SU507246A3 - Method of producing phosphoric acid esters - Google Patents
Method of producing phosphoric acid estersInfo
- Publication number
- SU507246A3 SU507246A3 SU1956353A SU1956353A SU507246A3 SU 507246 A3 SU507246 A3 SU 507246A3 SU 1956353 A SU1956353 A SU 1956353A SU 1956353 A SU1956353 A SU 1956353A SU 507246 A3 SU507246 A3 SU 507246A3
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- alkyl
- branched
- hydrogen
- carbon atoms
- general formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- 150000003014 phosphoric acid esters Chemical class 0.000 title claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000012433 hydrogen halide Substances 0.000 claims description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004001 thioalkyl group Chemical group 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000002440 hydroxy compounds Chemical class 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- -1 ester hydrochloride anhydrides Chemical class 0.000 description 7
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- DNCYBUMDUBHIJZ-UHFFFAOYSA-N 1h-pyrimidin-6-one Chemical compound O=C1C=CN=CN1 DNCYBUMDUBHIJZ-UHFFFAOYSA-N 0.000 description 3
- VFMCUTPRJLZEEW-UHFFFAOYSA-N 4h-pyrido[1,2-a]pyrimidine Chemical compound C1=CC=CN2CC=CN=C21 VFMCUTPRJLZEEW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YSYSCJKUUFTREM-UHFFFAOYSA-N 6h-pyrimido[1,2-a]pyrimidine Chemical compound N1=CC=CN2CC=CN=C21 YSYSCJKUUFTREM-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PAZSAZYCZWMYHU-UHFFFAOYSA-N butanedioic acid;phosphoric acid Chemical class OP(O)(O)=O.OC(=O)CCC(O)=O PAZSAZYCZWMYHU-UHFFFAOYSA-N 0.000 description 1
- KMJJJTCKNZYTEY-UHFFFAOYSA-N chloro-diethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)OCC KMJJJTCKNZYTEY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SPQUPNFNFAQPOF-UHFFFAOYSA-L dipotassium;pyridine;carbonate Chemical compound [K+].[K+].[O-]C([O-])=O.C1=CC=NC=C1 SPQUPNFNFAQPOF-UHFFFAOYSA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- 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
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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)
Description
(54) СПОСОБ ПОЛУЧЕНИЯ ЭФИРОВ ФОСФОРНЫХ 1СИСЛОТ(54) METHOD FOR OBTAINING ESHPS OF PHOSPHATE 1 SILF
II
Изобретение относитс к способу чени новых эфиров фосфорных кислот формулы IThis invention relates to a process for the synthesis of phosphoric acid esters of the formula I
..
,.f:VY.f: VY
D D
,,
ОABOUT
где RI - группа метин (СН-) или атом азота; Вг - водород, алкил С, -Сз или нитрогруппа; Нз водород , алкил Cj -€3 с разветвленной или пр мой цепью, хлор, бром, алкилоксикарбонил, в котором алкил содержит 1-4 атомов углерода, фенил или тиоалкил, в котором алкил содержит 1-3 атомов углерода; R4 - алкил с пр мой или разветвленной цепью; RS - алкил С -Сз с пр мой или разветвленной цепью, алкоксил, в котором алкил содержит 1-3 углеродных атомов, или аминогруп- where RI is the group of methin (CH-) or nitrogen atom; Br is hydrogen, alkyl C, -C3 or a nitro group; Hydrogen, alkyl Cj - € 3 branched or straight chain, chlorine, bromine, alkyloxycarbonyl, in which alkyl contains 1-4 carbon atoms, phenyl or thioalkyl, in which alkyl contains 1-3 carbon atoms; R4 is straight or branched alkyl; RS is a straight or branched C-C3 alkyl, alkoxy, in which alkyl contains 1–3 carbon atoms, or an amino group
па - N;pa - N;
где R и R одинаковые илиwhere R and R are the same or
различные и представл ют либо атом водорода, либо алкил CI-CB с пр мой или разветвленной цепью. Эти соединени обладают ценными пестидидными свойствами, в частности инсектицидньтми, нематошздными или акарицидными и могут найти применение в сельском хоз йстве.;distinct and represent either a hydrogen atom or a straight or branched CI-CB alkyl. These compounds have valuable pestidine properties, in particular, insecticidal, nematoshzdny or acaricidal, and can be used in agriculture;
Способ получени зфиров фосфорных кислот общей формулы I согласно изобретению основан на известной реакции конденсации оксисоединений с эфирогалоидангидридами фосфорных кислот и заключаетс в том, что оксисоединение общей формулыThe method for preparing phosphoric acid succinates of general formula I according to the invention is based on the known condensation reaction of oxo compounds with ester hydrochloride anhydrides of phosphoric acids and consists in the fact that the oxo compound of the general formula
он R he r
«I"I
Ч/.-хH.- x
оabout
где RI, Rj и R3 - как указано выше, подвергают взаимодействию с эфирогалоидангидридом тиофосфорной кислоты общей формулыwhere RI, Rj and R3, as indicated above, are reacted with thiophosphoric acid ester hydrogen halide anhydride of the general formula
.-ОПц.-OPts
1-«.one-".
где R4 и RS имеют указанные вьпие значени ; На - атом хлора или брома, в среде инертного органического растворител в прис}т:ствии акцептора галоидоводорода.where R4 and RS have the indicated meanings; Na - chlorine or bromine atom, in the environment of an inert organic solvent in the presence of an acid halide acceptor.
В качестве растворител могут быть использованы ацетон, этилацетат ацетонитрил и другие, а акцептором галоидоводорода может служить тригAcetone, ethyl acetate, acetonitrile and others can be used as a solvent, and a trigenerator can serve as a hydrogen halide acceptor.
этиламин, пиридин ихш углекислый калий. Целевые продукты вьщел ют известными приемами.ethylamine, iridum pyridine carbonate potassium. Target products are known methods.
Пример.2- (Дизтокситиофосфорилокси) гшридо (1, 2 а ) пиримидин 4-онExample 2- (Distoxythiophosphoryloxy) gshrido (1, 2 a) pyrimidine 4-one
Смешивают 40 г 2 - гадрокаширидо (1, 2 а) пиримидин Фона, 34 г углекислого кали в 400 см ацетона и 39 см диэтилхлоротиофосфата. Полученную суспензию переменшвают в течение 16ч при комнатной температуре, а затем нагревают с обратным холодильником в течение 5ч. После удалени минеральных солей растворитель вьшаривают досуха . Полученное масло кролетографируют на силикагеле , злюиру смесью циклогексан, ацетон и хчороформ в соотноше1ши 1:1:1. После вьшариваюш элюента получают 1Уг 2 - (диэтокситиофосфорилокси ) га1ридо (1, 2 а) пиримидин Фона в виде белых кристаллов, плав щихс при 82°С. .40 g of 2-gadrocashirido (1, 2 a) pyrimidine background, 34 g of potassium carbonate in 400 cm of acetone and 39 cm of diethyl chlorothiophosphate are mixed. The resulting suspension is alternated for 16 hours at room temperature, and then heated under reflux for 5 hours. After removal of the mineral salts, the solvent is evaporated to dryness. The resulting oil is rabetined on silica gel, fused with a mixture of cyclohexane, acetone and choroform in a ratio of 1: 1: 1. After extracting the eluent, 1Ug 2 - (diethoxythiophosphoryloxy) halide (1, 2 a) pyrimidine von is obtained in the form of white crystals, melting at 82 ° C. .
Вычислено,о: С 45,86; Н4,81; N8,91; Р9,85.Calculated, o: C 45.86; H4.81; N8.91; R9.85.
Cj2Ht3N2O4PS.Cj2Ht3N2O4PS.
Найдено,-. С46,0; Н4,8; N8,7; Р10,1.Found, -. C46.0; H4.8; N8.7; Р10,1.
Пример 2.2- (Д метоксииюфосфорилокси ) пиридо (1, 2 а) пиримидин 4-онExample 2.2- (D methoxyuiphosphoryloxy) pyrido (1, 2 a) pyrimidine 4-one
Перемешивают 60 г 2-гидрокси пиридо (1, 2 а) пиримидин 4-она и 52 г углекислого кали в 1000 см ацетона и нагревают с обратным холодильником в течение 30 шн. Быстро ввод т 46 см О, 0-диметилх.1юротиофосфата и нагревают с обратным холодильником в течение 4 ч. После охлаждени удал ют отсасыванием минеральные соли и вьшаривают досуха растворитель. Получают красное масло, которое вьошвают в 300 см лед ной воды. Полученный осадок отсасывают и промывают метанолом. Затем сушат его и раствор ют в хлороформе , потом отфильтровывают на сшшкате маг1ш и вьшаривают досуха. Таким образом получают 9,5 г2 - (диметокситиофосфорилокси) пиридо (1, 2 а) пиримидина - 4 - она в виде белых кристаллов, плав щихс при 125° С .60 g of 2-hydroxy pyrido (1, 2 a) pyrimidine 4-one and 52 g of potassium carbonate in 1000 cm of acetone are stirred and heated under reflux for 30 mo. 46 cmO, 0-dimethyl- 1uroiophosphate are quickly introduced and heated under reflux for 4 hours. After cooling, the mineral salts are removed by suction and the solvent is evaporated to dryness. A red oil is obtained, which is dissolved in 300 cm of ice water. The precipitate obtained is filtered off with suction and washed with methanol. It is then dried and dissolved in chloroform, then filtered off over a shaker and evaporated to dryness. Thus, 9.5 g of 2 - (dimethoxythiophosphoryloxy) pyrido (1, 2 a) pyrimidine - 4 - is obtained in the form of white crystals melting at 125 ° C.
Вычислено,%: С 41,96; Н 3,88; N9,78; Р 10,82. - CioHiiN204PS.Calculated,%: C 41.96; H 3.88; N9.78; R 10.82. - CioHiiN204PS.
Найдено,%:С41,9; Н4,; N9,6; Р11,0. Примерз. 2-(N- метил - О -зтилтиофосфорамидокси ) пиридо (1, 2 а) пиримидин 4-онFound,%: C41.9; H4; N9.6; Р11,0. Froze 2- (N-methyl-O-methyl-pyrophosphoramidoxy) pyrido (1,2 a) pyrimidine 4-one
Смешивают 12 г 2-гидрокси пиридо (1, 2 а) пиримидин 4-она и 10,3 г углекислого кали в 500 см ацетона. Перемеашвают при комнатной температуре в тече1ше 30 мин и прибавл ют 13 г N-метил, О-зтилхлороамидотиофосфата и нагревают с обратным холодилышком в течение 24 ч. Отсасьтают образовав1 ийс осадок и концентрируют растворитель. Хроматографируют на силикагеле , элюиру смесью: хлороформ, ацетон и циклогексан в ахпиошении 1:1:1. После вьтаривани получают 1,5г 2 - (N - метил - О -эти;ггиофосфорамидокси ) ииридо (1,2 а) пиримидин Фона в виде крист;3ллическогс) твердого веlinciiiia кремового илета, плав щегос при 95° С.12 g of 2-hydroxy pyrido (1, 2 a) pyrimidine 4-one and 10.3 g of potassium carbonate in 500 cm of acetone are mixed. The mixture is stirred at room temperature for 30 minutes and 13 g of N-methyl, O-methyl chloroamide thiophosphate are added and the mixture is heated under reflux for 24 hours. The precipitate is formed and the solvent is concentrated. Chromatographic on silica gel, eluting with a mixture of: chloroform, acetone and cyclohexane in a pressure of 1: 1: 1. After evaporation, 1.5 g of 2 - (N - methyl - O-ethy; ggiophosphoramidoxy) irido (1,2 a) pyrimidine Background is obtained in the form of crista;
Вычислено,%: С 44,29; Н4,39; N 14,09; Р 10,38.Calculated,%: C, 44.29; H4.39; N 14.09; R 10.38.
CiiHisNaOsPS.CiiHisNaOsPS.
Найдено,%: С 44,2; Н 4,8; N 13,8; Р 10,3.Found,%: C 44.2; H 4.8; N 13.8; R 10.3.
П Р и м е Р 4. 2 - (Дизтокситиофосфорилокси) 8- метилпиридо (1, 2а) пиримидин- 4- онP R and e R 4. 2 - (Distoxythiophosphoryloxy) 8-methylpyrido (1, 2a) pyrimidine-4-one
Смешивают 17,6 г 2 - шдрокси 8 - метилпиридо (1, 2 а) пиримидин 4 - она и 13,8 г углекислого кали в 400 см ацетона. Перемешивают 30 мин при комнатной температуре и прибавл ют 18,8 г 0,0 - дизтилхлоротиофосфата. Перемешивают в течение 24ч при комнатной температуре и удал ют отсасьтанием минеральные соли. Концентрируют растворитель и хроматографируют полученное масло на силикагеле, элюиру смесью хлороформ, ацетон и циклогексан в соотношении 1:1:1. После вьшаривани злюента получают масло, которое кристаллизуют в гексане. Отсасьшают и получают 11,8 г 2 - (Дизтокситиофосфорилокси) 8 - метилпиридо (1, 2 а) 1шригушдин 4 - она в виде светло- желтых кристаллов, плав щихс при 75° С.17.6 g of 2-shdroxy 8-methylpyrido (1, 2 a) pyrimidine 4 — she and 13.8 g of potassium carbonate in 400 cm of acetone are mixed. The mixture is stirred at room temperature for 30 minutes and 18.8 g of 0.0-distilchlorothiophosphate are added. Stir for 24 hours at room temperature and remove the mineral salts with suction. The solvent is concentrated and the resulting oil is chromatographed on silica gel, eluting with a mixture of chloroform, acetone and cyclohexane in a 1: 1: 1 ratio. After extraction of the solvent, an oil is obtained which is crystallized in hexane. 11.8 g of 2 - (Distoxythiophosphoryloxy) 8 - methyl pyrido (1, 2 a) 1 shrygushdin 4 - it is obtained in the form of light yellow crystals melting at 75 ° C.
Вычис11ено,%: С 47,56; Н5,22; N 8,53; Р9,43.Calculated:%: C 47.56; H5.22; N 8.53; P9.43.
Ci3H,,N204PS.Ci3H ,, N204PS.
Найдено,%: С 47,5; Н 5,1; N 8,3; Р9,5.Found,%: C 47.5; H 5.1; N 8.3; P9,5.
При мер 5. 2- (Диметокситиофосфорилокси ) 8- метилпиридо (1, 2 а) пиримидин 4- онExample 5. 2- (Dimethoxythiophosphoryloxy) 8-methylpyrido (1,2a) pyrimidine 4-one
Смешивают 17,6 г 2 - гадрокси - 8 - метилпиридо (1, 2 а) 4 - она и 13,6 г углекислого кали в 400 см -ацетона. Перемеишвают в течение 30 мин при комнатной температуре и прибавл ют 16 г 0,0-диметилхлоротиофосфата. Перемешивают в течение 24ч при комнатной температуре и удал ют отсасьшанием мине1мльные соли. Концентрируют растворитель и хроматографируют остаток на силикагеле, злюиру смесью хлороформ, ацетон и циклогексан в соотношении 1:1:1. После испарени злюента получают 6,2 г 2 - (диметокситиофосфорилокси ) 8 - метилпиридо (1, 2 а) пиримидин 4 - она в виде желтых кристаллов, плав щихс при 110° С.17.6 g of 2-gadroxy-8-methylpyrido (1, 2 a) 4-she and 13.6 g of potassium carbonate in 400 cm-acetone are mixed. The mixture is stirred for 30 minutes at room temperature and 16 g of 0,0-dimethylchlorothiophosphate are added. Stir for 24 hours at room temperature and remove the mineral salts with suction. The solvent is concentrated and the residue is chromatographed on silica gel, fused with a mixture of chloroform, acetone and cyclohexane in a 1: 1: 1 ratio. After evaporation of the solvent, 6.2 g of 2 - (dimethoxythiophosphoryloxy) 8 - methyl pyrido (1, 2 a) pyrimidine 4 - is obtained in the form of yellow crystals melting at 110 ° C.
Вычислено,%: С 44,0; Н4,36; N 9,33; Р 10,31.Calculated,%: C 44.0; H4.36; N 9.33; R 10.31.
CiiHi3N204PS.CiiHi3N204PS.
Найдено,%: С 44,0; Н 4,4; N 9,0; Р 10,3.Found,%: C 44.0; H 4.4; N 9.0; R 10.3.
Пример 6. 2- (Дизтокситиофосфорилокси) пиримидо (1, 2 а) пиримидин 4- онExample 6. 2- (Distoxythiophosphoryloxy) pyrimido (1, 2 a) pyrimidine 4-one
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7232088A FR2198697B1 (en) | 1972-09-11 | 1972-09-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU507246A3 true SU507246A3 (en) | 1976-03-15 |
Family
ID=9104093
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU1956353A SU507246A3 (en) | 1972-09-11 | 1973-09-10 | Method of producing phosphoric acid esters |
| SU762329602A SU733504A3 (en) | 1972-09-11 | 1976-03-04 | Insecticidal composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU762329602A SU733504A3 (en) | 1972-09-11 | 1976-03-04 | Insecticidal composition |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US3904624A (en) |
| JP (1) | JPS5648481B2 (en) |
| BE (1) | BE804654A (en) |
| BR (1) | BR7306999D0 (en) |
| CH (1) | CH575430A5 (en) |
| DD (1) | DD109316A5 (en) |
| DK (1) | DK138899B (en) |
| ES (1) | ES418627A1 (en) |
| FR (1) | FR2198697B1 (en) |
| GB (1) | GB1408718A (en) |
| GT (1) | GT198065690A (en) |
| HU (1) | HU168852B (en) |
| IL (1) | IL43034A (en) |
| IT (1) | IT1047946B (en) |
| NL (1) | NL7312432A (en) |
| OA (1) | OA04553A (en) |
| SU (2) | SU507246A3 (en) |
| TR (1) | TR18108A (en) |
| YU (1) | YU36304B (en) |
| ZA (1) | ZA735709B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2703712A1 (en) * | 1977-01-29 | 1978-08-03 | Bayer Ag | SUBSTITUTED PYRIMIDINONE ANGLE CLAMP ON (DI) -THIO ANGLE CLAMP ON -PHOSPHORUS- (PHOSPHONE) -ACIDESTER OR. -ESTERAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES, ACARICIDES AND NEMATICIDES |
| US4395551A (en) * | 1981-12-10 | 1983-07-26 | Uniroyal, Inc. | Pyridopyrimidinone compounds |
| US4634690A (en) * | 1981-12-10 | 1987-01-06 | Uniroyal Chemical Company, Inc. | Substituted pyrimidinyl organophosphorus insecticides |
| US4472389A (en) * | 1981-12-10 | 1984-09-18 | Uniroyal, Inc. | Substituted pyrimidinyl organophosphorus insecticides |
| JPS60125077U (en) * | 1984-01-30 | 1985-08-23 | 織田 義男 | Nailing support |
| JP2532677Y2 (en) * | 1991-03-13 | 1997-04-16 | 株式会社 日本バノック | Lashing device |
| WO1992017478A1 (en) * | 1991-04-08 | 1992-10-15 | Duquesne University Of The Holy Ghost | 5-ALKYL-6-[[AMINO]METHYL]PYRIDO[2,3-d]PYRIMIDINE DERIVATIVES AND METHODS OF PREPARING AND USING THESE DERIVATIVES |
| US5508281A (en) * | 1991-04-08 | 1996-04-16 | Duquesne University Of The Holy Ghost | Derivatives of pyrido [2,3-d] and [3,2-d] pyrimidine and methods of using these derivatives |
| US5939420A (en) * | 1991-04-08 | 1999-08-17 | Duquesne University Of The Holy Ghost | Pyrrolo 2,3d!derivatives |
| US5346900A (en) * | 1991-04-08 | 1994-09-13 | Duquesne University Of The Holy Ghost | 5-alkyl-6-[[amino]methyl]pyrido[2,3-D]pyrimidine derivatives and methods of using these derivatives |
| US5877178A (en) * | 1991-04-08 | 1999-03-02 | Duquesne University Of The Holy Ghost | Pyrimidine derivatives and methods of making and using these derivatives |
| US6962920B2 (en) | 1992-09-23 | 2005-11-08 | Duquesne University Of The Holy Ghost | Pyrimidine derivatives and methods of making and using these derivatives |
| US6537999B2 (en) | 1996-06-06 | 2003-03-25 | Duquesne University Of The Holy Ghost | Pyrimidine derivatives and methods of making and using these derivatives |
| US6106033A (en) * | 1997-08-26 | 2000-08-22 | Ewald Witte Gmbh & Co. Kg | Catch-hook arrangement for a front hood or the like on motor vehicles |
| RU2656592C2 (en) * | 2012-06-19 | 2018-06-06 | Дау Глоубл Текнолоджиз Ллк | Heterocyclic antimicrobial compounds for use in water-containing systems |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1239695B (en) * | 1964-12-24 | 1967-05-03 | Bayer Ag | Process for the preparation of phosphorus, phosphonic, thionophosphorus or thionophosphonic acid esters |
| BE788828A (en) * | 1971-09-16 | 1973-03-14 | Roussel Uclaf | NEW HETEROCYCLIC ORGANOPHOSPHORUS DERIVATIVES AND PROCESS OF PREPARATION |
-
1972
- 1972-09-11 FR FR7232088A patent/FR2198697B1/fr not_active Expired
-
1973
- 1973-08-15 DD DD172908A patent/DD109316A5/xx unknown
- 1973-08-21 IL IL43034A patent/IL43034A/en unknown
- 1973-08-21 ZA ZA735709A patent/ZA735709B/en unknown
- 1973-09-04 US US394078A patent/US3904624A/en not_active Expired - Lifetime
- 1973-09-10 BE BE135484A patent/BE804654A/en not_active IP Right Cessation
- 1973-09-10 IT IT52424/73A patent/IT1047946B/en active
- 1973-09-10 SU SU1956353A patent/SU507246A3/en active
- 1973-09-10 YU YU2404/73A patent/YU36304B/en unknown
- 1973-09-10 BR BR6999/73A patent/BR7306999D0/en unknown
- 1973-09-10 ES ES418627A patent/ES418627A1/en not_active Expired
- 1973-09-10 CH CH1293873A patent/CH575430A5/xx not_active IP Right Cessation
- 1973-09-10 NL NL7312432A patent/NL7312432A/xx active Search and Examination
- 1973-09-11 JP JP10175773A patent/JPS5648481B2/ja not_active Expired
- 1973-09-11 HU HURO749A patent/HU168852B/hu unknown
- 1973-09-11 DK DK497773AA patent/DK138899B/en unknown
- 1973-09-11 OA OA55010A patent/OA04553A/en unknown
- 1973-09-11 TR TR18108A patent/TR18108A/en unknown
- 1973-09-11 GB GB4259273A patent/GB1408718A/en not_active Expired
-
1976
- 1976-03-04 SU SU762329602A patent/SU733504A3/en active
-
1980
- 1980-10-03 GT GT198065690A patent/GT198065690A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2345762B2 (en) | 1977-04-21 |
| IT1047946B (en) | 1980-10-20 |
| FR2198697A1 (en) | 1974-04-05 |
| IL43034A (en) | 1976-05-31 |
| ES418627A1 (en) | 1976-02-16 |
| JPS4992096A (en) | 1974-09-03 |
| TR18108A (en) | 1976-09-30 |
| US3904624A (en) | 1975-09-09 |
| GT198065690A (en) | 1982-03-27 |
| GB1408718A (en) | 1975-10-01 |
| BR7306999D0 (en) | 1974-06-27 |
| YU36304B (en) | 1982-06-18 |
| SU733504A3 (en) | 1980-05-05 |
| DE2345762A1 (en) | 1974-03-21 |
| DK138899C (en) | 1979-04-23 |
| DD109316A5 (en) | 1974-11-05 |
| YU240473A (en) | 1981-08-31 |
| HU168852B (en) | 1976-07-28 |
| BE804654A (en) | 1974-03-11 |
| OA04553A (en) | 1980-04-30 |
| IL43034A0 (en) | 1973-11-28 |
| DK138899B (en) | 1978-11-13 |
| JPS5648481B2 (en) | 1981-11-16 |
| FR2198697B1 (en) | 1975-09-12 |
| ZA735709B (en) | 1974-10-30 |
| CH575430A5 (en) | 1976-05-14 |
| NL7312432A (en) | 1974-03-13 |
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