DE2133795A1 - Tertiary phosphine oxides - as insecticides fungicides - flame retardants and corrosion inhibitors - Google Patents
Tertiary phosphine oxides - as insecticides fungicides - flame retardants and corrosion inhibitorsInfo
- Publication number
- DE2133795A1 DE2133795A1 DE2133795A DE2133795A DE2133795A1 DE 2133795 A1 DE2133795 A1 DE 2133795A1 DE 2133795 A DE2133795 A DE 2133795A DE 2133795 A DE2133795 A DE 2133795A DE 2133795 A1 DE2133795 A1 DE 2133795A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- group
- tertiary phosphine
- phosphine oxides
- formula
- 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
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 title claims description 6
- 230000007797 corrosion Effects 0.000 title 1
- 238000005260 corrosion Methods 0.000 title 1
- 239000003063 flame retardant Substances 0.000 title 1
- 239000000417 fungicide Substances 0.000 title 1
- 239000003112 inhibitor Substances 0.000 title 1
- 239000002917 insecticide Substances 0.000 title 1
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 4
- 125000005041 acyloxyalkyl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004423 acyloxy group Chemical group 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 125000001589 carboacyl group Chemical group 0.000 abstract description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 abstract description 2
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 abstract 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 abstract 1
- 125000004414 alkyl thio group Chemical group 0.000 abstract 1
- 239000011953 free-radical catalyst Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- -1 3-propyl Chemical group 0.000 description 2
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WQAWEUZTDVWTDB-UHFFFAOYSA-N dimethyl(oxo)phosphanium Chemical compound C[P+](C)=O WQAWEUZTDVWTDB-UHFFFAOYSA-N 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JKLUVCHKXQJGIG-UHFFFAOYSA-N 2-Methylenebutan-1-ol Chemical compound CCC(=C)CO JKLUVCHKXQJGIG-UHFFFAOYSA-N 0.000 description 1
- VXIRJOHCLXLYOA-UHFFFAOYSA-N 2-methylidenehexan-1-ol Chemical compound CCCCC(=C)CO VXIRJOHCLXLYOA-UHFFFAOYSA-N 0.000 description 1
- BXJQZHHEWYUFAC-UHFFFAOYSA-N 2-methylidenepentan-1-ol Chemical compound CCCC(=C)CO BXJQZHHEWYUFAC-UHFFFAOYSA-N 0.000 description 1
- QXWHISNFDZLFAV-UHFFFAOYSA-N 3-methylbut-3-enyl butanoate Chemical compound CCCC(=O)OCCC(C)=C QXWHISNFDZLFAV-UHFFFAOYSA-N 0.000 description 1
- ZPLYSVMRQUOURS-UHFFFAOYSA-N 3-methylideneheptan-1-ol Chemical class CCCCC(=C)CCO ZPLYSVMRQUOURS-UHFFFAOYSA-N 0.000 description 1
- JYMUQYLETHLSAN-UHFFFAOYSA-N 5-methylhex-5-en-1-ol Chemical compound CC(=C)CCCCO JYMUQYLETHLSAN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- NLDFTWSUPLJCQD-UHFFFAOYSA-N prop-1-en-2-yl propanoate Chemical compound CCC(=O)OC(C)=C NLDFTWSUPLJCQD-UHFFFAOYSA-N 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
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)
Abstract
Description
Verfahren zur Herstellung tertiärer Phosphinoxyde Zusatz zur Patentanmeldung P 20 40 280.6 (HOE 70/F 150)) Gegenstand der Hauptanmeldung sind tertiäre phosphinoxyde der Formel in welcher R1 und R2 Alkylgruppen mit 1 bis 12 Kohlenstoffatomen, n eine Zahl von 2 bis 4 und R die Gruppen der Formel -OR3 und -NR4R5 bedeuten, wobei R3 eine niedere Alkylgruppe, eine niedere Alkanoylgruppe oder die Carbamoylgruppe und außerdem, wenn n 3 oder 4 bedeutet, ein Wasserstoffaton bedeutet, R4 fUr ein Wasserstoffatom oder eine niedere Alkylgruppe, eine niedere Alkanoylgruppe oder eine niedere Carboalkoxygruppe und R5 fUr ein Wasserstoffatomen oder eine niedere Alkylgruppe stehen und wobei die Gruppe der Formel -NR4R5 auch für die Gruppe der Formel steht, in welcher in eine ganze Zahl von 2 bis 5 bedeutet, und ein Verfahren zu ihrer Herstellung, das dadurch gekennzeichnet istm daß man Dialkylphosphinoxyde der allgemeinen Formel in welcher R1 und R2 die vorgenannten Bedeutungen besitzen, in Gegenwart von katalyschen Mengen an Radikalbildnern und/ oder bei Bestrahlung mit UV-Licht bei einer Temperatur zwischen etwa 50° und etwa 2500C mit Olefinen der Formel CH2=CH-(CH2)n-2-R worin n und R die vorstehend genannten Bedeutungen besitzen, umsetzt.Process for the preparation of tertiary phosphine oxides Addition to patent application P 20 40 280.6 (HOE 70 / F 150)) The main application relates to tertiary phosphine oxides of the formula in which R1 and R2 are alkyl groups with 1 to 12 carbon atoms, n is a number from 2 to 4 and R is the groups of the formula -OR3 and -NR4R5, where R3 is a lower alkyl group, a lower alkanoyl group or the carbamoyl group and, moreover, if n is 3 or 4 denotes, denotes a hydrogen atom, R4 denotes a hydrogen atom or a lower alkyl group, a lower alkanoyl group or a lower carboalkoxy group and R5 denotes a hydrogen atom or a lower alkyl group, and the group of the formula -NR4R5 also denotes the group of the formula in which m denotes an integer from 2 to 5, and a process for their preparation, which is characterized in that dialkylphosphine oxides of the general formula in which R1 and R2 have the aforementioned meanings, in the presence of catalytic amounts of radical formers and / or upon irradiation with UV light at a temperature between about 50 ° and about 2500C with olefins of the formula CH2 = CH- (CH2) n-2 -R in which n and R have the meanings given above.
In weiterer Ausgestaltung dieser Erfindung wurde nun gefunden, daß man tertiäre Phosphinoxyde der Formel in welcher R1 und R2 die vorstehend genannten Bedeutungen haben und Y eine niedere Alkylgruppe und Z eie niedere Bydroxyalkyl-, eine niedere Alkoxyalkyl- oder eine niedere Acyloxyalkylgruppe bedeutet oder eine Gruppe der Formel OR6, in welcher R6 eine niedere Alkylgruppe oder eine niedere Alkanoylgruppe bedeutet, erhalten kann, wenn man nach den Verfahren der Hauptanmeldung Olefine der Formel in welcher Yund Z die vorstehend genannten Bedeutungen haben, einsetzt.In a further embodiment of this invention, it has now been found that tertiary phosphine oxides of the formula in which R1 and R2 have the meanings given above and Y is a lower alkyl group and Z is a lower hydroxyalkyl, a lower alkoxyalkyl or a lower acyloxyalkyl group or a group of the formula OR6 in which R6 is a lower alkyl group or a lower alkanoyl group, can be obtained if, according to the process of the main application, olefins of the formula in which Y and Z have the meanings given above, is used.
R1 und R2 bedeuten Alkylgruppen, die im allgemeinen 1 bis 12 C-Atome, vorzugsweise 1 bis 6, insbesondere 1 bis 4 C-Atome, enthalten.R1 and R2 denote alkyl groups, which generally have 1 to 12 carbon atoms, preferably contain 1 to 6, in particular 1 to 4, carbon atoms.
Unter niederen Alkyl-, niederen Hydroxyalkyl-, niederen Alkoxy-, niederen Alkoxyalkyl- und niederen Alkanoyl-bzw. Acyloxy-Gruppen sind solche zu verstehem die jeweils in den aliphatischen Ketten 1 bis 4 C-Aton.e aufweisen.Among lower alkyl, lower hydroxyalkyl, lower alkoxy, lower Alkoxyalkyl and lower alkanoyl or. Acyloxy groups are to be understood as such each of which has 1 to 4 carbon atoms in the aliphatic chains.
Für die Umsetzung verwendbare Olefine sind demzufolge beispielswiese 2-Methyl-2-propen-1ol, 2-Äthyl-2-propen-1-ol, 2-Propyl-2-propen-1-ol, 2-Butyl-2-propen-1-ol, 3-Methyl-3-buten-1-ol und die entsprechenden 3-Äthyl-, 3-Propyl- und 3-Butyl-3-buten-1-ole oder das 5-Methyl-5-hexen-1-ol, ferner Essigsäureisopropenylester, Propionsäure-isopropenylester, Buttersäure-3-methyl-3-butenylester, ferner 1-Methoxy- bzw. 1-Äthoxy- oder 1-Butoxy-2-methylpropen-2.Olefins which can be used for the reaction are accordingly, for example 2-methyl-2-propen-1ol, 2-ethyl-2-propen-1-ol, 2-propyl-2-propen-1-ol, 2-butyl-2-propen-1-ol, 3-methyl-3-buten-1-ol and the corresponding 3-ethyl, 3-propyl and 3-butyl-3-buten-1-ols or 5-methyl-5-hexen-1-ol, also isopropenyl acetate, isopropenyl propionate, Butyric acid 3-methyl-3-butenyl ester, furthermore 1-methoxy- or 1-ethoxy- or 1-butoxy-2-methylpropen-2.
Bevorzugt werden solche Olefine der Formel II eingesetzt, in denen Y eine Methylgruppe und Z eine Hydroxymethyl-, eine Methoxy-, Äthoxy- oder eine Acetoxy-Gruppe ist.Preference is given to using those olefins of the formula II in which Y is a methyl group and Z is a hydroxymethyl, a methoxy, ethoxy or a Is acetoxy group.
Die Verfahrensbedingungen und die Verwendungsmöglichkeiten für die neuen Produkte entsprechen denen der Hauptanmeldung.The process conditions and the possible uses for the new products correspond to those of the main application.
Beispiel 1 161 g Dimetylphosphinoxyd werden unter Stickstoffatomphäre auf 120°C erhitzt und dazu 147 g 2-Methyl-2-propen-1-ol, vermischt mit 3 g Azobisisobutyronitril, nährend 2,5 Stunden bei dieser Temperatur, die bis 1300C ansteigen kann, unter lebhaftem Rühren eingetropft. Anschließend wird 1 Stunde nachgerUhrt und destillier'. Man erhält 270 g 3-Dinethylphosphinyl-2-methyl-propanol-1, Kp0,3: 130°C.Example 1 161 g of dimethylphosphine oxide are added under a nitrogen atom heated to 120 ° C and added 147 g of 2-methyl-2-propen-1-ol, mixed with 3 g of azobisisobutyronitrile, about 2.5 hours at this temperature, which can rise to 1300C, under brisk Stir added dropwise. The mixture is then stirred and distilled for 1 hour. Man receives 270 g of 3-dinethylphosphinyl-2-methyl-propanol-1, boiling point 0.3: 130 ° C.
Das Entspricht einer Ausbeute von 88 s der Theorie ber.: 48,0 % C; 10,00 S H; 20,7 % P gef.: 118,0 % C; 10,05 » H; 20,4 SP Beispiel 2 200 g Dinethylphosphinoxyd werden unter Stickstoffatmosphäre auf 120°C erhitzt und dazu 256 g Essigsäureisopropenylester, vermischt mit 3,5 g Azobisisobutyronitril, während 3 Stunden bei dieser Temperatur unter lebhaften RUhren eingetropft.This corresponds to a theoretical yield of 88 s calc .: 48.0% C; 10.00 SH; 20.7% P found: 118.0% C; 10.05 »H; 20.4 SP Example 2 200 g of dimethylphosphine oxide are heated to 120 ° C. under a nitrogen atmosphere and 256 g of isopropenyl acetate, mixed with 3.5 g of azobisisobutyronitrile, are added dropwise over 3 hours at this temperature with vigorous stirring.
Anschließend wird destilliert. Man erhält 420 g 2-Dimethylphosphinylisopropylacetat, Kp0,3: 110°C Das entspricht einer Ausbeute von 92 % d. Th. It is then distilled. 420 g of 2-dimethylphosphinylisopropyl acetate are obtained, boiling point 0.3: 110 ° C. This corresponds to a yield of 92% of theory. Th.
ber.: 47,2 % C; 8,43 % H; 17,4 % P gef.: 47,1 % C; 8,51 % II; 17,2 I Pcalc .: 47.2% C; 8.43% H; 17.4% P found: 47.1% C; 8.51% II; 17.2 I P
Claims (2)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2133795A DE2133795A1 (en) | 1971-07-07 | 1971-07-07 | Tertiary phosphine oxides - as insecticides fungicides - flame retardants and corrosion inhibitors |
| NL7110875A NL7110875A (en) | 1970-08-13 | 1971-08-06 | |
| IT27445/71A IT945930B (en) | 1970-08-13 | 1971-08-11 | PROCESS FOR THE PREPARATION OF TERTIARY PHOSPHINOXIDES |
| CA120,375A CA944349A (en) | 1970-08-13 | 1971-08-12 | Process for the preparation of tertiary phosphine oxides |
| FR7129708A FR2104344A5 (en) | 1970-08-13 | 1971-08-13 | |
| GB3823171A GB1356180A (en) | 1970-08-13 | 1971-08-13 | Tertiary phosphine oxides and a process for their preparation |
| BE771302A BE771302A (en) | 1970-08-13 | 1971-08-13 | Tertiary phosphine oxides - as insecticides fungicides - flame retardants and corrosion inhibitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2133795A DE2133795A1 (en) | 1971-07-07 | 1971-07-07 | Tertiary phosphine oxides - as insecticides fungicides - flame retardants and corrosion inhibitors |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2133795A1 true DE2133795A1 (en) | 1973-01-25 |
Family
ID=5812936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2133795A Pending DE2133795A1 (en) | 1970-08-13 | 1971-07-07 | Tertiary phosphine oxides - as insecticides fungicides - flame retardants and corrosion inhibitors |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2133795A1 (en) |
-
1971
- 1971-07-07 DE DE2133795A patent/DE2133795A1/en active Pending
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OHN | Withdrawal |