CS241545B2 - Method of s-(thiophosphoryl)-thioglycol acid's bromides production - Google Patents
Method of s-(thiophosphoryl)-thioglycol acid's bromides production Download PDFInfo
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- CS241545B2 CS241545B2 CS280184A CS280184A CS241545B2 CS 241545 B2 CS241545 B2 CS 241545B2 CS 280184 A CS280184 A CS 280184A CS 280184 A CS280184 A CS 280184A CS 241545 B2 CS241545 B2 CS 241545B2
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- Czechoslovakia
- Prior art keywords
- bromides
- thiophosphoryl
- production
- ppm
- temperature
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 7
- 150000001649 bromium compounds Chemical class 0.000 title description 3
- 239000002253 acid Substances 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- -1 2-dimethylpropoxythiophosphorylthioglycolic acid Chemical compound 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
Description
Předmětem vynálezu, je způsob výroby bromidů-S-( thiofosforyl Jthioglykolové kyseliny obecného vzorce IThe present invention provides a process for the preparation of bromides-S- (thiophosphoryl) thioglycolic acid of the formula I
R SO \llIIR SO \ III
P—S—CH2-C—Br(I) P-S-CH2-Br, -C (L)
R{ kdeR { where
R a R1 jsou stejné nebo rozdílné a znamenají alkoxylovou skupinu s 1 až 5 atomy uhlíku nebo -aryloxylovou skupinu se 6 atomy uhlíku. Uvedené bromidy jsou novými sloučeninami, které nebyly dosud popsány v literatuře. V důsledku jejich reaktivní struktury mají široké použití v organické syntéze. Částečně mohou být tyto sloučeniny použity jaiko výchozí látky pro · výrobu pesticidů, které jsou deriváty dithiokyselin fosforu. Díky tomu, že v jejich struktuře jsou přítomny takové hetero-atomy jako fosfor, síra a brom, mají vlastnosti příměsí do1 plastifikačních přísad, nehořlavých plastických hmot i rafinačních lubrikačních činidel.R 1 and R 1 are the same or different and are C 1 -C 5 alkoxy or C 6 -C 6 -aryloxy. Said bromides are novel compounds not previously described in the literature. Due to their reactive structure, they have wide application in organic synthesis. In part, these compounds can be used as starting materials for the production of pesticides which are derivatives of phosphorous dithioacids. Due to the presence of heteroatoms such as phosphorus, sulfur and bromine in their structure, they have the properties of admixtures in 1 plasticizers, non-flammable plastics and refining lubricants.
Nové bromidy-S- (thiofosforyl) thioglykolové kyseliny obecného vzorce INovel-S- (thiophosphoryl) thioglycolic acid bromides of formula (I)
R SO \llII p—s—CH2—C—Br(I) rS kdeR SO \ llII p-S-CH2-Br, -C (I) where r
R a R1 jsou stejné nebo rozdílné a znamenají alko<xyl s 1 až 5 atomy uhlíku nebo aryloxylovou skupinu, se 6 atomy uhlíku, se získají reakcí thioxofosfátosulfenylbroinidu obecného vzorce IIR 1 and R 1 are the same or different and are C 1 -C 5 -alkoxy or C 6 -C 6 aryloxy, obtained by reaction of thioxophosphate sulfenylbroinide of formula II
R S \llR S \ ll
P—S—Br (II)P — S — Br (II)
R1 kdeR 1 where
R a R1 mají výše uvedený význam, s 1 až 3 moly ketonu vzorce CH2—C=O.R 1 and R 1 are as defined above, with 1 to 3 moles of the ketone of formula CH 2 -C = O.
Reakce se provádí při teplotě pod +10 °C, výhodně při teplotě od —20 do· +5 °C, v· prostředí aprotického rozpouštědla nebo směsí takových rozpouštědel. Jako· aiprotická rozpouštědla se užívají chlorid uhličitý, chloroform, dichlormethan, benzen, hexan, toluen a ropný benzin.The reaction is carried out at a temperature below + 10 ° C, preferably at a temperature of from -20 to + 5 ° C, in an aprotic solvent environment or mixtures of such solvents. Carbon dioxide, chloroform, dichloromethane, benzene, hexane, toluene and petroleum gasoline are used as aprotic solvents.
Produkt připravený způsobem podle vynálezu se izoluje z reakční směsi destilací za sníženého tlaku řádově 0,13 až 0,66 kPa po předchozím odstranění rozpouštědla, při teplotě do +5 °C, výhodně při teplotě od —10 do· 0 °C a tlaku 0,1 až 1,3 kPa. Tyto produkty mohou být použity pro další syntézu v surovém stavu pouze po odstranění rozpouštědel za výše uvedených podmínek.The product prepared by the process according to the invention is isolated from the reaction mixture by distillation under reduced pressure of the order of 0.13 to 0.66 kPa after previous removal of the solvent, at a temperature of up to +5 ° C, preferably at a temperature of -10 to 0 ° C and a pressure of 0. 1 to 1.3 kPa. These products can be used for further crude synthesis only after removal of the solvents under the above conditions.
Způsob podle vynálezu poskytuje surové bromidy ve výtěžku kolem 95 až 98 % čistoty 95 až 100 %, což bylo zjištěno na základě spektrální analýzy produktu nukleární rezonancí Ή a 31P.The process of the present invention yields crude bromides in a yield of about 95 to 98% purity of 95 to 100% as determined by spectral analysis of the product by nuclear resonance ární and 31 P.
Dále uvedené příklady blíže osvětlují postup podle vynálezu aniž by jej jakkoliv omezovaly.The following examples illustrate the process of the invention without limiting it in any way.
Příklad 1Example 1
Roztok 3,5 g čerstvě připraveného 0,0-A solution of 3,5 g of freshly prepared 0,0-
2,2-dimethylpropylthioxofosfatosulfonylbrOmidu [0,01 mol) ve 30 ml chloridu uhličitého se za míchání sytí parami ketenu po dobu 2 hodin při teplotě od —5 do 0 °C, až je pozorována změna barvy reakční směsi na světle žlutou.2,2-dimethylpropylthioxophosphatosulfonylbromide [0.01 mol] in 30 ml of carbon tetrachloride was saturated with ketene vapor for 2 hours at -5 to 0 ° C with stirring until a color change of the reaction mixture to light yellow was observed.
Rozpouštědlo se oddestiluje při teplotě 0 stupňů Celsia za tlaku 1,3 kPa, získá se 3,9 gramu (100 °/o) žluté olejovitá kapaliny, která byla na základě spektrální analýzy Ul a 31P identifikována jako· bromid-S-(2,2-dimethylpropoxythiofosforyljthioglykolové kyseliny.The solvent was distilled off at 0 DEG C. under a pressure of 1.3 kPa, to give 3.9 g (100 ° / o) of a yellow oil which was based on the spectral analysis, Ul and 31, identified as P · bromide-S- (2 2-dimethylpropoxythiophosphorylthioglycolic acid.
31P 4- 91,9 ppm, (Cló) ext. 85% H3PO4, -Ή mrj (CC12) ó 1,26 ppm (18 H, Bu1—), ó 3,9 ppm (4H, —CH2O—) JPH 12 Hz, δ 4,5 ppim (2H, —SCH2—) JP_H 21,7 Hz. 31 P 4- 91.9 ppm, (Cl 6) ext. 85% H3PO4, -Ή mc (CC12) δ 1.26 ppm (18 H, Bu 1 -), δ 3.9 ppm (4H, —CH2O-) J PH 12 Hz, δ 4.5 ppim (2H, - SCH 2 - ? P? H 21.7 Hz.
Příklad 2Example 2
Roztokem 2,36 g (0,05 mol) O,O-dimethylthioxofosfatosulfenylbromidu ve 30 ml chloroformu se nechá procházet keten 2,5 hodi ny, teplota byla udržována v rozmezí od —8 do —5 °C. Realkční roztok byl míchán, paik se ponechá 45 minut při teplotě 4-10 °C. Rozpouštědloi se oddestiluje při teplotě od 0 do 5 °C za sníženého tlaku 1,3 kPa, získá seA solution of 2.36 g (0.05 mol) of O, O-dimethylthioxophosphatosulfenyl bromide in 30 ml of chloroform was passed through the ketene for 2.5 hours, maintaining the temperature at -8 to -5 ° C. The solution was stirred, allowing the solution to stand at 4-10 ° C for 45 minutes. The solvent is distilled off at a temperature of from 0 to 5 ° C under reduced pressure of 1.3 kPa to give
2,8 g (95 %) bromidu -S-(dimethoxythiofosforyl) thioiglykolové kyseliny.2.8 g (95%) -S- (dimethoxythiophosphoryl) thioiglycolic acid bromide.
δ31Ρ 4- 96,0 ppm (CC14) ext. 85% H3PO4, 41 mrj (CC14) (5 4,58 ppm (6H, CH3O-) JHP δ 31 Ρ 4- 96.0 ppm (CC1 4 ) ext. 85% H 3 PO 4 , 41 IU (CCl 4 ) (δ 4.58 ppm (6H, CH 3 O-) J HP
18,7 Hz, δ 5,07 ppm (2H, —SCH2—) JPH 21,7 Hz.18.7 Hz, δ 5.07 ppm (2H, -SCH 2 -), PH J 21.7 Hz.
Příklad 3Example 3
Roztok 5,8 g (0,02 mol) čerstvě připraveného OjO-diisoipropylthiaxoíosfatosulfenylbromidu ve 25 ml dichlormethanu se sytí při teplotě od —2° do 0 °C ketonem, až se získá světle žlutě zbarvená reakční směs. Destilací se izoluje 5,6 g (84,3 %) bromidu-S-(diisoopropoxythiofoisforyl)thioglykolové kyseliny, teplota varu 76 až 78 °C/0,65 kPa.A solution of 5.8 g (0.02 mol) of freshly prepared O, O-diisoipropylthiaxoophosphatosulfenyl bromide in 25 ml of dichloromethane is saturated with a ketone at a temperature of from -2 ° to 0 ° C until a light yellow reaction mixture is obtained. 5.6 g (84.3%) of S- (diisoopropoxythiophosphoryl) thioglycolic acid bromide are isolated by distillation, b.p. 76-78 ° C / 0.65 kPa.
Ó31P 4- 87,5 ppm (CH2Cb) ext. 85% H3PO4, 41 mrj (CC14) 5 1,3 ppm (12 H CH3-), ó 4,2 ppm (2H — SCH2) JPII 21,7 Hz. 31 31 P 4- 87.5 ppm (CH 2 Cb) ext. 85% H 3 PO 4 , 41 µm (CCl 4 ) δ 1.3 ppm (12 H CH 3 -), δ 4.2 ppm (2H-SCH 2 ) J PII 21.7 Hz.
Příklad 4Example 4
Roztek 18,05 g (0,05 molu) 0,0-difenylthioxofosfatoisulfenylbromidu v 50 ml chloridu uhličitého se sytí ketenem po 2 hodiny, přičemž byla teplota udržována od 0 °C doA solution of 18.05 g (0.05 mol) of O, O-diphenylthioxophosphatoisulfenyl bromide in 50 ml of carbon tetrachloride is saturated with ketene for 2 hours, maintaining the temperature from 0 ° C to 0 ° C.
4- 6 °C. Rozpouštědlo se oddestiluje při teplotě od 0 do1 5 °C za sníženého tlaku 1,3 až4-6 ° C. The solvent was distilled off at a temperature of from 0 to 1 5 ° C under reduced pressure of 1.3 to
1,5 kPa a získá se 18,7 g (92,7 %) bromidu1.5 kPa to give 18.7 g (92.7%) of the bromide
5- (difenoxythiofoisforyl jthioglykolové kyseliny ve formě olejovitá kapaliny, δ 31P 4- 87,0 ppm.5- (diphenoxythiophosphoryl) thioglycolic acid as an oily liquid, δ 31 P 4- 87,0 ppm.
Pro C14H12BrO3PS2 vypočteno:For C 14 H 12 BrO 3 PS 2 calculated:
41,7 % C, 2,9 % H, 7,6 % P, nalezeno:H, 2.9%; P, 7.6%; found:
42,0 % C, 3,1 % H, 7,1 % P.H, 3.1; H, 7.1%.
PREDMETSUBJECT
1. Způsob výroby bromidů S-(thiofosforyljthioglykolové kyseliny obecného vzorce IA process for the preparation of S- (thiophosphoryl) thioglycolic acid bromides of the general formula I
R SO \llIIR SO \ III
P—S—CH2~C—Br(I) z P-S-CH2-C-Br (I) from
R1 kdeR 1 where
R a R1 jsou stejné nebo rozdílné a znamenají alkoxylovou skupinu s 1 až 5 atomy uhlíku nebo aryloxylovou skupinu se 6 atomy uhlíku, vyznačující se tím, že se nechá thioxofosfatosulfenylbromiid obecného vzorce IIR 1 and R 1 are the same or different and are C 1 -C 5 alkoxy or C 6 aryloxy, characterized in that thioxophosphatosulfenyl bromide of the formula II is left
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL24149183A PL137160B1 (en) | 1983-04-14 | 1983-04-14 | Process for preparing bromides of -s-/dialkoxythiophosphoryl/-thioglycolic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS241545B2 true CS241545B2 (en) | 1986-03-13 |
Family
ID=20016635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS280184A CS241545B2 (en) | 1983-04-14 | 1984-04-12 | Method of s-(thiophosphoryl)-thioglycol acid's bromides production |
Country Status (6)
| Country | Link |
|---|---|
| BG (1) | BG42357A3 (en) |
| CS (1) | CS241545B2 (en) |
| DD (1) | DD217521A5 (en) |
| IN (1) | IN158583B (en) |
| PL (1) | PL137160B1 (en) |
| RO (1) | RO89405A (en) |
-
1983
- 1983-04-14 PL PL24149183A patent/PL137160B1/en unknown
-
1984
- 1984-04-12 CS CS280184A patent/CS241545B2/en unknown
- 1984-04-13 DD DD26197284A patent/DD217521A5/en unknown
- 1984-04-13 BG BG065086A patent/BG42357A3/en unknown
- 1984-04-14 RO RO84114259A patent/RO89405A/en unknown
- 1984-04-19 IN IN254/CAL/84A patent/IN158583B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IN158583B (en) | 1986-12-13 |
| BG42357A3 (en) | 1987-11-14 |
| RO89405A (en) | 1986-06-30 |
| PL241491A1 (en) | 1984-10-22 |
| DD217521A5 (en) | 1985-01-16 |
| PL137160B1 (en) | 1986-05-31 |
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