CA2100588A1 - Process for the direct synthesis of organotin chlorides and their use - Google Patents
Process for the direct synthesis of organotin chlorides and their useInfo
- Publication number
- CA2100588A1 CA2100588A1 CA002100588A CA2100588A CA2100588A1 CA 2100588 A1 CA2100588 A1 CA 2100588A1 CA 002100588 A CA002100588 A CA 002100588A CA 2100588 A CA2100588 A CA 2100588A CA 2100588 A1 CA2100588 A1 CA 2100588A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- chloride
- aryl
- tin
- chlorides
- 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.)
- Abandoned
Links
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
- 150000001805 chlorine compounds Chemical class 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 16
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 16
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims abstract description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001348 alkyl chlorides Chemical class 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 5
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 4
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 abstract 2
- -1 alkyl tin halides Chemical class 0.000 description 4
- 229910008066 SnC12 Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- INTLMJZQCBRQAT-UHFFFAOYSA-K trichloro(octyl)stannane Chemical compound CCCCCCCC[Sn](Cl)(Cl)Cl INTLMJZQCBRQAT-UHFFFAOYSA-K 0.000 description 3
- 150000001347 alkyl bromides Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XXLJTZALNKUUEP-UHFFFAOYSA-N 3-ethoxyhexan-3-ol Chemical compound CCCC(O)(CC)OCC XXLJTZALNKUUEP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241001331845 Equus asinus x caballus Species 0.000 description 1
- 229910008046 SnC14 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 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
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- SBOSGIJGEHWBKV-UHFFFAOYSA-L dioctyltin(2+);dichloride Chemical compound CCCCCCCC[Sn](Cl)(Cl)CCCCCCCC SBOSGIJGEHWBKV-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229950004492 octil Drugs 0.000 description 1
- 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 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YSCVYRUCAPMZFG-UHFFFAOYSA-K trichlorotin Chemical compound Cl[Sn](Cl)Cl YSCVYRUCAPMZFG-UHFFFAOYSA-K 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract A process for the direct synthesis of oroganotin chlo-rides of the formula RnSnCl4-n n = 1 - 2 and R being a linear or branched or cycloaliphatic alkyl having 4 to 18 carbon atoms, by reacting tin(II) chloride with alkyl chlorides, characterized in that the reaction is carried out in the presence of amines of the general formula A) R1a N [(CH2CH2O)m CH2CH2OR2]3-a and/or ammonium chlorides of the formula B) R1b N? [(CH2CH2O)m CH2CH2OR2]4-b C1?
a = 0, 1 or 2;
b = 0, 1, 2 or 3;
R1 is a linear or branched or cycloaliphatic alkyl with 2 to 24 C atoms, aryl, alkyl aryl or substituted aryl and, if a = 2 or b = 2 or 3, the R1 groups may be the same or different;
R2 is H, a linear or branched alkyl with 1 to 20 C at-oms, aryl, substituted aryl or alkyl aryl; and m = 1 - 20 The organotin chlorides produced in this fashion are especially suited as intermediate products for the pro-duction of thermostabilizers for PVC resins.
a = 0, 1 or 2;
b = 0, 1, 2 or 3;
R1 is a linear or branched or cycloaliphatic alkyl with 2 to 24 C atoms, aryl, alkyl aryl or substituted aryl and, if a = 2 or b = 2 or 3, the R1 groups may be the same or different;
R2 is H, a linear or branched alkyl with 1 to 20 C at-oms, aryl, substituted aryl or alkyl aryl; and m = 1 - 20 The organotin chlorides produced in this fashion are especially suited as intermediate products for the pro-duction of thermostabilizers for PVC resins.
Description
21~0rj~))8 Process for the Direct Synthesis of Organotin Chlorides and Their Use !
Specification The present invention relates to a process for the di-. rect synthesis of organotin chlorides of the general formula RnSnCl4-n n = 1 - 2 and R being a linear or branched or cycloaliphatic alkyl having 4 to 18 carbon atoms, . :
including mixtures of such compounds by reacting tin(II) chloride with alkyl chlorides and the use of the produced organotin chlorides.
The reaction between tin(II) chloride and alkyl chlo-rides is a known reaction according to the following stoichiometry:
SnC12 + R'-Cl --> R'SnC13 (R' = alkyl) In the course o~ such a synthesis, the following reac-tion follows as a side reaction:
Specification The present invention relates to a process for the di-. rect synthesis of organotin chlorides of the general formula RnSnCl4-n n = 1 - 2 and R being a linear or branched or cycloaliphatic alkyl having 4 to 18 carbon atoms, . :
including mixtures of such compounds by reacting tin(II) chloride with alkyl chlorides and the use of the produced organotin chlorides.
The reaction between tin(II) chloride and alkyl chlo-rides is a known reaction according to the following stoichiometry:
SnC12 + R'-Cl --> R'SnC13 (R' = alkyl) In the course o~ such a synthesis, the following reac-tion follows as a side reaction:
2 R' SnC13 ---~ R2'Sn~l2~SnC14 ~ ' .
:, .
~ ! .
,' . ~ . ; ; ~ t . ,' . ; , ; ' ' l . ~
'. ', ' . ': ` ' ' ' " . ' ' ' ' ' ' ' , ', ' ' , , ' . ,', :' ' . ' '.". . ' ',,'~ . ' ', ' . ' ' ' ' ' '. '`' . , ,'." " ' ' ',:' '',; '. ', ' '': , ' -- -- \
2~ ~0~8 The following ~in(IV) compounds are of an industrial importance since they can be converted to desired final products by known reactions:
R'4Sn, R'3SnCl, R'2SnC12, R'SnC13 Processes for the direct synthesis of organotin halides are already described in numerous patents, in particular using alkyl bromides and iodides as starting halides.
It is e.g. known from US-PS 3 ~57 868 that the reaction of the direct synthesis is promoted by the presence of tertiary amines and/or quaternary a~monium salts, whereby the latter can be formed "in situ" from the used tertiary amine and the used alkyl halide.
, The reaction is furthermore promoted by the presence of polar solvents and/or catalyzers, which can react with the tin. For this purpose alcohols, esters or amides are occasionally used.
In the direct synthesis of alkyl tin halides alkyl chlorides have a lower reactivity with respect to me-tallic tin or tin(II) chloride as co~pared with the corresponding alkyl bromides and iodides.
Moreover, ~he reaction rate and the yield of desired reaction product decreases with an increasing number of carbon atoms in the alkyl chain within the alkyl chlo-rides, it being already difficult to carry out the di-rect synthesis i~ C4 alkyl chloride (butyl chloride) is used. The al~yl tin halides are consequently often pro-duced using the corresponding alkyl aluminum compounds . .. , , . . .- . ,.. .. " .. .:.. , ........ : . , . , . ~ . : . . :
.... : . .. ~ .. , , .. , . . . . ., : : : . :
: :' . , , : :, , , ' . ~ ,, , . . .:
-.;: ~ ' ,, ', ,, :. :. ... . .
: . .: - . . . .
2 1 ~
or Grignard reagents, which requires a considerable ex-tra expenditure of costs and process steps.
The present invention is based on the object of provid-ing a process for the direct synthesis of organotin chlorides from tin(II) chloride using ~lkyl chlorides with four or more C atoms which can be carried out in simple fashion and with a good yield.
This object is attained according to the invention by a process of the type mentioned at the beginning, which is characterized in that the reaction is carried out in the presence of amines of the general formula :; `
A) Rla N [(CH2CH20)m CH2CH2R2]3 a and/or ammonium chlorides of the formula B3 Rlb N~ [(CH2CH20)m CH2CH2R 34-b Cl a = 0, 1 or 2;
b = 0, 1, 2 or 3;
Rl i5 a linear or branched or cycloaliphatic alkyl with 2 to 24 C atoms, aryl, alkyl aryl or substituted aryl and, i~ a = 2 or b = 2 or 3, the R1 qroups may be th~
same or different;
R2 is H, a linear or branched alkyl with 1 to 20 C at-oms, aryl, substituted aryl or alkyl aryl; and m = 1 - 20 .. ... . . . . . . . . ......................... . . . . .
' . i ~ . ,.~ -' ' ' :. ::
2 ~
The present invention relates especially to the direct synthesis of organotin chlorides starting from alkyl chlorides, the use of which has been more difficult so far due to their low reactivity than that of the corresponding bromides and iodides.
According to the invention it became surprisingly ap-parent that the direct synthesis of organotin chlorides by reacting tin(II) chloride with alkyl chlorides can be carried out very effectively and efficiently if the reaction is carried out in the presence of amines of the aforementioned formula A or ammonium chlorides of the aforementioned formula B. If amines of the formula A are used, quaternary ammonium salts are formed in situ.
The reaction is suitably carried out at a temperature between 20 and 200C, preferably between 140 and 190C
in the presence of 0.05 to 4 mole, especially preferred of 0.33 to 0.5 mole, of the amine of the formula A
and/or of the ammonium chloride of the formula B per mole of tin(II) chloride. The reaction time is suitably 3 to 24 hours, preferably 6 to 10 hours. Moreover, the reaction is suitably carried out with 1 to 6 mole, preferably 1 to 3 mole of alkyl chloride per mule of tin(II) chloride. Butyl, octyl or dodecyl chloride are preferably used as alkyl chlorides for the direct syn-thesis.
According to another embodiment metallic tin can addi-tionally be used for the direct synthesis in addition to tin(II) chloride. Mixtures of monoalkyl tin and dialkyl tin chlorides can be obtained as reaction prod-ucts.
, '.
.
`' 2l~a~
The amine and/or the ammonium chloride can be recovered subsequently after the completed reaction by known chemical processes and be used again. Distillation un-der reduced pressure can be carried out for recovering the non-reacted alkyl chloride and/or the possibly used solvent.
The organotin chlorides produced according to the in-vention are especially suited as intermediate products for the production of thermostabilizers, e.g. alkyl tin mercapto compounds, for PVC resins.
The following examples explain the invention.
The reaction products were analyzed using thin-layer chromatography.
Example 1 .
An ammonium chloride of the formula [(C4H9)3 N~ tCH~ CH2 OCH2 CH2 OCH2 CH20~] . Cl (MW 353.9; 95.5 g; 0.27 mole), SnCl2 anhydrous (MW 189.62; 51.2 g; 0.27 mole) and octyl chloride (MW 148.7; 60 g; 0.4 mole) . are added to a ~lask provided with stirrer, thermometer and cooler.
- : . ,. , , .: : . : :
.
2 ~
The dissolution of SnC12 in ammonium chloride is exo-thermal, the temperature increasing to 60C. The reac-tion itself is carried out with stirring at 160 to 165C for 8 hours.
The unreacted octyl chloride is distilled off after the reaction has taken place. 54.7 g of monooctyl tin trichloride is obtained by means of solYent extraction.
No further alkyl tin derivatives could be detected by means of thin layer chromatography.
Yield: 60~.
' Example 2 Tin powder (50 g; 0.42 mole), SnCl2 anhydrous (112.5 g; 0,59 mole) and diethyl ethoxy ethanol amine of the formula (C2H5)2 - N CH2CH20CH2CH20H (MW 161.25; 22~5 g; 0.14 mole) were added to a reaction flask provided with thermome-ter, cooler, stirrer and dropping funnel.
The reaction is carried out at 180C, 195.5 g (1.31 mole) of octyl chloride being added dropwise for 6 hours and the temperature being kept at 180C.
After the complete addition of the octyl chloride, the reaction mixture is maintained at this temperature for : -:~ ~ . . , , . , . . : , ,, :
,, . .. . ~ .
::
~' ' ' ~ " ' ' ;;' ,. :' ' :' , :
.
2.~a~
further 4 hours, and the excess of octil chloride isdistilled off.
The yield of monooctyl tin trichloride, ~ased on a used tin(II) chloride, is 85.0%. 90% of the used tin metal were reacted.
The final product has the following composition:
50.9% monooctyl tin trichloride and 4B.1% dioctyl tin dichloride.
Example 3 70.5 g of a coconut amine of the formula C13H27N [(cH2cH2o)2-cH2cH2oH~2 (MW 463; 70.5 g; 0.152 mole~
and SnC12 anhydrous (MW 189.62; 100 g; 0.527 mGle) are added to a flask provided with stirrer, thermometer and cooler.
Butyl chloride (MW 92.5) i5 introduced into the flask at 160 to 170C at such a rate that the temperature re-mains approximately constant for 8 hours.
During this time, approx. 34 g (0.3676 mole) of butyl chloride are reacted. Then, the reaction mixture is filtered, and monobutyl tin trichloride (MW 282.2) is distilled at reduced pressure. The yield of monobutyl . .
, :: : . . .. . ;
: . .:. : - . . : , . . .
: - , . . :
,, f ~
210~a~8 tin trichloride is approx. 53.9%, based on the used tin(II) chloride. Dibutyl tin dichloride can be de-tected by ~eans of thin-layer chromatography as a reaction by-product in the distillation residue.
: . ., : , . ' : .; ,, . , ' ,'.. - :." ''~ '.,': ' , "; ,~ ,'' ' ,~'' , :
, ' ' . ~ . ~ ,
:, .
~ ! .
,' . ~ . ; ; ~ t . ,' . ; , ; ' ' l . ~
'. ', ' . ': ` ' ' ' " . ' ' ' ' ' ' ' , ', ' ' , , ' . ,', :' ' . ' '.". . ' ',,'~ . ' ', ' . ' ' ' ' ' '. '`' . , ,'." " ' ' ',:' '',; '. ', ' '': , ' -- -- \
2~ ~0~8 The following ~in(IV) compounds are of an industrial importance since they can be converted to desired final products by known reactions:
R'4Sn, R'3SnCl, R'2SnC12, R'SnC13 Processes for the direct synthesis of organotin halides are already described in numerous patents, in particular using alkyl bromides and iodides as starting halides.
It is e.g. known from US-PS 3 ~57 868 that the reaction of the direct synthesis is promoted by the presence of tertiary amines and/or quaternary a~monium salts, whereby the latter can be formed "in situ" from the used tertiary amine and the used alkyl halide.
, The reaction is furthermore promoted by the presence of polar solvents and/or catalyzers, which can react with the tin. For this purpose alcohols, esters or amides are occasionally used.
In the direct synthesis of alkyl tin halides alkyl chlorides have a lower reactivity with respect to me-tallic tin or tin(II) chloride as co~pared with the corresponding alkyl bromides and iodides.
Moreover, ~he reaction rate and the yield of desired reaction product decreases with an increasing number of carbon atoms in the alkyl chain within the alkyl chlo-rides, it being already difficult to carry out the di-rect synthesis i~ C4 alkyl chloride (butyl chloride) is used. The al~yl tin halides are consequently often pro-duced using the corresponding alkyl aluminum compounds . .. , , . . .- . ,.. .. " .. .:.. , ........ : . , . , . ~ . : . . :
.... : . .. ~ .. , , .. , . . . . ., : : : . :
: :' . , , : :, , , ' . ~ ,, , . . .:
-.;: ~ ' ,, ', ,, :. :. ... . .
: . .: - . . . .
2 1 ~
or Grignard reagents, which requires a considerable ex-tra expenditure of costs and process steps.
The present invention is based on the object of provid-ing a process for the direct synthesis of organotin chlorides from tin(II) chloride using ~lkyl chlorides with four or more C atoms which can be carried out in simple fashion and with a good yield.
This object is attained according to the invention by a process of the type mentioned at the beginning, which is characterized in that the reaction is carried out in the presence of amines of the general formula :; `
A) Rla N [(CH2CH20)m CH2CH2R2]3 a and/or ammonium chlorides of the formula B3 Rlb N~ [(CH2CH20)m CH2CH2R 34-b Cl a = 0, 1 or 2;
b = 0, 1, 2 or 3;
Rl i5 a linear or branched or cycloaliphatic alkyl with 2 to 24 C atoms, aryl, alkyl aryl or substituted aryl and, i~ a = 2 or b = 2 or 3, the R1 qroups may be th~
same or different;
R2 is H, a linear or branched alkyl with 1 to 20 C at-oms, aryl, substituted aryl or alkyl aryl; and m = 1 - 20 .. ... . . . . . . . . ......................... . . . . .
' . i ~ . ,.~ -' ' ' :. ::
2 ~
The present invention relates especially to the direct synthesis of organotin chlorides starting from alkyl chlorides, the use of which has been more difficult so far due to their low reactivity than that of the corresponding bromides and iodides.
According to the invention it became surprisingly ap-parent that the direct synthesis of organotin chlorides by reacting tin(II) chloride with alkyl chlorides can be carried out very effectively and efficiently if the reaction is carried out in the presence of amines of the aforementioned formula A or ammonium chlorides of the aforementioned formula B. If amines of the formula A are used, quaternary ammonium salts are formed in situ.
The reaction is suitably carried out at a temperature between 20 and 200C, preferably between 140 and 190C
in the presence of 0.05 to 4 mole, especially preferred of 0.33 to 0.5 mole, of the amine of the formula A
and/or of the ammonium chloride of the formula B per mole of tin(II) chloride. The reaction time is suitably 3 to 24 hours, preferably 6 to 10 hours. Moreover, the reaction is suitably carried out with 1 to 6 mole, preferably 1 to 3 mole of alkyl chloride per mule of tin(II) chloride. Butyl, octyl or dodecyl chloride are preferably used as alkyl chlorides for the direct syn-thesis.
According to another embodiment metallic tin can addi-tionally be used for the direct synthesis in addition to tin(II) chloride. Mixtures of monoalkyl tin and dialkyl tin chlorides can be obtained as reaction prod-ucts.
, '.
.
`' 2l~a~
The amine and/or the ammonium chloride can be recovered subsequently after the completed reaction by known chemical processes and be used again. Distillation un-der reduced pressure can be carried out for recovering the non-reacted alkyl chloride and/or the possibly used solvent.
The organotin chlorides produced according to the in-vention are especially suited as intermediate products for the production of thermostabilizers, e.g. alkyl tin mercapto compounds, for PVC resins.
The following examples explain the invention.
The reaction products were analyzed using thin-layer chromatography.
Example 1 .
An ammonium chloride of the formula [(C4H9)3 N~ tCH~ CH2 OCH2 CH2 OCH2 CH20~] . Cl (MW 353.9; 95.5 g; 0.27 mole), SnCl2 anhydrous (MW 189.62; 51.2 g; 0.27 mole) and octyl chloride (MW 148.7; 60 g; 0.4 mole) . are added to a ~lask provided with stirrer, thermometer and cooler.
- : . ,. , , .: : . : :
.
2 ~
The dissolution of SnC12 in ammonium chloride is exo-thermal, the temperature increasing to 60C. The reac-tion itself is carried out with stirring at 160 to 165C for 8 hours.
The unreacted octyl chloride is distilled off after the reaction has taken place. 54.7 g of monooctyl tin trichloride is obtained by means of solYent extraction.
No further alkyl tin derivatives could be detected by means of thin layer chromatography.
Yield: 60~.
' Example 2 Tin powder (50 g; 0.42 mole), SnCl2 anhydrous (112.5 g; 0,59 mole) and diethyl ethoxy ethanol amine of the formula (C2H5)2 - N CH2CH20CH2CH20H (MW 161.25; 22~5 g; 0.14 mole) were added to a reaction flask provided with thermome-ter, cooler, stirrer and dropping funnel.
The reaction is carried out at 180C, 195.5 g (1.31 mole) of octyl chloride being added dropwise for 6 hours and the temperature being kept at 180C.
After the complete addition of the octyl chloride, the reaction mixture is maintained at this temperature for : -:~ ~ . . , , . , . . : , ,, :
,, . .. . ~ .
::
~' ' ' ~ " ' ' ;;' ,. :' ' :' , :
.
2.~a~
further 4 hours, and the excess of octil chloride isdistilled off.
The yield of monooctyl tin trichloride, ~ased on a used tin(II) chloride, is 85.0%. 90% of the used tin metal were reacted.
The final product has the following composition:
50.9% monooctyl tin trichloride and 4B.1% dioctyl tin dichloride.
Example 3 70.5 g of a coconut amine of the formula C13H27N [(cH2cH2o)2-cH2cH2oH~2 (MW 463; 70.5 g; 0.152 mole~
and SnC12 anhydrous (MW 189.62; 100 g; 0.527 mGle) are added to a flask provided with stirrer, thermometer and cooler.
Butyl chloride (MW 92.5) i5 introduced into the flask at 160 to 170C at such a rate that the temperature re-mains approximately constant for 8 hours.
During this time, approx. 34 g (0.3676 mole) of butyl chloride are reacted. Then, the reaction mixture is filtered, and monobutyl tin trichloride (MW 282.2) is distilled at reduced pressure. The yield of monobutyl . .
, :: : . . .. . ;
: . .:. : - . . : , . . .
: - , . . :
,, f ~
210~a~8 tin trichloride is approx. 53.9%, based on the used tin(II) chloride. Dibutyl tin dichloride can be de-tected by ~eans of thin-layer chromatography as a reaction by-product in the distillation residue.
: . ., : , . ' : .; ,, . , ' ,'.. - :." ''~ '.,': ' , "; ,~ ,'' ' ,~'' , :
, ' ' . ~ . ~ ,
Claims (7)
1) A process for the direct synthesis of organotin chlorides of the formula RnSnCl4-n n = 1 - 2 and R being a linear or branched or cycloaliphatic alkyl having 4 to 18 carbon atoms, by reacting tin(II) chloride with alkyl chlorides, characterized in that the reaction is carried out in the presence of amines of the general formula A) R1a N [(CH2CH2O)m CH2CH2OR2]3-a and/or ammonium chlorides of the formula B) R1b N? [(CH2CH2O)m CH2CH2OR2]4-b C1?
a = 0, 1 or 2;
b = 0, 1, 2 or 3;
R1 is a linear or branched or cycloaliphatic alkyl with 2 to 24 C atoms, aryl, alkyl aryl or substituted aryl and, if a = 2 or b = 2 or 3, the R1 groups may be the same or different;
R2 is H, a linear or branched alkyl with 1 to 20 C at-oms, aryl, substituted aryl or alkyl aryl; and m = 1 - 20
a = 0, 1 or 2;
b = 0, 1, 2 or 3;
R1 is a linear or branched or cycloaliphatic alkyl with 2 to 24 C atoms, aryl, alkyl aryl or substituted aryl and, if a = 2 or b = 2 or 3, the R1 groups may be the same or different;
R2 is H, a linear or branched alkyl with 1 to 20 C at-oms, aryl, substituted aryl or alkyl aryl; and m = 1 - 20
2. A process according to claim 1, characterized in that R2 is a linear or branched alkyl with 1 to 4 C-atoms.
3. A process according to claim 1 or 2, characterized in that m = 1 - 10, in particular 1 - 3.
4. A process according to at least any of claims 1 to 3, characterized in that butyl chloride, octyl chloride or dodecyl chloride is used as alkyl chloride.
5. A process according to at least any of claims 1 to 4, characterized in that the amine and/or the ammonium chloride is used in a ratio of 0.05 to 4 mole, in particular 0.33 to 0.5 mole, per mole of tin(II) chloride.
6. A process according to at least any of claims 1 to 5, characterized in that, in addition to tin(II) chloride, additional metallic tin is still used for the direct synthesis.
7. Use of the organotin chlorides produced according to the process according to at least any of claims 1 to 6 as intermediate products for the production of thermo-stabilizers for polyvinyl chloride resins.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4101760.9 | 1991-01-22 | ||
| DE4101760A DE4101760A1 (en) | 1991-01-22 | 1991-01-22 | METHOD FOR THE DIRECT SYNTHESIS OF ORGANOZINCHLORIDES AND THE USE THEREOF |
| PCT/DE1992/000037 WO1992012984A1 (en) | 1991-01-22 | 1992-01-21 | Method for the direct synthesis of organo-tin chlorides, and the use of such chlorides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2100588A1 true CA2100588A1 (en) | 1992-07-23 |
Family
ID=6423463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002100588A Abandoned CA2100588A1 (en) | 1991-01-22 | 1992-01-21 | Process for the direct synthesis of organotin chlorides and their use |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0557465A1 (en) |
| JP (1) | JPH06504540A (en) |
| AU (1) | AU1176292A (en) |
| CA (1) | CA2100588A1 (en) |
| DE (1) | DE4101760A1 (en) |
| WO (1) | WO1992012984A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3340283A (en) * | 1964-05-20 | 1967-09-05 | M & T Chemicals Inc | Preparation of organotin-trihalides |
| US3824264A (en) * | 1972-06-08 | 1974-07-16 | Cosan Chem Corp | Preparation of monohydrocarbyl tin trihalides |
| GB1472498A (en) * | 1975-03-20 | 1977-05-04 | Chugoku Marine Paints | Method for producing monoalkyl-tin-trihalides |
| JPS5242824A (en) * | 1975-09-29 | 1977-04-04 | Sankyo Yuki Gosei Kk | Process for preparation of methyltin chloride |
| EP0433473A1 (en) * | 1989-12-18 | 1991-06-26 | Chemische Werke München Otto Bärlocher GmbH | Method for the direct synthesis of organotin compounds and their use |
-
1991
- 1991-01-22 DE DE4101760A patent/DE4101760A1/en not_active Withdrawn
-
1992
- 1992-01-21 CA CA002100588A patent/CA2100588A1/en not_active Abandoned
- 1992-01-21 WO PCT/DE1992/000037 patent/WO1992012984A1/en not_active Application Discontinuation
- 1992-01-21 JP JP4503009A patent/JPH06504540A/en active Pending
- 1992-01-21 AU AU11762/92A patent/AU1176292A/en not_active Abandoned
- 1992-01-21 EP EP92903073A patent/EP0557465A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992012984A1 (en) | 1992-08-06 |
| EP0557465A1 (en) | 1993-09-01 |
| JPH06504540A (en) | 1994-05-26 |
| DE4101760A1 (en) | 1992-07-23 |
| AU1176292A (en) | 1992-08-27 |
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