DE1155431B - Process for the production of phosphorus compounds - Google Patents
Process for the production of phosphorus compoundsInfo
- Publication number
- DE1155431B DE1155431B DEF33599A DEF0033599A DE1155431B DE 1155431 B DE1155431 B DE 1155431B DE F33599 A DEF33599 A DE F33599A DE F0033599 A DEF0033599 A DE F0033599A DE 1155431 B DE1155431 B DE 1155431B
- Authority
- DE
- Germany
- Prior art keywords
- phosphorus compounds
- phosphorus
- reaction
- parts
- stand
- 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
- 150000003018 phosphorus compounds Chemical class 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 4
- 125000006414 CCl Chemical group ClC* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical class CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 claims 1
- 229910001413 alkali metal ion Inorganic materials 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 8
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical class NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- KGXGPHUJJBHGDL-UHFFFAOYSA-N n,n-bis(chloromethyl)carbamoyl chloride Chemical compound ClCN(CCl)C(Cl)=O KGXGPHUJJBHGDL-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 241001124076 Aphididae Species 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 241001454295 Tetranychidae Species 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003151 ovacidal effect Effects 0.000 description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241000255581 Drosophila <fruit fly, genus> Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3294—Compounds containing the structure R2P(=X)-X-acyl, R2P(=X)-X-heteroatom, R2P(=X)-X-CN (X = O, S, Se)
-
- 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
- C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
- C07F9/096—Compounds containing the structure P(=O)-O-C(=X)- (X = O, S, Se)
-
- 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
- C07F9/1654—Compounds containing the structure P(=X)n-X-acyl, P(=X)n-X-heteroatom, P(=X)n-X-CN (X = O, S, Se; n = 0, 1)
- C07F9/1656—Compounds containing the structure P(=X)n-X-C(=X)- (X = O, S, Se; n = 0, 1)
-
- 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
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2433—Compounds containing the structure N-P(=X)n-X-acyl, N-P(=X)n-X-heteroatom, N-P(=X)n-X-CN (X = O, S, Se; n = 0, 1)
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/307—Acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
-
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
- C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (X = O, S, Se)
-
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
- C07F9/4093—Compounds containing the structure P(=X)-X-C(=X)- (X = O, S, Se)
-
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
F 33599 IVb/12 οF 33599 IVb / 12 ο
BEKANNTMACHUNG DER ANMELDUNG UNDAUSGABEDER AUSLEGESCHRIFT: 10. OKTOBER 1963NOTICE THE REGISTRATION ANDOUTPUTE EDITORIAL: OCTOBER 10, 1963
Gegenstand der Erfindung ist ein Verfahren zur Herstellung neuartiger Phosphorverbindungen der allgemeinen Formel IThe invention relates to a process for the production of novel phosphorus compounds general formula I.
X'X '
X"—C —X O (S)OX "- C - X O (S) O
N C-S71-PN CS 71 -P
Xi"-C-X1 Xi'Xi "-CX 1 Xi '
-Ri
R2 -Ri
R 2
in welcher η 0 oder 1 ist, X, X', X", X1, X1', X1" für Halogen oder die Gruppein which η is 0 or 1, X, X ', X ", X 1 , X 1 ', X 1 " represent halogen or the group
(S)O
Sn P(SO
S n P
RiRi
R2 R 2
Verfahren zur Herstellung von
PhosphorverbindungenProcess for the production of
Phosphorus compounds
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft,
LeverkusenPaint factories Bayer Aktiengesellschaft,
Leverkusen
Dr. Hugo Malz, Leverkusen,Dr. Hugo Malz, Leverkusen,
Dr. Günter Oertel, Köln-Flittard,Dr. Günter Oertel, Cologne-Flittard,
und Dr. Hans Holtschmit, Köln-Stammheim,and Dr. Hans Holtschmit, Cologne-Stammheim,
sind als Erfinder genannt wordenhave been named as inventors
stehen, X, X', Xi, Xi' außerdem jedoch auch fur H stehen können und Ri, R2 gleiche oder verschiedene, eventuell substituierte Kohlenwasserstoffreste, die auch über O-, S- oder N-Atome mit dem Phosphoratom verbunden sein können, sein sollen.however, X, X ', Xi, Xi' also stand for H can stand and Ri, R2 are the same or different, possibly substituted hydrocarbon radicals, which also have O, S or N atoms with the phosphorus atom can be connected, should be.
Die Herstellung dieser neuen Verbindungsklasse erfolgt in an sich bekannter Weise, indem entweder thiolgruppenhaltige Phosphorverbindungen mit Carbamidsäurechloriden der allgemeinen Formel IIThis new class of compounds is produced in a manner known per se by either Phosphorus compounds containing thiol groups with carbamic acid chlorides of the general formula II
Y'
Y"—C —Y OY '
Y "- C - YO
N C-Cl IIN C-Cl II
Yi"-C-YiYi "-C-Yi
Yi'Yi '
in welcher Y, Y', Y", Yi, Yi', Yi" für Halogen oderin which Y, Y ', Y ", Yi, Yi', Yi" for halogen or
RiRi
Wasserstoff stehen sollen und wobei pro Methylgruppe mindestens ein Halogenatom vorhanden sein soll, oder aber der Arbuzov-Reaktion fähige Phosphorverbindungen mit diesen Carbamidsäurechloriden umgesetzt werden.Should be hydrogen and at least one halogen atom per methyl group or phosphorus compounds capable of the Arbuzov reaction with these carbamic acid chlorides implemented.
Als solche Verbindungen sollen im Sinne der Ausführungen von Kosolapoff, »Organo phosphorus compounds«, 1950, S. 121 bis 122 (Kapitel 7, Abschnitt IA), alle diejenigen Derivate des dreiwertigen Phosphors verstanden werden, die eine Estergruppierung —OR3 (R3 = organischer Rest) im Molekül enthalten.As such compounds, in the sense of Kosolapoff's remarks, “Organo phosphorus compounds ", 1950, pp. 121 to 122 (Chapter 7, Section IA), all those derivatives of the trivalent Phosphorus are understood to have an ester group —OR3 (R3 = organic radical) in the Molecule included.
Bei Verwendung jeweils molarer Mengen an Phosphorverbindungen und Carbamidsäurechloriden nimmt dabei die Reaktion folgenden Verlauf:When using molar amounts of phosphorus compounds and carbamic acid chlorides the reaction takes the following course:
A. II+ Me-S— PA. II + Me-S-P
■Y"■ Y "
-C-Y' O-C-Y'O
RiRi
(S)O R2 (S) OR 2
C-S-C-S-
+ MeCl+ MeCl
IIIIII
Yi"-C-YiYi "-C-Yi
Yi'
Me = Alkalimetalläquivalent bzw. NH4Yi '
Me = alkali metal equivalent or NH4
R2 R 2
309 727/297309 727/297
(S)
B. ΙΓ+R —Ο —Ρ(S)
B. ΙΓ + R —Ο —Ρ
RiRi
R = ein gegebenenfalls chlorsubstituierter niederer Alkylrest.R = an optionally chlorine-substituted lower alkyl radical.
Es ist auch möglich, die zur Anwendung gelangende Menge an Phosphorverbindungen gegenüber den Carbamidsäurechloriden über das in Gleichung A und B genannte Molverhältnis von 1 : 1 hinaus zu vergrößern. In diesem Falle gelingt es, auch die an den beiden Methylgruppen des Carbamidsäurechlorids (II) stehenden Halogenatome mit den zuvor genannten Phosphorverbindungen zur Reaktion zu bringen. Dabei erhält man Verbindungen der allgemeinen Formel I, wobei die Symbole X, X', X", Xi, Xi', Xi" für Reste der allgemeinen FormelIt is also possible to use the amount of phosphorus compounds used compared to the Carbamic acid chlorides above the molar ratio of 1: 1 given in equations A and B enlarge. In this case, the two methyl groups of the carbamic acid chloride are also successful (II) standing halogen atoms with the abovementioned phosphorus compounds to react bring. This gives compounds of the general formula I, where the symbols X, X ', X ", Xi, Xi ', Xi "for residues of the general formula
(S)O
-Sn-P(SO
-S n -P
/
V /
V.
RiRi
entsprechend der Menge der über das Molverhältnis 1 : 1 angewandten Phosphorverbindungen stehen. Es ist bereits vorgeschlagen worden, die in dieser Umsetzung zu verwendenden Carbaminsäurechloride (II) nach dem Verfahren der deutschen Patentanmeldung F 33106 IVb/12o (deutsche Auslegeschrift 1 132 118) herzustellen. Sie sind aber auch durch Halogenierung entsprechender Dialkylcarbamidsäurechloride nach bekannten Verfahren zugänglich. Da sie sehr reaktionsfreudige Verbindungen darstellen, empfiehlt es sich, die hier beschriebene Herstellung neuartiger Phosphorverbindungen in Gegenwart inerter Lösungs- oder Verdünnungsmittel vorzunehmen. Bewährt haben sich dabei insbesondere Kohlenwasserstoffe, Äther oder Ketone. Die Reaktionsfreudigkeit der Halogenatome in den Carbamidsäurechloriden (II) ist insofern unterschiedlich, als zunächst das an der Carbonylgruppe stehende Chloratom — meist sehr energisch — reagiert, bevor die an den Methylgruppen stehenden Halogenatome ausgetauscht werden. Es ist daher im allgemeinen von Vorteil, die meist stark exotherm verlaufende erste Stufe der Reaktion durch entsprechende Kühlung etwas zu mäßigen. Da der Austausch der an den Methylgruppen stehenden Halogenatome im alias gemeinen langsam abläuft, ist es in den Fällen, in denen eine solche Reaktion überhaupt erwünscht ist, ratsam, die Reaktionsgeschwindigkeit dieser zweiten Stufe durch eine entsprechende Temperaturerhöhung zu steigern.corresponding to the amount of phosphorus compounds used in a molar ratio of 1: 1. It has already been proposed that the carbamic acid chlorides to be used in this reaction (II) according to the procedure of the German patent application F 33106 IVb / 12o (German Auslegeschrift 1 132 118). However, they are also obtained by halogenation of corresponding dialkylcarbamic acid chlorides accessible by known methods. Since they are very reactive connections, it is recommended that the production of novel phosphorus compounds described here be carried out in the presence inert solvent or diluent. In particular, they have proven themselves Hydrocarbons, ethers or ketones. The reactivity of the halogen atoms in the carbamic acid chlorides (II) is different in that the first chlorine atom attached to the carbonyl group - usually very vigorously - reacts before the halogen atoms on the methyl groups are exchanged will. It is therefore generally advantageous to use the first, which is usually strongly exothermic To moderate the stage of the reaction by appropriate cooling. Since the exchange of the Halogen atoms, also known as methyl groups, runs slowly, it is in the cases in which to whom such a reaction is at all desirable, it is advisable to reduce the reaction rate of this second Level by increasing the temperature accordingly.
Die Verbindungen fallen entweder in Form farbloser bis schwach braungefärbter, nicht unzersetzt destillierbarer Öle oder in Form von Kristallen an. Sie sollen vor allem als Pflanzenschutzmittel Verwendung finden.The compounds fall either in the form of colorless to slightly brown-colored, not undecomposed distillable oils or in the form of crystals. They are primarily intended to be used as pesticides Find.
Gegenüber den aus der deutschen Patentschrift 1 096 617 bekannten analog gebauten Verbindungen zeichnen sich die Verfahrensprodukte durch eine wesentlich bessere Wirkung bei der Anwendung gegen eine Reihe von Schadinsekten aus. Diese unerwartete technische Überlegenheit geht aus den im folgenden tabellarisch zusammengestellten Ergebnissen von Vergleichsversuchen hervor:Compared to the compounds of similar construction known from German Patent 1,096,617 the process products are characterized by a significantly better effect when used against a range of insect pests. This unexpected technical superiority comes from the im the following results from comparative tests, which are compiled in a table:
VergleichsversucheComparative experiments
telarius)(Tetranychus
telarius)
Anwendung gegenApplication against
Wirkstoffkonzentration
in°/oActive ingredient concentration
in ° / o
Abtötung der SchädlingeKilling the pests
in °/o nach 24 Stunden 48 Stundenin ° / o after 24 hours 48 hours
f »f »
[(C2H5O)2P — S — CH2 —[(C 2 H 5 O) 2 P - S - CH 2 -
— 2N — C- 2 N - C
IlIl
Q 1Q 1
S — P(OC2Hs)2
(erfindungsgemäß)
(CHa)2CHO SS - P (OC 2 Hs) 2
(according to the invention)
(CHa) 2 CHO S
P-S-CH2-CH2-S-C-NH2
(CHa)2CHO OPS-CH 2 -CH 2 -SC-NH 2
(CHa) 2 CHO O
(bekannt aus(known from
deutscher Auslegeschrift 1 096 671)German interpretation document 1 096 671)
FliegenTo fly
Blattläuse SpinnmilbenAphids spider mites
FliegenTo fly
BlattläuseAphids
Spinnmilben 0,1
0,01Spider mites 0.1
0.01
0,1
0,01
0,1
0,010.1
0.01
0.1
0.01
0,1
0,1
0,10.1
0.1
0.1
100
100100
100
100
50100
50
100 60 (ovizide Wirkung)100 60 (ovicidal effect)
0 00 0
3030th
eine ovizide Wirkung)an ovicidal effect)
(Cl — CHa)2N — C — S — P(OC2Hs)2 (Cl - CHa) 2 N - C - S - P (OC 2 Hs) 2
O SO S
In eine Lösung von 17,65 g Bis-chlormethylcarbamidsäurechlorid in 100 ml Aceton wird eine Lösung von 22,4 g 0,0-diäthylthioltüionophosphorsaurem Kalium in 100 ml Aceton unter Rühren eingetropft. In exothermer Reaktion trübt sich die zunächst klare Lösung unter Abscheidung von KCl alsbald. Man läßt sie noch etwa 1^ Stunde bei etwa 300C nachrühren und saugt dann das abgeschiedene KCl auf der Nutsche ab. Das hellgelbe Filtrat wird im Vakuum eingedampft. Das dabei zurückbleibende ölige Produkt wird in Äther aufgenommen und zweimal mit Wasser gewaschen. Nach Trocknen über Natriumsulfat dampft man das Lösungsmittel ab und erhält 31 g eines hellgelben klaren Ols, das sich nicht unzersetzt destillieren läßt.In a solution of 17.65 g of bis-chloromethylcarbamic acid chloride in 100 ml of acetone, a solution of 22.4 g of 0.0-diethylthioltionophosphoric acid potassium in 100 ml of acetone is added dropwise with stirring. In an exothermic reaction, the initially clear solution soon becomes cloudy with the separation of KCl. It is left for about 1 hour at about 30 ^ 0 C. for and then sucks the deposited KCl on the suction filter. The light yellow filtrate is evaporated in vacuo. The oily product that remains is taken up in ether and washed twice with water. After drying over sodium sulfate, the solvent is evaporated off and 31 g of a pale yellow clear oil which cannot be distilled without decomposition are obtained.
C7Hi4O3NPS2Cl2:
BerechnetC 7 Hi 4 O 3 NPS 2 Cl 2 :
Calculated
C 25,8, H 4,3, N 4,3, P 9,5, S 19,6, Cl 21,8%;
gefundenC 25.8, H 4.3, N 4.3, P 9.5, S 19.6, Cl 21.8%;
found
C 26,0, H 4,4, N 4,5, P 9,3, S 19,1, Cl 21,8%.C 26.0, H 4.4, N 4.5, P 9.3, S 19.1, Cl 21.8%.
Beispiel 2
(C2H5O)2P-S-CH2-In-C-S-P(OC2Hs)2 Example 2
(C 2 H 5 O) 2 PS-CH 2 -In-CSP (OC 2 Hs) 2
S J2 O SSJ 2 OS
In eine Lösung von 33,6 g 0,0-diäthylthiolthionophosphorsaurem Kalium in 150 ml Aceton läßt man unter Rühren eine Lösung von 8,8 g Bis-chlormethylcarbamidsäurechlorid in 50 ml Aceton eintropfen. Nach Abklingen der zunächst kräftig exothermen Reaktion erhitzt man unter Rühren noch etwa 1Ii Stunde lang zum Sieden und saugt anschließend bei Raumtemperatur das ausgefallene KCl auf einer Nutsche ab. Das hellgelbe Filtrat wird im Vakuum eingedampft, worauf man den öligen Rückstand in Äther aufnimmt und zweimal mit Wasser wäscht. Nach Trocknen über Natriumsulfat und Verdampfen des Äthers erhält man 29 g eines hellgelben Öls.A solution of 8.8 g of bis-chloromethylcarbamic acid chloride in 50 ml of acetone is added dropwise with stirring to a solution of 33.6 g of potassium 0,0-diethylthiolthionophosphoric acid in 150 ml of acetone. After decay of the initially strongly exothermic reaction is heated with stirring for about 1 hour Ii to boiling and then the precipitated KCl filtered off with suction at room temperature. The light yellow filtrate is evaporated in vacuo, whereupon the oily residue is taken up in ether and washed twice with water. After drying over sodium sulfate and evaporation of the ether, 29 g of a light yellow oil are obtained.
Ci5H34O7NP3S6:Ci 5 H 34 O 7 NP 3 S 6 :
BerechnetCalculated
C 28,8, H 5,5, N 2,2, P 14,9, S 30,7%; gefunden
C 29,0, H 5,6, N 2,5, P 14,6, S 29,8%.C 28.8, H 5.5, N 2.2, P 14.9, S 30.7%; found
C 29.0, H 5.6, N 2.5, P 14.6, S 29.8%.
Beispiel 3 (ClCHa)2N — C — S — P(OCH3)2 Example 3 (ClCHa) 2 N - C - S - P (OCH 3 ) 2
O SO S
In der im Beispiel 1 beschriebenen Weise setzt man äquimolare Mengen von Bis-chlormethylcarbamidsäurechlorid
und 0,0-dimethylthiolthionophosphorsaurem
Kalium in Aceton als Lösungsmittel um und erhält in über 90%iger Ausbeute ein gelbes, nicht unzersetzt
destillierbares Öl.
C5HIoO3NPS2CI2:In the manner described in Example 1, equimolar amounts of bis-chloromethylcarbamic acid chloride and potassium 0,0-dimethylthiolthionophosphoric acid are reacted in acetone as solvent and a yellow oil which cannot be distilled without decomposition is obtained in over 90% yield.
C 5 HIoO 3 NPS 2 CI 2 :
Berechnet ... N 4,7, P 10,4, S 21,5, Cl 23,8%; gefunden ... N 4,8, P 11,0, S 21,8, Cl 22,6%.Calculated ... N 4.7, P 10.4, S 21.5, Cl 23.8%; found ... N 4.8, P 11.0, S 21.8, Cl 22.6%.
Cl2CHCl 2 CH
Cl3CCl 3 C
N-C-S-P(OC2Hs)2 O SNCSP (OC 2 Hs) 2 OS
In 28 g eines durch Chlorierung von Bis-chlormethylcarbamidsäurechlorid hergestellten Pentachlor-In 28 g of one obtained by chlorinating bis-chloromethylcarbamic acid chloride manufactured pentachlor
dimethylcarbamidsäurechlorids vom Kp.12 100 bis 105° C — in 150 ml Aceton gelöst — wird unter
Rühren eine Lösung von 22,4 g Ο,Ο-diäthylthiolthionophosphorsaurem
Kalium in 100 ml Aceton eingetropft. In kräftig exothermer Reaktion färbt sich dabei die zunächst klare Lösung unter Abscheidung
von KCl gelb. Anschließend erhitzt man kurze Zeit (10 Minuten) zum Sieden und saugt bei
Raumtemperatur das abgeschiedene KCl ab. Beim Eindampfen im Vakuum erhält man einen schmierigen
Rückstand, der in warmem Äther aufgenommen wird. Beim Kühlen der Ätherlösung mit CO2 fallen farblose
Kristalle aus. Nach Absaugen werden diese Kristalle auf Ton getrocknet. Dabei erhält man farblose,
schwach rosa schimmernde Kristalle mit einem Schmelzpunkt von 1020C. Ausbeute etwa 70% der
Theorie.
C7HIiO3NPS2CI5:dimethylcarbamidsäurechlorids from bp 12 100 to 105 ° C - dissolved in 150 ml of acetone - a solution of 22.4 g of Ο, Ο-diethylthiolthionophosphorsaurem potassium in 100 ml of acetone is added dropwise with stirring. In a strong exothermic reaction, the initially clear solution turns yellow with the separation of KCl. The mixture is then heated to boiling for a short time (10 minutes) and the KCl which has separated out is filtered off with suction at room temperature. Evaporation in vacuo leaves a greasy residue which is taken up in warm ether. When the ether solution is cooled with CO2, colorless crystals precipitate. After suction these crystals are dried on clay. This gives colorless, pale pink shimmering crystals with a melting point of 102 ° C. Yield about 70% of theory.
C 7 HIiO 3 NPS 2 CI 5 :
BerechnetCalculated
C 19,6, H 2,6, N 3,3, P 7,2, S 14,9, Cl 41,3%;C 19.6, H 2.6, N 3.3, P 7.2, S 14.9, Cl 41.3%;
gefunden
C 19,7, H 2,6, N 3,5, P 7,5, S 15,1, Cl 41,2%.found
C 19.7, H 2.6, N 3.5, P 7.5, S 15.1, Cl 41.2%.
KC2H5O)2P-S-CH2-KC 2 H 5 O) 2 PS-CH 2 -
N-C-S-P(OC2Hs)2 NCSP (OC 2 Hs) 2
In eine Lösung von 28,1 g 0,0-diäthylthiolphosphorsaurem Ammonium in 150 ml Aceton läßt man unter Rühren eine Lösung von 8,8 g Bis-chlormethylcarbamidsäurechlorid in 50 ml Aceton eintropfen und arbeitet nach etwa Vastündigem Erhitzen zum Sieden — wie im Beispiel 2 beschrieben — auf. Dabei erhält man in etwa 85%iger Ausbeute ein goldgelbes klares Öl.In a solution of 28.1 g of 0,0-diethylthiolphosphorsaurem Ammonium in 150 ml of acetone is allowed to stir a solution of 8.8 g of bis-chloromethylcarbamic acid chloride Drip in 50 ml of acetone and works after heating to boiling for about an hour - as described in example 2 - on. A clear golden yellow is obtained in about 85% yield Oil.
Ci5H34OiONP3S3:
BerechnetCi 5 H 34 OiONP 3 S 3 :
Calculated
C 31,2, H 5,9, N 2,4, P 16,2, S 16,7%; gefunden
C 30,9, H 5,9, N 2,6, P 15,9, S 15,9%.C 31.2, H 5.9, N 2.4, P 16.2, S 16.7%; found
C 30.9, H 5.9, N 2.6, P 15.9, S 15.9%.
C1CH2C1CH2
C1CH2C1CH2
Beispiel 6 OExample 6 O
IlIl
N — CO- P( — OCHa)2 N - CO- P (- OCHa) 2
Zu 35,5 Teilen Di-(chlormethyl)-carbamidsäurechlorid werden bei 30 bis 400C unter Kühlung 24,8 Teile Trimethylphosphit getropft. Es erfolgt eine heftige Reaktion unter Abspaltung von Methylchlorid. Nach dem Abklingen der Wärmetönung wird das Reaktionsgemisch 30 Minuten auf 500C und dann 15 Minuten auf 1000C erhitzt. Durch kurzes Anlegen von Vakuum bei 100 0C werden flüchtige Bestandteile aus dem Reaktionsprodukt abdestilliert. Im Rückstand verbleiben 48 Teile (96% der Theorie) des gewünschten Esters in Form eines gelben Öls, welches nicht ohne Zersotzung destilliert werden kann.35.5 parts of di (chloromethyl) -carbamidsäurechlorid 24.8 parts of trimethyl phosphite are added dropwise at 30 to 40 0 C under cooling. A vigorous reaction takes place with elimination of methyl chloride. After the heat development has subsided, the reaction mixture is heated to 50 ° C. for 30 minutes and then to 100 ° C. for 15 minutes. By briefly applying a vacuum at 100 ° C., volatile constituents are distilled off from the reaction product. 48 parts (96% of theory) of the desired ester remain in the residue in the form of a yellow oil which cannot be distilled without disintegration.
Analyse (Molgewicht 250):Analysis (molecular weight 250):
Berechnet ... C 24,0, H 4,0,' N 5,6, P 12,4%; gefunden ... C 23,8, H 3,99, N 5,9, P 11,4%.Calculated ... C 24.0, H 4.0, 'N 5.6, P 12.4%; Found ... C 23.8, H 3.99, N 5.9, P 11.4%.
ClCH2 OClCH 2 O
N — CO — P( — OC2H5>2N - CO - P (- OC 2 H5> 2
CICH2CICH2
17,7 Teile DHchlormethyO-carbamidsäurechlorid werden mit 16,6 Teilen Triäthylphosphit in der im Beispiel 6 beschriebenen Weise umgesetzt. Das Reaktionsprodukt ist ein klares, hellgelbes öl und wird in theoretischer Ausbeute (27,8 Teile) erhalten.17.7 parts of DHchloromethyl O-carbamic acid chloride are reacted in the manner described in Example 6 with 16.6 parts of triethyl phosphite. The reaction product is a clear, light yellow oil and is obtained in theoretical yield (27.8 parts).
Analyse (Molgewicht 278):Analysis (molecular weight 278):
Berechnet ... C 30,2, H 5,0, N 5,0, P 11,3%; gefunden ... C 30,9, H 4,97, N 5,5, P 10,5%.Calculated ... C 30.2, H 5.0, N 5.0, P 11.3%; Found ... C 30.9, H 4.97, N 5.5, P 10.5%.
Beispiel 8 CICH2 OExample 8 CICH2 O
\ Il\ Il
N — CO — P( — OCH2CH2Cl)2 ClCH2 N - CO - P (- OCH 2 CH 2 Cl) 2 ClCH 2
Zu 17,7 Teilen Di-(chlormethyl)-carbamidsäurechlorid werden bei 6O0C 27 Teile Tri-(chloräthyl)-phosphit getropft. Nach dem Abklingen der exothermen Reaktion wird die Mischung 2 Stunden auf 9O0C erwärmt. Das als Nebenprodukt gebildete Dichloräthan wird anschließend bei 1000C im Vakuum abdestilliert. Im Rückstand bleiben 34,5 Teile des gewünschten Esters in Form eines hellgelben Öls.To 17.7 parts of di (chloromethyl) -carbamidsäurechlorid be at 6O 0 C, 27 parts of tri (chloroethyl) phosphite dropwise. After the exothermic reaction, the mixture is heated for 2 hours at 9O 0 C. The dichloroethane formed as a by-product is subsequently distilled off at 100 0 C in vacuo. 34.5 parts of the desired ester remain in the residue in the form of a pale yellow oil.
4040
4545
(C2H5O-J2P-CH2 O(C 2 H 5 OJ 2 P-CH 2 O
N — CO — P(— OC2Hs)2
(C2H5O-)2P —CH2
ON - CO - P (- OC 2 Hs) 2 (C 2 H 5 O-) 2 P -CH 2
O
17,7 Teile Di-(chlormethyl)-carbamidsäurechlorid werden bei 6O0C unter Kühlung mit 70 Teilen Triäthylphosphit vermischt. Die Mischung wird nach dem Abklingen der exothermen Reaktion auf 1000C erhitzt, bis kein Äthylchlorid mehr entweicht. Danach wird im Vakuum bei 1000C das überschüssige Triäthylphosphit abdestilliert. Im Rückstand bleiben 48 Teile (100% der Theorie) des gewünschten Esters in Form eines farblosen Öls.17.7 parts of di (chloromethyl) -carbamidsäurechlorid triethyl phosphite are mixed at 6O 0 C under cooling with 70 parts. The mixture is heated to 100 0 C by the exothermic reaction until no more ethyl chloride escapes. Thereafter, the excess triethyl phosphite is distilled off at 100 ° C. in vacuo. 48 parts (100% of theory) of the desired ester remain in the residue in the form of a colorless oil.
Claims (1)
X'common formula
X '
C-ClYO
C-Cl
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE613266D BE613266A (en) | 1961-04-05 | ||
NL274266D NL274266A (en) | 1961-04-05 | ||
DEF33106A DE1132118B (en) | 1961-02-01 | 1961-02-01 | Process for the preparation of bis (chloromethyl) carbamic acid chloride |
DEF33599A DE1155431B (en) | 1961-04-05 | 1961-04-05 | Process for the production of phosphorus compounds |
US168252A US3234305A (en) | 1961-02-01 | 1962-01-23 | Thiophosphorus acid esters |
DK45662A DK103001C (en) | 1961-04-05 | 1962-01-31 | Agent for controlling harmful organisms and method for producing the phosphorus compounds contained therein. |
FR886554A FR1316042A (en) | 1961-04-05 | 1962-01-31 | New phosphorus compounds and their preparation process |
GB364762A GB948581A (en) | 1961-04-05 | 1962-01-31 | New nitrogen-containing organo-phosphorus compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF33599A DE1155431B (en) | 1961-04-05 | 1961-04-05 | Process for the production of phosphorus compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1155431B true DE1155431B (en) | 1963-10-10 |
Family
ID=7095163
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEF33599A Pending DE1155431B (en) | 1961-02-01 | 1961-04-05 | Process for the production of phosphorus compounds |
Country Status (5)
Country | Link |
---|---|
BE (1) | BE613266A (en) |
DE (1) | DE1155431B (en) |
DK (1) | DK103001C (en) |
GB (1) | GB948581A (en) |
NL (1) | NL274266A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1096671B (en) * | 1957-05-10 | 1961-01-05 | Bayer Ag | Pest repellants |
-
0
- BE BE613266D patent/BE613266A/xx unknown
- NL NL274266D patent/NL274266A/xx unknown
-
1961
- 1961-04-05 DE DEF33599A patent/DE1155431B/en active Pending
-
1962
- 1962-01-31 DK DK45662A patent/DK103001C/en active
- 1962-01-31 GB GB364762A patent/GB948581A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1096671B (en) * | 1957-05-10 | 1961-01-05 | Bayer Ag | Pest repellants |
Also Published As
Publication number | Publication date |
---|---|
BE613266A (en) | |
NL274266A (en) | |
DK103001C (en) | 1965-11-01 |
GB948581A (en) | 1964-02-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE917668C (en) | Process for the preparation of neutral esters of dithiophosphoric acid | |
DE1134372B (en) | Process for the production of phosphine or. Thionophosphinic acid esters | |
DE814294C (en) | Process for the preparation of insecticidal phosphorus compounds | |
DE1155431B (en) | Process for the production of phosphorus compounds | |
DE1768399C3 (en) | O-alkyl-O-aryl-thiol-phosphoric acid esters, processes for their preparation and insecticidal and acaricidal agents containing these compounds | |
DE1183494B (en) | Process for the production of phosphorus, phosphonic or thionophosphorus, -phosphonic acid esters | |
DE1223381B (en) | Process for the preparation of amidido (thio) phosphorus (- phosphonous) - acid esters | |
DE1206425B (en) | Process for the production of phosphoric acid esters | |
DE1150972B (en) | Process for the production of thio- or dithiophosphorus - (- one, -in) acid esters | |
DE1136328B (en) | Process for the production of dithiolphosphoric acid esters | |
DE2031750C3 (en) | Benzisoxazolo (thiono) phosphorus (phosphonic) acid esters, process for their preparation and their use | |
DE1153746B (en) | Process for the preparation of thiophosphorus - (- phosphon, -phosphine) - or dithiophosphorus - (- phosphon, -phosphine) acid esters | |
DE1137012B (en) | Process for the production of phosphonic or thionophosphonic acid esters | |
DE1126382B (en) | Process for the preparation of thiophosphoric acid esters | |
DE1106314B (en) | Process for the preparation of unsaturated phosphoric acid or thiophosphoric acid esters containing sulfoxyl or sulfonyl groups | |
DE1793188C3 (en) | O-alkyl-0-phenyl-thiolphosphoric acid ester, process for their preparation and compositions containing them | |
DE1518060C (en) | 0.0 dialkyl square brackets on 2- (acetamido) ethyl square brackets on dithiophosphate and process for the preparation of these compounds | |
DE1192202B (en) | Process for the production of (thiono) phosphorus (on, in) acid esters | |
DE1643706C (en) | Thinonophosphon (or) acid esters | |
DE818046C (en) | Process for the preparation of acyl compounds of dialkyl selenophosphoric acids | |
DE1106317B (en) | Process for the preparation of esters of the thioic acids of phosphorus | |
DE1443264C (en) | Thiol or thionothiolphosphorus or -phosphonic acid esters and process for their preparation | |
DE1156070B (en) | Process for the production of phosphorus, phosphonic, phosphine or thiophosphorus, phosphonic and phosphinic acid esters | |
DE1198350B (en) | Process for the production of dialkylenol phosphates of alpha-alkoxalyl lactones which are effective as pest control agents | |
DE1115738B (en) | Process for the preparation of open-chain or cyclic quinoxalino-2, 3-thiophosphoric acid esters |