GB807598A - Method for the manufacture of o-aryl o-lower alkyl phosphorochloridothioates - Google Patents
Method for the manufacture of o-aryl o-lower alkyl phosphorochloridothioatesInfo
- Publication number
- GB807598A GB807598A GB9041/57A GB904157A GB807598A GB 807598 A GB807598 A GB 807598A GB 9041/57 A GB9041/57 A GB 9041/57A GB 904157 A GB904157 A GB 904157A GB 807598 A GB807598 A GB 807598A
- Authority
- GB
- United Kingdom
- Prior art keywords
- aryl
- methyl
- lower alkyl
- trichlorophenyl
- reacting
- 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.)
- Expired
Links
- -1 alkyl phosphorochloridothioates Chemical class 0.000 title abstract 30
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 title 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract 4
- 239000011541 reaction mixture Substances 0.000 abstract 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 229910021529 ammonia Inorganic materials 0.000 abstract 3
- 150000005840 aryl radicals Chemical class 0.000 abstract 3
- 238000009835 boiling Methods 0.000 abstract 3
- HPFKOFNYNQMWEF-UHFFFAOYSA-N chloro-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(Cl)=S HPFKOFNYNQMWEF-UHFFFAOYSA-N 0.000 abstract 3
- 239000012442 inert solvent Substances 0.000 abstract 3
- 239000002904 solvent Substances 0.000 abstract 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 abstract 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 150000005826 halohydrocarbons Chemical class 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- 239000003755 preservative agent Substances 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 abstract 1
- 239000002023 wood Substances 0.000 abstract 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
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
-
- 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
- C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
An O-aryl O-lower alkyl-phosphorochloridothioate wherein the lower alkyl group contains 1 to 3 carbon atoms is obtained by reacting from 1 to 7 molecular proportions of a C1-C3 alkanol with one molecular proportion of an O-aryl phosphorodichloridothioate at a temperature at which hydrogen chloride is formed as a product of reaction while continuously withdrawing the hydrogen chloride in the gaseous state from the reaction mixture as formed, the said temperature being at least 15 DEG C. below the boiling-point at 760 millimetres pressure of the alkanol employed. The term "aryl" is defined as an aromatic hydrocarbon radical which may be unsubstituted or substituted by one or more substituents such as chlorine, bromine, alkyl, alkoxy, nitro, cyclohexyl, benzyl and phenyl. The hydrogen chloride may be continuously withdrawn from the reaction mixture by carrying out the reaction under reduced pressure, or while passing an inert gaseous entraining agent through the mixture, or by effecting the reaction in the presence of an inert solvent having a low solvent power for hydrogen chloride. Suitable gaseous entraining agents include nitrogen, methyl chloride, carbon dioxide or air, while suitable solvents include the hydrocarbon and halohydrocarbon solvents boiling at temperatures not exceeding 165 DEG C., e.g. methylene dichloride (or dibromide), ethylene dichloride, chloroform, carbon tetrachloride, benzene, chlorobenzene and toluene. The reaction may be carried out under such conditions that the reaction mixture boils, e.g. by using a suitable inert solvent, provided the boiling temperature is within the defined temperature range. When the formation of hydrogen chloride is substantially complete the reaction mixture may be distilled under reduced pressure at temperatures up to 15 DEG C. below the boiling-point at 760 millimetres pressure of the employed alkanol to separate excess alkanol and then at temperatures up to 90 DEG C. to separate low-boiling constituents such as inert solvent and obtain the desired product as a liquid or crystalline residue. Examples are given for the production of O-aryl O-lower alkyl phosphorochloridothioates in which the lower alkyl radical is methyl and the aryl radical is 2,4,6-trichlorophenyl, 2,4,5-trichlorophenyl, 2-chloro-4-nitrophenyl, 2,5-dichlorophenyl, 4 - chlorophenyl, and 2,4 - dichlorophenyl, respectively, and in which the lower alkyl radical is ethyl and the aryl radical is 2,4,5-trichlorophenyl and 2,4-dichlorophenyl, respectively. Other products which are stated to have been prepared are those in which the lower alkyl radical is methyl and the aryl radical is phenyl, 3-ethylphenyl, 4-nonylphenyl, 4 - secondary - butylphenyl, 4 - tertiary - butylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 2,5 - dimethylphenyl, 4 - tertiarybutyl - 2 - methylphenyl, 2 - bromo - 4 - tertiary - butylphenyl, 2 - chloro - 4 - tertiary - butylphenyl, 3,5 - dimethylphenyl, 4 - chloro - 2 - cyclohexylphenyl, 2-cyclohexylphenyl, 3-phenylphenyl, and 2-phenylphenyl respectively. The products are stated to be useful as pesticides and as preservatives for paper, paint and wood. O - (2,4,6 - trichlorophenyl) O - methyl - phosphoroamidothioate is obtained by reacting the corresponding phosphorochloridothioate with excess ammonia in chlorobenzene at 5 DEG to 15 DEG C. O - (2,4,5 - trichlorophenyl) O - ethyl - phosphoroamidothioate and the corresponding -N-ethyl phosphoramidothioate are obtained by reacting the corresponding phosphorochloridothioate with excess ammonia and excess ethylamine respectively in benzene at 10 DEG C. O-(2-chloro - 4 - nitrophenyl) O - methyl-, O - (2,5 - dichlorophenyl) O - methyl -, and O - (4 - chlorophenyl) O - methyl - phosphoroamidothioates are also obtained by reacting the corresponding phosphorochloridothioate with excess ammonia. O-aryl phosphorodichloridothioates are obtained by reacting at least two mols. of thio phosphoryl chloride with one mol. of an alkali metal salt of a phenol or suitably substituted phenol.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US807598XA | 1956-04-30 | 1956-04-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB807598A true GB807598A (en) | 1959-01-21 |
Family
ID=22159429
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9041/57A Expired GB807598A (en) | 1956-04-30 | 1957-03-19 | Method for the manufacture of o-aryl o-lower alkyl phosphorochloridothioates |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB807598A (en) |
-
1957
- 1957-03-19 GB GB9041/57A patent/GB807598A/en not_active Expired
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2911335A (en) | Thiophosphate ester fungicides | |
US2670347A (en) | Thiophosphoric acid derivatives and method of preparing the same | |
US2033740A (en) | Esters of phenylcarbamic acid | |
GB807598A (en) | Method for the manufacture of o-aryl o-lower alkyl phosphorochloridothioates | |
GB965997A (en) | Phosphorus-containing heterocyclic esters | |
US3218347A (en) | Halophenyl bis-carbonates | |
GB969829A (en) | New phosphoric acid esters and process for their manufacture | |
US2887506A (en) | Method for the manufacture of o-aryl o-lower alkyl phosphorochloridothioates | |
Bourne et al. | The E 1cB mechanism for thiocarbamate ester hydrolysis: equilibrium and kinetic studies | |
GB820522A (en) | Thiophosphoric acid esters and their production | |
GB921801A (en) | Dithiophosphoric acid esters | |
GB796484A (en) | O-aryl o-methyl phosphoroamidothioates | |
GB1346475A (en) | Process for the production of substituted thionophosphoryl chlorides | |
GB962828A (en) | New organic phosphine derivatives | |
US3152146A (en) | Halogenated omicron-phenylene carbonates | |
US2640832A (en) | Nu-(halomethyl)-maleimide and process for preparing the same | |
GB806280A (en) | O-aryl o-loweralkyl n-alkenyl phosphoroamidothioates | |
US2843602A (en) | 2, 3-di(chloroalkoxy)-p-dioxanes | |
US3441590A (en) | Process for preparing s-(2-chloroethyl) thiocarbamates from s-(2-chloroethyl) isothiocarbamyl chlorides | |
US3547992A (en) | Cof-substituted-n-trifluoromethyl-phenylsulfenamides | |
GB833156A (en) | O-aryl phosphoroamidohydrazidothioates | |
GB983886A (en) | New monothiophosphoric acid esters | |
GB807610A (en) | Bis-phosphoroamidothioates | |
GB864021A (en) | Manufacture of phosphorus-containing ethylene imine type compounds | |
US3146253A (en) | Novel phosphorus and chlorine containing tricyclic heterocycles |