GB2148898A - Method for producing organic phosphoric acid esters - Google Patents
Method for producing organic phosphoric acid esters Download PDFInfo
- Publication number
- GB2148898A GB2148898A GB08426641A GB8426641A GB2148898A GB 2148898 A GB2148898 A GB 2148898A GB 08426641 A GB08426641 A GB 08426641A GB 8426641 A GB8426641 A GB 8426641A GB 2148898 A GB2148898 A GB 2148898A
- Authority
- GB
- United Kingdom
- Prior art keywords
- group
- substituted
- compound
- formula
- phosphorothioate
- Prior art date
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- Granted
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052717 sulfur Chemical group 0.000 claims abstract description 5
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000004043 oxo group Chemical group O=* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- PWYIUEFFPNVCMW-UHFFFAOYSA-N propaphos Chemical compound CCCOP(=O)(OCCC)OC1=CC=C(SC)C=C1 PWYIUEFFPNVCMW-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- -1 phosphoric acid ester halide Chemical class 0.000 description 14
- 239000002585 base Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- MJMACUIRWXDBHT-UHFFFAOYSA-N 1-(4-chlorophenyl)-1H-pyrazol-4-ol Chemical compound C1=C(O)C=NN1C1=CC=C(Cl)C=C1 MJMACUIRWXDBHT-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- JHUCCRNKXWBDTO-UHFFFAOYSA-N ethoxy(propylsulfanyl)phosphinic acid Chemical compound CCCSP(O)(=O)OCC JHUCCRNKXWBDTO-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KAUABWYBFARJAF-UHFFFAOYSA-N 1h-pyrazol-4-ol Chemical class OC=1C=NNC=1 KAUABWYBFARJAF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 102220347004 c.89G>A Human genes 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZEXSWWSPNTYEJC-UHFFFAOYSA-N dihydroxy-propoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCOP(O)(O)=S ZEXSWWSPNTYEJC-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003129 miticidal effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000005406 washing 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
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
-
- 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
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- 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
- C07F9/6509—Six-membered rings
- C07F9/650905—Six-membered rings having the nitrogen atoms in the positions 1 and 2
-
- 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
- C07F9/6509—Six-membered rings
- C07F9/6512—Six-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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
An improvement in the known method for producing organic phosphoric acid esters of the formula: <IMAGE> wherein R1 is a lower alkoxy group, R2 is a lower alkoxy group or a lower alkylthio group, R3 is a substituted or unsubstituted phenyl group or a substituted or unsubstituted heterocyclic group and X is an oxygen or sulfur atom, which comprises reacting a compound of the formula: <IMAGE> wherein R1, R2 and X are as defined above and Y is a halogen atom with a compound of the formula: R3OH wherein R3 is as defined above under basic conditions in a solvent, the improvement lying in that the reaction solvent is a mixture of water and a water-immiscible solvent, the mixture forming two layers.
Description
SPECIFICATION
Method for producing organic phosphoric acid esters
This invention relates to a method of producing organic phosphoric acid ester derivatives having insecticidal, miticidal, fungicidal and other activities and useful as agricultural chemicals. More particularly, the invention relates to an improvement in the method of producing compounds of the general formula:
wherein R1 is a lower alkoxy group, R2 is a lower alkoxy group or a lower alkylthio group,
R3 is a substituted or unsubstituted phenyl group or a substituted or unsubstituted heterocyclic group and X is an oxygen or sulfur atom, which comprises reacting a compound of the general formula:
wherein Rl, R2 and X are as defined above and Y is a halogen atom, with a compound of the general formula::
R30H (III) wherein R3 is as defined above, under basic conditions in a solvent, the improvement lying in that the reaction solvent is a mixture of water and a water-immiscible solvent, the mixture forming two layers.
It is widely known that organic phosphoric acid ester derivatives are producible by reacting, in the manner of esterification, an organic phosphoric acid ester halide with a hydroxylcontaining compound such as an alcohol or a phenol (for example, British Patents No.
1306028, No. 1315888, No. 1340297 and
No. 2047250, and United States Patents No.
4163052, No. 4315008, No. 3728297 and
No. 3723456). This esterification is generally carried out in an organic solvent while the use of water is avoided since the starting organic phosphoric acid ester halide is decomposed very easily in the presence of water. Thus, for instance, United States Patent No. 431 5008 discloses a method of reacting a 4-hydroxypyrazole derivative with an O-ethyl S-n-propyl (di)thiophosphoric acid ester halide in an organic solvent inert to the reaction (e.g. acetonitrile) to give the corresponding organic phosphoric acid ester derivative. However, this and other known methods are not yet fully satisfactory because of low yield and low purity of the objective compounds and because of complicated and troublesome procedures resulting from the use of organic solvents in carrying out the reaction.
The present inventors continued their studies in the development of a method of producing the objective compounds (i) in a manner easier and simpler from the industrial standpoint and found that, in the known method for producing the compound (I) which comprises reacting the compound (II) with the compound (III) under basic conditions in a solvent, when the reaction solvent is a mixture of water and a water-immiscible solvent, the mixture forming two layers, unexpectedly, (i) the reaction proceeds in highly improved yield, i.e. almost quantitatively, (ii) the isolation of the objective compound (I) is very easy and simple, and thus (iii) the objective compound (i) is obtained in high yield and high purity. Continued investigations based on the above finding have led to completion of the present invention.
The reaction of the compounds (II) and (Ill) in accordance with the present invention proceeds almost quantitatively in a mixture of water and a water-immiscible solvent, the mixture forming two layers, contrary to the so-far prevailing common knowledge in chemistry that water is inadequate as the reaction solvent since organic phosphoric acid ester halides, namely the compounds (it), are very unstable to water. So, the reaction in accordance with the present invention can be used conveniently in a quantitative analysis of the compound (oil).
In the above general formulas, R, is a lower alkoxy group which includes a straight or branched lower alkoxy group containing 1 to 4 carbon atoms, such as methoxy, ethoxy, npropoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy; R2 is (1) a lower alkoxy group which includes a straight or branched lower alkoxy group containing 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, or (2) a lower alkylthio group which includes a straight or branched lower alkylthio group containing 1 to 4 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio or tert-butylthio;;
R3 is (1) a substituted or unsubstituted phenyl group which includes a phenyl group which may optionally be substituted by 1 to 3 substituents each selected from among (i) a lower alkyl group containing 1 to 4 carbon atoms, (ii) nitro, (iii) halogen, (iv) a lower alkylthio containing 1 to 4 carbon atoms and (v) cyano, or (2) a substituted or unsubstituted heterocyclic group which includes a 5- or 6membered heterocyclic group which is capable of bonding through a carbon atom and contains 1 to 4 nitrogen atoms and which may optionally be substituted by 1 to 3 substituents each selected from (a) a phenyl group which may have 1 to 3 substituents each selected from among a lower alkyl group containing 1 to 4 carbon atoms, a lower alkoxy group containing 1 to 4 carbon atoms, a lower alkylthio group containing 1 to 4 carbon atoms, nitro, halogen and trifluoromethyl, (b) a lower alkoxycarbonyl group containing 1 to 4 carbon atoms in the alkoxy moiety, (c) an oxo group, (d) halogen and (e) a lower alkyl group containing 1 to 4 carbon atoms; X is an oxygen or sulfur atom, and Y is a halogen atom such as fluorine, chlorine, bromine or iodine.
Referring to the above Pçs, the halogen includes fluorine, chlorine, bromine and iodine; the lower alkylthio group containing 1 to 4 carbon atoms, the lower alkoxy group containing 1 to 4 carbon atoms, and the lower alkoxy moiety containing 1 to 4 carbon atoms in the lower alkoxycarbonyl group respectively include those specifically mentioned in relation to R2; and the lower alkyl group containing 1 to 4 carbon atoms includes a straight or branched lower alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
The 5- or 6-membered heterocyclic group containing 1 to 4 nitrogen atoms as represented by the above R3 includes, among others, (1) saturated or unsaturated 5- or 6membered heterocyclic groups containing one nitrogen atom, such as pyrrolyl, pyridyl, pyrrolidinyl, pyrrolinyl and piperidyl, (2) saturated or unsaturated 5- or 6-membered heterocyclic groups containing two nitrogen atoms, such as imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl and piperazinyl, and (3) saturated or unsaturated 5- or 6-membered heterocyclic groups containing 3 or 4 nitrogen atoms, such as triazolyl and tetrazolyl.
Among the possible cases mentioned above preferred are those cases where R, is a lower alkoxy group, R2 is a lower alkylthio group, X is an oxygen atom and R3 is a saturated or unsaturated 5- or 6-membered heterocyclic group which contains two nitrogen atoms and may optionally be substituted with a phenyl group which may have 1 to 3 substituents each selected from among a C14 alkyl group, a C14 alkoxy group, a C14 alkylthio group, nitro, halogen and trifluoromethyl.
Among the substituted or unsubstituted heterocyclic groups represented by R3 particularly preferred are unsaturated 5-membered heterocyclic groups which contain two nitrogen atoms and may optionally be substituted by a phenyl group unsubstituted or substituted by 1 to 3 halogen atoms.
A typical example of the compounds (I) may be a compound of the formula:
wherein R,. is a C14 alkoxy group, R2. is a C14 alkoxy group or a C, 4 alkylthio group, R3 is (1) a phenyl group which may optionally be substituted by 1 to 2 substituents each selected from a C, 4 alkyl group and a C14 alkylthio group, or (2) an unsaturated 5- or 6membered heterocyclic group which contains 1 or 2 nitrogen atoms and may optionally be substituted by 1 to 3 substituents each selected from (i) a phenyl group which may optionally be substituted by a halogen atom, (ii) a C14 alkyl group, (iii) an oxo group and (iv) a halogen atom, and X is as defined above. In the formula (la), the groups represented by R", R2t, and R3, respectively include those mentioned in relation to R1, R2 and R3.
More specifically, the compounds represented by the general formula (I) include the following:
O,O-Dimethyl 0-(4-cyanophenyl) phosphorothioate,
O,O-Diethyl 0-(2,4-dichlorophenyl) phosphorothioate,
O,O-Diethyl 0-(5-phenyl-3-isoxazolyl) phosphorothioate,
O,O-Diethyl 0-(3,5,6-trichloro-2-pyridyl) phosphorothioate, O-Ethyl S-n-propyl 0-[1 -(4-chlorophenyl)-4-py- razolyl] phosphorothioate, O, O-Diethyl 0-(2-isopropyi-4-methylpyrimidin- 6-yl) phosphorothioate, O,O-Dimethyl 0-(4-methylthio-m-tolyl) phosphorothioate, 0-(3, 5, 6-Trichloro-2-pyridyl) O,O-dimethyl phosphorothioate,
O, O-Diethyl 0-(2, 3-dihydro-3-oxo-2-ophenyl-6- pyridazinyl) phosphorothioate, and (4-Methylthiophenyl) di-n-propyl phosphate, among others.
In producing the objective compounds (I) in accordance with the invention, the compound (Il) is used in an amount of about 0.5 to about 3 moles, preferably about 1 to about 1.05 moles, per mole of the compound (III).
The water-immiscible solvent to be used in the present reaction may be a solvent having a solubility in water of 0.01-5% (weight/ volume) at 25"C, preferably 0.01-1% (weight/volume) at 25vC. Suitable examples of the water-immiscible solvent include aromatic hydrocarbons, such as benzene, toluene and xylene, and halogenated hydrocarbons, such as methylene chloride, chloroform and carbon tetrachloride. Among these solvents preferred are aromatic hydrocarbons such as benzene, toluene and xylene. The water-immiscible solvent is used in an amount to form two layers with water, the amount being 0.5 to 10 parts by volume, preferably about 2 parts by volume relative to water.The amount of water used in the invention may be about 5 to 200 moles, preferably 10 to 30 moles per mole of the compound (III).
The reaction is carried out smoothly under basic conditions wherein a pH value of the reaction mixture under stirring is 7.1 to 14.0, preferably 10 to 11.
For conducting the reaction under basic conditions, a base is used in an amount about equivalent to an amount based on the compound (II). Suitable examples of the base are inorganic bases, for example, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, alkali metal hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate, alkaline earth metal carbonates such as calcium carbonate and the like. Among them, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are particularly preferred. The base may be added to the reaction system once or by several portions to keep the reaction mixture under basic conditions.
The reaction proceeds in the two layer solvent system comprising an aqueous layer and a layer of a water-immiscible solvent. Thus, the reaction may be effected, for example, by adding the compound (III) to a mixture of water and a water-immiscible solvent and then adding thereto the compound (II) while maintaining the pH of the reaction mixture under stirring within the basicity region by addition of a base, or by dissolving the compound (III) in a two-layer liquid phase comprising an aqueous solution of a base and a waterimmiscible solvent and adding the compound (II) to the resulting solution while maintaining the pH of the reaction mixture under stirring within the basicity region by adding a base as necessary.In the invention, the compound (II) may be added to the rection system in the form of a solution in a water-immiscible solvent.
The reaction can be effected in practice without particular problems within a temperature range of about 0 C to about 50 C, suitably about 5"C to about 1 5'C.
The reaction may be complete in about 30 minutes to about 6 hours. The completion of the reaction can be confirmed by high performance liquid chromatography or thin layer chromatography, for instance. After completion of the reaction, the reaction mixture may be adjusted to pH 12 to 13.5 with such a base as mentioned above and the aqueous layer may be separated, whereby the unreacted compound (III) and byproducts may be removed.
The thus-produced compounds (I) can be isolated and purified by per se known methods of separation and purification, such as concentration, concentration under reduced pressure, distillation under reduced pressure, pH adjustment, solvent replacement, solvent extraction, crystallization, recrystallization and chromatography.
The starting compounds (II) and (III) to be used in practicing the invention are producible by per se known methods, such as the methods described in British Patent No.
2047250 and United States Patents No.
4163052 and No. 4315008, for instance, or their analogous methods.
The present invention will be described hereinafter in further detail by way of an experimental example and working examples.
It should, however, be understood that these examples are merely illustrative of the pesent invention and should by no means be construed as limiting the scope of the invention and that changes and modifications may be made by one skilled in the art without departing from the spirit of the pesent invention.
The symbols used in the examples and the experiement have the following meanings.
ml : milliliter g : gram % : percent
ODS (C-18): "LS -410 ODS SIL" manufac
tured by TOVO SODA MANU
FACTURING CO. LTD. in JA
PAN
: : diameter b.p. : boiling point d20 : density at 20"C ('C: centigrade degree) m.p.: melting point cm : centimeter
Example 1
Production of 0-[1-(4-chlorophenyl)-4-pyra- zolyl] O-ethyl S-n-propyl phosphorothioate
Water (24.5 ml) is added to 15.02 g (0.075 mole) of 1 -(4-chlorophenyl)-4-hydroxy- pyrazole, followed by addition of 2.25 g (0.0563 mole) of sodium hydroxide. Stirring promotes dissolution and gives a homogeneous solution.To the solution is added 56.8 ml of toluene and, with vigourous stirring, a toluene solution (30.8 g) containing 15.35 g (0.0757 mole) of O-ethyl S-n-propyl phosphorochloride is added dropwise over 2.5 hours, during which the reaction temperature is maintained at 15"C and the pH of the reaction mixture is kept at 10.5 by addition of 10% (weight/volume) aqueous sodium hydroxide. After completion of the dropping, the reaction temperature is raised to 25"C and stirring is continued at this temperature for 2 hours. Thereafter, the mixture is cooled to 5"C, adjusted to pH 1 3.5 with 28% (weight/volume) aqueous sodium hydroxide and stirred for 30 minutes, followed by phase separation. The toluene layer is washed with 40 ml of water.The toluene solution obtained
by phase separation after washing is concentrated under reduced pressure to give the title
compound.
Yield 27.9 g
Purity 96.4% [determined by HPLC (high
perforamce liquid chromatography; column
ODS (C-18) 40 X 25 cm, temperature-40'C,
mobile phase-acetonitrile/water)]
Yield on 100% purity basis 26.9 g (99.5%)
Comparative experiment
Produxtion of O-[ 1 -(4-chlorophenyl)-4-pyra- zolyl] O-ethyl S-n-propyl phosphorothioate by the method described in British Patent No.
2047250.
1 -(4-Chlorophenyl)-4-hydroxypyrazole (15.02 9, 0.075 mole) is dissolved in 80 ml
of acetone. Thereto are added 12.0 g of
anhydrous sodium carbonate and 15.35 g
(0.0757 mole) of O-ethyl S-n-propyl phospho
rochloride. The mixture is heated under reflux
for 2.5 hours. Thereafter, the acetone is distilled off, toluene is added to the residue, and
the resulting toluene solution is washed with
water and dried over anhydrous sodium sul
fate. The toluene is then distilled off to give O-[ 1 -(4-ch lorophenyl)-4-pyrazolyl] O-ethyl S-n
propyl phosphorothioate.
Yield 22.77 g
Purity 93.9% (determined by HPLC (high per
formance liquid chromatography) in the same
manner as Example 1)
Yield on 100% purity basis 21.38g(78.1%) Example 2
The following orgaic phosphoric acid ester
derivatives are producible in the same manner
as Example 1: :
(1) O,O-Diethyl 0-(2-isopropyl-4-methylpyri
midin-6-yl) phosphorothioate
dark brown liquid
b.p. 83-84C/0.0002 mmHg, d20 1.116
(2) O,O-Dimethyl 0-(4-methylth io-m-tolyl) phosphorothioate
colorless liquid
b.p. 87"C/0.01 mmHg, d20 1.5698
(3) 0-(3,5,6-Trichloro-2-pyridyl) O,O-dime
thyl phosphorothioate
white crystals m.p. 45.5-46.5"C (4) O,O-Dimethyl 0-(2, 3-dihydro-3-oxo-2- phenyl-6-pyridazinyl) phosporothioate white crystals
m.p. 54.5-56.0'C
(5) (4-Methylthiophenyl) di-n-propyl phos
phate
light yellow liquid
b.p. 176'C/0.85 mmHg
Claims (7)
1. A method for producing a compound of the formula:
wherein R1 is a lower alkoxy group, R2 is a lower alkoxy group or a lower alkylthio group,
R3 is a substituted or unsubstituted phenyl group or a substituted or unstubstituted heterocyclic group and X is an oxygen or sulfur atom which comprises reacting a compound of the formula:
wherein R1, R2 and X are as defined above and Y is a halogen atom with a compound of the formula: R3OH (III) wherein R3 is as defined above under basic conditions in a solvent, characterised in that the reaction solvent is a mixture of water and a water-immiscible solvent, the mixture forming two layers.
2. A method according to claim 1, wherein the compound (I) is a compound of the formula:
wherein Ria is a C14 alkoxy group, R2. is a C14 alkoxy group of a C14 alkylthio group, R3, is (1) a phenyl group which may optionally be substituted by 1 to 2 substituents each selected from a C14 alkyl group and a C14 alkylthio group, or (2) an unsaturated 5- or 6membered heterocyclic group which contains 1 or 2 nitrogen atoms and may optionally be substituted by 1 to 3 substitutents each selected from (i) a phenyl group which may optionally be substituted by a halogen atom, (ii) a C14 alkyl group, (iii) an oxo group and (iv) a halogen atom, and X is an oxygen or sulfur atom.
3. A method according to claim 1, wherein R1 is a lower alkoxy group, R2 is a lower alkylthio group, X is an oxygen atom and R3 is a saturated or unsaturated 5- or 6membered heterocylic group which contains two nitrogen atoms and may optionally be substituted with a phenyl group which may have 1 to 3 substitutents each selected from among a C14 alkyl group, a C14 alkoxy group, a C14 alkylthio group, nitro, halogen and trifluoromethyl.
4. A method according to claim 1 or 3, wherein R3 is an unsaturated 5-membered heterocyclic group which contains two nitrogen atoms and may optionally be substituted with a phenyl group unsubstituted or substituted by 1 to 3 halogen atoms.
5. A method according to claim 1, wherein the compound of formula (I) is O- Ethyl S-n-propyl 0-(1 -(4-chlorophenyl)-4-pyra- zolyl] phosphorothioate.
6. A method according to claim 1, wherein the compound (I) is selected from any one of: O, O-Diethyl 0-(2-isopropyl-4-methylpyrimidin6-yl) phosphorothioate, O,O-Dimethyl 0-(4-methylthio-m-tolyl) phosphorothioate, 0-3,5,6-Trichloro-2-pyridiyl, O,O-dimethyl phosphorothioate, O, O-Diethyl 0-(2, 3-dihydro-3-oxo-2-phenyl-6- pyridazinyl) phosphorothioate and (4-Methylthiophenyl) di-n-propyl phosphate.
7. A method according to claim 1 substantially as herein described with reference to either of the specific examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58205580A JPS6097986A (en) | 1983-10-31 | 1983-10-31 | Production of organophosphoric acid ester derivative |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8426641D0 GB8426641D0 (en) | 1984-11-28 |
| GB2148898A true GB2148898A (en) | 1985-06-05 |
| GB2148898B GB2148898B (en) | 1987-09-09 |
Family
ID=16509229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08426641A Expired GB2148898B (en) | 1983-10-31 | 1984-10-22 | Method for producing organic phosphoric acid esters |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS6097986A (en) |
| CH (1) | CH661515A5 (en) |
| DE (1) | DE3439347A1 (en) |
| DK (1) | DK508884A (en) |
| GB (1) | GB2148898B (en) |
| SG (1) | SG2590G (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2663333B1 (en) * | 1990-06-14 | 1993-09-17 | Norsolor Sa | PHOSPHORUS ACRYLIC COMPOUNDS, PROCESS FOR PRODUCING THE SAME AND NOVEL POLYMERS THEREOF. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1490138A (en) * | 1975-08-07 | 1977-10-26 | Dow Chemical Co | Process for preparing phosphorothioates and phenyl-phosphonothioates |
| GB1553000A (en) * | 1976-12-06 | 1979-09-19 | Stauffer Chemical Co | Process for the preparation of phenyl substituted phosphorus esters |
-
1983
- 1983-10-31 JP JP58205580A patent/JPS6097986A/en active Granted
-
1984
- 1984-10-22 GB GB08426641A patent/GB2148898B/en not_active Expired
- 1984-10-25 DK DK508884A patent/DK508884A/en not_active Application Discontinuation
- 1984-10-26 DE DE19843439347 patent/DE3439347A1/en not_active Withdrawn
- 1984-10-29 CH CH5166/84A patent/CH661515A5/en not_active IP Right Cessation
-
1990
- 1990-01-15 SG SG25/90A patent/SG2590G/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1490138A (en) * | 1975-08-07 | 1977-10-26 | Dow Chemical Co | Process for preparing phosphorothioates and phenyl-phosphonothioates |
| GB1553000A (en) * | 1976-12-06 | 1979-09-19 | Stauffer Chemical Co | Process for the preparation of phenyl substituted phosphorus esters |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3439347A1 (en) | 1985-05-09 |
| GB2148898B (en) | 1987-09-09 |
| JPH04996B2 (en) | 1992-01-09 |
| JPS6097986A (en) | 1985-05-31 |
| SG2590G (en) | 1990-07-06 |
| DK508884D0 (en) | 1984-10-25 |
| DK508884A (en) | 1985-05-01 |
| CH661515A5 (en) | 1987-07-31 |
| GB8426641D0 (en) | 1984-11-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19931022 |