HRP960516A2 - Process for the selective synthesis of sylilalkyl disulfides desulfurating the corresponding polysulphides with nucleophylic reagenses - Google Patents
Process for the selective synthesis of sylilalkyl disulfides desulfurating the corresponding polysulphides with nucleophylic reagenses Download PDFInfo
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- HRP960516A2 HRP960516A2 HR19541404.7A HRP960516A HRP960516A2 HR P960516 A2 HRP960516 A2 HR P960516A2 HR P960516 A HRP960516 A HR P960516A HR P960516 A2 HRP960516 A2 HR P960516A2
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- 238000000034 method Methods 0.000 title claims description 18
- 229920001021 polysulfide Polymers 0.000 title claims description 10
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 150000002019 disulfides Chemical class 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 20
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000005077 polysulfide Substances 0.000 claims description 9
- 150000008117 polysulfides Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 230000000269 nucleophilic effect Effects 0.000 claims description 4
- 239000012434 nucleophilic reagent Substances 0.000 claims description 3
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000005425 toluyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- -1 silylalkyl mercaptans Chemical class 0.000 description 4
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 4
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- RJWJCQLFAYQGBG-UHFFFAOYSA-L disodium;sulfite;hydrate Chemical compound [OH-].[Na+].[Na+].OS([O-])=O RJWJCQLFAYQGBG-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229910000057 polysulfane Inorganic materials 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IKRMQEUTISXXQP-UHFFFAOYSA-N tetrasulfane Chemical group SSSS IKRMQEUTISXXQP-UHFFFAOYSA-N 0.000 description 2
- 150000007944 thiolates Chemical class 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical compound [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0898—Compounds with a Si-S linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
Razmatrani izum se odnosi na postupak za selektivnu sintezu sililalkildisulfida desulfuriranjem odgovarajućih polisulfida s nukleofilnim reagensima.
Trialkoksipropilpolisulfidi su odlični fazni posrednici za ugradnju materijala koji sadrže kisik u matrice kaučuka. Naročito u gumarskoj industriji nalazi trietoksisilil-propiltetrasulfan ([ (C3CH2O)3SiCH2CH2CH2]2S4) široku primjenu u gumama pojačanim silicijevom kiselinom. Pritom dolazi do vezanja silana na slobodne hidroksilne grupe silicijeve kiseline na jednoj strani i poprečnog umrežavanja poput vulkanizacije s kaučukom, na drugoj strani. Za specijalne primjene svrsishodno je, da silan nije opremljen s tetrasulfanskom-, nego s manje reaktivnom disulfanskom funkcijom. Sinteza sililalkildisulfana opisuje se zajedno s njima odgovarajućim polisulfidima u različitim patentima i publikacijama.
DE-PS 2 405758 i DE-PS 2 542534 odnose se na proizvodnju polazeći od merkaptoalkilsilana i sumpora, kod koje se oslobađa sumporovodik.
Više metoda dobivanja polazi od in situ proizvedenih disulfida, s kojima se tada provode nukleofilne supstitucije na halogenalkilsilanima. Ovi postupci razlikuju se samo u sintezi disulfida nukleofila. Prema DE-PS 3 311340 proizvodi se disulfid reakcijama između sumporovodika, natrija i sumpora u etanolu.
Prema US-PS 5,405,985 koristi se za proizvodnju vodena otopina natrij-sulfida zajedno sa sumporom. Stručnjacima je dovoljno poznato, da kod reakcija između sulfida i sumpora nastaju smjese različitih polisulfida, tako da kod nukleofilne supstitucije može rezultirati opet samo smjesa polisulfana različite dužine lanca. Isto vrijedi za reakcije između merkaptana odnosno tiolata i sumpora. Osim toga je poznato, da se iz ovih smjesa produkata mogu samo uz velike poteškoće izolirati odgovarajući disulfani.
U DE-PS 2 360470 opisuje se doduše način za proizvodnju čistog bis(sililalkil)disulfana oksidacijom odgovarajućeg merkaptana sa sulfuril-kloridom; međutim kod ove metode nastaju jako korozivni nusprodukti (SO2, HCl). Nusreakcije na sililnom ostatku uzrokuju osim toga smanjenje iskorištenja na željenom produktu (Primjer: 63,3 %). Daljnja oksidativna varijanta nalazi se u EP-A1 217178. Ovdje se odgovarajuće tiolate oksidira jodom u disulfide. Nakon skupe proizvodnje sililalkil-merkaptana proces zahtijeva dva daljnja koraka reakcije.
Zadaća je izuma pripremiti jednostavan postupak, koji visokim iskorištenjem vodi do željenog sililalkildisulfida.
Predmet izuma je postupak za proizvodnju bis(sililalkil)disulfana opće formule
(R1R2R3SiR4)2 S2 (I)
u kojoj znače:
R1, R2, R3: jednaki ili različiti jedan od drugoga, razgranate ili nerazgranate alkil- i/ili alkoksi skupine s dužinom lanca od 1 do 8 C-atoma, pri čemu je prvenstveno prisutna najmanje jedna alkoksi skupina. Vodik ili jednovalentni arilni ostaci, osobito fenil, toluil, benzil
R4: dvovalentni alkilidni ostatak s dužinom lanca od 1 do 8 C-atoma, prvenstveno 2 do 4 C-atoma ili
[image]
koji je karakteriziran time, da se sililalkil-polisulfide (-sulfane) ili sililalkilpolisulfanske smjese opće formule
(R1R2R3SiR4)2Sn (II),
u kojoj R1, R2, R3 i R4 imaju značenje iz formule (I), a n odgovara cijelom broju između 3 i 20, osobito između 3 i 103 konvertira s nukleofilnim spojem općih formula
M+ CN- (III) ili
M+2 SO32- (IV),
u kojima znače:
M+ alkalijski kation, s C1-C4-alkilom djelomično, potpuno supstituiran ili nesupstituiran amonijev ion, ili polovinu zemnoalkalijskog- ili cinkovog iona, ili opće formule
R5R6R7P (V)
u kojoj R5, R6, R7, mogu imati isto značenje kao R1, R2, R3 u formuli (I), pri čemu se primjenjuje spojeve prema opčim formulama (III) do (V) ekvimolarno prema broju sumpornih atoma koje se uklanja iz spoja prema općoj formuli (II), prvenstveno pojedinačno, ali također u smjesi, nastalu krutinu se otfiltrira, a dobiveni disulfan pročisti.
Postupak se može provesti kako u sistemu bez otapala, tako također uz dodatak otapala. Naročito su pogodna takva, u kojima je primijenjeni nukleofilni spoj barem djelomično topiv.
Primjenjiva su alifatska otapala, kao na pr. pentan, heksan ili smjese različitih razgranatih i nerazgranatih alkana ili aromatska otapala, kao na pr. benzen, toluen ili ksilen ili eter, kao na pr. dietileter, dibenzileter, metil-terc.-butileter.
Kao organsko otapalo primjenjuje se prvenstveno linearni ili razgranati alkohol s 1-8 C-atoma, kao na pr. metil-, etil-, propil-, butil- ili pentil-alkohol. Prikladni su također cikloalkil-alkoholi s 5-8 C-atoma, fenol ili benzil-alkohol.
Svrsishodno je, da bi se na pr. izbjegla preesterifikacija, primijeniti uvijek skupini R1, R2, R3 (alkoksi) korespondirajući alkohol. Po potrebi, od prednosti može biti također primjena smjese ovih alkohola, npr. ako R1, R2, R3 imaju u spoju različita značenja.
Osobitim načinom izvođenja izuma provodi se reakcija u 2-faznom sistemu, ako se otapalo kao na pr. voda, ne miješa s primijenjenim sulfanom.
U ovom slučaju primjenjuje se jedan od poznatih faznotransfernih katalizatora, npr. Aliquat 336 (C8H17)3N+CH3Cl- u uobičajenim količinama, (vidi E.V. Dehmlow, S.S. Dehmlow, "Phase Transfer Catalysis" 2. izdanje, Weinheim 1983).
Reakciju se može provoditi kako kod sobne temperature, tako također kod viših temperatura. Da bi vrijeme reakcije bilo što je moguće kraće, svrsishodno je provoditi reakciju kod povišenih temperatura, prvenstveno kod temperature vrenja primijenjenog otapala.
Za uspješnost postupka je nevažno, da li se izvodi bez pritiska ili pod pritiskom- Provedba izuma ilustrira se slijedećim primjerima.
U pogodnom načinu izvođenja izuma uspijeva proizvodnja disulfida pojednostavljenim postupkom.
Ne pokazuje se nužnim, da se polisulfane koje se desulfurira, odvojeno proizvodi. Prema izumu uspijeva ove sintetizirati in situ, i "postupkom u jednom loncu" odmah konvertirati u željene disulfide.
U tu svrhu proizvede se otopinu, po potrebi suspenziju, koja sadrži
a) polisulfid ili smjesu polisulfida opće formule M+2 Sn, pri čemu M+ i n imaju ranije navedena značenja,
b) nukleofilni reagens ili smjesu različitih mikleofilnih reagensa općih formula M+CN-, M+2SO32-, R5 R6 R7 p, u kojima M+, R5, R6 R7 imaju već gore spomenuta značenja
c) organosilicijev spoj opće formule
Cl-R4-Si(R1R2R3)3 (VI),
u kojoj R1, R2, R3, R4 imaju gore navedeno značenje,
u molarnom odnosu od osobito 0,4 do 0,7 (a) : 1 do 1,1 (ta) : 1 (c).
Pritom rezultira odnos (a) : (b) iz broja sumpornih atoma koje treba ukloniti iz (II).
Kao otapalo, posebno u odnosu na (VI) primjenjuje se prvenstveno alkohol, koji korenspondira s R1, R2, R3 iz (I) u njihovom značenju kao alkoksi skupine.
Redoslijed kojim se umješava sastojke u otapalo, prvenstveno kod temperature od 20 °C do 35 °C, nema naročiti utjecaj.
Nasuprot tome odvija se reakcija kod povišene temperature, naročito u području od 40 °C do temperature refluksa otapala primijenjenog u smjesi.
Općenito se primjenjuje 10 do 90 tež.%-tna otopina organo-silicijevog spoja, u odnosu na ukupnu težinu reakcione smjese.
Nakon reakcije ohladi se smjesu, ukloni otapalo pod vakuumom i pročisti zaostalu krutinu prikladnim otapalima, posebno petroleterom, u kojima se otapa željeni disulfid. Nakon odvajanja otapala nade se čisti disulfan. Primjeri razjašnjavaju točan postupak.
Primjer 1
Desulfuriranje bis (trietoksisililpropil) tetrasulfana s Na CN u etanolu
U trogrlu tikvicu od 250 ml s magnetskom miješalicom i refluksom stavi se 67,37 g (0,125 mol) bis(trietoksisililpropil)tetrasulfana u 60 ml etanola. K ovoj smjesi doda se 12,25 g (0,250 mol) praškastog natrij-cijanida. Smjesa se zagrijava 4 h uz refluks. Nakon ohlađenja na sobnu temperaturu oddestilira se otapalo na rotacionom isparivaču. Kruto-tekuću smjesu ostavi se stajati 2 h kod sobne temperature do potpune kristalizacije krutine i filtrira. Kolač dobiven filtriranjem ispere se tri puta s 50 ml petroletera. Nakon uklanjanja petroletera iz filtrata dobije se čisti bis(trietoksisililpropil)tetrasulfan. (Kontrola putem H-NMR-spektroskopije). Iskorištenje: 97 %.
Primjer 2
Desulfuriranje bis (trietoksisililpropil) tetrasulfana s KCN u etanolu
U posudu od 200 l od puhanog stakla s brzohodnom miješalicom stavi se 67,34 kg (125 mol) bis(trietoksisililpropil)tetrasulfana u 60 l etanola. K tome se uz miješanje doda 16,28 kg (250 mol) krutog ka:lij-cijanida. Pod dušikom se 4 h zagrijava us refluks. Nakon uklanjanja otapala kod 80 °C pod vakuumom, ostavi se ohladiti i filtrira istaloženu krutinu. Filtrirani ostatak ispere se ponovno s po 10 l petroletera. Otapalo se ukloni iz filtrata kod 70 °C u vakuumu. Dobije se 58,8 kg (124 mol) čistog bis(trietoksisililpropil)disulfana (kontrola putem %-NMR-spektroskopije), Iskorištenje: 99 %.
Primjer 3
Desulfuriranje bis(trietoksililpropil) tetrasulfana s NaCN u 2-faznom sistemu
U trogrlu tikvicu od 500 ml s magnetskom miješalicom, hlađenjem uz refluks i lijevkom za dokapavanje, stavi se 19,6 g (0,4 mol ) NaCN u 160 ml vode i zagrijava na 90 °C. Kod postizanja ove temperature dokapava se unutar 45 min smjesa od 107,8 g (0,2 mol) bis(trietoksisililpropil)-tetrasulfana, 120 ml toluena i 5 g faznotransfernog katalizatora Aliquat 336. Nakon završetka dodavanja miješalo se još 2 h kod ove temperature, ohladilo i konačno otfiltriralo od 12,4 g netopivog materijala. Odijeljene su organska i vodena faza filtrata i organska faza uparena u vakuumu. Dobije se 90,4 g (0,19 mol) čistog bis(trietoksisililpropil)disulfana (kontrola putem 1H-NMR-spektroskopije). Iskorištenje: 95 %.
Primjer 4
Desulfuriranje bis(trietoksisililpropil)tetrasulfana s trifenilfosfanom u etanolu
U trogrlu tikvicu od 250 ml s magnetskom miješalicom i' povratnim hladilom stavi se 67,37 g (0,125 mol) bis(trietoksisililpropil)tetrasulfana u 60 ml etanola. K ovoj smjesi doda se 65,57 g (0,250 mol) krutog trifenilfosfana. Smjesu se zagrijava 4 h uz refluks- Nakon ohlađenja na sobnu temperaturu oddestilira se otapalo na rotacionom isparivaču. Kruto-tekuću smjesu ostavi se stajati 2 h kod sobne temperature do potpune kristalizacije krutine i filtrira. Kolač dobiven filtriranjem ispere se tri puta s 50 ml petroletera. Nakon uklanjanja petroletera iz filtrata dobije se čisti bis(trietoksisililpropil)disulfan (kontrola putem 1H-NMR- spektroskopije). Iskorištenje: 98 %.
Primjer 5
Desulfuriranje bis(trietoksisililpropil)tetrasulfana s natrij-sulfit hidratom
U trogrloj tikvici od 1000 ml s KPG-miješalicom, povratnim hladilom i lijevkom za dokapavanje zagrijava se smjesa od 160 ml vode i 105,9 g (0,85 mol) natrij-sulfit hidrata na 90 °C. Kod ove temperature dokapava se unutar 30 min smjesa od 226,4 g (0,42 mol) bis(trietoksisililpropil)-tetrasulfana, 20 ml etanola i 5,0 g Aliquat 336.
Nakon završetka dokapavanja doda se daljnjih 100 ml etanola i miješa 3,5 h kod 80 °C. Nakon ohlađenja reakcione smjese na sobnu temperaturu, odijeli se vodena faza. Otapalo se oddestilira od organske faze na rotacionom isparivaču u vakuumu. Dobije se 198,9 g (0,41 mol) bis(trietoksisililpropil )disulfana (kontrola putem 1H-NMR-spektroskopije). Iskorištenje: 99 %.
Primjer 6
Desulfuriranje in situ proizvedenog bis(trietoksisililpropil)tetrasulfana s NaCN
U trogrlu tikvicu od 500 ml s magnetskom miješalicom i povratnim hladilom stavi se smjesa od 43,5 g (0,25 mol) polisulfida prosječnog sastava Na2S4, 24,5 g (0,5 mol) NaCN i 120,4 g (0,5 mol) klorpropiltrietoksisilana u 120 ml etanola i zagrijava 2 h uz refluks.
Nakon ohlađenja smjese produkta na sobnu temperaturu, ukloni se otapalo u vakuumu, otopi preostali ostatak sa 150 ml petroletera i filtrira. Ostatak od filtriranja opere se tri puta s po 50 ml petroletera. Iz sakupljenih filtrata ukloni se otapalo u vakuumu. Dobije se 108,7 g (0,21 mol) čistog disulfana (kontrola putem 1H-NMR-spektroskopije). Iskorištenje: 94 %.
Claims (6)
1. Postupak za proizvodnju bis(sililalkil)disulfana opće formule
(R1R2R3SiR4)2 S2 (I),
u kojoj znače:
R1, R2, R3: jednaki ili različiti jedan od drugoga, razgranate ili nerazgranate alkil-i/ili alkoksi-skupine s duljinom lanca od 1 do 8 C-atoma, vodik ili jednovalentni arilni ostatak, naročito fenil, toluil, benzil
R4: dvovalentni alkilidni ostatak duljine lanca od 1 do 8 C-atoma, prvenstveno 2 do 4 C-atoma ili
[image]
naznačen time, da se sililalkilpolisulfide ili smjese sililalkilpolisulfida opće formule
(R1R2R3SiR4)2Sn (II),
u kojoj R1, R2, R3 i R4 imaju značenje iz formule (I) a n odgovara cijelom broju između 3 i 20, posebno između 3 i 10, konvertira s nukleofilnim spojem općih formula
M+ CN- (III) ili
M+2 SO32- (IV),
u kojima znače:
M+ alkalijski kation, supstituirani ili nesupstituirani amonijev ion, ili polovinu zemnoalkalijskog- ili cinkovog iona, ili opće formule
R5R6R7P (V)
u kojoj R5, R6, R7, mogu imati isto značenje kao R1, R2, R3 u formuli (I), pri čemu se primjenjuje spojeve prema općim formulama (III) do (V) ekvimolarno prema broju sumpornih atoma koje se uklanja iz spoja prema općoj formuli (II), nastalu krutinu se otfiltrira, a dobiveni disulfan pročisti.
2. Postupak prema zahtjevu 1, naznačen time, da se spojeve prema formulama (III) do (V) primjenjuje u smjesi.
3. Postupak prema zahtjevima 1 i 2, naznačen time, da se reakciju provodi u prisutnosti otapala, koje otapa nukleofilne spojeve.
4. Postupak prema zahtjevima 1 i 3, naznačen time, da se reakciju provodi kod temperature između 20°C i temperature vrenja primijenjenog otapala.
5. Postupak prema zahtjevima 1 do 4, naznačen time, da se reakciju provodi u dvofaznom sistemu u prisutnosti faznotransfernog katalizatora.
6. Postupak prema zahtjevu 1, naznačen time, da se silialkilpolisulfane opće formule (II), koje se konvertira, in situ sintetizira, tim što se proizvede otopina, koja sadrži
a) polisulfid ili smjesu polisulfida opće formule M+2 Sn, pri čemu M+ i n imaju jednako značenje kao prije;
b) nukleofilni reagens iz skupine M+CN-, M+2 SO32-, R5 R6 R7 P, pojedinačno ili zajedno, pri čemu: M+, R5, R6 R7 imaju već spomenuta značenja
c) organosilicijev spoj opće formule Cl-R4 - Si(R1R2R3)3 (IV), u kojoj R1, R2, R3 i R4 imaju gore navedeno značenje u molarnom odnosu od 0,4 do 0,7 (a): 1 do 1,1 (b) : 1 (c), ova smjesa međusobno reagira, a željeni disulfid odijeli se uobičajenim pročišćavanjem.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19541404A DE19541404A1 (de) | 1995-11-07 | 1995-11-07 | Verfahren zur selektiven Synthese von Silylalkyldisulfiden |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HRP960516A2 true HRP960516A2 (en) | 1998-02-28 |
| HRP960516B1 HRP960516B1 (en) | 2002-04-30 |
Family
ID=7776798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HR960516A HRP960516B1 (en) | 1995-11-07 | 1996-11-05 | Process for the selective synthesis of sylilalkyl disulfides desulfurating the corresponding polysulphides with nucleophylic reagenses |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US5663395A (hr) |
| EP (1) | EP0773224B1 (hr) |
| JP (1) | JPH09169774A (hr) |
| KR (1) | KR970027094A (hr) |
| CN (1) | CN1070862C (hr) |
| AU (1) | AU713295B2 (hr) |
| BR (1) | BR9605476A (hr) |
| CA (1) | CA2189601A1 (hr) |
| CZ (1) | CZ318096A3 (hr) |
| DE (2) | DE19541404A1 (hr) |
| ES (1) | ES2168424T3 (hr) |
| HR (1) | HRP960516B1 (hr) |
| HU (1) | HU217297B (hr) |
| PL (1) | PL183494B1 (hr) |
| PT (1) | PT773224E (hr) |
| SI (1) | SI0773224T1 (hr) |
| SK (1) | SK143596A3 (hr) |
| TW (1) | TW382018B (hr) |
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| DE19734295C1 (de) * | 1997-08-08 | 1999-02-25 | Degussa | Verfahren zur Herstellung von Organosiliciumdisulfanen hoher Reinheit |
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| DE19848482C1 (de) * | 1998-10-21 | 2000-06-08 | Degussa | Verfahren zur Herstellung von Organosiliciumdisulfanen |
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| US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
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-
1995
- 1995-11-07 DE DE19541404A patent/DE19541404A1/de not_active Withdrawn
-
1996
- 1996-09-23 ES ES96115226T patent/ES2168424T3/es not_active Expired - Lifetime
- 1996-09-23 SI SI9630415T patent/SI0773224T1/xx unknown
- 1996-09-23 DE DE59608364T patent/DE59608364D1/de not_active Expired - Fee Related
- 1996-09-23 PT PT96115226T patent/PT773224E/pt unknown
- 1996-09-23 EP EP96115226A patent/EP0773224B1/de not_active Expired - Lifetime
- 1996-10-30 PL PL96316746A patent/PL183494B1/pl unknown
- 1996-10-30 TW TW085113256A patent/TW382018B/zh not_active IP Right Cessation
- 1996-10-30 CZ CZ963180A patent/CZ318096A3/cs unknown
- 1996-11-04 CN CN96120660A patent/CN1070862C/zh not_active Expired - Fee Related
- 1996-11-05 HR HR960516A patent/HRP960516B1/xx not_active IP Right Cessation
- 1996-11-05 JP JP8292755A patent/JPH09169774A/ja not_active Abandoned
- 1996-11-05 US US08/743,842 patent/US5663395A/en not_active Expired - Fee Related
- 1996-11-05 CA CA002189601A patent/CA2189601A1/en not_active Abandoned
- 1996-11-06 KR KR1019960052353A patent/KR970027094A/ko not_active Application Discontinuation
- 1996-11-06 AU AU70624/96A patent/AU713295B2/en not_active Ceased
- 1996-11-06 HU HU9603081A patent/HU217297B/hu not_active IP Right Cessation
- 1996-11-06 SK SK1435-96A patent/SK143596A3/sk unknown
- 1996-11-07 BR BR9605476A patent/BR9605476A/pt active Search and Examination
Also Published As
| Publication number | Publication date |
|---|---|
| CA2189601A1 (en) | 1997-05-08 |
| TW382018B (en) | 2000-02-11 |
| ES2168424T3 (es) | 2002-06-16 |
| CN1070862C (zh) | 2001-09-12 |
| AU713295B2 (en) | 1999-11-25 |
| PL183494B1 (pl) | 2002-06-28 |
| BR9605476A (pt) | 1998-08-11 |
| AU7062496A (en) | 1997-05-15 |
| CN1156149A (zh) | 1997-08-06 |
| US5663395A (en) | 1997-09-02 |
| JPH09169774A (ja) | 1997-06-30 |
| HU9603081D0 (en) | 1996-12-30 |
| DE59608364D1 (de) | 2002-01-17 |
| EP0773224A3 (de) | 1998-03-18 |
| DE19541404A1 (de) | 1997-05-15 |
| HU217297B (hu) | 1999-12-28 |
| SK143596A3 (en) | 1997-05-07 |
| PL316746A1 (en) | 1997-05-12 |
| KR970027094A (ko) | 1997-06-24 |
| CZ318096A3 (en) | 1997-05-14 |
| EP0773224A2 (de) | 1997-05-14 |
| PT773224E (pt) | 2002-05-31 |
| SI0773224T1 (en) | 2002-06-30 |
| HRP960516B1 (en) | 2002-04-30 |
| HUP9603081A2 (en) | 1997-10-28 |
| HUP9603081A3 (en) | 1998-09-28 |
| EP0773224B1 (de) | 2001-12-05 |
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