CS201056B1 - Method of preparing o-alkyl-o-isobutyl chlorthiophosphates - Google Patents
Method of preparing o-alkyl-o-isobutyl chlorthiophosphates Download PDFInfo
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- CS201056B1 CS201056B1 CS240379A CS240379A CS201056B1 CS 201056 B1 CS201056 B1 CS 201056B1 CS 240379 A CS240379 A CS 240379A CS 240379 A CS240379 A CS 240379A CS 201056 B1 CS201056 B1 CS 201056B1
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- CS
- Czechoslovakia
- Prior art keywords
- isobutyl
- alkyl
- preparing
- chlorthiophosphates
- preparation
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- -1 O-isobutyl O-propyl chlorothiophosphate Chemical compound 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- IJHRFLJHRSNMGI-UHFFFAOYSA-N [Mg].C=C Chemical group [Mg].C=C IJHRFLJHRSNMGI-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- RXFDVRBGXXDRFO-UHFFFAOYSA-N butoxy-chloro-ethoxy-sulfanylidene-$l^{5}-phosphane Chemical class CCCCOP(Cl)(=S)OCC RXFDVRBGXXDRFO-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
Vynález sa týká sposobu přípravy 0-alkyl O-izobutylchlórtiofosfátov. O-alkyl-O-izobutylchlortiofosfáty připravené spósobom podlá vynálezu představuji významné medziprodukty pře výrobu niektorých nových organofosfořových zlúčenin.The invention relates to a process for the preparation of O-alkyl O-isobutyl chlorothiophosphates. The O-alkyl-O-isobutylchlorotriophosphates prepared by the process of the invention are important intermediates for the production of some novel organophosphorus compounds.
Doteraz je známa například příprava Q-etyl-O-butylchlórtiofosfátov pásobením etylátu horečnatého na O-alkyldichlórtiofosfáty /Ž. obšč. chim. 27, 1908 (1957)/, příprava 0,0-di-butylchlórtiofosfátu reakciou O-butyldichlórtiofosfátu s butylátom sodným, připraveným z butylalkoholu a sodíka /J. Ind. Chem. Soc. 43, 575 (1966)/, příprava 0-butyl O-metylchlór-tiofosfátu pSsobením metanolu a hydroxidu sodného na O-butyldichlortiofůsfát /Ž. obšč. chim. 26, 2577 (1956)/. Nevýhodou vyššie spomínaných sposobov je, že spravidle pri přípravě sa vychádza ž O-alKyldichlórtiofosfátu s vyšším počtom uhlíkov v alkyl skupině ako dva a že tieto zlúčeniny sa dajú připravil prakticky iba z tiochloridu fosforečného a odpovedajúceho vyššieho alkoholu v přítomnosti pyridinu /USA pat. č. 3 365 532/, čo zíažuje izoláciu očekávaných produktov a výtažky sa pohybujú len okolo 75 %. fialšou nevýhodou známých příprav vyšších O-alkyldichlórtiofosfátov je, že technické produkty obsahujú aj část nezřeagovaného tiochloridu fosforečného, čo v případe O-izobutyldichlórtiofosfátu vedie k následnéj reakcii s alkoholátmi, za vzniku příslušných 0-izobutyl Ο,Ο-dialkyltiofosfátov povedla očekávaného 0-alkyl O-izobutylchlórtiofosfátu.For example, the preparation of Q-ethyl-O-butyl chlorothiophosphates by multiplication of magnesium ethylate to O-alkyldichlorothiophosphates (R) is known to date. obšč. chim. 27, 1908 (1957)], the preparation of O, O-butyldichlorothiophosphate with sodium butylate prepared from butyl alcohol and sodium [J. Indian. Chem. Soc. 43, 575 (1966)], the preparation of O-butyl O-methyl-chloro-thiophosphate by treatment of methanol and sodium hydroxide with O-butyldichlorotiophosphate (Ž. obšč. chim. 26, 2577 (1956)]. A disadvantage of the above-mentioned methods is that as a rule O-alkyl dichlorothiophosphate with a higher number of carbons in the alkyl group is two, and that these compounds can be prepared practically only from phosphorous thiochloride and the corresponding higher alcohol in the presence of pyridine / US Pat. No. 3,365,532, which makes it difficult to isolate the expected products and yields are only about 75%. a more violent disadvantage of the known preparations of higher O-alkyldichlorothiophosphates is that the technical products also contain a portion of unreacted phosphorous thiochloride, which in the case of O-isobutyldichlorothiophosphate leads to subsequent reaction with alcoholates to give the corresponding O-isobutyl Ο, poved-dialkyl thioc -isobutylchlorothiophosphate.
201 OSO201 OSO
Sposob přípravy 0-butyl O-etylchlórtiofosfátov pomocou etylétu horečnatého je nevýhodný ako pre obtiažnu přípravu etylátu horečnatého, tak sj pre manipuláciu s etylátom horečnatým. Výtažky sa taktiež pohybujú len okolo 70 % teorie.The process of preparing O-butyl O-ethyl chlorothiophosphates by means of magnesium ethylene is disadvantageous both for the difficult preparation of magnesium ethylate and for the handling of magnesium ethylate. Extracts are also only around 70% of theory.
Výše uvedené nevýhody nemá spásob přípravy 0-alkyl O-izobutylchlórtiofosfátov obecného vzorca IThe above-mentioned disadvantages have no process for the preparation of O-alkyl O-isobutyl chlorothiophosphates of the general formula I
RORO
/ch3/2chch2o (I S v ktorom R znamená alkyl s 1 až 4 atómami uhlíka alebo 2-chlóretyl, podle vynálezu, ktorého podstata spočívá v tom, že sa nechá reagovat O-alkyldichlórtiofosfát vzorca. IX/ CH 3/2 CHCH 2 O (IS wherein R denotes alkyl having 1 to 4 carbon atoms or 2-chloroethyl, according to the invention whose principle consists in that, by reacting an O-alkyldichlórtiofosfát formula. IX
RO - P Cl·,RO - P Cl ·,
II (11)II ( 11 )
S v ktorom R má už uvedený význam pri teplote do 20 °C s izobutylalkoholátom sodným alebo draselným, připadne rozpuštěným v izobutylalkohole, s výhodou v prostředí organického inertného rozpúštadla hlavně takého, v ktorom sa připravil východiskový O-alkyldichlórtio-fosfát vzorca II.Wherein R is as hereinbefore defined at a temperature of up to 20 ° C with sodium or potassium isobutyl alcoholate, optionally dissolved in isobutyl alcohol, preferably in an organic inert solvent, mainly one in which the starting O-alkyldichlorothiophosphate of formula II has been prepared.
Velkou výhodou sposobu přípravy O-alkyl O-izobutylchlórtiofosfátov podlá vynálezu je, že popři vysokých výtažkoch /spravidla nad 85 , dosahuje sa aj vysoká čistota produktu.A great advantage of the process for the preparation of the O-alkyl O-isobutyl chlorothiophosphates according to the invention is that, in addition to the high yields / generally above 85, high purity of the product is also achieved.
Dalej je to skutočnost, že vzladom k východiskovému O-alkyldichlórtiofosfátu vystačí sa s molárnym pomerom izobutylalkoholátu sodného, alebo draselného v rozmedzí 1 : 1 až 1 : 1,1 s výhodou s pomerom 1 : 1,05.It is furthermore that, relative to the starting O-alkyldichlorothiophosphate, a molar ratio of sodium or potassium isobutyl alcoholate in the range of 1: 1 to 1: 1.1, preferably 1: 1.05, is sufficient.
Naaledujúci příklad bližšie osvětluje predmet vynálezu.The following example illustrates the invention in more detail.
PříkladExample
0-etyl-O-izobutylchlórt iofosfátO-ethyl-O-isobutylchlorotrophosphate
K 89,5 g O-etyldichlórtiofoefótu /0,5 molu/ rozpuštěnému v 300 ml toluénu aa za miešania v priebehu 25 minút pri teplote 0 až 4 °C přidalo 275 g zmes izobutylalkoholu a toluénu, ktorá obsahovala 0,514 molu izobutylalkoholátu draselného /připraveného z hydroxidu draselného a izobutylalkoholu/. V miešaní sa pokračovalo 3 hodiny pri teplote 20 až 25 °C. Po dvojnásobnom premytí vodou /500 ml/, při druhom premytí okyselené 10 ml kyseliny soínej. Toluénová vrstva sa vysušila chloridom vápenatým, po oddestilovaní toluénu sa zbytok přečistil destiláciou za zníženého tlaku. Získalo sa 97,7 g produktu o t. v. 103 °C/2,1 kPa, ktorý obsahoval 97,4 % O-etyl-O-izobutylchlórtiofosfétu, čo odpovedá 88,1 %-nému výtažku.To 89.5 g of O-ethyldichlorothiophoefate (0.5 mol) dissolved in 300 ml of toluene and stirred for 25 minutes at 0 to 4 ° C was added 275 g of a mixture of isobutyl alcohol and toluene containing 0.514 mol of potassium isobutyl alcohol / prepared from potassium hydroxide and isobutyl alcohol. Stirring was continued for 3 hours at 20-25 ° C. After washing twice with water (500 ml), in the second wash, acidified with 10 ml of brine. The toluene layer was dried with calcium chloride, after distilling off the toluene, the residue was purified by distillation under reduced pressure. 97.7 g of a product with a melting point of 103 ° C / 2.1 kPa was obtained which contained 97.4% of O-ethyl-O-isobutylchlorothiophosphate, which corresponds to an 88.1% yield.
Podobným postupom boli připravené následovně látky:The following substances were prepared in a similar manner:
Ο,Ο-diizobutylchlórtiofosfát o t. v. 120 °C/1,6 kPa a výtažku 90,5 ž-nomΟ, Ο-diisobutylchlorothiophosphate, b.p. 120 ° C / 1.6 kPa and yield 90.5 µm
0-izobutyl O-metylchlórtiofosfát o t. v. 91 °C/1,3 kPa a výtažku 85,1 %-nomO-isobutyl O-methylchlorothiophosphate, b.p. 91 ° C / 1.3 kPa, 85.1% yield
0-/2-chlóretyl/ O-izobutylchlórtiofosfát o t. v. 69 až 70 °C/13 Pa a výtažku 86,8 %-nomO- (2-chloroethyl) O-isobutylchlorothiophosphate, b.p. 69-70 ° C / 13 Pa, 86.8% yield
0-izobutyl O-propylchlórtiofosfát o t. v. 68 až 70 °C/66 Pa a výtažku 88,0 ^-nom.O-isobutyl O-propyl chlorothiophosphate, b.p. 68-70 [deg.] C./0.6 mbar and a yield of 88.0%.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS240379A CS201056B1 (en) | 1979-04-09 | 1979-04-09 | Method of preparing o-alkyl-o-isobutyl chlorthiophosphates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS240379A CS201056B1 (en) | 1979-04-09 | 1979-04-09 | Method of preparing o-alkyl-o-isobutyl chlorthiophosphates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS201056B1 true CS201056B1 (en) | 1980-10-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS240379A CS201056B1 (en) | 1979-04-09 | 1979-04-09 | Method of preparing o-alkyl-o-isobutyl chlorthiophosphates |
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| Country | Link |
|---|---|
| CS (1) | CS201056B1 (en) |
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1979
- 1979-04-09 CS CS240379A patent/CS201056B1/en unknown
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