SU268417A1 - METHOD FOR OBTAINING N-ACYL-S-ETHER - Google Patents
METHOD FOR OBTAINING N-ACYL-S-ETHERInfo
- Publication number
- SU268417A1 SU268417A1 SU1276183A SU1276183A SU268417A1 SU 268417 A1 SU268417 A1 SU 268417A1 SU 1276183 A SU1276183 A SU 1276183A SU 1276183 A SU1276183 A SU 1276183A SU 268417 A1 SU268417 A1 SU 268417A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- acyl
- ether
- obtaining
- mol
- acetone
- Prior art date
Links
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000008079 hexane Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003385 sodium Chemical class 0.000 description 3
- -1 N-acylated cysteine ester Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- HPFKOFNYNQMWEF-UHFFFAOYSA-L chloro-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [O-]P([O-])(Cl)=S HPFKOFNYNQMWEF-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UFDFFEMHDKXMBG-UHFFFAOYSA-N 2-acetamidoprop-2-enoic acid Chemical compound CC(=O)NC(=C)C(O)=O UFDFFEMHDKXMBG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N Diethyl dithiophosphoric acid Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- SKRDXYBATCVEMS-UHFFFAOYSA-N Isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- DWKVPAJIUJRQDW-UHFFFAOYSA-N chloro-di(propan-2-yloxy)-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)OP(Cl)(=S)OC(C)C DWKVPAJIUJRQDW-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- MSMRAGNKRYVTCX-LURJTMIESA-N ethyl (2R)-2-acetamido-3-sulfanylpropanoate Chemical compound CCOC(=O)[C@H](CS)NC(C)=O MSMRAGNKRYVTCX-LURJTMIESA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000749 insecticidal Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
Description
Изобретение относитс к -способу получени эфиров хМ-ацил-З - (О,О - диалкилтиофосфорил ) -цистеина общей формулыThe invention relates to the XM-acyl-3 - (O, O-dialkylthiophosphoryl) -cysteine β-ester production method of the general formula
RO.RO.
/P-S-CH -CH-COOR НО/ III/ P-S-CH -CH-COOR HO / III
SNHCOR,SNHCOR,
где R, R, R - одинаковые или разные алкильные радикалы.where R, R, R are the same or different alkyl radicals.
Указанные соединени предлагают получать взаимодействием натриевого производного N-ацилированного эфира цистеина с диалкилхлортиофосфатом при нагревании: в среде органического растворител с последующим выделением целевого продукта известным способом. Полученные соединени могут быть использованы в качестве инсектицидов и акарицидов.These compounds propose to prepare by reacting the sodium derivative of N-acylated cysteine ester with dialkyl chlorothiophosphate when heated: in an organic solvent medium, followed by isolation of the target product in a known manner. The compounds obtained can be used as insecticides and acaricides.
Пример 1. К алкогол ту натри , приготовленному из 0,23 г (0,01 м.олъ металлического натри в 15 мл сухого этилового спирта при 25-г-30°С прибавл ют при перемешивании по капл м 1,91 г (0,01 моль) O-этил-N-aцeтилцистеина в 10-15 мл ацетона и, не выдел полученное натриевое производное О-этил-Nацетилцистеина , при 50°С добавл ют 2,16 г. (0,01 моль диизопропилхлортиофосфата в 10-15 мл ацетона. Реакционную смесь выдерживают при этом температуре в течениеExample 1. To a sodium alcoholate prepared from 0.23 g (0.01 mol of metallic sodium in 15 ml of dry ethyl alcohol at 25-g-30 ° C, 1.91 g (0 , 01 mol) O-ethyl-N-acetylcysteine in 10-15 ml of acetone and, the resulting sodium derivative of O-ethyl-N-acetylcysteine is not isolated, 2.16 g is added at 50 ° C (0.01 mol of diisopropyl chlorothiophosphate in 10- 15 ml of acetone. The reaction mixture is maintained at this temperature for
5 час, о.хлаладают, выпавший осадок поваренной соли отфильтровывают, промывают ацетоном и фильтрат концентрируют в вакууме. Остаток раствор ют в бензоле или в хлороформе , промывают водой. Органический слой сушат над безводным сульфатом натри и концентрируют в вак)уме. Очистку вещества производ т путем многократного высаживани из смеси эфира с гексаном при охлаждеНИИ или хроматографическим путем на колонне , наполненной носителем - силикагелем марки КСП в системе гексан : ацетон в соотношении 4 : 1 или 3 : 2.5 hours, cool off, the precipitated sodium chloride precipitate is filtered off, washed with acetone and the filtrate is concentrated in vacuo. The residue is dissolved in benzene or in chloroform, washed with water. The organic layer is dried over anhydrous sodium sulfate and concentrated in vac) mind. The substance was purified by repeatedly precipitating from a mixture of ether and hexane while cooling or chromatographically on a column filled with a silica gel carrier in the PSC system in the hexane: acetone ratio of 4: 1 or 3: 2.
Пример 2. К 2,05 г (0,11 моль диэтилдитиофосфорной кислоты в 30 мл ксилола или толуола добавл ют 1,71 г (0,01 моль) изопропилового эфира N-ацетил-а-аминоакриловой кислоты в 20-25 мл ксилола или толуола иExample 2. To 1.75 g (0.11 mol of diethyldithiophosphoric acid in 30 ml of xylene or toluene, 1.71 g (0.01 mol) of N-acetyl-a-amino-acrylic acid isopropyl ester in 20-25 ml of xylene or toluene and
нагревают реакционную смесь при 90-95°С при перемешивании в течение 5-7 час. После охлаждени реакционную смесь нейтрализуют 5%-ным раствором соды и промывают дважды холодной водой. Органический слойheat the reaction mixture at 90-95 ° C with stirring for 5-7 hours. After cooling, the reaction mixture is neutralized with a 5% soda solution and washed twice with cold water. Organic layer
сушат безводным сульфатом натри и концентрируют в вакууме.dried with anhydrous sodium sulfate; and concentrated in vacuo.
Очистку производ т путем многократного высаживани из смеси эфира с гексаном при охлаждении или хроматографическим путемPurification is carried out by repeated precipitation from a mixture of ether and hexane with cooling or by chromatography.
КСП в системе гексан: ацетон в соотношенииPSC in the system hexane: acetone in the ratio
4: 1 или 3 : 2. Полученный О-изопронил-Ы-ацетил- (О,О-диэтилтиофосфорил) -цистеин представл ет собой сиропообраз 1ую нрозрачную жидкость соломенного цвета:4: 1 or 3: 2. The O-isopronyl-L-acetyl- (O, O-diethylthiophosphoryl) -cysteine obtained is a syrupy syrup of straw colored liquid:
«20 1,4985; df 1,1624. Выход 1,14 г (29,2% от теоретического, счита на изонропиловый эфир N-ацетил-а-аминоакриловой кислоты).“20 1.4985; df 1.1624. Yield 1.14 g (29.2% of theory, calculated on isopropyl ester of N-acetyl-α-amino-acrylic acid).
Найдено, %: N 3,81, 3,76; Р 8,53, 8,29;Found,%: N 3.81, 3.76; R 8.53, 8.29;
517,65, 17,77.517.65, 17.77.
Ci2H24N05PS2.Ci2H24N05PS2.
Вычислено, %: N 3,91; Р 8,66; S 17,94. Найдено MRo 90,21. Вычислено MRD 89,99.Calculated,%: N 3.91; P 8.66; S 17.94. Found MRo 90.21. Calculated MRD 89.99.
Строение полученных веществ подтверждено данными элементарного анализа молекул рных рефракций и инфракрасных спектров.The structure of the obtained substances was confirmed by the data of elementary analysis of molecular refractions and infrared spectra.
Предмет изобретени Subject invention
Способ получени эфиров М-ацил-5-(0,Одиалкилтиофосфорил )-цистеина общей формулы:The method of producing M-acyl-5- (0, Odalkylthiophosphoryl) -cysteine esters of the general formula:
ROvRov
P-S-CH,-CH-COORP-S-CH, -CH-COOR
RORO
NHCORNHCOR
где R, R, R - одинаковые или разные алкильные радикалы, отличающийс тем, что натриевое производное N-ацилированного эфира цистеина подвергают взаимодействию с диалкилхлортиофосфатом при нагревании в среде органического растворител , с последующим выделением целевого продукта известным способом.where R, R, R are the same or different alkyl radicals, characterized in that the sodium derivative of N-acylated cysteine ester is reacted with dialkyl chlorothiophosphate when heated in an organic solvent medium, followed by isolation of the target product in a known manner.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU268417A1 true SU268417A1 (en) |
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