CH257649A - Process for the preparation of a phosphorus-containing ester. - Google Patents
Process for the preparation of a phosphorus-containing ester.Info
- Publication number
- CH257649A CH257649A CH257649DA CH257649A CH 257649 A CH257649 A CH 257649A CH 257649D A CH257649D A CH 257649DA CH 257649 A CH257649 A CH 257649A
- Authority
- CH
- Switzerland
- Prior art keywords
- formula
- ester
- phosphoric acid
- groups
- phosphorus
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 150000002148 esters Chemical class 0.000 title description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title description 6
- 229910052698 phosphorus Inorganic materials 0.000 title description 6
- 239000011574 phosphorus Substances 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 5
- DSNRZTVNAUGXKR-UHFFFAOYSA-N (2,3-diethyl-4-nitrophenyl) dihydrogen phosphate Chemical compound CCC1=C(OP(O)(O)=O)C=CC([N+]([O-])=O)=C1CC DSNRZTVNAUGXKR-UHFFFAOYSA-N 0.000 claims description 4
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012458 free base Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 1
- -1 ester halides Chemical class 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical group CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 1
- JKIFPWHZEZQCQA-UHFFFAOYSA-N 2-nitrobenzenethiol Chemical class [O-][N+](=O)C1=CC=CC=C1S JKIFPWHZEZQCQA-UHFFFAOYSA-N 0.000 description 1
- MUCCHGOWMZTLHK-UHFFFAOYSA-N 2-nitronaphthalen-1-ol Chemical class C1=CC=C2C(O)=C([N+]([O-])=O)C=CC2=C1 MUCCHGOWMZTLHK-UHFFFAOYSA-N 0.000 description 1
- SEEZWGFVHCMHJF-UHFFFAOYSA-N 2-nitrosophenol Chemical class OC1=CC=CC=C1N=O SEEZWGFVHCMHJF-UHFFFAOYSA-N 0.000 description 1
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000003944 halohydrins Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000005209 naphthoic acids Chemical class 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- XJLRCPYQIPAQCA-UHFFFAOYSA-N phenoxathiine 10,10-dioxide Chemical class C1=CC=C2S(=O)(=O)C3=CC=CC=C3OC2=C1 XJLRCPYQIPAQCA-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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CURNJKLCYZZBNJ-UHFFFAOYSA-M sodium;4-nitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1 CURNJKLCYZZBNJ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
-
- 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
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
Description
Verfahren zur Herstellung eines phosphorhaltigen Esters. Es hat sich grezeigt@ da¯ man wertvolle phosphorhaltige Ester der Formel
EMI1.1
dadurch herstellen kann. dass man phosphor- haltige Esterhalogenide der Formel
EMI1.2
suit Verbindungen der Formel
Aru me (LI) nunseizt und gegebenenfalls in die erhaltenen Ester noch Substituenten einf hrt, wobei Ri und R2 untereinander gkeiche oder ver schiedene. gegebenenfalls substituierte Reste nichtaromatischen Charakters der Gruppe der Alkyle.
Aralkyie und Cycloalkyle, deren Kohlenstoffkette durch Heteroatome oder Heteroatomgrtippen unterbrochen sein können, Ar-einen ein-oder mehrkernigen Rest aromatischen Charakters der Gruppe der Isound Heterocyclen, der, falls er nicht mehr kernig und nicht an Schwefel gebunden ist. mindestens einen Substituenten enthÏlt. y1, y2, y, und y1-O-oder-S-und Me ein Alkalimetallion oder ein wie die- ses reagierendes Kation bedeuten.
Die mit R, undRbezeichnetenReste haben kinen aromatischen Charakter. das heisst die dem phosphorhaltigen Ester zu gtunde liegenden Verbindungen R, y, H und R2Y2H hesitzen den Charakter von Alkoho- len bzw. Merca. ptanen. Im Gegensatz da. zu soll der Rest Ar, welcher auch ein heterozyklischer Rest sein kann, aromatischen Charakter aufweisen, was dann der Fall ist, wenn die dem phosphorhal. tigen Esber zugrunde liegende Verbindung AryADIe den Charakter eines Phenolates hat.
Falls lls die mit Ar bezeichneten Reste mehrere Oxy-bzw. Sulfhydrylgruppen oder w. enn sie als, Substituenten. aromatische Oxy- oder Sulfhydrylgruppen enthaltende Reste besitzen, so können diese bzw deren Salze so mit den Phosphorsäure bzw. Thiophosphorsäureesterhalogeniden umgesetzt werden, dass nur eine oder mehrere der Oxy-oder Sulfhydrylgruppen verestert werden. Sind die mit Ar be-zeichneten Reste mehrkernig, so ka. nn ein Teil der Ejerne vollständig oder nur teilweise hydriert bzw. gesÏttigt sein, wobei aber der an-y4Me gebundene Kern seinen aromatischen Charakter beibehalten muss.
In den eventuell an die Reste R1, R2 und Ar gebundenen Aminogxuppen können ein Teil oder alle freien H-Atome durch organische Reste ersetzt sein, oder es können die Aminogruppen quaterniert sein oder Teile eines Ringes bilden.
In den Resten Ri und R2 und Ar bzw. deren Substituenten eventuell vorlandene OH-Gruppen können verÏthert oder verestert sein und vorhandene Sulfo-, Sulfin-oder Carbonsäurereste a-midiert oder verestert sein oder in Form ihrer Salze vorliegen.
Bei der Ausführung des Verfahrens kön- nen beispielsweise folgende unter die Formel I fallende Verbindungen als besonders geeignete genannt werden : Chloride der Phosphorsäure-dimethylester,-diäthylester, -diisopropylester, -diisobutylthioester der Formel
EMI2.1
-diglykolester der Formel
EMI2.2
-di-chloräthylester der Formel
EMI2.3
-methyl-allylester der Formel
EMI2.4
-dibenzylester, -di- (phenyläthyl)-ester der Formel
EMI2.5
-di- (äthylbutyl)-ester der Formel
EMI2.6
-methyl-n-dodecyl-ester, -di-(ÏthoxyÏthyl)-ester der Formel
EMI2.7
-di- (phenoxyathyl)-ester der Formel
EMI2.8
-di-(diÏthylaminoÏthyl)
-ester der Formel
EMI2.9
-di- (acetylglycol)-ester der Formel
EMI2.10
-di-acetamidoathyl-ester der Formel
EMI2.11
-di-rhodanäthyl-ester der Formel
EMI2.12
-di-nitroäthyl-ester der Formel
EMI3.1
-di-furfuryl-ester der Formel
EMI3.2
-isopropyl-tetrahydrofurfuryl-ester der Formel
EMI3.3
-di- (di-ehloracetylglycol)-ester der Formel
EMI3.4
-di- (diacetonyl)-ester der Formel
EMI3.5
-dicyclohexylester, -di-(α
-chlor-¯-oxypropyl)-ester der Formel
EMI3.6
-di- (chloräthyl-st äthyl)-ester der Formel
EMI3.7
Chloride der Thiophosphorsäure-dibenzylester der Formel
EMI3.8
-diamylester der Formel
EMI3.9
An Stelle dieser beispielsweise genannten Alkyl-, Aralkyl-und Cycloalkylreste können nuch andere und anders substituierte bzw. mit andern Heteroatomen oder Heteroatomgruppen in der Kohlenstoffkette unterbro chenue Reste in Fra. ge kommen. An Stell, der Chloride können in vielen Fällen aueh die entsprechenden Fluoride. Bromide und Jodide verwendet werden.
Als geeignete Verbindungen der Formel @ II seien beispielsweiseerwähnt : Alkalisalze der verschiedenen Mono-Tind Poly-Nitrophenole. Mono- und Poly-Chlorphenole, Mono nitro-mono-und-poly-chlorphenole, Dinitro rnono-nnd-poly-chlorphenole, Trinitro-mono- t'lilor-und-polychlorphenole, Nitrosophenole.
Oxy-phenyls ulfone, Oxy-diphenylsulfone, Dioxyphenylsulfone, Oxy-phenylsulfoxyde, Oxyphenylamine, Oxyphenylamide, Oxy- phenylÏther, Oxyphenylsulfide, Oxyphenyl- disulfide, Oxyphenylrhodanide, Oxyazobenzole, PhenolsulfonsÏuren, Amide der Phenol sulfonsä, uren, Ester der Phenolsulfonsäuren, OxybenzolcarbonsÏuren, OxybenzolcarbonsÏureamide, OxybenzolcarbonsÏureester, Oxyphenylketone, Dioxybenzole, OxyphenylphosphorsÏuredialkylester, Naphthole, Nitronaphthole, Halogennaphthole, Naphthoesäu- ren, Monooxydiphenyle, Di-oxydiphenyle, Nitrothiophenole, Chlorthiophenole, Oxychino- line, Merca. ptobenzothiazole,
das natriumsalz des 3-Oxypyridins und das Natriumsalz des Thiophenols.
Die Verbindungen der Formel I können mit den Verbindungen der Formel II in wÏsseriger oder alkoholischer Losung bzw. Suspension oder in einem ändern Losungsmittel, wie Chloroform, Benzol, Trichloräthylen usw., gelöst oder suspendiert miteinander zur Reaktion gebracht werden.
An Stelle der Alkalisalze der oben genannten, unter Formel II fallenden Verbindungen konnen in vielen Fällen auch andere Salze, z. B. solche der Erdalkalien oder der Amine und Ammoniumhydroxyde, verwendet werden, sofern letztere nicht mit dem Phosphorsäureesterhalogenid unter Amidbildung reagieren, und an Stelle der Verbindungen können auch deren Homologe und Sub stitutionsprodukte zur Anwendung gelangen, wobei eventuell am Kern der Verbindungen enthaltene Seitenketten ebenfalls substituiert sein können.
Die auf diese Weise erhältlichen Verbindungen sind bei gewöhnlicher Temperatur meistens viskose Flüssigkeiten, die in vielen Fällen im Valkuum unzersetzt bzw. fast un- zersetzt destillierbar sind.
Sie sind in wässeriger Lösung bzw. Suspension haltbar und in Ölen sowie organisehen Lösungsmitteln löslich. Sie eignen sich besonders zur Herstellung von Mitteln zur Bekämpfung von Schädlingen, aber zum Teil auch als Zusätze zu Schmier-und Antirost- mitteln, ferner als, Zusatze in Antischaummitteln und Eühlflüssigkeiten.
In den durch Umsetzung der Verbindungen der Formel I mit solchen der Formel II erhältlichen Estern können weitere Substituenten eingeführt oder vorha. ndene ausge- tauscht werden ; z. B. k¯nnen Sulfo-, Nitround Nitrosogruppen, Halogenatome und Chlormethylgruppen u. sw. in den, oder die aromatischen Rerne eingeführt werden, wobei Nitro-oder Nitrosogruppen. zu Aminogruppen reduziert werden können. Ferner können Amino-oder Hydroxylgruppen alkyliert bzw. acyliert und Säuregruppen verestert bzw. amidiert werden.
Es kann auch aus Halogenhydringrup- pen Halogenwasserstoff abgespalten werden, wobei Alkylenoxydgruppen entstehen.
Gegensta. nd vorliegender Erfindung ist ein Verfahren zur Herstellung des Diäthyl- p-nitrophenyl-phosphorsäureesters, welches dadurch gekennzeichnet ist, daB Diäthyl- phosphorsäurechlorid mit dem wasserlösli chen Salz aus einer stickstofRfreien Base und p-Nitrophenol umsgesetzt wird.
Der Diäthyl-p-nitrophenyl-phosphorsäure ester ist eine neue Verbindung vom Kp.o,@ 174 bis 1770. Er stellt ein gelbes, dickflüssiges, in Wasser kaum lösliches, aber darin leicht emulgierbares Í1 dar, das als Insecticid verwendet werden soll.
Beispiel:
Zu 86 g in 200 cm3 Trichloräthylen gel¯stem DiÏthylphorsÏurechlorid trägt man bei etwa 0 C portionenweise 80,5 g trockenes p-Nitrophenolnatrium ein. Nach vollendeter Reaktion wird vom gebildeten Kochsalz abgesaugt und das Lösungsmittel abdestilliert. Man erhält als Rückstand ein Endprodukt, das zur Hauptsache aus einer Verbindung der Formel
EMI4.1
besteht und das durch Hochvakuumdestillation gereinigt werden ka. nn. Es stellt dann ein gelbes, dickflüssiges, in Wasser kaum losliches, aber sehr leicht darin emulgierbares Í1 dar.
P-Gehalt ber. 11,27 % gef. 11,8 % N-Gehalt ber. 5,09 % gef. 4,78 % Spez. Gew. : 1, 288/15 Ep. : 174 bis 177 /0, 6mmHg.
Die Reaktionsbedingungen können ohne wesentlichen Einfluss auf den Verlauf der Reaktion in ziemlich weiten Grenzen variiert werden.
Process for the preparation of a phosphorus-containing ester. It has turned out to be valuable phosphorus-containing esters of the formula
EMI1.1
can thereby produce. that one phosphorus-containing ester halides of the formula
EMI1.2
suit compounds of the formula
Aru me (LI) is added and optionally also introduces substituents into the esters obtained, where Ri and R2 are identical or different to one another. optionally substituted radicals of non-aromatic character from the group of alkyls.
Aralkyls and cycloalkyls, the carbon chain of which can be interrupted by heteroatoms or groups of heteroatoms, Ar-a mono- or polynuclear radical of aromatic character from the group of iso and heterocycles which, if it is no longer nuclear and is not bonded to sulfur. contains at least one substituent. y1, y2, y, and y1-O- or -S- and Me denote an alkali metal ion or a cation which reacts like this.
The radicals denoted by R, and R have no aromatic character. That is to say, the compounds R, y, H and R2Y2H underlying the phosphorus-containing ester have the character of alcohols or Merca. ptanen. In contrast there. to the radical Ar, which can also be a heterocyclic radical, should have aromatic character, which is the case when the phosphorus. The compound AryADIe on which it is based has the character of a phenolate.
If lls the radicals denoted by Ar several oxy or. Sulfhydryl groups or w. hen they are, substituents. have radicals containing aromatic oxy or sulfhydryl groups, these or their salts can be reacted with the phosphoric acid or thiophosphoric acid ester halides in such a way that only one or more of the oxy or sulfhydryl groups are esterified. If the residues labeled Ar are polynuclear, then ka. Some of the nuclei are completely or only partially hydrogenated or saturated, although the nucleus bound to -y4Me must retain its aromatic character.
In the amino groups possibly bonded to the radicals R1, R2 and Ar, some or all of the free H atoms can be replaced by organic radicals, or the amino groups can be quaternized or form parts of a ring.
OH groups that may be present in the radicals Ri and R2 and Ar or their substituents can be etherified or esterified and sulfo-, sulfinic or carboxylic acid radicals present can be amidated or esterified or in the form of their salts.
When carrying out the process, for example, the following compounds falling under the formula I can be mentioned as particularly suitable: Chlorides of phosphoric acid dimethyl ester, diethyl ester, diisopropyl ester, diisobutyl thioester of the formula
EMI2.1
-diglycol ester of the formula
EMI2.2
-di-chloroethyl ester of the formula
EMI2.3
methyl allyl ester of the formula
EMI2.4
dibenzyl ester, di (phenylethyl) ester of the formula
EMI2.5
-di (ethylbutyl) ester of the formula
EMI2.6
-methyl-n-dodecyl ester, di (ÏthoxyÏthyl) ester of the formula
EMI2.7
di (phenoxyethyl) esters of the formula
EMI2.8
-di (diÏthylaminoÏthyl)
-ester of the formula
EMI2.9
di (acetylglycol) esters of the formula
EMI2.10
-di-acetamidoethyl ester of the formula
EMI2.11
-di-rhodanethyl ester of the formula
EMI2.12
-di-nitroethyl ester of the formula
EMI3.1
-di-furfuryl ester of the formula
EMI3.2
-isopropyl-tetrahydrofurfuryl ester of the formula
EMI3.3
-di (di-chloroacetylglycol) esters of the formula
EMI3.4
di (diacetonyl) esters of the formula
EMI3.5
-dicyclohexyl ester, -di - (?
-chlor-¯-oxypropyl) ester of the formula
EMI3.6
-di (chloroethyl-st ethyl) ester of the formula
EMI3.7
Chlorides of the thiophosphoric acid dibenzyl ester of the formula
EMI3.8
-diamyl ester of the formula
EMI3.9
Instead of these alkyl, aralkyl and cycloalkyl radicals mentioned by way of example, other and differently substituted or with other heteroatoms or heteroatom groups in the carbon chain interrupted radicals in Fra. came. Instead of the chlorides, in many cases the corresponding fluorides can also be used. Bromides and iodides can be used.
Examples of suitable compounds of the formula @ II are: alkali salts of the various mono-tins poly-nitrophenols. Mono- and poly-chlorophenols, mono-nitro-mono-and-poly-chlorophenols, dinitro-mono-nnd-poly-chlorophenols, trinitro-mono-t'lilor-and-polychlorophenols, nitrosophenols.
Oxy-phenylsulfones, oxy-diphenylsulfones, dioxyphenylsulfones, oxy-phenylsulfoxides, oxyphenylamines, oxyphenylamides, oxyphenyl ethers, oxyphenylsulfides, oxyphenyl disulfides, oxyphenylrhodanides, oxyphenylrhodanides, oxyphenylrhodanides, oxyazobenzenes, oxyazobenzoic acids, phenolsulfonamides, phenolsulfonamides, oxyazobenzenes, oxyazobenzenes, oxyazobenzoic acids, phenolsulfonic acids, oxyazobenzenesulfoxides, oxyazobenzenesulfoxides, oxyazobenzenes, oxyazobenzenes. Oxybenzenecarboxylic acid esters, oxyphenyl ketones, dioxybenzenes, oxyphenylphosphorus dialkyl esters, naphthols, nitronaphthols, halogen naphthols, naphthoic acids, monooxydiphenyls, di-oxydiphenyls, nitrothiophenols, chloroorthiophenols, oxychlorothiophenols. ptobenzothiazole,
the sodium salt of 3-oxypyridine and the sodium salt of thiophenol.
The compounds of the formula I can be dissolved or suspended with the compounds of the formula II in aqueous or alcoholic solution or suspension or in another solvent, such as chloroform, benzene, trichlorethylene, etc., to react with one another.
Instead of the alkali metal salts of the abovementioned compounds falling under formula II, other salts, e.g. B. alkaline earths or amines and ammonium hydroxides, provided the latter do not react with the phosphoric acid ester halide to form amides, and instead of the compounds, their homologues and substitution products can also be used, with side chains contained in the core of the compounds also being substituted could be.
The compounds obtainable in this way are mostly viscous liquids at ordinary temperature, which in many cases can be distilled undecomposed or almost undecomposed in vacuo.
They can be kept in an aqueous solution or suspension and are soluble in oils and organic solvents. They are particularly suitable for the production of agents for combating pests, but in some cases also as additives to lubricants and anti-rust agents, and also as additives in anti-foam agents and cooling liquids.
Further substituents can be introduced or present in the esters obtainable by reacting the compounds of the formula I with those of the formula II. which are exchanged; z. B. sulfo, nitroso and nitroso groups, halogen atoms and chloromethyl groups u. sw. are introduced into the, or the aromatic rings, with nitro or nitroso groups. can be reduced to amino groups. In addition, amino or hydroxyl groups can be alkylated or acylated and acid groups can be esterified or amidated.
Hydrogen halide can also be split off from halohydrin groups, with alkylene oxide groups being formed.
Object The present invention is a process for preparing the diethyl p-nitrophenyl phosphoric acid ester, which is characterized in that diethyl phosphoric acid chloride is reacted with the water-soluble salt of a nitrogen-free base and p-nitrophenol.
The diethyl-p-nitrophenyl-phosphoric acid ester is a new compound from Kp.o, @ 174 to 1770. It is a yellow, viscous, hardly soluble in water, but easily emulsifiable oil, which is to be used as an insecticide.
Example:
80.5 g of dry sodium p-nitrophenol are added in portions to 86 g of diethylphosphoric acid chloride dissolved in 200 cm3 of trichlorethylene at about 0 C. When the reaction is complete, the sodium chloride formed is filtered off with suction and the solvent is distilled off. The residue obtained is an end product, which mainly consists of a compound of the formula
EMI4.1
exists and that can be purified by high vacuum distillation. nn. It is then a yellow, viscous Í1 that is hardly soluble in water but very easily emulsifiable in it.
P content calculated 11.27% 11.8% N content calculated 5.09% 4.78% spec. Wt.: 1, 288/15 Ep.: 174 to 177 / 0.6mmHg.
The reaction conditions can be varied within fairly wide limits without any significant influence on the course of the reaction.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH257649T | 1947-07-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH257649A true CH257649A (en) | 1948-10-31 |
Family
ID=4472270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH257649D CH257649A (en) | 1947-07-16 | 1947-07-16 | Process for the preparation of a phosphorus-containing ester. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH257649A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2836534A (en) * | 1954-02-11 | 1958-05-27 | Monsanto Chemicals | Phosphorus-sulfur compounds |
| US2885429A (en) * | 1956-04-02 | 1959-05-05 | Dow Chemical Co | O-biphenylyl o, o-dialkyl phosphoro-thioates |
| US2894017A (en) * | 1956-04-26 | 1959-07-07 | Bayer Ag | Thiophosphoric acid esters and their production |
| US2895982A (en) * | 1956-04-09 | 1959-07-21 | Shell Dev | Complex nitrophenyl phosphates |
| US2897227A (en) * | 1956-04-04 | 1959-07-28 | Dow Chemical Co | S-(chlorophenyl) o,o-dialkyl phosphorodithioates |
| US2896406A (en) * | 1953-02-16 | 1959-07-28 | Standard Oil Co | Rocket propulsion method |
| US2912452A (en) * | 1956-04-21 | 1959-11-10 | Bayer Ag | Thiophosphoric acid esters and their production |
| US2979522A (en) * | 1954-12-30 | 1961-04-11 | Pittsburgh Coke And Chemical C | Dialkyl nitroalkyl dithiophosphates |
| US3042703A (en) * | 1956-03-22 | 1962-07-03 | Bayer Ag | Thiophosphoric acid esters and their production |
| US3082239A (en) * | 1959-04-29 | 1963-03-19 | Bayer Ag | Thiophosphoric acid esters and process for their production |
| US3107164A (en) * | 1962-03-27 | 1963-10-15 | Stauffer Chemical Co | Herbicidal methods employing omicron, omicron-diallyl omicron-aryl phosphate esters |
| US3170835A (en) * | 1957-04-15 | 1965-02-23 | Monsanto Co | Nitromethylbenzyl-phosphorothioic acid diesters and nematocidal methods employing same |
-
1947
- 1947-07-16 CH CH257649D patent/CH257649A/en unknown
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2896406A (en) * | 1953-02-16 | 1959-07-28 | Standard Oil Co | Rocket propulsion method |
| US2836534A (en) * | 1954-02-11 | 1958-05-27 | Monsanto Chemicals | Phosphorus-sulfur compounds |
| US2979522A (en) * | 1954-12-30 | 1961-04-11 | Pittsburgh Coke And Chemical C | Dialkyl nitroalkyl dithiophosphates |
| US3042703A (en) * | 1956-03-22 | 1962-07-03 | Bayer Ag | Thiophosphoric acid esters and their production |
| US2885429A (en) * | 1956-04-02 | 1959-05-05 | Dow Chemical Co | O-biphenylyl o, o-dialkyl phosphoro-thioates |
| US2897227A (en) * | 1956-04-04 | 1959-07-28 | Dow Chemical Co | S-(chlorophenyl) o,o-dialkyl phosphorodithioates |
| US2895982A (en) * | 1956-04-09 | 1959-07-21 | Shell Dev | Complex nitrophenyl phosphates |
| US2912452A (en) * | 1956-04-21 | 1959-11-10 | Bayer Ag | Thiophosphoric acid esters and their production |
| US2894017A (en) * | 1956-04-26 | 1959-07-07 | Bayer Ag | Thiophosphoric acid esters and their production |
| US3170835A (en) * | 1957-04-15 | 1965-02-23 | Monsanto Co | Nitromethylbenzyl-phosphorothioic acid diesters and nematocidal methods employing same |
| US3082239A (en) * | 1959-04-29 | 1963-03-19 | Bayer Ag | Thiophosphoric acid esters and process for their production |
| US3107164A (en) * | 1962-03-27 | 1963-10-15 | Stauffer Chemical Co | Herbicidal methods employing omicron, omicron-diallyl omicron-aryl phosphate esters |
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