GB2026491A - A method for preparing organotin compounds. - Google Patents
A method for preparing organotin compounds. Download PDFInfo
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- GB2026491A GB2026491A GB7925073A GB7925073A GB2026491A GB 2026491 A GB2026491 A GB 2026491A GB 7925073 A GB7925073 A GB 7925073A GB 7925073 A GB7925073 A GB 7925073A GB 2026491 A GB2026491 A GB 2026491A
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- United Kingdom
- Prior art keywords
- sulphide
- alkali metal
- product
- carbon atoms
- reaction
- Prior art date
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 239000002585 base Substances 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 150000004820 halides Chemical class 0.000 claims description 9
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229960002446 octanoic acid Drugs 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 239000005643 Pelargonic acid Substances 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical class SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- -1 mercaptoalcohol ester Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- KUKGHAPVFWTPBL-UHFFFAOYSA-K SCCC(C(=[O+][S-])[O-])CCCCCC.C(CCC)[Sn+3].SCCC(C(=[O+][S-])[O-])CCCCCC.SCCC(C(=[O+][S-])[O-])CCCCCC Chemical compound SCCC(C(=[O+][S-])[O-])CCCCCC.C(CCC)[Sn+3].SCCC(C(=[O+][S-])[O-])CCCCCC.SCCC(C(=[O+][S-])[O-])CCCCCC KUKGHAPVFWTPBL-UHFFFAOYSA-K 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical class [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase 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
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C07F7/226—Compounds with one or more Sn-S linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Organotin derivatives of mercaptoalcohol esters having the formula <IMAGE> wherein R and R' are hydrocarbon groups and m is 2 or 3, are prepared by reacting a monoorganotin trihalide in sequence with stoichiometric amounts of a base, a mercaptoalcohol, an alkali metal sulphide or disulphide and a carboxylic acid or an ester thereof.
Description
SPECIFICATION
A method for preparing organotin compounds
United States Patent No. 2,870,182 disclosed compounds of the general formula RnSnA4n, wherein R represents one of a specified group of hydrocarbon radicals, n is 1, 2 or 3 and A represents the residue obtained following removal of the hydrogen atom from the -SH group of a mercaptoalcohol ester. The Patent further discloses that compounds of this formula can be prepared by first reacting the mercaptoalcohol with a carboxylic acid in the presence of an esterification catalyst and subsequently reacting the resultant ester with an organotin halide or oxide or with an organostannoic acid. This method of preparation has the following disadvantages.Firstly, formation of the mercaptoalcohol ester is an equilibrium reaction which almost always requires an acidic catalyst and removal of water during the reaction to obtain a useful yield of the desired product within a reasonable period of time. The acid catalyst may promote a number of undesirable side reactions, including polymeization of the mercaptoalcohol. The polymer may contain end groups that will subsequently react with the organotin compound, with the result that the reaction product is not nearly as effective as the desired monomeric ester derivative in its intended use as a stabilizer for vinyl chloride polymers. Secondly, removal of water is required during preparation of the ester and during reaction of the ester with the organotin compound.Removal of water requires heating, which not only increases processing costs due to the additional energy input but can result in larger amounts of undesirable by-products due to side reactions. In addition, part of the mercaptoalcohol usually distils off with the water.
The present invention is based on the discovery that these disadvantages can be avoided if the mercaptoalcohol is first reacted with the organotin compound and then esterified. Reactions of organotin halides and oxides with both mercaptans and alcohols are reported in the chemical literature. One would therefore expect a mixture of products containing tin-oxygen and tin-sulphur bonds. Surprisingly, under the conditions of the method according to the invention described below only the mercaptide portion of the mercaptoalcohol reacts with the organotin compound. The hydroxyl portion of the molecule remains available for subsequent esterification with a carboxylic acid.
This invention provides a method for preparing an organotin compound of the formula
wherein each of Rand R', which latter group may contain one or more substituents, is an alkyl group containing 1 to 20 carbon atoms, or a cycloalkyl, aralkyl, aryl or alkaryl group, and m is 2 or 3, said method comprising the following steps: 1) reacting a monoorganotin trihalide of the formula RSnX3, wherein Xis chlorine, bromine or iodine, with
an aqueous solution containing a stoichiometric amount of a base selected from ammonium hydroxide
and alkali metal and alkaline earth metal hydroxides, the ratio of the number of equivalent weights of
base to the number of moles of monoorganotin trihalide being 1:1; 2) adding an equimolar amount, based on said monoorganotin trihalide, of 2-mercaptoethanol or
3-mercaptopropanol to the resultant mixture; 3) adding to the resulting reaction product an alkali metal sulphide or an alkali metal disulphide, the
number of moles of sulphide or disulphide being equal to the number of moles of tin present in said
reaction product; 4) removing the aqueous phase of the reaction mixture; and 5) reacting the product of step 3) with an equimolar amount, based on said monoorganotin trihalide, of a
carboxylic acid, R'COOH, or an ester R'COOR" wherein R" is an alkyl group containing 1 to 20 carbon
atoms.
In carrying out the first step of the method, all of the base can be added initially to react with the organotin halide. Alternatively, most of the base, usually about 90% of the total, may be added initially and the remainder is added following addition of the alkali metal sulphide. The term "stoichiometric amount" used herein means one mole of a monofunctional base, such as sodium hydroxide, and 0.5 mole of a difunctional base, such as calcium hydroxide, for each mole of monoorganotin trihalide.
When R is an alkyl group it may, for example, be methyl, ethyl, n-propyl or iso-propyl. Examples of suitable cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl and cyclooctyl. When R is aryl it is preferably phenyl but may also be naphthyl, anthrecenyl or biphenyl. Examples of suitable aralkyl radicals are benzyl and p-phenylethyl. Examples of suitable alkaryl groups are tolyl, xylyl and other alkyl-substituted phenyl radicals.
The reaction between the halogen atoms of the organotin halide and the base is rapid at ambient temperature and often highly exothermic. The addition of the organotin halide should therefore be gradual and the reaction mixture should be simultaneously stirred and cooled to prevent localised overheating. It may be desirable to continue stirring the reaction mixture after all of the organotin halide has been added in order to improve heat transfer and increase the rate of cooling. The resultant solution of an organotin hydroxy-halide is then reacted with the mercaptoalcohol. The rate of this reaction is considerably slower than the rate at which the initial organotin halide reacts with a base. It may therefore be desirable to maintain the mixture at a temperature from 40 to 1 00 C. to complete the reaction in a reasonable length of time, usually 5 to 60 minutes.The number of moles of mercaptoalcohol added is equal to the number of equivalent weights of base employed in the initial step of the method.
When the reaction of the organotin compound with the mercaptoalcohol is completed, the resultant mixture is combined with one mole of an alkali metal sulphide for every mole of tin present in the reaction mixture when the final product contains 2 sulphur atoms per molecule. When the product contains 3 sulphur atoms an equimolar amount of an alkali metal sulphide is employed. The sulphide can be formed by reacting equimolar amounts of the corresponding alkali metal sulphide and elemental sulphur. Preferably the sulphide or disulphide is added to the organotin component gradually, since the reaction may be exothermic. The sulphide or sulphide can be added as a solid or in an aqueous solution. Any base not added during the initial hydrolysis of the halide is added at this time.
Following the completion of the addition of sulphide the mercaptoalcohol residue is esterified by addition of an equimolar amount of the desired carboxylic acid or ester. R' may contain one or more substituents such as halogen, hydroxyl, alkoxy and nitro groups. In contrast to conventional esterification reactions, a stoichiometric excess of carboxylic acid is not required, nor is it necessary to add a catalyst. Octanoic acid, also known as caprylic acid, is preferred because products prepared using this acid do not have the disagreeable odour which characterises this class of organotin compounds. Another suitable acid is pelargonic acid. When an ester of the acid is employed, the alcohol residue preferably contains 1 to 4 carbons to facilitate removal of the alcohol by distillation during the transesterification reaction.In those instances when the final organotin compound is intended for use as a stabilizer for a halogenated polymer, such as polyvinyl chloride, it may be desirable to employ an alcohol of higher molecular weight containing from 12 to 20 carbon atoms as the alcohol component of the ester. In this instance the alcohol R"OH will not be removed during the transesterification but is isolated together with the final organotin product. The alcohol serves as a lubricant or processing acid in the stabilized halogenated polymer composition.
Once the acid or ester has been added, the aqueous phase of the reaction mixture is removed and discarded. Following removal of the aqueous phase, the reaction mixture is heated to 100-1800C. to effect the esterification or transesterification reaction. When the by-product is water or a volatile alcohol boiling below 120 C., the by-product may be continuously removed during the reaction by use of a distillation apparatus.
To minimize overheating and the accompanying decomposition of the product the last of the water is preferably removed under a reduced pressure equivalent to 10-100 mm. of mercury. Once all of the water or alcohol has been removed the final liquid organotin compound remains in the reaction vessel. It may be necessary to filter the product to remove small amounts of solid materials.
The products obtained by the method according to the invention are particularly effective heat stabilizers for vinyl chloride polymers and other halogen-containing polymers of high moleclarweight. The compounds are employed for this purpose at the conventional concentration of 0.1 to 10% by weight
Organotin derivatives of mercaptoalcohol esters may also be used as antioxidants for a variety of materials.
EXAMPLE- Preparation of monobutyltin-2-mercaptoethyl-caprylate sulphide.
A reaction vessel was charged with 141.1 g (0.5 mole) of monobutyltin trichloride and 150 ce water and 29.0 g (0.5 mole) of ammonium hydroxide were gradually added to the resulting solution at a rate sufficient to maintain the temperature of the reaction mixture at or below 60"C. without external cooling of the reactor.
Stirring of the reaction mixture was continued for five minutes following completion of the addition of ammonium hydroxide, 39.85 g (0.5 mole) of 2-mercaptoethanol were then added and the contents of the reactor were stirred and heated to a temperature of 60"C. for 1/2 hour.The reaction mixture was then allowed to cool to 40"C. and 65.0 g (0.5 mole) of solid sodium sulphide were added at a rate such that the temperature of the reaction mixture did not exceed 60"C. The reaction mixture was stirred for 20 minutes following completion of the addition and the temperature was maintained at 60"C. using external heating. 79.12 g (0.5 mole) of methyl caprylate were then added and the contents of the reactor were stirred for ten minutes and the aqueous phase of the reaction mixture was then removed and discarded. The organic phase was heated at 140"C. under a nitrogen atmosphere using a distillaton apparatus until the evolution of methanol ceased.
The reaction mixture was then cooled and filtered to yield relatively pure monobutyltin-2mercaptoethylcaprylate sulphide. This compound did not have the offensive odour characteristic of monoorganotin or diorganotin derivatives of mercaptoethanol esters. An unpleasant odour characterises analagous compounds obtained when the aforementioned n-octanoic acid ester is replaced by the oleic ester of 2-mercaptoethanol. This difference in odour is also true for the corresponding methyltin derivatives.
These compounds may be prepared by using methyltin trichloride in place of butyltin trichloride.
Claims (12)
1. A method for preparing an organotin compound of the formula
wherein each of Rand R', which latter group may contain one or more substituents, is an alkyl group containing 1 to 20 carbon atoms, or a cycloalkyl, aralkyl, aryyl or alkaryl group, and m is 2 or 3, said method comprising the following steps: 1) reacting a monoorganotin trihalide of the formula RSnX3, wherein Xis chlorine, bromine or iodine, with
an aqueous solution containing a stoichiometric amount of a base selected from ammonium hydroxide
and alkali metal and lakaline earth metal hydroxides, the ratio of the number of equivalent weights of
base to the number of moles of monoorganotin trihalide being 1:1; 2) adding an equimolar amount, based on said monoorganotin trihalide, of 2-mercaptoethanol or
3-mercaptopropanol to the resulting mixture; 3) adding to the resulting reaction product an alkali metal sulphide or an alkali metal disulphide, the
number of moles of sulphide or sulphide being equal to the number of moles of tin present in said
reaction product; 4) removing the aqueous phase of the reaction mixture; and 5) reacting the product of step 3) with an equimolar amount, based on said monoorganotin trihalide, of a
carboxylic acid, R'COOH, or an ester R'COOR" wherein R" is an alkyl group containing 1 to 20 carbon
atoms.
2. A method as claimed in Claim 1, wherein each of Rand R' is an alkyl group containing from 1 to 20 carbon atoms.
3. A method as claimed in Claim 2, wherein R is butyl.
4. A method as claimed in Claim 1, wherein the carboxylic acid is caprylic acid or pelargonic acid.
5. A method as claimed in Claim 1, wherein m is 2.
6. A method as claimed in Claim 1, wherein Xis chlorine.
7. A method as claimed in Claim 1, wherein the base reacted with the organotin halide is ammonium hydroxide.
8. A method as claimed in Claim 1, wherein the alkali metal sulphide is sodium sulphide.
9. A method as claimed in Claim 1, werein R" contains from 1 to 4 carbon atoms.
10. A method as claimed in Claim 1, wherein the alkali metal sulphide is formed by reacting equimolar amounts of the corresponding alkali metal sulphide and elemental sulphur.
11. A method as claimed in Claim 1, wherein the product of step 3 is reacted with a carboxylic acid ester
R'COOR" and the alcohol R"OH formed as a by-product of the reaction is removed by distillation prior to isolating the organotin compound.
12. A method as claimed in Claim 1, substantially as described herein with reference to the foregoing
Example.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/926,516 US4187239A (en) | 1976-11-02 | 1978-07-20 | Method for preparing organotin compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2026491A true GB2026491A (en) | 1980-02-06 |
| GB2026491B GB2026491B (en) | 1983-04-27 |
Family
ID=25453321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7925073A Expired GB2026491B (en) | 1978-07-20 | 1979-07-18 | Method for preparing organotin compounds |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS6033398B2 (en) |
| BE (1) | BE877802R (en) |
| DE (1) | DE2928679A1 (en) |
| FR (1) | FR2431502A2 (en) |
| GB (1) | GB2026491B (en) |
| IT (1) | IT1188758B (en) |
| NL (1) | NL7905659A (en) |
| PL (1) | PL117187B1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3697566A (en) * | 1968-11-30 | 1972-10-10 | Kyodo Chem Co Ltd | Novel organo-tin compounds |
| CA1052804A (en) * | 1974-03-08 | 1979-04-17 | Kenneth R. Molt | Organotin mercaptide process |
| US4104292A (en) * | 1976-11-02 | 1978-08-01 | M&T Chemicals Inc. | Method for preparing organotin compounds |
| US4124618A (en) * | 1976-11-02 | 1978-11-07 | M&T Chemicals Inc. | Method for preparing bis(organotin mercaptoalkanol ester) sulfides |
-
1979
- 1979-07-16 DE DE19792928679 patent/DE2928679A1/en active Granted
- 1979-07-18 GB GB7925073A patent/GB2026491B/en not_active Expired
- 1979-07-18 JP JP54090483A patent/JPS6033398B2/en not_active Expired
- 1979-07-18 FR FR7918564A patent/FR2431502A2/en active Granted
- 1979-07-19 PL PL1979217217A patent/PL117187B1/en unknown
- 1979-07-19 BE BE0/196384A patent/BE877802R/en not_active IP Right Cessation
- 1979-07-19 IT IT09491/79A patent/IT1188758B/en active
- 1979-07-20 NL NL7905659A patent/NL7905659A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2431502B2 (en) | 1983-12-23 |
| DE2928679A1 (en) | 1980-02-07 |
| BE877802R (en) | 1980-01-21 |
| PL217217A3 (en) | 1980-04-21 |
| FR2431502A2 (en) | 1980-02-15 |
| GB2026491B (en) | 1983-04-27 |
| IT7909491A0 (en) | 1979-07-19 |
| PL117187B1 (en) | 1981-07-31 |
| JPS6033398B2 (en) | 1985-08-02 |
| IT1188758B (en) | 1988-01-28 |
| NL7905659A (en) | 1980-01-22 |
| JPS5519263A (en) | 1980-02-09 |
| DE2928679C2 (en) | 1989-01-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |