DE1060869B - Process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexahalogen-4, 7-endomethylene-4, 7, 8, 9-tetra-hydrophthalane - Google Patents
Process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexahalogen-4, 7-endomethylene-4, 7, 8, 9-tetra-hydrophthalaneInfo
- Publication number
- DE1060869B DE1060869B DER23390A DER0023390A DE1060869B DE 1060869 B DE1060869 B DE 1060869B DE R23390 A DER23390 A DE R23390A DE R0023390 A DER0023390 A DE R0023390A DE 1060869 B DE1060869 B DE 1060869B
- Authority
- DE
- Germany
- Prior art keywords
- endomethylene
- acid ester
- hexahalogen
- mol
- derivatives
- 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 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- 150000002148 esters Chemical class 0.000 claims description 11
- 150000001447 alkali salts Chemical class 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 aliphatic alcohols Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-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
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- ZKDDJTYSFCWVGS-UHFFFAOYSA-M sodium;diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CCOP([S-])(=S)OCC ZKDDJTYSFCWVGS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- AIRYWGWRGZRADS-UHFFFAOYSA-N butoxy-butylsulfanyl-sulfanylidenephosphanium;sodium Chemical compound [Na].CCCCO[P+](=S)SCCCC AIRYWGWRGZRADS-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- CPUDLRLOFJLISR-UHFFFAOYSA-N diethyl(trihydroxy)-$l^{5}-phosphane Chemical compound CCP(O)(O)(O)CC CPUDLRLOFJLISR-UHFFFAOYSA-N 0.000 description 1
- 210000002837 heart atrium Anatomy 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GUCVHDYRKMSBOJ-UHFFFAOYSA-M sodium;diethyl phosphate Chemical compound [Na+].CCOP([O-])(=O)OCC GUCVHDYRKMSBOJ-UHFFFAOYSA-M 0.000 description 1
- ABRPCPUEDVVPRS-UHFFFAOYSA-M sodium;dipropyl phosphate Chemical compound [Na+].CCCOP([O-])(=O)OCCC ABRPCPUEDVVPRS-UHFFFAOYSA-M 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Description
Verfahren zur Herstellung von Derivaten der 4, 5, 6, 7, 10, 10-Hexahalogen-4, 7-endomethylen-4, 7, 8, 9-tetrahydrophthalane In der deutschen Auslegeschrift 1 006 431 wurde ein Verfahren zur Herstellung von Derivaten des 4, 5, 6, 7, 10, 10-Hexachlor-4, 7, 8, 9-tetrahydrophthalans beschrieben, bei dem diese Verbindung durch Behandlung mit üblichen Bromierungsmitteln in das entsprechende 1-Bromderivat übergeführt und das in 1=Stellung befindliche Bromatom anschließend durch Umsetzung mit gegebenenfalls substituierten Alkoholen, Phenolen, Mercaptanen oder Carbonsäureanhydriden ausgetauscht wird.Process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexahalogen-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane In German Auslegeschrift 1 006 431 a process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexachloro-4, 7, 8, 9-tetrahydrophthalans described in which this compound by treatment converted into the corresponding 1-bromo derivative with conventional brominating agents and the bromine atom in the 1 = position is then optionally reacted with substituted alcohols, phenols, mercaptans or carboxylic anhydrides are exchanged will.
In weiterer Ausbildung dieses Verfahrens wurde überraschenderweise gefunden, daß man zu einer Klasse wertvoller und neuer Verbindungen kommt, wenn man anstatt der bei dem bekannten Verfahren fit.. die weitere Umsetzung der 1-Brom-4, 5, 6, 7, 10, 10-hexahalogen-4, 7-endomethylen-4, 7, 8, 9-tetrahydrophthalane verwendeten Alkohole, Phenole, Mercaptane oder Carbonsäureanhydride die Alkalisalze von O, O-Dialkylestern der Phosphorsäure, Thiophosphorsäure, Dithiophosphorsäure, die Dialkylester der phosphorigen Säure oder deren Alkalisalze verwendet. Im allgemeinen benutzt man als Alkalisalz der genannten Ester das Natriumsalz, wobei als Alkoholkomponente des jeweils zur Umsetzung gelangenden Esters niedere aliphatische Alkohole mit 1 bis 8 Kohlenstoffatomen in Betracht kommen. Spezielle Vertreter sind beispielsweise die Alkalisalze folgender Ester : 0, O-Dimethyl-phosphorsäureester, O, O-Diäthyl-phosphorsäureester, O, O-Di-n-propyl-phosphorsäureester, O, Q-Di-i-amyl-phosphorsäureester, O, O-Diäthyl-thiophosphorsäureester, 0, O-Di-n-propyl-thiophosphorsäureester, 0, O-Di-n-butyl-thiophosphorsäureester, O, O-Diãthyl-dithiophosphorsäureester, 0, O-Di-n-propyl-dithiophosphorsãureester, 0, O-Di-n-butyl-dithiophosphorsãureester, O, O-Di-n-octyl-dithiophosphorsãureester, 0, O-Dimethyl-phosphorigsäureester, O, Q-Diäthyl-phosphorigsãureester, O, O-Di-n-propyl-phosphorigsäureester oder die Alkalisalze der genannten Phosphorigsäureester. In further training this process was surprisingly found that one comes to a class of valuable and new connections when one instead of the in the known process fit .. the further implementation of 1-bromo-4, 5, 6, 7, 10, 10-hexahalogen-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane were used Alcohols, phenols, mercaptans or carboxylic acid anhydrides are the alkali salts of O, O-dialkyl esters of phosphoric acid, thiophosphoric acid, dithiophosphoric acid, the dialkyl esters of Phosphorous acid or its alkali salts are used. Generally one uses as the alkali salt of the esters mentioned, the sodium salt, with the alcohol component of the ester used in each case is lower aliphatic alcohols with 1 up to 8 carbon atoms come into consideration. Special representatives are for example the alkali salts of the following esters: 0, O-dimethyl-phosphoric acid ester, O, O-diethyl-phosphoric acid ester, O, O-Di-n-propyl-phosphoric acid ester, O, Q-Di-i-amyl-phosphoric acid ester, O, O-diethyl thiophosphoric acid ester, 0, O-di-n-propyl-thiophosphoric acid ester, 0, O-di-n-butyl-thiophosphoric acid ester, O, O-diethyl-dithiophosphoric acid ester, 0, O-di-n-propyl-dithiophosphoric acid ester, 0, O-di-n-butyl-dithiophosphoric acid ester, O, O-di-n-octyl-dithiophosphoric acid ester, 0, O-dimethyl phosphorous acid ester, O, Q-diethyl phosphorous acid ester, O, O-di-n-propyl phosphorous acid ester or the alkali salts of the phosphorous acid esters mentioned.
Natürlich eignen sich auch die entsprechenden Mischester, z. B. O, O-Methyläthylphosphorsäureester bzw.Of course, the corresponding mixed esters are also suitable, e.g. B. O, O-methylethylphosphoric acid ester or
-phosphorigsãureester.-phosphorous acid esters.
Die Umsetzung wird am besten in der Weise ausgeführt, daß man zu dem in Lösung befindlichen 1-Brom-phthalan die Alkalisalze der erwahnten Ester in geeigneten Mengen hinzufügt, diese Mischung unter RiickfluBkiihlung alsdann auf dem Wasserbad erhitzt, bis die Umsetzung beendet ist, worauf man nach Abdampfen des Lösungsmittels die gewünschte Verbindung erhält. Als Lösungsmittel eignet sich z. B. Benzol, Toluol, Dioxan, Tetrachlorkohlenstoff oder n-Heptan. Implementation is best carried out in such a way that you can the 1-bromophthalane in solution, the alkali salts of the esters mentioned in Add appropriate amounts, this mixture is then refluxed on heated in a water bath until the reaction has ended, which is followed by evaporation of the solvent obtains the desired compound. Is suitable as a solvent z. B. benzene, toluene, dioxane, carbon tetrachloride or n-heptane.
Die erfindungsgemäß hergestellten Verbindungen eignen sich als Schadlingsbekämpfungsmittel und sind gute Weichmacher. Alle erfindungsgemäßen Verbindungen sind selbst im Vakuum nur unter Zersetzung destillierbar. The compounds prepared according to the invention are suitable as pest control agents and are good plasticizers. All compounds according to the invention are themselves in a vacuum Can only be distilled with decomposition.
Zu ihrer Kennzeichnung können daher nur die Brechungsindizes angegeben werden.Therefore, only the refractive indices can be used to identify them will.
Die erfindungsgemäß hergestellten Ester können mit großem Vorteil als Weichmacher bei der Verarbeitung von Polyvinylchlorid, Polyvinylacetalen, Polyester, Polyamiden und Celluloseacetat verwendet werden. The esters prepared according to the invention can be used to great advantage as a plasticizer in the processing of polyvinyl chloride, polyvinyl acetals, polyester, Polyamides and cellulose acetate can be used.
Beispiel 1 In 20 ccm Dioxan wurden 4, 2 g (0, 010 Mol) 1-Brom-4, 5, 6, 7, 10, 10-hexachlor-4, 7-endomethylen-4, 7, 8, 9-tetrahydrophthalan gelöst und mit 3, 5 g (0, 020 Mol) Natriumdiäthylphosphat 5 Stunden unter Rühren am Rückflußkühler erhitzt. Das Reaktionsprodukt wurde nach Zugabe von 100 ccm Wasser in 50 ccm Benzol aufgenommen und die Benzolschicht nach Trocknung eingedampft. In einer Ausbeute von 3, 8 g konnte der O, O Diathyl-[4, 5, 6, 7, 10, 10-hexachlor-4, 7-endomethylen-4, 7, 8, 9-tetrahydrophthalanyl- (1)]-phosphorsäureester erhalten werden, der aus einer öligen Flüssigkeit bestand, die den Brechungsindex n2D = 1, 5502 besaß. Example 1 In 20 cc of dioxane, 4.2 g (0.010 mol) of 1-bromo-4, 5, 6, 7, 10, 10-hexachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane dissolved and with 3.5 g (0.020 mol) of sodium diethyl phosphate for 5 hours with stirring on the reflux condenser heated. The reaction product was after the addition of 100 cc of water in 50 cc of benzene added and the benzene layer evaporated after drying. In one yield of 3, 8 g could the O, O diethyl- [4, 5, 6, 7, 10, 10-hexachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalanyl- (1)] - phosphoric acid ester can be obtained from a oily liquid which had the refractive index n2D = 1.5502.
Beispiel 2 Es wurden 4, 2 g (0, 010 Mol) 1-Brom-4, 5, 6, 7, 10, 10-hexachlor-4, 7-endomethylen-4, 7, 8, 9-tetrahydrophthalan und 2, 1 g (0, 010 Mol) Natriumdiäthyldithiophosphat 8 Stunden auf dem Wasserbad erhitzt. Das Reaktionsprodukt wurde in Benzol aufgenommen, mit Wasser gewaschen und die mit Natriumsulfat getrocknete Benzolschicht im Vakuum eingedampft. Den nach einiger Zeit erstarrenden Rückstand kristallisierte man aus n-Hexan um und er- @ilt 3,5 g des bei 98 bis 100°C schmelzenden O,O-Di-@thyl-[4,5,6,7,10,1-hexachlor-4,7-endomethylen-4,7,8,9-etrahydrophthalanyl-(1) j-dithiophosphorsäureesters. Es @andelet sich un eine ölige Flüsslgkeit, deren Brechungsndex nicht bestimmt werden konnte. Example 2 There were 4.2 g (0.010 mol) of 1-bromo-4, 5, 6, 7, 10, 10-hexachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane and 2.1 g (0.010 moles) of sodium diethyl dithiophosphate Heated on a water bath for 8 hours. The reaction product was taken up in benzene, washed with water and the benzene layer dried with sodium sulfate in vacuo evaporated. The residue, which solidified after some time, was crystallized out n-hexane and @ilt 3.5 g of that which melts at 98 to 100 ° C O, O-Di- @thyl- [4,5,6,7,10,1-hexachloro-4,7-endomethylene-4,7,8,9-ethrahydrophthalanyl- (1) j-phosphorodithioic acid ester. It is an oily liquid whose refractive index could not be determined.
4.-'Beispiel 3 Man löste 4,2 g (0,010 Mol) 1 Brom 4,5,6,7,10,10-hexahlor-4,7-endomethylen-4,7,8,9-tetrahydrophthalan in 0 ccm Benzolk und erwarrmet nach Zugabe von 3,8 g 0,020 Mol) Natriumdiathylthiophosphal 12 Stunden unter intensivem Rühren auf dem Wasserbad. Die Reakionslösung wurde mit Wasser gewaschen und die mit {ätriumsulfat getrocknete'Benzolscnicht im Vaknum @ingedampft. Als Rückstand erheilt man 4,4 g des @,@-Diäthyl-[4,5,6,7,10,10-hexachlor-4,7-endomethylen-# 7, 8, 9-tetrahydrophthalanyl- (1)]-thiophosphrosäuresters. Diese Verbindung war eine ölige Flüssigkeit mit Lem Brechungsindex nô = 1, 5580. 4 .- 'Example 3 4.2 g (0.010 mol) of 1 bromine 4,5,6,7,10,10-hexahloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalane were dissolved in 0 cc of benzene and, after adding 3.8 g of 0.020 mol) of sodium diethylthiophosphorus, warms up 12 hours with intensive stirring on the water bath. The reaction solution was with Washed with water and the benzene, dried with atrium sulfate, is not evaporated in a vacuum. 4.4 g of the @, @ - diethyl- [4,5,6,7,10,10-hexachloro-4,7-endomethylene- # 7, 8, 9-tetrahydrophthalanyl (1)] thiophosphoric acid ester. This connection was an oily liquid with Lem refractive index nô = 1.5580.
Beispiel 4 7, 8 g (0, 020 Mol) 1-Brom-10,10-difluor-4, 5, 6, 7-tetrahlor-4, 7-endomethylen-4, 7, 8, 9-tetrahydrophthalan wur-Len in 50 ccm Benzol gelöst und nach Zugabe von 6, 1 g 0, 030 Mol) Natriumdipropylphosphat 8 Stunclen unter Ziihren am RiickfluBkiihler erhitzt. Die Reaktionslösung vurde mit Wasser gewaschen und die getrocknete Benzolchicht im Vakuum eingedampft. In einer Ausbeute von ', 4 g erhielt man den O, O-Dipropyl- [10, 10-difluor-,5,6,7-tetrachlor-4, 7-endomethylen-4, 7, 8, 9-tetrahydro-) hthalanyl- (l)]-phosphorsaureester. Auch dieser Ester ) estand aus einer öligen Flüssligkeit. Sein Brechungsndex wurde zu n2D0. = th5352 festgestelltt Beispiel 5 Man löste 7,8 g (0.02 Mol) 1-Brom-10,10-diflor-@,5,6,7-tetrachlor-4,7-endomethylen-4,7,8,9,-tetrahydro-) hthalan in 40 ccm Dioxan und erwärmte nach Zugabe on 6, 3 g (0, 030 Mol) Natriumdiäthyldithiophosphat 0 Stunden unter Rühren auf dem Wasserbad. Das Reakionsprodukt wurde im Vakuum eingedampft, der Rücktand in Benzol aufgenommen und die mit Wasser gevaschene und anschließend mit Natriumsulfat getrocknete 3enzolschicht im Vakuum eingedampft. In einer Ausmeute von 7, 6 g wurde der O, O-Diäthyl- [10, 10-difluor-:, 5, 6, 7-tetrachlor-4, 7-endomethylen-4, 7, 8, 9-tetrahydro- phthalanyl-(1)]-dithiophosphorsäuresester erhalten. Es handelte sich um eine ölige Flüssigkeit mit dem Brechungsindex nD20 = 1, 5563. Example 4 7, 8 g (0, 020 mol) of 1-bromo-10,10-difluoro-4, 5, 6, 7-tetrahedral-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalan was dissolved in 50 cc of benzene and after adding 6.1 g of 0.030 mol) of sodium dipropyl phosphate, 8 hours with stirring heated at the return heat exchanger. The reaction solution was washed with water and the dried benzene layer evaporated in vacuo. In a yield of 1.4 g obtained the O, O-dipropyl- [10, 10-difluoro-, 5,6,7-tetrachloro-4, 7-endomethylene-4, 7, 8, 9-tetrahydro-) hthalanyl- (l)] phosphoric acid ester. This ester) also stood from an oily liquid. Its refractive index became n2D0. = th5352 detected EXAMPLE 5 7.8 g (0.02 mol) of 1-bromo-10,10-difloro - @, 5,6,7-tetrachloro-4,7-endomethylene-4,7,8,9, -tetrahydro-) were dissolved hthalan in 40 cc of dioxane and heated after the addition of 6.3 g (0.030 mol) of sodium diethyldithiophosphate 0 hours while stirring on the water bath. The reaction product was evaporated in vacuo, the residue taken up in benzene and the washed with water and then 3enzene layer dried with sodium sulfate and evaporated in vacuo. In a pack of 7, 6 g was the O, O-diethyl- [10, 10-difluor- :, 5, 6, 7-tetrachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydro- phthalanyl (1)] - dithiophosphoric acid ester obtained. It acted is an oily liquid with the refractive index nD20 = 1.5563.
Beispiel 6 W.. o Es wurden 7, 8 g (0, 020 Mol) 1-Brom-10, 10-difluor-4, 5, 6, 7-tetrachlor-4, 7-endomethylen-4, 7, 8, 9-tetrahydrophthalan in 40 ccm Dioxan gelöst und nach Zugabe von 10, 5 g (0, 040 Mol) Natriumdibutyldithiophosphat 10 Stunden unter Rühren auf dem Wasserbad erwärmt. Die Reaktionslösung wurde mit 200 ccm Wasser versetzt und mit 50 ccm Benzol extrahiert. Nach Trocknung und Eindampfen der Benzolschicht im Vakuum erhielt man in einer Ausbeute von 8,1 g den O,O-Dibutyl-[10,10-diflour-4, 5, 6, 7-tetrachlor-4, 7-endomethylen-4, 7, 8, 9-tetrahydrophthalanyl-(1)]-dithiophosphoräureester, der aus einer öligen Flüssigkeit bestand, die dem Brechungsindex nD20 = 1,5405 besaß Beispiel'7 Auf dem Wasserbad wurden wurden 4,2 g (0,010 Mol) 1-Brom-4,5,6,7,10,10-hexachlor-4,7-endomehylen-4,7,8,9-tetrahydrophfhalan sowie 2,1 g (0.015 Mol) diäthylkphosphorige Saure 3 Stunden am'Rücknüßkühler erwärmt. Das im Vakuum eingedampfte Reaktionsprodukt erstarrte über Nacht und zeigte nach der Behandlung mit Petroläther einen Schmelzpunkt von 228°C. Die Ausbeute betrug 2,25 g O,O-Diäthyl-[4,5,6,7,10,10-hexaclor-4,7-endomethylen-4,7,8,9-tetrahydrophthalanyl-(1)]-phosphorsäureester. Sein Brechungsinde wrude zu nD20 = 1,5502 festgestellt. Example 6 W .. o There were 7, 8 g (0, 020 mol) of 1-bromo-10, 10-difluoro-4, 5, 6, 7-tetrachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane in 40 cc of dioxane dissolved and after adding 10.5 g (0.040 mol) of sodium dibutyldithiophosphate 10 Heated for hours on a water bath while stirring. The reaction solution was with 200 ccm of water and extracted with 50 ccm of benzene. After drying and evaporation the benzene layer in vacuo was obtained in a yield of 8.1 g of the O, O-dibutyl- [10,10-difluor-4, 5, 6, 7-tetrachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalanyl- (1)] - dithiophosphoric acid ester, which consisted of an oily liquid which had the refractive index nD20 = 1.5405 EXAMPLE 7 4.2 g (0.010 mol) of 1-bromo-4,5,6,7,10,10-hexachloro-4,7-endomehylene-4,7,8,9-tetrahydrophthalane were added to the water bath and 2.1 g (0.015 mol) of diethyl phosphorous acid heated for 3 hours on a re-nut cooler. The reaction product evaporated in vacuo solidified overnight and showed treatment with petroleum ether has a melting point of 228 ° C. The yield was 2.25 g of O, O-diethyl- [4,5,6,7,10,10-hexacloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalanyl- (1)] phosphoric acid ester. Its refractive index was found to be nD20 = 1.5502.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER23390A DE1060869B (en) | 1958-05-22 | 1958-05-22 | Process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexahalogen-4, 7-endomethylene-4, 7, 8, 9-tetra-hydrophthalane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER23390A DE1060869B (en) | 1958-05-22 | 1958-05-22 | Process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexahalogen-4, 7-endomethylene-4, 7, 8, 9-tetra-hydrophthalane |
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| DE1060869B true DE1060869B (en) | 1959-07-09 |
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| DER23390A Pending DE1060869B (en) | 1958-05-22 | 1958-05-22 | Process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexahalogen-4, 7-endomethylene-4, 7, 8, 9-tetra-hydrophthalane |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1006431B (en) * | 1955-11-05 | 1957-04-18 | Ruhrchemie Ag | Process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexachloro-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane |
| DE1013290B (en) * | 1956-02-04 | 1957-08-08 | Ruhrchemie Ag | Process for the production of insecticides |
| DE1020346B (en) * | 1954-06-30 | 1957-12-05 | Ruhrchemie Ag | Insecticides and processes for their manufacture |
| DE1022236B (en) * | 1956-08-11 | 1958-01-09 | Ruhrchemie Ag | Process for the preparation of 1,3-disubstituted derivatives of 4,5,6,7,10,10-hexachloro-4,7-endo-methylene-4,7,8,9-tetrahydrophthalane |
-
1958
- 1958-05-22 DE DER23390A patent/DE1060869B/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1020346B (en) * | 1954-06-30 | 1957-12-05 | Ruhrchemie Ag | Insecticides and processes for their manufacture |
| DE1006431B (en) * | 1955-11-05 | 1957-04-18 | Ruhrchemie Ag | Process for the preparation of derivatives of 4, 5, 6, 7, 10, 10-hexachloro-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane |
| DE1013290B (en) * | 1956-02-04 | 1957-08-08 | Ruhrchemie Ag | Process for the production of insecticides |
| DE1022236B (en) * | 1956-08-11 | 1958-01-09 | Ruhrchemie Ag | Process for the preparation of 1,3-disubstituted derivatives of 4,5,6,7,10,10-hexachloro-4,7-endo-methylene-4,7,8,9-tetrahydrophthalane |
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