RU2411247C2 - Method for synthesis of ether-acid fluorides of alkyl(aryl)phosphonous acids - Google Patents
Method for synthesis of ether-acid fluorides of alkyl(aryl)phosphonous acids Download PDFInfo
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- RU2411247C2 RU2411247C2 RU2009110613/04A RU2009110613A RU2411247C2 RU 2411247 C2 RU2411247 C2 RU 2411247C2 RU 2009110613/04 A RU2009110613/04 A RU 2009110613/04A RU 2009110613 A RU2009110613 A RU 2009110613A RU 2411247 C2 RU2411247 C2 RU 2411247C2
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- Prior art keywords
- aryl
- alkyl
- synthesis
- ether
- acid fluorides
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- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000002253 acid Substances 0.000 title claims abstract 3
- 238000003786 synthesis reaction Methods 0.000 title abstract description 7
- 230000015572 biosynthetic process Effects 0.000 title abstract description 5
- 150000002222 fluorine compounds Chemical class 0.000 title abstract 2
- 125000003118 aryl group Chemical group 0.000 claims description 8
- VVRKSAMWBNJDTH-UHFFFAOYSA-N difluorophosphane Chemical class FPF VVRKSAMWBNJDTH-UHFFFAOYSA-N 0.000 claims description 4
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 abstract 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 3
- RFONJRMUUALMBA-UHFFFAOYSA-N 2-methanidylpropane Chemical compound CC(C)[CH2-] RFONJRMUUALMBA-UHFFFAOYSA-N 0.000 abstract 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract 2
- 239000013067 intermediate product Substances 0.000 abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 6
- -1 phosphonic acid ester hydrofluorides Chemical class 0.000 description 5
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AMJMBJIZKKMZIE-UHFFFAOYSA-N difluoro(methyl)phosphane Chemical compound CP(F)F AMJMBJIZKKMZIE-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Abstract
Description
Изобретение относится к области фосфорорганических соединений, а именно к способу получения эфирофторангидридов алкил(арил)фосфоновых кислот общей формулыThe invention relates to the field of organophosphorus compounds, and in particular to a method for producing alkyl (aryl) phosphonic acid ester hydrofluorides of the general formula
RP(OR')FRP (OR ') F
где R=СН3, С2Н5, i-С3Н7, С4Н9, i-C4H9; R'=СН3, С2Н5, С3Н7, i-С3Н7, С4Н9, i-С4Н9, С6Н5, С6H11 where R = CH 3 , C 2 H 5 , i-C 3 H 7 , C 4 H 9 , iC 4 H 9 ; R '= CH 3 , C 2 H 5 , C 3 H 7 , i-C 3 H 7 , C 4 H 9 , i-C 4 H 9 , C 6 H 5 , C 6 H 11
путем взаимодействия алкил(арил)дифторфосфинов RPF2 с триметилалкоксисиланами общей формулы (СН3)3SiOR' где R'=R'=СН3 by reacting alkyl (aryl) difluorophosphines RPF 2 with trimethylalkoxysilanes of the general formula (CH 3 ) 3 SiOR 'where R' = R '= CH 3
С2H5, С3Н7, i-С3Н7, С4Н9, i-С4Н9, С6Н5, С6Н11 С 2 H 5 , С 3 Н 7 , i-С 3 Н 7 , С 4 Н 9 , i-С 4 Н 9 , С 6 Н 5 , С 6 Н 11
в соотношении 1:1 в отсутствии растворителя при температуре от -30 до +20°С в течение от 30 мин до 1 ч.in a ratio of 1: 1 in the absence of solvent at a temperature of from -30 to + 20 ° C for from 30 minutes to 1 hour
Задачей изобретения является синтез целевых соединений с высоким выходом и более технологичным способом.The objective of the invention is the synthesis of target compounds with high yield and more technological way.
Ранее указанные соединения были получены реакцией эфирохлорангидридов метилфосфонистых кислот фторидом цезия при 20°С [1].Previously, these compounds were obtained by the reaction of methylphosphonic acid ester chlorides with cesium fluoride at 20 ° С [1].
Недостатком способа является низкий выход (60-70%) целевых соединений, а также использование дорогостоящего фторида цезия.The disadvantage of this method is the low yield (60-70%) of the target compounds, as well as the use of expensive cesium fluoride.
Наиболее близким по существу способом является способ, основанный на реакции алкил(арил)дифторфосфинов со спиртами [2-4]. Реакцию проводят в растворах этилового эфира или бензола в присутствии акцепторов фтористого водорода: триэтиламина [2], аммиака [3], а также алкоголятов натрия [3] или лития [4].The closest essentially method is a method based on the reaction of alkyl (aryl) difluorophosphines with alcohols [2-4]. The reaction is carried out in solutions of ethyl ether or benzene in the presence of acceptors of hydrogen fluoride: triethylamine [2], ammonia [3], as well as sodium alcoholate [3] or lithium [4].
Недостатками способа являются использование горючего растворителя, необходимость использования метода фильтрации, а также низкий (8-70%) выход целевых продуктов.The disadvantages of the method are the use of a combustible solvent, the need to use the filtration method, and the low (8-70%) yield of the target products.
Поставленная задача решается предлагаемым способом синтеза целевых соединений в отсутствие растворителя при низких температурах. Выход целевых соединений составляет 80-95%. Нижний интервал температуры обусловлен температурой кипения исходного алкил(арил)дифторфосфина.The problem is solved by the proposed method for the synthesis of target compounds in the absence of a solvent at low temperatures. The yield of the target compounds is 80-95%. The lower temperature range is due to the boiling point of the starting alkyl (aryl) difluorophosphine.
ПРИМЕР 1. Метиловый эфирофторангидрид метилфосфонистой кислотыEXAMPLE 1. Methyl methylphosphonic acid methyl ester fluoride
В колбу конденсируют 0,1 моль метилдифторфосфина при -30°С и по каплям прибавляют 0,1 моль триметилметоксисилана. Смесь нагревают до 20°С и выдерживают при перемешивании в течение 30 мин. Фракционированием выделяют продукт с выходом 80% с т.кип. 56-57°С при 750 мм рт.ст., d4 20 1,0148.0.1 mol of methyl difluorophosphine is condensed into the flask at -30 ° C and 0.1 mol of trimethylmethoxysilane is added dropwise. The mixture is heated to 20 ° C and kept under stirring for 30 minutes. By fractionation, a product is isolated with a yield of 80% with so on. 56-57 ° C at 750 mmHg, d 4 20 1.0148.
ПРИМЕР 2. Этиловый эфирофторангидрид метилфосфонистой кислотыEXAMPLE 2. Ethyl methylphosphonic acid ethyl ester fluoride hydride
В вышеописанных условиях из 0,1 моль метилдифторфосфина и 0,1 моль триметилэтоксисилана при 20°С в течение 1 ч получают продукт с выходом 90% с т.кип. 61-63°С при 751 мм рт.ст., nD 20 1,3930, d4 20 1,0435.Under the above conditions, from 0.1 mol of methyldifluorophosphine and 0.1 mol of trimethylethoxysilane at 20 ° C for 1 h, the product is obtained in 90% yield, b.p. 61-63 ° C at 751 mmHg, n D 20 1.3930, d 4 20 1.0435.
Остальные эфирофторангидриды алкил(арил)фосфонистых кислот получены аналогично. Физико-химические свойства и выход полученных продуктов приведены в табл.1, а их спектральные характеристики - в табл.2.The remaining alkyl (aryl) phosphonous acid ester hydrofluorides are obtained in a similar manner. The physicochemical properties and yield of the obtained products are given in Table 1, and their spectral characteristics are shown in Table 2.
Выход и свойства синтезированных эфирофторангидридов алкил(арил)фосфонистых кислот общей формулы RP(OR')FTABLE 1
The yield and properties of the synthesized alkyl (aryl) phosphonous acid esters of the general formula RP (OR ') F
Данные ЯМР 31Р-спектры синтезированных соединений общей формулы RP(OR')FTABLE 2
NMR data 31 P spectra of the synthesized compounds of General formula RP (OR ') F
ЛитератураLiterature
1. А.А.Кролевец, А.В.Адамов, А.Г.Попов, П.В.Петровский, И.В.Мартынов - Авт. Свид. СССР №1490123 от 1.03.89.1. A.A. Krolevets, A.V. Adamov, A.G. Popov, P.V. Petrovsky, I.V. Martynov - Author. Testimonial. USSR No. 1490123 dated 1.03.89.
2. Г.И.Дрозд, С.З.Ивин, В.В.Шелученко - ЖВХО им. Д.И.Менделеева, 1967, т.12, №4, с.474-475.2. G.I. Drozd, S.Z. Ivin, V.V. Sheluchenko - ZhVHO them. D.I. Mendeleev, 1967, v. 12, No. 4, p. 474-475.
3. Г.И.Дрозд, С.З.Ивин, В.Н.Кулакова, В.В.Шелученко - ЖОХ, 1968, т.38, №3, с.576-581.3. G.I. Drozd, S.Z. Ivin, V.N. Kulakova, V.V. Sheluchenko - ZhOKh, 1968, v. 38, No. 3, p. 566-581.
4. D.Daktemieks, G.-V.Roschenthaler, R.Schmutzler - J.Fluor. Chem, 1978, v.12, N5, p.413-426.4. D. Daktemieks, G.-V. Roschenthaler, R. Schmutzler - J. Fluor. Chem, 1978, v. 12, N5, p. 413-426.
Claims (1)
RP(OR')F,
где R=СН3, С2Н5, i-С3Н7, С4Н9, i-C4H9, R'=СН3, С2Н5, С3Н7, i-С3Н7, С4Н9, i-C4H9, С6Н5, С6Н11,
отличающийся тем, что он заключается в обработке алкил(арил)дифторфосфинов триметилалкоксисиланами общей формулы
(СН3)3SiOR',
где R'=СН3, С2Н5, С3Н7, i-С3Н7, С4Н9, i-С4Н9, С6Н5, С6Н11,
при (-30)÷(20)°С в течение 30-60 мин. A method of producing an alkyl (aryl) phosphonous acid ester fluoride acid of the general formula
RP (OR ') F,
where R = CH 3 , C 2 H 5 , i-C 3 H 7 , C 4 H 9 , iC 4 H 9 , R '= CH 3 , C 2 H 5 , C 3 H 7 , i-C 3 H 7 , C 4 H 9 , iC 4 H 9 , C 6 H 5 , C 6 H 11 ,
characterized in that it consists in the treatment of alkyl (aryl) difluorophosphines with trimethylalkoxysilanes of the general formula
(CH 3 ) 3 SiOR ',
where R '= CH 3 , C 2 H 5 , C 3 H 7 , i-C 3 H 7 , C 4 H 9 , i-C 4 H 9 , C 6 H 5 , C 6 H 11 ,
at (-30) ÷ (20) ° С for 30-60 minutes
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230271985A1 (en) * | 2020-01-20 | 2023-08-31 | Lier Chemical Co., Ltd. | Preparation method for glufosinate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1490123A1 (en) * | 1987-10-05 | 1989-06-30 | Военная Краснознаменная академия химической защиты им.Маршала Советского Союза С.К.Тимошенко | Method of producing asterofluoroanhydrides of alkylphosphonic acids |
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2009
- 2009-03-23 RU RU2009110613/04A patent/RU2411247C2/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1490123A1 (en) * | 1987-10-05 | 1989-06-30 | Военная Краснознаменная академия химической защиты им.Маршала Советского Союза С.К.Тимошенко | Method of producing asterofluoroanhydrides of alkylphosphonic acids |
Non-Patent Citations (1)
| Title |
|---|
| ДРОЗД Г.И. и др. ЖОХ, 1968, т.38, вып.3, с.576-581. КУЛАКОВА В.Н. и др. ЖОХ, 1969, т.39, вып.3, с.579-582. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230271985A1 (en) * | 2020-01-20 | 2023-08-31 | Lier Chemical Co., Ltd. | Preparation method for glufosinate |
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| RU2009110613A (en) | 2010-09-27 |
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