US2912448A - Hydrocarbontin isodithiocarbamates and process of preparation - Google Patents

Hydrocarbontin isodithiocarbamates and process of preparation Download PDF

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US2912448A
US2912448A US541537A US54153755A US2912448A US 2912448 A US2912448 A US 2912448A US 541537 A US541537 A US 541537A US 54153755 A US54153755 A US 54153755A US 2912448 A US2912448 A US 2912448A
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Hugh E Ramsden
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Primerica Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • C08K5/58—Organo-tin compounds containing sulfur

Definitions

  • This invention relates to organotin dithiocarbamates and more particularly to the hydrocarbontin isodithiocarbamates of .
  • R, R, R", R" ⁇ and R""- may -be any hydrocarbonradicals. They-may be,'-for-example,
  • cycloalkyl radical such as :cyclopropyl
  • They may also represent any aryl, aralkyl or alkaryl'hy- Arnong these may be mentioned,
  • ethyl, tolyl, xylyl, xenyl, cinnamyl and methylbenzyl may also be any alkenyl, alkynylior .cycloalkenyl radical. Included in these are propenyl,;butenyl, hexenyl, cyclopentenyl, butadienyl, .cyclopentadienyl, cyclohexenyl as well as long chain unsaturated alkylradicals derived from unsaturated fats.
  • the hydrocarbontin isodithiocarbamates.ofrthe present invention are prepared by reacting.anvisodithiocarbamic acid with a hydrocarbontincompound having a readily replaceable functional group bonded ...to ,tin. Hydrocarbontin reactants of particular .utility..are the hydrocarbontin oxides.
  • the intermediate isodithiocarbamic acid may be made by reacting. a primaryamine-with carbon disulfide and a metal hydroxide preferably.anqalkali metal hydroxide, and then :reacting .thex-metal .dithiocarbamate,
  • Hydrocarbontin halides may be substituted :for the hydrocarbontin oxides in the above sequence of reactions.
  • the reaction between the isodithiocarbamic acid and the hydrocarbontin halides may be .described by the following equations:
  • H ..N R (11) 'R N;CS-R+RRS11Xn RRSn s-0-s+.R; s11 int 1 r.In which R, R R", R' and R""- are hydrocarbon radicals'rand X is a halide like chloride. 7 V Likewise, in Reactions 4 to l1-the hydrocarbon radicals ;of the isodithiocarbamic acid reactant may :be the same vorxdiiferent from each other.
  • Amongthe-hydrocarbontin oxide reactants that may sbensed in :the process ofthe present invention, illustrated in :Equations 4 and'8, may be mentioned dimethyltin oxide, diethyltin oxide, sdiprop'yltin oxide, di-n-butyltin oxide, -.di-isob.utyltin oxide, -di-isoamyltin oxide and diophenyltin oxide.
  • the preferredorganotin oxide'reactants are,-;dimethyltin oxide; and .dien-butyltin oxide.
  • any primary amine may be used.
  • the preferred primary alkyl amine is butylamine.
  • 'Alkenyl and alkyinyl amines may also be used in Reaction 4 above. These include propenyl amine, butenyl amines, hexenyl amines, butadienyl amines as well as amines having long chain unsaturated alkyl radicals derived from unsaturated fats.
  • cycloalkyl amines Primary saturated and unsaturated cycloalkyl amines, arylamines, aralkylamines are also useful in Reaction 4.
  • preferred amines in this grouping are cyclohexylamine, aniline and benzylamine.
  • the intermediate isodithiocarbamic acids are prepared by the reacting the metal salt of the dithiocarbamic acid with an organic halide.
  • organic halide Any organic halide may be used, for example, in Reaction 4 above. Included among these are the alkyl chlorides, for example, those having from 1 to 18 carbon atoms per alkyl radical which include methyl chloride, ethyl chloride, n-propyl chloride, isopropyl chloride, n-butyl chloride, tert-butyl chloride, pentyl chloride, hexyl chloride, heptyl chloride, octyl chloride, nonyl chloride, decyl chloride, hendecyl chloride, tridecyl chloride, tetradecyl chloride, pentadecyl chloride, hexadecyl chloride, ethylhexyl chloride.
  • Saturated and unsaturated cycloalkyl chlorides, aryl chlorides and aralkyl chlorides may also be used in Reaction 4.
  • Alkenyl and alkynyl chlorides may also be used in Reaction 4 above. These include propenyl chloride, butenyl chlorides, hexenyl chlorides, butadienyl chlorides as well as long chain unsaturated alkyl radicals derived from unsaturated fats.
  • the reaction conditions for the preparation of the organotin isodithiocarbamates of the present invention vary with the particular isodithiocarbamic acid made or employed and the particular organotin reactant selected.
  • the organotin isodithiocarbamates are made according to the present invention by the reaction of the isodithiocarbamic acid with the organotin reactant at a temperature between room temperature and about 150 I 1 C.
  • the reaction is carried out at an elevated temperature between about 60 C. and 135 C.
  • the manner in which the product is recovered is dependent on the physical state of the product.
  • the products When the products are liquid they may be separated from the reaction mixture by a separatory "funnel and then stripped of solvent.
  • the reaction mixture was allowed to stand overnight. The next morning it appeared as an orange liquid with some solid crystalline material on its surface.
  • the heater was turned on (30 v.) as well as the stirring and 126.5 gm. (1.0 mole) benzyl chloride was slowly added. The addition of the benzyl chloride was completed in 1 hour and the pot temperature at this time was 78 C.
  • the reaction mix now had a yellow color.
  • the reaction was continued for another 4 hours and then the heat was turned off and the reaction mixture cooled to a temperature of about 60 C. Two layers appeared, an oil layer and an aqueous layer. These layers were separated. The oil layer weighed 239.2 gms. It contained a slight amount of water.
  • reaction sequence may be described by the'followmg:
  • the initial pot temperature was C.
  • the reaction was exothermic and there was an immediate rise in temperature. Three minutes :after startthe pot temperature was C. and the mix had a cloudy pink color. Ten minutes later /2 of the CS had been added.
  • the pot temperature was 48 C. and the mix appeared as a clear orange liquid. Seven. minutes later A of the CS had been added.
  • the Pot Ztemperaturewas1-54""C. .andnthe mix was a cloudyloranget-liquid.
  • the addition .of CS was -completediten minutes later.
  • the pot temperature was 57 C. and the mix was an orange slurry.
  • the reaction was allowed to proceed for another ten minutes at which time-:the gpot temperature was 54 C. At this point the dropwise addition of 126.5 grns.
  • the flask was placed in the set up and the heater and stirrer were turned on. The reaction was allowed to proceed for one hour and 40 minutes at which time the oxide had dissolved and the 2 pot temperature was 107 C. The reaction was continued for another three hours and then the heater and stirrer were turned off. The reaction mix was allowed to stand overnight. The next day some solid crystalline material was present which was separated by filtration under suction. Dry weight was 48.3 and was labelled A.
  • the filtrate was stripped by jet water vacuum distillation yielding a light brown liquid labelled B.
  • reaction sequence may be described by the following:
  • H Dibutyltin bis S(N-butyl-S'-benzyl isodithiocarbamate)
  • a mixture of 73 gm. (1.0 mole) of BuNH and 40.9 grn. (Bakers, pellets 98.2%) (1.0 mole) of NaOH in 250 ml. of H 0 was charged in the flask.
  • 76 gm. (1.0 mole) of CS was added dropwise to the flask.
  • the temperature of the mix at this time was 60 C.
  • the pot temperature was 73 C. and water was distilling. The water was separated off.
  • the reaction was continued for another 4 hours and 8 minutes at the end of which time the pot temperature was 90- C. and all'of the H 0 had come over.
  • the reaction mix was then allowed to cool. Seven minutes later the pot temperature was 40 C. and 124.4 gms. (0.5 mole) of Bu SnO was added.
  • the heater and stirrer were turned on. 21 minutes later the pot temperature was 80 C. and 2+ ml. of H 0 had comeover. 36 minutes later the pot temperature was C. and the oxide had been completely dissolved. 7+ ml. of H 0 had come over.
  • the reaction was continued for another 17 minutes and then the heat was turned otf.
  • the reaction mix was allowed to stand about 5 days. The mix'was then stripped using a downward vacuum stripping assembly. This was done in 2 hours and 10 minutes. The final temperature was C. Most of the benzene had come out of the product. The residue was bottled (wt. 322.3 gm.).
  • hydrocarbontin isodithiocarbamates of the present invention are useful as stabilizers for vinyl resins, particularly chlorine-containing vinyl resins such as polyvinyl chloride, polymeric vinylidine chloride, copolymers of vinyl chloride and styrene and copolymers of vinyl chloride with vinyl acetate.
  • vinyl resins particularly chlorine-containing vinyl resins such as polyvinyl chloride, polymeric vinylidine chloride, copolymers of vinyl chloride and styrene and copolymers of vinyl chloride with vinyl acetate.
  • the hydrocarbontin isodithiocarbamates of the character described when added to the vinyl resin in amounts equal to 0.5 to 10.0 parts by weight of stabilizer to 100 parts of resin are eifective as stabilizers.
  • 1.0 to 3.0 parts by weight of stabilizer to 100 parts by weight resin is preferred.
  • a general test method was used to test the effectiveness of the products of this invention as stabilizers for polyvinyl chloride resins.
  • the resin used was Geon 101 (produced by B. F. Goodrich Co.) unless otherwise specified.
  • the stabilizer was incorporated into a mixture of 100 parts by weight of resin and 50 parts by weight of a plasticizer (here Flexal DOP (dioctyl phthalate)).
  • the weight of stabilizer was determined by its analysis. Thus enough stabilizer was used to provide 0.374 part by weight of Sn. This was done in order to determine the relative merits of the various compounds.
  • the mixture was then milled for minutes on a tworoll differential speed mill heated to 3203-25 F. and removed as a sheet. Portions of the sheet were then placed in a single cavity mold (6" x 6" x 40 mills) preheated to 275 F. The mold was placed on a press and raised to 320 F. under 10,000 pounds total pressure. When the mold reached 320 F. the pressure was increased to 40,000 pounds and held until the temperature reached 330 F. This procedure required 5 to 5 /2 minutes. The mold and press platens were then cooled and the pressed sheet removed.
  • the pressed sheet was cut into 1 x 6" strips and placed in clips on a tray so that the strips would hang vertically.
  • the tray was then placed in a circulating air oven held at 320 C. Samples were removed after one hour, two hours, three hours and four hours of heat aging. Samples were rated visually. Summary of tests are indicated as follows:
  • organotin isodithiocarbamates of this invention are effective as antioxidants and antiozonants in the range of 0.1 to 3.0 parts of stabilizer per parts of rubbery compound.
  • n is an integer from 1 to 3 inclusive
  • a is an integer from 0 to 2 inclusive, the sum of n+a being not greater than 3 and R, R, R" and R' are hydrocarbon radicals.
  • R",,Sn SO NR wherein n is an integer from 1 to 3, and R, R" and R' are hydrocarbon radicals.
  • a process for the preparation of hydrocarbontin isodithiocarbamates which comprises reacting and isodithiocarbamic acid of formula with an organotin compound selected from the class consisting of hydrocarbontin halides and hydrocarbontin oxides, wherein R and R" are hydrocarbon groups.
  • a process for the preparation of a hydrocarbontin isodithiocarbamate of claim 1 which comprises reacting a primary amine with CS and an alkali metal hydroxide to form the corresponding alkali metal salt of a dithiocarbamic acid, reacting said salt with a hydrocarbon halide to form the corresponding isodithiocarbamic acid and then reacting the isodithiocarbamic acid with a hydrocarbontin compound selected from the group consisting of hydrocarbontin halides and hydrocarbontin oxides to produce the corresponding hydrocarbontin isodithiocarbamate.

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  • Chemical & Material Sciences (AREA)
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Description

.drocarbon radical. phenyl, naphthyl, anthracyl, biphenylyl, benzyl,;phenyl- I United States Patent HYDROCARBONTIN ISODITHIOCARBAMATE-S AND PROCESS OF PREPARATION Hugh E. Ramsden, Metuchen, NJ assignor to Metal 8: Thermit Corporation,.New York, N.Y., a corporation of New Jersey No Drawing. Application October 19,1955
7 'Serial No. 541,537
13 Claims. (Cl. 260-4293) This invention relates to organotin dithiocarbamates and more particularly to the hydrocarbontin isodithiocarbamates of .general formula:
wherein "Rf'RyR" and R' are 'the same or different the form:
.RIIII :wherein R, R, R", R and-R are the same or'dif- .ferent hydrocarbon radicals.
In all the above-formulas R, R, R", R"{ and R""-=may -be any hydrocarbonradicals. They-may be,'-for-example,
any .alkyl radical such as methyl, ethyl,=n'-propy1, isopropyl, n-butyLiso-butyl, tert-butyl, pentyl, hexyl, ethyl- .hexyl, heptyl, octyl nonyl, hendecyl, dodecyl, 'tridecyl, itetradecyl, entadecyl, hexadecyl, etc.
They may also represent any cycloalkyl radical such as :cyclopropyl,
.cyclobutyl, rcyclopentyl, :cycyohexyl, Zcycloheptyl, 'etc.
They may also represent any aryl, aralkyl or alkaryl'hy- Arnong these may be mentioned,
ethyl, tolyl, xylyl, xenyl, cinnamyl and methylbenzyl. They may also be any alkenyl, alkynylior .cycloalkenyl radical. Included in these are propenyl,;butenyl, hexenyl, cyclopentenyl, butadienyl, .cyclopentadienyl, cyclohexenyl as well as long chain unsaturated alkylradicals derived from unsaturated fats. Q
The hydrocarbontin isodithiocarbamates.ofrthe present invention are prepared by reacting.anvisodithiocarbamic acid with a hydrocarbontincompound having a readily replaceable functional group bonded ...to ,tin. Hydrocarbontin reactants of particular .utility..are the hydrocarbontin oxides. The intermediate isodithiocarbamic acid may be made by reacting. a primaryamine-with carbon disulfide and a metal hydroxide preferably.anqalkali metal hydroxide, and then :reacting .thex-metal .dithiocarbamate,
2 so formed, with an organic halide. The synthesis may be illustrated as follows:
rv'zsn s-i}=N-R g It is to be understood, however, thatthis invention-is notrestricted to the particular method of forming the isodithiocarbamic acid which :has been illustrated in these equations.
Hydrocarbontin halides may be substituted :for the hydrocarbontin oxides in the above sequence of reactions. In this process, the reaction between the isodithiocarbamic acid and the hydrocarbontin halides may be .described by the following equations:
"R-N=O--S-'-R'-+ R SnX R",sn -sf 1-s-R'] H NR v 1 IR:N=C*S-YR' +:Rr'RSnX R2"RSn S-'C-S'B:
H ..N=R (11) 'R N;CS-R+RRS11Xn RRSn s-0-s+.R; s11 int 1 r.In which R, R R", R' and R""- are hydrocarbon radicals'rand X is a halide like chloride. 7 V Likewise, in Reactions 4 to l1-the hydrocarbon radicals ;of the isodithiocarbamic acid reactant may :be the same vorxdiiferent from each other.
Amongthe-hydrocarbontin oxide reactants that may sbensed in :the process ofthe present invention, illustrated in :Equations 4 and'8, may be mentioned dimethyltin oxide, diethyltin oxide, sdiprop'yltin oxide, di-n-butyltin oxide, -.di-isob.utyltin oxide, -di-isoamyltin oxide and diophenyltin oxide. The preferredorganotin oxide'reactants are,-;dimethyltin oxide; and .dien-butyltin oxide. I-ncluded inn-the .hydrocarbontinhalide reactants that cam-be used tert-butyltin chloride, tri-isoamyltin chloride, diethyl-npropyltin chloride, diethyl-n-amyltin chloride, methyltin trichloride, triphenyltin chloride, tii-p-tolyltin chloride, tri-m-tolytin chloride, trio-o-tolyltin chloride, tri-2,5- xylytin chloride, tri-fi-naphthyltin chloride, tri-benzyltin chloride, tri-cyclohexyltin chloride, diphenyltin dichloride, di-o-tolyltin dichloride, di-p-tolyltin dichloride, phenylethyltin dichloride, dibenzyltin dichloride, di-cyclohexyltin dichloride, phenyltin trichloride, o-tolyltin trichloride, p-tolyltin trichloride. g
In the preparation of the intermediates used in this invention according to Reaction 4, any primary amine may be used. These'include primary alkyl amines such as, for example those having from 1 to 18 carbon atoms per alkyl group which include: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine; pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, hendecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, ethylhexylamine. The preferred primary alkyl amine is butylamine. 'Alkenyl and alkyinyl amines may also be used in Reaction 4 above. These include propenyl amine, butenyl amines, hexenyl amines, butadienyl amines as well as amines having long chain unsaturated alkyl radicals derived from unsaturated fats.
Primary saturated and unsaturated cycloalkyl amines, arylamines, aralkylamines are also useful in Reaction 4. Among these may be mentioned cyclopropylamine, cyclobutylamine, cyclohexylamine, cyclopentylamine, cyclohexenylamine, aniline, B-naphthylamine, phenylethylamine, benzylamine, p-tolylamine, anthracylamine, biphenylylamine, o-tolylamine, xylylamines, xenylamines, cinnamylamine and methylbenzylamine. Among the preferred amines in this grouping are cyclohexylamine, aniline and benzylamine.
As noted above the intermediate isodithiocarbamic acids are prepared by the reacting the metal salt of the dithiocarbamic acid with an organic halide. Any organic halide may be used, for example, in Reaction 4 above. Included among these are the alkyl chlorides, for example, those having from 1 to 18 carbon atoms per alkyl radical which include methyl chloride, ethyl chloride, n-propyl chloride, isopropyl chloride, n-butyl chloride, tert-butyl chloride, pentyl chloride, hexyl chloride, heptyl chloride, octyl chloride, nonyl chloride, decyl chloride, hendecyl chloride, tridecyl chloride, tetradecyl chloride, pentadecyl chloride, hexadecyl chloride, ethylhexyl chloride. Saturated and unsaturated cycloalkyl chlorides, aryl chlorides and aralkyl chlorides may also be used in Reaction 4. Among these may be mentioned cyclopropyl chloride, cyclobutyl chloride, cyclohexyl chloride, cyclopentyl chloride, cyclohexenyl chlorides, chlorobenzene, chloronaphthalene, phenylethyl chloride, benzyl chloride, p-tolyl chloride, chloroanthracene, biphenyl chlorides, o-tolyl chloride, xylyl chlorides, xenyl chloride, cinnamyl chloride, methylbenzyl chlorides. Alkenyl and alkynyl chlorides may also be used in Reaction 4 above. These include propenyl chloride, butenyl chlorides, hexenyl chlorides, butadienyl chlorides as well as long chain unsaturated alkyl radicals derived from unsaturated fats.
The reaction conditions for the preparation of the organotin isodithiocarbamates of the present invention vary with the particular isodithiocarbamic acid made or employed and the particular organotin reactant selected. In general the organotin isodithiocarbamates are made according to the present invention by the reaction of the isodithiocarbamic acid with the organotin reactant at a temperature between room temperature and about 150 I 1 C. Preferably the reaction is carried out at an elevated temperature between about 60 C. and 135 C.
The manner in which the product is recovered is dependent on the physical state of the product. When the products are liquid they may be separated from the reaction mixture by a separatory "funnel and then stripped of solvent.
The following examples are further illustrative of the present invention. It is to be understood, however, that the present invention. is not restricted thereto.
EXAMPLE 1 Dimet hyltin his S(N- l uz l S'-ben zylisodithiocarbamate) A 2000 ml. 3 neck reaction flask was equipped with a stainless steel anchor stirrer, a Glas-Col heating jacket, a 3 way adapter'with arefluxcondens'er and dropping funnel. A pot thermometer was located in ofl center adapter. A mixture of 73.0 gms. (1.0 mole) of butylamine and 41.0 gms. (1.0 mole) of NaOH (Bakers, pellets 98.2%) in 250 ml. of H 0 was charged into the flask. 76.0 gms (1.0 mole) of CS was slowly added to the flask and the temperature rose immediately. 40 minutes after start the temperature was 58 C. and the addition of the CS was completed. The mix appeared as a fairly clear orange solution.
The reaction mixture was allowed to stand overnight. The next morning it appeared as an orange liquid with some solid crystalline material on its surface. The heater was turned on (30 v.) as well as the stirring and 126.5 gm. (1.0 mole) benzyl chloride was slowly added. The addition of the benzyl chloride was completed in 1 hour and the pot temperature at this time was 78 C. The reaction mix now had a yellow color. The reaction was continued for another 4 hours and then the heat was turned off and the reaction mixture cooled to a temperature of about 60 C. Two layers appeared, an oil layer and an aqueous layer. These layers were separated. The oil layer weighed 239.2 gms. It contained a slight amount of water. (Theory at this point=239.0 gms.) This product was placed in a covered beaker and allowed to stand overnight. The next day this product was again charged into the flask of the set up. 82.3 gm. (0.5 mole) of dimethyltin oxide and 200 ml. of toluene was added to the flask. The heater was set at 50 v. and the stirrer was turned on. The reaction was allowed to proceed for two hours and 10 minutes and the heater was turned DE. ml. of H 0 were removed from the reaction mix. The reaction mixture was allowed to stand in the set about two days. The heater and stirrer were then again turned on. A yellow solid was dispersed through the reaction mix. The reaction was allowed to proceed about another 7 hours and then heater was turned off. The reaction mix was allowed to stand over night. The next day it was filtered under suction. 20.7 gms. of a white precipitate and a light brown filtrate were obtained.
Filtrate was stripped by vacuum distillation to a pot temperature of C. and at 5 mm. of mercury. The product is a light brown liquid which weighed 211.7 gms. Analysis:
Precipitate Sn=50.06% Cl=2.23% Sulfur (comb.)=7.26% Distillate Sn=0.10%
Cl=0.73% Sulfur (comb.) =23.96%. This may contain toluene.
Distillation pot residue- Sn=24.5l% Cl=0.28% Sulfur (comb.)=l7.90% Theoretical mol. wt. 624.7 Theoretical Sn=19.0% Theoretical Sulfur=20.5%
i -l ams The reaction sequencemary be 'described as followsi CHaCl Dibutylti'n .bis "S(N-ibe'nzyl-".S" benzyfl l'isodith'iocafbamate') Using the same apparatus described-in-Example 1, a mixture -of 73. 9 gins. (1 .9 -mole) ofbenzylamine and 4.1.0 gins. (1.0 mole) ofiNaOl-l fiBakers, pellets 98.2%)
.in 200-ml. of H was chargedueinto the flask. ..-76.0 .gms. of CS was slowly added to-the'z flask.
At start the pot-temperature was 38 C. The ;temperature immediately rose and there' was 1-a ;pink :coloration :inthe reaction .mix. .Five minutes taftenstartthe temperature was -47 -:C. and :the [mix appeared as 2a :cloudy solution. .One :minute .after .that -t'he. pot tem- -perature was 50 C. .andthe mix appeared .as a=clear :orangesolution. Four-"minutes later-the pot temperature was 55 C. and .some' refluxingstarted. .TheJ-mix appeared as -a cloudy -organic.-.-solutionwcontaining dis- ;persed solids. The addition-of CS, was icomplete .20 .minutes after'rstart. The temperature at -this-=time was :50 C. This reaction ;was continued vfor another .:minutes at which time-'ithe pot temperature was-42 C. Addition of 126.5 ,gms.-,(1;0 mole) of benzyl chloride was -.then begun. -'ElEhis was complete'dfin minutes -.at which time .the .pot temperature was 56 'C. The heat was then turned on (-40 v.) 1.0 minutes after -.the heat was turned on-the -temperature 1 was 66 C. and the -.reaction had .a yellow color. Heating was :con-
tinued :for another .30 minutes and then the heater was turnedoif. The reaction .mix wasmllowed-to stand :for about 10 minutes andthen pO1lI'd -into a-separatory funnel. 235.1 gms. of'the light brown viscous oil was recovered (86.2% of theory). This oil was-ireturned :to ithe reaction flask. 124.4.gms. (0.5 mole yof dibutyl- "tin oxide and 200 ml. of toluene were ."thennadded to :thesflask and heat applied. .30.:minutes after this addition the temperature was 103 C. Some foarnsappeared in-the reaction mix and it had a yellow' color. :2 ml. of H O were removed from the mix. 5 minutes later .the pot -.tem perature was' 1-12-- C -Fhe-=dibnyltin-:oxide had dissolved and 4.0 ml. of H O were removed. The reaction was continued for another 25 minutes at which time the pot temperature was 123 C. 6.0 ml. of H 0 were removed from thereactionmix. 'Ihesheat was then turned off. The reaction mixture was allowed to stand about 3 days and then a white solid was removed by filtration under suction.
63.8 .grams. The afiltrate was=stripped by. vacuum distilation to 125 C. at '10 mm. of mercury. Residue was a light brown" liquid. Weight=2'74.6 grams.
Analysis:
Precipitate- Sn: 1 .05 Sulfur (comb.) 11.80% Residue -.Sn=21.23% l "Sulfur (conib. ='16.67%
This had a dry weight of "Theoretical T1161. =wt.=776'27 Theoretical Sn= 15.3%
"Theoretical *sulfur='- 16.5%
The reaction sequence may be described by the'followmg:
CHzNHg CSr-I-NaOH BuzSNO EXAMPLE 3 Dibutyltin bis S(N-cycl0hexyl S' benzyl isothiocarbamate) Using the apparatus described in Example 1, a mixture of 992 gms. (1.0 mole) of .cyclohexylamine and 41.0 gms. (1.0 mole) of NaOH -(-Bakers, pellets 98.2%) in 200 ml. of H 0 was charged into the flask. 76.0 gms. (1.0 mole) of CS was slowly added to the flask.
The initial pot temperature was C. The reaction was exothermic and there was an immediate rise in temperature. Three minutes :after startthe pot temperature was C. and the mix had a cloudy pink color. Ten minutes later /2 of the CS had been added. The pot temperature was 48 C. and the mix appeared as a clear orange liquid. Seven. minutes later A of the CS had been added. The Pot Ztemperaturewas1-54""C. .andnthe mix was a cloudyloranget-liquid. The addition .of CS was -completediten minutes later. The pot temperature was 57 C. and the mix was an orange slurry. The reaction was allowed to proceed for another ten minutes at which time-:the gpot temperature was 54 C. At this point the dropwise addition of 126.5 grns. (1.0 mole) ifi'benzylchloride was begun. Two minutes later the :addition was temporarily stopped because the reaction mix was .too thick. The pot temperature at this time was C.- ml. of H 0 was added to the mix to ithin it out. This reduced the pot temperature to 44 C. l'Ihe heater *waszturned on :(40 v.) and the addition of irbenzyl chloride ,was continued. Twenty-five minutes after the addition of benzyl chloride was continued 0f the benzylchloride :had been added. -The pot temperature was 67 C. and the reaction mix appeared as '"l5'a thin, yellow, cloudy liquid. The addition of the bentime the pot temperature was 92 C. The reaction mixture now appeared as two liquid layers. The bottom layer is a light brown oil and the top layer is The mix was heated for another 30 minutes and the heat was turned oflE to cool the mixture. The mix was allowed to stand overnight. The next day the bottom oily layer had become rather viscous. On pouring into a separatory funnel, the oily layer turned into a yellow solid. The water was poured ofl and the solid was dissolved in toluene. This was allowed to stand till the next day. As much H O as possible was removed from the toluene solution. The remainder was poured into a clean 2 liter flask and 124.4 gms. (0.5 mole) of dibutyltin oxide was added. The flask was placed in the set up and the heater and stirrer were turned on. The reaction was allowed to proceed for one hour and 40 minutes at which time the oxide had dissolved and the 2 pot temperature was 107 C. The reaction was continued for another three hours and then the heater and stirrer were turned off. The reaction mix was allowed to stand overnight. The next day some solid crystalline material was present which was separated by filtration under suction. Dry weight was 48.3 and was labelled A.
The filtrate was stripped by jet water vacuum distillation yielding a light brown liquid labelled B.
Analysis of A:
Sn=0.99% Sulfur (comb.)=l3.19%
Analysis of B:
Sn= 19.06 Sulfur (comb.) 16.19% Theoretical:
Sn: 15.6 S=16.8%
The reaction sequence may be described by the following:
H NH:
032+ NaOH H H:
H: i H. NH-C-SNa CHzCl i 56 H: ISI H: SH H NHC-S-CH H: H N=ti}-SCH H 2 H H, H, H H 60 l BnzSnO E A LE Dibutyltin bis S(N-butyl-S'-benzyl isodithiocarbamate) Using the same apparatus described in Example 1, a mixture of 73 gm. (1.0 mole) of BuNH and 40.9 grn. (Bakers, pellets 98.2%) (1.0 mole) of NaOH in 250 ml. of H 0 was charged in the flask. 76 gm. (1.0 mole) of CS was added dropwise to the flask. The temperature of mix'in flask was 20 C. and the stirrer was turned on. The addition of the CS was completed in 10 min. The temperature of the reaction mix rose to approximately -80 C. The mix appeared as a deeporange red nearly clear solution. Five minutes after completion of the addition of C8 126.5 gm. 1.0 mole) of benzyl chloride was added to the'reaction mix.; Addition of benzyl chloride was completed in about 7 minutes. At this time a yellow oil separated from a lower colorless aqueous layer in the reaction flask. The temperature at this time was -95 C. approximately. The reaction continued and 13 minutes later the temperature was 78 C. Ten minutes after this, 200 ml. of benzene was added. The oil layer dissolved in the benzene. The temperature of the mix at this time was 60 C. Ten minutes after the addition of the henzene, the lower layer was siphoned ofif. The benzene layer'was washed with 100 m1. of distilled H 0. 15 minutes later with a Barrett water separator in the system the heater and stirrer were turned on. Nine minutes later the pot temperature was 73 C. and water was distilling. The water was separated off. The reaction was continued for another 4 hours and 8 minutes at the end of which time the pot temperature was 90- C. and all'of the H 0 had come over. The reaction mix was then allowed to cool. Seven minutes later the pot temperature was 40 C. and 124.4 gms. (0.5 mole) of Bu SnO was added. The heater and stirrer were turned on. 21 minutes later the pot temperature was 80 C. and 2+ ml. of H 0 had comeover. 36 minutes later the pot temperature was C. and the oxide had been completely dissolved. 7+ ml. of H 0 had come over. The reaction was continued for another 17 minutes and then the heat was turned otf. The reaction mix was allowed to stand about 5 days. The mix'was then stripped using a downward vacuum stripping assembly. This was done in 2 hours and 10 minutes. The final temperature was C. Most of the benzene had come out of the product. The residue was bottled (wt. 322.3 gm.).
Analysis:
Percent Sn 17.43 Percent S mercapto 9.45 Percent S (combustion) 17.23 Percent C 53.13 Percent H 7.13
I BmSnO The hydrocarbontin.isodithiocarbarnates.ofthe present ness ofthe hydrocarbontin isodithiocarbamates of the present invention.
Use as vinyl resin stabilizer The hydrocarbontin isodithiocarbamates of the present invention are useful as stabilizers for vinyl resins, particularly chlorine-containing vinyl resins such as polyvinyl chloride, polymeric vinylidine chloride, copolymers of vinyl chloride and styrene and copolymers of vinyl chloride with vinyl acetate. In connection with vinyl resins, it has been found that the hydrocarbontin isodithiocarbamates of the character described when added to the vinyl resin in amounts equal to 0.5 to 10.0 parts by weight of stabilizer to 100 parts of resin are eifective as stabilizers. However, for commercial use, 1.0 to 3.0 parts by weight of stabilizer to 100 parts by weight resin is preferred.
A general test method was used to test the effectiveness of the products of this invention as stabilizers for polyvinyl chloride resins. The resin used was Geon 101 (produced by B. F. Goodrich Co.) unless otherwise specified.
The stabilizer was incorporated into a mixture of 100 parts by weight of resin and 50 parts by weight of a plasticizer (here Flexal DOP (dioctyl phthalate)). The weight of stabilizer was determined by its analysis. Thus enough stabilizer was used to provide 0.374 part by weight of Sn. This was done in order to determine the relative merits of the various compounds.
The mixture was then milled for minutes on a tworoll differential speed mill heated to 3203-25 F. and removed as a sheet. Portions of the sheet were then placed in a single cavity mold (6" x 6" x 40 mills) preheated to 275 F. The mold was placed on a press and raised to 320 F. under 10,000 pounds total pressure. When the mold reached 320 F. the pressure was increased to 40,000 pounds and held until the temperature reached 330 F. This procedure required 5 to 5 /2 minutes. The mold and press platens were then cooled and the pressed sheet removed.
The pressed sheet was cut into 1 x 6" strips and placed in clips on a tray so that the strips would hang vertically. The tray was then placed in a circulating air oven held at 320 C. Samples were removed after one hour, two hours, three hours and four hours of heat aging. Samples were rated visually. Summary of tests are indicated as follows:
Summary table Code: 1, dark amber; 2, light amber; 3, tan; 4, yellow;
5, pale yellow; 6, faint yellow; 7, colorless.
APPEARANCE AFTER HEAT AGING Stabilizer from Example No.
0hr. 1hr. 2hrs. 3hrs. 4hrs.
No stabilizer Example 4 Use as anliozonant and antioxidant 10 'namicor static'exposure. They "also improve -heat'resistanceand retarddiscoloration of rubber compositions containing them. Of particular interest in thisr'egard is the following compound:
L'TriphenyI tin S(N-cyclohexyl-S-cyclohexyl isodithiocarbamate) The organotin isodithiocarbamates of this invention are effective as antioxidants and antiozonants in the range of 0.1 to 3.0 parts of stabilizer per parts of rubbery compound.
While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not limited thereto but is to be construed broadly and restricted solely by the scope of the appended claims.
What is claimed is:
1. Organotin isodithiocarbamates of general formula:
wherein n is an integer from 1 to 3 inclusive, a is an integer from 0 to 2 inclusive, the sum of n+a being not greater than 3 and R, R, R" and R' are hydrocarbon radicals.
2. Organotin isodithiocarbamates of general formula:
R",,Sn SO=NR wherein n is an integer from 1 to 3, and R, R" and R' are hydrocarbon radicals.
3. Organotin isodithiocarbamates according to claim 2 .wherein R, R" and R' are selected from the class consisting of alkyl, aryl, aralkyl and cycloalkyl radicals.
4. A process for the preparation of hydrocarbontin isodithiocarbamates which comprises reacting and isodithiocarbamic acid of formula with an organotin compound selected from the class consisting of hydrocarbontin halides and hydrocarbontin oxides, wherein R and R" are hydrocarbon groups.
5. A process for the preparation of a hydrocarbontin isodithiocarbamate of claim 1 which comprises reacting a primary amine with CS and an alkali metal hydroxide to form the corresponding alkali metal salt of a dithiocarbamic acid, reacting said salt with a hydrocarbon halide to form the corresponding isodithiocarbamic acid and then reacting the isodithiocarbamic acid with a hydrocarbontin compound selected from the group consisting of hydrocarbontin halides and hydrocarbontin oxides to produce the corresponding hydrocarbontin isodithiocarbamate.
6. Dimethyltin bis S(N-butyl S'-benzyl isodithiocarbamate).
7. Dibutyltin bis S(N-benzyl-S'-benzyl isodithiocarbamate).
8. Dibutyltin bis S(N-cyclohexyl-S'-benzyl isodithiocarbamate).
9. Dibutyltin bis S(N-butyl-S'-benzyl isodithiocarbamate).
10. A process according to claim 5 wherein said primary amine is butylamine, said hydrocarbon halide is benzyl chloride and said hydrocarbontin compound is dimethyltin oxide.
11. A process according to claim 5 wherein said primary amine is benzylamine, said hydrocarbon halide is benzyl chloride and said hydrocarbontin compound is dibutyltin oxide.
References Cited in the file of this patent UNITED STATES PATENTS Miller et a1 Dec. 17, 1946 Hill Oct. 11, 1949 Gregory Apr. 28, 1953 Weinberg et a1. May 22, 1956 McDermott Mar. 26, 1957

Claims (2)

1. ORGANOTIN ISODITHIOCARBONATES OF GENERAL FORMULA
5. A PROCESS FOR THE PREPARATION OF A HYDROCARBONTIN ISODITHIOCARBAMATE OF CLAIM 1 WHICH COMPRISES REACTING A PRIMARY AMINE WITH CS2 AND AN ALKALI METAL HYDROXIDE TO FORM THE CORRESPONDING ALKALI METAL SALT OF A DITHIOCARBAMIC ACID, REACTING SAID SALT WITH A HYDROCARBON HALIDE TO FORM THE CORRESPONDING ISODITHIOCARBAMIC ACID AND THEN REACTING THE ISODITHIOCARBAMIC ACID WITH A HYDROCARBONTIN COMPOUND SELECTED FROM THE GROUP CONSISTING OF HYDROCARBONTIN HALIDES AND HYDROCARBONTIN OXIDES TO PRODUCE THE CORRESPONDING HYDROCARGBONATIN ISODITHIOCARBOAMATER.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248283A (en) * 1959-03-05 1966-04-26 Philips Corp Method of killing fungi with bis (triphenyltin) oxide
US3264230A (en) * 1961-12-29 1966-08-02 Union Carbide Corp Epoxide compositions containing tin curing catalysts
US3284383A (en) * 1961-12-29 1966-11-08 Union Carbide Corp Epoxide compositions
US3445492A (en) * 1961-11-03 1969-05-20 American Potash & Chem Corp Alkylene or arylene bis(organosilyl,germanyl or stannyl imidophosphoranes,arsanes or stibanes) and the preparation thereof
US3544608A (en) * 1968-02-05 1970-12-01 Dow Chemical Co Tricyclohexyltin isothiocyanate and a process for making organotin salts
US3901930A (en) * 1972-08-04 1975-08-26 Ciba Geigy Corp Hydrophilic and difficulty volatile biocidal triorganolead compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2412903A (en) * 1944-02-01 1946-12-17 California Research Corp Compounded lubricating oil
US2484508A (en) * 1946-10-07 1949-10-11 Du Pont Organodistannonic acids
US2636891A (en) * 1950-12-27 1953-04-28 Du Pont Heterocyclic organo-tin compounds containing oxygen, sulfur, and tin in the ring
US2746946A (en) * 1952-01-11 1956-05-22 Metal & Thermit Corp Vinyl resins stabilized with organotin sulfides
US2786814A (en) * 1953-09-21 1957-03-26 Exxon Research Engineering Co Tin-containing dithiocarbamate compounds and lubricants containing them

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2412903A (en) * 1944-02-01 1946-12-17 California Research Corp Compounded lubricating oil
US2484508A (en) * 1946-10-07 1949-10-11 Du Pont Organodistannonic acids
US2636891A (en) * 1950-12-27 1953-04-28 Du Pont Heterocyclic organo-tin compounds containing oxygen, sulfur, and tin in the ring
US2746946A (en) * 1952-01-11 1956-05-22 Metal & Thermit Corp Vinyl resins stabilized with organotin sulfides
US2786814A (en) * 1953-09-21 1957-03-26 Exxon Research Engineering Co Tin-containing dithiocarbamate compounds and lubricants containing them

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248283A (en) * 1959-03-05 1966-04-26 Philips Corp Method of killing fungi with bis (triphenyltin) oxide
US3445492A (en) * 1961-11-03 1969-05-20 American Potash & Chem Corp Alkylene or arylene bis(organosilyl,germanyl or stannyl imidophosphoranes,arsanes or stibanes) and the preparation thereof
US3264230A (en) * 1961-12-29 1966-08-02 Union Carbide Corp Epoxide compositions containing tin curing catalysts
US3284383A (en) * 1961-12-29 1966-11-08 Union Carbide Corp Epoxide compositions
US3544608A (en) * 1968-02-05 1970-12-01 Dow Chemical Co Tricyclohexyltin isothiocyanate and a process for making organotin salts
US3901930A (en) * 1972-08-04 1975-08-26 Ciba Geigy Corp Hydrophilic and difficulty volatile biocidal triorganolead compounds

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