MXPA96004467A - Tionation procedure using phosphorus and elemental sulfur - Google Patents

Abstract

A novel process for the preparation of elemental phosphorus and elemental sulfur reaction products under reaction conditions wherein phosphorus and sulfur are combined in a premix at temperatures below the reaction temperature is described, the premix may contain a diluent which is preferably the product of the reaction, phosphorus pentasulfide can be prepared by heating the premix at reaction temperatures in which lower exothermic temperatures and reduced vibration are observed, organophosphorus and thionate products can be prepared by the reaction of elemental sulfur and elemental phosphorus together with an organic compound where the proportion of phosphorus and sulfur generally corresponds to P2S5, the procedure avoids the need to separately prepare phosphorus pentasulfide to prepare thioninated and organophosphorus compounds

Description

TION PROCEDURE USING ELEMENTARY PHOSPHORUS AND SULFUR This application is a continuation in the case of the application Serial No. 08/219, 227, filed on March 29, 1994. This invention refers to novel procedures for the production of sulfur phosphorus, forming a liquid mixture of sulfur and phosphorus. It maintains said material as a liquid and can be adjusted to provide a precise and safe feed to the reactor, to prepare said phosphorus sulphides, such as phosphorus phosphide.

BACKGROUND OF THE INVENTION The usual commercial method for preparing commercial quantities of phosphorus sulphides, in particular phosphorus pentasulphide, is to introduce liquid phosphorus and liquid sulfur with a liquid into a boiling mass, consisting of phosphorus pentasulide, to effect a continuous reaction between phosphorus and sulfur. The product can be removed from the reactor by continuous distillation of the reaction product. The control of the reaction is obtained by means of the addition of the reagents and the proportions in which they are being added. Said procedure is described in US 2,794,705 ,. of Hudson .. While the Hudson's total diet regime. If the reg- istration of the total active input is controlled mainly by observing the temperature of the reaction, the con- trol of the appropriate proportions of the reactant that is being added can only be provided, definitively, by the product lysis. General chicken of several hours is required to determine the result of readjusting the feeding regimes, the temperature, the residence time and the flushing regimes, based on the analytical work. Because the reaction of the forum and the sulfur is rapid and exothermic at the high temperatures commonly used, it has often been tried to make the reaction more controllable and efficient. In SU 1,301,774, the heat reaction of the phosphorus and sulfur reaction is monitored by conducting the reaction at a temperature of 130 ° 0 to 175 ° C and providing a sulfur phosphorus ratio of 3.5-4.0: 1, until that the temperature of e increase and then adding the phosphorus to give the desired quantity this desired step, that is, a ratio of sulfur to phosphorus of 5: 2. In another attempt to * control the e my en-t or to In the efficiency, a continuous-circuit reactor containing a liquid reaction mixture that is circulated with inuamente has been deaerated. The phosphorus and sulfur liquid reactants are introduced into the circuit, in order to prevent a large concentration of phosphorus from forming, feeding the phosphorus to the circuit at a point where there is a concentration of sulfur. The reactor forum in a gaseous state is described in US Pat. No. 5,198,202, Courant and co-inventors, there is a problem of vibration, due to the kinetics of the reaction between phosphorus and sulfur at these elevated temperatures, such as They are usually found when the product is removed by distillation.A solution to that problem is to use smaller reactors or to use a two-stage reactor * In a first stage, usually a small reactor, phosphorus and sulfur are fed at a rate that provide a phosphorus content of approximately 28% In a second stage, the desired amount of phosphorus is added to give the desired sulfur If during the first stage the reactor is operated At the boiling point of the mixture, in the second stage it is operated at a temperature of only 300 to 3530C Said procedure is described in the German patent of This 119,198, granted to Strauss. Even though the prior art *, noted in the foregoing, is directed to the improved safety of the procedure, other advances are necessary to give a truly efficient procedure, which is operated in a more secure and accurate manner.

BRIEF DESCRIPTION OF THE INVENTION An improved process for reacting phosphorus and sulfur in the molten state has been discovered, allowing efficient, safe and controlled reactions with greater precision; said improvement comprising providing a feed material for the reaction that is a premix comprising elemental phosphorus and elemental sulfur at relatively low temperatures and in predetermined proportions. Such mixtures of elemental phosphorus and elemental phosphorus have been known, but had not been never used as a feed material in a large-scale industrial process, incorporating phosphorus and sulfur reactions in the molten state. An example of such a reaction is the procedure for preparing phosphorus sui fi ures, typically in a continuous process, when sulfur and phosphorus are mixed at relatively low temperatures, below their temperature. This reaction, generally considered to be inferior to aligner. * of 120 ° C, a very fluid liquid can be formed .. This liquid is an atomic mixture of sulfur and phosphorus. These mixtures are described in the report of VV Ellapornov and I "I. Sol-olova, in Tzves, F? Z" Kh., 21, pages 153 - L58 (1952), also by R. Bouioch in Cornpt,. rend ,, pages 165-168 (1902) and by 'Van Wazer, Phosphorus and its Compounds, to o 1, page 289, Tnterscience, New York (1950).

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view of a possible system for forming the liquid premix material to be supplied * in a process for reacting sulfur and fo ore. Figure 2 is a phase diagram of the solids-Li-liquid ratio of the White phosphorus ezclas / sulfur at temperatures below about 100 ° C. Figure 3 is a phase diagram of the compounds produced in the reaction of phosphorus with sulfur, by * the temperature of activation.

DETAILED DESCRIPTION OF THE INVENTION In accordance with this invention, an improved process is provided for the production of the compounds resulting from the reaction of sulfur and phosphorus, wherein the improvement comprises providing a premix of elemental phosphorus and elemental sulfur at temperatures below the temperature of reaction of the aforementioned elements. The most obvious advantage of the present invention is that the phosphorus sulfide reaction operator prepares and rapidly analyzes, by the physical properties of a premixed feed mixture, the exact proportion desired in the phosphorus product. final. Analytical procedures are well known by which * the "mixture can be analyzed and corrections can be made to bring the mixture to the desired scale or to the exact ratio before entering the reaction. The refractive index, the viscosity and the ospection, such as infrared or visible light spectroscopy, are used, the exact proportions of phosphorus and sulfur will be dictated by the type of product desired, the product being widely used sulfur and, in particular, "phosphorus phosphate", Another advantage of the process of this invention, particularly in the production of phosphorus sulfides, is the reduction in the amount of vibration that occurs in the reactor, since the The pre-blended phosphorus and sulfur assures the operator that the occurrence of localized phosphorus concentrations will be less likely. the great opportunity to adequately sanitize the reagents of the premix, before introducing them into the reactor. A uniform mixture promotes the unbalance potential of the reactants in the reactor, eliminating the fundamental cause of most of the vibration commonly experienced in the action that produces phosphate pentasulide. The phosphorus and sulfur pre-mixture according to this invention is generally maintained at a temperature of 100 ° C or less, and is typically maintained at the scale of 30 ° C to 80 ° C,, -VDrox? Clam te, through typical files. I also know , hey keep the mixture under water, as it is known to trust the white phosphorus. Since said temperature scale is below the reaction temperature of these elements, that is, approximately 120 ° C, it is only necessary to protect the mixtures from the heat sources. However, for safety reasons, the containment tank and the transport lines are usually equipped with heating and cooling means to control * the temperature of the mixture. The phosphorus typically employed in the process of this invention is white phosphorus. Typically, phosphorus melts at 44.1 ° C and, therefore, easily combines with sulfur, (resulting in a mixture that remains easily in the liquid state.) Elemental sulfur also exhibits diverse allotropic forms, both in liquid phase. In the solid phase, the rhombic form cpstal? na melts at 112 ° C, while the monoclinic form melts at 119 ° C. There are three liquid forms of sulfur, known.The form of low temperature, SI, is supposed to be a ring of Eight members The Sp and Su forms are not well defined, their existence is well established.The Su form, for example, is not soluble either in carbon disulfide or in liquid phosphorus. As long as Sp can be short chain, equilibrium mixtures contain the forms of liquid sulfur L. When elemental phosphorus and elemental sulfur are mixed at temperatures of less than approximately 120 ° C, they do not react until start at temperatures ma Instead of reacting, they form alloys that are liquids that behave well at such low temperatures of only 10 ° C, depending on the proportion of phosphorus and sulfur content. The elements quickly dissolve in one another to form alloys, most of which are fluids, clear liquids, straw yellow color, even at room temperature. At a phosphorus / sulfur content corresponding to the pentasul phosphorus furo, the liquids crystallize to bright yellow crystals, at temperatures of 80 ° C. The phase diagram of these mixtures will be discussed below, with reference to the attached figure 2. Typically, in a process for the production of a common sulfide, such as P2O &, the proportion of the elements, by weight, is on the scale of 72% to 75%, approximately, of sulfur atoms, and of 25% to approximately 20% phosphorus atoms. Pentasul is widely used as an intermediate to fire a wide range of different compounds, such as insecticides, oil additives and rubber chemicals. Accordingly, one of the preferred prerequisites of this invention will contain phosphorus and sulfur in a proportion corresponding to said compound. A minor portion of the diluent for the phosphorus and sulfur mixture may also be included in the premix of this invention. Preferably, said diluent is the phosphorus sulfide which is to be produced in the reaction between phosphorus and sulfur in the molten state. For example, P2O5 can be employed as a diluent in the phosphorus and sulfur premix in the process for preparing phosphorus pentasulphide. Said diluent provides a love absorber of the exothermic temperature that occurs when the reaction temperature is reached. A minor portion * means an amount of up to less than 50% by weight of the total mixture; and usually it is on the scale of 2% to 35%, approximately, of the total mixture. Very typically, the amount of diluent P2O5 is on the approximate 2% scale % by weight of the total premix. It has been discovered that the diluent P2O5 allows the easy and rapid dissolution of phosphorus and sulfur, to a homogeneous mass. Other sulphides of phosphorus may also be used as diluents in the elemental premix Je phosphorus and sulfur, such as 'Ornpues os P2S and P2S3. These compounds can be found in low melting points and would help to put elemental sulfur and phosphorus in solution. A typical premix for production <Phosphorus phosphorus would comprise 72% 78%, approximately, of sulfur atoms; from 25% to 28%, approximately, of phosphorus atoms and from approximately 2% to 10% of phosphate pentasulide, all loreenta is by weight with respect to the premix. I: l P2 Ss solid added to the premix of phosphorus and elemental sulfur, allows the crystallization of the system to be a solid stable to air. Other compatible diluents can also be used to prepare the phosphorus and sulfur premix, such as carbon disulfide; but said diluent is usually removed by evaporation before reaching the reaction conditions, when the mixture is brought into the molten state. The use of said diluents is not preferred, since they increase the complexity of the reaction, as regards the recovery of the diluent. It is preferred to use the product to be produced as a diluent, since it is not removed from the product, avoiding the cost of recovery and recirculation. When preparing a premix of phosphorus and sulfur without a diluent, such As noted earlier, it has been found convenient to add solid sulfur to the molten phosphorus. This addition is most conveniently made. by passing molten water through a gaseous or liquid phase in the mixing chamber, to solidify the sulfur before it makes contact with the phosphorus layer, no reaction occurs and the sulfur dissolves. -e in the phase of molten phosphorus The typical refrigerants that are used for the purpose of reducing the temperature of sulfur and, thus, the mixing temperature, are water or gaseous carbon dioxide. addition allows for more rapid and uniform mixing of the two molten materials.While combining the materials in the molten state, and then melting the mixture within the scope of the present invention, such a process is not preferred, except for a small-scale operation. For large-scale operations, it is very convenient to mix each material in the molten state.In the preferred order of addition, indicated in the back, the most convenient and quick means to obtain the desired result is Adjust it evenly before allowing the procedure to proceed to the reaction conditions. Additionally, the premix may be allowed, after thorough mixing in the molten state, to be cooled to the fully solid state and stored for future use. By reheating the liquid state, the premix can be used in reactions involving phosphorus and sulfur. In another embodiment of this invention, the cooling or regulating medium is replaced by a reactive reagent in the reaction involving * sulfur and phosphorus or elementals. The sulfur is placed in the reactor and then the phosphorus is fed to the reactor, in a continuous manner Lacla. For example, instead of water or carbon dioxide in the mixing chamber, as a reagent or cooler, on the molten elemental sulfur, a reagent such as an alcohol or a mixture of alcohols, in contact with sulfur. The phosphorus 1 is fed into the system through the reagent layer. Fl phosphor passes through the reagent layer (alcohol) reaching the medium rich in liquid sulfur that lies below the alcohol phase. It has been discovered that, upon contact with the sulfur present in the sulfur-rich medium, which is maintained at the activation temperature, a reaction occurs involving not only phosphorus and sulfur, but also the reagent layer ( alcohol), thereby producing a compound of the type that is known to be produced by the reaction of phosphate pentasul furo and the reactant, such as alcohol or the mixture of alcohols. The reaction can be controlled by means of the phosphorus addition rate, in order to avoid excessive heating and other traditional problems that go into the reaction of the pentasul phosphorus furo and organic materials, such as alcohols. Secondly, the hydrogen sulphide stripping regime is also more easily controlled by the process of this invention. Because of this discovery, a process has been found to produce organic * phosphorus derivatives, without the need to prepare, in a separate system, the well-known intermediate: pent asu1 phosphorus furo. It is easier to describe the invention by means of the attached figures.

DETAILED DESCRIPTION OF THE DRAWINGS Figure L shows a possible way to practice the method of this invention. The reactor * in which the phosphorus and sulfur actually react is not rinsed, since such reactors are well known in the art and can be operated substantially as currently practiced in accordance with this invention. Figure 1 shows a closed tank 1, equipped with a means 5 3 consisting of an arrow and an impeller to agitate the lower portion of the contents of the tank. The transmission means for the medium 3 is not shown and can be any known phosphor drive means. Molten sulfur is introduced into the tank through conduit 5.

Typically, molten sulfur is maintained at around 50 ° C, it is expected to give fluidity for handling purposes. The upper portion 7 of tank 1 contains an inert atmosphere with respect to molten sulfur, such as carbon dioxide or nitrogen. Under the inert atmosphere of portion 7, there is a layer of cooling medium 9, conveniently water or other means of inlay, through which the molten sulfur, as indicated by the particles 11. The cooling medium 9 is a liquid in the which both sulfur and phosphorus are substantially insoluble. When the particles of molten sulfur pass through the cooling medium 9, are fiery cooled remain in the amorphous state. Cooling medium 9 is maintained at a temperature in the range of 60 ° C to 70 ° C, approximately, and typically at f * 5 ° C "At a convenient point below portion 7 of the tank is '?: located the duct 13, which is provided with the intention of introducing phosphorus into the tank 1. Also the phosphorus is kept in a state. Sulfur and phosphorus combine in the tank, in area 15 below the cooling medium layer. By means of the agitation, shown in Figure 1 with a transmission shaft and the impeller 3, the sulfur and phosphorus are mixed thoroughly before they are discharged from the tank through the conduit 17, by means of gravity or by mechanical pumping (not shown). The conduit 17 is associated with a reactor in which the sulfur and phosphorus are reacted at elevated temperatures, typically in the range of about 120 to 125 ° C. Typically, the reactor allows the phosphorus sulfide to be distilled from the reactor by any suitable reactor known in the art to be used for those reactions, including those in which the reaction product is removed as a liquid or as a liquid. solid. While in the 15th area of the tank, phosphorus and sulfur are not only mixed per se, or that said mixture is also inspected, it will be necessary to determine its consi • tion. It may be provided to optically examine the mixture, or otherwise. It is also possible to use ducts associated with the tank 1 to extract, periodically or continuously, samples of the mixture for analysis. One such constant analysis scheme is described in U.S. Patent 5,260,026 to F Id and co-inventors, and such a description is incorporated herein by reference. The present system is not recommended to be used with laser spectroscopy, such as that which can be used * in the tank described in the cited patent. The energy introduced in the present system must be carefully controlled and limited in order to avoid the initiation of a reaction between phosphorus and sulfur that, once initiated, would sustain itself. In accordance with the results of the analysis of the mixture in the area 15 of tank 1, the amount of sulfur or phosphorus can be varied to give the precise proportion of the desired mixture. Typically, the area 15 of tank 1 is large enough to allow * a certain amount of retention time in tank 1, so that adjustments can be made to the phosphorus or sulfur feed rates. Another advantage of the method of the present invention lies in the fact that the size of tank 1 is minimized, in order to provide a small amount of phosphorus and sulfur premix stocks. Since the materials that are being handled are in a liquid state, the procedure is easily carried out with pumps, at controlled regimes and with mixtures that do not leak until placed in a suitable reactor, which can also be * Immuno size Figure 2 shows a phase diagram indicating mixtures of white phosphorus and sulfur, at temperatures below about 100 ° C. In figure 2, the abscissa indicates the percentage amount of (atoms of) phosphorus in The ordinate indicates the temperature in degrees C. Line 1 of Figure 2 defines the lowest temperature of the fully liquid (melted) mixtures, as shown in Figure 2, a 74-degree eutectic mixture occurs. o-percent of phosphorus having a liquid temperature of 9.8 ° C. In area A of Figure 2, solid solutions occur that have the same crystal structure as the S molecule. Solids solutions occur in area B of Figure 2. in the The crystal structure is the same as in the Pi molecule. In the C area of Figure 2 there are solid solutions that are T ezclas of crystals of both types, A and B. In area D of Figure 2 variable quantities of type A crystals are found in a liquid medium, with the amounts of crystalline material dependent on temperature, as shown by line 2. In area E of figure 2, crystals of type B occur in the liquid , wherein the amount of the crystals depends on the temperature, as indicated above in line 3. In the improved procedures of this invention, all of the mixtures shown in Figure 2 are useful. The liquid mixtures in areas D and E of figure 2 are easily handled, while the mixtures of areas A, B and C are solid. However, the reactions in which phosphorus and sulfur become part are normally conducted at emperatures that would render liquid or almost liquid to all the mixtures described in figure 2. Figure 3 shows the phase status of the products of reaction of phosphorus and sulfur. It is seen that the phases The strength of said compositions varies according to the amount of phosphorus in the system, with polymorphs evident on the sulfur-rich side of the system. In part, figure 3 is taken from the diagram of R. Forth ann and A. Schneider, Z. Physi.

Che .. (49), page 22, 1966, with additional information pertaining to the sulfur-rich compositions that have less than the amount of phosphorus required for the pentasul phosphorus furo. It is shown that a composition having 79% phosphorus is a liquid that does not solidify until reaching temperatures of more than 50 ° C below and 0 ° C.

TIONATION REACTIONS As will be shown below, by the various working examples of this invention, the process of this invention provides a wide range of reaction reactions. Previously said reactions employed an organic reagent, such as a sulphide of apolonophosphine, typically, 2,4-furan disulfide of 2,4-fc > Ls (? -? Netox? Fem l) -1, 3-d? T? Ad? Fosfetano, also known as "Lawessen reagent". The reaction reagent was prepared by reaction of an aplo compound, such as aniso, and phosphorus pentasulide. A full discussion of this reagent and its variations, as well as its various uses, is given in an article that appeared in Tot rahed on, volume 41, No. 22, pages 10. £ .061-5087 (1985), by M. P. Cava and I. I. Levinson, which is incorporated here as a reference. It has now been discovered, in accordance with this invention, that elemental phosphorus and elemental sulfur can be directly employed to prepare useful compounds such as petroleum additives, rubber chemicals, synthetic intermediates and insecticides, by direct reaction with the organic material. appropriate, elemental sulfur and elemental phosphorus, in the presence of an organic precursor of Lawessen's reagent, without the need to separately form the previously known intermediate, the reactant of l.awessen. In accordance with the process of this invention, the need is avoided not only to prepare the pentasul phosphorus furo, but also the need for an intermediate prepared by the reaction of an organic precursor of Lawessen and pentasul phosphorus furo, to supply the reactant. ivo of I. awessen. In general, the process of this invention comprises the reaction of elemental phosphorus and elemental sulfur in amounts corresponding generally to P2O5 which, as noted above, is usually on the weight scale of about 72% to 75% of Sulfur atoms and from about 25% to 28% _ of phosphorus atoms, with an organic compound that is going to thio ar, in the presence of an organic precursor * of a Lawessen reagent. Typically the reaction mixture comprises elemental sulfur, an organic compound to be thionated and an organic precursor of Lawessen's reagent. This reaction mixture is usually heated under an inert atmosphere, and elemental phosphorus is introduced into the reaction mixture. The reaction mixture is raised to a sufficient degree to cause elemental phosphorus and elemental phosphorus to react. Typically, the temperature of the reaction is from 115 ° C to 125 ° C, approximately. Once the reaction is started, the temperature is usually controlled by the rate of phosphorus addition. Combine an organic precursor reagent typically used to prepare a Lawessen reagent, under conditions that allow the reaction of elemental phosphorus and elemental sugar and an organic reagent to be run, provide a product 0 r an i co t ion. Typical organic materials are described in 1 to puh 1 cation before annotated, as reactive organic precursors to form various reagents of .awessen, by reaction with pentasul furo de fosforo. Said aromatic materials include: amsol, naphthalene, methoxybenzene, ethoxy benzene, toluene, naphthalene, etc. The reactions which previously involved a Lawessen reagent for thionation can now be carried out according to this invention, using the organic precursor reagent of Lawessen reagent, noted above, elemental phosphorus, elemental sulfur and the organic material which is leaving. at lori *.

Any number of organic compounds according to this invention, which includes the aromatic and aliphatic ketones which are converted to the corresponding thioketones, can be processed. Other organic compounds include the Grignard reagents, the amines, the alkoxides and the hydrazones which, in the process of this invention, produce dithiophosphonic acids, dithiophos phonocarides, dithiophosphonates and diaza osfoli as, respectively. The esters and the lactones substituted with 0 and with S, thioester, diesters and thiones are also converted, using the organic precursor reagent of Lawesson's reagent, elemental phosphorus, elemental sulfur and the organic material to be tilled. The Llainids, alkylamides, aryl-lactams, alkyl lactams and amides and lactase unsaturated, can be transformed to their corresponding analogs by the process of this invention, in which the Organic H-ecursor of Lawesson's reagent, elemental phosphorus, elemental sulfur and organic material to be transformed *. There are many examples of t -carboxyboxinides in the above-noted publication, by M- P. Cava and r. T. Levmson, which can now be prepared by the process of this invention, by deriving the preparation and use of Phosphorus phosphorus fure or Lawessen reagent. It can be prepared * < Hydroxy substituted hydroxybenzamines and an organic precursor of Lawessen's reagent, elemental phosphorus L and elemental sulfur. In a similar manner, substituted and unsubstituted beta-iolactans are prepared from beta-lactams; enaminot canvases, from enammonas; hydrides from hydrazides; Hydroxy ipdazines and hydroxypyridazones are formed to rnercaptopipdazines and rnercapt opipdazones; ureas to thioureas; and the amide thiones that give t? oran? Jas. Rather, any reaction in which the l.awessen reagent is used with an organic compound to be thionated, can now be placed with the process of this invention, in which elementary phosphorus is reacted, elemental sulfur, an organic precursor of Lawessen's reagent and an organic compound to be thionarinated. Pesticides according to this invention can be conveniently synthesized by means of the reaction of alkyl or alkyl alcohols. co with elemental phosphorus and elemental sulfur, to produce dialkyl fos forodit IOICO acids. In most cases, the alcohol is placed in an appropriate filter, along with elemental sulfur, and elemental phosphorus is added to the reactor. By heating the contents of the reactor to an activation temperature, so that the elemental sulfur and the elemental phosphorus react, phosphorodithioafo is formed according to the type of alcohol used. (In suitable reactor is usually equipped with reflux condenser, means to provide * an inert atmosphere and heating means.) Most alcohols are high boiling point, that is, boil above the activation temperature of elemental phosphorus and elemental sulfur, in such cases, the reaction occurs directly and efficiently when the sulfur / fossil gold activation temperature is reached, however, in the case of lower boiling alcohols, such as methyl alcohols, Ethyl and propyl, including their isomers, The initial reaction temperature is kept slightly below the boiling point of alcohol, although the reaction rate at lower temperatures is relatively low, as the production of dialkyl acids proceeds. phosphorodi thioics or their esters, increases the boiling point of the reaction mixture, allowing an increase in the temperature of the reaction. n, thereby increasing the reaction rate. It is preferred to use the phosphorus and sulfur premix described above with the low boiling alcohols., instead of the independent addition of each element to the reactor. Typically, alcohols which have 1 to 20 ring atoms are commonly available and are useful in the process of this invention, however, any alcohol that can be made liquid reaction temperatures, from OD to 350 ° C, it can be conveniently employed in the methods of this invention. The addition of the apical and alkyl acids can also be effected in accordance with this invention of the invention similar to that described above, with respect to the alcohol. It has been found that elemental phosphorus and elemental sulfur in a proportion generally corresponding to that of P2O5, results in thioacids of the process. Commonly available acids include: benzoic acid, alkyl acids, wherein the alkyl group contains from 1 to 20 carbon atoms, polynuclear aryl acid, including naphthoic acid. Also included are aplo substituted alkyl acids, such as substituted or unsubstituted phenoxy acetic acids.

THE REAGENT OF NOKES In US Pat. No. 2,811,255 a processing aid for the recovery of metals from ore had been described; and said patent is incorporated herein as a reference. The processing aid is used as a depressant reagent and at the same time as a r * eact LVO detergent, which reduces the formation of foam, and which also improves the recovery of the metal. According to the patent, the processing aid * is sodium thiophosphate, which is prepared by dissolving sodium hydroxide in water, and then adding pentasul phosphorus furo. This mixture is stirred until the sulfide is completely dissolved. Typically, flow media is provided to maintain the temperature of the mixture below the boiling point. Hydrogen sulfide is released as the thiophosphate is formed. This very efficient reagent takes its name from the inventor of the aforementioned US patent. In accordance with that invention, the Nokes reagent is prepared by introducing sulfur into an aqueous caustic solution and then introducing phosphorus into the sulfur layer with sufficient heat to initiate a reaction of phosphorus and sulfur. The contact with the aqueous caustic solution is avoided by transferring the phosphorus to the sulfur layer, where it reacts at the activation temperature. The addition of phosphorus is controlled so as to control the reaction rate and the resulting reaction temperature as the reagent is formed. The process of this invention, in such a manner, avoids the need to prepare the pentasul. phosphorus furo, its shipment, storage and handling.

ALTERNATIVE PROCEDURES Due to the wide variety of organic and inorganic compounds which are used in the process, various methods of addition should be employed, The above processes can be operated in various ways and in various ways, according to this invention. Since the reactivity and physical properties of the various reagents with respect to phosphorus and sulfur are well known, it can be said that "sulfur or phosphorus can be added to a suitable reactoid, in any order, or together, in a premix, as noted above, with respect to the process for preparing phosphorus sulphides, said modifications include reversing the addition, that is, adding the sulfur to a suitable reactor containing the phosphorus and the other reactants. The foregoing describes the invention in general, and a more complete understanding can be had by reference to the following specific examples, which are given herein for illustrative purposes. only, and does not trust -imitate the scope of the invention.

DESCRIPTION OF THE PREFERRED MODALITIES EXAMPLE 1 It was placed in a flask equipped with two side arms and a heating mantle, 0.2782 g of sulfur, O.L075 g of phosphorus and 0.154 g of pentasul f? R * o of phosphorus, while the flask was being swept with nitrogen. A thermocouple was placed in the flask to monitor * the temperature of the contents. With the flask covered with a continuous nitrogen purge, the flask was heated, thereby melting the contents to a homogeneous solution. Then this solution was heated to 124 ° C, (after which an exothermic reaction occurred which raised the temperature at 225 ° C. After cooling the product was analyzed by X-ray diffraction, which indicates that it was produced in the reaction P2O5 EXAMPLE 2 It was placed in a flask equipped with or described in Example 1, 0.112 g of phosphorus and 0.3 L53 g of sulfur, which are the correct proportions for P2 O5. With a constant purge of nitrogen and with the flask covered, the contents were heated to a temperature of 77.5 ° C, which resulted in the formation of a liquid mixed mixture in the flask. Then that mixture was heated to a temperature in the range of 119 ° C to 122 ° C, approximately, resulting in an exothermic reaction. The heating medium was switched off and the reaction raised the temperature of the contents to 520 ° C. Pentasul phosphorus furo was produced.

EXAMPLE 3 To a calibrated flask was added as described in Example 1, 0.1210 g of phosphorus, 0.3 L47 g of sulfur and 0.0285 g of P2O5. The contents were slowly heated to make the materials a molten mixture. The mixture seemed to melt. After the melt was mixed thoroughly, the temperature was raised to the scale of L17 ° C to 122 ° C, which initiated an exothermic reaction. The heating was discontinued and the contents of the flask reached a temperature of 248 ° C. Pentasul furo (Je phosphorus.

EXAMPLE 4 A series of experiments was carried out to determine the safety of the premix of elemental phosphorus and sulfur. The mixtures contained the proportion of phosphorus and sulfur corresponding to pentasul phosphorus furo. Various mixtures of the pre-ormed pentasul phosphorus phosphorus compound were added to these mixtures. After mixing perfectly in the molten state (Jo, the mixtures were cooled to room temperature, solidifying them in that way.) The mixtures were then exposed to the air at room temperature (approximately 22 ° C) "The results of these experi These appear in the following table I. In table T, the amount of P2O5 is given in percentage by weight with respect to the total of the mixture.

TABLE I % of P2O5 Comments on nature Mue t i -a added. Phosphoric Control Nothing spontaneously burned at room temperature. 1 4.0 Do not smoke at room temperature. 2 4.0 It does not burn at room temperature. 3 4.0 Does not burn at room temperature 4 2.0 The environment is not burned to the ground 6.0 Does not burn at room temperature 6 8.5 The environment is not burned From the data in Table T above it has been shown that the premix compositions of this invention, which contain P2O5 at doping levels, are not pyrophs at room temperature. The utility of the pre-rimmed feed material, provided in accordance with this invention, is increased by the pacification of an otherwise gold-bearing material.

EXAMPLE 5 A series of experiments was carried out to demonstrate the reduced exotherm that occurs in the reaction of phosphorus and sulfur, in the process to produce pentasul phosphorus furo. Mixes of phosphorus and sulfur were prepared and mixed with various amounts of P2O5. After mixing thoroughly in the molten state, the mixtures will react to produce pentasul phosphorus furo in a round flask, equipped with a temperature sensing means and a heating mantle. The beginning of the temperature and the maximum exotherm temperature of the adiabatic reaction were observed. The indication of the character * of the reaction was also noted. The data and observations are summarized below in Table II, where the amount of phosphorus phosphorus is given as a percentage by weight with respect to the total mixture and the temperature is given in degrees Celsius.

TABLE II % in Temp, Temp. Sample weight i ni - of exo Comments P205 cial terrna Control nothing 119 520 Explosion and fire Control nothing 121 580 Explosion and fire 4. 0 124 225 No explosion or explosion, rapid evaporation. 2 P; 120 236 > explosion or fire, rapid evaporation, 6. 50 122 248 No explosion or explosion, rapid evaporation.

From the data in Table TT, it is shown that the exotherm temperature (the maximum temperature "stable" during the adiabatic reaction) of the reaction producing P2O5 is reduced to approximately half that of the uncombined mixtures, and that the Reaction nt vo place * with explosion and fire. From the above it is seen that the procedures that involve the reaction of phosphorus and sulfur in the molten state can be carried out at lower temperatures and with greater safety than previously known.

EXAMPLE 6 The premix of this invention was employed in a reaction involving phosphorus and sulfur in the molten state, where dialkyl phosphoroditic acid IOICO was directly produced by incorporating an appropriate amount of an alcohol into the molten mixture of elemental phosphorus and elemental sulfur. A 10 ml 2.4023 g of an oxoalcohol (a mixture containing alcohols to the 7 and 3 carbon atoms) was placed in a flask. The alcohol mixture was boiled without a reflux condenser at 105-110 ° C dur-ante 2 to 4 minutes, under nitrogen, to remove water and impurities (low boiling point) After the purification step, only 2.3791 g of alcohol remained, the purified alcohol was cooled to 40 ° C and combined with 0.7303 g of quality sulfur. of reagent. This mixture was stirred at the efflux and in a nitrogen atmosphere (for five minutes, at a lower temperature * at 30 ° C. Then it was transferred to the mixture of sulfur and alcohol 0.2841 g (white dry phosphorus phosphorus). It was mixed perfectly under nitrogen atmosphere, for 15 minutes.

The stirred mixture was slowly heated to a temperature of 107-114 ° C for two hours, and then the temperature was raised to the 115-L22 ° C scale to increase the speed of the reaction and to ensure complete reaction of the mixture. As the reaction proceeded, hydrogen sulfide was released and removed from the top, the reaction was ompleted in about 5 hours, and it was found in this reaction that it was critical to control the reaction to maintain the temperature below 114 ° C during the first two hours The higher temperatures during this time resulted in an exothermic reaction that was very difficult to control Fl product, a liquid containing a small amount of white / yellow silver crystals , at room temperature, it was analyzed by NMR with 14P, which indicated that it contained 89% by weight of pure dialkyl phosphorodic acid, which is surprising because it reacted In the prior art, said alcohols with P2O5 formed gave an average yield of 80% of the desired product. A series of reactions was carried out as described above, with various amounts of excess alcohol and a slight adjustment in the phosphorus content of the premix composition. The pre-mixture (elemental phosphorus and elemental sulfur generally corresponded to that of pentasul phosphorus furo) The percentage yield on the quantity of product desired in the final reaction mixture is based on the following table III. the result of a typical commercial production operation, in which the alcohol is reacted under the typical conditions of the prior art, with preformed phosphate pentasul furo.

TABLE III % of excess% of yield - Show% of P of alcohol Commercial - 18 «78.18 1 27.85 2.7 * 87.91 2 27.05 4.0 * 89.40 3 27.05 4.0 * 06.18 4 28.00 6.50 76.45 28.00 nothing 88.73 6 28.00 nothing 81.08 * Approximate amount. From the above data it is seen that a small excess of alcohol above the stoichiometric amount provides the maximum yield of the desired product.

EXAMPLE 7 The procedure of Example 6 was repeated, except that a series of different alcohols was used. In all operations, the phosphorus content was 27.00%, based on the total amount of phosphorus element l and sulfur at the end. The amount of excess (ie, alcohol at or below the stoichiometric amount, in each operation, is shown in the following table.) The yield shown in the table is based on the theoretical yield of the acid. ialquil fo forodit IOICO produced.

TABLE IV Ope ra% of% of alcohol Excessive alcohol di-LC) Num. Of alcohol mee n to L n-butanol 2.10 82.07 2 2-et l-l-hexanol 2.20 97.50 3 n- pentanoi 3.20 82.51 L5 4 n- pentanoi 2.30 82.66 LSO -oct anol 2.60 93.54 b n-pent ano! 2.80 81.37 7 n-pent anol -1.20 78.60 8 40/60% by weight / weight of n- 0 pentanol and isobutanol 2.20 88.14 9 n-but anus! 2.50 79.8 n- hexanol 2.30 80.00 11 20/40/40% by weight / weight of opropanol / i obutanol /? -! et il -1-hexanol 4.80 98. 0 EXAMPLE 8 A stirring bar, 12.5 g of reagent-grade toluene, 5.37 g of anisole (an organic precursor of the reagent of the reagent) were placed in a 50 ml round bottom flask. ? essen), 3.57 g of 3, 2-p? p dazona and 3.38 g of sulfur. The flask was equipped with a reflux condenser and then the mixture was stirred under a blanket of nitrous nitrogen for 10 minutes. Then 1.2810 g of phosphorus was added to the flask, with vigorous stirring, for another 15 minutes, under inert atmosphere, at room temperature. The addition of phosphorus is controlled, which acts as a control, confirming the reaction. By continuing to mix the atmosphere and the inert atmosphere, the temperature of the contents of the r * r * az was raised to a scale of 115-127 °. C for seven hours, resulted in the formation of dark emerald green crystals of 3 -inercaptopy r *? dazina, which was recovered for the purpose of mining < I gave him a gift.

EXAMPLE 9 The procedure of Example 8 was repeated except that the 3,2-pipdazone was substituted for an equivalent amount of 3,6-dihydroxy pyrazole. The reaction resulted in the production of cr *? st ales dark orange of 3,6-dunercapto í r Ldazi n,.

EXAMPLE 10 It was placed in a round bottom flask, 25 rnl, 6.57 g of rn-cresol, which was heated to a temperature within the range of 104 ° C to 108 ° C, to remove the water. The remaining rn-cresol weighed 6.42 g. 2.35 g of sulfur was added to the cresol at a container temperature of less than 37 ° C. The mixture ba or inert nitrogen atmosphere was stirred and the flask was fitted with a reflux condenser, while maintaining the temperature below 30 ° C. Then 0.91 g of white phosphorus was quickly added to the flask, after which the system was purged to ensure an inert atmosphere. The temperature was then increased to about 104-105 ° C and maintained for about 5 hours. The warm-up was interrupted during the night and resumed at a scale of 110-120oC for a further 1:45 hours. A reaction occurred, as indicated by the cjespi endimient or hydrogen sulphide and the removal of phosphorus and sulfur from the flask. It became evident that a diarylphosphorodium thioic acid was produced.

EXAMPLE 11 . 10.3 g of p-nonyl-inenol was placed in a 25-milliliter flask. The material was heated under an inert atmosphere of nitrogen, with stirring, at a temperature within the range of 105 ° C to 0 ° C during * 5 minutes, to remove moisture, thereby reducing the weight from the alkyl phenol to about 10.2 g. After cooling the alkylpheni below 37 ° C, 1.82 g of sulfur was added to the flask while stirring. The flask was fitted with a reflux condenser and the mixture was heated under a nitrogen atmosphere at a temperature below 32 ° C. Then 0.7 g of phosphorus was added to the flask and the inert atmosphere was restored. The flask was allowed to cool to room temperature. Heat was applied to the flask and the temperature was raised to 113 ~ 1L5 ° C for one hour. Hydrogen sulfide started to come off the flask as the temperature increased \ gt; above about 99.8 ° C and increased in amount as the temperature increased. The temperature was then increased to the range of 118-123 ° C for two hours. After stopping overnight, the system was reheated to the 118-125 ° C scale for 1:40 more hours. Phosphorus and sulfur were no longer visible, and ciparecio that an acid diap Lfosforodit i OJ CO.

EXAMPLE 12 A 6.94 g hexanoic acid was placed in a 25 ml round bottom flask. The acid was heated to boiling, and then cooled to below 35 ° C, giving 6.8 g of hexanoic acid in the flask. 1.86 g of sulfur was quickly added to the flask, followed by stirring under a nitrogen atmosphere, for a period of 10 to 15 minutes. then 0.72 g of white phosphorus was added and the mixture was heated under nitrogen, with stirring. The temperature was raised to 1QI-103 ° C for one hour, as hydrogen sulfide began to fall off and then to 104-110 ° C for another seven hours, at which time all the phosphorus and all the sulfur seemed to have reacted. . It became evident that thiocarboxylic acid was produced.

EXAMPLE 13 It is charged to a reactor equipped with a reflux condenser, a heating mantle, a stirring medium and a reliable medium to supply * an inert nitrogen atmosphere, 3.5488 g of isopropyl alcohol and 2.2360 g of sulfur. This mixture was stirred for 15 minutes under an inert atmosphere and with reflux conditions. Then, 0.8780 g phosphorus was quickly introduced into the mixture and the agitation continued. The temperature of the mixture when the phosphorus was added was approximately 73 ° C and rose gradually over a period of two hours to 76 ° C "Hydrogen sulfide started to be released from the reactor, with orme the temperature increased to 73 ° C, and increase in volume as the temperature increased. After two hours the temperature rose slightly above 80 ° C for 1.5 hours to 82 ° C. Then, when the desired quantity of product was increased in the reaction mixture, the temperature was increased to 86 ° C and it was maintained at that temperature for another 11 hours. All the phosphorus and all the sulfur had disappeared and the reactor temperature was increased to the 130-132 ° C scale. The analysis of the reaction mixture by proton nuclear magnetic resonance indicated a yield of 85% of the theoretical, based on the amount of alcohol employed.

EXAMPLE 14 The procedure of Example 13 was repeated, except that isopropanol was replaced by ethanol. An excess of 7% ethanol was used, which totaled 3.8990 g, and a phosphorus premix was added to the reactor. / sulfur. The premix amounted to 3.3712 g, which consisted of 0.9355 g (Phosphorus and 2.4357 g of sulfur) After preheating the alcohol under inert atmosphere for 15 minutes in the reactor *, the prezet was added at room temperature. slowly heated the reaction mixture with the following profile.- Temperature scale Time ° C hours. 78 -. 78 - 81.5 5 82 - 87 3 90 - 105 2 102 - 130 1 The pre-mixture disappeared from the reactor * after about 10 hours of reaction time, after which the temperature rose rapidly during the last hour. The analysis of the reaction mixture indicated that it contained the dimethyl phosphorodi tioate thioster in a yield of 60% of the theoretical, based on the amount of phosphorus used. Although the invention has been described in terms of specific modalities that are pointed out in considerable detail, it should be understood that this description is given by way of illustration only and that "E > The invention is not necessarily limited to it, given that alternative modalities and techniques of operation will be evident to those who are experts in the field, in view of the description. Consequently, the modifications that can be made are contemplated without departing from the spirit of the invention described.

Claims (3)

1. NOVELTY OF THE INVENTION CLAIMS 1. A process for preparing organotin compounds, characterized in that it comprises the steps of: (a) introducing into a suitable reactor, under an inert atmosphere, an organic compound to be thionated and an organic precursor of Lawessen's reagent; (b) adding to the reactor at least a stoichiometric amount of elemental sulfur and at least an amount of elemental phosphorus to react with said stoichiometric amount of sulfur, while heating the contents of the reactor to a temperature such that react sulfur and phosphorus, thereby thickening the organic compound; and (c) recovering the product returned from the reactor.
2. 2. The process according to the invention, characterized in that the organic precursor (Lawessen's reagent is a compound of type 3. The method of confounding with claim 2, further characterized in that The process according to claim 1, further characterized in that elemental sulfur is included in the reactor, in step (a) and the speed of the reaction by the Adding regime of the forum e1 ement a1., 5.- A process for preparing a compound selected from the group consisting of 3-merca? to r *? daz? na and 3,6-d? mercaptop? pdaz? na, characterized in that it comprises reacting the corresponding pyridazone or pipdaizine with elemental phosphorus and elemental sulfur, in the presence of an organic precursor of the Lawessen reagent, under an inert atmosphere, above the activation temperature of the reaction of the phosphorus and the sulfur. 6.- A procedure according to claim 1, further characterized in that the organic compound to be thionarinated is selected from the group consisting of the Gpgnard reagents, amines, alkoxides, harmful dyes, pipdazones and hydrazones, to produce the dlt lofosfmicos acids, fos onoami odi tionat os, di tjofos fonat os, fupdaizinas and diazafos f olí as correspondien es, - respectively. 7. The process according to claim 1, further characterized in that the organic compound to be thionarinated is selected from the group consisting of aryl- and chylketones; alkyl and aryl alcohols; laetamas, ara lmides, alkylamides, benzides substituted with hydroxy, beta-lactains, enarnmons and benzamides, to produce the thioketones, tosforodithioates,, iolactams, thioarnides, thiobenzamides substituted with hydroxy, beta-t-lactamas, narninot and Corresponding thiobenzates, r especivarnent e. 8. A process for preparing a dialkyl phosphorodithioic acid, characterized in that it comprises: (a) combining an alkyl alcohol with sulfur elementa and phosphorus eLernental; sulfur and phosphorus being present in amounts generally corresponding to those of P2? s; (b) heating the mixture of (a) to a temperature that causes the sulfur and phosphorus to react; and (c) recovering from the reaction mixture a dia-L-phosphodiesforodithioic acid. 9. The process according to claim 8, further characterized in that the mixture of step (a) contains an excess etch of alkyl alcohol. 10. The process according to claim 9, further characterized in that the alcohol is a mixture of alcohols to the chirals of 7 to 9 carbon atoms. 11. A process for the production of diakyl phosphorodic acid, characterized in that it comprises: providing a reactor * containing a lower layer (elemental sulfur) under a layer of liquid alkyl alcohol, of high boiling point, and contact with it, admit elemental phosphorus into the reactor and pass it through the layer of alkyl alcohol, which comes into contact with the sulfur layer at a reaction temperature of sulfur and phosphorus, which occurs a reaction entered the phosphorus, el and alcohol, which produces dialkyl phosphoroditic acid IOICO. 12. The process according to claim 11, further characterized in that the alcohol is selected from the group consisting of n-but anol, 2-ethyl-1-hexanol, n-pentanol and isooctanol. 13. A process for the production of a dialkyl dithosothioate, characterized in that it comprises: mixing an alcohol selected from the group consisting of methanol and ethanol with elemental phosphorus and elemental sulfur; wherein the amounts of phosphorus and sulfur generally correspond to those of P2O5; wherein a prerequisite of phosphorus and sulfur is added to the alcohol in a suitable reactor * and the <1 is raised. The temperature is up to the activation temperature for the reaction of phosphorus and sulfur. 14. A process for preparing sodium phophthous, characterized in that it comprises combining in a reactor-suitable elemental sulfur and sodium hydroxide; then add elemental phosphorus to the reactor in a ratio of sulfur to phosphorus which generally corresponds to that of P2O5; and heating the contents of the reactor to such a temperature that the sulfur and phosphorus react. 15. A process for preparing diaphophosphorodithioic acid, characterized in that it comprises combining in a suitable reactor a compound substituted with hydroxy, substantially anhydrous and elemental sulfur and phosphorus "< The reactor contents are heated to a temperature at which the phosphorus and sulfur react; the proportion of phosphorus and sulfur generally corresponding to that of P2O5. 16. The process according to claim 15, further characterized in that the aplo compound is rn-cresol. 17. The process according to claim 15, further characterized because the aplo compound is fi - non? 1 phenol. 18. A process for preparing a thiocarboxylic acid, characterized in that it comprises combining with sulfur a substantially anhydrous carboxylic acid, in a suitable reactor, under inert atmosphere, and then phosphorus is added to the reactor, while the contents of the reactor are heated to the reactor. a temperature at which 1 sulfur and phosphorus react; the proportion of phosphorus and sulfur corresponding to the 2OS. 19. The process according to claim 18, further characterized in that the carboxylic acid is hexane ico acid. SUMMARY OF THE INVENTION A novel process for the preparation of products of the reaction of elemental phosphorus and elemental sulfur is described under reaction conditions wherein phosphorus and sulfur are combined in a premix at temperatures below the reaction temperature; the pre-mixture may contain * a diluent that is prefera bly the product of the reaction; phosphorus pentasulfide can be prepared by heating the premix at reaction temperatures in which lower exothermic temperatures and reduced vibration are observed; organophosphorus and thionate products can be prepared by the reaction of elemental sulfur and elemental phosphorus together with an organic compound wherein the proportion of phosphorus and sulfur generally corresponds to P2 S5; the process avoids the need to prepare phosphorus pentasulphide first to prepare thioninated and organophosphorus compounds. P96 / 660F AMENDED CLAIMS PURSUANT TO ARTICLE 19 OF THE PATENT COOPERATION TREATY. b 1. A process for preparing thionic organic compounds, characterized in that it comprises the steps of: (a) introducing into an appropriate reactor *, under an inert atmosphere, an organic compound to be thionated and a precursor Lf) organic (Lawessen's reagent Jel; (b) add to the reactor at least one stoichiometric amount of elemental sulfur and at least a quantity of elemental white phosphorus, to react with the amount equiomet r *? sulfur, while heating the contents 15 of the reactor- at a temperature at which the sulfur and white phosphorus react; tjonando that way the organic compound; and (c) recovering the reactor from the product being pressed. 2.- The procedure of conformity with the reivmdi-20 cacion 1, also characterized because the organic precursor of Lawesson's reaction is a compound of aplo.
3. 3. The method according to claim 2, further characterized in that the sun-activated compound. 2! \ 40 4. The process according to claim 1, further characterized in that elemental sulfur is included in the reactor in step (a) and the reaction rate is controlled by the addition rate of the elemental white phosphorus. 5. A process for preparing a compound selected from the group consisting of 3-rnercapt opipdazi na and 3,6-d? Rnercaptop? R? Daz? Na, characterized in that it comprises reacting * the corresponding pindazone or pyridaizm with white elemental phosphorus and elemental sulfur, in the presence of an organic precursor of Lawessen's reagent, under an inert atmosphere, above the activation temperature of the reaction of white phosphorus and sulfur. 6. A process according to claim 1, further characterized in that the organic compound to be thionarinated is selected from the group consisting of the Gpgnard reagents, amines, alkoxides, pipda inas, pipdazones and hydrazones, for to produce the phosphoric ditic acids, phosphonates, dodithromes, dith phosphates, pyridazines and diazaphosphols, respectively. 7. The process according to claim 1, further characterized in that the organic compound that is to be selected from the group consisting of apl and alkylketones is selected; alkyl and apical alcohols; Lact ama, ar'i 1 arnides, 1 qui 1 amida, benzamides substituted with -hydroxy, beta-lactams, ena inonas and benzamides, trust firoducir * thioketones, fosf or * od? T ioatos,, + i ct ama wave, taoarnides, thiobenzarnides substituted with hydroxy, beta-thiolactans, enarnmotionas and corresponding thiobenzamides, respectively. 8. A process for preparing a dialkyl osphorodium ionic acid, characterized in that it comprises: (a) combining an alkyl alcohol with elemental sulfur and elemental white phosphorus; Sulfur and white phosphorus being present in amounts that generally correspond to (Jel P2O5; (b) heating the mixture of (a) to a temperature which causes the sulfur and white phosphorus to react; and (c) recovering from the reaction mixture the dialkyl phosphate forod 1 1oic acid. 9. The process according to claim 8, further characterized in that the mixture of step (a) contains a stoichiometric excess of alkyl alcohol. LO.- The process according to claim 9, characterized in that the alcohol is a mixture of alkyl alcohols of 7 to 9 carbon atoms. 11. A proce ent for the production of dial acid n quil fosforodi ioLCo, characterized by comprising providing a reactor containing a bottom layer (Je elemental sulfur under a layer of high alcohol Quilico point Je boiling liquid, and in contact with it, admit * phosphorus or 1 elemental ancole into the reactor and pass it through the layer of alkyl alcohol, so that it makes contact with the sulfur layer at a reaction temperature of sulfur and white phosphorus, so that a reaction between the white phosphorus, sulfur and alcohol producing said dialkyl ac fosforoditioi been co occurs. 12. the process according to claim 11, charact curly also because alcohol gr upo-select that consists of n-butanol, 2-hexanol -et l-1, n- pentane L ei 13. ooctan L -?. a process for producing a dialkyl or ditiofosforoditioat, character-ized in that it comprises mixing a Selected Alcohol of the group consisting of inet anol and ethanol with elemental white phosphorus and elemental sulfur, where the amounts of white phosphorus and sulfur generally correspond to those of P2O5; where a premix of white phosphorus and sulfur is added to the alcohol, 'in a suitable reactor and the temperature rises - * «. the activation temperature for a reaction of white phosphorus and sulfur. 14. A process for preparing sodium thiophosphate, characterized in that it comprises: combining in a suitable reactor elemental sulfur and sodium hydroxide; then add elemental white gold to the reactor in a ratio of sulfur to white phosphorus which corresponds generically to that of P O5 and heat the contents of the reactor to a temperature at which the sulfur and white phosphorus react. 15. A process for preparing diaplfosforodithioic acid, characterized in that it comprises, in a suitable reactor, a mixture of substituted hydroxy, substantially anhydrous and elemental sulfur and elemental white phosphorus, while heating the contents of the reactor at a temperature at which they react. white phosphorus and sulfur; corresponding The ratio of white phosphorus and sulfur, generically, to P2? s. 16. The method according to claim 15, further characterized in that the aplo compound is rn-cresol. 17. The process according to claim L5, further characterized in that the celery compound is fi-nonyl phenol. 10, .- A process for preparing a carboxylic acid i 1 co, characterized in that it comprises combining a carboxylic acid? Substitute anhydride with sulfur in a suitable reactor, under inert atmosphere, and then add white phosphorus to the reactor, while heating the contents of the reactor to a temperature at which sulfur and white gold react; the proportion of white phosphorus and sulfur corresponding generally to those of P2O5. 19. The process according to the claim L8, ac + ep ac ed also because the carboxylic acid is hexanoic acid. R 20. In a process in which phosphorus and sulfur are reacted under the reaction conditions, the improvement which comprises providing said reaction with a premix of elemental phosphorus and elemental sulfur, at a temperature lower than the reaction temperature of said elements . 21. The method according to claim 20, further characterized in that the pre-mixture in the liquid state is provided. 22. The method according to claim 21, further characterized in that the prerequisite is tot a Lrnenfe 1 i quida. 23. The method according to claim 21, further characterized in that the liquid contains phosphorus or sulfur at least partially in the solid state. 24 ..- The procedure according to the claim ¬ * cation 20, further characterized in that the prerequisite is provided in the solid state process. 25. The process according to claim 24, further characterized in that the premix contains 26.- The process according to claim 24, further characterized in that the premix contains soli two (Jei ti po 4, 27.- The The method according to claim 24, further characterized in that the pre-mixture contains both of the S8 type with (Jel tLpo P4.) 28.- The process according to claim 20, further characterized in that the premix is formed in the liquid state in A mixing tank equipped with temperature control means and means for stirring the premix 29.- The conformity process with claim 21, further characterized in that the pee cla is maintained at a temperature in the range of 10 ° C to 80 ° C. ° C. 30.- In a process in which phosphorus and sulfur are reacted under reaction conditions to produce a product, the improvement characterized in that it comprises pro To see in this reaction a preecy of elemental phosphorus and elemental sulfur at a lower temperature of the reaction temperature (The elements and a minor amount of a diluent. 31.- The process according to claim 30, further characterized because the dLluyente is the product (Jel procedure * n which phosphorus and sulfur are reacted ba or conditions and the action. 32 .- The procedure in accordance with reiv dication 30, also characterized in that the diluent is present in the approximate scale (Je 2% to 35% by weight -; OI '? relationship to the e ezo La. 33. The method according to claim 32, further characterized in that the digester is present on the scale of approximately 2% to 10%. 34.- The conforming procedure with the claim 30, also characterized because the phosphorus and sulfur reaction produces a phosphorus sulphide and the diluent is the phosphorus sulphide. 35.- The procedure according to claim 34, characterized in that the diluent is present in the premix in the approximate range of 2% to 35%. 36.- The method according to claim 35, character- ized in addition because the diluent is present in the scale from 2% to 10%, approximately. 37. The method according to claim 34, further characterized in that the prerequisite contains about 72% to 75% of atoms of "sulfur and from 25% to 28% of phosphorus atoms and a minor amount * of pentasulfide of match. 38.- The procedure in accordance with the area v indi oac on 37, also characterized in that the phosphorus pentasulfide in the premixture is present at a scale of approximately 2% to 35%. 39.- The procedure according to the re.iv.mdi-cacion 37, characterized in addition because the elemental sulfur is present in the premix in the approximate scale of 2 to 10%. 40.- In a process for phosphorus pentasulfide, where elemental sulfur is reacted with element phosphorus under reaction conditions, the improvement characterized in that it comprises providing in the reaction a premix containing about 22% to 25% of atoms of fo elemental gold and from 75% to 78% of elemental sulfur atoms, at a temperature lower than the reaction temperature of said elements. 41. The process according to claim 40, characterized in that the premix contains additionally a minor amount of a diluent. 42. The process according to claim 41, further characterized in that the diluent is phosphorus pentasulfate and is present in the scale of approximately 2% to 10%, based on the weight of the premix. 43. The method according to claim 42, further characterized in that the temperature of initiation of the reaction is within the range of 120 to 125 ° C, approximately, and the temperature of the exotherm is within the range of the scale from 225 ° C to 250 ° C, approximately., 44. The operation according to claim 40, further characterized in that the prerequisite is provided in the reaction in the liquid state. 45.- The procedure for preparing a feed material for a process in which phosphorus and sulfur are reacted, under reaction conditions, will give a product; characterized in that it comprises combining * fos elemental gold] and elemental sulfur at a temperature below the reaction temperature of dLchoc elements, with a minor amount * of a diluent, comprising a compound that < - > s The product of said reaction. 46. The process according to claim 45, further characterized in that the product is pentasul phosphorus furo and the feedstock comprises about 74% to 78% of sulfur atoms, about 22% to 28% of phosphorus atoms and about 2% to 35% of pentasul phosphorus furo. 47.- The method according to claim 46, further characterized in that the supply material is provided in liquid state. 48. The method according to claim 47, further characterized in that the feed material is totally liquid. 49.- The method according to claim 47, further characterized in that the liquid contains phosphorus or sulfur, at least partially in the crystal state! do not. 50.- The process according to claim 45, further characterized in that the feed material is provided in the solid state in the process. 51.- The method according to claim 50, further characterized in that the premix comprises crystals of type Se. 52. The method according to claim 50, further characterized in that the feedstock comprises crystals of the type P ". 53. The method according to claim 50, further characterized in that the feedstock comprises crystals of both Se type and PA type. 54. The process according to claim 45, further characterized because the liquid feed material 1 is formed in a mixing tank equipped with temperature control means and means for stirring the pre-mix. 55. The method according to claim 45, further characterized in that the feed material is maintained at a temperature within the range of about 30 ° C to 80 ° C. 56.- A process for preparing a compound selected from the group consisting of 3-? Nercaptop? Pdazin and 3, 5-d? Nercapto? P dazina, characterized in that it comprises reacting the pyridazone or correspondingly corresponding pin with elemental phosphorus and elemental sulfur, under inert atmosphere, a temperature higher than the activation temperature of the reaction of said phosphorus and sulfur. 57.- A composition characterized in that it comprises elemental sulfur, elemental fupon and approximately 2 percent to 35 percent phosphorus pentasulfide, by weight; so that said composition is stable in air at a lower temperature than the activation of the reaction of the fos forum and the azu f i * e. 58. - A composition in accordance with re-dida tion 56, also acter-ized because the sulfur is present > - > n the approximate scale of 25% to 28% by weight, and the gold fos is present in the approximate range of 72% to 78% by weight. 59. The composition comprising, by weight: about 25 to 28 percent elemental sulfur and about 72 to 78 percent elemental phosphorus and about 2 percent to 10 percent phosphorus pentasulfide; so that said composition is stable in ai e \ a lower temperature * to the activation of the phosphorus and sulfur reaction.