US3232933A

US3232933A - 1-thiocarbamyl-2-imidazolidinethiones and a process for their preparation

Info

Publication number: US3232933A
Application number: US103962A
Authority: US
Inventors: Gundel Wolfgang
Original assignee: Dehydag Gmbh
Current assignee: Dehydag Deutsche Hydrierwerke GmbH
Priority date: 1960-04-30
Filing date: 1961-04-19
Publication date: 1966-02-01
Anticipated expiration: 1983-02-01
Also published as: DE1175244B

Description

United States Patent Claims. circa-24111:

This: invention relates to a: process, for producing. 1- thiocarhamyL- 2 -imidazolidinethione andl N-substituted derivatives. These compounds are also known as N-thiocarba-myl.substitutedethylene t-hioureas.

In United States patent applicationSerial No. 91,331, filed February 24, 1961, there isdescribedia processofi producing substitutedthioureasa According to, this process, an aliphatic ester. oi anv N mono-substituted, dithioearbasnic acid, whichester. containsla'. free hydrogenatom attached. to. the nitrogen atom. in the acid'. moiety and a water-solubilizing group: in the alcohol moiety,. is: dissolved in water and. reacted. at a temperature between about C. and about. 100 C. with the stoichiometri'c amount of a reactant selected from the group consisting of ammonia, primary monoamines, secondary monoamines and polyamines the presence of an alkaline reactant selected from the group consisting of alkali metal hydroxides, ammonia, primary monoam-ines, secondary nionoamines-andipolyamines.

In this manner it is possible to obtain mono-,. dior trisubst-ituted thioureas of the: general formula:

Specifically, the process results in substituted thioureas of the formula:

I 2'] R-NHJ3N v z z wherein z is an integer selected from 1 and 2; R is a radical selected from the group consisting of (A) alkylene having from 3 to 18 carbon atoms and the formula:

wherein R represents a member of. the group consisting of hydrogen and lower alkyl. and w represents aninteger selected from 1 to 8, when z is 2 and (B). alkyI having from 1 to 22 carbon atoms, alkenyl having from 3' to 22 carbon atoms, pheuylalkyl having from 7 to 22 carbon atoms, phenyl, naphthyl, alkylphenyl having from 7 to 22 carbon atoms, alkylnaphthyl having from 11 to 22 carbon atoms, nitrophenyl and nitroaminophenyl, when 2 is 1; and R and R represent radicals selected from the 3,232,933 Patented Feb. 1, 1966 group'consisting of hydrogen, alkyl having-from 1' to 22 carbon atoms, a' lkenyl having from 3'- to 22 carbonatoms, hydroxylalkyl having from 2 to 22" carbon atoms, cycloalkyl having from 5 to' 6' carbon atoms, alkylcycloalkyl having from 7 t'o-22carbon-at'orns, alkylcyclo'alkenyl hav-- ing from 7 to 22 carbon atoms, aminoa'lkyl having from 2 to 22 carbon atoms, phenyl, naphthyl, am-inophenyl, aminonaphthyl, 'phenylalkylhaving from 7 to 22- carbon atoms,- alkylphenyl having from 7 to 22 carbon atoms,

allcylnaphthyl havingfrom H to 22 carbon atoms, alkyla-minoalky l having from 3 to 22 carbon atoms, dialkylaminoa'lkyl having from 4 to 22- carbon atoms, aminoalkyla-minoalkyl having from 4- to 22' carbon atoms; and,

when taken together, alkylene-having4 toS- carbon atoms,

alkylaminoalkyl having 4 carbon atoms and alkylony alky'l'having 4 carbon atoms;

It is believed that in this process, under-the influence of alkali, which in many cases may be replaced by anadditional molecule ofamine, an isothiocyanic acidester (mustard oil) is initially formed inaccordancewith the following equation:

This isotliiocyanic acid ester thenreacts by additionwith theammonia or the primary or secondary aminein known fashion, and leads. to t-he formation ofthe mono-, dior tri-substitut'ed thio-ureas inaccordance with' the following equations:

By analogous procedures, it is also possible by this process to obtain alkylene-bis-thioureas wherein both va-lerices of the terminalnitrogen atoms are oc'cupied by organic radicals. Alkylene bis-thioureas which may be obtained by the method described below have the general wherein R represents an alkylene group having from 3 to 18 carbon atoms'and the formula:

wherein R is a member selected from the group consisting of hydrogen and lower alkyl and w represents an integer selected from 1 to 8.-

These products are obtained by reacting an aliphatic diester of alkylene-N,N'-bis-dithiocarbamic acid, which diester contains free or replaceable nitrogen atoms in the acid moiety and a Water-solubilizing group in each alcohol moiety, and whose alkylene group has from 3 to 18 carbon atoms and the formula:

-(IJ H. CIJH CH R \R: 1 h

wherein R is a member selected from the group consisting of hydrogen and lower alkyl and w represents an integer selected from 1 to 8, with two molsof ammonia or two mols of a primary or secondary amine in the presence of an alkali.

I have now found that l-thiocarbamyl-Z-imidazolidinethione and N-substituted derivatives may be obtained by reacting an aqueous solution of an aliphatic ester of ethylene-1,Z-bis-dithiocarbamic acid, which ester contains a free hydrogen atom attached to the nitrogen atom in the acid moiety and a water-solubilizing group in the alcohol moiety, with ammonia or primary or secondary monoamine or polyamine in the presence of alkalis, preferably alkali metal hydroxides. If desired, it is possible to operate Without the addition of alkali metal hydroxides, if a corresponding increase in the amount of ammonia or amine is provided.

It is an object of the invention to produce ethylene thiourea derivates substituted on one of the nitrogen atoms by a thiocarbamyl or N-substituted thiocarbamyl radical by reactions conducted in aqueous media.

It is a further object of this invention to produce 1- thiocarbamyl-Z-imidazolidinethione and derivatives substituted on the nitrogen atoms by reacting ammonia or an amine with an aqueous solution of an aliphatic ester of ethylene-1,2-bis-dithiocarbamic acid, which ester contains a free hydrogen atom attached to the nitrogen atom in the acid moiety and a water-solubilizing group in the alcohol moiety in the presence of an alkali.

These and other objects of the invention will become apparent as the description thereof proceeds.

When aliphatic esters of ethylene-l,Z-bis-dithiocarbamic acid or corresponding bis-dithioesters which have hydrocarbon substituents attached to the ethylene radical, that is, for example with a bis-dithioester of the general formula:

wherein R represents hydrogen or a lower alkyl group and X represents the alcohol moiety containing a watersolubilizing group, are reacted with ammonia or an amine in the presence of an alkali, contrary to expectations, the intermediate bis-isothiocyanic acid esters of ethylene of the formula:

which form under the influence of the alkali, do not combine with two molecules of the primary or secondary amine, but rather with only one molecule, even if an excess of the amine is present. The compounds formed in this manner do not react in the cold with amines and thus no longer contain a free isothiocyanate group. This is indicated with certainty by their infrared spectra, 50 that it is justified on the basis of their composition and their behavior to designate them as derivatives of dithiobi'urets in accordance with the following tautomeric formulas:

wherein R is a radical selected from the group consist ing of hydrogen and lower alkyl; and R and R represent radicals selected from the group consisting of hydrogen, alkyl having from 1 to 22 carbon atoms, alkenyl having from 3 to 22 carbon atoms, hydroxyalkyl having from 2 to 22 carbon atoms, cycloalkyl having from 5 to 6 car" bon atoms, canboxyalkyl having from 2 to 8 carbon atoms, alkylcycloalkyl having from 7 to 22 carbon atoms, alkyl cycloalkenyl having from 7 to 22 carbon atoms, aminoalkyl having from 2 to 22 carbon atoms, phenyl, naphthyl, aminophenyl, aminonaphthyl, phenylalkyl having from 7 to 22 carbon atoms, alkylphenyl having from 7 to 22 carbon atoms, alkylnaphthyl having from 11 to 22 carbon atoms, alkylaminoalkyl having from 3 to 22 carbon atoms, dialkylaminoalkyl having from 4 to 22 carbon atoms, aminoalkylaminoalkyl having from 4 to 22 carbon atoms, and when taken together, alkylene having 4 to 5 carbon atoms, alkylaminoalkyl having 4 carbon atoms and alkyloxyalkyl having 4 carbon atoms.

The above formulas designating the compounds as 1- thiocarbamyl-2-imidazolidinethiones are specially indicated by the fact that secondary amines, such as diethylamine, where another formulation (7-membered ring) is not possible, react in the same manner.

The practical performance of the reaction is effected by first reacting, in accordance with known methods, 1,2- ethylene diamine or also 1,2-ethylene diamines whose hydrogen atoms are replaced by preferably short chain hydrocarbon radicals of the formula:

wherein R represents a member selected from the group consisting of hydrogen and lower alkyl, such as 1,2- propylene diamine, 2,3-butylene diamine and the like, in aqueous solution with two equivalents of carbon disulfide and alkali metal hydroxide, preferably in the cold, and subsequently reacting the ethylene-1,2-bis-dithiocarbamic acid salt formed thereby with two equivalents of an alkali metal salt of as reactive as possible lower haloalkanoic acid (such as chloroacetic acid and chloropropionic acid) or with a lower haloalkane sulfonic acid (such as bromoethane sulfonic acid, bromopropane sul fonic acid and 3-bromo-2-oxy-propane sulfonic acid.

In place of the lower haloalkanoic acid salts or haloalkane sulfonic acid salts it is also possible to employ inner anhydrides of lower hydroxyalkanoic acids (such as propiolactone or butyrolactone) or of lower hydroxyalkane sulfonic acids( such as 1,3propanesultone or 1,4- butanesultone). The use of the latter compounds has proved to be especially advantageous with respect to the final yield, because the sultones, particularly the 1,3-sultones, react so rapidly and completely with the ethylenebis-dithiocarbamates that the alkaline reaction of the still unreacted bis-dithiocarbamates does not have a cleaving effect upon the esters already formed. The ethylenebis-dithiocarbamyl ester salts thus obtained have the formula:

2 s s Z Y.(alas t NH tH tH NH aeta). wherein R represents a radical selected from the group consisting of hydrogen and lower alkyl; Y represents a Water-solubilizing group selected from the group consisting of --COOMe and -SO Me and Me represents an alkali metal; Z represents a radical selected from the group consisting of hydrogen and hydroxy; n represents an integer from 1 to 4; and m represents an integer from 1 to 2. These alkali metal salts, such as the sodium ethylene 1,2-bis-(dithiocarbamyl-S-propane-w-sulfonate) formed with the aid of 1,3-propane-sultone, may be further reacted without isolation because the subsequent reactions may also be performed in water. However, they may, if necessary, also be isolated by salting out and drying and may be further reacted after their isolation.

For transformation into the dithiobiuret derivatives according to the invention, the aqueous solution of the starting alkali metal salt is admixed, accompanied by vigorous stirring, with .at least one equivalent of ammonia or of a primary or secondary amine which may be of an alipha'tic, -cycloalip'hatic or araliphatic nature.

Suitable monoamines or -polyamines of the formula for the reaction with "the ethylene- 1,2 bis-dithiocarbamic acid esters are the primary and secondary amines with 1 to '22 carbon atoms, 'such as alkylamines having from 1 to 22 carbon atoms, for example, ethylamine, 'butylamine, oc'tylam'ine, dodecyla'mine, octadecyl-amine; dialkylamines having from 2 to 22 carbon atoms, for example, dimethylamine, diethylamine, dioctylamine; alkenylamines having from 3 to 22 carbon atoms, for example, oleylamine; phenylalky-lam-ines having from 7 to 22 carbon atoms, for example, benzylamine; hydroxyalkylamines having from '2 to '22 carbon atoms, for example, ethanolamine; cycloalkylamines having from 5 to 6 carbon atoms, for example, cyclohexylamine; alkylcycloalkylamines having from 7 to 22 carbon atoms, for example, methylcyclohexylamine; alkylcycloalkenylamines having from 7 to 22 carbon atoms, for example, naphthenylamine; alkylene diamines having from 2 to 22 carbon atoms, for example, ethylenediarnine, propylenediamine, butylenediamine; alkylaminoalkylamines having from 3 to 22 carbon atoms, for example, N-ethyl-ethylenediarnine; dialkylaminoalkylamines having from 4 to 22 "carbon atoms, for example, N,N-diethyl-propylenediamine, N,N-diethyl-ethylene-diamine, N,N-dimethyl-propylenediamine; polyalkylamines having "from 4 to 22 carbon atoms, for example, diethylenetriamine; piperidine; pyrrolidine; piperazine, morpholine and glycine.

Accompanied by cleavage of both dithiocarbamyl radicals at the CSS-bond, two equivalents of mercaptoalkane carboxylic acid salts or mercaptoalkanesulfonic acid salt are formed. The ethylene-bis-isothiocyanic acid, which is thereby formed as an intermediate, combines with the ammonia or amines present, whereby the formation of the dithiobiuret structure occurs, accompanied by ring closure.

The reaction between these starting components takes place smoothly by stirring for several hours, possibly at elevated temperatures of to 100 C., preferably 50 to 60 C. The reaction, however, should be conducted at temperatures of 60 C. -or below, if possible. If the amine reactant used in the reaction, such as the high molecular weight amines of the fatty series, is difficultly soluble in water, a solution .promoter, such as alcohol, may be added to the mixture without adversely influencing the yield. The substituted thioureas produced in this manner are all so diflicultly soluble in water that they separate out of the reaction mixture in crystalline form after a short period of time and may be isolated by Ifiltration.

It has been found that when primary amines are reacted, .the alkali metal hydroxide may be substantially,

and in many cases even completely, replaced by excess amine without changing the course of the reaction. When secondary amines are used, the concurrent use of the full amount of alkali metal hydroxide is in most cases indispensable and large excesses of amine are best avoided if the reaction is to lead to the product according to the invention and if the formation of tetra-alkylated ethylenebis-thioureas is to be avoided. Substituted ethylene-bisthioureas do not form until the dithiobiurets are treated at elevated temperatures for longer periods of time with amines. This is a reaction which generally proceeds more readily with the dithiobiuret produced from secondary amines than with those produced from primary amines,

'6 which is the reason why, when secondary amines are employed, an excess of amine must be avoided, whereas, with primary amines, the alkali metal hydroxide may substantially be replaced by the amine.

To illustrate the course of the reaction, assuming the use of 1,3-propanesultone as the esterification agent and ethylamine as the amine reactant, the react-ion proceeds according to the following equation:

The colorless compounds which are obtainable with satisfactory yields by the present process and whose preparation is illustrated by the following examples, are valuable brightening additives 'for electroplating bath's or intermediate products for their preparation. Furthermore, they may be employed ascorrosion inhibitors and vulcanization accelerators. The mercaptoalkane carboxylic acids or mercaptoalkane sulfonic acids formed as side products may be used for the same purposes; in addition, they are valuable agents for permanent wave preparations.

The following examples are illustrative of my invention. They are not to be considered as limitative, however, as other expedi'ents known to those skilled in the art can be employed.

EXAMPLE I 1 -bmyl'thiocarbamyl-2-imidazolidinethib71e /C=S OH2.N

/C=S C Hg-NH Sodium etl1ylene-l,2-bis-(dithioealrbanfyl-S p roprane wsulfonate) was prepared by slowly adding 12 parts by Weight of ethylene diamine (0.2 mol) and then .parts by Weight of a 20% sodium hydroxide solution (0.4 mol) to a vigorously stirred suspension of 3.0.4 parts by weight of carbon disulfide (0.4 mol) in 150 parts by volume of water. The solution was stirred until it became clear, then 49 parts by Weight of 1,3-propanesultone (0.4 mol) were added thereto and the reaction mixture was stirred. The sodium ethylene-1,2-bis-(dithiocarbamyl-S-propane-w-sulfonate) was obtained by salting out. p I

parts by weight of sodium ethy1ene-1,2bis(ditliiocarbamyl s-prop-ane w-sulfonate) (0.2 mol) were dissolved in 300 parts 'by volume of water and the resulting solution, after adding 15 parts by weight of butylamine (0.2 mol), Wasadmixed droptwise with 80 parts by Weight of a 20% sodiumhydroxidesolution '(0. 1'mol). The 1- butylthiocarbamyl-2-imidazolidinethione formed thereby separated out after a short period of time in crystalline form. After stirring the mixtur for several hours, toward the end while cooling it on ice, the precipitate was separated by vacuum filtration and the product, which was formed in ample quantity, was recrystallized from seven times its amount of isopropanol. The melting point of the analytically pure substance was -137" C.

The same compound was obtained when, in place of the 20% sodium hydroxide, an equivalent amount of butylamine, that is, a total of 43.8 parts by Weight of this amine (0.6 mol), was added to the sol-utionof sodium '7 ethylene 1,2 bis(dithiocarbamyl-S-propane-w-sulfonate) prepared according to the method described in the preceding example. After six hours of reaction at room temperature the yield was 53% of theory.

EXAMPLE II 1-n-0ctyllhiocarbamyl-2imidazolidinethione CH2NH /C==S GHQ-N /C=S CgH1 NH By Working in close analogy to the method described in the previous example, but using 26 parts by weight of n-octylamine (0.2 mol) in place of butylamine, 1-noctylthiocarbamyl-Z-irnidazolidinethione was obtained with a yield of 65%, which was recovered analytically pure by recrystallization from isopropanol. The melting point was 101l01.5 C.

EXAMPLE III l-doa'ecylthiocarbamyl-Zimidazolidinethione CHa-NE /C=S OH N /C=S C12H25""NH 125 parts by volume of alcohol, 37 parts by weight of dodecylamine (0.2 mol) and 80 parts by volume of sodium hydroxide (0.4 mol) were added to a solution of 100 parts by weight of sodium ethylene-1,2-bis- (dithiocarbamyl-S-propane-w-sulfonate) (0.2 mol) in 300 parts by volume of water. The l-dodecylthiocarbamyl- 2-imidazolidinethione which separated out with excellent yield in the course of several hours stirring at room temperature was obtained in the form of fine needles by recrystallization from twenty times its amount of acetone, methanol or isopropanol; the analytically pure needles melted at 105107 C. t

For the preparation of a vulcanizable rubber compo sition for automobile tires, the following ingredients were admixed by kneading:

Parts by weight After shaping, this mixture was vulcanized for twentyfive minutes at 145 C. in the usual manner.

EXAMPLE 1V 1-dimethylthiocarbamyI-Z-imidazolidinetlzione CHrNH C S CHz-N\ C Ha C: S

/N C H3 12 parts by weight of ethylene diamine (0.2 mol) and then 80 parts by weight of a 20% sodium hydroxide solution (0.4 mol) were slowly added to a vigorously stirred suspension of 30.4 parts by weight of carbon disulfide (0.4 mol) in 150 parts by volume of water. The

8 solution became clear after two hours of stirring, and then 49 parts by weight of 1,3-propanesultone (0.4 mol) were added thereto and the mixture was stirred until the reaction mixture had become virtually neutral. After addition of 32.5 parts by weight of a 33% aqueous dimethylamine solution (0.25 mol) and an additional parts by weight of 20% sodium hydroxide (0.4 mol) the reaction mixture began to turn cloudy and the l-dimethylthiocarbamyl-Z-imidazolidinethione began to separate out in crystalline form. After stirring the reaction mixture for several additional hours, toward the end at the temperature of ice, the precipitate was separated by vacuum filtration and was washed with water. 22 parts by weight of the product were obtained, which corresponds to a yield of 58% of theory. Recrystallized from 40 times its amount of ethyl alcohol, the compound was obtained analytically pure and had a melting point of 184 to 186 C.

EXAMPLE V 1-diethylthiocarbamyl-Z-imidazolidinethione o HzNI-I /o= s C Hr-N EXAMPLE VI 1-thiocarbamyl-Z-imidazolidinethione OHz-NH /o=s CHz-N /C=S NH:

By working in close analogy to the method described in Example I, that is, by adding 80 parts by weight of 20% sodium hydroxide (0.4 mol) and 70 parts by weight of 25% ammonia while stirring to a solution prepared by parts by weight of sodium ethylene-1,2-bis- (dithiocarbamyl-S-propane-w-sulfonate) (0.2 mol) and 250 parts by weight of water, the 1-thiocarbamyl-2- imidazolidinethione formed thereby crystallized out soon thereafter. The reaction mixture was allowed to stand overnight, the precipitate was separated by vacuum filtration and was then recrystallized from 100 times its amount of water. The analytically pure compound, which was obtained with a yield of about 20%, melte at 192-194 C.

EXAMPLE VII J -pen tamethylenethiocarbamyl-2-imidazolidinethione CHz-NH CH2N CH2CH5 CH2 N CI-I2CH:

17 parts by weight of piperidine (0.2 mol) and 80 parts by weight of 20% sodium hydroxide (0.4 mol) were added to a solutionof sodium ethylene-1,2-bis- (dithiocarbamyl-Sr-propane-w-sulfonate) prepared as described in Example 1-pentamet -hylenethiocarbamyl- Z-imidazolidinethione which formed with a yield of 60% was recrystallized from 80' times its amount of isopropanol or from a mixture of dimethylforrnamide and water, and had a melting point; of l78179 C.

The same compound was obtained when, in place of 1,3-propanesultone, 46.6 parts by weight of sodium monochloroacetate (0.4 mol-)- were added to a solution of sodium ethylene-1,Z biS-dithiocarbamic acid prepared as described in Example IV, and after stirring this mixture for 4 hours, 17 parts by weight of piperidine (0.2 mol) and 80 parts by weight of 20% sodium hydroxide (0.4 mol) were added thereto. The crystalline product which separated out after several hours stirring with somewhat smaller yield was identical with the product obtained above.

EXAMPLE VIII 1-(3-0xapentamethylene -thiocarbamyl Z-imidalolidinethione c Hz-NH onz -N QHzr- H2,-

\N. fiz Cz By following the procedure described in Example IV, but using in place of dimethylamine 17 .5' parts by weight of morpholine (0.2- mol) 1 -(3' oxapentarnethylene)- thiQcarbamyl-Z-imidazolidinethione Was obtained which, recrystallized from a mixture of equal parts of dimethylformamide in water, had a melting point of 191-192- C.

1-benzylthiocarbamyl-Z-imia'azolidinethjone C= S C -Na C= S CH5FC H z -NH Following a procedure analogous to that described in Example IV, but using 21.5 parts by weight of benzylamine (0.2 mol) in place of dimethylamine, l-benzylthiocarbamyl-2-imidazolidinethione was obtained with a yield of 68% of theory. After recrystallization from times its amount of isopropanol, the product was obtained' analytically pure and had a melting; point of 132-133 C.

EXA L X By following a procedure analogous to that described in Example I, but using 19.6 parts by weight of cyclohexylamine (0.2 mol) in place of butylamine, l-cyclohexylthiocarbamyl-2-ilrnidazplidinethione was obtained with a yield of of theory. Recrystallized from 7 times its amount of methanol, it has a melting point of 150152 C.

1Q EXAMPLE X1 1; 1"-(ethylene-di thiocarbamyl) -bis- Z-imidqzqlidinethione Y. ol ow gt e. p ocedu e cr ed n. Examp e V ut using; 6.6. par s. y w t: ofi' thy en d amine -L mol) in place of dimethylamine, 14 parts by weight; of the shiob u e ay n e bet fo mul w re tained; w t av e d. ff 2. 5 heo y- Whe Pre initated from 15 times its amount of; a mixture. of; 2 parts of dimethylf ormamide and 1 part of water the product ad ame t n ppiutoi. .1.

EXAMPLE X-I-I 1-carboxymethy lthiocarbamyl-Z-imidazplidinethione 120 parts by weight of a 211% sodium hydroxide solu tion (0.6 mol) and 27:9 parts by weight of ethyl glycine hydrochloride (0.2 mol) were added, while. stirring, to an aqueous solution of parts, by weight of sodium ethylene-1,2 bis-(dithiocarbamyl-S-propaue-w-sulfonate) 0.2 mol) which was prepared in a manner analogous to that described in Example I'V, and the resultant reaction mixture was stirred 0112 hours at room temperature and then for an additional hour; atLS C. The slightly turbid mixture was filtered and the filtrate was then made just acid to congo red by adding diluted hydrochloric acid. An ample amount of crystalline l-carboxymethylthiocarbamyl-2-imidazolidinethione separated out and the mixture was allowed to stand for several hours on ice. Thereafter it was vacuum filtered, the filter cake was dried and recrystallized from alcohol; or; methanol. The analytically pure product was, obtained the form of long needles having a melting point of 186-l88 C.

LS-prQpyIenediamine (0.2 mol) were added to a solution of sodium ethylene-1,2-bis-(dithiocarbamyl-s-propane t sulfonate) (0.2 mol) prepared analogous to the method described in Example IV. The l-(3'-diethylamino-propylthiocarbamyl) 2 imidazolidinethione which crystallized out after a short period of time'was separated by vacuum filtration after stirring the mixture for 3 hours and was then recrystallized from 15 times its amount of ethanol. 25 parts by weight of the product, correspond ing to a yield of 45% of theory, were obtained. The analytically pure base which is readily soluble in dilute acids had a melting point of 151-153 C.

8 to 12 rngs. of the above compound were added to a nickel electroplating bath which contained 265 gms. per liter of crystalline nickel sulfate, 53 gms. per liter of crystalline nickel chloride, and 33 gms. per liter of boric acid, and in addition contained 2.5 gms. of sodium di-oltoluyl-disulfimide and 0.2 gm. of sodium dodecylsul-fate (as wetting agent). When this electroplating bath was operated at temperature of 55 C. a full bright electroplate was obtained within a current density range of 0.5 to 8 amperes per decimeter with an excellent leveling effect.

For the preparation of a vulcanizable rubber composition for automobile tires, the following ingredients were admixed by kneading:

Parts by weight Smoked sheets 100 Zinc oxide 3 Carbon black 45 Spruce rosin 2.5 Stearic acid 3 Parafi'in 0.75

Phenylnaphthalene 1.5 1-(3-diethylamino propylthiocarbamyl) 2 imidazolidinethione (as accelerator) 0.6 Sulfur 3.0

After shaping, this mixture was vulcanized for 25 minutes at 145 C. in the usual manner.

EXAMPLE XIV 1-dz'methylthiocarbamyl-4(0r -methyl-2- imidazolidinethione By using a procedure closely analogous to that described in Example IV, but using 14.8 parts by weight 1,2- propylenediamine in place of 1,2-ethylenediamine, well crystallized l-dimethylthiocarbamyl methyl-Z-imidazolidinethione was obtained with a 44% yield under the conditions described for the reaction with dimethylamine in Example IV. However, the question remains open as to whether the methyl group is in the 4-position or in the 5-position of the imidazoline ring or whether a mixture of isomers is obtained. The compound crystallized from times its amount of alcohol in the form of coarse, colorless crystals which have a melting point of 163- 164 C.

1 2 EXAMPLE XV 1-(3'-diethylcvmino-propylzhiocarbamyl) -4 (0r 5) -methyl- 2-imidaz0lidinethionc CH3-C H-NII CHI-N and 26 parts by weight of N,N-diethyl-1,3-propylenediamine (0.2 mol) and parts by weight of 20% sodium hydroxide were added to a solution of sodium propylene- 1,2-bis(dithiocarbamyl-S-propane-w-sulfonate) prepared in a manner analogous to that described in Example IV, but using 14.8 parts by weight of 1,2-propylenediamine (0.2 mol) in place of 1,2-ethylenediamine. The 1-(3- diethylamino --propylthiocarbamyl) methyI-Z-imidazolidinethione which soon separated out in crystalline form with a yield of about 43% of theory was separated by vacuum filtration after 4 hours of stirring, washed with water, dried and recrystallized from 6 times its amount of isopropanol or a mixture of equal parts of gasoline and benzene. The question as to whether the methyl group is in the 4-position or in the 5-position of the imidazoline ring or whether a mixture of isomers is obtained remains open. The compound had a melting point of 104- 105 C.

EXAMPLE XVI 1-(3'-dimethylamino-propylthiocarbamyl) -2- imidazolidinethione GHQ-NH C H2-N O: S CHr-N (IJHFCHT-N CHI By using a procedure analogous to that described in Example XIII, but using 20.4 parts by weight of N,N- dimethyl-1,3-propylenediamine (0.2 mol) in place of N,N diethyl-1,3 propylenediamine, 1-(3-dimethylamino-propylthiocarbamyl) -2-imidazolidinethione was obtained with a yield of about 43% of theory. Recrystallized from 15 times its amount of isopropanol, it had a melting point of 161-163" C.

EXAMPLE XVII 1 (2 '-die thy lamino-ethylthiocarbamyl) -2-im idazolidinethione CHz-NH C: S CHrN C: S O Hz-N C 2115 GHzN 13 a When the N,N-diethyl-1,3-propylenediamine used in Example XIII was replaced by 23.2 parts by weight of N,N-diethyl-l,2-ethylene diamine (0.2 mol) and the same procedure was used, 1-(2'-diethylaminoethylthiocarbamyl)-2-imidazolidinethione was obtained which, recrystallized from 10 times its amount of isopropanol, had a melting point of 131-l33 C.

EXAMPLE XVIII 1 -[3'- (morpholine-N) -prpylthi0carbamyl] -2-imia'az0lidinethione CHrNE C: S CHT-N/ C: S CHz-NH GET-CH1 C H?- C Hz-N /O CHr-CH:

Using a procedure analogous to that described in the two preceding examples, but using 29 parts by weight of N-morpholine-1,3-propylenediamine (0.2 mol) as the basic reactant, 1-[3'-(morpholine-N)-propylthiocarbamyl]-2-imidazolidinethione was obtained with a satisfactory yield. It had a melting point of 142.5l43.5 C. By recrystallization from 10 times the amount of isopropanol it was obtained in its pure form.

The above examples disclose many of the embodiments of my invention. It is to be understood that other embodiments, such as utilization of other reactants, alkali metal hydroxides, etc., known to those skilled in the art, may be employed without departing from the spirit of the invention or the scope of the appended claims.

I claim:

1. The process of producing l-thiocarbamyl-Z-imidazolidinethione of the formula:

wherein R is a radical selected from the group consisting of hydrogen and lower alkyl; and R and R are radicals selected from the group consisting of hydrogen, alkyl of from 1 to 22 carbon atoms, alkenyl of from 3 to 22 carbon atoms, hydroxyalkyl of from 2 to 22 carbon atoms, carboxyalkyl of from 2 to 8 carbon atoms, cycloalkyl of from 5 to 6 carbon atoms, alkylcycloalkyl of from 7 to 22 carbon atoms, alkylcycloalkenyl of from 7 to 22 carbon atoms, aminoalkyl of from 2 to 22 carbon atoms, phenylalkyl of from 7 to 22 carbon atoms, alkylaminoalkyl of from 3 to 22 carbon atoms, dialkylaminoalkyl of from 4 to 22 carbon atoms, aminoalkylaminoalkyl of from 4 to 22 carbon atoms, and, when taken together with the nitrogen atom, piperidino, pyrrolidino, piperazino and morpholino, which comprises the steps of reacting a watersoluble ester compound of the formula:

2 s R R s a Y-(a)...S t NH iH iH NH t S (CH .Y,

wherein R is a radical selected from the group consisting of hydrogen and lower alkyl; Y is a water-solubilizing group selected from the group consisting of COOMe and SO Me and Me is an alkali metal; Z is a radical selected from the group consisting of hydrogen and hydroxy; n represents an integer from 1 to 4; and m represents an integer from 1 to 2, dissolved in an aqueous solution with the stoichiometric amount of a compound having the formula where R and R have the above meanings, in the presence of an alkaline reactant selected from the group consisting of alkali metal hydroxides and where R; and R have the above meanings, at a temperature between about 20 C. and about C. and recovering said 1-thiocarbamyl 2fimidazolidinethione.

2. The process of producing l-thiocarbamyl-Z-imidazolidinethione which comprises the steps of reacting sodium ethylene-1,2-bis-(dithiocarbamyl-S-propane-w-sulfonate), dissolved in an aqueous solution with the stoichiometric amount of ammonia in the presence of sodium hydroxide at a temperature between about 20 C. and 60 C. and recovering said 1-thiocarbamyl-Z-imidazolidinethione. I

3. The process of producing l-butylthiocarbamyl-Z-imidazolidinethione which comprises the steps of reacting sodium ethylene-1,2-bis-(dithiocarb amyl-S-propane-w-sulfonate), dissolved in an aqueous solution with the stoichiometric amount of butylamine in the presence of sodium hydroxide at a temperature between about 20 C. and 60 C. and recovering said 1-'butylthiocarbamyl-2-imidazolidinethione.

4. The process of producing l-butylthiocarbamyl-2-imidazolidinethione which comprises the steps of reacting sodium ethylene-1,2-bis-(dithiocarbamyl-S-propane-w-sulfonate), dissolved in an aqueous solution with the stoichiometric amount of butylamine in the presence of an excess of butylamine at a temperature between about 20 C. and 60 C. and recovering said l-butylthiocarbamyl-Z- imidazolidinethione.

5. The process of producing l-thiocarbamyl-Z-imidazolidinethione of the formula:

wherein R is a radical selected from the group consisting of hydrogen and lower alkyl; and R and R are radicals selected from the group consisting of hydrogen, alkyl of from 1 to 22 carbon atoms, alkenyl of from 3 to 22 carbon atoms, hydroxyalkyl of from 2 to 22 carbon atoms, carboxyalkyl of from 2 to 8 carbon atoms, cycloalkyl of from 5 to 6 carbon atoms, alkylcycloalkyl of from 7 to 22 carbon atoms, alkylcycloalkenyl of from 7 to 22 carbon atoms, a-minoalkyl of from 2 to 22 carbon atoms, phenylalkyl of from 7 to 22 carbon atoms, alkylaminoalkyl of from 3 to 22 carbon atoms, dialkylaminoalkyl of from 4 to 22 carbon atoms, aminoalkylaminoalkyl of from 4 to 22 carbon atoms, and, when taken together with the nitrogen atom, piperidino, pyrrolidino, piperazino and morpholino, which comprises the steps of reacting alkali metal salts of a dithiocarbamic acid of the formula:

where R has the above assigned meaning with a watersolubilizing esterifying component selected from the group consisting of alkali metal lower haloalkanoates, alkali metal lower haloalkane sulfonates, lower hydroxyalkanoic acid lactones and lower hydroxyalkane sulfonic acid sultones, dissolving the water-soluble ester compound formed thereby of the formula:

wherein R is a radical selected from the group consisting of hydrogen and lower alkyl; Y is a water-solubilizing group selected from the group consisting of COOMe and SO Me and Me is an alkali metal; Z is a radical selected from the group consistingof hydrogen and hydroxy; n is an integer from 1 to 4; and m is an integer from 1 to 2, dissolved in -an aqueous solution with the stoichiometric amount of a compound having the formula where R and R have the above meanings, in the presence of an alkaline reactant selected from the group consisting of alkali metal hydroxides and Where R and R have the above meanings, at a temperature between about 20 C. and about 100 C. and recovering said 1-thiocarbamyl-Z-imidazolidinethione.

16 6. 1-thiocarbamyl-2-imidazolidinethione. 7. 1-butylthiocarbamyl-2-irnidazo1idinethione. 8. 1-octylthiocarbamyl-2-imidazolidinethione.

l-dimethylthiocarbamyl-Z-imidazolidinethione. 10. 1-(3-oxapentamethylene) -thiocarbamyl-2-imidazolidinethione.

References Cited by the Examiner UNITED STATES PATENTS WALTER A. MODANCE, Primary Examiner.

DUVAL T. MCCUTCHEN, NICHOLAS S. RIZZO,

Examiners.

Claims

1. THE PROCESS OF PRODUCING 1-THIOCARBAMYL-2-IMIDAZOLIDINETHIONE OF THE FORMULA: 1-(R1-N(-R2)-C(=S)-),2-(S=),4,5-DI(R-)IMIDAZOLIDINE WHEREIN R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALKYL; AND R1 AND R2 ARE RADICALS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL OF FROM 1 TO 22 CARBON ATOMS, ALKENYL OF FROM 3 TO22 CARBON ATOMS, HYDROXYALKYL OF FROM 2 TO 22 CARBON ATOMS, CARBOXYALKYL OF FROM 2 TO 8 CARBON ATOMS, CYCLOALKYL OF FROM 5 TO 6 CARBON ATOMS, ALKYLCYCLOALKYL OF FROM 7 TO 22 CARBON ATOMS, ALKYLCYCLOALKYL OF FROM 7 TO 22 CARBON ATOMS, AMINOALKYL OF FROM 2 TO 22 CARBON ATOMS, PHENYLALKYL OF FROM 7 TO 22 CARBON ATOMS, ALKYLAMINOALKYL OF FROM 3 TO 22 CARBON ATOMS, DIALKYLAMINOALKYL OF FROM 4 TO 22 CARBON ATOMS, AMINOALKYLAMINOALKYL OF FROM 4 TO 22 CARBON ATOMS, AND, WHEN TAKEN TOGETHER WITH THE NITROGEN ATOM, PIPERIDINO, PYRROLIDINO, PIPERAZINO AND MORPHOLINO, WHICH COMPRISES THE STEPS OF REACTING A WATERSOLUBLE ESTER COMPOUND OF THE FORMULA: (Y-)M(CH(-Z))N-S-C(=S)-NH-(CH(-R))2-NH-C(=S)-SWHEREIN R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALKYL; Y IS A WATER-SOLUBILIZING GROUP SELECTED FROM THE GROUP CONSISTING OF -COOME AND -SO3ME AND ME IS AN ALKALI METAL; Z IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND HYDROXY; N REPRESENTS AN INTEGER FROM 1 TO 4; AND M REPRESENTS AN INTEGER FROM 1 TO 2, DISSOLVED IN AN AQUEOUS SOLUTION WITH THE STOICHIOMETRIC AMOUNT OF A COMPOUND HAVING THE FORMULA R1-NH-R2 WHERE R1 AND R2 HAVE THE ABOVE MEANINGS IN THE PRESENCE OF AN ALKALINE REACTANT SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND R1-NH-R2 (CH(-Z))N(-Y)M WHERE R1 AND R2 HAVE THE ABOVE MEANINGS AT A TEMPERATURE BETWEEN ABOUT 20*C. AND ABOUT 100*C. AND RECOVERING SAID 1-THIOCARBAMYL-2-IMIDAZOLIDINETHIONE. 7. 1-BUTYLTHIOCARBAMYL-2-IMIDAZOLIDINETHIONE. 10. 1-(3''OXAPENTAMETHYLENE)-THIOCARBAMYL-2-IMIDAZOLIDINETHIONE.