GB1567828A - Reaction products made from hydrazinenitro phenol reactions - Google Patents

Description

(54) REACTION PRODUCTS MADE FROM HYDRAZINE NITRO PHENOL REACTIONS (71) We, THE LUBRIZOL CORPORATION, a corporation organised and existing under tfie laws of the State of Ohio, United States of America, of P.O.

Box No. 17100 Euclid Station, Cleveland, Ohio, 44117, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to products which may be used as additives in lubricants based on oils of lubricating viscosity and normally liquid fuel. The invention also includes fuels, lubricants and additive concentrates containing these products.

The reduction of certain aromatic nitro compounds to aromatic amino compounds using hydrazine or hydrazine hydrate in the presence or absence of metal-containing catalysts such as platinum, nickel, and palladium is known. See for example, "Chemical Reviews", Vol. 65, page 51 et seq., (1965), entitled "Hydrazine as A Reducing Agent for Organic Compounds"; Huang-Minlon, "Journal of the American Chemical Society", Vol. 70, pages 2802-2805 (1948) and P. N. T. Bavin, "Canadian Journal of Chemistry", Vol. 36, pages 238-241(1958).

The improvement of the performance characteristics of lubricants based on oils of lubricating viscosity (e.g., oils and greases) in normally liquid fuel (especially those used in internal combustion engines) through the use of additives has been known for several decades. Still in these days of growing material shortages, spiralling equipment replacement costs, politically sensitive petroleum supplies, inflation, new types of engines, fuels and lubricants and environmental consciousness, the search for new, effective, alternate lubricant and fuel additives continues unabated.

The nitrogen-containing organic products of the present invention are made by reacting (A) at least one nitro phenol of the formula

Formula I wherein R is a substantially hydrocarbon substitutent of at least 10 aliphatic carbon atoms; a, b and c are each integer from 1 up to a number three times the number of aromatic rings present in Ar with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic nucleus having 0 to 3 optional substituents selected from lower alkyl, lower alkoxyl, halo, and combinations of two or more of said substituents, with (B) at least one hydrazine source, optionally in the presence of at least one metalcontaining hydrazine decomposition catalyst.

The term "phenol" is used in this specification in its art-accepted generic sense to refer to hydroxy aromatic compounds having at least one hydroxyl group bonded directly to a carbon of an aromatic ring.

In a preferred embodiment of this invention, the reaction of (A) with (B) takes place in the absence of metal-containing hydrazine decomposition catalyst. This means the reaction of (A) and (B) takes place in a reaction mass that does not contain a sufficient amount of catalyst to significantly or substantially affect the rate or course of decomposition or reaction of the hydrazine source present. It does not mean that the reaction takes place in the total absence of all metals which are hereinbelow described. Such metals may be present in pure, alloyed or chemical combined form as parts of metallic equipment such as stirrers, pipes, vessels, probes, etc., and in such form they may be in contact with the reaction mass without significantly affecting the course or rate of the decomposition or reaction of the hydrazine source present in the mass. In such cases, for the purpose of the present description, the reaction is said to take place in the absence of a metalcontaining hydrazine decomposition catalyst.

Lubricants based on oils of lubricating viscosity, normally liquid fuels, and additive concentrates containing the above-described nitrogen-containing products are also within the scope of this invention.

The Aromatic Nucleus, Ar The aromatic nucleus Ar, can be a single aromatic ring such as a benzene ring, a pyridine ring, a thiophene ring, a 1,2,3,5 - tetrahydronaphthalene nucleus, etc., or it can be a polycyclic aromatic nucleus. Such polycyclic nuclei can be of the fused type wherein an aromatic ring is fused at two points to another ring such as found in naphthalene, anthracene, azanaphthalene, etc. Polycyclic aromatic nuclei also can be of the linked type wherein at least two nuclei (either mono or polycyclic) are linked through bridging linkages to each other. Such bridging linkages can be chosen from the group consisting of carbon-to-carbon single bonds, ether linkages, keto linkages, sulfide linkages, polysulfide linkages of 2 to 6 sulfur atoms, sulfinyl linkages, sulfonyl linkages, alkylene linkages, alkylidene linkages, lower alkylene ether linkages, alkylene keto linkages, lower alkylene sulfur linkages, lower alkylene polysulfide linkages of 2 to 6 carbon atoms, amino linkages, polyamino linkages and mixtures of such divalent bridging linkages. In certain instances, more than one bridging linkage can be present in Ar between two aromatic nuclei. For example, a fluorene nucleus has two benzene rings linked by both a methylene linkage and a covalent bond. Normally, Ar will contain only carbon atoms in the aromatic rings per se although in certain Ar nuclei heterocyclic rings such as pyridyl, thienyl and furanyl can be present.

The number of aromatic rings, fused, linked or both, in Ar play a role in determining the integer values of a, b and c in Formula I. For example, when Ar is or contains a single aromatic ring, a, b and c are each 1 to 3. When Ar contains 2 aromatic rings, a, b and c can each be an integer of 1 to 6, that is, up to three times the number of aromatic rings present (in naphthalene, 2). With a tricyclic Ar moiety, a, b and c can each be an integer of I to 9. For example, when Ar is a triphenyl moiety, a, b and c can each independently be an integer of 1 to 9. The values of a, b and c are obviously limited by the fact that their sum cannot exceed the total unsatisfied valences of Ar.

The single ring aromatic nucleus which can be the Ar moiety can be represented by the general formula ar(Q)m wherein ar represents a single ring aromatic nucleus (e.g., benzene, pyridine or thiophene) of 4 to 6 carbons, each Q independently represents a lower alkyl group, lower alkoxy group or halogen atom, and m is 0 to 3. As used in this specification and appended claims, "lower" refers to groups having 7 or less carbon atoms such as lower alkyl and lower alkoxyl groups. Halogen atoms include fluorine, chlorine, bromine and iodine atoms; usually the halogen atoms are bromine and chlorine atoms.

Specific examples of such single ring Ar moieties include the following:

etc. wherein Me is methyl, Et is ethyl and Pr is n-propyl.

When Ar is a polycyclic fused-ring aromatic nucleus, it can be represented by the general formula

wherein ar. Q and m are as defied hereinabove, m' is 1 to 4 and represent a pair of fusing bonds fusing two rings so as to make two carbon atoms part of the rings of each of two adjacent rings. Specific examples of fused ring aromatic nuclei Ar are:

etc.

When the aromatic nucleus Ar is a linked polycyclic aromatic nucleus it can be represented by the general formula ar-(-Lng-ar-)w-(Q)w wherein w is an integer of 1 to about 20, ar is as described above with the proviso that there are at least 3 unsatisfied (i.e., free) valences in the total of ar groups, Q and m are as defined hereinbefore, and each Lng is a bridging linkage individually chosen from carbon-to-carbon single bonds, ether linkages (-0-), keto linkages

sulfide linkages (-S-), polysulfide linkages of 2 to 6 sulfur atoms (-S2-8-), sulfinyl linkages (-S(O))-), sulfonyl linkages (-S(O)2), alkylene linkages (e.g., -C H2-, -qH2-CH2-,

etc.), alkylidene linkages (e.g., -CR02-), alkylene ether linkages (e.g., -CH2O -CH2O-CH2-, -CH2-CH2O-, -CH2CH2-OCH2CH2-,

etc.), alkylene keto linkages (e.g.,

alkylene sulfide linkages (e.g., wherein one or more -O-'s in the examples of alkylene ether linkages is replaced with an -S- atom) alkylene polysulfide linkages (e.g., wherein one or more -o-'s is replaced with a-S2-6-group), amino linkages (e.g., -N-, -CH2N-, -CH2NCH2-, -alk-N-, where alk is alkylene, etc.), and polyamine linkages (e.g.,-N(alkN)1-10, where the unsatisfied free N valences are taken up with H atoms or R groups), each R being a lower alkyl group.

Specific examples of Ar when it is a linked polycyclic aromatic nucleus include:

Usually all these Ar nuclei are unsubstituted except for the R, -OH and -NO2 groups (and any bridging groups).

For such reasons as cost, availability and performance, etc., the Ar nucleus is normally a benzene nucleus, lower alkylene bridged benzene nucleus, or naphthaizne nucleus. Thus, a typical Ar nucleus is a benzene or naphthalene nucleus having 3 to 5 unsatisfied valences, so that one or two of said valences may be satisfied by a hydroxyl group with the remaining unsatisfied valences being, insofar as possible, either ortho or para to a hydroxyl group. Usually Ar is a benzene nucleus having 3 to 4 unsatisfied valences so that one can be satisfied by a hydroxyl group with the remaining 2 or 3 being either ortho or para to the hydroxyl group.

The Aliphatic Substituent, R The nitro phenols used in this invention contain, directly bonded to the aromatic nucleus Ar, a substituent, R, of at least 10 aliphatic carbon atoms. This R group can have up to about 700 carbon atoms. This R is usually aliphatic in nature but in some instances it can be substantially aliphatic and contain 1 carbocyclic group (e.g., aromatic or alicyclic group) for every 10 aliphatic carbons present.

Typically, however, R is purely aliphatic. More than one such group can be present, but usually, no more than 2 or 3 such groups are present for each aromatic ring in the aromatic nucleus Ar. Often, but not necessarily, there is one R group for each aromatic ring. The total number of R groups present is indicated by the value for "a" in Formula I. Usually the R group has at least about 30 carbon atoms and up to about 500, more typically, from about 50 to about 500 aliphatic carbon atoms.

Typically when only one R group and -OH substituent are present, the R group is ortho or para to the -OH substituent. Usually the aliphatic substituent R is purely hydrocarbyl in nature; it can, however, be hydrocarbon in nature and contain, in addition to carbon and hydrogen, up to about 10 weight percent other elements such as oxygen (usually in the form of ether or hydroxyl groups), sulfur (usually in the form of sulfide or thiol groups), and halogens (particularly chlorine and bromine). The R group is normally substantially saturated which means it can contain up to 1 carbon-to-carbon double bond per every 10 carbon-to-carbon single bonds. Preferably, however, R is completely saturated and contains no double bonds.

Generally the aliphatic R substituents are made from homo- or interpolymers (e.g., copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-l, isobutene, butadiene, isopropene, 1hexene, l-octene, etc. Typically, these olefins are aliphatic hydrocarbon 1monoolefins. A preferred source of the substituent R is poly(butene) obtained by polymerization of a C4 refinery stream having a total butene content of 30 to 75 weight percent and isobutene content of 20 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than 80% of total repeat units) isobutene repeating units of the configuration

The attachment of the aliphatic R substituent to the aromatic nucleus Ar of the nitro phenols used in this invention can be accomplished by a number of techniques well known to skilled workers in the art. A particularly suitable technique is the Friedel-Crafts reaction, wherein an olefine (e.g., a polymer containing an olefinic bond), or halogenated or hydrohalogenated analog thereof, is reacted with a phenol. The reaction occurs in the presence of a Lewis acid catalyst (e.g., boron trifluoride and its complexes with ethers, phenols, hydrogen fluoride, etc.; aluminum chloride, aluminum bromide, zinc dichloride, etc.).

Methods and conditions for carrying out these reactions are well known; see, for example, the discussion in the article entitled, "Alkylation of Phenols" in Kirk Othmer Encyclopedia of Chemical Technology, Second Edition, Vol. 1, pages 894-895, Interscience Publishers, a division of John Wiley and Company, N.Y., 1963. Other equally appropriate and convenient techniques for attaching the aliphatic R substituent to the aromatic nucleus Ar will occur readily to those skilled in the art.

As will be appreciated from inspection of Formula I the nitro phenols used in this invention contain at least one of each of the following substituents: a hydroxyl group, a R group as defined above, and a nitro group, -NO2. Each of the foregoing groups must be attached to a carbon atom which is a part of an aromatic ring in the Ar nucleus. They need not, however, each be attached to the same aromatic ring if more than one aromatic ring is present in the Ar nucleus.

In a preferred embodiment, the nitro phenols used in this invention contain 1 or 2 each of the foregoing substituents and but a single aromatic ring, most preferably a benzene ring. This preferred class of nitro phenols can be represented by the formula

Formula II wherein R' is a substantially hydrocarbon substituent having an average of from about 30 to about 700, usually about 50 to about 500 aliphatic carbon atoms located ortho or para to a hydroxyl group; R" is a member selected from lower alkyl, lower alkoxyl, and halo; and z is 0 or 1. The substituent R' is of the same general character as R and the discussion of the character of R applies equally to R'.

Usually R' is an alkyl or alkenyl substituent and z is 0.

In a still more preferred embodiment of this invention, the nitro phenol used is of the formula

Formula III wherein R* is an alkyl or alkenyl group derived from homopolymerized or interpolymerized C2~10 l-olefins located para to an -OH group and has an average of from about 50 to about 500 carbon atoms; R"' is selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo; and z is 0 or 1.

Usually R* is derived from polymerized ethylene, propylene, butylene and mixtures thereof. Typically, it is derived from polymerized propylene or butylenes.

In one embodiment z is 0; in another embodiment z is 1, R"' is nitro, only one --OH group is present and the nitro group, R"', is located ortho to it.

The nitro phenols used in this invention can be prepared by a number of synthetic routes. These routes can vary in the type of reactions used and the sequence in which they are employed. For example, an aromatic hydrocarbon, such as benzene, can be alkylated with an alkylating agent such as a polymeric olefin to form an alkylated aromatic intermediate. This intermediate can then be < itrated, for example, to form a polynitro intermediate and one of the nitro groups in this intermediate converted to a hydroxyl group through fusion with caustic to provide the desired nitro phenol.

Another useful route to the nitro phenols used in this invention involves the alkylation of a phenol with an olefinic alkylating agent to form an alkylated phenol.

This alkylated phenol can then be nitrated to form a nitro phenol.

Techniques for alkylating phenols are well known to those skilled in the art as the above-noted article in Kirk-Othmer Encyclopedia of Chemical Technology demonstrates. Techniques for nitrating phenols are also well known. See, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Second Edition, Vol. 13, the article entitled "Nitrophenols", page 888 et seq., as well as the treatises "Aromatic Substitution; Nitration and Halogenation" by P. B. D. De La Mare and J. H. Ridd, N.Y., Academic Press, 1959; "Nitration and Aromatic Reactivity" by J.

G. Hogget, London, Cambridge University Press, 1961; and "The Chemistry of the Nitro and Nitroso Groups", Henry Feuer, Editor, Interscience Publishers, N.Y., 1969.

Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid with acids such as sulfuric acid or boron trifluoride, NO2, N2O3, N2O4, N2O5, NO2CI, NO2Br, mixtures of alkali and alkaline earth metal nitrates with mineral acids (e.g., H2SO4), alkanoyl nitrates (e.g., acetyl nitrate) and mixtures of two or more of these nitrating agents. Generally nitric acid of a concentration of, for example, about 30--900/, is a convenient nitrating reagent. Substantially inert liquid diluents such as acetic or butyric acid can aid in carrying out the reaction by improving reagent contact and heat transfer properties.

Conditions and procedures for nitrating hydroxy aromatic compounds are well known in the art. For example, the reaction cau be carried out at temperatures of about -15"C to about 150"C. Usually nitration of alkyl phenols is conveniently carried out between about 25--75"C.

Generally, depending on the particular nitrating agent, about 0.5--4 moles of nitrating agent is used for every mole of aromatic ring present in the hydroxy aromatic intermediate to be nitrated. If more than one aromatic ring is present in the Ar nucleus, the amount of nitrating agent can be increased proportionately according to the number of such rings present. For example, a mole of naphthalene-based aromatic intermediate has, for purposes of this disclosure, the equivalent of two "single ring" aromatic rings so that about 1--4 moles of nitrating agent would generally be used. When nitric acid is used as a nitrating agent usually about 1.0 to about 3.0 moles per mole of aromatic ring is used. Up to about a 5molar excess of nitrating agent (per aromatic ring) may be used when it is desired to drive the reaction forward or carry it out rapidly.

Nitration of a phenol generally takes 0.25 to 24 hours, though it may be convenient to react the nitration mixture for longer periods, such as 96 hours.

The typical route to the nitro phenols used in this invention just described can be summarized as nitrating with at least one nitrating agent at least one phenol of the formula (R)aAr(OH)c wherein each R is a substantially hydrocarbon substituent of at least about 30, typically about 30 to about 700, aliphatic carbon atoms; at least one R is in a position ortho or para to at least one -OH substituent attached directly to Ar'; a and c are each independently integers of 1 up to three times the number of aromatic rings in Ar', their sum not exceeding the number of unsatisfied valences in Ar', and Ar' is an aromatic nucleus having at least one hydrogen bonded to a carbon of an aromatic ring and 0 to 3 optional substituents selected from lower alkyl, lower alkoxyl, halo, nitro and combinations of said optional substituents. In other respects Ar' is the same as Ar and the description of the latter given herein above applies equally to Ar'. Usually Ar' is a benzene nucleus and R has an average of about 50 to about 500 carbons and typically is derived from homopolymerized or interpolymerized C2~10 olefins and mixtures thereof.

Typically, such nitrated phenols are made by nitrating with a nitrating agent at least one compound of the formula

Formula IV wherein R' and R" are as described hereinabove and R' is usually located in a position ortho or para to the hydroxyl group; and z is0 or 1. Typically R' is para to the hydroxyl group and z is O.

Certain nitro phenols used in this invention having linked aromatic nuclei can be made by several alternative synthetic sequences. For example, a hydrocarbonsubstituted phenolic compound such as those described hereinabove can be first reacted with a linking reagent such as an aldehyde or ketone (e.g., formaidehyde) to form a linked product having, for example, methylene linkages between aromatic nuclei. These linked intermediates can then be nitrated by the procedures described hereinabove to give the desired linked nitro phenol. Such a sequence can be illustrated by the following sequence:

Formula V Alternatively, a nitro phenol with a single ring or fused multi-ring aromatic nucleus made, for example, as described hereinabove, can be reacted with the linking reagent such as aldehyde, formaldehyde to give the desired linked nitro phenol. This sequence can be illustrated by the following sequence:

Formula VI Still another route to linked nitro phenols used in this invention having linked aromatic nuclei is through the condensation of a hydrocarbon-substituted phenol and a nitrophenol which can or cannot be hydrocarbon-substituted with the aid of a linking agent such as sulfur, formaldehyde, etc. This sequence can be illustrated by the sequence:

Formula VII

R and R"' in Formulae V-VII are as described hereinabove.

The Hydrazine Source (B) The term 'hydrazine source' used in the present specification means a compound or mixture of compounds which is capable of producing hydrazine under the conditions of the reaction of (A) with (B) in sufficient quantities to react with the nitro phenol (A) present; it includes hydrazine itself. Many such hydrazine sources are known to those of skill in the art. See, for example, the book entitled "Hydrazine" by Charles C. Clark, published by the Mathieson Chemical Corporation of Baltimore, Maryland (1953), particularly pages 31 through 71 and 120 through 124; and the book entitled "The Chemistry of Hydrazine" by L. F.

Audrieth and B. A. Ogg, published by John Wiley and Son, New York (1951), especially pages 209 through 223.

Among the more common, and therefore preferred hydrazine sources, are hydrazine itself, hydrazine hydrate and solutions of hydrazine and water, as well as hydrazinium salts of, for example, sulfuric and hydrochloric acid, semicarbazides and thiosemicarbazides and their analogous salts; hydrazine dicarboxylates of lower alkalols (e.g., ROOCNHNHCOOR) and their dimers as well as the amino guanidines and their --NHNHH- sulfuric and hydrochloric acid salts and benzene sulfonyl hydrazides and their bisoxy analogs. Mixtures of hydrazine sources can also be used. This list is not intended to be exhaustive or in any way limit the invention and many useful hydrazine sources similar to those listed will occur to those skilled in the art.

For reasons of economy and ease of handling, hydrazine and particularly its solution with water and other solvent/diluents is preferred. A typical hydrazine source is a mixture of water and hydrazine containing about 64," hydrazine, although similar mixtures containing more or less hydrazine (about 20--800/,; more often, about 370% hydrazine) can be used.

Techniques of using such hydrazine sources in chemical reactions are well known to those of skill in the art, as for example is shown by the books cited above and the article entitled "Hydrazine" in Kirk-Othmer Encyclopedia of Chemical Technology, Second Edition, Vol. 11, pages 164196, Interscience Publishers, New York, New York (1966). These are hereby incorporated by reference for their relevant disclosures in regard to techniques for using hydrazine sources.

The Reaction of the Nitro Phenol (A) with the Hydrazine Source (B) In the process used for preparing the nitrogen-containing organic products of this present invention, about 1.5 to about 5 moles of the hydrazine source (B) are usually present for each equivalent of the nitro phenol (A) present. A mole of hydrazine source is that amount of hydrazine source, as described hereinabove, which provides a mole of hydrazine (NH2NH2) under the conditions of the reaction, An equivalent of nitro phenol is that amount of nitro phenol which contains 1 mole of nitro groups. For example, a mole of mono nitro phenol contains 1 mole of nitro groups, while a mole of di-phenol contains 2 moles of nitro groups. Therefore, an equivalent of the di-nitro phenol will be half a mole of phenol.

Preferably, there is present for each equivalent of nitro phenol (A), about 1.5 to about 2.5 moles of hydrazine source. The hydrazine source need not all be present at the beginning of the reaction of (A) with (B) and it can be added continuously or incrementally as the reaction proceeds.

For reasons of economy and convenience, it is desirable that the stoichiometric amount of hydrazine source react with the nitro phenol. As is well known to those of skill in the art, however, organic reactions often do not proceed until a stoichiometric amount of reactants has been consumed and, in the present Invention, it is sufficient that about 50 mole percent of the nitro groups present in the nitro phenol (A) have reacted with the hydrazine source.

The reaction of (A) with (B) generally occurs at temperatures above about 50"C. Usually the reaction takes place at a temperature above about 100"C and below about 350"C.

The reaction of (A) with (B) generally takes place over a period of about 2 to about 24 hours; longer times such as about 96 hours can be used. Typically, the reaction occurs in a period of about 4--8 hours, after about 6 hours.

The nitrogen-containing organic products can be recovered by techniques of isolation and purification such as distillation, extraction, crystallization, centrifugation, etc., well known to those of skill in the art. Usually, however, it is possible to employ the nitrogen-containing products for their intended use without further purification or isolation from the mixtures in which they are formed.

Sometimes for reasons of appearance and/or storage stability, simple purification techniques such as filtration of the reaction mass with the aid of well-known filtration aids such as diatomaceous earth, powdered charcoal, etc., are all that is used to treat the reaction mass. The choice of appropriate techniques and the occassions for their use are well within the skill of those skilled in the art to which this invention pertains.

As noted hereinabove, the reaction of (A) with (B) can optionally take place in the presence of at least one metal-containing hydrazine decomposition catalyst. A number of such catalysts are known to those skilled in the art and the following discussion of them is intended to be merely exemplary and no way limiting. For a general discussion of the reaction of hydrazine and hydrazine sources with such catalysts, see the books entitled "Hydrazine" and "The Chemistry of Hydrazine".

as well as the article "Hydrazine" in Kirk-Othmer Encyclopedia of Chemical Technology which are ali cited hereinabove. Among the metals which can be contained in the hydrazine decomposition catalyst useful in the present invention are platinum, palladium, nickel, copper, iron, ruthenium, cobalt, rhodium, osmium and mixtures of two or more of any of these. The catalyst can be elemental metal, alloys of various metals, metal compounds such as inorganic salts, oxides, etc.; salts of metals with organic acids such as carboxylates and sulfonates; and coordination complexes with appropriate ligands. Catalysts can be used in any of their wellknown forms, such as finely divided unsupported metals, thin metal films deposited on active or inactive substrates or electrodes, and in the various conformations such as pellets, spirals, etc., commonly used in large processing equipment.

Particularly preferred are finely divided metal which are generally known as hydrogenation catalysts and include palladium, platinum and nickel. Metals which have been treated chemically and/or physically to modify their activity (e.g., Raney nickel) are often used. See, for example, the references cited in the "Chemical Reviews" article entitle removed by filtration. Stripping of the product filtrate first to 2300/760 tor (vapor temperature), then to 205 /50 tor (vapor temperature), provides purified alkylated phenol as a residue.

To a mixture of 265 parts of purified alkyl phenol, 176 parts blend mineral oil and 42 parts of petroleum naphtha having a boiling point of approximately 200 is slowly added a mixture of 18.4 parts concentrated nitric acid (69-70%) and 35 parts water. The reaction mixture is stirred for 3 hours at about 30450, stripped to 1200/20 tor (vapor temperature) and filtered to provide an oil solution of the desired nitro phenol intermediate.

Example 2 A mineral oil solution (1900 parts) of an alkylated, nitrated phenol as described in Example 1 containing 43% mineral oil is heated under a nitrogen atmosphere to 145". Then, 70 parts of hydrazine hydrate is slowly added to the mixture over 5 hours while its temperature is held at about 145". The mixture is then heated to 1600 for one hour while 56 parts of aqueous distillate is collected. A,l additional 7 parts of hydrazine hydrate is added and the mixture is held at 1400 for an additional hour. Filtration at 1300 provides an oil solution of the desired product containing 0.50/, nitrogen.

Example 3 To a mixture of 800 parts of polybutene-substituted phenol prepared essentially as described in Example 1, and 944 parts of diluent mineral oil at 59" is added 72 parts of concentrated nitric acid. The reaction is controlled so as to keep the reaction temperature between 59 and 68". The reaction mixture is stirred for two hours at 6973 and then heated to 1400 while nitrogen is slowly passed through it and water is removed by distillation. Hydrazine hydrate (90 parts) is then slowly added to the mixture at 1300 to 1370 over 3 hours. The mixture is stirred for 0.5 hour at this temperature and then heated to 1600 while nitrogen is slowly passed through it and provision is made for collecting the aqueous distillate. The residue is an oil solution of the desired product.

Example 4 A mixture of 609 parts of polybutene-substituted phenol prepared essentially as described in Example 1 and 454 parts of mineral diluent oil is blended at 570. To this mixture is added, over 8 hours, 46.5 parts of nitric acid (66.3%). The mixture is stirred for 1.5 hours at 58--63" and then heated to 142" for 1.7 hours while nitrogen is slowly passed through it. The mixture is held at 143145 for 0.5 hour and then cooled to 114". During the reaction, 23 parts of distillate is collected. Filtration of the mixture at 113126 provides an oil solution of the desired nitro intermediate having a nitrogen content of 0.64%.

Example 5 To 320 parts of the oil solution of the polybutene-substituted nitrated phenol described in Example 4 is added 12 parts of aqueous hydrazine (64% hydrazine) over 6.25 hours at a temperature of 1600. Filtration provides an oil solution of the desired product having a nitrogen content of 0.59%.

Example 6 To a mixture of 3000 parts of an alkylated phenol made essentially as described in Example 1 having a polybutene substituent of about 70 carbon atoms and 3000 parts of glacial acetic acid at 510 is added 540 parts of concentrated nitric acid over three hours. During the addition, the mixture is held at 5163 . The mixture is stored at room temperature for 18 hours and then heated to 1200 for 6 hours while nitrogen is slowly passed through it. Provision is made for collecting the aqueous distillate. The reaction is then stripped to 1400/28 tor (vapor temperature) and the residue filtered at 1200 to provide the desired final product having a nitrogen content of 2.55%. On this basis, it is calculated that the product contains an average of two nitro groups per alkylated phenol.

Example 7 To a mixture of 545 parts of the alkylated dinitro phenol described in Example 6 and 340 parts of diluent mineral oil at 125 is added 100 parts of hydrazine hydrate. This addition is carried out under a nitrogen atmosphere for a 2.5 hour period while the temperature is held at 122125 . The reaction mixture is then refluxed at 1230 for 2.5 hours and heated for an additional 2 hours to 1550 while provision is made for collecting aqueous distillate. A slow stream of nitrogen is passed through the reaction mixture at 150155 for an additional 2 hours and the residue is filtered to provide an oil solution of the desired product having a nitrogen content of 1.16%.

Example 8 To a mixture of 361 parts of tetrapropenyl-substituted phenol and 271 parts of glacial acetic acid at 717 is added a mixture of 90 parts nitric acid (70% HNO3) and 90 parts of glacial acetic acid. The addition is carried out over 1.5 hours while the reaction mixture is cooled externally to 717 . The cooling bath is removed and the reaction stirred for 2 hours at room temperature. Stripping to 1340/35 tor (vapor temperature) and filtration provides as a residue the desired nitrated intermediate having a nitrogen content of 65%.

Example 9 To 303 parts of the nitrated intermediate described in Example 8 at 1250 under a nitrogen atmosphere is added 100 parts of hydrazine hydrated over a 2.4 hour period. The mixture is refluxed for 2.5 hours and then distilled to a vapor temperature of 155". A slow stream of nitrogen is passed through the reaction mixture while it is kept at a temperature of 155 to 1900. Filtration of the residue provides the desired final product which has a nitrogen content of 4.89%.

As previously indicated the nitrogen-containing products of this invention may be used as additives for lubricant compositions based on oils of lubricating viscosity. These lubricant compositions find use in various applications such as the lubrication of internal combustion engines. The additives act as detergents and dispersants for engine sludge that accumulates in the oil during its use. They are particularly useful in oils subjected to high temperature of cyclic environments such as those encountered in on-off or heavy-duty engine operation.

Exemplary lubricant compositions of this invention include crankcase lubricating oils for compression-ignited and spark-ignited internal combustion engines such as diesel, Otto and two-cycle (two-stroke) automobile and truck engines, marine and railroad engines and the like. For the purposes of this description, Wankel engines are considered to be two-cycle engines. Engines used in power garden equipment saws and similar applications can also use the lubricant compositions of this invention. Automatic transmission fluids, transaxle lubricants, gear lubricants, industrial oils such as metal-working lubricants, hydraulic fluids and other oil and grease compositions can also be benefited by the nitrogen-containing compositions of this invention.

The lubricant compositions of this invention can be based on natural oils, synthetic oils, natural oil mixtures, synthetic oil mixtures and natural oil-synthetic oil mixtures. Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solventtreated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils. Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as homopolymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers, chlorinated polybutylenes, etc.); poly(l-hexenes), poly(loctenes), poly(l-decenes), etc. and mixtures thereof; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.

Alkylene oxide homopolymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils.

These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1 000, diethyl ether of polypropylene glycol having a molecular weight of 1000--1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C2 Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2 - ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester form by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2ethylhexanoic acid and the like.

Esters useful as synthetic oils also include those made from C5 to C,2 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra - (2 - ethylhexyl)silicate, tetra - (4 - methylhexyl)silicate, tetra(p - tert - butylphenyl)silicate, hexyl - (4 methyl - 2 - pentoxy)disiloxane, poly(methyl)siloxanes, poly(methylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans and the like.

In refined, unrefined and rerefined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the lubricant composition of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve on or more properties. Many such purification techniques are known to those of skill in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by processes, similar to those used to obtain refined oils, applied to refined oils which have been already used in service.

Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.

In general, a minor amount such as about 0.05-30, usually about 0.1-15 parts (by weight) of at least one nitrogen-containing product of this invention is dissolved or stably dispersed in 100 parts of oil to produce a satisfactory lubricant. The invention also contemplates the use of other additives in combination with the composition of this invention. Such additives include, for example, auxiliary detergents and dispersants of the ash-producing or ashless type, oxidationinhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers and anti-foam agents.

The term "stably dispersed" as used in this specification is intended to refer to a product (e.g., a single additive or compound, a mixture of two or more additives or compounds, etc.) which is dispersed in a given medium to an extent which allows it to function in its intended manner. Thus, for example, where a product of this invention is used in an oil, it is sufficient that the product be suspended in an oil in an amount sufficient to enable the oil to possess one or more of the desired properties imparted to it by the suspended product. Such suspension can be achieved in various conventional ways such as constantly circulating the oil or splashing it in various types of lubricating systems. Conventional dispersants (such as the acylated nitrogen dispersants disclosed in U.S. Patent 3,219,666) often found in lubricating oils and fuels can be used to promote the stable dispersion or suspension of the product. In any event, the products of this invention are "soluble" or "stably dispersible" in the normally liquid media in which they are used in at least the minimum concentrations set forth elsewhere herein. Thus, the terminology "soluble" and "stably dispersible" is used in a conventional manner and will be understood to those of ordinary skill in the art.

As used in the specification, the term "substantially inert" when used to refer to solvents, diluents, base oils, and the like, is intended to mean that the solvent, diluent, etc., is inert to chemical or physical change under the conditions in which it is used so as not to materially interfere in an adverse manner with the preparation, storage, blending and/or functioning of the nitrogen-containing products, oils, fuels, or concentrates of this invention in the context of their intended use. For example, small amounts of a solvent, diluent, etc. can undergo minimal reaction or degradation without preventing the making and using of the invention as described herein. In other words, such reaction or degradation, while technically discernible, would not be sufficient to deter the practical worker of ordinary skill in the art from making and using the invention for its intended purposes. "Substantially inert" as used herein is, thus, readily understood and appreciated by those of ordinary skill in the art.

The nitrogen-containing products of this invention can also be used in minor amounts in fuels where they function as engine sludge detergent/dispersants, carburetor detergents, and demulsifying agents. Fuel compositions of this invention usually contain a major portion of a normally liquid fuel such as hydrocarbonaceous petroleum distillate fuel (e.g., motor gasoline as defined by ASTM Specification D-439-73 and diesel fuel or fuel oil as defined by ASTM Specification D-396). Normally liquid fuel compositions comprising nonhydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methylethyl ether, nitromethane) are also within the scope of this invention as are liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale, and coal. Normally liquid fuels which are mixtures of one or more hydrocarbonaceous fuel and one or more non-hydrocarbonaceous material are also contemplated. Examples of such mixture are combinations of gasoline and ethanol, diesel fuel and ether, gasoline and nitromethane, etc. Particularly preferred is gasoline, that is, a mixture of hydrocarbons having an ASTM boiling point of 60"C at the 10% distillation point to about 205"C at the 90sub distillation point.

Generally, these fuel compositions contain an amount of at least one nitrogencontaining product of this invention sufficient to impart dispersant, detergent or demulsifying properties to the fuel; usually this amount is about 1 to about 10,000, preferably 4 to 1000, parts by weight of the nitrogen-containing product per million parts hy weight of fuel. Preferred are gasoline-based fuel compositions which exhibit engine sludge dispersancy and detergency and carburetor detergency properties.

The fuel compositions of this invention can contain, in addition to the products of this invention, other additives which are well known to those of skill in the art. These can include anti-knock agents such as tetra-alkyl lead compounds, lead scavengers such as halo-alkanes (e.g., ethylene dichloride and ethylene dibromide), deposit preventors or modifiers such as triaryl phosphates, dyes, cetane improvers, anti-oxidants such as 2,6 - di - tertiary - butyl - 4 - methylphenol, rust inhibitors, such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, anti-icing agents and the like. Refined mineral oils, especially bright stocks, and oily homoand interpolymerized lower olefins such as ethylene/propylene copolymers, polypropylene and polybutenes, etc. are often used in fuel compositions (especially gasolines) to reduce deposit formation in the induction systems of engines using such fuels.

In certain preferred fuel compositions of the present invention, the aforedescribed products of this invention are combined with other ashless dispersants in gasoline. Such ashless dispersants are preferably esters of a mono- or polyol and a high molecular weight mono- or polycarboxylic acid acylating agent containing at least 30 carbon atoms in the acyl moiety. Such esters are well known to those of skill in the art. See, for example, French Patent 1,396,645; British Patents 981,950 and 1,055,337; and U.S. Patents 3,255,108; 3,311,558; 3,331,776; 3,346,354; 3,522,179; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428; 3,708,522; and British Patent Specification 1,306,529. Generally, the weight ratio of the products of this invention to the aforesaid ashless dispersants is about 0.1 to about 10.0; preferably about 1 to about 10 parts of product of this invention to 1 part ashless dispersant.

In still another embodiment of this invention, the inventive nitrogencontaining products can be combined with Mannich condensation products formed from substituted phenols, aldehydes, polyamines, and amino pyridines to make lubricants and/or fuel additives. Such condensation products are described in U.S. Patents 3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,724,277.

The nitrogen-containing products of this invention can be added directly to the fuel or lubricating oil to form the fuel and lubricant compositions of this invention or they can be diluted with at least one substantially inert, normally liquid, organic solvent/diluent such as mineral oil, xylene, alcohol, nitro lower alkane chloro lower alkane, or a normally liquid fuel as described above, to form an additive concentrate which is then added to the fuel or lubricating oil in sufficient amounts to form the inventive fuel and lubricant composition described herein. These concentrates generally contain about 30 to about 90 percent of the nitrogen-containing product of this invention and can contain in addition any of the above-described conventional additives, particularly the aforedescribed ashless dispersants in the aforesaid proportions. The remainder of the concentrate is the solvent/diluent.

This invention also includes two-cycle engine lubricating oils containing the hereinbefore described nitrogen-containing products. In general, these two-cycle engine lubricating oil compositions contain about 98 to about 55% oil or mixture of oils of lubricating viscosity. Typical compositions contain about 90 to about 70 i/n oil. The presently preferred oils are mineral oils and mineral oil-synthetic polymerand/or ester oil mixtures. Oily polybutene fractions of molecular weight of about 250 to about 1000 (as measured by vapor phasc osmometry) and fatty acid ester oils of polyols such as pentaerythritol and trimethylol propane are typical useful synthetic oils.

These oil compositions contain about 2 to about 30%, typically about 5 to about 20, of at least one nitrogen-containing product as described hereinbefore.

Other additives such as auxiliary detergents and dispersants of the ash-producing or ashless type, anti-oxidants, coupling agents, pour point depressing agents, extreme pressure agent, color stabilizers and anti-foam agents can also be present.

Detergent-dispersants of ashless types and ash-producing metallic types are used to control piston ring sticking and general engine cleanliness. Heavy duty twocycle lubricants require the use of suitable ashless dispersants because ash-forming detergents tend to form combustion chamber deposits which induce preignition.

Other formulations for use in less severe service can contain calcium, barium or magnesium sulfonates or phenates either singly, in combination with one another, or in combination with ashless dispersants. Anti-oxidants can be included to promote lubricant thermal stability.

Polymeric VI improvers have been and are being used in two-cycle oils to improve lubricant film strength and engine cleanliness. Dye may be used for identification purposes and to indicate whether a two-cycle fuel mix contains lubricant. Coupling agents are incorporated into some products to provide better component solubilities and improved fueVlubricant mix water tolerance.

Anti-wear and lubricity improvers, particularly sulfurized sperm oil and sulfurized sperm oil substitutes and other fatty acid and vegetable oils, such as castor oil, are used in two-cycle engine oils for special applications, such as racing and for very high fueVlubricant ratios. Scavengers or combustion chamber deposit modifiers are sometimes used to promote better spark plug life and to remove carbon deposits. Halogenated compounds and/or phosphorus-containing materials may be used for this application.

Rust and corrosion inhibitors of all types are and may be incorporated into two-cycle oil formulations. Odorants or deodorants are sometimes used for aesthetic reasons.

Lubricity agents such as synthetic polymers (e.g., polyisobutene having a number average molecular weight in the range of about 750 to about 15,000, as measured by vapor phase isomometry or gel permeation chromatography), polyol ether (e.g., poly(oxyethylene - oxypropylene)ethers) and ester oils (e.g., the ester oils described above) can also be used in the two-cycle engine oil compositions of this invention. Natural oil fractions such as bright stocks (the relatively viscous products formed during conventional lubricating oil manufacture from petroleum) can also be used for this purpose. They are usually present in the two-cycle oil in the amount of about 3 to about 20% of the total oil composition.

The two-cycle engine oils of this invention can also contain auxiliary detergent-dispersants. Typical examples are the amide, amine salt and/or amidine products formed by reaction of fatty acids of 5 to about 22 carbon atoms (e.g., isostearic acid and mixtures of isostearic and stearic acid) with an alkylene polyamine of 2 to about 10 amino groups and 2 to about 20 carbon atoms, such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, etc., including commercially available mixtures of such alkylene polyamines. Such auxiliary detergent-dispersants are represented by those disclosed in U.S. Patent No. 3,169,980.

Diluents such as petroleum naphthas boiling at the range of about 3890 (e.g., Stoddard Solvent) can also be included in the oil compositions of this invention, typically in an amount of 5 to 25%.

An illustrative two-cycle engine oil lubricant composition contains 2-10% of one or more of the nitrogen-containing products described hereinbefore such as that described in Example 2, and a base oil composed of about 7080 parts by volume 650 neutral oil, 8-12 parts by volume bright stock and 1020 parts by volume Stoddard Solvent.

As is well known to those skilled in the art, two-cycle engine lubricating oils can be added directly to the fuel to form a mixture of oil and fuel which is then introduced into the engine cylinder. Such lubricant-fuel oil mixtures are within the scope of this invention. These lubricant-fuel blends generally contain per 1 part of oil about 15-250 parts fuel, typically they contain 1 part oil to about 50100 parts fuel.

Another typical example of the two-cycle engine lubricating oils of this invention is the following: Percent Component (by wt) Base oil1 60.0 Bright stock2 10.0 Stoddard Solvent 15.0 Nitrogen-containing phenol additive3 15.0 1A solvent-refined neutral oil having a viscosity of 650 SUS at 98.80 C.

2Having a viscosity of 150 SUS at 98.80C.

3A mineral oil solution containing a nitrogen-containing composition as described in Example 7.

Because of Section 9 of the Patents Act 1949, attention is directed to our copending Patent Application No. 28544/77, (Serial No. 1,553,464).

WHAT WE CLAIM IS: 1. A method for making nitrogen-containing organic products which comprises reacting (A) at least one nitro phenol of the formula

wherein R is a substantially hydrocarbon substituent of at least 10 aliphatic carbon atoms; a, b and c are each an integer from 1 to a number three times the number of aromatic rings present in Ar with the priviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic nucleus having 0 to 3 optional substituents selected from lower alkyl (as hereinbefore defined), lower alkoxyl (as hereinbefore defined), halo and combinations of two or more of said substituents, with (B) at least one hydrazine source (as hereinbefore defined), optionally in the presence of at least one metal-containing hydrazine decomposition catalyst.

2. A method as claimed in Claim 1 wherein the reaction of (A) with (B) takes place in the absence of said metallic catalyst.

3. A method as claimed in Claim 2 wherein the hydrazine source is hydrazine, semicarbazides, a hydrazine dicarboxylate of a lower alkanol (as hereinbefore defined), mixtures of two or more of these or mixtures of one or more of these with water.

4. A method as claimed in Claim 1 wherein the reaction of (A) with (B) takes place in the presence of a metal-containing hydrazine decomposition catalyst wherein the metal portion is selected from platinum, palladium, nickel, copper, iron, ruthenium, cobalt, rhodium, and mixtures of two or more of any of these.

5. A method as claimed in any preceding claim wherein Ar is a benzene nucleus, a, b and c are each 1 or 2 and at least one R group is located ortho or para to at least one -OH group directly bonded to the benzene nucleus, Ar.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (21)

**WARNING** start of CLMS field may overlap end of DESC **. polyamines. Such auxiliary detergent-dispersants are represented by those disclosed in U.S. Patent No. 3,169,980. Diluents such as petroleum naphthas boiling at the range of about 3890 (e.g., Stoddard Solvent) can also be included in the oil compositions of this invention, typically in an amount of 5 to 25%. An illustrative two-cycle engine oil lubricant composition contains 2-10% of one or more of the nitrogen-containing products described hereinbefore such as that described in Example 2, and a base oil composed of about 7080 parts by volume 650 neutral oil, 8-12 parts by volume bright stock and 1020 parts by volume Stoddard Solvent. As is well known to those skilled in the art, two-cycle engine lubricating oils can be added directly to the fuel to form a mixture of oil and fuel which is then introduced into the engine cylinder. Such lubricant-fuel oil mixtures are within the scope of this invention. These lubricant-fuel blends generally contain per 1 part of oil about 15-250 parts fuel, typically they contain 1 part oil to about 50100 parts fuel. Another typical example of the two-cycle engine lubricating oils of this invention is the following: Percent Component (by wt) Base oil1 60.0 Bright stock2 10.0 Stoddard Solvent 15.0 Nitrogen-containing phenol additive3 15.0 1A solvent-refined neutral oil having a viscosity of 650 SUS at 98.80 C. 2Having a viscosity of 150 SUS at 98.80C. 3A mineral oil solution containing a nitrogen-containing composition as described in Example 7. Because of Section 9 of the Patents Act 1949, attention is directed to our copending Patent Application No. 28544/77, (Serial No. 1,553,464). WHAT WE CLAIM IS:

1. A method for making nitrogen-containing organic products which comprises reacting (A) at least one nitro phenol of the formula

wherein R is a substantially hydrocarbon substituent of at least 10 aliphatic carbon atoms; a, b and c are each an integer from 1 to a number three times the number of aromatic rings present in Ar with the priviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic nucleus having 0 to 3 optional substituents selected from lower alkyl (as hereinbefore defined), lower alkoxyl (as hereinbefore defined), halo and combinations of two or more of said substituents, with (B) at least one hydrazine source (as hereinbefore defined), optionally in the presence of at least one metal-containing hydrazine decomposition catalyst.

2. A method as claimed in Claim 1 wherein the reaction of (A) with (B) takes place in the absence of said metallic catalyst.

3. A method as claimed in Claim 2 wherein the hydrazine source is hydrazine, semicarbazides, a hydrazine dicarboxylate of a lower alkanol (as hereinbefore defined), mixtures of two or more of these or mixtures of one or more of these with water.

4. A method as claimed in Claim 1 wherein the reaction of (A) with (B) takes place in the presence of a metal-containing hydrazine decomposition catalyst wherein the metal portion is selected from platinum, palladium, nickel, copper, iron, ruthenium, cobalt, rhodium, and mixtures of two or more of any of these.

5. A method as claimed in any preceding claim wherein Ar is a benzene nucleus, a, b and c are each 1 or 2 and at least one R group is located ortho or para to at least one -OH group directly bonded to the benzene nucleus, Ar.

6. A method as claimed in any preceding claim wherein 1.5 to 5 moles of the

hydrazine source (B) are present for each equivalent of the nitro phenol (A) and the reaction temperature is above 50"C.

7. A method for making nitrogen-containing organic products which comprises reacting (A) at least one nitro phenol of the formula

wherein R' is a substantially hydrocarbon substituent having an average of from 30 to 700 aliphatic carbon atoms located ortho or para to the hydroxyl group; R" is a member selected from lower alkyl (as hereinbefore defined), lower alkoxyl (as hereinbefore defined), and halo substituents; and z is 0 or 1, with (B) a hydrazine source (as hereinbefore defined) selected from hydrazine, semicarbazide, a hydrazine dicarboxylate of a lower alkanol (as hereinbefore defined), mixtures of two or more of these and mixtures of one or more of these with water, optionally in the presence of at least one metal-containing hydrazine decomposition catalyst.

8. A method as claimed in Claim 7 wherein the reaction of (A) with (B) takes place in the absence of said catalyst.

9. A method as claimed in Claim 8 wherein z is zero and R' is an alkyl or alkenyl group.

10. A method as claimed in Claim 9 wherein R' has an average of 50 to 500 carbon atoms.

11. A method as claimed in Claim 10 wherein R' is a polybutene derived group located para to the WH group.

12. A method as claimed in any one of Claims 7 to 11 wherein 1.5 to 5 moles of the hydrazine source (B) are present for each equivalent of the nitro phenol (A) and the reaction temperature is above 50"C.

13. A nitrogen-containing organic product made by the method claimed in any one of Claims 1 to 6.

14. A nitrogen-containing organic product made by the method claimed in any one of Claims 7 to 12.

15. A lubricant or normally liquid fuel comprising a major amount of at least one oil of lubricating viscosity or normally liquid fuel and a minor amount, sufficient to impart dispersancy/detergent properties to said lubricant or fuel, of at least one product as claimed in Claim 13.

16. A lubricant or normally liquid fuel comprising a major amount of at least one oil of lubricating viscosity or normally liquid fuel and a minor amount, sufficient to impart dispersancy/detergent properties to said lubricant or fuel, of at least one product as claimed in Claim 14.

17. An additive concentrate comprising at least one substantially inert, organic normally liquid solvent/diluent and 3W90 percent by weight of at least one product as claimed in Claim 13.

18. An additive concentrate comprising at least one substantially inert, organic, normally liquid solvent/diluent and 3090 percent by weight of at least one product as claimed in Claim 14.

19. A product as claimed in Claim 13, substantially as described in Example 2, 3, 5, 7 or 9.

20. A lubricant or normally liquid fuel as claimed in Claim 15 substantially as hereinbefore described.

21. An additive concentrate as claimed in Claim 17 substantially as hereinbefore described.