PL100056B1 - Sposob wytwarzania fosforo-dwuchloro-tiolanow - Google Patents
Sposob wytwarzania fosforo-dwuchloro-tiolanow Download PDFInfo
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- PL100056B1 PL100056B1 PL1976191916A PL19191676A PL100056B1 PL 100056 B1 PL100056 B1 PL 100056B1 PL 1976191916 A PL1976191916 A PL 1976191916A PL 19191676 A PL19191676 A PL 19191676A PL 100056 B1 PL100056 B1 PL 100056B1
- Authority
- PL
- Poland
- Prior art keywords
- mol
- phosphorus
- dichloro
- thiolate
- disulfide
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 59
- 238000002360 preparation method Methods 0.000 title claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000543 intermediate Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 28
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 23
- -1 aldehyde carboxylic acids Chemical class 0.000 claims 21
- 238000003756 stirring Methods 0.000 claims 21
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims 18
- 239000012320 chlorinating reagent Substances 0.000 claims 17
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 11
- 229960000583 acetic acid Drugs 0.000 claims 11
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 10
- 238000009835 boiling Methods 0.000 claims 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 10
- 239000002904 solvent Substances 0.000 claims 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 9
- 239000000203 mixture Substances 0.000 claims 9
- 235000011054 acetic acid Nutrition 0.000 claims 7
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 claims 7
- 229910052739 hydrogen Inorganic materials 0.000 claims 7
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims 6
- 239000012346 acetyl chloride Substances 0.000 claims 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 6
- 238000004458 analytical method Methods 0.000 claims 5
- 239000012362 glacial acetic acid Substances 0.000 claims 5
- 235000019260 propionic acid Nutrition 0.000 claims 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 5
- ONJROLGQWMBXAP-UHFFFAOYSA-N 2-methyl-1-(2-methylpropyldisulfanyl)propane Chemical compound CC(C)CSSCC(C)C ONJROLGQWMBXAP-UHFFFAOYSA-N 0.000 claims 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 4
- 150000007513 acids Chemical class 0.000 claims 4
- 150000001263 acyl chlorides Chemical class 0.000 claims 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 4
- 150000001735 carboxylic acids Chemical class 0.000 claims 4
- 238000004821 distillation Methods 0.000 claims 4
- 239000000047 product Substances 0.000 claims 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims 4
- 239000000376 reactant Substances 0.000 claims 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- 239000007795 chemical reaction product Substances 0.000 claims 3
- 239000003153 chemical reaction reagent Substances 0.000 claims 3
- 238000011065 in-situ storage Methods 0.000 claims 3
- 238000002156 mixing Methods 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- 238000003786 synthesis reaction Methods 0.000 claims 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 claims 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 238000004587 chromatography analysis Methods 0.000 claims 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 2
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims 2
- 238000000746 purification Methods 0.000 claims 2
- 239000011541 reaction mixture Substances 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000008096 xylene Substances 0.000 claims 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 1
- TXIBBNMZMRYADF-UHFFFAOYSA-N 1-(naphthalen-1-yldisulfanyl)naphthalene Chemical compound C1=CC=C2C(SSC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 TXIBBNMZMRYADF-UHFFFAOYSA-N 0.000 claims 1
- ULWYKDZVZIMBSK-UHFFFAOYSA-N 2,2-dichlorothiolane Chemical compound ClC1(Cl)CCCS1 ULWYKDZVZIMBSK-UHFFFAOYSA-N 0.000 claims 1
- CPKISUMKCULUNR-UHFFFAOYSA-N 2-methoxy-2-oxoacetic acid Chemical compound COC(=O)C(O)=O CPKISUMKCULUNR-UHFFFAOYSA-N 0.000 claims 1
- QXPDOTUXWYGEFD-UHFFFAOYSA-N 3,5-dimethylnaphthalene-1-thiol Chemical compound C1=CC=C(C)C2=CC(C)=CC(S)=C21 QXPDOTUXWYGEFD-UHFFFAOYSA-N 0.000 claims 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims 1
- VZQDBNWKBKWCFJ-UHFFFAOYSA-N 4-bromo-2-chlorobenzenethiol Chemical compound SC1=CC=C(Br)C=C1Cl VZQDBNWKBKWCFJ-UHFFFAOYSA-N 0.000 claims 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims 1
- MEEVQELVDKDHLB-UHFFFAOYSA-N 4-methyl-2-nitrobenzenethiol Chemical compound CC1=CC=C(S)C([N+]([O-])=O)=C1 MEEVQELVDKDHLB-UHFFFAOYSA-N 0.000 claims 1
- AXBVSRMHOPMXBA-UHFFFAOYSA-N 4-nitrothiophenol Chemical compound [O-][N+](=O)C1=CC=C(S)C=C1 AXBVSRMHOPMXBA-UHFFFAOYSA-N 0.000 claims 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 claims 1
- 206010021118 Hypotonia Diseases 0.000 claims 1
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 claims 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims 1
- 150000001243 acetic acids Chemical class 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- 235000011089 carbon dioxide Nutrition 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims 1
- 238000004508 fractional distillation Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 229950011008 tetrachloroethylene Drugs 0.000 claims 1
- 125000004001 thioalkyl group Chemical group 0.000 claims 1
- 150000007944 thiolates Chemical class 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Substances SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000004647 alkyl sulfenyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest sposób wytwarzania fosforo-dwuchloro-tiolanów, a zwlaszcza S-alkilo-,
-cykloalkilo-, aralkilo-, lub -arylo-fosforo-dwuchloro-tiolanów o duzej czystosci i z duzawydajnoscia.
Znane sposoby wytwarzania zwiazków opisanych w niniejszym wynalazku nie sa korzystne ze wzgledu na
ich wysokie koszty, czasochlonnosc, uzyskiwanie przewaznie produktów zanieczyszczonych, z niska wydajnoscia
itp. Wiadomo, ze np. S-alkilo-fosforo-dwuchloro-tiolany mozna wytwarzac poprzez chlorek alkilo-sulfenylu droga
chlorowania w niskiej temperaturze, a nastepnie dodania chlorku sulfenylu do trójchlorku fosforu w nadmiarze
cieklego dwutlenku siarki i w temperaturze -50°C. Jednakze wymagania stosowania niskich temperatur i nad¬
miaru dwutlenku siarki sa kosztowne oraz czasochlonne i dlatego wyraznie ograniczaja w praktyce ten sposób
wytwarzania.
W sposobie wedlug niniejszego wynalazku stwierdzono, ze moze byc prowadzony praktycznie ekonomicz¬
ny proces wytwarzania pewnych S-alkilo-, -cykloalkilo-, -aralkilo- lub -arylo-fosforo-dwuchloro-tiolanów. Proces
ten nie wymaga stosowania niskich temperatur lub cuchnacego i toksycznego dwutlenku siarki, a produkty otrzy¬
muje sie o duzej czystosci i z wysoka wydajnoscia.
Zwiazki wytwarzane sposobem wedlug niniejszego wynalazku sa uzytecznymi pólproduktami w procesach
wytwarzania pewnych 0,S-dwupodstawionych fosforo-chloro-tiolanów, które z kolei sa pólproduktami do
wytwarzania takich znanych organofosforoorganicznych pestycydów, jak opisane w patentach Stanów Zjedno¬
czonych nr 3374293, 3784654 i 3839509 oraz w szeregu innych patentów.
Fosforo-dwuchloro-tiolany wytwarzane sposobem wedlug niniejszego wynalazku przeprowadza sie
w 0,S-dwupodstawione fosforo-chloro-tiolany metodami znanymi specjalistom z tej dziedziny. Jeden ze sposo¬
bów polega na reakcji S-podstawionego fosforo-dwuchloro-tiolanu z alkoholem w obecnosci zwiazku wiazacego
kwas, np. trzeciorzedowej aminy w wyniku czego otrzymuje sie odpowiednio 0,S-dwupodstawiony fosforo-chlo-
rotiolan.
Sposobem wedlug niniejszego wynalazku wytwarza sie zwiazki o wzorze ogólnym R-S-P/=0/Cl2,
w którym R oznacza:1000S6
? a)grupe /Ct C{0/-alkilowa, korzystnie grupe /Ci -C7/-alkilowa, najkorzystniej grupe /C2 -C4/-alkilowa,
ewentualnie podstawiona grupa /Ci -C4/-alkoksylowa, korzystnie grupe metoksylowa lub etoksylowa; grupa
/Ci -C4/-tioalkilowa, korzystnie grupe tioffietylowa lub lioetylowa; lub atomem chlorowca, korzystnie atomem
chloru; ' - '^¦^¦V'':.; ; ^';;;.";. ¦. -•/¦:'; ¦ ¦.-¦¦;¦.; :•
b) grupe /C3 -C6 /-cykloalkilowa, korzystnie grupe cykloheksylowa; v
c) grupe /C7-C10/-aralkilowa, korzystnie grupe benzylowa lub fenyloetylowa, ewentualnie podstawiona
1-3 grupami /Ci -C5/-alkilowymi, korzystnie grupami metylowymi; grupami alkoksylow>rni, korzystnie meto¬
ksylowymi; atomami chlorowca, korzystnie atomami chloru;lub grupami nitrowymi;
lub d) grupe /C6-Clc/-arylowa^ korzystnie grupe fenylowa, ewentualnie podstawiona 1-3 grupami
/Ci --C5 /-alkilowymi, korzystnie grupami metylowymi; grupami /(^-CsZ-alkoksylowymi, korzystnie grupami
metoksylowymi; atomami chlorowca, korzystnie atomami chioru; lub grupami nitrowymi.
Sposobem wedlug wynalazku korzystnie wytwarza sie zwiazki, w których R oznacza grupe /Cr -C7/ alki¬
lowa, zwlaszcza grupe /C2-C4/-alkilowa.
W opisie oraz w
Claims (15)
1. Sposób wytwarzania fosforo-dwuchloro-tiolanów o wzorze ogólnym R-S-P/=0/Cl2, w którym R oznacza grupe /Ci —Ci 0/-alkilowa ewentualnie podstawiona grupa /Ci —C4/-alkoksylowa, grupa /Ci —C4/-tioalki- lowa lub atomem chlorowca, grupe /C3-C6/-cykloalkilowa, grupe /C7-Ci0/-aralkilowa ewentualnie podstawio¬ na 1—3 grupami /Ci —C5/-alkilowymi, /Ci—C5/-alkoksylowymi, atomami chlorowca lub grupami nitrowymi, lub grupe /C6—Ci o/-aryIowa ewentualnie podstawiona 1—3 grupami /C{ —C5 /-alkilowymi, /Ci —C5/-alkoksylowymi, atomami chlorowca iub grupami nitrowymi, znamienny t y m, ze chlorek sulfenylu o wzorze ogólnym R—S—Cl, w którym R ma wyzej podane znaczenie, poddaje sie reakcji z trójchlorkiem fosforu i woda lub kwasem karboksylowym w temperaturze —20°C — 50°C.
2. Sposób wedlug zastrz. 1,znamienny ty ni, ze stosuje sie chlorek sulfenylu wytworzony in situ w wyniku reakcji dwusiarczku o wzorze ogólnym RSSR, w którym R ma wyzej podane znaczenie z czynnikiem chlorujacym.
3. Sposób wedlug zastrz. 1 albo 2, z n a ni i e n n y ty m, ze reakcje prowadzi sie w obecnosci ooojetne- go rozpuszczalnika organicznego.
4. Sposób wedlug zastrz. 3, znamienny ty m, ze jako rozpuszczalnik stosuje sie aromatyczny weglowodór, aromatyczny lub alifatyczny chlorowcowany weglowodór lub ester kwasu karboksylowego-
5. Sposób wedlug zastrz. 1, z n a m i e n ny ty m, ze reakcje prowadzi sie w temperaturze od —5°C do 30°C.
6. Sposób wedlug zastrz. 1, z n a m i e n n y ty m, ze stosuje sie kwas karboksylowy o wzorze ogólnym Y—C/=0/—OH, w którym Y oznacza atom wodoru; grupe /Ct—C8/-alkilowa ewentualnie podstawiona 1-3 atomami chlorowca, lub grupe o wzorze ogólnym X—/CH2/n--, w którym X oznacza grupe cyjanowa; grupe fenylowa ewentualnie podstawiona 1-3 grupami ICX -.C5/-alkilowymi, /C^- Cs/-alkoksylowymi atomami chlo¬ rowca, lub grupami nitrowymi; lub grupa o wzorze ogólnym -C/=0/-R\ w którym R' oznacza grupe hydroksy¬ lowa; grupe /Ci-C5/-alkoksylowa lub grupe fenoksylowa ewentualnie podstawiona 1-3 grupami /Ci-C5/-alki¬ lowymi, /Ci—C5/-alkoksylowymi, atomami chlorowca lub grupami nitrowymi, a n oznacza liczbe od zera do 8.
7. Sposób wedlug zastrz. 6, znamienny ty m, ze jako czynnik chlorujacy stosuje sie chlor lub chlorek sulfurylu.
8. 3. Sposób wedlug zastrz. 7, znamienny t y m, ze stosuje sie chlorek sulfenylu o wzorze R-S-Cl, w którym R oznacza grupe /C2 -C4 /-alkilowa.
9. Sposób wedlug zastrz. 8, z n a m i e n n y t y m, ze stosuje sie kwas karboksylowy o wzorze ogólnym X*—C/=0/—OH, w którym X' oznacza grupe /Ci —C6/-alkilowa lub grupe fenylowa.
10. Sposób wedlug zastrz. 9, znamienny tym, ze czynnik chlorujacy dodaje sie do mieszaniny trójchlorku fosforu, dwusiarczku i kwasu karboksylowego.
11. Sposób wedlug zastrz. 10, znamienny ty m, ze do mieszaniny 1,0 mola trójchlorku fosforu, 0,5 mola dwusiarczku i 1,0 mola kwasu karboksylowego dodaje sie 1,0 do 1,5 mola czynnika chlorujacego.
12. Sposób wedlug zastrz. 9, znamienny tym, ze czynnik chlorujacy dodaje sie do mieszaniny dwusiarczku i kwasu karboksylowego, a nastepnie dopiero dodaje sie trójchlorek fosforu.100056 9
13. Sposób wedlug zastrz. 12, z n a m i e n n y t y m, ze 1,0-1,5 mola czynnika chlorujacego dodaje sie do mieszaniny 0.5 mola dwusiarczku i 1,0 mola kwasu karboksylowego, a nastepnie dodaje sie 1,0 mol trójchlor¬ ku fosforu.
14. Sposób wedlug zastrz. l.znamienny tym, ze stosuje sie chlorek sulfenylu, który tworzy sie in situ w wyniku reakcji merkaptanu o wzorze ogólnym RSH z czynnikiem chlorujacym przed dodaniem trójchlor¬ ku fosforu.
15. Sposób wedlug zastrz. 14, znamienny tym, ze jako czynnik chlorujacy stosuje sie chlor, jako kwas karboksylowy, stosuje sie kwas octowy i jako merkaptan, merkaptan n-propylowy. 9
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/607,078 US4056581A (en) | 1975-08-22 | 1975-08-22 | Process for the preparation of phosphorodichloridothiolates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| PL100056B1 true PL100056B1 (pl) | 1978-08-31 |
Family
ID=24430720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL1976191916A PL100056B1 (pl) | 1975-08-22 | 1976-08-20 | Sposob wytwarzania fosforo-dwuchloro-tiolanow |
Country Status (23)
| Country | Link |
|---|---|
| US (1) | US4056581A (pl) |
| JP (1) | JPS5231033A (pl) |
| AT (1) | AT366056B (pl) |
| AU (1) | AU1707276A (pl) |
| BE (1) | BE845223A (pl) |
| BR (1) | BR7605392A (pl) |
| CA (1) | CA1064954A (pl) |
| CH (1) | CH618984A5 (pl) |
| CS (1) | CS189784B2 (pl) |
| DD (1) | DD127791A5 (pl) |
| DE (1) | DE2635931A1 (pl) |
| EG (1) | EG12319A (pl) |
| ES (1) | ES450868A1 (pl) |
| FR (1) | FR2321501A1 (pl) |
| GB (1) | GB1552658A (pl) |
| HU (1) | HU175412B (pl) |
| IL (1) | IL50323A (pl) |
| IN (1) | IN145483B (pl) |
| NL (1) | NL7609143A (pl) |
| PL (1) | PL100056B1 (pl) |
| SU (1) | SU718012A3 (pl) |
| YU (1) | YU196776A (pl) |
| ZA (1) | ZA764491B (pl) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55139394A (en) * | 1979-04-19 | 1980-10-31 | Nippon Tokushu Noyaku Seizo Kk | Novel synthetic method of thiol phosphate ester chloride |
| US4462994A (en) * | 1981-05-19 | 1984-07-31 | Nissan Chemical Industries, Inc. | N-Containing heterocyclic ring-substituted O-arylphosphate derivatives, preparation thereof, and insecticides, acaricides and nematocides containing said derivatives |
| US4468388A (en) * | 1982-05-21 | 1984-08-28 | Rohm And Haas Company | Pesticidal N-(thio)acyl phosphorodiamido(di)thioates |
| US4468387A (en) * | 1982-05-21 | 1984-08-28 | Rohm And Haas Company | Pesticidal N-sulfonyl N'-oxalate phosphorodiamido(di)thioates |
| US4468389A (en) * | 1982-05-21 | 1984-08-28 | Rohm And Haas Company | Pesticidal N-sulfonyl phosphorodiamido(di)thioates |
| US4727178A (en) * | 1986-07-14 | 1988-02-23 | Stauffer Chemical Co. | Process for preparing phosphorodichloridothiolate |
| US5081272A (en) * | 1990-08-20 | 1992-01-14 | Imperial Chemical Industries Plc | Process for preparation of phosphorodichlorothioates |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3489825A (en) * | 1967-03-06 | 1970-01-13 | Chemagro Corp | Phosphonyl chlorides,thiophosphonyl chlorides and process of making same |
| GB1338857A (en) * | 1972-10-03 | 1973-11-28 | Chemie Kom Bitterfield Veb | Process for the production of phosphoric and thisphosphoric ester dichlorides |
| SU446510A1 (ru) | 1972-11-14 | 1974-10-15 | Всесоюзный научно-исследовательский институт фитопатологии | Способ получени хлорангидридов тиоловых эфиров кислот п тивалентного фосфора |
-
1975
- 1975-08-22 US US05/607,078 patent/US4056581A/en not_active Expired - Lifetime
-
1976
- 1976-07-14 CA CA256,975A patent/CA1064954A/en not_active Expired
- 1976-07-27 ZA ZA764491A patent/ZA764491B/xx unknown
- 1976-07-27 GB GB31159/76A patent/GB1552658A/en not_active Expired
- 1976-07-28 IN IN1350/CAL/76A patent/IN145483B/en unknown
- 1976-07-31 JP JP51091969A patent/JPS5231033A/ja active Pending
- 1976-08-10 DE DE19762635931 patent/DE2635931A1/de active Pending
- 1976-08-10 YU YU01967/76A patent/YU196776A/xx unknown
- 1976-08-11 EG EG494/76A patent/EG12319A/xx active
- 1976-08-16 BE BE169837A patent/BE845223A/xx not_active IP Right Cessation
- 1976-08-16 CH CH1042076A patent/CH618984A5/fr not_active IP Right Cessation
- 1976-08-16 HU HU76RO895A patent/HU175412B/hu unknown
- 1976-08-17 NL NL7609143A patent/NL7609143A/xx not_active Application Discontinuation
- 1976-08-17 CS CS765347A patent/CS189784B2/cs unknown
- 1976-08-18 BR BR7605392A patent/BR7605392A/pt unknown
- 1976-08-19 FR FR7625194A patent/FR2321501A1/fr active Granted
- 1976-08-19 DD DD7600194391A patent/DD127791A5/xx unknown
- 1976-08-20 PL PL1976191916A patent/PL100056B1/pl unknown
- 1976-08-20 AT AT0620276A patent/AT366056B/de not_active IP Right Cessation
- 1976-08-20 SU SU762389510A patent/SU718012A3/ru active
- 1976-08-20 IL IL50323A patent/IL50323A/xx unknown
- 1976-08-20 ES ES450868A patent/ES450868A1/es not_active Expired
- 1976-08-23 AU AU17072/76A patent/AU1707276A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CS189784B2 (en) | 1979-04-30 |
| EG12319A (en) | 1979-03-31 |
| NL7609143A (nl) | 1977-02-24 |
| YU196776A (en) | 1982-05-31 |
| JPS5231033A (en) | 1977-03-09 |
| CH618984A5 (pl) | 1980-08-29 |
| IN145483B (pl) | 1978-10-21 |
| ATA620276A (de) | 1981-07-15 |
| US4056581A (en) | 1977-11-01 |
| ZA764491B (en) | 1977-09-28 |
| FR2321501B1 (pl) | 1981-08-21 |
| SU718012A3 (ru) | 1980-02-25 |
| IL50323A (en) | 1980-01-31 |
| HU175412B (hu) | 1980-07-28 |
| AU1707276A (en) | 1978-03-02 |
| FR2321501A1 (fr) | 1977-03-18 |
| IL50323A0 (en) | 1976-10-31 |
| AT366056B (de) | 1982-03-10 |
| CA1064954A (en) | 1979-10-23 |
| DD127791A5 (de) | 1977-10-12 |
| GB1552658A (en) | 1979-09-19 |
| DE2635931A1 (de) | 1977-03-03 |
| BR7605392A (pt) | 1977-08-16 |
| ES450868A1 (es) | 1977-08-16 |
| BE845223A (fr) | 1977-02-16 |
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