IL32608A - (alkoxycarbonylpropenyl)phosphoro-(and dithiophosphoro)dichloridates(and dibromidates)and their preparation - Google Patents
(alkoxycarbonylpropenyl)phosphoro-(and dithiophosphoro)dichloridates(and dibromidates)and their preparationInfo
- Publication number
- IL32608A IL32608A IL32608A IL3260869A IL32608A IL 32608 A IL32608 A IL 32608A IL 32608 A IL32608 A IL 32608A IL 3260869 A IL3260869 A IL 3260869A IL 32608 A IL32608 A IL 32608A
- Authority
- IL
- Israel
- Prior art keywords
- signifies
- compound
- chlorine
- sulphur
- hydrogen
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 47
- 229910052801 chlorine Inorganic materials 0.000 claims description 31
- 239000000460 chlorine Substances 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal salt Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000007530 organic bases Chemical group 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 2
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 27
- 239000005864 Sulphur Substances 0.000 claims 14
- 150000002431 hydrogen Chemical class 0.000 claims 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 150000005311 thiohalides Chemical class 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 229940086542 triethylamine Drugs 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
- 239000000642 acaricide Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- 239000007966 viscous suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- JDPRRECMRPCSIF-UHFFFAOYSA-N ethyl 3-oxobutanoate;sodium Chemical compound [Na].CCOC(=O)CC(C)=O JDPRRECMRPCSIF-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HBBHCQMGWUQAGL-UHFFFAOYSA-N methyl 3-oxobutanoate;sodium Chemical compound [Na].COC(=O)CC(C)=O HBBHCQMGWUQAGL-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- OWNZHTHZRZVKSQ-UHFFFAOYSA-N tribromo(sulfanylidene)-$l^{5}-phosphane Chemical compound BrP(Br)(Br)=S OWNZHTHZRZVKSQ-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- C07F9/1403—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-unsaturated acyclic group
-
- 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
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
32608/2 (Alko-sycar¾onylpropenl)phosphor© - (and dithiophosphoro) dlohloridates (and d broaidates) and their preparation SAODOa Δ.0 C$30781 Case 150-2955 IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS The present invention relates to new organic phosphorus According to our invention.we provide compounds of formula I, in which R signifies an alkyl radical of 1 to 5 carbon atoms, X signifies a hydrogen, chlorine or bromine atom, the Y's, which are the same, each signify a chlorine or bromine atom, and Z signifies an oxygen or a sulphur atom.
According to our invention we also provide a process for the production of a compound of formula I,which comprises reacting a phosphoric oxy- or thio- chloride or bromide with a compound of formula II, . CH^CO-CHXCOOR II in which X and R are as defined above, in the presence of an acid acceptor, or with a salt of a compound of formula II.
The salt of the compound of formula II is preferably an alkali metal salt. - 2 - 130-^ 55 The reaction may be carried out without solvent or in the presence of a solvent which is inert under the reaction conditions, fo example an aromatic hydrocarbon,e .g. toluene or xylene, a halogenated hydrocarbon,e.g. chloroform or trichloroethylene, or an ether, e.g. dioxane. The acid acceptor may be an organic base, for example tri-ethylamine, or an inorganic base, for example sodium bicarbonate. The reaction may be carried out at a temperature of about -10° to +50°C, preferably at -10°C to room temperature. When a salt of a compound of formula II is used in place of the compound of formula II, it is no necessary to use an acid acceptor. It is preferred to use substantial equimolar proportions of the phosphorus halide, of the compound of formula II or of the salt of the compound of formula II and, if an acid acceptor is used, of the acid acceptor. The reaction is preferably carried out by stirring the reaction mixture for about half an hour at a temperature between -10° and +50°C, preferably at -10° to -+1 and then for about 15 minutes at room temperature. The reaction mixtu is then washed, optionally after the addition of a solvent when the reaction is effected without solvent, and, after drying, the solvent i removed at a bath temperature of about 20° to 50°C in a vacuum. The liquid residue may be distilled in a high vacuum to obtain the pure compound of formula I as an oil.
The compounds of formula I obtained in accordance with the process of the invention. predominantly have a cis configuration in the crotonic acid radical (i.e. the -CH^ group is cis to the -C00R group) when an organic base, e.g. triethylamine, is used as acid acceptor. When, .for example, sodium bicarbonate is used as acid · acceptor, the portion of cis configuration in the crotonic - 3 - 130-2955 acid radical of the compound of formula I is smaller than when triethyl-amine is used. When, for example, a sodium acetoacetic acid ester is used in place of the acetoacetic ester of formula II and an acid acceptor, then compounds of formula I predominantly having the trans form in the crotonic acid radical- are obtained. The stereoisomeric composition of the compounds of formula I may be determined in conventional manner by the nuclear magnetic resonance spectrum.
The compounds of formula I obtained in accordance with the process of the invention may be used as intermediates for the produc-tion of biocides , e.g. insecticides and acaricides. For example, the compounds of formula I react with a corresponding amount of an alkanol having 1 to 5 carbon atoms, in the presence of an acid acceptor to yield compounds on which both the halogen atoms Y on the phosphorus atom have been exchanged for alkoxy radicals. The halogen atoms Y on the phosphorus atom may also be exchanged for two different alkoxy radicals in two separate stages. In the first stage about 1 mol of an alkanol having, for example, 1 to carbon atoms, is reacted with a compound of formula I in the presence of, a preferably equimolar amount of, an acid acceptor and the resulting compound is then reacted in the second stage with about 1 mol of a different alkanol having, for example, 1 to 5 carbon atoms, again in the presence of, a preferably equivalent amount of, an acid acceptor. Alternatively both the halogen atoms Y of the compounds of formula I may be exchanged for amino radicals by reacting a compound of formula I with 2 mols of an amine, e.g. methylamine, dimethylamine or diethylamine, in the presence of an acid acceptor. It is also possible to exchange one halogen atom - 4 - 15^2955 Y for an alkoxy radical and to exchange the second halogen atom Y for an amino radical by a two stage reaction similar to that described above. In the first stage 1 mol of an alcohol and an acid acceptor are added to the compound of formula I, and in the second stage 1 mol of an amine and an acid acceptor are added to the reaction product of the first step. - By. the processes, described immediately above it is possible to obtain biocides., e.g. insecticides and acaricides.
The invention is illustrated, but in no way limited by the following Examples in which the temperatures are in degrees centigrade. - 5 - 130-2955 Γ EXAMPLE 1: 0- (1- Ethoxycarbonyl-l-propen-2-yl) phosphorodichloridate 130 g (l mol) of acetoacetic acid ethyl ester and 101 g (1 mol) of triethylamine are added over a period of half an hour to 1 g (1 mol) of phosphorus oxychloride in 500 cc of toluene with stirring and at a temperature of -10°, whereby triethylamine hydrochloride precipitates. The reaction mixture is subsequently stirred for a further half hour at a temperature between -10° and +10° and then for 15 minutes at 20°. The resulting precipitate is subsequently filtered off and the solvent in the filtrate is removed at a bath tem- 10 perature of 50° in a water jet vacuum to yield crude 0-(l-ethoxycarbonyl l-propen-2-yl) phosphorodichloridate. The pure compound has a B.P. of 77-78%).15 mm of Hg and has a refractive index of nJ) = 1.4700.
I Analysis: Molecular weight; 247.01 Found: C 29.8 H 3-7 CI 29. $ Calc: 29.2 3.7 28.75* Example 2: 0- (l-Ethoxycarbonyl-l-propen-2-yl) phosphorodichloridate II.5 g of sodium metal are pulverized in 1.2 liters of toluene at about 110° with a vibro mixer. 65 g of acetoacetic acid ethyl ester are then added dropwise to the sodium suspension at 20-40°. - 6 - "130-2955 After the reaction is completed the viscous suspension of sodium acetoacetic acid ethyl ester is addeddropwise to a solution of 77 g of phosphorus oxychloride in 100 cc of toluene at 10-20° . The reaction mixture is subsequently stirred at room temperature for half an hour and the toluene is then distilled off in a vacuum. The residue is taken up in ether, the precipitated sodium chloride is filtered off and the filtrate concentrated by evaporation. The resulting pure compound has a B.P. of 48-50°/] mm of Hg. It consists almost exclusively of 0- (l-ethoxycarbonyl-l-propen-2-yl) phosphorodichloridate having the trans form in the crotonic acid radical.
EXAMPLE 3 : 0- (l-Methoxycarbonyl-l-propen-2-yl) thiophosphorodichloridate 50.5 g (0.5 mols) of triethylamine are added with stirring over a period of 30 minutes and at a temperature of 10° to a mixture of 84.5 g (0.5 mols) of phosphorus thiochloride and 58 g (0.5 mols) of acetoacetic acid methyl ester, whereby triethylamine hydrochloride precipitates. The reaction mixture is subsequently stirred for a further half hour at a temperature between -10° and +10°, and then for 1 minutes at 20° . 250 cc of chloroform are then added to the reaction mixture, the mixture is washed, dried and the solvent removed in a water jet vacuum at a bath temperature of 50° . Crude 0- (1-methoxy-carbonyl-l-propen-2-yl) thiophosphorodichloridate is obtained. The pure compound has a B.P of 2°/5.10 ^ mm of Hg. The relationship cis:trans isomer in the crotonic acid radical is about 9: 1 · Analysis: Molecular weight: Found: C 24.4 CI 28.4 P 12.1 S 12.8 % Calc: 24.1 28.4 12.4 12.8 # EXAMPLE 4: 0- (1-Methoxycarbonyl-l-propen-2-yl) thiophosphorodichloridate. 4.6 g of sodium metal are pulverized in 0.3 liters of toluene at about 110° with a vibro mixer. 24 g of acetoacetic acid methyl ester are added dropwise to the sodium suspension at 20-40°. After the reaction is completed the viscous suspension of sodium acetoacetic acid methyl ester is added dropwise to a solution of 34 g of phosphorus thiochloride in 100 cc of toluene while stirring at -20°. The reaction mixture is subsequently stirred at room temperature for 30 minutes, is washed with ice water and after drying with sodium- sulphate the toluene is distilled off in a vacuum. The residue is distilled yielding 0-(l-methoxycarbonyl-l-propen-2-yl) thiophosphorodichloridate having a B.P. of mm of Hg. The compound exclusively consists of the trans form in the cro.tonic acid radical.
EXAMPLE 5: 0-(l-Chloro-l-methoxycarbonyl-l-propen-2-yl) phosphorodichloridothionate. .5 g (0.3 mols) of triethylamine are added at 10° with stirring and over a period of 1 hour to a mixture of 51 g (0.3 mols) of phosphorus thiochloride and 5 g (0.3 mols) of a-chloro-acetoacetic 32608/2 · - 8 - 150-2955 acid methyl ester in 100 cc of toluene. Stirring is subsequently continued at room temperature for about half an hour. The reaction mixture is then washed twice with ice water, the toluene layer ia separated, dried with sodium sulphate and the toluene is distilled off. Crude 0-(l-chloro-l-methoxycarbonyl-l-propen-5-yl) phosphoro-dichloridothionate is obtained. The pure compound has a B.P. of mm of Hg. The relationship oisttrans isomer in the crotonic acid radical is 9: 1· Analysis: Molecular weight: 283. . » Found: C 21.2 CI 36.8 P 11.1 3-11.00 Calc: 21.2 37- 5 10.9 11.5 * In analogous manner to that described in the above Example, employing as starting materials equimolar quantities of phosphorus thiobromide and a-bromo-acetoacel * ί acid methyl ester, the compound 0-(l-bromo-l-methoxycrrbo> l-propen-2-yl)pho3phorodibromidothionate may be produce d.
The following compounds of formula I are obtain in. manner analogous to that described in Examples 1, 3 ft
Claims (32)
1. A process for the production of compounds of formula I, in which R signifies an alkyl radical of 1 to carbon atoms, X signifies a hydrogen, chlorine or bromine atom, the Y's, which are the same, each signify a chlorine or bromine atom, and Z signifies an oxygen or a sulphur atom, which comprises reacting a phosphoric oxy- or thio-chloride or bromide with a compound of formula II, CH,CO-CHXCOOR II in which X and R are as defined above, in the presence of an acid acceptor, or with a salt of a compound of formula II.
2. A process as claimed in Claim 1, wherein the salt of the compound of formula II is an alkali metal salt.
3. A process as claimed in either of Claims 1 or 2, wherein the acid acceptor is an organic base. h.
4. A process as claimed in any of the preceding Claims, wherein there are used approximately equimolar proportions of the phosphoric oxy- or thio-halide and of the compound of formula II, or the salt thereof. - 12 - 13-2955
5. A process as claimed in any of the preceding Claims, wherein the reaction is carried out at a temperature of from -10°C to +50°C.
6. A process for the production of a compound of formula. I, substantially as hereinbefore described in any one of Examples 1 to 25»
7. A compound of formula I as defined in Claim 1, whenever produced by a process claimed in any of the preceding Claims.
8. A compound of formula I as defined in Claim 1.
9. · 0- (l-Ethoxycarbonyl-l-propen-2-yl) phosphorodichloridate.
10. 0-(l-Methoxycarbonyl-l-propen-2-yl) thiophosphorodichlor-idate .
11. 0- (l-Chloro-l-methoxycarbonyl-l-propen-2-yl) phosphoro-dichloridothionate.
012. A compound as claimed in Claim 8, wherein R signifies methyl, X signifies hydrogen, Y signifies chlorine and Z signifies oxygen.
13. A compound as claimed in Claim 8, wherein R signifies isopropyl, X signifies hydrogen, Y signifies chlorine and Z signifies oxygen.
14. A compound as claimed in Claim 8, wherein R signifies tert. butyl, X signifies hydrogen, Y signifies chlorine and Z signifies oxygen . 1 .
15. A compound as claimed in Claim 8, wherein R signifies tert. pentyl, X signifies hydrogen, Y signifies chlorine and Z signifies oxygen. - 15 - 13-2955
16. A compound as claimed in Claim 8, wherein R signifies ethyl, X signifies chlorine, Y signifies chlorine and Z signifies oxygen.
17. A compound as claimed in Claim 8, wherein R signifies n-propyl, X signifies chlorine, Y signifies chlorine and Z signifies oxygen.
18. A compound as claimed in Claim 8, wherein R signifies ethyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.
19. A compound as claimed in Claim 8, wherein R signifies n-propyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.
20. A compound as claimed in Claim 8, wherein R signifies isopropyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.
21. A compound as claimed in Claim 8, wherein R signifies n-butyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.
22. A compound as claimed in Claim 8, wherein R signifies isobutyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.
23. A compound as claimed in Claim 8, wherein R signifies sec-butyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.
24. A compound as claimed in Claim 8, wherein R signifies tert. butyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur. - - 13-2955 ''
25. A compound as claimed in Claim 8, wherein R signifies isopentyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.
26. A compound as claimed in Claim 8, wherein R signifies tert . pentyl, X signifies hydrogen, Y signifies chlorine and Z signifies sulphur.
27. A compound as claimed in Claim 8, wherein R signifies ethyl, X signifies chlorine, Y signifies chlorine and Z signifies sulphur.
28. A compound as claimed in Claim 8, wherein R signifies n-propyl, X signifies chlorine, Y signifies chlorine and Z signifies sulphur.
29. A compound as claimed in Claim 8, wherein R signifies isopropyl, X signifies chlorine, Y signifies chlorine and Z signifies sulphur.
30. A compound as claimed in Claim 8, wherein R signifies n-butyl, X signifies chlorine, Y signifies chlorine and Z signifies sulphur.
31. A compound as claimed in Claim 8, wherein R signifies n-pentyl, X signifies chlorine, Y signifies chlorine and Z .signifies sulphur.
32. A compound as claimed in Claim 8, wherein the -CH^ group is cis to the -COOR group in the crotonic acid radical. 3700/CR/HD
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1055168A CH507990A (en) | 1968-07-15 | 1968-07-15 | Insecticides containing halogenated organo phosphoric - acids |
| CH1705468A CH506563A (en) | 1968-11-16 | 1968-11-16 | Insecticides containing halogenated organo phosphoric - acids |
| CH1792568A CH511897A (en) | 1968-12-02 | 1968-12-02 | Insecticides containing halogenated organo phosphoric - acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL32608A0 IL32608A0 (en) | 1969-09-25 |
| IL32608A true IL32608A (en) | 1972-12-29 |
Family
ID=27176460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL32608A IL32608A (en) | 1968-07-15 | 1969-07-13 | (alkoxycarbonylpropenyl)phosphoro-(and dithiophosphoro)dichloridates(and dibromidates)and their preparation |
Country Status (6)
| Country | Link |
|---|---|
| BR (1) | BR6910696D0 (en) |
| DE (1) | DE1935630C3 (en) |
| ES (1) | ES369476A1 (en) |
| FR (1) | FR2012980A1 (en) |
| GB (1) | GB1262760A (en) |
| IL (1) | IL32608A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1587913A (en) * | 1976-09-08 | 1981-04-15 | Sandoz Ltd | Process for the production of unsaturated thiophosphate esters and ester amides |
| US5304585A (en) * | 1981-02-13 | 1994-04-19 | Minnesota Mining And Manufacturing | Dentin and enamel adhesive |
| CA1236844A (en) * | 1981-02-13 | 1988-05-17 | James E. Bunker | Dentin and enamel adhesives |
-
1969
- 1969-06-20 GB GB31237/69A patent/GB1262760A/en not_active Expired
- 1969-07-11 FR FR6923795A patent/FR2012980A1/fr not_active Withdrawn
- 1969-07-13 IL IL32608A patent/IL32608A/en unknown
- 1969-07-14 BR BR210696/69A patent/BR6910696D0/en unknown
- 1969-07-14 ES ES369476A patent/ES369476A1/en not_active Expired
- 1969-07-14 DE DE1935630A patent/DE1935630C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE1935630C3 (en) | 1979-05-03 |
| DE1935630A1 (en) | 1970-01-22 |
| BR6910696D0 (en) | 1973-02-22 |
| IL32608A0 (en) | 1969-09-25 |
| FR2012980A1 (en) | 1970-03-27 |
| DE1935630B2 (en) | 1978-09-07 |
| GB1262760A (en) | 1972-02-09 |
| ES369476A1 (en) | 1971-06-16 |
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