GB1580792A - Process for preparing organoin compounds - Google Patents
Process for preparing organoin compounds Download PDFInfo
- Publication number
- GB1580792A GB1580792A GB1461/76A GB86877A GB1580792A GB 1580792 A GB1580792 A GB 1580792A GB 1461/76 A GB1461/76 A GB 1461/76A GB 86877 A GB86877 A GB 86877A GB 1580792 A GB1580792 A GB 1580792A
- Authority
- GB
- United Kingdom
- Prior art keywords
- chloride
- salt
- reaction
- tin
- octyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 150000004820 halides Chemical class 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 239000011135 tin Substances 0.000 claims description 57
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 56
- 150000003839 salts Chemical group 0.000 claims description 52
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 48
- 239000011701 zinc Substances 0.000 claims description 46
- 229910052718 tin Inorganic materials 0.000 claims description 43
- 229910052725 zinc Inorganic materials 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 32
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 28
- 125000004429 atom Chemical group 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 19
- JTGNPNLBCGBCMP-UHFFFAOYSA-N tetraoctylstannane Chemical compound CCCCCCCC[Sn](CCCCCCCC)(CCCCCCCC)CCCCCCCC JTGNPNLBCGBCMP-UHFFFAOYSA-N 0.000 claims description 17
- -1 trioctyltin halide Chemical class 0.000 claims description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 6
- 150000004714 phosphonium salts Chemical class 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 150000001350 alkyl halides Chemical class 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 229940006461 iodide ion Drugs 0.000 claims description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 claims description 4
- 229910052740 iodine Chemical group 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- RIECPYZYOLVSJK-UHFFFAOYSA-N tert-butyl 2-dimethylsilyl-5-methylindole-1-carboxylate Chemical compound C[SiH](C)c1cc2cc(C)ccc2n1C(=O)OC(C)(C)C RIECPYZYOLVSJK-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- WFIYFFUAOQKJJS-UHFFFAOYSA-N tetraoctylphosphanium Chemical compound CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC WFIYFFUAOQKJJS-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 2
- 238000003811 acetone extraction Methods 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- SMAVBLSQIQGWLU-UHFFFAOYSA-M trioctylstannanylium;iodide Chemical compound CCCCCCCC[Sn](I)(CCCCCCCC)CCCCCCCC SMAVBLSQIQGWLU-UHFFFAOYSA-M 0.000 claims 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims 2
- 150000001348 alkyl chlorides Chemical class 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 11
- 238000009835 boiling Methods 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 150000004010 onium ions Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000006194 liquid suspension Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- 239000002879 Lewis base Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 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
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical compound [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CHYBTAZWINMGHA-UHFFFAOYSA-N tetraoctylazanium Chemical compound CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC CHYBTAZWINMGHA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Description
(54) PROCESS FOR PREPARING ORGANOTIN
COMPOUNDS
(71) We, ALBRIGHT AND
WILSON LIMITED, a British Company of Albright and Wilson House, Hagley Road
West, Oldbury, Warley, West Midlands,
England, formerly of P.O. Box 3, Oldbury,
Warley, West Midlands, England, do hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed to be particularly described in and by the following statement:- This invention relates to a process for preparing tetraorganotin compounds from elemental tin.
Organotin compounds can be prepared by reaction of tin halides with organo-metallic compounds such as
Grignard reagents. Processes have also been described in which organotin compounds are prepared directly from elemental tin.
Thus our British Patent Specification No.
1115646 describes a process for preparing predominantly diorganotin dihalides which comprises reacting tin with an aliphatic halide in the presence of a nitrogen, sulphur or phosphorus 'onium compound and a preformed tin II halide or organotin halide and in the optional presence as cocatalyst of a small amount of a metal which may be zinc among many others. In U.S. Patent No.
3085102 is described a similar process, but without the 'onium compound and preformed halide, but in which the cocatalyst is essential and is preferably magnesium. U.S. Patent No. 3547965 describes the preparation of triorganotin halides by reaction of organic halides with an equiatomic mixture of tin and zinc in the presence of an alcohol. U.S. Patent No.
3651108 describes the preparation of tetra organotin compounds by reaction of organic halides in the presence of an 'onium compound, or Lewis base, with tin and an alkaline or alkaline earth metal, in particular magnesium.
A process for preparing tetraorganotin compounds without using the hazardous alkaline or alkaline earth metals is described in our prior patent Application No. 2456/75 (Patent No. 1548365), as a process for preparing a tetraalkyltin compound which comprises passing a halide of formula RX where R is an alkyl group of 1 to 4 carbon atoms and X is a chlorine, bromine or iodine atom, into a heated suspension of metallic material, which is zinc and tin, or an alloy of tin and zinc, the atomic proportion of zinc to tin in said material being at least 0.5: 1, in a liquid comprising at least one organic quaternary ammonium or phosphonium salt or tertiary sulphonium salt, to produce a vapour effluent comprising substantially all the tetraalkyltin compound prepared.
We have now found a process wherein the tetraorganotin compound may be prepared in the liquid phase, without use of the hazardous alkali metals or alkaline earth metals.
The present invention provides a process for preparing a tetra organotin compound, which comprises reacting an organic halide of formula RX, wherein R is an alkyl group of 1--20 carbon atoms, or alkenyl group of 2-20 carbon atoms, and X is a chlorine, bromine or iodine atom, with a heated suspension of metallic material which is zinc and tin, or an alloy of tin and zinc, the atomic proportion of zinc to tin in the material being at least 0.5:1, in a liquid comprising at least one 'onium salt, which is an organic quaternary ammonium or phosphonium salt or tertiary sulphonium salt, to produce the tetraorganotin compound at least some of which is in the liquid. The tetraorganotin compound is usually recovered at least from the liquid phase after cessation of the reaction.
The reaction is carried out under conditions such that the organotin product of the reaction contains at least 500/o by weight of tetra organotin and the remainder (if any) contains a substantial proportion of triorganotin halide. Preferably, the product contains at least 70 /" (molar percentage) of tetraorganotin and up to 300/, of triorganotin halide and especially the product contains at least 90 /, and up to 10% of triorganotin halide. The composition of the organotin product depends for any particular combination of 'onium salt and organic halide on the molar proportion of the total of organic halide, which has reacted and is present in the liquid i.e. tht total of organic halide added apart from that (if any) evaporated, to the 'onium salt; the lower the proportion is, the higher is the proportion of tetraorganotin to triorganotin halide. The molar proportion of organic halide to salt is usually less than 25:1, preferably less than 20:1, e.g. less than 15:1. The molar proportion chosen depends on the nature of the organic halide and the desired composition of the product.
It is believed that there is a critical proportion of halide to salt below which the organotin product contains at least 90 /,, tetraorganotin; for octyl chloride the proportion is believed to be about 7:1, for butyl chloride it is believed to be in the 77.5:1 region, while for octyl iodide, it is believed to be in the 11-12:1 region. In a process in which organic halide is added progressively to the reaction, addition of more halide over the critical amount gives rise to a significant reduction in the proportion of teraorganotin in the product and often is accompanied by a rapid production of a gaseous byproduct believed to be the olefin corresponding to elimination from the organic halide.
In a preferred aspect the present invention provides a process for preparing a tetraorganotin compound, which comprises reacting an organic halide of formula RX, wherein R is an alkyl group of 1--20 carbon atoms, or alkenyl group of 2-20 carbon atoms, and X is a chlorine, bromine or iodine atom, with a heated suspension of metallic material which is zinc and tin, or an alloy of tin and zinc, the atomic proportion of zinc to tin in the material being at least 0.5:1, in a liquid comprising at least one organic quaternary ammonium or phosphonium salt of tertiary sulphonium salt, to produce a tetra organotin compound, at least some of which is in the liquid, the molar proportion of organic halide to salt being less than the critical proportion (especially up to 7:1) so that the organotin product of the reaction comprises at least 90 /n of the tetraorganotin and less than 10% of triorganotin halide. The tetraorganotin compound is usually recovered at least from the liquid phase after cessation of the reaction.
The organic group in the organic halide may be methyl, ethyl, n or isopropyl, n-, seciso- or tert- butyl, octyl, e.g. n-octyl, vinyl or allyl. The organic halide is preferably an alkyl or alkenyl halide each of 2 to 8, especially 4 to 8 carbon atoms. Butyl chloride and octyl chlorides are preferred.
A mixture of organic halides may be used to give a mixture of tetraorganotin products.
The amount of organic halide added is usually at least two moles per g atom of tin, e.g. 2.5-15 and preferably 2.5-7, e.g. 2.55 moles per g atom of tin; the total amount of organic halide added depends on the degree to which the reaction is taken to completion, i.e. for 100% reaction at least four moles organic halide per g atom of tin or 2 moles per g atom zinc (whichever is the smaller) is needed. The amount of halide added also depends on the amount which is unreacted and boils off as a gaseous effluent. When the process is for preparing organotin compounds comprising at least 90 /" tetraorganotin, the molar proportion of organic halide to salt is usually up to the critical proportion, e.g. from 4:1 to that proportion, such as up to 7:1, preferably 4 to 6.8:1, e.g. 4.5-5.5:1 or 5-6.7:1, especially 6-6.7:1. Especially preferred as a molar proportion is one in the range of x-l:l to x:l where x is the critical proportion.
The liquid contains the organic quaternary ammonium, or phosphonium salt or tertiary sulphonium salt often at a temperature of 100--300"C, e.g. 150- 250"C preferably 150--2200C. The salt is usually a halide, e.g. a chloride or bromide but especially an iodide; indeed, if the halide reactant is not itself an iodide, the presence of an iodide in the liquid is very desirable as it enhances the reaction rate.
The salt is commonly a salt of formula R'4 + Y, R'4 P Y or R'3 S Y, wherein each R' is an
alkyk group, e.g. of 1--13, especially 1--8, carbon atoms, or an aralkyl group of 7-19 carbon atoms, e.g. an aralkyl hydrocarbylgroup of 7-19 carbon atoms, such as benzyl, or a cycloalkyl group of 5-7 carbon atoms, e.g. cyclohexyl or an aryl group, e.g.
an aromatic hydrocarbyl group of 6-18 carbon atoms, such as a phenyl, tolyl, or naphthyl, and Y is a chloride, bromide or preferably an iodide ion. Examples of the salts are tetrabutyl ammonium and phosphonium halides, benzyltriethyl ammonium and phosphonium halides, tetra octylammonium and tetraoctylphosphonium halides, and trioctyl and tributyl sulphonium halides. The salt as such may be mixed with the tin and zinc or may be obtained by reaction in situ of the halide reactant of formula RX with the corresponding tertiary amine or phosphine or sulphide of formula R'3 N, R'3 P or R'2S preferably before addition of the tin and zinc. The groups R' in the quaternary or tertiary salt are preferably the same as R.
The salt may be present in an amount of at least 0.1 g mole per g atom of tin, e.g. 0.1- 1.5 g mole such as 0.1-0.8 and especially 0.4-0.8 g mole but is preferably present in an amount of at least 0.4, e.g. at least 0.6 molar proportion of salt per atomic proportion of tin, e.g. 0.6-1.5:1 especially 0.8-1.2:1, such as about 1:1. The mole amount of organotin product is often of the same order as the molar amount of the salt.
In addition to the salt the liquid contains tin and zinc which are preferably both solid, though if the temperature is high enough they are in the form of a molten alloy. The solid tin preferably has a maximum dimension of 5 mm, such as 501000 y especially 5150 ; it may be subdivided in the form of powder or comminuted material, or in sponge form or in the form of discs. The solid zinc is also preferably subdivided, e.g. with a maximum dimension of 5 mm, such as 5(w1000 y especially 5 150 ,u, e.g. in the form of powder or comminuted material; it may be in the form of granules. The atomic ratio of zinc to tin is usually 0.5:1 to 5: 1, preferably 1:1 to 4:1, e.g.
1.5:1 to 3.0:1, and especially 1.5:1 to 2.5:1; stoichiometry of the reaction suggests a ratio of about 2:1. While the tin and zinc are usually separate in elemental from, they may be in the form of a solid or liquid alloy consisting essentially of tin and zinc, usually in the desired atomic ratio for use in the process. The suspension is usually agitated, e.g. by stirring.
If the melting point of the salt is below the reaction temperature, the molten salt can provide the necessary liquid phase for the reaction and is the sole organic liquid present, as is preferred. If desired an organic diluent may be present and should have a boiling point under the reaction pressure substantially higher than the reaction temperature, e.g. at least 500C higher and be inert to the reactant.
Examples of such diluents are high boiling paraffin oils of b.p. greater than 3000 C, dodecane, tetradecane or tetralin. The diluent is needed to provide a liquid phase if the salt has a melting point higher than that of the reaction temperature or if the proportion of salt to the combined weight of tin and zinc is insufficient to provide an agitatable suspension. The minimum proportion of salt depends on the form of the tin and zinc; less salt can be used satisfactorily with powdered tin or zinc than with tin discs or zinc granules. However, where possible the reaction is carried out in the absence of any inert organic liquid diluent. The weight proportion of liquid phase (i.e. salt and diluent (if present) but excluding organic halide and organotin product) to the combined total weight of zinc and tin is preferably 0.10:1 to 10:1, though higher proportions may be used; the proportion is more preferably 0.5:1 to 5:1, e.g. 1:1 to 4:1.
The organic halide is preferably added to the hot suspension over the course of the reaction; the halide may be dropped onto the surface of the suspension but is preferably passed in under its surface. The temperature and pressure conditions of the reaction may be such that unreacted organic halide (and especially substantially all of the unreacted halide) evaporates and forms a gaseous effluent. The rate of addition of organic halide is usually then not very much greater than the rate of reaction in order to optimize production of organotin while minimizing the amount of unreacted organic halide in the effluent. As alkyl halides tend to decompose at high temperature, the rate of addition of organic halide and the temperature and pressure are usually also such that the total of the rate of reaction and rate of evaporation of halide into the effluent is at least twice and preferably at least 10 times the rate of decomposition of the halide.
Thus the temperature, pressure and rate of addition of organic halide depend on at least six factors. The first is the essential need for at least some of the tetraorganotin product to be in the liquid phase, i.e. the liquid should be at a temperature below the boiling point of the tetraorganotin under the pressure pertaining over the liquid.
Preferably the pressure and temperature are such that at least 50% and especially at least 90 /" of the tetraorganotin is in the liquid, the remainder (if any) being in a gaseous effluent. The second factor is the nature of the organic halide as it affects the rate of reaction, short chain alkyl halides reacting faster than long chain halides and iodides reacting faster than bromides, and chlorides. The third factor is the nature of the organic halide as it affects the rate of decomposition of the halides in the reaction medium for the order of stability of the alkyl halides is primary > secondary > tertiary. The fourth factor is the nature of the organic halide as it affects the stability of the tetraorganotin product in the reaction medium. The fifth factor is the nature of the salt because at too high a temperature the salts thermally decompose. The sixth factor is the need during the stepwise addition of halide for any unreacted organic halide (if unstable in the reaction medium at the temperature) to evaporate from the liquid forming a gaseous effluent so that if the reaction temperature is lower than the boiling point of the halide under atmospheric pressure, a reduced pressure is used under which the halide boils; a reduced pressure may be used in any event to enhance the rate of evaporation. It is not essential, however, that the unreacted organic halide evaporates if it is stable in the medium. Preferably, however, whether the unreacted halide evaporates or not, the halide is added at about the same rate as it reacts.
Alternatively, all the organic halide may be added in one portion from the start of the reaction, but this is less preferred as the reaction is exothermic.
Simple experiments can be carried out to determine suitable conditions of temperature, pressure and rate of addition applicable for any particular organic halide and salt. As a guide to temperature and pressure conditions, suitable conditions for butyl halides are reaction at 152500C, e.g. 150--190"C under atmospheric pressure, and for octyl halides are reaction at 150--300"C preferably 150--2500C, e.g.
15220"C under 10760 mm Hg pressure, e.g. 150--1900C such as 150- 1700C under atmospheric pressure. Thus preferably, the reaction is carried out with butyl chloride by addition thereof over the course of the reaction to a liquid above the boiling point of butyl chloride so that unreacted chloride may evaporate, but the octyl chloride may be added in one portion or over the course of reaction to the liquid at below the boiling point of the halide.
The reaction time depends on the nature of the organic group and the halogen in the halide, the reaction temperature, the pressure or absence of iodide ion in the reaction mixture, the proportion of 'onium catalyst and the degree to which the reaction is taken to completion. The reaction time is reduced with an increasing reactivity of the halide to nucleophilic attack, an increasing reaction temperature, the presence of iodide ion, an increasing amount of 'onium catalyst and a decreasing degree of reaction. However, reaction times of 1 to 24 hours at 15-2000C are often suitable.
In a particularly preferred aspect, the invention provides a process wherein an organic chloride which is butyl or octyl chloride, is passed into a suspension of solid zinc and solid tin in an atomic proportion of at least 0.5:1 in a molten salt of formula R'4 + - N Y or R'4 P Y, wherein each R' is butyl when butyl chloride is reacted or octyl when octyl chloride is reacted, and Y is a chloride, bromide or iodide ion, at 130--180"C, the molar ratio of organic chloride added apart
from that (if any) evaporated to salt being in the range 4:1 to 7:1 and the molar proportion of salt to tin being 0.6:1 to 1.5:1 to give tetrabutyltin or tetraoctyltin.
The reaction is usually carried out in an
apparatus capable of condensing any gaseous effluent from the reaction. Any gaseous effluent from the reaction comprises unreacted organic halide but may
also contain some tetraorganotin compound. The unreacted halide in a continuous or repeated batch process can be recycled for reuse, optionally after removal of any tetraorganotin compound, e.g. by fractional distillation.
When the reaction has been taken to the desired degree of completion, the suspension contains the tetraorganotin compound, the salt, any unreacted tin and any unreacted zinc, and by product zinc chloride; it may or may not be substantially free of unreacted organic halide, and may also contain a tri organotin halide. The liquid may be reused, once the organotin compound(s) has been removed and once the zinc chloride byproduct has also been separated.
The suspension may be worked up by allowing it to settle, when an upper liquid phase usually separates from a lower suspension phase which also contains unreacted tin and/or zinc. The upper phase comprises the organotin product and, if the reaction was carried out in the absence of a diluent usually consists substantially of the organotin product. The lower phase comprises the salt, any unreacted tin and/or zinc and byproduct zinc chloride.
Unreacted organic halide (if any) may be present in either phase, and may be separated from the organotin product by fractional distillation and may be separated from the lower phase or recycled for reuse.
Preferably the reaction suspension is separated hot into a liquid organotin fraction and a lower liquid suspension, from which any tin and/or zinc residue can be filtered; the metal residue can be mixed with the necessary amount of fresh tin and/or zinc for reuse. Optionally the reaction suspension hot or cold or the lower phase hot or cold may be mixed with an organic solvent to aid the filtration stage.
Examples of suitable solvents are ketones of 3-6 carbon atoms, e.g. acetone, methyl ethyl ketone and methyl isobutyl ketone, and alkanols of 1-6 carbon atoms, e.g.
methanol, ethanol, propanols or butanols, and ethers, such as cvclic ones, e.g. dioxan and tetrahydrofuran or dialkyl ethers.
The mixture of 'onium salt and zinc chloride in the residual liquid, which has been separated from any unreacted tin and/or zinc, may itself be separated by being treated with aqueous alkali, e.g. an aqueous solution of an alkaline metal or alkaline earth metal hydroxide such as sodium or potassium hydroxide and the product extracted with an organic water immiscible solvent, such as a chlorinated aliphatic hydrocarbon, e.g. of 14 carbon atoms such as chloroform, 1.2-dichloroethane and methylene dichloride, to give an organic layer comprising 'onium compound e.g.
halide and an aqueous phase containing the zinc; the phases are separated, and the 'onium recycled for reuse. The solubility of quaternary 'onium chlorides and hydroxides in organic media is described by Brandstrom et al Acta. Chem. Scand, 1969, 23, 1215 and subsequent papers.
The organic phase may consist substantially of the organotin product or may be a mixture of the organotin product and solvent and/or unreacted organic halide; in the latter case the solvent and/or organic halide are distilled from the organic phase leaving an organotin fraction. The organotin product may be purified by distillation if desired to remove small amount of salts, solvent and any unreacted organic halide. The organotin compound usually comprises at least 50%, e.g. at least 70% and preferably at least 90 /n especially at least 95 /n such as 95-98%, of tetra organotin, the remainder being essentially triorganotin halide, in both of which the organic group is primarily based on the organic group in the organic halide but mixed products including organic groups from the salts may also be formed.
Alternatively, in the case of the tetraorganotin compounds from alkyl halides of 2 to 4 carbon atoms, especially ethyl halides and to a lesser extent propyl halides, at the end of the reaction the temperature/pressure conditions can be altered to distil off the organotin compound but this operation is less desirable than that involving extraction, as higher temperatures encouraging decomposition and/or very low pressures are often needed. The tetra organotin product may be used for preparing triorganotin halo compounds, e.g.
triorganotin chlorides substantially free from di and mono organotin compounds by mixing with the appropriate molar proportion of stannic halide, e.g. stannic chloride; similarly the corresponding diorgano and monoorganotin halides may be prepared.
The higher is the proportion of tetraorganotin to triorganotin halide in the organotin product, the higher is the volume efficiency of the plant producing the organotin product. The organotin halides are used as antifungal compounds or as intermediates for making such compounds or stabilizers, e.g. dibutyltin bis(isooctylthioglycollate), for polymeric materials, e.g. PVC. In particular the tetraalkyltin compounds may be disproportionated with stannic chloride to give a 2:1 molar mixture of mono alkyltin trihalide and dialkyltin dihalide useful as an intermediate for making mixtures of stabilizers, e.g. mercapto ester stabilizers for
PVC.
The invention is illustrated in the following Examples: EXAMPLE 1
Into a reaction flask fitted with a stirrer, a dropping funnel, thermometer and exit tube leading to a condenser and receiver was placed tin powder (59.35 g, 0.5 g atom), zinc powder (65.35 g, 1.0 g atom), and tetra nbutyl ammonium iodide (73.8 g, 0.2 mole).
The mixture was heated to 160--1800C to give a liquid suspension, which was stirred while n-butyl chloride (185 g, 2.0 mole) was slowly added with the temperature maintained at 160--1800C. The rate of addition was about 46 g/hr. Unreacted butyl chloride evaporated and collected as condensate in the receiver. After I hr, specimens of the condensate and liquid were taken and analyzed for their organotin content: the condensate was free of organotin while the liquid contained tetrabutyltin without any tributyltin halide.
The butyl chloride was added over 4 hr. The reaction mixture was allowed to cool and then acetone (about 75 ml) added to give an organic phase consisting substantially of organotins and liquid phase containing acetone, zinc, tin, zinc chloride and quaternary salt. The condensate (49.0 g) contained 2*7 /n of tetrabutyltin. The organic phase (57.5 g) contained 91.8% tetrabutyltin and 3.4 /n tributyltin chloride.
EXAMPLE 2
The process of Example 1 was repeated with n-octyl chloride (99 g, 0.67 mole), tin powder (29.67 g, 0.25 g atom), zinc powder (32.67 g. 0.5 g atom), tetra n-butyl ammonium iodide (73.8 g, 0.2 mole), a reaction temperature of l802000C, and a time of addition of the octyl chloride of 5 hr.
The organic phase produced after addition of acetone (about 75 ml) to the cooled reaction mixture weighed 42.0 g and contained by gas liquid chromatographic analysis a substantial proportion of tetraoctyl tin, but also mixed butyl octyltins and tri octyltin chloride. The condensate (octyl chloride) weighed 21.2 g.
EXAMPLE 3
Into a reaction flask fitted with a stirrer, a dropping funnel thermometer and exit tube leading to a condenser and receiver, was placed tin powder (29.7 g, 0.25 g atom), zinc powder (32.7 g, 0.5 g atom), and tetra noctyl phosphonium iodide (60.0 g, I mole).
The mixture was heated to 170--1800C to give a liquid suspension, which was stirred while n-octyl chloride (90.5 g, 0.61 mole) was slowly added with the temperature maintained at 170--1800C. The rate of addition was about 15 g/hr. After 6 hours, the above amount of octyl chloride had been added; at this time volatile compounds has started to collect in the receiver. The reaction was stopped. The reaction mixture was allowed to cool and then acetone added to give an organic phase consisting substantially of organotins and liquid phase containing acetone, zinc chloride, zinc, tin, and quaternary salt. The organic phase contained about 57 g organotins (about 0.095 mole tetra n-octyl tin and 0.005 mole other organotins).
EXAMPLE 4
The process of Example 3 was repeated with a reaction temperature of 165--1800C.
addition of octyl chloride over 1.25 his. in amount of 100 g (0.67 moles). The reaction liquid was analysed by Vapour Phase
Chromatography (VPC) during and after the reaction and the organotin product was predominantly tetra octyltin. The stirring was stopped and a top layer consisting essentially of organotins separated from a lower layer.
COMPARATIVE EXAMPLE A
The experiment of Example 4 was continued with addition of further octyl chloride (50 g) over 0.75 hours at i5() 170"C. Volatile compounds were given off during this period. Acetone extraction of the cooled reaction product gave an extract which VPC showed contained an increasing proportion of triorganotin chloride to tetraoctyltin over that of Example 4, namely 93 /n trioctyltin halide and 7% tetraoctyltin.
EXAMPLES 5-7 The process of Example 3 was repeated with the following molar amounts of octyl chloride, and tetra octyl phosphonium iodide salt, and g atoms of tin and zinc, and reactions at 155--1806C.
Moles Mole ratio
octyl g. atom g. atom Ratio Mole octyl chloride
Example chloride of Sn of Zn Zn:Sn Salt to salt
5 1.68 0.25 0.5 2:1 0.25 6.7:1
6 0.67 0.125 0.5 4:1 0.1 6.7:1
7 0.67 0.25 0.5 2:1 0.1 6.7:1
In the cases of Examples 5 and 6, the octyl chloride was added uniformly over 2 hr., but in the case of Example 7, the octyl chloride was present from the start of the reaction, which was continued for 0.5 hr. In all three cases, addition of more octyl chloride gave volatile products believed to comprise octene, which from Comparative Example
A corresponds to the production of tri octyltin chloride. VPC analysis on the reaction liquid during the reactions up to the addition of the extra octyl chloride shows the presence in the organotin product of substantially only tetraoctyltin, e.g.
95-98% tetraoctyltin and
Claims (25)
- **WARNING** start of CLMS field may overlap end of DESC **.has started to collect in the receiver. The reaction was stopped. The reaction mixture was allowed to cool and then acetone added to give an organic phase consisting substantially of organotins and liquid phase containing acetone, zinc chloride, zinc, tin, and quaternary salt. The organic phase contained about 57 g organotins (about 0.095 mole tetra n-octyl tin and 0.005 mole other organotins).EXAMPLE 4 The process of Example 3 was repeated with a reaction temperature of 165--1800C.addition of octyl chloride over 1.25 his. in amount of 100 g (0.67 moles). The reaction liquid was analysed by Vapour Phase Chromatography (VPC) during and after the reaction and the organotin product was predominantly tetra octyltin. The stirring was stopped and a top layer consisting essentially of organotins separated from a lower layer.COMPARATIVE EXAMPLE A The experiment of Example 4 was continued with addition of further octyl chloride (50 g) over 0.75 hours at i5() 170"C. Volatile compounds were given off during this period. Acetone extraction of the cooled reaction product gave an extract which VPC showed contained an increasing proportion of triorganotin chloride to tetraoctyltin over that of Example 4, namely 93 /n trioctyltin halide and 7% tetraoctyltin.EXAMPLES 5-7 The process of Example 3 was repeated with the following molar amounts of octyl chloride, and tetra octyl phosphonium iodide salt, and g atoms of tin and zinc, and reactions at 155--1806C.Moles Mole ratio octyl g. atom g. atom Ratio Mole octyl chloride Example chloride of Sn of Zn Zn:Sn Salt to salt5 1.68 0.25 0.5 2:1 0.25 6.7:16 0.67 0.125 0.5 4:1 0.1 6.7:17 0.67 0.25 0.5 2:1 0.1 6.7:1 In the cases of Examples 5 and 6, the octyl chloride was added uniformly over 2 hr., but in the case of Example 7, the octyl chloride was present from the start of the reaction, which was continued for 0.5 hr. In all three cases, addition of more octyl chloride gave volatile products believed to comprise octene, which from Comparative Example A corresponds to the production of tri octyltin chloride. VPC analysis on the reaction liquid during the reactions up to the addition of the extra octyl chloride shows the presence in the organotin product of substantially only tetraoctyltin, e.g.95-98% tetraoctyltin and 25 /" trioctyltin chloride. At the end of the reactions, the stirring was stopped and the top organotin layer separated from the lower layer. The yield of organotin compound was 40 /O in Example 7 based on the tin added to the reaction.EXAMPLE 8 The process of Example 3 was repeated with tin (0.125 g atom), zinc (0.25 g atom) and tetra octylphosphonium iodide (0.05 g mole) at 15--1700C with n-octyl iodide being added dropwise. The progress of the reaction was monitored by analysis by vapour phase chromatography. Up to the addition of about 132 g octyl iodide (0.55 g mole) which took about 2 hrs. the organotin product was about 95 /" tetraoctyltin and 5% trioctyltin iodide. When the total addition was about 144 g (0.6 mole) the organotin product was about 70% tetraoctyltin and 30% trioctyltin iodide with some vapour fraction, believed to be octene. The stirring was stopped, the reaction mixture was allowed to separate into 2 phases at above 100"C. The top layer consisted substantially of organotins and was separated from the lower phase containing the iodide salt, tin, zinc and zinc iodide as well as the excess of octyl iodide.EXAMPLE 9 The process of Example 1 was repeated with tin powder (0.25 g atom) zinc powder (0.5 g atom), tetra n butyl ammonium iodide (0.1 g mole) a reaction temperature of 160- 180"C and passage of butyl chloride (0.5 g mole) over 1 hr. Af.er completion of the addition, the reaction mixture was maintained for 4 hrs at 170--1800C. The reaction mixture was allowed to cool slightly, acetone (50 ml) was added to give two liquid phases. Petroleum ether bp 40 60"C 50 ml was added and the top layer obtained was separated. The organic phase was analyzed by GLC and shown to contain 0.0945 g mole tetrabutyltin and 0.004 g mole tributyltin chloride.WHAT WE CLAIM IS: 1. A process for preparing a tetraorganotin compound which comprises reacting an organic halide of formula RX where R is an alkyl group of 1 to 20 carbon atoms or alkenyl group of 2-20 carbon atoms and X is a chlorine, bromine or iodine atom, with a heated suspension of metallicmaterial, which is zinc and tin, or an alloy of tin and zinc, the atomic proportion of zinc to tin in said material being at least 0.5:1, in a liquid comprising at least one 'onium salt which is an organic quaternary ammonium or phosphonium salt or tertiary sulphonium salt, to produce a tetraorganotin compound, at least some of which is in the liquid.
- 2. A process according to Claim I wherein the organic halide is passed into the heated suspension over the course of the reaction.
- 3. A process according to Claim 1 or 2 wherein the molar proportion of organic halide to 'onium salt is less than a critical proportion such that the tetraorganotin compound produced contains less than 10% of triorganotin halide.
- 4. A process according to Claim 3 wherein the molar proportion of organic halide to 'onium salt is up to 7:1.
- 5. A process according to any one of Claims 1 " wherein the suspension is heated to 13--2000C.
- 6. A process according to any one of Claims 1-5 wherein the organic halide is an alkyl chloride.
- 7. A process according to any one of Claims ld wherein the organic halide is an alkyl halide of 2-8 carbon atoms.
- 8. A process according to Claim 7 wherein the organic halide is butyl chloride or octyl chloride.
- 9. A process according to any one of Claims 1-8 herein the atomic proportion of zinc to tin is from 1:1 to 4:1.
- 10. A process according to Claim 9 wherein the proportion is from 1.5:1 to 2.5:1.
- 11. A process according to any one of the preceding claims wherein the molar ratio of salt to tin is at least 0.4:1.
- 12. A process according to Claim 11 wherein the molar ratio of salt to tin is 0.8:1 to 1.2:1.
- 13. A process according to any one of Claims 1--12 wherein the salt is of formula R'4 N Y or R'4 +P Y, wherein each R' is an alkyl group of 1 to 12 carbon atoms and Y is a chloride, bromide or iodide.
- 14. A process according to Claim 13 wherein each R' in the salt is the same as the R group in the organic halide.
- 15. A process according to any of Claims 1--14 wherein there is an iodide present in the liquid during the reaction.
- 16. A process according to any one of Claims 1--15 wherein in the suspension the only organic liquid is molten quaternary ammonium or phosphonium salt.
- 17. A process according to any one of Claims 13-16 wherein an organic chloride which is butyl or octyl chloride is passed into a suspension of solid zinc and solid tin in an atomic proportion of at least 0.5:1 in a molten salt of formula R'4 N Y or R'4 +P Y, wherein each R' is butyl when butyl chloride is reacted or octyl when octyl chloride is reacted, and Y is a chloride, bromide or iodide ion, at 130--1800C, the molar ratio of organic chloride to salt being in the ratio 4:1 to 7:1 and the molar proportion of salt to tin being 0.6:1 to 1.5:1 to give tetrabutyltin or tetraoctyltin.
- 18. A process according to any one of the preceding claims wherein at the end of the reaction there is produced an upper layer comprising tetraorganotin compound and a lower layer, and the upper layer is separated.
- 19. A process according to any one of Claims 5-16, when not appendant to Claim 3 or 4, wherein the organic halide is passed into the heated suspension over the course of the reaction.
- 20. A process for preparing a tetraorganotin compound substantially as described in Example 1 or 2.
- 21. A process for preparing a tetraorganotin compound substantially as described in any one of Examples 3-7.
- 22. A process for preparing a tetraorganotin compound substantially as described in Example 8 or 9.
- 23. A tetraorganotin compound prepared by a process as claimed in any one of Claims 1-21.
- 24. A tetraorganotin compound prepared by a process as claimed in any one of Claims 2, 19 and 20.
- 25. A tetraorganotin compound prepared by a process as claimed in any one of Claims 4, 17, 21 and Claims 5-16 when appendant to Claim 4.
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GB1461/76A GB1580792A (en) | 1976-01-14 | 1977-01-11 | Process for preparing organoin compounds |
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GB2993776 | 1976-07-19 | ||
GB1461/76A GB1580792A (en) | 1976-01-14 | 1977-01-11 | Process for preparing organoin compounds |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0083981A1 (en) * | 1982-01-07 | 1983-07-20 | Manchem Limited | Production of organotin halides |
US4437949A (en) | 1982-01-07 | 1984-03-20 | Manchem, Limited | Electrolysis of tin complexes |
-
1977
- 1977-01-11 GB GB1461/76A patent/GB1580792A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0083981A1 (en) * | 1982-01-07 | 1983-07-20 | Manchem Limited | Production of organotin halides |
US4437949A (en) | 1982-01-07 | 1984-03-20 | Manchem, Limited | Electrolysis of tin complexes |
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