by halogen | |
| DE1081893B (en) | Process for the production of organic peroxides | |
| EP0000534A1 (en) | Process for the preparation of vinyl oxiranes | |
| DE1543353C3 (en) | ||
| DE935433C (en) | Process for the preparation of glycidic esters of sulfonic acids | |
| DE1259891B (en) | Process for the preparation of beta-halogen-substituted organic hydroperoxides | |
| DE1078127B (en) | Process for the production of peroxides | |
| DE895452C (en) | Process for the production of mono-vinyl and di-vinyl acetals | |
| DE622357C (en) | Process for the preparation of tertiary nitriles | |
| DE1081898B (en) | Process for the preparation of ª ‡ - (2-propyl-4, 5-methylenedioxy-phenyl) -aethyl-acetals | |
| DE1065401B (en) | Process for the preparation of monooxytriethers | |
| DE831992C (en) | Process for the production of unsaturated bisformals | |
| DE959458C (en) | Process for the preparation of allophanates of ª ‡ -Aethynyl carbinols | |
| DE859157C (en) | Process for the production of organic isocyanates | |
| DE1263779B (en) | Process for the production of 1, 3-dioxolan-5-ones | |
| DE1150069B (en) | Process for the production of an unsaturated 0, 0-dialkyl-thiono-thiol-phosphoric acid ester | |
| DE1238454B (en) | Process for the preparation of carbonyl compounds | |
| DE1146883B (en) | Process for the preparation of dithiophosphinic acid esters |