DE1021858B - Process for the preparation of aromatic oxacyclobutane derivatives - Google Patents
Process for the preparation of aromatic oxacyclobutane derivativesInfo
- Publication number
- DE1021858B DE1021858B DEF21928A DEF0021928A DE1021858B DE 1021858 B DE1021858 B DE 1021858B DE F21928 A DEF21928 A DE F21928A DE F0021928 A DEF0021928 A DE F0021928A DE 1021858 B DE1021858 B DE 1021858B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- oxacyclobutane
- derivatives
- preparation
- aromatic
- 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 7
- 238000002360 preparation method Methods 0.000 title claims description 6
- -1 aromatic oxacyclobutane derivatives Chemical class 0.000 title claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000004707 phenolate Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 17
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UKLWXKWTXHHMFK-UHFFFAOYSA-N 3-(chloromethyl)-3-ethyloxetane Chemical compound CCC1(CCl)COC1 UKLWXKWTXHHMFK-UHFFFAOYSA-N 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical class C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 5
- MCZYEFODKAZWIH-UHFFFAOYSA-N 3-(chloromethyl)-3-methyloxetane Chemical compound ClCC1(C)COC1 MCZYEFODKAZWIH-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- KAVGXOKHWPNOAL-UHFFFAOYSA-N benzene-1,3-diol;sodium Chemical compound [Na].OC1=CC=CC(O)=C1 KAVGXOKHWPNOAL-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ATEDDYVUNVYEIN-UHFFFAOYSA-N benzene-1,3,5-triol;sodium Chemical compound [Na].OC1=CC(O)=CC(O)=C1 ATEDDYVUNVYEIN-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Epoxy Resins (AREA)
Description
Verfahren zur Herstellung aromatischer Oxacyclobutanderivate Die Erfindung hat ein Verfahren zur Herstellung von aromatischen Oxacyclobutanderivaten zum Gegenstand, bei dem di- oder polyfunktionelle Phenolate mit 3-Halogenmethyl-oxacyclobutanen der allgemeinen Formel in der R1 ein Wasserstoffatom oder einen beliebigen organischen Rest bedeutet, umgesetzt werden.Process for the preparation of aromatic oxacyclobutane derivatives The invention relates to a process for the preparation of aromatic oxacyclobutane derivatives in which di- or polyfunctional phenolates with 3-halomethyl-oxacyclobutanes of the general formula in which R1 denotes a hydrogen atom or any desired organic radical.
Derartige Oxacyclobutanderivate entsprechen der folgenden allgemeinen Formel: worin R einen beliebigen zwei- oder mehrwertigen aromatischen Rest, der einen oder mehrere Benzolringe enthalten kann, z. B. Phenylen, Diphenylen, Naphthylen, -CEH4 # S02. CEH4-, -C,H4. CH, . C6H4-# -C6H4#C(CH3)2'C,H4-, -C6H4-0-C,H4-C H2 O-CH2-C 0 CHF CH, CH3 CH 2 C2 H5 0 C-CH2-0-- C- _ _0-CH2-C 0 CH2 CH2 CH 3 CH2 O-CH2-C 0 C2 H5 C2 H5 C H2 C2 H5 Die erfindungsgemäße Umsetzung kann so durchgeführt werden, daß das entsprechende Metallphenolat mit der äquivalenten Menge z. B. eines 3-Halogenmethyl-3-alkyl-oxacyclobutans auf 150 bis 250° so lange erhitzt wird, bis das Gemisch neutral reagiert. Die Reaktionszeit, die unter diesen Bedingungen 5 bis 15 Stunden beträgt, kann verringert werden, wenn die Reaktionskomponenten, gelöst in einem Lösungsmittel, umgesetzt werden. Als Lösungsmittel eignen sich für diesen Zweck z. B. Äthylenglykol, Diäthylenglykol und Triäthylenglykol. An dieser Methode zur Darstellung von Oxacyclobutanderivaten ist besonders überraschend, daß der Oxacyclobutanring trotz der scharfen alkalischen Re-oder von Novolaken abgeleitete Reste, R, H oder einen organischen Rest, wie z. B. Alkyl, Aralkyl, Cycloalkyl oder Aryl, und n eine ganze Zahl größer als 1, insbesondere 2, bedeutet.Such oxacyclobutane derivatives correspond to the following general formula: wherein R is any divalent or polyvalent aromatic radical which may contain one or more benzene rings, e.g. B. phenylene, diphenylene, naphthylene, -CEH4 # S02. CEH4-, -C, H4. CH,. C6H4- # -C6H4 # C (CH3) 2'C, H4-, -C6H4-0-C, H4-C H2 O-CH2-C 0 CHF CH, CH3 CH 2 C2 H5 0 C-CH2-0-- C- _ _0-CH2-C 0 CH2 CH2 CH 3 CH2 O-CH2-C 0 C2 H5 C2 H5 C H2 C2 H5. B. a 3-halomethyl-3-alkyl-oxacyclobutane is heated to 150 to 250 ° until the mixture reacts neutrally. The reaction time, which is 5 to 15 hours under these conditions, can be reduced if the reaction components dissolved in a solvent are reacted. Suitable solvents for this purpose are, for. B. ethylene glycol, diethylene glycol and triethylene glycol. What is particularly surprising about this method of preparing oxacyclobutane derivatives is that the oxacyclobutane ring, in spite of the sharp alkaline Re radicals or radicals derived from novolaks, R, H or an organic radical, such as. B. alkyl, aralkyl, cycloalkyl or aryl, and n is an integer greater than 1, in particular 2, is.
Derartige Verbindungen sind z. B. Verbindungen der folgenden Formeln aktionsbedingungen nicht angegriffen oder von den Glykolen aufgespalten wird.Such compounds are e.g. B. Compounds of the following formulas action conditions are not attacked or broken down by the glycols.
Dieses Verfahren ermöglicht eine einfache Darstellung reinster Polyoxacyclobutanderivate.This method enables a simple preparation of the purest polyoxacyclobutane derivatives.
Die Reaktionsprodukte sind feste oder flüssige Substanzen, die wertvolle Ausgangskomponenten für die Herstellung neuer, hochmolekularer Kunststoffe darstellen. Diejenigen Oxacyclobutanderivate, die nach dem erfindungsgemäßen Verfahren aus p,p'-Dioxydiphenyldimethylmethan erhalten werden, zeigen den besonderen Vorteil, daß sie kristalline Pulver mit Schmelzpunkten über 100° darstellen und daher bequem in den Handel gebracht werden können. Die entsprechenden Diepoxyde sind dagegen harzige Verbindungen, die zwar auch in fester Form mit Erweichungsprodukten über 100' hergestellt werden können, dann aber den Nachteil haben, daß sie nur einen geringen Gehalt an Epoxyd aufweisen.The reaction products are solid or liquid substances that are valuable Represent starting components for the production of new, high molecular weight plastics. Those oxacyclobutane derivatives which are obtained by the process according to the invention from p, p'-dioxydiphenyldimethylmethane obtained show the particular advantage that they are crystalline powders with melting points represent over 100 ° and can therefore be conveniently placed on the market. the corresponding diepoxyde are on the other hand resinous compounds that Although they can also be produced in solid form with softening products over 100 ', but then have the disadvantage that they have only a low content of epoxy.
In den folgenden Beispielen sind die angegebenen Teile Gewichtsteile. Beispiel 1 20,4 Teile p,p'-Dioxydiphenyl-dimethylmethan-Natrium werden in 130 Volumteilen Diäthylenglykol unter Erwärmen gelöst und mit 21 Teilen 3-Chiormethyl-3-äthyl-oxacyclobutan versetzt. Es wird zum Sieden erhitzt. Die Reaktion setzt sofort ein und verläuft unter Abscheidung von Kochsalz. Das Gemisch reagiert nach Beendigung der Reaktion neutral. Beim Abkühlen erstarrt das Gemisch, es wird mit Wasser verrührt und abgesaugt. Der getrocknete Rückstand stellt rohes p,p'-Bis-[3-äthy l-oxacy clobutyl-(3)-methoxy : -diphenyldimethylmethan dar. Es schmilzt bei 160 bis 164°. Ausbeute 28,6 Teile = 80 %. Nach dem Umkristallisieren aus Aceton beträgt der Schmelzpunkt 178°.In the following examples the parts given are parts by weight. Example 1 20.4 parts of p, p'-dioxydiphenyl-dimethylmethane-sodium are in 130 parts by volume Diethylene glycol dissolved with heating and treated with 21 parts of 3-chloromethyl-3-ethyl-oxacyclobutane offset. It is heated to the boil. The reaction starts immediately and proceeds with separation of common salt. The mixture reacts after the completion of the reaction neutral. On cooling, the mixture solidifies, it is stirred with water and filtered off with suction. The dried residue provides crude p, p'-bis [3-ethy l-oxacy clobutyl- (3) methoxy : -diphenyldimethylmethane. It melts at 160 to 164 °. Yield 28.6 parts = 80%. After recrystallization from acetone, the melting point is 178 °.
Das 3-Chlormethyl-3-äthyl-oxacyclobutan wird in bekannter Weise wie folgt erhalten: 890Teile Trimethylolpropan-dichlorhydrin und 312Teile Natriumhydroxyd, gelöst in 230 Teilen Wasser, werden in 600 Volumteilen Methanol 2 Stunden am Rückfluß erhitzt. Nach dem Waschen mit Wasser, Ausäthern und Destillation werden 576 Teile 3-Chlormethyl-3-äthyloxacyclobutan vom Kp.15 63 bis 73° erhalten, das entspricht einer Ausbeute von 82 °/a der Theorie. Beispiel 2 90 Teile Resorcin-Natrium werden in 600 Volumteilen Diäthylenglykol unter Erwärmen gelöst. Dann werden 165 Teile 3-Chlormethyl-3-äthyl-oxacyclobutan eingemischt, und es wird 1 Stunde unter Rühren zum Sieden erhitzt. Die auf Zimmertemperatur abgekühlte Reaktionsmischung wird in Wasser eingegossen, mit 1Vlethylenchlorid aufgenommen, über Natriumsulfat getrocknet und destilliert. Wenn das Methylenchlorid übergegangen ist, wird der Rückstand im Vakuum von überschüssigem 3-Chlormethyl-3-äthyl-oxacyclobutan befreit, das bei Kp." 66 bis 75' abdestilliert. Als Rückstand werden 156 Teile (= 89 % der Theorie) rohes m-Bis-[3-äthyl-oxacyclobutyl-(3)-methoxy]-benzol erhalten, das bei Kp.o,l 188 bis l93° destilliert werden kann. Beispiel 3 13 Teile 3-Chlormethyl-3-methyl-oxacyclobutan werden mit einer Lösung von 0,3 Teilen Resorcin-Natrium in 50 Volumteilen Diäthylenglykol gemischt und unter Rühren etwa 1 Stunde am Rückfluß gekocht. Die abgekühlte, mit Wasser verrührte Reaktionsmischung wird ausgeäthert und die ätherische Phase über Natriumsulfat getrocknet. Der Äther wird abdestilliert und der Rückstand im Vakuum von leichterflüchtigen Bestandteilen befreit. Es bleiben 13 Teile (= 860/, der Theorie) rohes m-Bis- 3-methyl-oxacyclobutyl-(3)-methoxy]-benzol zurück, das bei Kp.",3 170 bis 180° destilliert werden kann.The 3-chloromethyl-3-ethyl-oxacyclobutane is obtained in a known manner as follows: 890 parts of trimethylolpropane dichlorohydrin and 312 parts of sodium hydroxide, dissolved in 230 parts of water, are refluxed in 600 parts by volume of methanol for 2 hours. After washing with water, etherification and distillation, 576 parts of 3-chloromethyl-3-ethyloxacyclobutane with a boiling point of 63 ° to 73 ° are obtained, which corresponds to a theoretical yield of 82 °. Example 2 90 parts of resorcinol sodium are dissolved in 600 parts by volume of diethylene glycol with heating. 165 parts of 3-chloromethyl-3-ethyl-oxacyclobutane are then mixed in and the mixture is heated to the boil for 1 hour while stirring. The reaction mixture, cooled to room temperature, is poured into water, taken up in 1Vlethylene chloride, dried over sodium sulfate and distilled. When the methylene chloride has passed over, the residue is freed in vacuo from excess 3-chloromethyl-3-ethyl-oxacyclobutane, which distills off at bp "66 to 75 '. The residue is 156 parts (= 89% of theory) of crude m- Bis- [3-ethyl-oxacyclobutyl- (3) -methoxy] -benzene obtained, which can be distilled at boiling point 1.188 to 193 ° Example 3 13 parts of 3-chloromethyl-3-methyl-oxacyclobutane are mixed with a A solution of 0.3 part of resorcinol sodium is mixed in 50 parts by volume of diethylene glycol and refluxed with stirring for about 1 hour. The cooled reaction mixture, stirred with water, is extracted with ether and the ethereal phase is dried over sodium sulfate. The ether is distilled off and the residue in vacuo freed of more volatile constituents. There remain 13 parts (= 860 /, of the theoretical) of crude m-bis 3-methyl-oxacyclobutyl- (3) methoxy] benzene back, the "distilled at Kp. 3 170 to 180 ° can be.
Das 3-Chlormethyl-3-methyl-oxacyclobutan wird in bekannter Weise aus Trimethyloläthandichlorhydrin hergestellt. Die Umsetzung verläuft analog der im Beispiel 1 zur Darstellung von 3-Chlormethyl-3-äthy 1-oxacyclobutan näher beschriebenen Reaktion. Beispiel 4 66 Teile Novolak-Kalium, die 16,2 Teile Kalium enthalten, werden in 200 Volumteilen Diäthylenglykol gelöst und mit 60 Teilen 3-Chlormethyl-3-methyl-oxacyclobutan etwa 2 Stunden unter Rühren am Rückfluß erhitzt. Es wird mit Benzol verdünnt und anschließend mit Wasser ausgeschüttelt. Die organische Phase wird trocken gekocht, das Benzol im Vakuum abgedampft und der Rückstand bei 150° im Ölpumpenvakuum entgast. Erhalten werden 70 Teile (= 82 °;'o der Theorie) eines mit 3-ylethy l-oxacyclobutyl-methylgruppen verätherten Novolaks.The 3-chloromethyl-3-methyl-oxacyclobutane is made in a known manner Trimethyloläthandichlorhydrin produced. The implementation is analogous to the im Example 1 for the preparation of 3-chloromethyl-3-ethy 1-oxacyclobutane described in more detail Reaction. Example 4 66 parts of novolak potassium containing 16.2 parts of potassium become dissolved in 200 parts by volume of diethylene glycol and mixed with 60 parts of 3-chloromethyl-3-methyl-oxacyclobutane heated to reflux with stirring for about 2 hours. It is diluted with benzene and then shaken out with water. The organic phase is boiled dry, the benzene evaporated in vacuo and the residue degassed at 150 ° in an oil pump vacuum. 70 parts (= 82 °; 'o of theory) of one with 3-ylethy-l-oxacyclobutyl-methyl groups are obtained etherified novolaks.
Der zur Darstellung des Novolak-Kaliums verwendete Novolak wird in bekannter Weise durch Umsetzen von 94 Teilen Phenol mit 60 Teilen 30°;`oiger Formaldehyd-, und 1 Teil Oxalsäure bei 90' erhalten. Beispiel 5 64 Teile Phloroglucin-Natrium «-erden in 300 Volumteilen Diäthy lenglykol gelöst und mit 120 Teilen 3-Chlormethyl-3-methyl-oxacyclobutan 3 Stunden unter Rühren am Rückfluß erhitzt. Es wird in Wasser gegossen, mit Benzol aufgenommen, trocken gekocht und das Benzol im Vakuum abdestilliert. Der Rückstand wird bei 150° und 0,1 mm entgast. Es fallen 90 Teile (= 71 °f, der Theorie) eines braunen dickflüssigen Öls an, das zur Hauptsache aus 1,3,5-Tri--3'-methyl-oiacyclobutv_ 1-(3')-methoxy,-benzol besteht.The novolak used to represent the novolak potassium is in a known manner by reacting 94 parts of phenol, 60 parts of 30 °; `cent formaldehyde, and 1 part of oxalic acid receive at 90 '. EXAMPLE 5 64 parts of phloroglucinol sodium "earths" dissolved in 300 parts by volume of diethyl glycol and refluxed with 120 parts of 3-chloromethyl-3-methyl-oxacyclobutane for 3 hours with stirring. It is poured into water, taken up in benzene, boiled dry and the benzene is distilled off in vacuo. The residue is degassed at 150 ° and 0.1 mm. 90 parts (= 71 ° f, theory) of a brown, viscous oil are obtained, which mainly consists of 1,3,5-tri-3'-methyl-oiacyclobutv_ 1- (3 ') -methoxy, -benzene .
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF21928A DE1021858B (en) | 1956-12-14 | 1956-12-14 | Process for the preparation of aromatic oxacyclobutane derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF21928A DE1021858B (en) | 1956-12-14 | 1956-12-14 | Process for the preparation of aromatic oxacyclobutane derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1021858B true DE1021858B (en) | 1958-01-02 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF21928A Pending DE1021858B (en) | 1956-12-14 | 1956-12-14 | Process for the preparation of aromatic oxacyclobutane derivatives |
Country Status (1)
| Country | Link |
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| DE (1) | DE1021858B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1069120A1 (en) * | 1999-07-15 | 2001-01-17 | Toagosei Co., Ltd. | Naphthalene derivative, binaphthalene derivative and biphenyl derivative and cationically curable compound |
| US6255484B1 (en) | 1999-09-28 | 2001-07-03 | Ube Industries, Ltd. | Cyanurate compound having three oxetane ring groups and organic hardening compositions containing same |
| JP2002020376A (en) * | 2000-07-04 | 2002-01-23 | Toagosei Co Ltd | Method for producing tetramethyldiphenyl-methane derivative having oxetane ring and tetramethyldiphenylmethane derivative having oxetane ring |
| JP2003081958A (en) * | 2001-09-12 | 2003-03-19 | Toagosei Co Ltd | Diphenyl sulfide derivative having oxetane ring |
| JP3508502B2 (en) | 1997-09-30 | 2004-03-22 | 宇部興産株式会社 | Biphenyl derivative having oxetane ring |
| JP2004300136A (en) * | 2003-03-17 | 2004-10-28 | Nippon Steel Chem Co Ltd | Oxetane compound and method for producing the same |
| WO2007125795A1 (en) | 2006-04-27 | 2007-11-08 | Konica Minolta Medical & Graphic, Inc. | Active ray curable composition, active ray curable inkjet ink, image forming method using the active ray curable inkjet ink, and inkjet recording apparatus |
| WO2008096618A1 (en) | 2007-02-09 | 2008-08-14 | Konica Minolta Medical & Graphic, Inc. | Inkjet head, inkjet printer, and inkjet recording method |
| EP2347904A2 (en) | 2004-12-09 | 2011-07-27 | Konica Minolta Medical & Graphic, Inc. | Inkset, ink-jet recording method and ink-jet recording device utilizing uv-curable ink |
| JP2023520477A (en) * | 2020-04-03 | 2023-05-17 | 常州強力先端電子材料有限公司 | Synthetic method for synthesizing oxetane derivatives using a microreactor |
-
1956
- 1956-12-14 DE DEF21928A patent/DE1021858B/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3508502B2 (en) | 1997-09-30 | 2004-03-22 | 宇部興産株式会社 | Biphenyl derivative having oxetane ring |
| EP1069120A1 (en) * | 1999-07-15 | 2001-01-17 | Toagosei Co., Ltd. | Naphthalene derivative, binaphthalene derivative and biphenyl derivative and cationically curable compound |
| US6365760B1 (en) | 1999-07-15 | 2002-04-02 | Toagosei Co., Ltd. | Naphthalene derivative, binaphthalene derivative and biphenyl derivative and cationically curable compound |
| US6469108B2 (en) | 1999-07-15 | 2002-10-22 | Toagosei Co., Ltd. | Cationically curable oxetanyl-containing naphthalene and aromatic epoxy or oxetane compound |
| US6255484B1 (en) | 1999-09-28 | 2001-07-03 | Ube Industries, Ltd. | Cyanurate compound having three oxetane ring groups and organic hardening compositions containing same |
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