US3387012A - Production of dialiphatic tind dihalides - Google Patents
Production of dialiphatic tind dihalides Download PDFInfo
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- US3387012A US3387012A US486564A US48656465A US3387012A US 3387012 A US3387012 A US 3387012A US 486564 A US486564 A US 486564A US 48656465 A US48656465 A US 48656465A US 3387012 A US3387012 A US 3387012A
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- US
- United States
- Prior art keywords
- tin
- alkyl
- reaction
- iodide
- antimony
- 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.)
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- 238000004519 manufacturing process Methods 0.000 title description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 41
- 238000000034 method Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- -1 aliphatic halide Chemical class 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- KWQLUUQBTAXYCB-UHFFFAOYSA-K antimony(3+);triiodide Chemical compound I[Sb](I)I KWQLUUQBTAXYCB-UHFFFAOYSA-K 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 150000001348 alkyl chlorides Chemical class 0.000 description 10
- 150000001350 alkyl halides Chemical class 0.000 description 10
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 8
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 description 7
- SBOSGIJGEHWBKV-UHFFFAOYSA-L dioctyltin(2+);dichloride Chemical compound CCCCCCCC[Sn](Cl)(Cl)CCCCCCCC SBOSGIJGEHWBKV-UHFFFAOYSA-L 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- INTLMJZQCBRQAT-UHFFFAOYSA-K trichloro(octyl)stannane Chemical compound CCCCCCCC[Sn](Cl)(Cl)Cl INTLMJZQCBRQAT-UHFFFAOYSA-K 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000001351 alkyl iodides Chemical class 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 3
- HRFMZHBXTDWTJD-UHFFFAOYSA-N dihexyltin Chemical compound CCCCCC[Sn]CCCCCC HRFMZHBXTDWTJD-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 description 2
- SKIDNYUZJPMKFC-UHFFFAOYSA-N 1-iododecane Chemical compound CCCCCCCCCCI SKIDNYUZJPMKFC-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 150000001347 alkyl bromides Chemical class 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- RGWOAXNKJWTDFA-UHFFFAOYSA-N ethyl 11-bromoundecanoate Chemical compound CCOC(=O)CCCCCCCCCCBr RGWOAXNKJWTDFA-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- STWNJQOCTNSGLJ-UHFFFAOYSA-N (2-amino-5-methylphenyl)methanol Chemical compound CC1=CC=C(N)C(CO)=C1 STWNJQOCTNSGLJ-UHFFFAOYSA-N 0.000 description 1
- UAZUEJTXWAXSMA-UHFFFAOYSA-N 1,1-dichlorobut-1-ene Chemical compound CCC=C(Cl)Cl UAZUEJTXWAXSMA-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- GCDPERPXPREHJF-UHFFFAOYSA-N 1-iodododecane Chemical compound CCCCCCCCCCCCI GCDPERPXPREHJF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 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
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- IKIBSPLDJGAHPX-UHFFFAOYSA-N arsenic triiodide Chemical compound I[As](I)I IKIBSPLDJGAHPX-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MCNGJXAXOJDJKO-UHFFFAOYSA-M chloro(trioctyl)stannane Chemical compound CCCCCCCC[Sn](Cl)(CCCCCCCC)CCCCCCCC MCNGJXAXOJDJKO-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- OCTMHQBZAUWWOX-UHFFFAOYSA-L dichloro(didecyl)stannane Chemical compound CCCCCCCCCC[Sn](Cl)(Cl)CCCCCCCCCC OCTMHQBZAUWWOX-UHFFFAOYSA-L 0.000 description 1
- HENBEGVGPRLWIF-UHFFFAOYSA-N didecyltin Chemical compound CCCCCCCCCC[Sn]CCCCCCCCCC HENBEGVGPRLWIF-UHFFFAOYSA-N 0.000 description 1
- YREAYUWMESCMHJ-UHFFFAOYSA-L didodecyltin(2+);dichloride Chemical compound CCCCCCCCCCCC[Sn](Cl)(Cl)CCCCCCCCCCCC YREAYUWMESCMHJ-UHFFFAOYSA-L 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical class CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012063 pure reaction product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- FQDIANVAWVHZIR-OWOJBTEDSA-N trans-1,4-Dichlorobutene Chemical compound ClC\C=C\CCl FQDIANVAWVHZIR-OWOJBTEDSA-N 0.000 description 1
- BYQWEYFCJKJRHO-UHFFFAOYSA-K tribromo(butyl)stannane Chemical compound CCCC[Sn](Br)(Br)Br BYQWEYFCJKJRHO-UHFFFAOYSA-K 0.000 description 1
- KQHARJFIXZLBRU-UHFFFAOYSA-K trichloro(decyl)stannane Chemical compound CCCCCCCCCC[Sn](Cl)(Cl)Cl KQHARJFIXZLBRU-UHFFFAOYSA-K 0.000 description 1
- 238000007514 turning Methods 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
Definitions
- Organotin halides are prepared by reacting at elevated temperature metallic tin with an aliphatic halide, whose hydrocarbon group contains 4 to 12 carbon atoms, in the presence of a catalyst of the formula MeX wherein Me is a member of the group consisting of arsenic and antimony, X is a halogen of the group consisting of chlorine, bromine, and iodine, and n is an integer corresponding to the valance of Me.
- This invention relates to the production of alkyl tin halides.
- Still another object of the invention is to provide a process for the preparation of alkyltin halides where relatively cheap metallic tin can be used as starting material instead of tin tetrachloride.
- a further object of the invention is to provide a process for the preparation of alkyltin halides which does not involve the use of inflammable solvents whose recovery requires additional cost.
- dihydrocarbon tin dihalides can be prepared in good yields by direct reaction of metallic tin with alkyl or alkylene halides, or mixtures of different alkyl or alkylene halides, when the reaction is carried out in the presence of an arsenic or antimony halide, or mixtures thereof, in amounts of 1 to 8 mole percent, calculated on tin.
- the reaction proceeds in a single step according to the equation wherein X is halogen and R is alkyl.
- the principal reaction product is always dialkyltin dihalide.
- minor amounts of monoalkyltin trihalide and trialkyltin monohalide are formed.
- the process has particular commercial interest for the production of dialkyl and dialkylene tin dihalides where the hydrocarbon group contains 4-12 C atoms.
- Suitable metal halide catalysts are particularly arsenic (III) chloride, arsenic (III) bromide, arsenic (III) iodide, antimony (III) chloride, antimony (III) bromide, and antimony (III) iodide.
- arsenic (III) chloride arsenic (III) bromide
- arsenic (III) iodide arsenic (III) iodide
- antimony (III) chloride arsenic (III) bromide
- antimony (III) iodide antimony (III) chloride
- antimony (III) bromide antimony (III) iodide
- antimony (III) iodide antimony (III) iodide.
- pentavalent halides can be employed, particularly those which decompose wholly or in part at reaction temperature to the trivalent compounds.
- the reaction can be still further accelerated when, in addition to said metal halides, a secondary catalyst is added to the reaction mixture.
- secondary catalysts are dialkyltin halides in a concentration of 2 to 6 mole percent, calculated on metallic tin; preferably, dialkyltin dihalides are used whose alkyl groups are identical with the alkyl groups of the desired end product.
- Suitable mixtures contain, for instance, tin, alkyl chloride, and as reactive addition alkyl iodide in the mole ratio of 1:3.0-7.0:0.1-0.4, or tin, alkyl chloride, and alkyl bromide in the mole ratio of 1:3.0-6.0:0.21.3.
- a solvent is not required for the reaction, it may be added as a diluent to slow up the rate of reaction when particularly reactive alkyl halides are employed.
- Our new process is essentially independent of the form and grain size of the tin employed.
- the reaction can be carried out not only with finely powdered tin but also with coarser powder or tin foil or even with turnings.
- reaction time is surprisingly short.
- the required reaction time will be generally bet-ween 45 minutes and 6 hours.
- the time may be still shorter.
- the reaction is best carried out in the temperature range between 90 and 210 C.; these limits are, however, not critical and higher or lower temperatures may be used.
- the reaction mixture can be processed in accordance with known methods, and the alkyltin halides can be purified, for instance, by distillation.
- the alkyl halide used in excess can be recovered almost completely by distillation.
- alkyl iodide added to the alkyl chlorides is also recovered from the reaction mixture by distillation; as numerous tests have shown, 50-80 percent of the alkyl iodide remain unreacted in the reaction.
- the monoalkyltin trihalides obtained as by-products are valuable intermediary products and can be used as starting materials for the preparation of auxiliary agents in the plastics production.
- the new process has the advantage of requiring much less time and apparative installations.
- the new process makes it possible to use cheaper alkyl chlorides, e.g. those having more than 4 C atoms, which heretofore could not be reacted in a direct synthesis with economically satisfactory yields.
- Example 1 A mixture of G. Sn 18.0 n-Octyl chloride 150.0 n-Octyl iodide 7.6 Antimony (III) iodide 6.0
- Example 2 Example 1 was repeated but the amount of catalyst was reduced to 1.8 antimony (III) chloride. After refluxing for 6 /2 hours, all the tin had been reacted, except a residue of 0.3 g. After distilling off the excess n-octyl chloride and n-octyl iodide, there remained a residue of 48.0 g. (Sn content 28.64%), which consisted essentially of dioctyltin dichloride and monooctyltin trichloride. The monooctyltin trichloride was distilled off, and the residue was saponified with ZnNaOI-I at 100 C. Thereby, 28.3 g.
- Example 3 Example 3 Example '2 was repeated, with further addition of 2.0 g. of dioctyltin dichloride as auxiliary catalyst. The tin had reacted Within 4 hours, leaving a residue of 0.4 g. After distilling off the excess n-octylchloride, n-octyl iodide, and the monooctyltin trichloride, there was obtained a residue of 47.8 g. containing 3-8.0 g. of pure dioctyltin dichloride. Deducting the 2.0 g. of dioctyltin dichloride added as secondary catalyst, the obtained dioctyltin dichloride corresponded to a yield of 57% of theory.
- Example 4 Example 2 was repeated with further addition of 2.5 g. of antimony (III) iodide. In this case, the tin had completely reacted already after 2 hours of refluxing at C. Distillation of the excess n-octylchloride, n-octyl iodide, and monooctyltin trichloride left a residue of 49.0 g. of crude dioctyltin dichloride. Saponification of the residue with sodium hydroxide produced 31.4 g. of dioctyltin oxide (Sn found 33.0%; calc. 32.85%), corresponding to a yield of 57.5% of theory.
- Sn found 33.0%; calc. 32.85% dioctyltin oxide
- Example 5 A mixture of G. Tin 18.0 n-Octyl bromide 190.0 Antimony (III) iodide 4.0
- Example 6 A mixture of G. Tin 18.0 n-Octylchloride 113.0 n-Octylbromide 30.0 Antimony (III) iodide 6.0
- reaction mixture was refluxed under stirring in a vessel provided with a water separator at about 180 C. for a period of 45 minutes. After this time, the tin was completely consumed.
- the reaction mixture was processed as described in the preceding examples and yielding 30.8 g. of pure dioctyltin oxide.
- Example 7 A mixture of G. Tin 18.0 Decylchloride 179.0 Decyliodide 12.0 Antimony (III) iodide 6.0
- Example 8 A mixture of G. Tin 18.0 Laurylchloride 211.0 Lauryliodide 13.5 Antimony (III) iodide 6.0
- Example 9 A mixture of G. Tin 12.0 n-Hexylchloride 81.2 n-hexyliodi-de 4.6 Antimony (III) iodide 2.6
- Example 10 A mixture of Tin 18.0 n-Hexylbromide 167.0 Antimony (III) iodide 4.0
- Example 11 A mixture of Tin 18.0 1,4-dichloro-2-butene 45.0
- Example 13 A mixture of G. Tin 18.0 n-Octylchloride 150.0 n-Octyliodide 7.6 Arsenic (III) bromide 2.5
- Example 2 For purposes of comparison, a mixture similar to that used in Example 1 was reacted, which, however, contained instead of antimony iodide, in accordance with a known method, magnesium in the presence of an alcohol and an ether as catalyst. Said mixture consisted of 18 g. of tin, 67 g. of n-octylchloride, 4.3 g. of n-octyliodide, 2.7 g. of octanol, 12 g. of diethyleneglycol diethylether, and 0.18 g. of magnesium powder. It was refluxed 5 hours at 180 C. with stirring. After that time, the reaction mixture still contained 16 g. of unreacted tin and 1.5 g. of stannous chloride. Therefore, only 11.1 percent of the tin had reacted, part thereof with the formation of undesired inorganic tin compounds.
- a method for the production of organotin dihalides comprising reacting metallic tin at elevated temperature with an aliphatic halide, whose hydrocarbon group contains 4 to 12 carbon atoms, in the presence of a catalyst of the formula MeX wherein Me is a member of the group consisting of arsenic and antimony, X is a halogen of the group consisting of chlorine, bromine, and iodine, and n is an integer corresponding to the valence of Me.
- reaction mixture contains tin, alkyl chloride or bromide, and alkyl iodide in the mole proportions 1:3.07.0:0.10.4.
- reaction mixture contains tin, alkyl chloride, and alkyl bromide in the mole proportions 1:3.0-6.0:0.2l.3.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
United States Patent 3,387,012 PRODUCTION OF DIALIPHATIC TIN DIHALIDES Wolfgang Jasching, 26a Richard-Wagner-Strasse, Konigsbrnnn, Germany, and Volker Franzen, 24 Panorama- Strasse, Heidelberg, Germany No Drawing. Filed Sept. 10, 1965, Ser. No. 486,564 Claims priority, application 2germany, Sept. 12, 1964,
8 Claims. (Cl. 260-429.7)
ABSTRACT OF THE DISCLOSURE Organotin halides are prepared by reacting at elevated temperature metallic tin with an aliphatic halide, whose hydrocarbon group contains 4 to 12 carbon atoms, in the presence of a catalyst of the formula MeX wherein Me is a member of the group consisting of arsenic and antimony, X is a halogen of the group consisting of chlorine, bromine, and iodine, and n is an integer corresponding to the valance of Me.
This invention relates to the production of alkyl tin halides.
At present, the commercial production of alkyl tin halides is carried out essentially according to two methods which both start from tin tetrachloride. The one method uses a Grignard compound as alkylating agent, the other method employs an aluminum alkyl compound. Both procedures follow the general equation Much work has been done to render said methods economic. Nonetheless, they are not fully satisfactory because the procedure remains rather complicated and expensive.
It is, therefore, a principal object of this invention to provide a simplified process for the preparation of alkyl tin halides and more particularly a process where the alkyl tin halide can be prepared in a single step.
It is another object of the invention to provide a process which does not require a metal organic alkylating agent.
Still another object of the invention is to provide a process for the preparation of alkyltin halides where relatively cheap metallic tin can be used as starting material instead of tin tetrachloride.
A further object of the invention is to provide a process for the preparation of alkyltin halides which does not involve the use of inflammable solvents whose recovery requires additional cost.
Some methods are known which allow to react metallic tin directly with alkyl halides to form alkyl tin halides. Such direct syntheses, however, have succeeded only with especially reactive alkyl halides, such as iodides and certain bromides, or with such alkyl halides where the halogen atom is structurally activated, for instance by double "ice bonds. Direct syntheses with alkyl chlorides, for instance those where the alkyl group contains more than 4 C atoms, could not be carried out commercially with commercially attractive yields.
Particularly, no method is known which allows of producing dihexyl, dioctyl, or didecyl tin dichloride from metallic tin and the respective alkyl chlorides with economic yields. It is just those higher alkyl tin chlorides which are important for the preparation of corresponding organotin compounds which are useful as stabilizers for halogen containing resins, particularly polyvinyl chloride. Such higher alkyl tin compounds, for instance the dioctyl tin compounds, are much less toxic than the corresponding methyl, ethyl, propyl and butyl compounds and are, therefore, increasing used as physiologically harmless stabilizers.
We have now found that dihydrocarbon tin dihalides can be prepared in good yields by direct reaction of metallic tin with alkyl or alkylene halides, or mixtures of different alkyl or alkylene halides, when the reaction is carried out in the presence of an arsenic or antimony halide, or mixtures thereof, in amounts of 1 to 8 mole percent, calculated on tin. The reaction proceeds in a single step according to the equation wherein X is halogen and R is alkyl. In this process, the principal reaction product is always dialkyltin dihalide. In addition, minor amounts of monoalkyltin trihalide and trialkyltin monohalide are formed. The process has particular commercial interest for the production of dialkyl and dialkylene tin dihalides where the hydrocarbon group contains 4-12 C atoms.
Suitable metal halide catalysts are particularly arsenic (III) chloride, arsenic (III) bromide, arsenic (III) iodide, antimony (III) chloride, antimony (III) bromide, and antimony (III) iodide. However, also the corresponding pentavalent halides can be employed, particularly those which decompose wholly or in part at reaction temperature to the trivalent compounds.
In some cases, the reaction can be still further accelerated when, in addition to said metal halides, a secondary catalyst is added to the reaction mixture. Such secondary catalysts are dialkyltin halides in a concentration of 2 to 6 mole percent, calculated on metallic tin; preferably, dialkyltin dihalides are used whose alkyl groups are identical with the alkyl groups of the desired end product.
For a fast termination of the reaction, it is of advantage to use an excess of the alkyl halide, whereby a mole ratio of tin to alkyl halide of 1:3.0-7.0 is preferably employed. If less reactive alkyl halides, for instance the higher alkyl chlorides having 6-12 carbon atoms, are employed, it may be of advantage to add a more reactive alkyl halide, whose amount may remain far below the stoichiometrically required amount. Suitable mixtures contain, for instance, tin, alkyl chloride, and as reactive addition alkyl iodide in the mole ratio of 1:3.0-7.0:0.1-0.4, or tin, alkyl chloride, and alkyl bromide in the mole ratio of 1:3.0-6.0:0.21.3.
Though a solvent is not required for the reaction, it may be added as a diluent to slow up the rate of reaction when particularly reactive alkyl halides are employed.
Our new process is essentially independent of the form and grain size of the tin employed. The reaction can be carried out not only with finely powdered tin but also with coarser powder or tin foil or even with turnings.
It is of advantage to carry out the reaction under exclusion of moisture or with removal of water since in this way the formation of decomposition products, e.g. inorganic tin compounds (SnC'l and of volatile hydrocarbons can be substantially prevented. Moisture is readily removed continuously by separating out water, which may have been introduced by the reactants or also gen erated during the reaction, continuously by an azeotropic reflux distillation.
Even when alkyl chlorides are used, the reaction time is surprisingly short. Depending on the kind and amount of the additives and the temperature, the required reaction time will be generally bet-ween 45 minutes and 6 hours. With the more reactive alkyl halides, for instance the bromides, the time may be still shorter.
The reaction is best carried out in the temperature range between 90 and 210 C.; these limits are, however, not critical and higher or lower temperatures may be used.
The reaction mixture can be processed in accordance with known methods, and the alkyltin halides can be purified, for instance, by distillation. The alkyl halide used in excess can be recovered almost completely by distillation. Similarly, alkyl iodide added to the alkyl chlorides is also recovered from the reaction mixture by distillation; as numerous tests have shown, 50-80 percent of the alkyl iodide remain unreacted in the reaction.
The monoalkyltin trihalides obtained as by-products are valuable intermediary products and can be used as starting materials for the preparation of auxiliary agents in the plastics production.
Compared with the conventional Grignard synthesis, the new process has the advantage of requiring much less time and apparative installations. Particularly, the new process makes it possible to use cheaper alkyl chlorides, e.g. those having more than 4 C atoms, which heretofore could not be reacted in a direct synthesis with economically satisfactory yields.
The following examples are given to illustrate but not to limit the invention. In all examples, the tin was employed in the form of a fine powder, maximum grain size 6-25u. The last example is added to show, in comparison, the unsatisfactory results obtained with the conventional Grignard method.
Example 1 A mixture of G. Sn 18.0 n-Octyl chloride 150.0 n-Octyl iodide 7.6 Antimony (III) iodide 6.0
was refluxed under stirring for 70 minutes at about 180 C. in a vessel provided with a water trap. Subsequently, the clear reaction solution, which did no longer contain any tin, was distilled. Thereby, 91.6 g. of excess n-octyl chloride and 5.4 g. unreacted n-octyl iodide were recovered. The distillation residue of 68 g. contained 41.2 g. of pure dioctyltin dichloride (65.5% of theory), 10.5 g. of pure monooctyltin trichloride (20% of theory), traces of trioctyltin monochloride, and some tin (II) chloride.
If the same mixture but without the antimony (III) iodide catalyst, was refluxed in the same manner, no tin had been reacted after 8 hours of heating at 180 C.
Example 2 Example 1 was repeated but the amount of catalyst was reduced to 1.8 antimony (III) chloride. After refluxing for 6 /2 hours, all the tin had been reacted, except a residue of 0.3 g. After distilling off the excess n-octyl chloride and n-octyl iodide, there remained a residue of 48.0 g. (Sn content 28.64%), which consisted essentially of dioctyltin dichloride and monooctyltin trichloride. The monooctyltin trichloride was distilled off, and the residue was saponified with ZnNaOI-I at 100 C. Thereby, 28.3 g. of dioctyltin oxide were obtained in a yield of 51.7 percent of theory (Sn content found 33.05%; calc. 32.85% The monooctyltin trichloride fraction was also saponified and yielded 8.9 g. of octylstannonic acid (Sn found 44.2%; lcalc. 44.9%). The antimony remained in the aqueous saponification liquor.
Example 3 Example '2 was repeated, with further addition of 2.0 g. of dioctyltin dichloride as auxiliary catalyst. The tin had reacted Within 4 hours, leaving a residue of 0.4 g. After distilling off the excess n-octylchloride, n-octyl iodide, and the monooctyltin trichloride, there was obtained a residue of 47.8 g. containing 3-8.0 g. of pure dioctyltin dichloride. Deducting the 2.0 g. of dioctyltin dichloride added as secondary catalyst, the obtained dioctyltin dichloride corresponded to a yield of 57% of theory.
Example 4 Example 2 was repeated with further addition of 2.5 g. of antimony (III) iodide. In this case, the tin had completely reacted already after 2 hours of refluxing at C. Distillation of the excess n-octylchloride, n-octyl iodide, and monooctyltin trichloride left a residue of 49.0 g. of crude dioctyltin dichloride. Saponification of the residue with sodium hydroxide produced 31.4 g. of dioctyltin oxide (Sn found 33.0%; calc. 32.85%), corresponding to a yield of 57.5% of theory.
Example 5 A mixture of G. Tin 18.0 n-Octyl bromide 190.0 Antimony (III) iodide 4.0
found 33.3%; calc. 32.8%).
Example 6 A mixture of G. Tin 18.0 n-Octylchloride 113.0 n-Octylbromide 30.0 Antimony (III) iodide 6.0
was refluxed under stirring in a vessel provided with a water separator at about 180 C. for a period of 45 minutes. After this time, the tin was completely consumed. The reaction mixture was processed as described in the preceding examples and yielding 30.8 g. of pure dioctyltin oxide.
Example 7 A mixture of G. Tin 18.0 Decylchloride 179.0 Decyliodide 12.0 Antimony (III) iodide 6.0
was heated with agitation for 4 hours at C. After that time, the tin had been consumed to a residue of 1.8 g. The reaction mixture was filtered and the filtrate was distilled in vacuo to remove excess decyl chloride, unreacted decyl iodide, and monodecyltin trichloride formed as by-product. As distillation residue, there were obtained 33 g. of crude didecyltin dichloride (Sn found 26.1%; calc. 25.2%).
Example 8 A mixture of G. Tin 18.0 Laurylchloride 211.0 Lauryliodide 13.5 Antimony (III) iodide 6.0
was heated with stirring for 4 hours at 210 C. Within this time, 14.5 g. of tin had been reacted. The reaction mixture was processed as described in the preceding examples; on saponification of the obtained crude dilauryltin dichloride, 23.5 g. of dilauryltin oxide (Sn found 24.8%; calc. 25.1%) were obtained.
Example 9 A mixture of G. Tin 12.0 n-Hexylchloride 81.2 n-hexyliodi-de 4.6 Antimony (III) iodide 2.6
was shaken in a pressure tube 6 hours at 180 C. Thereby, 2 g. of the tin remained unreacted. Processing the reaction mixture in the :manner described hereinbefore yielded 11 g. of pure dihexyltin oxide (Sn found 38.9%; calc. 39.0%
Example 10 A mixture of Tin 18.0 n-Hexylbromide 167.0 Antimony (III) iodide 4.0
was refluxed with stirring in a vessel equipped with a water trap for /2 hour at 156 C. The clear reaction solution was filtered from the tin residue (0.1 g.). The filtrate was processed as set forth in Example 2. On saponification of the crude dihexyltin dibromide, 37.5 g. of dihexyltin oxide, corresponding to a yield of 57.5 percent, were obtained.
Example 11 A mixture of Tin 18.0 1,4-dichloro-2-butene 45.0
Diethyleneglycol diethyl ether (dried over sodium) as diluent 200.0 Antimony (III) iodide 4.0
were heated 3 hours at 95 C. with stirring. Thereby, 16.7 g. of the tin had reacted. After filtration, the reaction mixture was distilled. The first run contained the unreacted dichlorobutene and the diethyleneglycol diethylether; subsequently, pure reaction product distilled over at 82-83 C. 0.05 mm. 33.6 g. of dibutenyl tin dichloride were obtained (Sn found 24.7%; calc. 31.5%).
was refluxed 5 hours at 102 C. Thereby, 6.5 g. (54.2%) of the tin reacted to form essentially dibutyl tin dibrotnide and some monobutyltin tribromide.
If the test was repeated without the antimony iodide, 11.9 g. of the tin had not yet reacted after 5 hours. In other Words, there was substantially no reaction.
Example 13 A mixture of G. Tin 18.0 n-Octylchloride 150.0 n-Octyliodide 7.6 Arsenic (III) bromide 2.5
was refluxed with stirring in a vessel equipped with a water trap. After 4 hours, the tin had completely reacted. On processing the reaction mixture as in the preceding examples, 31.1 g. of pure dioctyl tin oxide were obtained.
For purposes of comparison, a mixture similar to that used in Example 1 was reacted, which, however, contained instead of antimony iodide, in accordance with a known method, magnesium in the presence of an alcohol and an ether as catalyst. Said mixture consisted of 18 g. of tin, 67 g. of n-octylchloride, 4.3 g. of n-octyliodide, 2.7 g. of octanol, 12 g. of diethyleneglycol diethylether, and 0.18 g. of magnesium powder. It was refluxed 5 hours at 180 C. with stirring. After that time, the reaction mixture still contained 16 g. of unreacted tin and 1.5 g. of stannous chloride. Therefore, only 11.1 percent of the tin had reacted, part thereof with the formation of undesired inorganic tin compounds.
We claim:
1. A method for the production of organotin dihalides comprising reacting metallic tin at elevated temperature with an aliphatic halide, whose hydrocarbon group contains 4 to 12 carbon atoms, in the presence of a catalyst of the formula MeX wherein Me is a member of the group consisting of arsenic and antimony, X is a halogen of the group consisting of chlorine, bromine, and iodine, and n is an integer corresponding to the valence of Me.
2. The method as claimed in claim 1 wherein said catalyst is applied in an amount of l to 8 mole percent, calculated on tin.
3. The method as claimed in claim 1 wherein said catalyst is a compound of trivalent arsenic or antimony.
4. The method as claimed in claim 1 wherein the reaction is carried out at a temperature of to 210 C.
5. The method as claimed in claim 1 comprising adding to the reaction mixture as secondary catalyst a dihydrocarbon tin halide, whose hydrocarbon group is the same as that of said aliphatic haides, in an amount of about 2 to 6 mole percent, calculated on metallic tin.
6. The method as claimed in claim 5 wherein the reaction mixture contains tin, alkyl chloride or bromide, and alkyl iodide in the mole proportions 1:3.07.0:0.10.4.
7. The method as claimed in claim 5 wherein the reaction mixture contains tin, alkyl chloride, and alkyl bromide in the mole proportions 1:3.0-6.0:0.2l.3.
8. The method as claimed in claim 1 comprising continuously removing water from the reaction mixture during reaction.
References Cited UNITED STATES PATENTS 2,852,543 9/1958 Blitzer et al 260429.7 3,085,102 4/1963 Yatagai et al 260429.7
FOREIGN PATENTS 25,664 2/1963 Japan.
TOBIAS E. LEVOW, Primary Examiner.
W. F. W. BELLAMY, Assistant Examiner.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DED45397A DE1217951B (en) | 1964-09-12 | 1964-09-12 | Process for the preparation of alkyltin halide mixtures with a high proportion of dialkyltin dihalides |
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US3387012A true US3387012A (en) | 1968-06-04 |
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US486564A Expired - Lifetime US3387012A (en) | 1964-09-12 | 1965-09-10 | Production of dialiphatic tind dihalides |
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US (1) | US3387012A (en) |
BE (1) | BE669340A (en) |
CH (1) | CH472431A (en) |
DE (1) | DE1217951B (en) |
GB (1) | GB1083908A (en) |
NL (1) | NL6511702A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3471539A (en) * | 1967-08-23 | 1969-10-07 | Nitto Kasei Co Ltd | Method for preparing triorganotin halides and bis(triorganotin) oxides |
US3475473A (en) * | 1966-10-11 | 1969-10-28 | Nitto Kasei Co Ltd | Process for preparing triorganotin halides and bis(triorganotin) oxides |
US3475472A (en) * | 1967-09-21 | 1969-10-28 | Nitto Kasei Co Ltd | Method for preparing triorganotin halides and bis(triorganotin) oxides |
US3519665A (en) * | 1968-01-25 | 1970-07-07 | Carlisle Chemical Works | Direct synthesis of dialkyltin dichloride |
US3547965A (en) * | 1966-12-07 | 1970-12-15 | Tadashi Takubo | Process for preparing trialkyltin halides |
US3872143A (en) * | 1970-06-06 | 1975-03-18 | Inst Przemyslu Organiczego | Process for the preparation of a mixture of n-octyltin chlorides which is entirely free from tri-n-octyltin chloride |
US3975417A (en) * | 1972-04-28 | 1976-08-17 | Sumitomo Chemical Company | Process for producing halogenated organotin compounds |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2852543A (en) * | 1954-10-14 | 1958-09-16 | Ethyl Corp | Process for the preparation of alkyl tin chlorides |
US3085102A (en) * | 1959-04-15 | 1963-04-09 | Nippon Catalytic Chem Ind | Process for producing alkyl tin halide compounds |
-
1964
- 1964-09-12 DE DED45397A patent/DE1217951B/en active Pending
-
1965
- 1965-08-27 CH CH1204165A patent/CH472431A/en not_active IP Right Cessation
- 1965-09-08 NL NL6511702A patent/NL6511702A/xx unknown
- 1965-09-08 BE BE669340A patent/BE669340A/xx unknown
- 1965-09-10 US US486564A patent/US3387012A/en not_active Expired - Lifetime
- 1965-09-13 GB GB38920/65A patent/GB1083908A/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2852543A (en) * | 1954-10-14 | 1958-09-16 | Ethyl Corp | Process for the preparation of alkyl tin chlorides |
US3085102A (en) * | 1959-04-15 | 1963-04-09 | Nippon Catalytic Chem Ind | Process for producing alkyl tin halide compounds |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3475473A (en) * | 1966-10-11 | 1969-10-28 | Nitto Kasei Co Ltd | Process for preparing triorganotin halides and bis(triorganotin) oxides |
US3547965A (en) * | 1966-12-07 | 1970-12-15 | Tadashi Takubo | Process for preparing trialkyltin halides |
US3471539A (en) * | 1967-08-23 | 1969-10-07 | Nitto Kasei Co Ltd | Method for preparing triorganotin halides and bis(triorganotin) oxides |
US3475472A (en) * | 1967-09-21 | 1969-10-28 | Nitto Kasei Co Ltd | Method for preparing triorganotin halides and bis(triorganotin) oxides |
US3519665A (en) * | 1968-01-25 | 1970-07-07 | Carlisle Chemical Works | Direct synthesis of dialkyltin dichloride |
US3872143A (en) * | 1970-06-06 | 1975-03-18 | Inst Przemyslu Organiczego | Process for the preparation of a mixture of n-octyltin chlorides which is entirely free from tri-n-octyltin chloride |
US3975417A (en) * | 1972-04-28 | 1976-08-17 | Sumitomo Chemical Company | Process for producing halogenated organotin compounds |
Also Published As
Publication number | Publication date |
---|---|
BE669340A (en) | 1965-12-31 |
NL6511702A (en) | 1966-03-14 |
DE1217951B (en) | 1966-06-02 |
CH472431A (en) | 1969-05-15 |
GB1083908A (en) | 1967-09-20 |
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