CA1052804A - Organotin mercaptide process - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The following reactions are carried out in the presence of aprotic solvents as catalysts or more preferably in the presence of water, preferably using wet, newly prepared organotin sulfides:

(1) (2) (3) (4) (5) wherein:
R, R2, R3, R4, R5 and R6 are alkyl, cycloalkyl, alkenyl, aryl or aralkyl;

R1 is , , allyl, methallyl or benzyl;
R7 is alkyl, cycloalkyl, alkenyl or aralkyl;
R11 is defined as R1;
R12 is alkyl or alkenyl;
X is chlorine or bromine;
m is 2 or 3; and n is 1 or 2.
The aprotic solvents are (a) , (b) , (c)

Description

105'~80'~

The present invention is directed to a new meth-od of preparing organotin mercaptide It i8 based on the reaction of organotin sulfides with active organic halides in the presence of specific aprotic solvents or more preferably in the presence of water. Preferably, wet, newly prepared organotin sulfides are used. The re-action~ involved are as follows:

S S, Rl S, Rl (1) (RSn)2S + 2RlX -~ RSn - S - Sn - R
.
X X
R~ R2 / SR

(2) / SnS + RlX ~~ Sn R4 \ / R4 R4 ~ R ~

(3) Rs; Sn - S - Sn - R5 + RlX ~ R5 j Sn - SRl + R5j SnX
R6 R6 R6 R~
S X X
,. . .

(4) (RSn)2S + 3RlX--~RSn(SRl)2 + RSn - SRl X

S SR

(S) RSn - SRl + RllX -~ RSn X SR
wherein:
R~ R2, R3~ R4~ R5, and R6 are alkyl, usually of 25 1 to 20 carbon atoms, cycloalkyl, usually of 5 to 6 carbon , ~
.

loS~ 4 atoms in the ring, alkenyl, usually of 2 to 20 or more frequently 3 to 18 carbon atoms, aryl, usually phenyl or alkyl phenyl having 1 to 4 carbon atoms in the alkyl group, or aralkyl, usually of 7 carbon atoms (R, R2, R3, R4, R5, and R6 preferably are methyl);

O O
ll ll 1 ~cH2~nC - OR7, ~CH2~m~C ~ R12~ benzyl~
,R14 CH2 = C - CH2 - where R14 is hydrogen or methyl;
Rll is defined as Rl;
R7 is alkyl usually of 1 to 20 carbon atoms, cycloalkyl usually having 5 to 6 carbon atoms in the ring, alkenyl, usually of 2 to 20 carbon atoms, more commonly 3 to 18 carbon atoms, or aralkyl, usually of 7 carbon atoms;
R12 is alkyl, usually of 1 to 19 carbon atoms, or alkenyl usually of 2 to 17 carbon atoms;
X is a halogen of atomic weight 35 to 80, i.e., chlorine or bromine;
n is an integer of 1 or 2; and m is an integer of 2 to 3.

When aprotic solvents are employed as catalysts said solvents are:
O Rg (a) R8C - X
Rlo 105~80~
Rg (b) / S = 0 Rlo Rg (c) N P = 0 , or Rlo _ 3 (d) N - methyl - 2 - pyrrolidone, where R8 is hydrogen or methyl and Rg and Rlo are methyl or ethyl. The preferred aprotic solvent catalyst i9 di-methyl formamide. The amount of aprotic solvent (whenemployed) can vary, for example, from 0.1 to 10 moles per mole of organotin sulfide, preferably 0.8 to 8 moles per mole of the organotin sulfide.
It is critical to use the catalyst or water since in the absence of the catalyst or water degradation reactions predominate and little or no product is formed.
As aprotic solvent catalysts there can be used for example, dimethyl formamide, dimethyl acetamide, di-ethyl formamide, diethyl acetamide, dimethyl sulfoxide, diethyl sulfoxide, tris(dimethylamino)pho~phine oxide, tris(diethylamino)phosphine oxide and N-methyl-2-pyrrol-idone.
It has further been found that water wet, pref-erably freshly prepared, wet, organotinsulfides are much more reactive than dried organotinsulfides and will react '105'~8B4 with isooctylchloroacetate or other active organic halides in the absence of catalysts such as dimethyl~ormamide or the others set forth above. Most preferably a slurry of organotin sulfide in water is employed.
Organotin sulfides are usually prepared by re-acting aqueous Na2S with organotin chlorides. The insol-uble organotin sulfides precipitate and are removed by filtration. Moisture is removed from the wet sulfides by heating at elevated temperatures. During the drying op-eration, it is possible that the polymeric sulfides are further polymerized and thus become less reactive. For these dried and less reactive sulfides, a catalyst, e.g., dimethylformamide) is required to effect reaction with active organic halides.
Unexpectedly, by contrast, wet newly prepared organotin sulfides react readily in the absence of a cata-lyst.
As compounds of the formula R1X or R11X there can be used in the present invention: methyl chloroace-tate, methyl bromoacetate, ethyl chloroacetate, propylchloroacetate, propyl bromoacetate, butyl chloroacetate, butyl bromoacetate, hexyl chloroacetate, hexyl bromoace-tate, octyl chloroacetate, octyl bromoacetate, isooctyl chloroacetate, isooctyl bromoacetate, 2-ethylhexyl chloro-acetate, 2-ethylhexyl bromoacetate, isodecyl chloroacetate, 105'~8¢4 isodecyl bromoacetate, decyl chloroacetate, decyl bromo-acetate, dodecyl chloroacetate, dodecyl bromoacetate, hexadecyl chloroacetate, hexadecyl bromoacetate, octadecyl chloroacetate, octadecyl bromoacetate, eicosanyl chloro-acetate, eicosanyl bromoacetate, cyclopentyl chloroacetate,cyclopentyl bromoacetate, cyclohexyl chloroacetate, cyclo-hexyl bromoacetate, benzyl chloroacetate, benzyl bromo-acetate, vinyl chloroacetate, vinyl bromoacetate, allyl chloroacetate, allyl bromoacetate, methallyl chloroacetate, methallyl bromoacetate, crotyl chloroacetate, crotyl bromo-acetate, 3-bromopropyl octoate, 2-bromoethyl pelargonate, 3-bromopropyl acetate, 3-bromopropyl stearate, 2-chloro-ethyl linoleate, 2-chloroethyl linolenoleate, oleyl chloro-acetate, oleyl bromoacetate, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-chloroethyl propionate, 2-bromoethyl propionate, 2-chloroethyl butyrate, 2-bromoethyl butyrate, 2-chloroethyl valerate, 2-bxomoethyl valerate, 2-chloro-ethyl pivalate, 2-bromoethyl pivalate, 2-chloroethyl cap-roate, 2-bromoethyl caproate, 2-chloroethyl octoate, 2-bromoethyl octoate, 2-chloroethyl decanoate, 2-bromoethyl decanoate, 2-chloroethyl laurate, 2-bromoethyl laurate, 2-chloroethyl palmitate, 2-bromoethyl palmitate, 2-chloro-ethyl stearate, 2-bromoethyl stearate, 2-chloroethyl eico-sanate, 2-bromoethyl eicosanate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 2-chloroethyl me~hacrylate, 2-~05'~80~

bromoethyl methacrylate, 2-chloroethyl crotonat~, 2-bromo-ethyl crotonate, 2-chloroethyl oleate, 2-bromoethyl ol~ate, allyl chloride, allyl bromide, methallyl chloride, meth-allyl bromide, benzyl chloride, benzyl bromide, methyl 2-chloropropionate, methyl 2-bromopropionate, methyl 3-chloropropionate, methyl 3-bromopropionate, ethyl 2-chloro-propionate, ethyl 2-bromopropionate, ethyl 3-chloropropi-onate, ethyl 3-bromopropionate, propyl 2-chloropropionate, propyl 3-bromopropionate, butyl 2-bromopropionate, butyl 3-chloropropionate, octyl 2-chloropropionate, octyl 3-chloropropionate, octyl 2-bromopropionate, octyl 3-bromo-propionate, isooctyl 2-chloropropionate, isooctyl 2-bromo-propionate, isooctyl 3-bromopropionate, isodecyl 2-chloro-propionate, isodecyl 2-bromopropionate, isodecyl 3-chloro-propionate, n-decyl 3-bromopropionate, dodecyl 2-chloro-propionate, tetradecyl 3-chloropropionate, hexadecyl 2-chloropropionate, hexadecyl 3-chloropropionate, octadecyl 2-chloropropionate, octadecyl 3-chloropropionate, octa-decyl 2-bromopropionate, octadecyl 3-bromopropionate, 2-ethylhexyl 3-chloropropionate, 2-ethylhexyl 2-chloropro-pionate, eicosanyl 3-chloropropionate, cyclohexyl 2-chloro-propionate, cyclohexyl 3-bromopropionate, cyclohexyl 3-chloropropionate, benzyl 2-chloropropionate, benzyl 3-chloropropionate, benzyl 2-bromopropionate, vinyl 2-chloro-propionate, vinyl 3-bromopropionate, allyl 2-chloropropi-105'~804 onate, allyl 3-chloropropionate, allyl 2-bromopropionate, allyl 3-br~mopropionate, methallyl 3-chloropropionate, crotyl 2-chloropropionate, oleyl 2-chloropropionate, oleyl 3-chloropropionate, oleyl 2-bromopropionate, oleyl 3-bromopropionate.
Examples of starting materials of the formula:
S
(RSn)2S
are monomethyltin sulfide, monoethyltin sulfide, mono-butyltin sulfide, monooctyltin sulfide, monododecyltinsulfide, monooctadecyltin sulfide, monoeicosanyltin sul-fide, monocyclohexyltin sulfide, monocyclopentyltin sul-fide, monovinyltin sulfide, mono-2-ethylhexyltin sulfide, monoallyltin sulfide, monomethallyltin sulfide, monooleyl-tin sulfide, monophenyltin sulfide, mono-p-tolyltin sul-fide, mono-p-butylphenyltin sulfide, monobenzyltin sul-fide.
Examples of starting materials within the for-mula:

/ SnS

are dimethyltin sulfide, diethyltin sulfide, methyl butyl-tin sulfide, dipropyltin sulfide, dibutyltin sulfide, di-hexyltin sul~ide, dioctyltin sulfide, di-2-ethylhexyltin ~ 0S'~804 sulfide, diisooctyltin sulfide, bis(dodecyltin) sulfide, bis(octadecyltin) sulfide, bis(eicosanyltin) sulfide, bis (cyclohexyltin) sulfide, divinyltin sulfide, diallyltin sulfide, dimethallyltin sulfide, dicrotyltin sulfide, di-oleyltin sulfide, diphenyltin sulfide, mono-methyl-mono-phenyltin sulfide, di-p-tolyltin sulfide, di-p-butylphenyl-tin sulfide, dibenzyltin sulfide.
Examples of starting materials within the for-mula:
. R4 \ / R4 R5 - Sn - S - Sn - R5 are: bis(trimethyltin~sulfide, bis(triethyltin)sulfide, bis(tributyltin)sulfide, bis(trioctyltin)sulfide, bis(tri-octadecyltin)sulfide, bis(trivinyltin)sulfide, bis(tri-allyltin)sulfide, bis(trimethallyltin).sulfide, bis(tri-oleyltin)sulfide, bis(triphenyltin)sulfide, bis(tri-p-tolyltin)sulfide, bis(tribenzyltin)sulfide.
Many of the products prepared in the present in-vention are old. Thus, Leistner U.S. Patent 2,641,596discloses some of the non-chlorine containing compounds prepared by reaction (3). Brecker U.S. Patent 3,565,931 shows many compounds which can be prepared from the com-pounds made by reaction (1). Hoye U.S. patent 3,542,825 discloses many compounds prepared by reaction (2) and (4) ~OS'~804 as does the similar Briti~h Patent 1,117,652. Wowk U.S.
Patent 3,665,025 and British Patent 1,297,550 disclose some of the compounds prepared by reaction (4) as well as compounds somewhat similar to those prepared in reaction S (1).
The organotin mercaptides prepared by reactions (1), (2), (3) and (4) are useful for the same purposes as Leistner, Brecker U.S. Patent 3,565,931, Brecker U.S.
Patent 3,630,992, Hoye, Wowk or British Patents 1,117,652 and 1,297,550. ~hey are particularly useful not only as stabilizers but as intermediates for making stabilizers for polyvinyl chloride resins by replacing the halogen atom or atoms with oxygen, carboxyl, mercaptyl, or ester mercaptyl; they are also less expensive than organotin mercaptides prepared from mercaptans and organotin oxides or halides.
The organotin mercaptide stabilizers prepared in reactions (1), (2) and (3) of the present invention can be used with halogen containing vinyl and vinylidene resins in which the halogen is attached directly to the carbon atoms. Preferably, the resin is a vinyl halide resin, more preferably, a vinyl chloride resin. Usually, the vinyl chloride resin is made from monomers consisting of vinyl chloride alone or a mixture of monomers compris-ing at least 7~% vinyl chloride by weight. When vinyl 105'~8~4 chloride copolymers are stabilized, preferably the copoly-mer of vinyl chloride with an ethylenically unsaturated compound copolymerizable therewith contains at lea~t 10%
of polymerized vinyl chloride.
As the halogen resin there can be employed chlorinated polyethylene having 14 to 75%, e.g., 27h chlorine by weight, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride, polyvinyl-idene fluoride, copolymers of vinyl chloride with 1 to 90/0, preferably, 1 to 3~% of a copolymerizable ethylenically unsaturated material such as vinyl acetate, vinyl buty-rate, vinyl benzoate, vinylidene chloride, diethyl fumar-ate, diethyl maleate, other alkyl fumarates and maleates, vinyl propionate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate and other alkyl acrylates, methyl metha-crylate, ethyl methacrylate, butyl methacrylate and other alkyl methacrylates, methyl alpha chloroacrylate, styrene, trichloroethylene, vinyl ethers such as vinyl ethyl ether, vinyl chloroethyl ether and vinyl phenyl ether, vinyl ke-tones such as vinyl methyl ketone and vinyl phenyl ketone,l-fluoro-l-chloroethylene, acrylonitrile, chloroacrylo-nitrile, allylidene diacetate and chloroallylidene di-acetate. Typical copolymers include vinyl chloride-vinyl acetate (96.4 sold commercially as VY~W), a vinyl chlor-ide-vinylacetate (87:13), vinyl chloride-vinyl acetate-105'~804 maleic anhydride (86:13-1), vinyl chloride-vinylidene chloride (95:5), vinyl chloride-diethyl fumarate (95:5), vinyl chloride-trichloroethylene (95:5), vinyl chloride-2-ethylhexyl acrylate (80:20).
The stabilizers of the present invention can be incorporated with the re~in by admixing in an appropriate mill or mixer or by any of the other well-known methods which provide for uniform distribution throughout the resin compositions. Thus, mixing can be accomplished by milling on rolls at 100-160C.
In addition to the novel stabilizers there can also be incorporated with the resin conventional additives such as plasticizers, pigments, fillers, dyes, ultraviolet light absorbing agents, densifying agents and the like.
If a plasticizer is employed, it is used in conventional amount, e.g., 30 to 150 parts per 100 parts of resin. Typical plasticizers are di-2-ethylhexyl phthal-ate, dibutyl sebacate, dioctyl sebacate, tricresyl phos-phate The tin containing stabilizers are normally used in an amount of 0.01 to 10% by weight of the resin, more preferably 0.1 to 5% of the tin compound is used by weight of the resin. The organotin mercaptide products of reac-tions (1), (2) and (3) are clear, mobile liquids that are soluble in hydrocarbon and polar solvents such as benzene, ~05'~8~4 toluene, acetone, and ethyl acetate. The mono- and dl-organotin sulfides used as starting materials in re~c-tions (1) and (2) are polymeric, high-melting solids and are insoluble in the reaction products and in most solvents that dissolve the reaction products. It is evident, t~ere-fore, that the reaction products are not mere solutions of the organotin sulfides.
Specific combinations of organotin sulfides and RlX compounds in addition to those set forth in the work-ing examples and mentioned as illustrative only and not as limiting are given below. The numbers indicate the number of moles of catalyst (and in reaction 1, also the moles of other reactant) per mole of starting sulfide.
Reaction (1) 1. Monomethyltin sulfide + 2 methyl chloroacetate 2, Monooctyltin sulfide + 2 methyl bromoacetate Monooctadecyltin sulfide + 2 isodecyl chloroacetate 4~ Monobenzyltin sulfide + 2 butyl chloroacetate

5. Monophenyltin sulfide + 2 cyclohexyl chloroacetate

6. Monoallyltin sulfide + 2 benzyl chloroacetate

7. Monomethyltin sulfide + 2 2-chloroethyl stearate

8. Monobutyltin sulfide + 2 2-chloroethyl oleate

9. Monocyclohexyltin sulfide + 2 2-chloroethyl acetate

10. Monomethyltin sulfide + 2 2-chloroethyl methacrylate

11. Monomethyltin sulfide + 2 dodecyl 3-chloropropionate

12. Monobutyltin sulfide + 2 allyl chloride Reaction (2)

13. Dimethyltin sulfide + ethyl chloroacetate

14. Dibenzyltin sulfide + propyl bromoacetate 5 15. Dioctyltin sulfide + decyl chloroacetate 16. Dibutyltin sulfide + sec. butyl chloroacetate 17. Di-p-tolyltin sulfide + cyclohexyl bromoacetate 18. Dioleyltin sulfide + phenylethyl chloroacetate 19. dimethyltin sulfide + 2-chloroethyl palmitate 10 20. Dibutyltin sulfide + 2-bromoethyl crotonate 21. Dicyclohexyltin sulfide + 2-chloroethyl pivalate 22. Dimethyltin sulfide + 2-chloroethyl acrylate 23. Dimethyltin ~sulfide + isooctyl 3-bromopropionate 24. Dibutyltin sulfide + methallyl bromide Reaction (3) 25. Bis (trimethyltin)sulfide + isopropyl chloroacetate 26. Bis(tribenzyltin)sulfide + 2-ethylhexyl chloroacetate 27, Bis(trioctyltin)sulfide + nonyl bromoacetate 28. Bis (tributyltin)sulfide + hexyl chloroacetate 20 29. Bis(triphenyltin)sulfide + isooctyl chloroacetate 30. Bis (triallyltin)sulfide + benzyl chloroacetate 31. Bis (trimethyltin)sulfide ~ 2-chloroethyl eicosanate 32. Bis(tributyltin)sulfide + bromoethyl methacrylate 33. Bis(tricyclohexyltin)sulfide + 2-chloroethyl myristate 25 34. Bis (trimethyltin)sulfide + 2-bromoethyl oleate ~05'~804 35. Bis(trimethyltin)sulfide + dodecyl 3-chloropropionate 36. Bis(tributyltin)sulfide + allyl chloride Reaction (4) 37. Monomethyltin sulfide + 3 methyl chloroacetate 38. Monooctyltin sulfide + 3 methyl bromoacetate 39. Monooctadecyltin sulfide + 3 isodecyl chloroacetate 40. Monobenzyltin sulfide + 3 butyl chloroacetate 41. Monophenyltin sulfide + 3 cyclohexyl chloroacetate 42. Monoallyltin sulfide + 3 benzyl chloroacetate 43. Monomethyltin sulfide + 3 2-chloroethyl stearate 44. Mono~utyltin sulfide + 3 2-chloroethyl oleate 45. Monocyclohexyltin sulfide + 3 2-chloroethyl butyrate 46. Monomethyltin sulfide + 3 2-chloroethyl methacrylate 47. Monomethyltin sulfide + 3 hexyl 3-chloropropionate 48. Monobutyltin sulfide + 3 allyl bromide The temperature is not critical, but heating is usually employed, preferably between 130-155C. The tem-perature is usually at least 90C. and can be as high as 200C. for example.
Unless otherwise indicated, all parts and per-centages are by weight.
The lack of reaction by a dried sulfide without the use of an aprotic solvent is shown in Example 1.
EXAMPLE 1:
One-tenth mole of dried dimethyltin sulfide was ~oszsO~
mixed with one-tenth mole of isooctylchLor~aceta~e arld heated under nitrogen. At 90C, solution of the solid dimethyltin sulfide was complete and a clear, nearly col-orless liquid resulted. After a 2-hour reaction period at 135-145C., the reaction mixture was cooled. At 90C., precipitation of unreacted dimethyltin sulfide began.
Precipitation was completed by cooling to 20C. The un-reacted dimethyltin sulfide was removed by filtration and freed of isooctylchloroacetate by washing with heptane.
~inety-seven percent of the starting dimethyltin sulfide was recovered unchanged.
The reactivity of wet, freshly prepared sulfides is shown by the following examples EXAMPLE 2:
To 0.4 M of ~a2S in 100 g water was added 0.4 M of aqueous (50% H2O) Me2SnC12 over a 30-minute period at 50-70C. The resulting slurry of Me2SnS was heated to 90C. and then mixed with 0.4 M of isooctylchloroacetate.
After heating to 95-105C. for 15 minutes, two clear lay-ers formed. The lower organic layer was removed and re-acted for 2 hours at 135-140C. under nitrogen. After cooling to 25C. the reaction mixture was filtered to re-move a trace of salt carried over from the wet sulfide.
The product is soluble in benzene in all proportions and is believed to have the following structure lOS'~:804 o CH3\ S -- CH2C -- C8H17 Sn Yield = 151 grams (155 calc) Cl - 9.0% (cal'c 9.16%) S - 8 . 3% (cal'c 8 . 2 6%) Two-tenths of a mole of the above product was reacted with O . 2 M of isooctylthioglycolate and 0.2 M of aqueous am-10 monia to form dimethyltin bis (isooctylthioglycolate) ingood yield. This compound was tested as a stabilizer for PVC and compared with dimethyltin bis(isooctylthioglyco-late) prepared in the conventional manner from dimethyltin dichloride and isooctylthioglycolate. Both performed

15 equally well, EXAMPLE 3:
To 0.2 M (mole) of Na2S in 50 g of H20 was added 0.2 M of aqueous Me2SnC12 in 30 minutes at 50-70C. The resulting slurry of Me2SnS was heated to 90C. and then 20 mixed with 0.2 M of 2-chloroethyloctanoate. After mixing and heating for 15 minutes at 95-105C. the Me2SnS dis-solved in the organic phase and two clear layers developed upon settling. The lower organic phase was removed and reacted for 2 hours at 145-155C. under nitrogen. Upon 25 cooling to 25C, no Me2SnS precipitated indicating com-~0~'~8~4 pletion of the reaction. This intermediate was reac~ed with 0.2 M of 2-mercaptoethyl octanoate and 0.2 M of aque-ous ammOnia to form dimethyltin bis(2-thioethyloctanoate).
Yield - 94.8% (based on Me2SnC12) 5Appearance - colorlesq oil PVC Stabilizer Performance - equivalent to the same compound prepared from Me2SnC12 and 2-mercaptoethyl octanoate.
The reactions involved in this example are believed to be:

10 Me2sncl2 + Na2S ~ Me2SnS

..

Me2SnS + ClCH2CH20CC7H15 ~ Me2Sn Cl (I) O O
.. ..
(I~ + HSCH2CH2OCC7Hls--~Me2Sn(S-CH2CH2oc C~H15)2 EXAMPLE 4:
To a mixture of 50 g water, 0;2 M MeSnC13 and 0.2 M isooctylthioglycolate was added .2 M of dilute aqueous NaOH then .2 M of dilute aqueous Na2S. The mix-ture was heated to 80C and then settled. The lower or-ganic phase was removed and mixed with 0.2 M iqooctyl-chloroacetate and heated under nitrogen to 145-155C. for 2 hours. Upon cooling, this intermediate wa3 converted to a finished stabilizer by treating with 0.1 mole of s.~ . .

105Z~04 aqueous ~a2S. The reactions involved are believed to be:

O S o ,. .. ..
MeSnC13 + HSCH2C-OC8Hl7 + NaOH + ~a2S ~ MeSn-SCH21-C8H17 O ., ~ ClCH2C-OC8H17 MeSn(, ~CH2C-OcgHl7)2 <

ClO

MeSn(ScH2c~Oc8Hl7)2 S O
~a2S
~ MeSn(ScH2c~OcgHl7)2 Yield - 105 g (94.4%) Appearance - colorless oil PVC Stabilizer Performance - equivalent to the same com-pound prepared from MeSnC13, isooctylthioglycolate and Na2S.
EXAMPLE 5:
To a mixture of 50 g water, 0.2 M MeSnC13 and 0.2 M isooctylthioglycolate was added 0.2 M of dilute aqueous ~aOH then 0.2 M of dilute aqueous ~a2S. The mix-ture was heated to 80C. and then settled. The lower organic phase was removed and mixed with 0.2 M isooctyl-chloroacetate and heated under nitrogen to 145-155C. for 2 hours. Upon cooling, this intermediate was mixed with 0.2 M isooctylthioglycolate and 0.2 M of aqueous ammonia to form methyltin tris-isooctylthioglycolate.

~05'~80~
Yield - 146 g (148.8 cal'c) Appearance - colorless oil PVC Stabilizer Performance - equivalent to the same compound made from MeSnC13, i900ctyl-thioglycolate and aqueous ammonia.
Reactions: O S O
.. .. ..
3 OH ~ ~a2S + HSCH2C-OcgHl7 ~ MeSnS-CH2C-1~8H17 ~ ClCH2C-OC8H17 Me I D ( I CH2C -OC~3N17 ) 2 ~ .

.. O
l HSCH2c-Oc8Hl7 ~ Mesn(scH2c-oc ~ 17)3 EXAMPLE 6:
The process of Example 4 was repeated except that 2-mercaptoethyl octanoate was used in place of iso-octylthioglycolate and 2-chloroethyloctanoate was used in place of isooctylchloroacetate in the same molar amounts to form thio-bis[methyltin bis(2-thioethyloctanoate)] in good yield.
Appearance - pale yellow oil PVC Stabilizer Performance - equivalent to the same compound prepared from MeSnC13, 2-mercaptoethyloctanoate and Na2S.

105'~8~4 Reactions: o S 0 ,.
MeSnC13+HSCH2CH20-CC7H15+MaOH+Na2S ~ Mesn-s-cH2cH2-oc77Hl5 o o ClCH2CH2-o-cc7Hl5 " ~ .
MeSn(S-CH2CH2-O-cc7Hl5)2 0 Cl "
¦ MeSn(SCH2cH2O-c-c7Hl5)2 10 ¦ ~a2S S O
~ MeSn(SCH2cH2O-c-c7Hl5)2 Example 7:
The process of Example 5 was repeated except that 2-mercaptoethyl octanoate was used in place of iso-octyl~hioglycolate and 2-chloroethyloctanoate was used in place of isooctyl chloroacetate in the same molar amounts to form methyltin tris(2-thioethyloctanoate) in good yield.
Appearance - colorless oil PVC Stabilizer Performance - equivalent to the same compound made from MeSnC13 and 2-mer-captoethyl octanoate.
Reactions:

105'~80g~
o S o ll ll ll MeSnC13+HSCH2CH20CC7Hls+NaOH~H2S ~ MeSn-SCH2CH20-CC ~7H15 o o c lCH2CH20C-c 7H15 5MeSn(sCH2cH2Oc-c7Hl5)2 ( ~1 ¦ HSCH2CH2C-C7H15 MeSn(scH2cH2O-cc7Hl5)3 EXAMPLE 8:
To 0.2 M of ~a2S in 50 g of H2O was added 0.2 M
of aqueous Me2SnC12 in 30 minutes at 50-70C. The result-ing slurry of Me2SnS was heated to 90C. and then mixed with 0.2 M of benzyl chloride. After mixing and heating for 10 minutes at 95-100C. the Me2SnS dissolved in the organic phase and two clear layers developed upon settling.
The lower organic phase was removed and reacted for 2 hours at 145-155C. under nitrogen. Upon cooling to 30C., this intermediate was reacted with 0.2 M isooctylthioglycolate and 0.2 M of aqueous ammonia to form dimethyltin isooctyl-thioglycolate-benzylmercaptide in good yield.
Appearance - yellow oil Performance - when tested in PVC this compound was found to be an effective stabilizer.
Reactions~
~ .

los~sa4 Me2SnC 12 + Na2S ~ Me2Sn 3 SCH2Ph Me2Sn PhCH2Cl \ Cl ,S-CH2Ph ) Me2Sn O
SC~2C-0c8Hl7 HscH2c-oc8Hl7 To a mixture of S0 g H20, 0.2 M MeSnC13 and 0.2M isooctyl-thioglycolate was added 0.2 M of dilute aqueous NaOH then 0.2 M of dilute aqueous Na2S. The mix-ture was heated to 80C. and then settled. The lower prod-uct layer was removed and mixed with 0.2 M of benzyl bro-mide and heated under N2 to 145-155C. for 2 hours. Upon cooling, this intermediate was mixed with 0.2 M of iso-octylthioglycolate and 0.2 M of aqueous ammonia to form methyltin bis(isooctylthioglycolate)benzylmercaptide in good yield.
Appearance - yellow oils Performance - when tested in PVC this compound was found to be an effective stabilizer.
Reactions-1~5'~80~

o S o ll ll ll MeSnC13 + HscH2c-oc8Hl7 ~ NaOH + Na2S ~ MeSn 5CH2c )C8Hl7 o S-CH2C-Oc8Hl7 PhCH2Br 5MeSn-S-CH2-Ph HscH2c-oc8Hl7 ¦~ MeSn(SCH2c-ocgHl7)2 S -CH2Ph EXAMPLE 10:
To 0.2 M of Na2S in 50 g of H20 was added 0.2 M
of aqueous Me2SnCl2 over a 30 minute period at 50-70C.
The resulting slurry of Me2SnS was heated to 90C. and then mixed with 0.2 M of isooctyl-3-chloropropionate.
After mixing and heating for 15 minutes at 95-105C., the Me2SnS dissolved in the organic phase and two clear layers developed upon settling. The lower organic phase was re-moved and reacted for 2 hours at 145-155C. under nitro-gen. Upon cooling, this intermediate was reacted with 0.2 M of isooctyl-3-mercaptopropionate and 0.2 M of aque-ou~ NaOH to form dimethyltin bis-isooctylthiopropionate in good yield.
Appearance - colorless oil Performance - when tested in PVC this compound was an effective stabilizer lOS'~804 Reactions:
Me2SnC12 + Na2S ~ Me2SnS
O O
1 ..
SCH2CH2cOc8Hl7 ClCH2CH2C-C8H17 , Me2Sn \ Cl O O
.. ..
HscH2cH2c-oc8Hl7 MeSn(scH2cH2c~OcgHl7)2 ~, NaOH
EXAMPLE 11:
A slurry of 0.5 mole of monomethyltin sulfide in water made by reacting aqueous Na2S with methyltin tri-chloride is mixed with 1.0 mole of isooctyl chloro-acetate and heated and further treated in the manner de-scribed in Example 2. The structure of the product isbelieved to be:

fl fl CH3 ,n-S-SnCH3 O

SCH2-cOc8Hl7 ..

Example 2 is repeated replacing the isooctyl chloroacetate by the same molar amount of isooctyl-3-chloropropionate to form:

~OS'~804 \ /
Sn CH3 SCH2c~2cOc8Hl7 EXAMPLE 13:
Example 2 i~ repeated replacing the dimethyltin dichloride by the same molar amount of dibutyltin dichlor-ide to form:
C~Hg / Cl Sn C4H / SCH2COc8~17 EXAMPLE 14:
Example 11 is repeated replacing the methyltin trichloride by the same molar amount of butyltin trichlo-ride to produce the corresponding butyl analogue of the product of Example 11.
EXAMPLE 15:
Example 2 is repeated replacing the i800ctyl chloroacetate by the same molar amount of i~ooctyl bromo-acetate to produce:
CH3 ~ r Sn 0 CH3 SCH2cOc8Hl7EXAMPLE 16:
Example 8 i~ repeated replacing the benzyl chlo-ride by the same molar amount of benzylbromide to fonm as _27-105'~84 the intermediate:

CH3\ Br Sn CH3 CH2-Ph The procedure of Example 11 is repeated except that 1.5 moles of isooctyl chloroacetate is employed.

The product is believed to be a mixture of equal molor amounts of:

Cl C

CH3Sn(ScH2cOcgHl7)2 and Cl O

CH3Sn-SCH2cOc8Hl7 Cl In making the starting compounds for reaction 5, there can be reacted a compound of the formula RSnC13 with a compound of the formula HSRl + alkali metal ~e.g., sodium or potassium) or ammonium sulfide in water. The compound HSRl can be any of the HSRl analogues of the compounds RlX set forth above.
In the process of the invention as illustrated in Examples 4-7 and 9, the organic phase reacted with the isooctyl chloroacetate, 2-chloroethyl octoate or the benzyl bromide was not dried and hence contained water.
As stated above, the temperature is not critical lOS'~804 but is preferably between 130-155C. The temperature is usually between 100C. and the boiling point of the cata-lyst when a catalyst is employed. All of the catalysts are liquids at the reaction temperatures.
EXAMPLE 18:
One-half mole of dlmethyltinsulfide was mixed with 0.5 M of isooctylchloroacetate and 75.0 grams of di-methylformamide and heated to 130 - 135C. for 2 hours.
Dimethylformamide was distilled from the reaction mixture by heating to a final pot temperature of 110C. at 10 mm Hg. The residue (product) was clarified by filtration yielding 188.5 gms (97.3% of theoretical) of pale yellow oil. It is soluble in heptane and acetone. An NMR spec-trum of the product was consistent with expected struc-ture:
O

C~ ~ S - CH2C - C8H17 CH "' ~ Cl Cl - 9.2% (calculated 9.16%) S - 8.4% (calculated 8.26%) EXAMPLE 19:
One-half mole of monomethyltin sulfide (CH3SnS)2S was mixed with 1.0 M of isooctylchloroacetate and 150 gms of dimethylformamide and heated to 130 -135C. for 2 hours. Dimethylformamide was recovered by 1Os~so4 vacuum stripping to 110C. at 10 mm Hg. The residue was clarified by filtration yielding 370.0 gms of yellow oil (95.0/O of theoretical). The product is soluble in benzene and acetone. The structure is believed to be fl Icl CN3Sn --S ' SnCH3 O ~ Q
, ~CH2COC8H17 SCH2CC8H17 Cl - 9.4% (calculated 9.12%) S - 11.9% (calculated 12.3%) A mixture of 0.1 ~ of dimethyltin sulfide, 0.1 M of ben yl chloride and 40 gms of dimethylformamide was heated to 130 - 135C. for 2 hours. After stripping to 110C. at lO mm Hg there remained 30.5 gms of pale yellow oil. The theoretical yield is 30.7 gms for:
CH3 / Cl / Sn CH3 SCH2Ph S - 10.2% (calculated 10.4%) Cl - 11.6% (calculated 11.5%) A mixture of 0.1 M of dimethyltin sulfide, 0.1 M of 2-chloroethyloctoate and 40 gms of dimethylformamide was heated under an atmosphere of nitrogen for 4 hours at ~05'~804 150C. After stripping to 120C at 10 mm Hg and filter-ing to clarify, there was obtained 34.2 gms of yellow oil. The theoretical yield is 39.7 gms for:
CH3 Cl Sn O
CH3 S - CH2 - CH2 - oC - C7H15 Cl - 8.6% (calculated 8.94%) S - 8.3% (calculated 8.06%) EXAMPLE 22:
One-half mole of dimethyltinsulfide was mixed with 0.5 M of isooctyl-3-chloropropionate and 75 grams of dimethylacetamide and heated at 145-155C. for 4 hours.
After stripping to 120C. at 10 mm Hg and filtering to clarify, there was obtained 194.6 grams of a yellow oil.
The theoretical yield is 200.7 grams for:
CH~ Cl Sn O
CH3 S - CH2 - CH2C - C8Hl7 Cl - 8.5% (calculated 8.84%) S - 8.1% (calculated 7.98%) EXANPLE 23:
A mixture of 0.1 M of dimethyltin sulfide, 0.1 M of isooctylchloroacetate and 40 gms of dimethylsulfox-ide was heated under nitrogen at 130C. for 1.5 hours.
After stripping to 110C. at 10 mm Hg there remained 32.0 ~o5',~804 gms of red oil.
\ /

Sn 0 CH3/ S ~ CH2COC8H17 5 S ~ 8.5% (calculated 8.26~/o) EXA,~lpLE 24 A mixture of 0.1 M of dimethyltinsulfide, 0.1 M
of isooctylchloroacetate and 30 gms of tris(dimethylamino) phosphine oxide was heated at 130C. for 2 hours. After stripping to 120C. at 10 mmHg there remai ned 37.1 gms of yellow oil.
CH3\ Cl Sn 0 / \ 11 15 Cl - 9. 3% (calculated 9.16%) EX~MPLE 2 S:
A mixture of 0.2 M of dibutyltin sulfide, 0.2 M
of isooctylchloroacetate and 40.0 gms of dimethylformamide was heated under ~2 for 2 hours at 130 - 135C. After stripping and filtering there was obtained 93.8 gms of yellow liquid. The theoretical yield is 94.3 gms for:

Sn / \
C4H9 S ~ CH2C ~ OC8H17 25 Cl - 7.2% (calculated 7.51%) . ., ,~

~(~5'~804 S - 6.5% (calculated 6.7Ph) EXAMPLE 26:
A mixture of 0.1 M of monobutyltin sulfide S
(C4HgSn)2S, 0.2M of isooctylchloroacetate and 40.0 gms of dimethylformamide was heated under nitrogen to 130 -135C. for 2 hours. After stripping to 120C at 10 mm Hg there was obtained 83.7 gms of viscous amber oil. The theoretical yield is 86.1 gms for:
10Cl Cl C4Hg- n S Sn - C4Hg I I

Cl - 8.Gh (calculated 8.22%) 15 S -10.7h (calculated 11.1%) EXAMPLE 27:
A mixture of 0.1 M of bis(tributyltin) sulfide, 0.1 M of isooctylchloroacetate and 20 gms of dimethylfor-mamide was heated for 2 hours at 130 - 135C. After 20 stripping and filtering there remained 91.3 gms of yellow oil.
Cl - 4.1% (calculated 4.32%).
EXAMPLE 28:
A mixture of 0.1 M of dimethyltin sulfide, 0.1 ~05'~804 M of isooctylbromoacetate and 20.0 gms of dimethylforma-mide, was heated under nitrogen for 2 hours at 130 -135C. After stripping to 110C. at 10 mm Hg there re-mained 37.8 gms of yellow oil. The theoretical yield is 43.2 gms for CH3\ Br Sn o / \

Br - 17.9% (calculated 18.5%) EX~MPhE 29 A mixture of 0.1 M of dimethyltin sulfide, 0.1 M of benzylbromide and 30 gms of dimethylformamide was heated to 130C. for 2 hours. After stripping there re-mained 33.8 gms of yellow oil. The theoretical yield is 35.2 for:

CH3 Br Sn CH3 CH2 - Ph Br - 21.9% (calculated 22.P~) EXAMPhE 30:

ne-half mole of monomethyltin sulfide (CH3SnS)2S was mixed with 1.5 M of isooctylchloroacetate and 150 gms of ~-methyl-2-pyrrolidone and heated to 130 - 135C. for 2 hours. The ~-methyl-2-pyrrolidone was recovered by vacuum stripping to 120C. at 10 mm Hg.

~05'~8~)4 The residue was clarified by filtration yielding 465 gms of amber oil (94.~/O of theoretical). Sulfur - 9.6% found (9.76% calculated); chlorine - 10.9% found (10.82% cal-culated). The postulated reaction is:

oCl O
~cat ' "
(CH3SnS)2S + 3ClCH2C-O-C8Hl7 ~ CH3Sn(S-CH2c-oc8Hl7)2 +
Cl O
"
CH3Sn-S -CH2C-OC8Hl7 Cl lO As shown in Example 30 by varying the mole ratio of monoorganotin sulfide to RlX compound from 1:2 to 1:3 the products obtained are changed. In place of the (CH3SnS)2S in Example 30 there can be used any of the S
other compounds of the formula (RSn)2S set forth above and in place of the isooctyl chloroacetate there can be used any of the other compounds of the formula RlX set forth above,

Claims (42)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A process of preparing an organotin halide mercaptide or a mixture of organotin halide and organotin mercaptide from an organotin sulfide comprising reacting:

(1) , (2) .

(3) , or (4) with a compound of the formula R11X, where R, R2, R3, R4, R5 and R6 are alkyl, cycloalkyl, alkenyl, aryl or aralkyl, R1 and R11 are , , , or benzyl, R7 is alkyl, cycloalkyl, alkenyl or aralkyl, R12 is alkyl or alkenyl, X is halogen of atomic weight 35 to 80, n is 1 or 2, m is 2 or 3, and R14 is hydrogen or methyl, said reaction being carried out either (a) while the organotin sulfide is in the water wet condition or (b) in the presence of an aprotic solvent catalyst having the formula:

(a) , (b) , (c) ,or (d) where R8 is hydrogen or methyl and R9 and R10 are alkyl of 1 to 2 carbon atoms.

2. A process according to claim 1 wherein the reaction is carried out while the organotin sulfide is in the water wet condition.

3. A process according to claim 2 wherein the reaction is carried out with a slurry of the organotin sulfide in water.

4. A process according to claim 1, wherein the temperature is 130 to 155°C.

5. A process according to claim 3 wherein the temperature is between 90°C. and 200°C., and R, R2, R3, R4, R5, and R6 are alkyl of 1 to 20 carbon atoms, cyclo-alkyl having 5 to 6 carbon atoms in the ring, alkenyl of 2 to 20 carbon atoms, phenyl, alkylphenyl having up to 4 carbon atoms in the alkyl group, R7 is alkyl of 1 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms in the ring, alkenyl of 2 to 20 carbon atoms or benzyl, R12 is alkyl of 1 to 19 carbon atoms or alkenyl of 2 to 17 carbon atoms.

6. A process according to claim 5, wherein X
is chlorine.

7. A process according to claim 6, wherein R
is alkyl of 1 to 8 carbon atoms.

8. A process according to claim 2, wherein the organotin sulfide has formula (1), (2), or (3).

9. A process according to claim 8 wherein the organotin sulfide has formula (2).

10. A process according to claim 9, comprising reacting 1 mole of with 1 mole of R1X to form:

11. A process according to claim 10 wherein the reaction is carried out using an aqueous slurry of the organotin sulfide.

12. A process according to claim 10 wherein R2 and R3 are methyl.

13. A process according to claim 12, wherein , or benzyl.

14. A process according to claim 13, wherein R7 is alkyl of 6 to 18 carbon atoms and R12 is alkyl of 5 to 17 carbon atoms.

15. A process according to claim 14, wherein R2 and R3 are both methyl and m is 2.

16. A process according to claim 8, wherein the organotin sulfide has formula (1).

17. A process according to claim 8, wherein the organotin sulfide has formula (3).

18. A process according to claim 2, wherein the organotin sulfide has formula (4).

19. A process according to claim 18, compris-ing reacting 1 mole of , with 1 mole of R11X.

20. A process according to claim 19 wherein R1 is or .

21. A process according to claim 20, wherein R7 is alkyl of 6 to 18 carbon atoms, R12 is alkyl of 5 to 17 carbon atoms and R11 is , , or benzyl.

22. A process according to claim 21 where R
is methyl and m is 2.

23. A process according to claim 2 wherein R, R2, R3, R4, R5 and R6 are alkyl of 1 to 8 carbon atoms and R1 and R11 are , or benzyl, R7 is alkyl of 1 to 18 carbon atoms, alkenyl of 3 to 18 carbon atoms, or benzyl, R12 is alkyl of 1 to 17 carbon atoms or alkenyl of 17 carbon atoms.

24. A process according to claim 1 wherein the reaction is carried out in the presence of the aprotic solvent catalyst.

-40-A process according to claim 24 wherein the reaction is carried out at a temperature at which the reaction proceeds up to the boiling point of the catalyst.

26. A process according to claim 25 wherein the temperature is 130 to 155°C. and the catalyst is used in an amount of 0.8 to 8 moles per mole of starting or-ganotin sulfide.

27. A process according to claim 25 wherein the temperature is from 100°C. to the boiling point of the catalyst and R, R2, R3, R4, R5 and R6 are alkyl of 1 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms in the ring, alkenyl of 2 to 20 carbon atoms, phenyl, alkylphenyl having up to 4 carbon atoms in the alkyl group, R7 is alkyl of 1 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms in the ring, alkenyl of 2 to 20 carbon atoms or benzyl, R12 is alkyl of 1 to 19 carbon atoms or alkenyl of 2 to 17 carbon atoms.

28 A process according to claim 27 wherein X
is chlorine.

29. A process according to claim 27 wherein the solvent is dimethyl formamide.

30. A process according to claim 27 wherein R
is alkyl of 1 to 8 carbon atoms.

31. A process according to claim 27 comprising reacting 1 mole of with 2 moles of R1X to form .

32. A process according to claim 27 comprising reacting 1 mole of with 3 moles of R1X to form .

33. A process according to claim 27 comprising reacting 1 mole of with 1 mole of R1X to form .

34. A process according to claim 27 comprising reacting 1 mole of with 1 mole of R1X
to form .

35. A process according to claim 27 wherein R is alkyl of 1 to 8 carbon atoms and R1 is where R7 is alkyl of 6 to 18 carbon atoms.

36. A process according to Claim 27, wherein R is alkyl of 1 to 8 carbon atoms and R1 is .

37. A process according to Claim 27, wherein R is alkyl of 1 to 8 carbon atoms and R1 is allyl or methallyl.

38. A process according to Claim 27, wherein R is alkyl of 1 to 8 carbon atoms and R1 is benzyl.

39. A compound of the formula:
wherein R stands for alkyl, cycloalkyl, alkenyl, aryl or aralkyl, R1 stands for , or benzyl, wherein R7 i s alkyl, cycloalkyl, alkenyl or aralkyl, R14 is hydrogen or methyl, and n is 1 or 2, and X is a halogen of atomic weight 35 to 80.

40. A compound according to Claim 39, wherein R1 is where R7 is alkyl, cycloalkyl, alkenyl or aralkyl and n is 1 or 2.

41. A compound according to Claim 39, wherein R1 is allyl or methallyl.

42. A compound according to Claim 39, wherein R1 is benzyl.