US3387012A - Production of dialiphatic tind dihalides - Google Patents

Production of dialiphatic tind dihalides Download PDF

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Publication number
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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tin
alkyl
reaction
iodide
antimony
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Jasching Wolfgang
Franzen Volker
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    • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US486564A 1964-09-12 1965-09-10 Production of dialiphatic tind dihalides Expired - Lifetime US3387012A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DED45397A DE1217951B (de) 1964-09-12 1964-09-12 Verfahren zur Herstellung von Alkylzinnhalogenidgemischen mit hohem Anteil an Dialkylzinndihalogeniden

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US (1) US3387012A (xx)
BE (1) BE669340A (xx)
CH (1) CH472431A (xx)
DE (1) DE1217951B (xx)
GB (1) GB1083908A (xx)
NL (1) NL6511702A (xx)

Cited By (7)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

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NL6511702A (xx) 1966-03-14
BE669340A (xx) 1965-12-31
DE1217951B (de) 1966-06-02
GB1083908A (en) 1967-09-20
CH472431A (de) 1969-05-15

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