US 2011 0028732A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0028732 A1 Trauth et al. (43) Pub. Date: Feb. 3, 2011

(54) NITRATED HYDROCARBONS, (86). PCT No.: PCT/US2009/0399.01 DERIVATIVES, AND PROCESSES FOR THEIR MANUFACTURE S371 (c)(1), (2), (4) Date: Sep. 27, 2010 (75) Inventors: Daniel M. Trauth, Crystal Lake, IL Related U.S. Application Data (US); George D. Green, Cary, IL (US); Raymond J. Swedo, Mt. (60) Eyal application No. 61/045.380, filed on Apr. Prospect, IL (US); Richard L. s James, Eros, LA (US); Ian A. Publication Classification Tomlinson, Midland, MI (US) (51) Int. Cl. C07D 263/04 (2006.01) Correspondence Address: C07C 205/05 (2006.01) The Dow Chemical Company C07C 205/01 (2006.01) P.O. BOX 1967, 2040 Dow Center CD7C 205/06 (2006.01) Midland, MI 48641 (US) C07C 215/02 (2006.01) C07C 239/08 (2006.01) (73) Assignees: ANGUS CHEMICAL (52) U.S. Cl...... 548/215; 7.3,So COMPANY, Buffalo Grove, IL s s (US): GLOBAL (57) ABSTRACT TECHNOLOGIES INC. , MidlandM1Clland, Provided is a process for the formation of nitrated compounds MI (US) by the nitration of hydrocarbon compounds with- dilute- - nitric acid. Also provided are processes for preparing industrially (21) Appl. No.: 12/934,817 useful downstream derivatives of the nitrated compounds, as well as novel nitrated compounds and derivatives, and meth (22) PCT Filed: Apr. 8, 2009 ods of using the derivatives in various applications. US 2011/0028732 A1 Feb. 3, 2011

NITRATED HYDROCARBONS, 0009. The invention further provides methods of using the DERIVATIVES, AND PROCESSES FOR THEIR nitrated hydrocarbons and derivatives thereof in various MANUFACTURE applications.

CROSS-REFERENCE TO PRIORAPPLICATION DETAILED DESCRIPTION OF THE INVENTION 0001. This application claims the benefit of U.S. Provi 0010. As noted above, in one aspect, the invention relates sional Application No. 61/045,380 filed Apr. 16, 2008. to a process for the nitration of hydrocarbons. The combina tion of reaction conditions, nitrating agent concentration, and FIELD OF THE INVENTION use of a downflow reactor according to the invention provides 0002 The invention relates to a process for making the process with a number of improvements over the prior art, nitrated hydrocarbons, such as nitroalkanes, nitrocycloal and particularly in terms of the reduced formation of oxida kanes, and nitroaralkyls, and to processes for making deriva tion byproducts and the increased conversion of starting tive compounds of the nitrated hydrocarbons. The invention materials to either desired product or to materials that are also relates to new nitrated hydrocarbons and new derivatives. readily recyclable or treatable. 0011. The invention process is carried out in a downflow BACKGROUND OF THE INVENTION configured reactor. That is, the reactor is positioned substan tially vertically and the reactants are introduced at the upper 0003. The nitration of hydrocarbons generally produces a end and the product mixture collected at the lower end of the variety of products depending upon the reaction conditions reactOr. and the feedstock structure. Certain products, however, may 0012 Operation of the reactor in a downflow mode be more desirable than others and it has been a long-time goal according to the invention provides nitrated compounds that to selectively produce the more useful nitrated compounds at contain relatively low levels of oxidation byproducts as com the expense of less useful compounds, such as oxidation pared to prior art systems, which generally utilize horizontal, byproducts. upflow, coiled or batch autoclave type apparatuses. Without 0004. In contrast to commercial vapor phase nitration, the wishing to be bound by any particular theory, it is believed mixed vapor-liquid phase or high pressure nitration of hydro that the advantages of the downflow reactor result primarily carbons has been postulated in the past to be a technique by from its ability to minimize the amount and residence time of which desirable nitroparaffins can be potentially produced. the liquid phase during the nitration reaction. The liquid See e.g., U.S. Pat. No. 2,489,320 (Nygaard et al.) and phase in general contains a low mole ratio of hydrocarbons to Albright, L. F., "Nitration of Paraffins. Chem. Engr., (1966) nitric acid, which favors oxidation chemistry at the expense of pp. 149-156. The prior art mixed vapor-liquid phase process, nitration. Oxidation therefore primarily occurs in the liquid however, was never practical for a number of reasons, includ phase. Because the gas in a downflow reactor is the continu ing because the conversion of nitric acid is low, the nitric acid ous phase and the liquid trickles down the reactor walls or is not readily recoverable, problems with reactor corrosion by packing, the amount of liquid phase(s) in the downflow reac the nitric acid, and difficulty in controlling reaction exotherm. tor is maintained at a low level. Consequently oxidation 0005. Obtaining a high yield of nitrated hydrocarbons is a chemistry is minimized. critical economic factor to be considered since low yields 0013. In contrast, in an upflow reactor, also referred to as necessitate the use of more feed and therefore result in higher a bubble column, the liquid is the continuous phase (and costs. Furthermore, when nitric acid is used as the nitrating bubbles rise quickly through the continuous liquid phase). agent, the unreacted nitric acid becomes a waste product and Thus, an upflow reactor maximizes the liquid holdup. costs are incurred for proper disposal of the waste. High Because, as noted above, oxidation primarily occurs in the conversion of the reactant hydrocarbon is also economically liquid phase, the upflow reactor maximizes the formation of critical in order to minimize capital and energy expenses oxidation byproducts. Similarly, coil and horizontal reactor associated with the purification and recycling of unreacted configurations also increase liquid residence time and there reactants. A need exists, therefore, for more economical, fore oxidation chemistry as compared to a downflow reactor. selective, and environmentally friendly processes for the A further disadvantage of coiled reactors is that they are not manufacture of nitrated hydrocarbons and their derivatives. well-suited for industrial scale production because of the difficulty of fabricating large scale reactors in this shape. BRIEF SUMMARY OF THE INVENTION 0014. The downflow configured reactor for use in the 0006. In one aspect, the invention provides a process for invention is preferably made of a corrosion resistant material, the nitration of hydrocarbons. The process comprises: pro Such as titanium. The reactor is optionally Surrounded by a viding a downflow configured reactor, reacting a hydrocar shell with input and output ports for circulating aheat transfer bon feedstock with aqueous nitric acid at a pressure of at least fluid. The heat transfer fluid, which can be, for example, an about 500 psi and a temperature of between about 140 and oil, allows the temperature of the reaction to be controlled to about 325 degrees Celsius; and recovering the formed within the desired parameters. It should be noted, however, nitrated compounds, wherein the aqueous nitric acid is a 10 to that because the reaction between the nitric acid and hydro 50 weight percent solution. carbon is exothermic, use of a shell and a heat transfer fluid 0007. In a second aspect, the invention provides processes are not required. The temperature of the reaction can be for preparing industrially useful downstream derivatives of regulated to be within the desired parameters by simply regu nitrated hydrocarbons. Such as nitroalcohols, aminoalcohols, lating the addition rate and/or concentration of the reactants. N-alkylaminoalcohols, alkylhydroxylamines, and oxazo 0015 To facilitate operation in downflow mode, the reac lidines. tor is generally of an elongated and linear shape, such as a 0008. In a third aspect, the invention provides nitrated tube, and is positioned so that reactants are added through an hydrocarbons, and derivatives thereof. entry port at or near the top of the reactor and then flowed US 2011/0028732 A1 Feb. 3, 2011

down the reactor for sufficient residence time to allow reac 0024 Examples of reactant hydrocarbons which may be tion to occur and formation of the desired product. The prod used in the process of the invention include, but are not uct mixture is collected through an exit port at or near the limited to, alkanes and cycloalkanes (including alkyl Substi tuted cycloalkanes), such as isobutane, n-butane, isopentane, bottom of the reactor. n-pentane, n-hexane, n-heptane, n-octane, 2,3-dimethylbu 0016. The reactor is optionally packed in order to improve tane, cyclohexane, cyclopentane, and methylcyclohexane: reactant mixing and heat transfer and/or to vary the reactor aryl alkanes such as ethylbenzene, toluene, Xylenes, isopro Volume. Suitable packing materials include, for example, pylbenzene: 1-methylnaphthalene and 2-methylnaphthalene glass beads, random packing, or structured packing, Such as and 4-methylbiphenyl; fused cycloalkanes, alkyl substituted those typically employed in distillation devices. Other pack fused aryl compounds, and fused cyclolalkane-aryl com ing materials are known in the art and may be used. pounds (including alkyl Substituted derivatives). Such as 0017. The hydrocarbon feed and nitric acid can be mixed, tetralin, decalin, and methylnaphthalene. The nitration of reactants that already have one or more nitro Substituents is or partially mixed, prior to entry into the reactor or, alterna also contemplated provided that the reactant still has an avail tively, they can be added individually, with mixing to occur able hydrogen. within the reactor. Further, the reactants, whether added 0025. In one preferred embodiment of the first aspect of together or individually, can be preheated prior to entry into the invention, the hydrocarbon is a linear or branched alkane the reactor. containing 4 or more carbon atoms, such as isobutane or 0.018. The nitric acid is delivered to the reactor in the form n-butane, and the nitric acid is delivered as 25-35 weight of an aqueous solution that contains at least about 10 weight percent, preferably about 30 weight percent, solution. For percent, preferably at least about 15 weight percent, more Such hydrocarbon materials, it is preferred to use a reaction preferably at least about 20 weight percent, of the acid. Fur temperature of between about 170 and 325 degrees Celsius and a pressure between about 800 and 1600 psi. For isobu ther, the solution contains no more than about 50 weight tane, a temperature of at least about 200 degrees and a pres percent, preferably no more than about 40 weight percent, sure of about 1000 to 1400 psi are particularly favorable. For and more preferably no more than about 35 weight percent, of n-butane, a temperature of at least about 220 degrees and a the acid. In further embodiments, the nitric acid solution pressure of about 1000 to 1500 psi are favorable. contains between about 15 and about 40 weight percent of the 0026. In another preferred embodiment, the hydrocarbon acid. In other embodiments, the nitric acid solution contains is a cyclic alkane, such as cyclohexane. The nitric acid is between about 18 and about 35 weight of the acid. preferably delivered as 25-35 weight percent, more prefer 0019. The mole ratio of hydrocarbon to nitric acid should ably about 30 weight percent, solution. For such hydrocar be at least about 1:1, more preferably at least about 1.2:1. bons, the preferred reaction temperature is at least 200 0020. The reaction temperature within the reactor is gen degrees Celsius and the preferred pressure is between about 600 and 1200 psi. erally controlled (for example with heat exchange fluid or 0027. In a further preferred embodiment, the hydrocarbon using heat generated from the reaction, as described above) to is an arylalkane, such as toluene, and the nitric acid is deliv at least about 140 degrees Celsius and to no more than about ered as 25-35 weight percent, more preferably about 30 325 degrees Celsius. In some embodiments, the temperature weight percent, Solution. The preferred reaction temperature is at least about 180 degrees, at least about 200 degrees, at for nitration of toluene is at least 180 degrees and the pre least about 230 degrees or at least about 240 degrees. In ferred pressure is between about 900 and 1200 psi. further embodiments, the temperature is no more than about 0028. As noted above, one of the advantages of the process 290 degrees, no more than about 280 degrees, no more than of invention is that it results in increased conversion rates of about 270 degrees, or no more than about 250 degrees. In starting reactants to either desired product or to materials that other embodiments, the temperature is between about 200 are readily recyclable or treatable, as compared to prior art and 250 degrees Celsius. systems. In some embodiments, therefore, at least 90 weight 0021. The pressure in the reactor is maintained at least %, more preferably at least 95 weight%, of the nitric acid is about 500 psi, more preferably at least about 1000 psi (68 consumed during the nitration reaction (determined as fol atm), and further preferably at least about 1200 psi (82 atm). lows: (grams nitric acid in-grams nitric acid out)/grams nitric Further preferably, the pressure is about 1600 psi (109 atm) or acid in). Most of the converted nitric acid that does not result less, preferably about 1500 psi (102 atm) or less, more pref in nitrated hydrocarbons is, for Some feedstocks, in the erably about 1400 psi (95 atm) or less. In further embodi readily recovered form of nitric oxide (NO). 0029. In a further preferred embodiment, the conversion ments, the pressure is between about 1000 psi (68 atm) and of hydrocarbon feedstock to nitrated hydrocarbon (deter 1400 psi (95 atm). Various methods known in the art can be mined by dividing the number of moles of nitrated hydrocar used for maintaining the pressure within the desired range bonformed by the number of moles of hydrocarbon that is fed including, for example, through the use of a back-pressure into the reaction) is at least 25 mole percent, more preferably regulator. at least 40 mole percent, and even more preferably at least 50 0022. The residence time of the reactants in the reactor is mole percent. preferably at least about 30 seconds, more preferably at least 0030 Preferred nitrated hydrocarbons prepared according about 90 seconds. Residence time can be controlled in various to the process of the invention include compounds of the ways including, for example, by the length and/or width of the formula (I): reactor or through the use of packing material. Residence time is determined by dividing the volume of the reactor by the inlet flow rates. 0023. Following sufficient residence time, the nitration products are collected from the reactor through the reactor's exit port. Further processing, such as distillation, may be carried out on the nitrated products to, for example, isolate or purify the desirable materials. US 2011/0028732 A1 Feb. 3, 2011 wherein R is C-C alkyl, C-C cycloalkyl, cycloalkyl pendently H, C-C alkyl, C-C cycloalkyl, or aryl. The alkyl-, aryl, or aryl-alkyl-, and R' is H or C-C alkyl: or R process of this embodiment comprises: (a) providing a and R' together with the carbon to which they are attached nitrated hydrocarbon of formula (I), wherein R is H, pre form a C-C cycloalkyl ring; and R, is H or C-C alkyl, pared as described above; and (b) condensing the nitrated provided that when R is an ethyl group, R' and R, are not hydrocarbon with an aldehyde in the presence of an alkaline simultaneously H. More preferred are compounds of formula catalyst. (I) wherein R is C-C alkyl or C-C cycloalkyl. Also pre 0035) A variety of alkaline catalysts can be used for the condensation reaction, although sodium hydroxide or trim ferred are compounds in which one of R' and R is an alkyl ethylamine are preferred. Aldehydes for the condensation group. step are generally of the formula R C(=O)—H and 0031. It should be noted that some of the nitrated com include, for instance, Such aldehydes as formaldehyde, pounds and derivatives described herein are formed as mix acetaldehyde, propionaldehyde, butyraldehyde, Valeralde tures. For example, the nitration of n-hexane forms 1, 2 and hyde, cyclohexanecarbaldehyde, and benzaldehyde (option 3-nitrohexanes concurrently. While it may be desirable to ally Substituted with alkyl, nitro, alkoxy, hydroxy, halogen, obtain one or more of the isomers in a Substantially pure form, amide or ester groups), with formaldehyde being particularly in many applications isomer purity is not necessary and the preferred. Typically the reaction involves batchwise or con combined mixture is generally suitable for use as is. The tinuously reacting the nitrated compound with an aqueous invention therefore encompasses mixtures of two or more of solution of the aldehyde at a mole ratio of about 1:1 and at a the nitrated compounds, and mixtures of two or more of their temperature of approximately 70-80°C. The catalyst is pref derivatives. erably used in an amount Sufficient to provide a normality of 0032. In a second aspect, the invention provides processes about 0.01-0.05 in the reaction mixture. Typically, the reac for the preparation of a variety of downstream derivatives (or tion is conducted without solvent. The product can be used mixtures thereof) from the nitrated hydrocarbons described directly as the aqueous solution or it can be recovered such as above, and preferably from the compounds of formula (I) (see by Stripping off volatiles under vacuum. Various known tech Scheme 1). Such derivatives are useful in many industrially niques, such as crystallization, may be used for further puri important applications. fying the product.

SCHEME 1 R4 NO R = H R2 NO R2 NO R3 N/ He- He- Hip y R OH R OH R X O R5 R5 R5 II III IV | R = H or C-C alkyl | NH-OH R2 N(R')2 R R. R OH V R 5 VI

0033. Thus, according to one embodiment of the second 0036. For nitroalkanes of formula (I) in which the nitro aspect of the invention, a process is provided for the prepa group is present on a carbon bearing two hydrogens (i.e., R' ration of a nitroalcohol of the formula II: and Rare both H), the condensation may optionally occur up to two times to generate a nitroalcohol with two hydroxy groups (i.e., R in formula (II) is —CH(R)OH) by using two II NO or more equivalents of the aldehyde. 0037. In some embodiments, preferred compounds of for mula (II) prepared according to the above process are those OH wherein R is C-C alkyl, more preferably C-C alkyl. Also R5 preferably, R is C-C alkyl. Further preferably, R is H. 0038. In other embodiments, preferred compounds of for 0034 wherein R is C-C alkyl, C-C cycloalkyl, mula (II) are those wherein RandR together with the carbon cycloalkyl-alkyl-, aryl, or aryl-alkyl-; R is H. C-C alkyl, to which they are attached form a C-C cycloalkyl ring, more or CH(OH) R, provided that when R is an ethyl group, R preferably a cyclohexyl ring. is not H; or Rand R together with the carbon to which they 0039 Particularly preferred compounds of formula (II) are attached form a C-C2 cycloalkyl ring; and R is inde are: 2-methyl-2-nitro-1-octanol; 2-ethyl-2-nitro-1-heptanol: US 2011/0028732 A1 Feb. 3, 2011

2-nitro-2-propyl-1-hexanol; 2-methyl-2-nitro-1-hexanol: 0045. According to a third embodiment, a process is pro 2-ethyl-2-nitro-1-pentanol; and 1-hydroxymethyl-1-nitrocy vided for the preparation of an oxazolidine of the formula clohexane. (IV): 0040. In a second embodiment of the second aspect of the invention, a process is provided for the preparation of an IV aminoalcohol of the formula (III): R4 R Y III NH2 R5C) O OH wherein R is C-C alkyl, C-C cycloalkyl, cycloalkyl R5 alkyl-, aryl, or aryl-alkyl-; R is H or C-C alkyl, provided that when R is an ethyl group, R is not H; or RandR together wherein R is C-C alkyl, C-C cycloalkyl, cycloalkyl with the carbon to which they are attached form a C-C, alkyl-, aryl, or aryl-alkyl-; R is H. C-C2 alkyl, or cycloalkyl ring; and R is H; or R. R. and the atoms to which CH(OH) R, provided that when R is an ethyl group, R is they are attached form an oxazolidine ring that is optionally not H; or RandR together with the carbon to which they are substituted with C-C alkyl; and R is H, C-C alkyl, attached form a C-C2 cycloalkyl ring; and R is indepen C-C cycloalkyl, or aryl. The process of this embodiment dently H, C-C alkyl, C-C cycloalkyl, or aryl. The pro comprises: (a) providing an aminoalcohol of formula (III) cess of this embodiment comprises: (a) providing a nitroal prepared as described above; and (b) reacting the aminoalco cohol of formula (II) prepared as described above; and (b) hol of formula (III) with formaldehyde. chemically reducing the nitroalcohol to the aminoalcohol. 0046 Single oxazolidine structures of formula (IV) may Chemical reduction of nitro compounds to amine is well be produced by the reaction of equimolar amounts of form known and a variety of techniques may be found in “Com aldehyde and the aminoalcohol of formula (III). Bis-oxazo prehensive Chemical Transformations”. Richard C. Larock lidines can be prepared by using 2 or greater equivalents of ed.; VCH Publishers, 1989, pages 411-415. Hydrogenation in formaldehyde with a compound of formula (III) in which R the presence of a hydrogenation catalyst is preferred. is CH(OH) R. 0041 Hydrogenation with a hydrogenation catalyst is a 0047. Typically, the reaction is conducted without solvent well known technique and the conditions for the reaction can at about 50-70° C. temperature for a period of 1-2 hours. The be easily determined by a person of ordinary skill in the art. product can be directly used without additional processing as Suitable catalysts include, without limitation, Raney nickel, the aqueous solution obtained from the condensation reac platinum and palladium. Raney nickel is preferred. Typically, tion, or further purification can be carried out, such as by the hydrogenation is conducted in an aqueous methanol or distillation and/or crystallization. ethanol solution at a temperature of about 70-100° C. and a 0048 Oxazolidines of formula (IV) are useful in a variety pressure of about 400-600 p.s.i.g. The catalyst is used in a of applications, including as curing agents, such as for phe concentration of between about 2 and 10 weight percent of the nolic novolac resins, or as biocides. In some embodiments, nitroalcohol to be hydrogenated. The product can be readily preferred compounds of formula (IV) prepared according to recovered through filtration of catalyst, followed by stripping the above process are those wherein R is C-C alkyl, more of solvents. Various known techniques, such as crystallization preferably C-Clo alkyl. Also preferably, R is H or C-Cs or distillation, may be used for further purifying the product. alkyl. Further preferably, R is H. 0042. The aminoalcohols of formula (III) are useful, for 0049. In other embodiments, preferred compounds of for instance, as neutralizing agents and pigment dispersants such mula (IV) are those wherein R and Ra, together with the as in paints and coatings, as CO or HS Scavengers in petro carbon to which they are attached, form an oxazolidine ring. leum refinery operations and natural gas processing, and as 0050. According to a fourth embodiment of the second catalysts or hardeners in epoxy or polyurethane applications. aspect of the invention, a process is provided for the prepa In some embodiments, preferred compounds of formula (III) ration of an N-alkylhydroxylamine of the formula V: are those wherein R is C-C alkyl, more preferably C-C, alkyl. Also preferably, R is C-C alkyl. Further preferably, R is H. In some embodiments, it is preferred that R is phenyl, optionally Substituted with hydroxy, halogen, nitro, R NH-OH C-C alkoxy, —CO-C-C alkyl, or—CONRR, where R and R are independently H or C-C alkyl. R. R. 0043. In other embodiments, preferred compounds of for mula (III) are those wherein RandR together with the carbon 0051 wherein R is C-C alkyl, C-C cycloalkyl, to which they are attached form a C-C cycloalkyl ring, more cycloalkyl-alkyl-, aryl, or aryl-alkyl-, and R' is H, or C-C, preferably a cyclohexyl ring. alkyl; or RandR' together with the carbon to which they are 0044 Particularly preferred compounds of formula (III) attached form a C-C cycloalkyl ring; and R is H or C-C, are: 2-amino-2-methyl-1-octanol; 2-amino-2-ethyl-1-hep alkyl, provided that when R is an ethyl group. R' and R, are tanol; 2-amino-2-propyl-1-hexanol; 2-amino-2-methyl-1- not simultaneously H. The process of this embodiment com hexanol; 2-amino-2-ethyl-1-pentanol; and 1-amino-1-hy prises: (a) providing a nitrated hydrocarbon of formula (I) droxymethylcyclohexane. prepared as described above; (b) chemically reducing the US 2011/0028732 A1 Feb. 3, 2011 nitrated hydrocarbon to the hydroxylamine. Chemical reduc 0057. In its third aspect, the invention provides novel tions of nitro compounds to hydroxylamines are well known nitrated hydrocarbons and novel derivative compounds. and a variety of techniques may be used. Examples of chemi According to a first embodiment of this third aspect, the cal reducing agents used to prepare hydroxylamines from nitrated hydrocarbons are of the formula I-1: nitroalkanes include samarium iodide, Zn/NH4C1, aluminum amalgam, and lithium aluminum hydride. Partially hydroge nating the nitrated hydrocarbon in the presence of a hydroge I-1 nation catalyst is a preferred technique. 0052 Partial hydrogenation of a nitro groups to hydroxy lamines is well known in the art and described, for instance, in U.S. Pat. No. 5,288,907 which is incorporated herein by reference. A preferred catalyst for the partial hydrogenation is 0058 wherein R7 is linear C-C, alkyl; and R is H or Pd/AlO, although other well known catalysts may be used. linear C-Cs alkyl, provided that RandR together with the Typically the hydrogenation is conducted in water or metha carbon to which they are attached form a linear Co-Cs alkyl nol at 50-75° C. and 30-600 p.s.i.g. H., with good agitation chain, and provided that the compound is not: 1-nitrodecane, for 4-6 hours. The product can be recovered by filtering off the 2-nitrodecane, 1-nitroundecane, 2-nitroundecane, 3-nitroun catalyst, then storing, and using directly as an aqueous solu decane, 4-nitroundecane, 5-nitroundecane, 6-nitroundecane, tion, or further isolation can done. Such as by recrystalliza 1-nitrododecane, 2-nitrododecane, 3-nitrododecane, 4-nitro tion. dodecane, 5-nitrododecane, 6-nitrododecane, 1-nitrotride 0053 Compounds of formula (V) function as radical scav cane, 2-nitrotridecane, 3-nitrotridecane, 6-nitrotridecane, engers and are therefore useful in a variety of applications, 1-nitrotetradecane, 1-nitropentadecane, 1-nitrohexadecane, Such as stabilizers and/or corrosion control agents in fuel, 2-nitrohexadecane, 1-nitroheptadecane, 1-nitrooctadecane, stabilizers of monomers, or as short-stopping agents in rubber or 2-nitrooctadecane. polymerizations. In some embodiments, preferred com 0059 Preferred compounds according to formula I-1 pounds of formula (V) are those wherein and R is C-C alkyl include those wherein R and R together with the carbon to and R' is C-C alkyl. Also preferred are compounds wherein which they are attached form a linear C-C alkyl, Ca-Cs RandR' together with the carbon to which they are attached alkyl, C-Cls alkyl, Co-Calkyl, Co-Calkyl, or Co-C form a C-C cycloalkyl ring, more preferably a Cs-Coring. alkyl. Particularly preferred compounds of formula (V) are N-tert butylhydroxylamine, N-sec-butylhydroxylamine, N-cyclo I0060 Also preferred are compounds wherein R and R' hexylhydroxylamine, mixtures of n-N-hexylhydroxy are unsubstituted. lamines, mixtures of n-N-Octylhydroxylamines. 0061 Particularly preferred compounds according to for mula I-1 are: 3-nitrodecane, 4-nitrodecane, 5-nitrodecane, 0054 The nitrated hydrocarbons and derivatives thereof 4-nitrotridecane, 5-nitrotridecane, 7-nitrotridecane, 2-ni can be further derivatized to provide additional useful mate trotetradecane, 3-nitrotetradecane, 4-nitrotetradecane, 5-ni rials. By way of one non-limiting example, the aminoalcohol trotetradecane, 6-nitrotetradecane, 7-nitrotetradecane, 2-ni of formula (III) can be mono or bis-alkylated at the amine to tropentadecane, 3-nitropentadecane, 4-nitropentadecane, yield N-alkylated aminoalcohols of formula VI: 5-nitropentadecane, 6-nitropentadecane, 7-nitropentade cane, 8-nitropentadecane, 3-nitrohexadecane, 4-nitrohexade cane, 5-nitrohexadecane, 6-nitrohexadecane, 7-nitrohexade VI Cane, 8-nitrohexadecane, 2-nitroheptadecane, 3-nitroheptadecane, 4-nitroheptadecane, 5-nitroheptade cane, 6-nitroheptadecane, 7-nitroheptadecane, 8-nitrohepta R OH decane, 9-nitroheptadecane, 3-nitrooctadecane, 4-nitroocta decane, 5-nitrooctadecane, 6-nitrooctadecane, 7-nitrooctadecane, 8-nitrooctadecane, and 9-nitrooctade CaC 0055 wherein R is C-C alkyl, C-C cycloalkyl, 0062. In a second embodiment of its third aspect, the cycloalkyl-alkyl-, aryl, or aryl-alkyl-; R is H. C-C2 alkyl, invention provides a nitroalcohol of the formula II-1: or CH(OH) R, provided that when R is an ethyl group, R is not H; or RandR together with the carbon to which they are attached form a C-C2 cycloalkyl ring; R is indepen II-1 dently H, C-C alkyl, C-C cycloalkyl, or aryl; and R is NO independently H or C-C alkyl. Compounds of formula VI find use, for instance, as neutralizing agents, dispersants and polyurethane catalysts. A preferred alkylated compound according to this example is 1-hydroxymethyl-1-(N,N-dim ethylamino)cyclohexane. 0063 wherein R is linear C-C, alkyl; and R' is H, 0056. The compound of formula VI is prepared by reduc linear C-Cs alkyl, or CH-OH, or R. R', and the carbon to tive alkylation (e.g., methylation) using 1 or 2 equivalents of which they are attached form an eight membered cycloalkyl an aldehyde as the alkyl source (e.g., formaldehyde for ring; provided that: methylation) and hydrogen over a hydrogenation catalyst, 0064 when R' is H or linear C-C alkyl, R and R', such as Raney nickel, at elevated temperature (e.g., 70-130° together with the carbon to which they are attached, form a C.) and pressure (e.g., 600-750 psi). linear Cs-Cs alkyl chain, US 2011/0028732 A1 Feb. 3, 2011

0065 when R' is CH-OH, R is linear C-C alkyl; and yielding procedures are preferred. One Such suitable proce 0066 the compound is not: 2-nitro-1-hexanol, 2-nitro-1- dure well known in the art is described in Kornblum, et al., J. heptanol, 2-nitro-1-octanol, 2-methyl-2-nitro-1-heptanol, or Am. Chem. Soc., Vol. 76, pp. 3209-3211, 1954. By way of 2-nitro-1-dodecanol. illustration, a typical procedure for the preparation of 1-ni 0067 Preferred compounds according to formula II-1 trooctane is provided in the examples below. include those wherein when R' is Horlinear C-Cs alkyl, R 0072. In a third embodiment, the invention provides ami and R', together with the carbon to which they are attached, noalcohols of the formula III-1: form a linear C7-Cls alkyl, Co-Cs alkyl, C1-C1s alkyl, Cis Cs alkyl, Cis-Cls alkyl, Cs-C alkyl, Cs-C alkyl, Cs-C2 alkyl, Cs-Co alkyl, or Cs-Cs alkyl chain. III-1 0068. Further preferred are compounds wherein when R' NH2 is CH-OH, R is linear C-C alkyl, or C-C alkyl. 0069. Also preferred are compounds wherein R and R' are unsubstituted. 0070 Particularly preferred compounds according to for mula II-1 are: 2-methyl-2-nitro-1-pentanol, 2-ethyl-2-nitro wherein R'' is linear C-C, alkyl; and R' is H. linear C-Cs 1-butanol, 2-methyl-2-nitro-1-hexanol, 2-ethyl-2-nitro-1- alkyl, or CH-OH; or R', R', and the carbon to which they pentanol, 2-ethyl-2-nitro-1-hexanol, 2-nitro-2-propyl-1- are attached form a C-C cycloalkyl ring: pentanol, 2-nitro-1-nonanol, 2-methyl-2-nitro-1-octanol, provided that: 2-ethyl-2-nitro-1-heptanol, 2-nitro-2-propyl-1-hexanol, 0073 when R'' is H or linear C-C alkyl, R'' and R', 2-nitro-1-decanol, 2-methyl-2-nitro-1-nonanol, 2-ethyl-2-ni together with the carbon to which they are attached, form a tro-1-octanol, 2-nitro-2-propyl-1-heptanol, 2-butyl-2-nitro linear C-Cs alkyl chain; 1-hexanol, 2-nitro-1-undecanol, 2-methyl-2-nitro-1-decanol, 0074 when R' is CHOH, R'' is linear C-C, alkyl; and 2-ethyl-2-nitro-1-nonanol, 2-propyl-2-nitro-1-octanol, 2-bu 0075 the compound is not: 2-amino-1-heptanol, 2-amino tyl-2-nitro-1-heptanol, 2-methyl-2-nitro-1-undecanol, 2-methyl-1-hexanol, 2-amino-1-octanol, 2-amino-2-ethyl-1- 2-ethyl-2-nitro-1-decanol. 2-propyl-2-nitro-1-nonanol, 2-bu hexanol, 2-amino-1-nonanol, 2-amino-2-methyl-1-octanol, tyl-2-nitro-1-octanol. 2-pentyl-2-nitro-1-heptanol, 2-nitro-1- 2-amino-1-decanol, 2-amino-2-octyl-1,3-propanediol. tridecanol, 2-methyl-2-nitro-1-dodecanol, 2-ethyl-2-nitro-1- 2-amino-2-butyl-1-hexanol, 2-amino-1-undecanol, 2-amino undecanol, 2-propyl-2-nitro-1-decanol, 2-butyl-2-nitro-1- 1-dodecanol, 2-amino-2-decyl-1,3-propanediol, 2-amino-1- nonanol. 2-pentyl-2-nitro-1-octanol, 2-nitro-1-tetradecanol, tridecanol, 2-amino-2-methyl-1-dodecanol, 2-amino-1-tet 2-hydroxymethyl-2-nitro-1-tetradecanol, 2-methyl-2-nitro radecanol, 2-amino-2-dodecyl-1,3-propanediol, 2-amino-2- 1-tridecanol, 2-ethyl-2-nitro-1-dodecanol, 2-propyl-2-nitro methyl-1-tridecanol, 2-amino-1-pentadecanol, 2-amino-2- 1-undecanol, 2-butyl-2-nitro-1-decanol, 2-pentyl-2-nitro-1- tridecyl-1,3-propanediol, 2-amino-1-hexadecanol, 2-amino nonanol, 2-hexyl-2-nitro-1-octanol, 2-nitro-1-pentadecanol, 2-tetradecyl-1,3-propanediol. 2-amino-2-methyl-1- 2-hydroxymethyl-2-nitro-1-pentadecanol, 2-methyl-2-nitro pentadecanol, 2-amino-2-hexyl-1-decanol, 2-amino-1- 1-tetradecanol, 2-ethyl-2-nitro-1-tridecanol, 2-propyl-2-ni heptadecanol, 2-amino-2-pentadecyl-1,3-propanediol. tro-1-dodecanol, 2-butyl-2-nitro-1-undecanol. 2-pentyl-2-ni 2-amino-1-octadecanol, or 2-amino-2-hexadecyl-1,3-pro tro-1-decanol, 2-hexyl-2-nitro-1-nonanol, 2-heptyl-2-nitro panediol. 1-octanol, 2-nitro-1-hexadecanol, 2-hydroxymethyl-2-nitro 0076 Preferred compounds according to formula III-1 1-hexadecanol, 2-methyl-2-nitro-1-pentadecanol, 2-ethyl-2- include those wherein, when R'' is H or linear C-C alkyl, nitro-1-tetradecanol. 2-propyl-2-nitro-1-tridecanol, 2-butyl R'' and R' together with the carbon to which they are 2-nitro-1-dodecanol. 2-pentyl-2-nitro-1-undecanol, 2-hexyl attached form a linear Cs-C1s alkyl, Co-C1s alkyl, C2-C1s 2-nitro-1-decanol, 2-heptyl-2-nitro-1-nonanol, 2-nitro-1- alkyl, Ca-Cs alkyl, C-Cls alkyl, C-C alkyl, C-C, heptadecanol, 2-hydroxymethyl-2-nitro-1-heptadecanol, alkyl, C-C alkyl, Co-Co alkyl, or C-C alkyl chain. 2-methyl-2-nitro-1-hexadecanol, 2-ethyl-2-nitro-1-pentade 0077. Further preferred are compounds wherein, when canol. 2-propyl-2-nitro-1-tetradecanol, 2-butyl-2-nitro-1- R" is CH-OH, R'' is linear C7-Cs alkyl, C, -C alkyl, tridecanol. 2-pentyl-2-nitro-dodecanol, 2-hexyl-2-nitro-1- C7-C alkyl, C7-Co alkyl, Co-C7 alkyl, C1-C1, alkyl, C undecanol, 2-heptyl-2-nitro-1-decanol, 2-nitro-1- C, alkyl, or Cs-C, alkyl. octadecanol, 2-hydroxymethyl-2-nitro-1-octadecanol, 0078. Also preferred are compounds wherein R'' and R' 2-methyl-2-nitro-1-heptadecanol, 2-ethyl-2-nitro-1-hexade are unsubstituted. canol. 2-propyl-2-nitro-1-pentadecanol, 2-butyl-2-nitro-1- 0079 Particularly preferred compounds according to for tetradecanol, 2-pentyl-2-nitro-1-tridecanol, 2-hexyl-2-nitro mula III-1 are: 2-amino-2-ethyl-1-pentanol, 2-amino-2-me 1-dodecanol, 2-heptyl-2-nitro-1-undecanol, 2-octyl-2-nitro thyl-1-heptanol, 2-amino-2-propyl-1-pentanol, 2-amino-2- 1-decanol, 2-nitro-1-nonadecanol, 2-methyl-2-nitro-1- heptyl-1,3-propanediol. 2-amino-2-ethyl-1-heptanol, octadecanol, 2-ethyl-2-nitro-1-heptadecanol, 2-propyl-2- 2-amino-2-propyl-1-hexanol, 2-amino-2-methyl-1-nonanol, nitro-1-hexadecanol, 2-butyl-2-nitro-1-pentadecanol, 2-amino-2-ethyl-1-octanol, 2-amino-2-propyl-1-heptanol, 2-pentyl-2-nitro-1-tetradecanol, 2-hexyl-2-nitro-1-tride 2-amino-2-nonyl-1,3-propanediol, 2-amino-2-methyl-1-de canol, 2-heptyl-2-nitro-1-dodecanol, 2-octyl-2-nitro-1-unde canol, 2-amino-2-ethyl-1-nonanol, 2-amino-2-propyl-1-oc canol, and 1-hydroxymethyl-1-nitrocyclooctane. tanol, 2-amino-2-butyl-1-heptanol, 2-amino-2-methyl-1-un 0071. It should be noted that that the nitration process decanol, 2-amino-2-ethyl-1-decanol, 2-amino-2-propyl-1- described above is the preferred procedure by which most of nonanol, 2-amino-2-butyl-1-octanol, 2-amino-2-pentyl-1- the compounds of formula I-1 are prepared. However, the heptanol, 2-amino-2-undecyl-1,3-propanediol, 2-amino-2- process tends to provide low yields of 1-nitroalkane products. ethyl-1-undecanol, 2-amino-2-propyl-1-decanol, 2-amino-2- Therefore, for preparing 1-nitroalkane products, other higher butyl-1-nonanol, 2-amino-2-pentyl-1-octanol, 2-amino-2-

US 2011/0028732 A1 Feb. 3, 2011 azacyclopentane, 4-pentyl-4-undecyl-1-Oxa-3- temperature profile along the reactor's length. The reactor is azacyclopentane, 4-decyl-4-hexyl-1-Oxa-3-azacyclopentane, 46" long and has a shell which is 1.25" OD 304 stainless steel 4-heptyl-4-nonyl-1-Oxa-3-azacyclopentane, 4.4-dioctyl-1- with a /2" OD (0.37"ID) type 2 titanium process tubing and oxa-3-azacyclopentane, 4-heptadecyl-1-Oxa-3-azacyclopen a /s." OD (0.093"ID) type 2 titanium thermowell. A very fine, tane, 5-heptadecyl-1-aza-3,7-dioxabicyclo[3.3.0 octane, movable thermocouple is inserted into the thermowell for the 4-hexadecyl-4-methyl-1-Oxa-3-azacyclopentane, 4-ethyl-4- temperature profile measurement. The thermowell can be pentadecyl-1-Oxa-3-azacyclopentane, 4-propyl-4-tetradecyl 1-Oxa-3-azacyclopentane, 4-butyl-4-tridecyl-1-Oxa-3-azacy removed and the reactor filled with packing. The reactor is clopentane, 4-dodecyl-4-pentyl-1-Oxa-3-azacyclopentane, mounted vertically. The nitric acid and hydrocarbon reactant 4-hexyl-4-undecyl-1-Oxa-3-azacyclopentane, 4-decyl-4- streams are mixed in a Swagelok “T” at room temperature heptyl-1-Oxa-3-azacyclopentane, and 4-octyl-4-nonyl-1- prior to entering the reactor. Hot oil used is fed to the reactor oxa-3-azacyclopentane. shell countercurrent to the reactants. The reactor effluent is I0086. In a fifth embodiment of its third aspect, the inven cooled in a shell-and-tube heat exchanger using city water as tion provides the following hydroxylamines: 2-(hydroxy the coolant. The effluent is then depressurized with the gases lamino)hexane, 3-(hydroxylamino)hexane, 2-(hydroxy and liquids collected, measured, and analyzed. lamino)octane, and 3-(hydroxylamino)octane. 0092. In the examples below, the mass balance of the 0087 Alkyl as used in this specification, encompasses nitration reaction is determined by GC/MS for gases, aque straight and branched chain aliphatic groups having the indi ous, nitrated hydrocarbons, and scrubber liquids, Karl Fisher cated number of carbonatoms. If no number is indicated (e.g., titration for water content, potentiometric titration for strong/ aryl-alkyl-), then 1-6 alkyl carbons are contemplated. Pre weak acid quantification, and HPLC for weak acid identifi ferred alkyl groups include, without limitation, methyl, ethyl, cation and quantification. Reactant residence times are cal propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pen culated based on the volume of the reactor divided by the tyl, hexyl, heptyl, and octyl. Unless otherwise indicated, the flowrates of the feeds at room temperature and the indicated alkyl group is optionally substituted with 1, 2, or 3, preferably reaction pressure. 1 or 2, more preferably 1, substituents that are compatible with the syntheses described herein. Such substituents 0093. In the Examples, the hydrocarbon compound is include, but are not limited to, nitro, halogen, carboxylic acids nitrated using nitric acid as the nitrating agent. Process con (e.g., Co-C-COOH), and C-C alkene. Unless otherwise ditions as well as key performance measurements are pro indicated, the foregoing Substituent groups are not them vided in Table 1. selves further substituted. 0094. Example 2 (cyclohexane nitration at 600 psi and 0088 An “aryl group is a C6-C12 aromatic moiety com 210°C.) shows that lower operating pressure tends to reduce prising one to three aromatic rings. Preferably, the aryl group raw material conversion and yields. The lower conversion is is a C6-C10 aryl group. Preferred aryl include, without limi partially offset by the presence of significantly more nitric tation, phenyl, naphthyl, anthracenyl, and fluorenyl. More oxide which may be recovered as nitric acid. Lower conver preferred are phenyl and naphthyl. Unless otherwise indi sion can also be compensated for by increasing the residence cated, the aryl group is optionally Substituted with 1, 2, or 3. time in the reactor. preferably 1 or 2, more preferably 1, substituents that are compatible with the syntheses described herein. Such sub 0.095 Example3 demonstrates the use of packing material stituents include, but are not limited to, C-C alkyl, nitro, in the reactor. Packing increases mixing and heat transfer in halogen, carboxylic acids (e.g., Co-C-COOH), and C-C, the reactor, but also increases the amount of liquid holdup in alkene. Unless otherwise indicated, the foregoing Substituent the reactor which favors increased formation of oxidation groups are not themselves further Substituted. byproducts. 0089. The term "cycloalkyl refers to saturated and par 0096 Introducing packing significantly increased nitric tially unsaturated cyclic hydrocarbon groups having the indi acid conversion (compared to example 2). However, the low cated number of ring carbon atoms. If no number is specified, nitric acid and cyclohexane yields show that the increased then 3 to 12 carbons, preferably 3 to 8 carbons, and more conversion primarily goes to oxidation byproducts. preferably 3 to 7 carbons, are contemplated. Preferred 0097. The process conditions of Example 8 provide rela cycloalkyl groups include, without limitation, cyclopropyl. cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclo tively low nitric acid conversion (for n-butane). Examples 9 hexenyl, cycloheptyl, and cyclooctyl. Unless otherwise indi and 10 demonstrate how the process conditions can be cated, the cycloalkyl group is optionally substituted with 1, 2, changed to improve the conversion levels. or 3, preferably 1 or 2, more preferably 1, substituents that are 0098. Example 9 shows that nitric acid conversion is sig compatible with the syntheses described herein. Such sub nificantly increased (compared to Example 8) by using a stituents include, but are not limited to, C-C alkyl, nitro, higher temperature. The Example also demonstrates that the halogen, carboxylic acids (e.g., Co-C-COOH), and C-C, increase in nitric acid conversion occurs despite the use of less alkene. A preferred substituent is C-C alkyl. excess n-butane. 0090 The following examples are illustrative of the inven 0099 Example 10 demonstrates that nitric acid conver tion but are not intended to limit its scope. sion is significantly increased (compared to example 8) by increasing the pressure. This occurs despite the use of less EXAMPLES excess n-butane. 0091 General. Various aspects of the invention are dem 0100 Example 11 shows that nitric acid conversion is onstrated using a lab scale reactor. The reactor is a single tube significantly increased (compared to example 8) by increas shell-and-tube heat exchanger with a thermowell located axi ing the oil temperature and pressure. In this case the same ally down the center of the reactor in order to determine the mole ratio of reactants is used as in Example 8. US 2011/0028732 A1 Feb. 3, 2011

TABLE 1 Process Conditions and Key Performance Measurements for Exemplary Hydrocarbons Nitrated According to the Invention. Pressure Temp. Feed:HNO3 (HNO3) Time NA HC NA HC Ex Feed (psi) (° C.) (mol) (wt.%) (s) conversion conversion yield yield 1 cyclohexane 1200 210 2.5: 30 120 99.9 34.8 1.01 128 2 cyclohexane 600 210 2.O: 30 120 78.0 25.9 1.67 1.29 3 cyclohexane 600 230 2.O: 30 75 1OOO 32.7 2.74 2.58 (packed) 4 isobutane 1200 210 1.65: 30 120 95.9 23.0 1.64 0.83 5 isobutane 1OOO 220 1.3: 30 120 95.6 29.0 1.76 O.94 6 isobutane 14OO 2OO 1.3: 30 120 95.5 29.7 1.89 0.82 7 n-butane 12SO 220 1.6: 30 120 95.2 42.8 124 O.92 8 n-butane 1OOO 2OO 2.O: 30 120 57.5 28.7 2.81 169 9 n-butane 1OOO 240 1.2: 30 120 95.2 43.7 1.54 0.92 10 n-butane 1SOO 2OO 1.2: 30 120 95.1 52.9 1.39 O.87 11 n-butane 1SOO 240 2.O: 30 120 97.9 36.4 O.94 0.87 12 toluene 900 18O 2.375: 30 120 71.1 28.9 1.15 1.45 13 toluene 1200 160 1.75: 30 120 73.7 32.3 1.10 1.14 14 toluene 1200 2OO 3: 30 120 91.6 23.9 O.84 120 Nitric Acid Conversion = 100 x (grams nitric acid in-grams nitric acid out) grams nitric acid in. bHC (hydrocarbon) Conversion = 100 x (grams HC in-grams HC out), grams HC in. Nitric Acid Yield=grams nitric acid consumed grams nitro-HC produced. Grams nitric acid consumed = (moles nitric acid fed-moles NO produced) x 63. This calculation treats unreacted nitric acid as a yield loss. (Note: 63 g/mole is the molecular weight of nitric acid) (HC yield = grams HC consumed gnitro-HC produced. Grams HC consumed = grams HC in-grams HC out. This calculation treats unreacted HC as being recoverable.

0101 Additional data for the n-butane nitration examples (Examples 7-11) are provided in Table 2, including selectivity TABLE 2-continued data. 2-Nitrobutane selectivity is calculated as 100x(grams 2-nitrobutane made/(grams 2-nitrobutane made+grams 1-ni- E 2-nitrob lectivi 2-nth bylie trobutane made). The 2-nitrobutane:carboxylic acid weight X. nitrobutane selectivity acid weight ratio ratio is calculated as grams 2-nitrobutane/(grams of acetic 9 93.9 2.7 acid-grams of propionic acid-grams of butyric acid). s

TABLE 2 2-nitrobutane:carboxylic 0102 Table 2 shows the selectivity to 2-nitrobutane is Ex. 2-nitrobutane selectivity acid weight ratio consistent over a wide range of process conditions demon 7 95.2 4.0 strating the robustness of the process of the invention. 8 94.8 2.3 0103) Further examples of nitrated compounds and pro cess conditions are provided in Table 3.

TABLE 3

residence mole ratio, nitric acid time, hydrocarbon: nitric strength, hot oil pressure, hydrocarbon Seconds acid wt.% temp., C. psig 1-nitro 2-nitro 3-nitro 4-nitro

n-pentane 2O 2.5 30 205 400 4.7 24.3 71.1 NA n-hexane 2O 2.5 30 200 OOO 3.2 49.7 47.1 NA n-Octane 2O 2 30 215 OOO 2.1 34.2 32.1 31.6 Isopentane 2O 3 30 8O 400 Mixture of Isomers 3-methylpentane 2O 3 30 70 400 Mixture of Isomers 2,3 dimethylbutane 2O 3 30 70 400 Mixture of Isomers cyclopentane 2O 2 30 220 900 100% Methylcyclopentane 2O 4 2O 90 400 Mixture of Isomers Methylcyclohexane 2O 2 30 200 200 Mixture of Isomers Ethylcyclohexane 2O 3 30 85 400 Mixture of Isomers Isopropylcyclohexane 2O 3 30 85 400 Mixture of Isomers Tert-butylcyclohexane 2O 3 30 90 400 Mixture of Isomers cyclooctane 2O 2 30 215 200 100% Isooctane 2O 2 30 210 OOO Mixture of Isomers n-hexadecane 2O 2 30 220 600 Mixture of Isomers Tetralin 2O 3 30 55 OOO Mixture of Isomers Decalin 2O 3 25 85 400 Mixture of Isomers ethylbenzene 2O 3 30 55 500 : n-Propylbenzene 2O 3 30 75 OOO : US 2011/0028732 A1 Feb. 3, 2011 10

TABLE 3-continued residence mole ratio, nitric acid time, hydrocarbon: nitric strength, hot oil pressure, hydrocarbon Seconds acid wt.% temp., C. psig 1-nitro 2-nitro 3-nitro 4-nitro

Cumene 90 2 30 140 1SOO : Isobutylbenzene 120 2 30 145 1SOO : The amounts of 1-nitro, 2-nitro, etc. are the relative amounts of the nitro isomers. The calculation involves summing all of the isomers then determining the distribution using gc area 96. * - For aromatic compounds, the nitration occurs exclusively at the carbon next to the ring,

Example 12 Preparation of 1-Nitrooctane TABLE 5 0104. This example is illustrative of an alternative proce- Nitrated Compound dure for the preparation of 1-nitroalkanes. 1-nitroisobutane 0105. In a 3-neck flask fitted with a stirrer, dropping funnel 1-nitrobutane and reflux condenser protected by a drying tube, are placed E. 100 g (0.65 mol) of silver nitrite and 150 mL anhydrous ether. 1-ni E. 0106. The mixture is cooled to 0°C. and then, with con- 2-nitrohexane tinuous stiffing (in the absence of light), 120 g (0.5 mol) of 1-nitroheptane n-octyl iodide are added over a period of 2 hours. After the ;ION addition is complete, the mixture is stirred at 0° C. for 24 4-nitroheptane hours, followed by stiffing at room temperature for an addi- 1-nitrooctane tional 36 hours. The silver salts are removed by filtration and 2-nitrooctane washed with ether. The combined ether solutions is concen- IGN trated to an oil which is rectified under reduced pressure. The 2-nitrononane product boiling between 71.5-72°C/3 torris collected (64.9 3-nitrononane 9. 83% yield). 4-nitrononane 0107 Examples of nitrated compounds that are prepared ity. as described in Examples 1-11 above (using appropriate start- 2-nitrodecane ing hydrocarbon) are listed in Table 4. 3-nitrodecane 4-nitrodecane 5-nitrodecane TABLE 4 1-nitroundecane 2-nitroundecane Typical Purity 3-nitroundecane Nitrated Compound (GC) BP or MP 4-nitroundecane 5-ni 2-nitroisobutane >98% water azeotrope 6 nitroundecane 56 C.185 torr 1-nitrododecane (77% nitro/23% water) 2-nitrododecane 2-nitrobutane Mixture of 1 and 2 3-nitrododecane isomers 4-nitrododecane 2-nitropentane Nearly 1:1 mixture 58 C. 10 torr 5-nitrododecane of 2,3 isomers 6-nitrododecane (>98.5% by GC) 1-nitrotridecane 3-nitrohexane Mixture 2,3- 56-58 C.;9.5 torr 2-nitrotridecane somers 3-nitrotridecane 4-nitrooctane Mixture of 2,3,4 66–76° C.f4 torr 4-ni-OC(C8le soners 5-nitrotridecane (>99.5% by GC) 6-nitrotridecane 1-nitrocyclopentane 95-99% 76° C. 19 torr 7-nitrotridecane 1-nitrocyclohexane >98% 1-nitrotetradecane 1-nitrocyclooctane 92% nitrocyclooctane, 76 C.1.2 torr 2-nitrotetradecane 5% nitrocyclooctene 3-nitrotetradecane phenylnitromethane 90% + contaminants 83 C.;23 torr 4-nitrotetradecane 1,1,3,3- Mixture of 5-nitrotetradecane tetramethylnitrobutane nitroISOmers 6-nitrotetradecane 1-methyl-1- 80% + isomers 7-nitrotetradecane nitrocyclopentane 1-nitropentadecane 1-methyl-1- 60% + isomers 46-59 C.1 torr 2-nitropentadecane nitrocyclohexane 3-nitropentadecane 1-phenylnitroethane >979, 95.2 torr 4-nitropentadecane 2-phenyl-2-nitropropane >70% 90 C.O.3 torr 5-nitropentadecane 6-nitropentadecane 7-nitropentadecane 0108. Following the procedures described above and mak- 8-nitropentadecane ing non-critical variations, the following additional nitrated 1-nitrohexadecane compounds are prepared from the appropriate starting hydro- 2-nitrohexadecane carbon (Table 5). US 2011/0028732 A1 Feb. 3, 2011 11

TABLE 5-continued TABLE 6-continued Nitrated Compound Typical Purity Nitroalcohol (area % GC or LC) BP or MP 3-nitrohexadecane 4-nitrohexadecane 2-nitro-2-propyl-1-hexanol Mixture of 2,3,4- 5-nitrohexadecane isomers 6-nitrohexadecane 1-hydroxymethyl-1- 93.5% 7-nitrohexadecane nitrocyclopentane 8-nitrohexadecane 1-hydroxymethyl-1- 95% 1-nitroheptadecane nitrocyclohexane 2-nitroheptadecane 1-hydroxymethyl-1- 51% 3-nitroheptadecane nitrocyclooctane 4-nitroheptadecane (1,1-bis-hydroxymethyl-1- >99% Mp = 96.4° C. 5-nitroheptadecane nitromethyl)benzene 6-nitroheptadecane 2-nitro-2-phenyl-1-propanol 86.5% (LC) Mp = 52-53 C. 7-nitroheptadecane 8-nitroheptadecane 9-nitroheptadecane 1-nitrooctadecane 0111 Following the procedures described above and mak 2-nitrooctadecane ing non-critical variations, the following additional nitroal 3-nitrooctadecane cohols are prepared from the appropriate starting hydrocar 4-nitrooctadecane 5-nitrooctadecane bon (Table 7). 6-nitrooctadecane 7-nitrooctadecane TABLE 7 8-nitrooctadecane 9-nitrooctadecane Nitroalcohol phenylnitromethane naphthylnitromethane 2-nitro-1-pentano nitromethylbiphenyl 2-hydroxymethyl 2-nitro-1-pentanol 2-methyl-2-nitrobutane 2-nitro-1-hexanol 3-nitropropylbenzene 2-hydroxymethyl 2-nitro-1-hexanol 2-methyl-2-nitro -pentanol 2-e hyl-2-nitro-1-butanol 2-nitro-1-heptano Example 13 2-hydroxymethyl 2-nitro-1-heptanol 2-methyl-2-nitro -hexanol Preparation of 2-Methyl-2-Nitro-1-Butanol 2-nitro-1-octanol 2-methyl-2-nitro -nonanol 2-e hyl-2-nitro-1-octanol 0109. A 2-liter 3-neck flask is equipped with a mechanical 2-nitro-2-propyl-1 -heptanol stirrer, a reflux condenser with a nitrogen bubbler, an addition 2-butyl-2-nitro-1- hexanol funnel and a temperature controller with heating mantle and 2-nitro-1-undecan ol thermocouple. The flask is charged with aqueous formalde 2-hydroxymethyl 2-nitro-1-undecanol hyde solution (420 mL, 37% active, 5.64 mol) and 4 mL 2-methyl-2-nitro -decanol 2-ethyl-2-ni ro-1-nonanol triethylamine catalyst. The addition funnel is charged with 2-propyl-2-nitro-1 -octanol 2-nitrobutane (554.1 g, 5.37 mol). The 2-nitrobutane is added itro-1- heptanol dropwise, over a period of 7 hours to the formaldehyde solu -dodecan ol tion, which is being stirred under nitrogen. The reaction is roxymethyl 2-nitro-1-dodecanol hyl-2-nitro -undecanol maintained at 40° C. during the addition. After all the 2-ni hyl-2-ni ro-1-decanol trobutane is added, the turbid mixture is warmed to 45° C. for 2-propyl-2-nitro-1 -nonanol 30 min, and then heating and stirring are discontinued over 2-butyl-2-nitrO-1-octanol night. If a GC analysis indicates the reaction is not yet com 2-pentyl-2-nitro-1 -heptanol 2-nitro -tridecanol plete; an additional 10.9 g aqueous formaldehyde is added 2-hydroxyme 2-nitro-1-tridecanol and the mixture stirred at 45° C. for 2.5 hours. Upon cooling 2-me hyl-2-nitro-1-dodecanol to room temperature, the reaction mass separates into an oil 2-ethyl-2-nitro -undecanol layer with a smaller, separate water layer. The oil layer is 2-propyl-2-nitro-1 -decano 2-butyl-2-nitro -nonanol collected (1022.8 g. 97.9% of theory) and GC indicates 2-pentyl-2-nitro-1 -octanol 94.8% purity. The oil is used without further purification. 2-nitro -tetradecanol 0110. Additional examples of nitroalcohols that are pre 2-hydroxyme 2-nitro-1-tetradecanol pared as described above (Substituting the appropriate start 2-me hyl-2-nitro-1-tridecanol 2-ethyl-2-nitro -dodecanol ing materials) are listed in Table 6. 2-propyl-2-nitro-1 -undecanol 2-butyl-2-nitro -decanol TABLE 6 2-pentyl-2-nitro-1 -O3O 2-hexyl-2-nitro-1- octanol Typical Purity 2-nitro-1-penta ecanol Nitroalcohol (area % GC or LC) BP or MP 2-hydroxymethyl 2-nitro-1-pentadecanol 2-me hyl-2-nitro-1-tetradecanol 2-methyl-2-nitro-1-butanol 95% 2-ethyl-2-nitro -tridecanol 2-ethyl-2-nitro-1-pentanol Mixture with 2 2-propyl-2-nitro-1 -dodecanol methyl-2-nitro-1- 2-butyl-2-nitro -undecanol hexanol: 93% by GC 2-pentyl-2-nitro-1 -decanol US 2011/0028732 A1 Feb. 3, 2011 12

toluene under identical conditions. The yield of crude, TABLE 7-continued stripped product is 196.6 g (79% of theory). The product is vacuum distilled through a fractionating column packed with Nitroalcohol stainless steel mesh; the product boiling between 85-86° 2-hexyl-2-nitro-1-nonanol C./15 torris collected. GC analysis indicates >97% purity for 2-heptyl-2-nitro-1-octanol the water white oil. 2-hydroxymethyl-2-nitro-1-octanol 2-methyl-2-nitro-1-heptanol 0113. Additional examples of aminoalcohols that are pre 2-ethyl-2-nitro-1-hexanol pared as described above (Substituting the appropriate start 2-nitro-2-propyl-1-pentanol ing materials) are listed in Table 8. 2-nitro-1-nonanol 2-hydroxymethyl-2-nitro-1-nonanol 2-methyl-2-nitro-1-octanol TABLE 8 2-ethyl-2-nitro-1-heptanol 2-nitro-1-decanol Typical Purity 2-hydroxymethyl-2-nitro-1-decanol Aminoalcohol (GC) BP or MP 2-nitro-1-hexadecanol 2-hydroxymethyl-2-nitro-1-hexadecanol 2-amino-2-methyl-1-butanol 97.8% 85-86 C.F 15 torr hyl-2-nitro-1-pentadecanol 2-amino-2-methyl-1-hexanol Mixture with 2- 103-106 C. 15 mm 2-ethyl-2-nitro-1-tetradecanol amino-2-ethyl-1- -2-nitro-1-tridecanol pentanol. 96% 2-amino-2-propyl-1-hexanol Mixture of 2,3,4 99 C.? 2.2 mm 2-butyl-2-nitro-1-dodecanol isomers. 92.2% ecanol 2-hexyl-2-nitro-1-decanol 1-hydroxymethyl-1- 96.6% 111-112 C. 15 mm -2-nitro-1-nonanol aminocyclopentane 1-hydroxymethyl-1- 98.6% 106-108 C. 7 torr -heptadecano aminocyclohexane 2-hydroxymethyl-2-nitro-1-heptadecanol 1-hydroxymethyl-1- hyl-2-nitro-1-hexadecanol aminocycloheptane itro-1-pentadecanol 1-hydroxymethyl-1- 71.5% 139-141 C.9 mm -2-nitro-1-tetradecanol 2-butyl-2-nitro-1-tridecanol aminocyclooctane (mp = 40-50 C.) 2-pentyl-2-nitro-dodecanol (1,1-bis-hydroxymethyl-1- >99% Mp = 117.4° C. 2-hexyl-2-nitro-1-undecanol aminomethyl)benzene 2-heptyl-2-nitro-1-decanol 2-amino-2-phenyl-1-propanol 79% 115-121 C. 2.2 mm 2-nitro-1-octadecanol 2-hydroxymethyl-2-nitro-1-octadecanol 2-methyl-2-nitro-1-heptadecanol 0114. Following the procedures described above and mak 2-ethyl-2-nitro-1-hexadecanol ing non-critical variations, the following additional aminoal 2-propyl-2-nitro-1-pentadecanol 2-butyl-2-nitro-1-tetradecanol cohol compounds are prepared from the appropriate starting 2-pentyl-2-nitro-1-tridecanol materials (Table 9). 2-hexyl-2-nitro-1-dodecanol 2-heptyl-2-nitro-1-undecanol TABLE 9 2-octyl-2-nitro-1-decanol 2-nitro-1-nonadecanol Aminoalcohol 2-hydroxymethyl-2-nitro-1-nonadecanol 2-methyl-2-nitro-1-octadecanol 2-amino-1-pentano 2-ethyl-2-nitro-1-heptadecanol 2-amino-2-propyl ,3-propanediol 2-propyl-2-nitro-1-hexadecanol 2-amino-1-hexanol 2-butyl-2-nitro-1-pentadecanol 2-amino-2-butyl-1,3-propanediol 2-pentyl-2-nitro-1-tetradecanol 2-amino-2-methyl-1-pentanol 2-hexyl-2-nitro-1-tridecanol 2-amino-2-ethyl-1-butanol 2-heptyl-2-nitro-1-dodecanol 2-amino-1-heptano 2-octyl-2-nitro-1-undecanol 2-amino-2-pentyl-1,3-propanediol 2-amino-2-ethyl-1-pentanol 2-amino-1-octanol 2-amino-2-hexyl-1,3-propanediol 2-amino-2-methyl-1-heptanol Example 14 2-amino-2-ethyl-1-hexanol 2-amino-2-propyl-1-pentanol Preparation of 2-Amino-2-Methyl-1-Butanol 2-amino-1-nonano 2-amino-2-heptyl-1,3-propanediol 0112 A 2-liter Parr autoclave is charged with methanol 2-amino-2-methyl-1-octanol (300 mL) and Raney Nickel catalyst (R-3 111 grade, 26.5 g. 2-amino-2-ethyl-1-heptanol 2-amino-1-decano wet weight). The reactor is sealed, purged with nitrogen fol 2-amino-2-octyl-1,3-propanediol lowed by purging with hydrogen and then brought up to 65° 2-amino-2-methyl-1-nonanol C. under 625 psi hydrogen pressure. With rapid stirring, a 2-amino-2-butyl-1-nonanol solution of 2-nitro-2-methyl-1-butanol. in water (450g total 2-amino-2-pentyl-1-octanol 2-amino-1-tetradecanol solution, 71% actives) is added over 1.5 hours while main 2-amino-2-dodecyl-1,3-propanediol taining 65° C./610 psi hydrogen. When the addition is com 2-amino-2-methyl-1-tridecanol pleted, the reaction is allowed to continue for an additional 10 2-amino-2-ethyl-1-dodecanol 2-amino-2-propyl-1-undecanol minutes followed by cooling to room temperature. The auto 2-amino-2-butyl-1-decanol clave is vented, opened and the crude product isolated via 2-amino-2-pentyl-1-nonanol vacuum filtration. The methanol solvent is removed on a 2-amino-2-hexyl-1-octanol rotary evaporator at 50° C./29" vacuum, followed by azeotro 2-amino-1-pentadecanol pically removing the last remnants of water with 100 mL US 2011/0028732 A1 Feb. 3, 2011

TABLE 9-continued TABLE 9-continued

Aminoalcohol Aminoalcohol 2-amino-2-tridecyl-1,3-propanediol 2-amino-1-octadecanol 2-amino-2-me hyl-1-tetradecanol 2-amino-2-hexadecyl-1,3-propanediol 2-amino-2-ethyl-1-tridecanol 2-amino-2-methyl-1-heptadecanol 2-amino-2-propyl-1-dodecanol 2-amino-2-ethyl-1-hexadecanol 2-amino-2-butyl-1-undecanol 2-amino-2-propyl-1-pentadecanol 2-amino-2-pen tyl-1-decanol 2-amino-2-butyl-1-tetradecanol 2-amino-2-hexyl-1-nonanol 2-amino-2-pentyl-1-tridecanol 2-amino-1-hexadecanol 2-amino-2-hexyl-1-dodecanol 2-amino-2-tetradecyl-1,3-propanediol 2-amino-2-heptyl-1-undecanol 2-amino-2-me hyl-1-pentadecanol 2-amino-2-octyl-1-decanol 2-amino-2-ethyl-1-tetradecanol 2-amino-1-nonadecanol 2-amino-2-propyl-1-tridecanol 2-amino-2-heptadecyl-1,3-propanediol 2-amino-2-butyl-1-dodecanol 2-amino-2-methyl-1-octadecanol 2-amino-2-pen tyl-1-undecanol 2-amino-2-ethyl-1-heptadecanol 2-amino-2-hexyl-1-decanol 2-amino-2-propyl-1-hexadecanol 2-amino-2-hep tyl-1-nonanol 2-amino-2-butyl-1-pentadecanol 2-amino-1-hep adecanol 2-amino-2-pentyl-1-tetradecanol 2-amino-2-pen adecyl-1,3-propanediol 2-amino-2-hexyl-1-tridecanol 2-amino-2-me hyl-1-hexadecanol 2-amino-2-heptyl-1-dodecanol 2-amino-2-ethyl-1-pentadecanol 2-amino-2-octyl-1-undecanol 2-amino-2-ethyl-1-octanol 1-hydroxymethyl-1-aminocyclononane 2-amino-2-pro pyl-1-heptanol 1-hydroxymethyl-1-aminocyclodecane 2-amino-2-butyl-1-hexanol 1-hydroxymethyl-1-aminocycloundecane 2-amino-1-un ecanol 1-hydroxymethyl-1-aminocyclododecane 2-amino-2-nonyl-1,3-propanediol 2-amino-2-me hyl-1-decanol 2-amino-2-ethyl-1-nonanol 2-amino-2-pro pyl-1-octanol Example 15 2-amino-2-butyl-1-heptanol Preparation of 3-Oxa-1-azaspiro4.5 decane 2-amino-1-do ecanol 2-amino-2-decyl-1,3-propanediol 0115 To a 500 mL flask containing 1-amino-cyclohexyl 2-amino-2-me hyl-1-undecanol methanol (135 g, 1.05 mol) and methanol (50 mL) is added 2-amino-2-ethyl-1-decanol methyl formcel (53 mL of 55% formaldehyde in methanol/ 2-amino-2-pro pyl-1-nonanol water, 1.06 mol) dropwise over a 1 hour period. During the 2-amino-2-butyl-1-octanol addition, the stirred solution is warmed gently from room 2-amino-2-pentyl-1-heptanol temperature to 37° C. After the addition is completed, the 2-amino-1-tridecanol mixture is allowed to stir overnight at room temperature. The 2-amino-2-un ecyl-1,3-propanediol clear, colorless reaction mixture is stripped on a rotary evapo 2-amino-2-me hyl-1-dodecanol 2-amino-2-ethyl-1-undecanol rator (50° C./29" vacuum). The resulting oil is distilled under 2-amino-2-pro pyl-1-decanol vacuum giving a clear, colorless, mobile liquid with a boiling 2-amino-2-pro pyl-1-tetradecanol point of 43° C./0.8 torr. A total of 123.4 g is collected (83% 2-amino-2-butyl-1-tridecanol yield). AGC analysis indicates 95.6% purity. 2-amino-2-pentyl-1-dodecanol 0116. Following the procedures described above and mak 2-amino-2-hexyl-1-undecanol ing non-critical variations, the following oxazolidine com 2-amino-2-hep tyl-1-decanol pounds are prepared from the appropriate starting aminoal cohol (Table 10).

TABLE 10 Oxazolidine Starting Aminoalcohol 4-propyl-1-Oxa-3-azacyclopentane 2-amino-1-pentanol 5-propyl-1-aza-3,7-dioxabicyclo[3.3.0 octane 2-amino-2- hydroxymethyl-1-pentanol 4-ethyl-4-methyl-1-Oxa-3-azacyclopentane 2-amino-2-methyl-1-butanol 4-butyl-1-Oxa-3-azacyclopentane 2-amino-1- hexanol 5-butyl-1-aza-3,7-dioxabicyclo[3.3.0 octane 2-amino-2- hydroxymethyl-1-hexanol 4-propyl-4-methyl-1-Oxa-3-azacyclopentane 2-amino-2-methyl-1-pentanol 44-diethyl-1-Oxa-3-azacyclopentane 2-amino-2-ethyl-1-butanol 4-pentyl-1-Oxa-3-azacyclopentane 2-amino-1- heptano 5-pentyl-1-aza-3,7-dioxabicyclo[3.3.0 octane 2-amino-2- hydroxymethyl-1-heptanol 4-butyl-4-methyl-1-Oxa-3-azacyclopentane 2-amino-2-methyl-1-hexanol 4-ethyl-4-propyl-1-Oxa-3-azacyclopentane 2-amino-2-ethyl-1-pentanol 4-hexyl-1-Oxa-3-azacyclopentane 2-amino-1-octanol 5-hexyl-1-aza-3,7-dioxabicyclo[3.3.0 octane 2-amino-2- hydroxymethyl-1-octanol 4-methyl-4-propyl-1-Oxa-3-azacyclopentane 2-amino-2-methyl-1-heptanol 44-dipropyl-1-Oxa-3-azacyclopentane 2-amino-2-ethyl-1-hexanol 4-butyl-4-ethyl-1-Oxa-3-azacyclopentane 2-amino-2- propyl-1-pentanol 4-heptyl-1-Oxa-3-azacyclopentane 2-amino-1-nonanol 5-heptyl-1-aza-3,7-dioxabicyclo[3.3.0 octane 2-amino-2- hydroxymethyl-1-nonanol 4-hexyl-4-methyl-1-Oxa-3-azacyclopentane 2-amino2-methyl-1-octanol 4-ethyl-4-pentyl-1-Oxa-3-azacyclopentane 2-amino-2-ethyl-1-heptanol

US 2011/0028732 A1 Feb. 3, 2011

TABLE 10-continued Oxazolidine Starting Aminoalcohol 4-butyl-4-dodecyl-1-Oxa-3-azacyclopentane 2-amino-2-butyl-2-tetradecanol 4-pentyl-4-undecyl-1-Oxa-3-azacyclopentane 2-amino-2-pentyl-1-tridecanol 4-decyl-4-hexyl-1-Oxa-3-azacyclopentane 2-amino-2-hexyl-1-dodecanol 4-heptyl-4-nonyl-1-Oxa-3-azacyclopentane 2-amino-2-heptyl-1-undecanol 44-dioctyl-1-Oxa-3-azacyclopentane 2-amino-2-octyl-1-decanol 4-heptadecyl-1-Oxa-3-azacyclopentane 2-amino-1-nonadecanol 5-heptadecyl-1-aza-3,7-dioxabicyclo[3.3.0 octane 2-amino-2-hydroxymethyl-1-nonadecanol 4-hexadecyl-4-methyl-1-Oxa-3-azacyclopentane 2-amino-2-methyl-1-octadecanol 4-ethyl-4-pentadecyl-1-Oxa-3-azacyclopentane 2-amino-2-ethyl-1-heptadecanol 4-propyl-4-tetradecyl-1-Oxa-3-azacyclopentane 2-amino-2-propyl-1-hexadecanol 4-butyl-4-tridecyl-1-Oxa-3-azacyclopentane 2-amino-2-butyl-2-pentadecanol 4-dodecyl-4-pentyl-1-Oxa-3-azacyclopentane 2-amino-2-pentyl-1-tetradecanol 4-hexyl-4-undecyl-1-Oxa-3-azacyclopentane 2-amino-2-hexyl-1-tridecanol 4-decyl-4-heptyl-1-Oxa-3-azacyclopentane 2-amino-2-heptyl-1-dodecanol 4-octyl-4-nonyl-1-Oxa-3-azacyclopentane 2-amino-2-octyl-1-undecanol 3-oxa-1-azaspiro4.4nonane 1-amino-1-hydroxymethylcyclopentane 3-oxa-1-azaspiro4.5 decane 1-amino-1-hydroxymethylcyclohexane 3-oxa-1-azaspiro4.7dodecane 1-amino-1-hydroxymethylcyclooctane

Example 16 Use of Oxazolidine Derivatives as Phenolic Resin -continued Curing Agents Compound A DSC Analyses: 0117 DSC analyses are performed using a TA Instruments Model Q100 differential scanning calorimeter. Scans for screening hardeners with novolac resins are run from 25°C. CO to 250° C. at AT=10° C./minute with a nitrogen flow of 50 cc/minute. High volume (100LL) aluminum pans are used. A (inventive) small hole is punched in the top before crimping. After the initial scan, the samples are cooled back to room temperature, then the scans are re-run to obtain T. data. 0118. In order to demonstrate the utility of the oxazo Compound B lidines of the methods and/or compounds of the invention as p hardeners, a series of formulations are prepared using com mercially available PF novolac resins. In order to facilitate mixing of components, the resins in this study are used as 80 wt.% solutions in ethanol. Any variations observed in the curing behavior of these formulations are attributed to the hardener/catalyst being evaluated. ZOLDINETM ZE, struc (inventive) ture shown below, is used as the baseline for comparison since it is a known curing agent for phenolic novolac resins. The formulations are adjusted to keep the molar ratio of hardener to phenolic resin reactive sites constant. 0119 The formulations are evaluated using a differential Compound C scanning calorimeter (DSC: TA Instruments Model Q100) to observe curing onset and peak temperatures and heats of curing for the curing events taking place. The DSC Scans are run at AT=10° C./minute from 25° C. to 250° C. under a nitrogen flow of 50 cc/minute. The data obtained in this study (inventive) are summarized in Table 11 below.

Zoldine ZE

Compound D

(inventive) (comparative) US 2011/0028732 A1 Feb. 3, 2011 16

TABLE 11

Onset Peak 1 Onset Peak 2 Observations Example # Hardener PHR (Heat J/g) (Heat J/g) After Cure Baseline 1 ZE 33.3 166/194 (264) None No exotherm, (comparative) Tg > 200 C. Baseline 2 ZE 44.2 171/198 (244 None No exotherm, (comparative) Tg > 200 C. Example 16-1 Compound A 48 58.1/96.5 (28.8) 202224.1 No exotherm, (161.2) Tg = 110 C. Example 16-2 Compound B 72 55/193.5 (129.2) None No exotherm, Tg = 140 C. Example 16-3 Compound C 72 1614/192.3 (47.2) None No exotherm, Tg = 38 C. Example 16-4 Compound D 76 62.3/105.5 (11.0) 163.31849 No exotherm, (65.4) Tg = 58 C. PHR = parts of hardener per 100 parts resin solution

0120. As can be seen by the data in Table 11, the novel wherein R is C-C alkyl, C-C cycloalkyl, cycloalkyl hardeners of the invention cure novolac resins, and provide alkyl-, aryl, or aryl-alkyl-, and R' is Hor C-C alkyl; or the ability to adjust the cured polymer Tg over a broad range. R and R' together with the carbon to which they are 0121 While the invention has been described above attached form a C-C2 cycloalkyl ring; and R is Hor according to its preferred embodiments, it can be modified C-C alkyl, provided that when R is an ethyl group, R' within the spirit and scope of this disclosure. This application and Rare not simultaneously H. is therefore intended to cover any variations, uses, or adapta 11. A process for preparing a nitroalcohol of formula II: tions of the invention using the general principles disclosed herein. Further, the application is intended to cover such departures from the present disclosure as come within the II known or customary practice in the art to which this invention NO pertains and which fall within the limits of the following claims. 1. A process for the selective nitration of hydrocarbons, the OH process comprising: Rs providing a down-flow configured reactor; reacting a hydrocarbon feedstock with aqueous nitric acid wherein R is C-C alkyl, C-C cycloalkyl, cycloalkyl at a pressure of at least about 500 psi and a temperature alkyl-, aryl, or aryl-alkyl-; R is H. C-C2 alkyl, or of between about 150 and about 325 degrees Celsius; CH-OH, provided that when R is an ethyl group, R is and not H; or RandR together with the carbon to which they recovering the formed nitrated compounds, are attached form a C-C2 cycloalkyl ring; and R is wherein the aqueous nitric acid is a 10 to 50 weight percent independently H, C-C alkyl, C-C cycloalkyl, or Solution. aryl, the process comprising: 2. (canceled) (a) providing a nitrated hydrocarbon of formula (I) wherein 3. A process according to claim 1 wherein the aqueous R is H, prepared according to claim 10; and nitric acid is a 18 to 35 weight percent solution. (b) condensing the nitrated hydrocarbon with an aldehyde 4. A process according to claim 1 wherein the molar ratio of of formula R C(=O)—H in the presence of an alka hydrocarbon feedstock to nitric acid is at least about 1.2 to 1. line catalyst to provide the nitroalcohol of formula (II). 5. A process according to claim 1 wherein the temperature 12. A process for preparing an aminoalcohol of formula 200 degrees Celsius or greater. (III): 6. (canceled) 7. (canceled) 8. (canceled) III 9. A process according to claim 1 wherein the hydrocarbon NH2 feedstock is selected from alkanes; aryl alkanes; naphthyl alkanes; and biaryl alkanes. 10. A process according to claim 1 wherein the nitrated OH compound is of the formula (I): Rs wherein R is C-C alkyl, C-C cycloalkyl, cycloalkyl alkyl-, aryl, or aryl-alkyl-; R is H. C-C2 alkyl, or R. N. CH(OH) R, provided that when R is an ethyl group, R’ is not H; or R and R together with the carbon to >{R which they are attached form a C-C cycloalkyl ring; and R is independently H, C-C alkyl, C-C, cycloalkyl, or aryl, the process comprising: US 2011/0028732 A1 Feb. 3, 2011 17

(a) providing a nitroalcohol of formula (II) prepared R is independently H, C-C alkyl, C-C2 cycloalkyl, according to claim 11; and or aryl; and R is independently H or C-C alkyl, the (b) chemically reducing the nitroalcohol to provide the process comprising: aminoalcohol of formula (III). (a) providing an aminoalcohol of formula (III) prepared as 13. A process for preparing an oxazolidine of formula (IV): according to claim 12; and (b) reductively alkylating the aminoalcohol in the presence IV of an aldehyde, hydrogen, and a hydrogenation catalyst R4 to provide the compound of formula VI. R Y 16. A compound of formula I-1:

R5PC) O I-1

wherein R is C-Co alkyl, C-C cycloalkyl, cycloalkyl alkyl-, aryl, or aryl-alkyl-; R is H or C-C2 alkyl, pro vided that when R is an ethyl group, R is not H; or Rand R together with the carbon to which they are attached form a C-C cycloalkyl ring; and R is H; or RandR wherein R is linear C-C, alkyl; and R is H or linear and the atoms to which they are attached forman oxazo C-Cs alkyl, provided that RandR together with the lidine ring that is optionally substituted with C-C, carbon to which they are attached form a linear Co-Cs alkyl; and R is H. C-C2 alkyl, C-C2 cycloalkyl, or alkyl chain, and provided that the compound is not: aryl, the process comprising: 1-nitrodecane, 2-nitrodecane, 1-nitroundecane, 2-ni (a) providing an aminoalcohol of formula (III) prepared as troundecane, 3-nitroundecane, 4-nitroundecane, 5-ni according to claim 12; and troundecane, 6-nitroundecane, 1-nitrododecane, 2-ni (b) reacting the aminoalcohol of formula (III) with form trododecane, 3-nitrododecane, 4-nitrododecane, aldehyde to provide the oxazolidine of formula (IV). 5-nitrododecane, 6-nitrododecane, 1-nitrotridecane, 14. A process for preparing an N-alkylhydroxylamine of 2-nitrotridecane, 3-nitrotridecane, 6-nitrotridecane, formula (V): 1-nitrotetradecane, 1-nitropentadecane, 1-nitrohexade cane, 2-nitrohexadecane, 1-nitroheptadecane, 1-ni trooctadecane, or 2-nitrooctadecane. 17. A compound according to claim 16 selected from the group consisting of 3-nitrodecane, 4-nitrodecane, 5-nitrode cane, 4-nitrotridecane, 5-nitrotridecane, 7-nitrotridecane, 2-nitrotetradecane, 3-nitrotetradecane, 4-nitrotetradecane, 5-nitrotetradecane, 6-nitrotetradecane, 7-nitrotetradecane, 2-nitropentadecane, 3-nitropentadecane, 4-nitropentade wherein R is C-C alkyl, C-C cycloalkyl, cycloalkyl cane, 5-nitropentadecane, 6-nitropentadecane, 7-nitropenta alkyl-, aryl, or aryl-alkyl-, and R' is H, or C-C2 alkyl; decane, 8-nitropentadecane, nitrohexadecane, 4-nitrohexa or R and R' together with the carbon to which they are decane, 5-nitrohexadecane, 6-nitrohexadecane, attached form a C-C2 cycloalkyl ring; and R is Hor 7-nitrohexadecane, 8-nitrohexadecane, 2-nitroheptadecane, C-C alkyl, provided that when R is an ethyl group, R' 3-nitroheptadecane, 4-nitroheptadecane, 5-nitroheptade and R, are not simultaneously H, the process compris cane, 6-nitroheptadecane, 7-nitroheptadecane, 8-nitrohepta 1ng: decane, nitroheptadecane, 3-nitrooctadecane, 4-nitrooctade (a) providing a nitrated hydrocarbon of formula (I) pre cane, 5-nitrooctadecane, 6-nitrooctadecane, nitrooctadecane, pared according to claim 10; 8-nitrooctadecane, and 9-nitrooctadecane. (b) chemically reducing the nitrated hydrocarbon to pro 18. A compound of formula II-1: vide the N-alkylhydroxylamine of formula (V). 15. A process for preparing a compound of formula VI: II-1 NO VI

R OH wherein R is linear C-C, alkyl; and R' is H. linear C-Cs alkyl, or CH-OH, or R. R', and the carbon to which they are attached form an eight membered wherein R is C-C alkyl, C-C cycloalkyl, cycloalkyl cycloalkyl ring; alkyl-, aryl, or aryl-alkyl-; R is H. C-Cl2 alkyl, or provided that: CH(OH) R, provided that when R is an ethyl group, when R' is Horlinear C-Cs alkyl, RandR' together R’ is not H; or R and R together with the carbon to with the carbon to which they are attached form a which they are attached form a C-C cycloalkyl ring; linear Cs-Cs alkyl chain;