EP0937020A1

EP0937020A1 - Functionalization of hydrocarbyl-containing compounds

Info

Publication number: EP0937020A1
Application number: EP97932514A
Authority: EP
Inventors: Gerald Kenneth Cook; John Robert Brigg; David Micheael Anthony Minahan
Original assignee: Union Carbide Chemicals and Plastics Technology LLC
Current assignee: Union Carbide Chemicals and Plastics Technology LLC
Priority date: 1996-11-08
Filing date: 1997-07-03
Publication date: 1999-08-25
Also published as: WO1998019983A1; KR20000053144A; CA2271025A1; JP2002510282A; AU3595497A; CN1235591A

Abstract

This invention is directed to processes for producing acyclic or cyclic alcohols or glycols, carbonyls, oxiranes or aziridines from hydrocarbyl group-containing compounds, particularly lower alkanes such as methane, ethane, propane or butanes, in which the hydrocarbyl group-containing compounds are converted under regioselective conditions to a functionalized ultimate precursor from which the final products can be produced. In its broadest sense, regioselective conditions are reaction zone conditions which are highly selective to the production and recovery of the desired functionalized compound, be it the ultimate precursor or an intermediate to the production of the ultimate precursor.

Description

FUNCTIONALIZATION OF HYDROCARBYL-CONTAINING COMPOUNDS

FIELD OF THE INVENTION

This invention is directed to processes for producing acyclic or cyclic alcohols or glycols, carbonyls, oxiranes or aziridines from hydrocarbyl group-containing compounds, particularly lower alkanes such as methane, ethane, propane or butanes, in which hydrocarbyl group-containing compounds are converted under regioselective conditions to a functionalized ultimate precursor from which the final products can be produced. In its broadest sense, regioselective conditions are reaction zone conditions which are highly selective to the production and recovery of the desired functionalized compound, be it the ultimate precursor or an intermediate to the production of the ultimate precursor. More specifically, regioselective conditions are conditions under which a given sp³ carbon atom with one or more bonds to hydrogen (a hydrocarbyl group carbon) of the hydrocarbyl- group containing compound can essentially be functionalized at a C— H bond only once in a process of formation of the ultimate precursor in which the functionalized carbon atom remains essentially sp³. Regioselective conditions are established by 1) maintaining the ultimate precursor and any functionalized intermediate(s) from which the precursor can be produced in a phase different from at least one of the functionalizing reagent and any catalyst that may be employed during the functionalization process, or 2) utilizing in the reaction zone of any functionalization reaction a constituent capable of segregating the desired functionalized compound from at least one of the functionalizing reagent and any catalyst such as, for example, a molecular sieve coated or impregnated with the stabilizing agent that is selective to segregating the ultimate precursor from the remaining reactants. The functionalizing step can include one or more functionalization reactions performed under regioselective conditions in order to produce a desired functionalized precursor to the final product (the ultimate precursor) convertible to the final product at high selectivity. In a most preferred embodiment, the present invention is directed to processes in which the enhanced selectivity of the ultimate precursor to the final product and functionalized intermediates to the ultimate precursor is accomplished through the use of one or more stabilizing agents which prevent further activation of the functionalized carbon atom(s) under the reaction conditions employed to produce the ultimate precursor and any functionalized intermediate thereto in combination with one or more of the regioselective process parameters described in 1) or 2), above. The ultimate precursor produced from the functionalization process of the present invention is then reacted a) under conditions, optionally in the presence of a catalyst, sufficient to convert the precursor to the desired final product or b) with at least one nucleophile, optionally in the presence of a catalyst, to produce the desired final product.

BACKGROUND OF THE INVENTION

A number of processes have been disclosed for the conversion of methane into hydrocarbons and hetero compounds in which the reactions are homogeneous phase reactions which, in some instances, employ same phase catalysts. For example, U.S. Patent No. 2,492,983 discloses a homogeneous phase reaction of sulfur trioxide and methane in the presence of mercuric sulfate, as catalyst, to produce an ester, i.e., a methyl ester of sulfuric acid, which may be recovered or further hydrolyzed to methanol. U.S. Patent No. 2,492,984 describes the conversion of methane to higher boiling hydrocarbons such as branched-chain aliphatic hydrocarbons by a process in which sulfur trioxide and methane are subjected to a homogeneous phase reaction in the presence of a sulfonation catalyst to yield methanol or a sulfonated derivative (which is decomposed to methanol) and then the methanol is subjected to dehydration and condensation conditions to produce hydrocarbons having at least four carbon atoms. U.S. Patent No. 2,492,985 discloses a process for the oxidation of low molecular weight hydrocarbons to form oxygenated organic compounds in the presence of a liquid catalyst.

The prior art also disclosed processes for the single step production of hetero compounds. For example, U.S. Patent No. 2,493,038 describes the production of organic derivatives by reacting a reaction mixture of methane and sulfur trioxide in the presence of catalysts such as mercury sulfate. U.S. Patent No. 4,723,041 is directed to the process for the oxidation of olefins to carbonyl compounds in the presence of a catalyst system which is a polyoxoanion component and a palladium component to which is added a redox active metal component such as a salt of Cu, Mn and Fe. U. S. Patent No. 4,853,357 relates to a single stage liquid phase oxidation of olefϊns to carbonyl compounds using a catalyst system of heteropolyoxoanions and isopolyoxoanions and palladium, wherein redox active metals such as salts of Cu, Mn and Fe and nitrile ligands are added, alternatively or simultaneously, to the catalyst.

Other prior art processes produce hetero compounds by reactions which employ aqueous solutions from which the desired products must be separated from the remaining reactants and reaction products and sometimes also from the catalyst (which in turn must then be recovered from the aqueous solution). For example, U. S. Patent No. 5,506,363 relates to the oxidation of olefins to carbonyl compounds by polyoxoanion oxidants in aqueous solution, catalyzed by palladium. U.S. Patent No. 5,557,014 describes the oxidation of an olefin to a carbonyl product using an aqueous catalyst solution comprising a palladium catalyst, a polyoxoanion oxidant comprising vanadium, and hydrogen ions.

U.S. Patent Nos. 5,233,113 and 5,306,855 describe processes for converting lower alkanes, such as methane, into alkyl oxyesters which are then converted into higher hydrocarbons. The processes involve contacting methane with an acid and oxidizing agent in the presence of a catalyst to form a methyl oxyester, optionally reacting the methyl oxyester with a nucleophile to form a methyl intermediate such as methanol (when the nucleophile is water), and thereafter converting the methyl intermediate to a higher hydrocarbon.

All of the above-mentioned processes suffer from any of a number of shortcomings. Generally, they are carried out such that the desired product is in the same phase as the catalyst and one or more of the reactants, which causes significant difficulty in separating the desired product from the catalyst and reactants. Also, the presence of the product with the other components in a homogeneous phase is susceptible to the production of undesired by-products which typically also have to be separated from the other reactants, catalyst, stabilizing agent, and the desired product. Further, several processes employ homogeneous catalysts, thus also requiring catalyst reclamation processes. Moreover, several of the processes are not highly selective to the products produced.

As evidenced by the above-mentioned patents, for a long time people have been researching processes to convert hydrocarbyl group- containing compounds such as alkanes, especially those which can be obtained inexpensively from natural or refinery gases, such as ethane, to more valuable products such as ethanol, ethylene glycol, carbonyls, oxiranes, and aziridines. Industry continues to search for methods of producing these products from cheap raw materials by processes which are relatively simple and highly selective to the desired final products. Such methods would represent a significant advance in the state of the art.

SUMMARY OF THE INVENTION

The present invention is directed to a process for producing at least one of acyclic alcohols, cyclic alcohols, acyclic glycols, cyclic glycols, carbonyls, oxiranes and aziridines, which process comprises the steps of: a) functionalizing, under regioselective conditions, only one sp³ carbon atom at a carbon - hydrogen bond of at least one hydrocarbyl group of a starting material comprising a hydrocarbyl group containing compound to produce a functionalized hydrocarbyl group containing precursor from which a final product comprising at least one of acyclic alcohols, cyclic alcohols, acyclic glycols, cyclic glycols, carbonyls, oxiranes and aziridines can be produced, and b) reacting the functionalized hydrocarbyl group containing precursor under conditions sufficient to produce the final product. More particularly, the process is carried out such that the functionalized carbon atom remains essentially an sp³ carbon atom in the ultimate precursor.

An aspect of the invention is directed to a process for the production of aliphatic and cyclic alcohols from alkanes comprising the steps of: a) functionalizing a starting material comprising acyclic or cyclic hydrocarbon by reacting the same, under regioselective conditions, with a stabilizing agent comprising an sp³ carbon atom protecting group to produce a mono-functionalized hydrocarbyl group containing precursor; b) hydrolyzing the mono-functionalized hydrocarbyl group containing precursor to produce alcohol.

Another aspect of the invention is directed to a process for the production of aliphatic or aromatic diol, comprising the steps of: a) functionalizing a starting material selected from a group comprising aliphatic and aromatic hydrocarbon by reacting the starting material, under regioselective conditions, with a stabilizing agent comprising an sp³ carbon atom protecting group to produce a di- functionalized hydrocarbyl group containing precursor; b) hydrolyzing the di-functionalized hydrocarbyl group containing precursor to produce diol.

A further aspect of the invention is directed to a process for the production of carbonyl compounds, comprising the steps of: a) functionalizing a starting material selected from a group comprising aliphatic and aromatic hydrocarbon by reacting the starting material, under regioselective conditions, with a stabilizing agent comprising an sp³ carbon atom protecting group to produce a di-ester; b) converting the di-ester to a vinyl ester by reacting the di-ester in the presence of a basic reaction constituent; and c) hydrolyzing the vinyl ester to produce carbonyl compound The invention has particular utility in the production of such products from starting materials comprising lower alkanes, particularly methane and ethane.

DESCRIPTION OF THE INVENTION

The invention is directed to processes for producing acyclic or cyclic alcohols or glycols, carbonyls, oxiranes or aziridines from starting material selected from hydrocarbyl group-containing compounds. A hydrocarbyl group is an sp³ carbon atom to which one or more hydrogen atoms are bound. An sp³ carbon atom is a carbon atom with four atoms bound to it. The process comprises the step of producing, under regioselective conditions, a functionalized precursor from which the final product can be produced (heretofore described as the ultimate precursor). More specifically, the ultimate precursor is produced by a process which includes functionalizing, under regioselective conditions, an sp³ carbon atom at the C-H bond of at least one hydrocarbyl group of a hydrocarbyl group-containing compound and, most preferably, the functionalized carbon atom of the ultimate precursor is essentially sp³. Preferably, the ultimate precursor is produced by a functionalization process wherein at least one of the starting material and a functionalized intermediate which can be converted selectively to the ultimate precursor interacts or reacts with at least one stabilizing agent to produce the ultimate precursor. A stabilizing agent is defined as a material or chemical compound which interacts with, or reacts with, an intermediate formed from a reaction at an sp³ carbon atom of a hydrocarbyl group of a hydrocarbyl group-containing compound to form an sp³ carbon atom functionalized hydrocarbyl group of a hydrocarbyl group-containing compound. Most preferably, the stabilizing agent substantially stops further functionalization at the said sp³ carbon atom. In particular, further functionalization at the said sp³ carbon atom includes any reaction process which results in a reduction of the number of hydrogen atoms bound to the said sp³ carbon atom. The ultimate precursor is then reacted a) under conditions, and optionally in the presence of a catalyst, sufficient to produce to the desired final product or b) with at least one nucleophile, and optionally in the presence of a catalyst, under conditions sufficient to produce the desired final product. The starting material for the process of the present invention is a hydrocarbyl-group containing compound which is selected from among alkanes, mixtures containing alkane, alkaryls, and organic compounds containing at least one hetero atom selected from N, P, S, Si, O, B, halogens, Al, and Se (hetero compounds). Hetero compounds include alcohols, esters, acids, ketones, amines, aldehydes, halides, amides, nitriles, thiols, imines, ethers, organometallics, siloxanes, and the like. The process of the present invention is particularly suited to, and most preferably utilizes, starting materials which are lower alkanes such as methane, ethane, propanes and butanes or mixtures thereof.

The functionalization step is accomplished in one or more reactions, with the reaction conditions and constituents being selected based upon the desired functionality of the ultimate precursor, the need to conduct the functionalization process under regioselective conditions and the selectivity of the functionalization process to the production of the ultimate precursor or a desired intermediate thereto.

The functionalization process of the present invention is carried out under regioselective conditions. In its broadest sense, regioselective conditions are reaction zone conditions which are highly selective to the production and recovery of the desired functionalized compound, be it the ultimate precursor or an intermediate to the production of the ultimate precursor. More specifically, regioselective conditions are conditions under which a given sp³ carbon atom with one or more bonds to hydrogen (a hydrocarbyl group carbon) of the hydrocarbyl-group containing compound can essentially be functionalized at a C-H bond only once only once in a process of formation of the ultimate precursor in which the functionalized carbon atom remains essentially sp³. Regioselective conditions are established by 1) maintaining the ultimate precursor and any functionalized intermediate(s) from which the precursor can be produced in a phase different from at least one the functionalizing reagent and any catalyst that may be employed during the functionalization process, or 2) utilizing in the reaction zone of any functionalization reaction a constituent capable of segregating the desired functionalized compound from at least one of the functionalizing reagent and any catalyst such as, for example, a molecular sieve coated or impregnated with the stabilizing agent that is selective to segregating the ultimate precursor from the remaining reactants.

The first mentioned mechanism for establishing regioselective conditions can be accomplished by carrying out the functionalization reaction(s) under conditions of temperature, pressure and time of reaction which, in combination, a) yield distinct, separable phases, one of which contains the functionalized intermediate(s) and b) maintain at least the stabilizing agent in a phase readily separable from the functionalized product. By way of example, the reactants can be supplied to a reaction zone provided with a protic or an aprotic solvent to the functionalized product. It is desirable when using such solvents to control the ionic strength of the solution by, for example, the addition of salts including bisulfates, such as sodium bisulfate. Aprotic solvents include certain ketones, ethers, hydrocarbons, esters, anhydrides, dialkyl amides, acetonitrile, carbon dioxide and molten salts such as, for example, tetra-alkylammonium salts of acetate, ethylsulfate and orthophosphate. Protic solvents include, for example, H₂0, alcohols, protic amines and amides, carboxylic acids, molten salts, strong liquid acids such as sulfuric acid, fuming sulfuric acid (oleum), methanesulfonic acid, phosphoric acid, nitric acid, perfluoroacids such as trifluoroacetic acid, and trifluoromethanesulfonic acid, hydrochloric acid, and the like, and mixtures thereof. Regioselective conditions can be accomplished in liquid phase reactions using combinations of the above solvents by providing a reaction menstruum having at least two substantially immiscible liquid phases; for example, sulfuric acid and reagent alkane, oleum and supercritical carbon dioxide. Also, the ultimate precursor, as well as any functionalized intermediates to the ultimate precursor, may themselves act as a substantially immiscible liquid phase in the reaction menstruum.

An example of the second mentioned mechanism being the use of a molecular sieve, coated or impregnated with the stabilizing agent, that is capable of segregating/separating the functionalized intermediates from other reaction constituents. Another example of the second mentioned mechanism being the use of known molecular recognition mechanisms other than molecular sieves, such as via a biphasic mechanism including micelle formation or hydrophobic- hydrophilic solvent partitioning, for example, wherein the reaction medium is aqueous sulfuric acid and reagent alkane is dissolved in micellar aggregates of alky sulfonate surfactants. The stabilizing agent(s) useful in the functionalization process of the invention preferably comprise one or more of a Lewis acid, a Bronsted acid (for example, a strong liquid acid), or combinations of such acids. The Lewis acids and Bronsted acids are selected from among: zeolites; sulfonated zirconia; fluorinated or chlorinated aluminas; borates; polyoxometalates (supported or unsupported); pillared clays; perfluorosulfonic acid ion-exchange resins (e.g., Nation™ resins available from E.I. duPont de Nemours & Co.); sulfonic acid ion- exchanged resins (e.g., Amberlyst™ resins available from Rohm & Haas Company); acid resins; supported acids, e.g., sulfuric acid, phosphoric acid, boric acid and fluorosulfonic acid on silica, niobium oxide and the like; mixed metal oxides (e.g., Siθ2/MgO, Siθ2/Al2θ3, and the like); supported and unsupported phosphates, sulfates and sulfides; zinc oxide; bismuth, tin and lead compounds; antimony pentafluoride; boron trifluoride. Strong liquid acids include acids such as HNO3, H2SO4, CF3CO2H, CF3SO3H, H3PO4, H₂Se0₄, HBr, HC1, HF, HPA's (heteropolyacids), B(OH)3, H4P2O7, H2S2O7, and acid salts of these acids such as NaHS0 , KH2PO4, and the like. Organic acids may also be used, such as CF3CO2H, CI3CCO2H, HB(C₆F₅)4, HB(C₆H₃-3, 5- (CF3)2) 4 and the like. A base such as NH4OH, or the like, may be useful for certain functionalization reactions, but would be less preferred. Further, the stabilizing agent may be di-functional and/or may have a bridged or cyclic structure.

The stabilizing agent(s) utilized in the functionalization process of the invention may enforce regioselective conditions as in the first mentioned mechanism by contacting, in a liquid reaction medium, the hydrocarbyl group of a hydrocarbyl-containing compound in the presence of the functionalization catalyst and stabilizing agent to form a reactive ester, such as a vaporizable ester of the hydrocarbyl group, as a product. The ester may comprise a carboxylate, an acetate and trifluoroacetate, a sulfate or trifluoromethylsulfonate, borate, carbonate, formate, phosphate, and the like. The reaction conditions can be maintained such that the ester immediately vaporizes, thus maintaining regioselective conditions. In one embodiment of the invention, the hydrocarbyl group of a hydrocarbyl-containing compound is contacted with an oxidizing agent in the presence of an activation catalyst and stabilizing agent to form a cyclic ester as an oxidation product. The ester portion of the cyclic ester may comprise an ester of a polybasic acid, a borate, carbonate, phosphate, sulfate, or sulfonate. The reaction conditions are maintained such that the ester vaporizes and thereby can be easily separated from the reagents and other, higher boiling point by products.

As described above, at least the functionalization reaction can be carried out in the presence of a catalyst. Suitable C-H activation catalysts which may be utilized in the functionalization process of this invention are heterogeneous catalysts comprising an ion exchange resin partially exchanged with one or more of transition metals, main group metals and metalloids, halides, and lanthanides, for example, Co, Cu, Re, Fe, Ni, Nb, Mo, V, Cr, W, U, Ta, Ti, Zr, Zn, Hf, Mn, Pt, Pd, Sn, Sb, Bi, Ce, As, Ag, Au, Os, Rh, Ir, Hg, Te, Tl, Se, I and Br, perfluorosulfonic acid ion-exchange resins, spinels, perovskites, molecular sieves, silica, magnesia, zinc oxide, bismuth oxide, tin oxide, lead oxides, aluminum phosphates, polyoxymetalates, oxides supported on alumina, titania, silica, and the like, supported metals and mixtures thereof, colloidal metals, metal oxides, and the like. In some instances, these catalysts may be bound to the conjugate base of the stabilizing acid used and/or one or more ligands such as thiols, amines, thiocarboxylates, perfluoroalkyls, halides and pseudohalides, cyanides, thiosulfates, and the like. The catalyst is preferably one having a regioselective-imparting structure comprising a cage or layer structure, such as zeolite.

Solid acid stabilizing agents alone or in combination with heterogeneous catalysts are particularly preferred because they 1) can be easily separated from a gaseous or liquid product stream, 2) are not readily consumed or deactivated by the reaction and thus do not require immediate regeneration (therefore, they also offer economic advantages to this otherwise unique process), and 3) display a range of acid strengths, such that acidity can be tailored to a particular reaction to improve product selectivity and/or reaction rate.

Combinations of regioselective imparting structures are also within the scope of the present invention. For example, solids comprising a catalyst having a cage or layer structure with the stabilizing agent contained therein or, for example, a solid stabilizing agent in the form of a molecular sieve impregnated, coated, etc. with a catalyst are combinations which function both as the stabilizing agent and catalyst.

Additionally, the functionalization may be carried out in the presence of an oxidant when necessary, to return the reduced form of the functionalization catalyst to its active state, or to consume reaction byproducts. Oxidizing agents include peroxides such as hydrogen peroxide, benzoyl peroxides, alkyl peroxides such as tert-butylperoxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, methyl hydroperoxide, halogens (preferably chlorine), oxygen, ozone, sulfur trioxide, hypochlorites, metal dioxygen complexes, metal hydroperoxide complexes, metal peroxide complexes, metal oxo complexes, phosphomolybdic acid, peracids such as peracetic acid and persulfuric acid, or their salts such as sodium perborate and sodium percarbonate, sulfuric acid and the like. Additionally, oxidizing agents with electrical potential above about 0.6v, as well as persulfonates are suitable for use herein. Further, N2O and NO_x may be used in place of or in addition to one or more of the oxidizing agents. Also, the oxidizing agent may be diluted with an inert material, for example, an oxidizing agent such as sulfur trioxide may be diluted with sulfur dioxide. The oxidation reaction can also be accomplished utilizing an electrochemical system.

Oxidizing agents, when utilized, may be generated in situ by, for example, the reaction of water and carbon monoxide in the presence of oxygen or from hydrogen and oxygen in the presence of a catalyst such as rhodium or supported palladium to produce hydrogen peroxide. Further, the generation of peroxide in situ reduces the amount of peroxide generated during the reaction and obviates the need for purchase, generation or storage of the material outside of the reactor.

The oxidation reaction may be carried out in the presence or absence of an activation catalyst suitable to enhance the activity of the oxidation reaction. For example, when an oxidizing agent is reacted with the hydrocarbyl-group containing compound in the presence of a strong acid stabilizer, either in solid or liquid form, any of a variety of known oxidation activation catalysts such as Cu, Zn, Pd, Ag, Cd, In, Mn, Cr, V, Sn, Sb, Te, Pt, Au, Hg, Ti, Pb, Bi, Ga, Ge, As, Po, Rh, Ir, Os, and Ru catalysts can be used. The preferred catalysts comprise catalysts selected from at least one of Ni, Co, Fe, Mn, Cr, V and elements selected from Group IIIB to VIIB of the Periodic Table of the Elements and their oxides and carbonates.

Generally, the functionalization process is carried out at a temperature between about 20°C and about 300°C, preferably between about 90°C and about 200°C, and a pressure between about atmospheric and about 10,000 psig, preferably between about 50 psig and about 2,000 psig, and for a time sufficient to produce the desired functionalized product. More specifically, the reaction conditions of temperature, pressure and time to react are selected not only to maintain regioselectivity in the reaction zone but also to insure a reaction selective to the production of the desired intermediate (the ultimate precursor).

The ultimate precursor is further reacted after separation. Such further reaction can include molecular reorientation as, for example, described below with respect to the production of carbonyls or the ultimate precursor may be further reacted with a nucleophile. The nucleophiles include water, carboxylic acids such as terephthalic acid, halides, pseudohalides, ammonia, amines, alcohols, metal complexes, acrylic acid, and the like, the selection of which is based upon the desired product. Reactions of the ultimate precursor with a nucleophile are generally carried out at a temperature in the range of from about 20°C to about 200°C, at a pressure in the range of about 15 psig to about 5,000 psig for a time ranging from about 1 second or less to 10 hours or greater, preferably in the range of about 10 minutes to 5 hours.

The production of aliphatic and cyclic alcohols from alkanes in accordance with the process of the present invention can be schematically represented as follows:

C_xH_y + HSA + Ox _^ ^{^} C_xH_(y._υSA + H₂(Ox)

C_xH_(y._υSA + H₂0 _^ C^_y.uOH + HSA

Net: C_xH_y + Ox + H₂0 ^ C_xH_(y-1)OH + H₂(Ox)

where SA is a stabilizing agent and Ox is an oxidant. Note that the above scheme is not meant to imply a specific stoichiometry in terms of the oxidant as the actual stoichiometry depends on the specific nature of the oxidant. Examples of processes according to this embodiment of the invention include the steps of supplying an alkane, preferably a lower alkane (C1-C4 alkane) to a reaction zone, supplying a suitable functionalization catalyst (C-H bond activation catalyst) to the zone, selected from the group of supported metals, metal oxides, perfluorosulfonic acid ion exchange resins, and ion exchange resins partially exchanged with one or more of the following elements: Co, Cu, Re, Fe, Ni, Mo, V, Cr, Ti, Zr, Zn, Hf, Mn, Pt, Pd, Sn, Ag, Au, Rh, Hg, Te, TI, supplying a stabilizing agent selected from the group of sulfuric acid, Nation™ resin, phosphoric acid, trifluoroacetic acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, boric acid, boron trifluoride, sulfonated zirconia, zeolite Y, and carbon dioxide, to the zone, optionally supplying an oxidant selected from the group of 0₂, SO3, H2O2, NO2, N2O, alkyl peroxides such as tert- butylperoxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, methyl hydroperoxide, phosphomolybdic acid, peracids such as peracetic acid and persulfuric acid, or their salts such as sodium perborate and sodium percarbonate, sulfuric acid and the like, to the zone, maintaining the reaction zone at temperatures within the range of about 20-350 °C, preferably, 50-300 °C and more preferably 90-200 °C and pressures within the range of about atmospheric or below to 10,000 psig or greater, preferably, 100-5000 psig, and more preferably 500-3000 psig for times ranging from about 1 second or less to 10 hours or greater, preferably, 1 minute to 8 hours, and more preferably 10 minutes to 5 hours, in order to functionalize the alkane to a mono- functional state, and thereafter hydrolyzing the mono-functionalized intermediate to produce an aliphatic alcohol. Regioselective conditions for the production of the functionalized intermediate would, for example, preferably be maintained by maintaining reaction conditions, e.g. reaction temperature, residence time, and alkane conversion, such that undesired over-functionalization does not occur, selection of a stabilizing agent that adequately stabilizes the functionalized alkane against further functionalization, and control of the produced water concentration such that stabilized intermediates are not hydrolyzed prematurely under functionalization conditions where the produced alcohol could be further functionalized. The functionalized intermediate could then be easily separated by filtration from the insoluble components of the process, and by phase separation or distillation from the remaining process components. The hydrolysis reaction would typically be carried out at temperatures within the range of about 20-350 °C, preferably, 30-250 °C and more preferably 50-200 °C and pressures within the range of about ambient or below to 1000 psig, preferably, ambient to 750 psig, and more preferably ambient to 500 psig, for times ranging from about 1 second to 10 hours, preferably 1 minute to 5 hours, and more preferably 10 minutes to 1 hour.

The conversion of, for example, an alkane to a glycol in accordance with the process of the present invention can be schematically represented as follows:

C_xH_y + 2HSA + Ox ^ C_xH_(y.₂₎(SA)₂ + H₄(Ox)

C_xH_(y.₂₎(SA)₂ + 2H₂0 ^ C_xH_(y._υ(OH)₂ + 2HSA

Net: C_xH_y + Ox ^ C_xH_(y-1)(OH)₂ + H₄(Ox)

where SA is a stabilizing agent and Ox is an oxidant. Note that the above scheme is not meant to imply a specific stoichiometry in terms of the oxidant as the actual stoichiometry depends on the specific nature of the oxidant. Examples of processes according to this embodiment of the invention include the steps of supplying an alkane, preferably a lower alkane (Ci-C4 alkane) to a reaction zone, supplying a suitable functionalization catalyst (C-H bond activation catalyst) to the zone, selected from the group of supported metals, metal oxides, perfluorosulfonic acid ion exchange resins, and ion exchange resins partially exchanged with one or more of the following elements: Co, Cu, Re, Fe, Ni, Mo, V, Cr, Ti, Zr, Zn, Hf, Mn, Pt, Pd, Sn, Ag, Au, Rh, Hg, Te and TI, supplying a stabilizing agent selected from the group of sulfuric acid, Nation™ resin, phosphoric acid, trifluoroacetic acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, boric acid, boron trifluoride, sulfonated zirconia, zeolite Y, and carbon dioxide, to the zone, optionally supplying an oxidant selected from the group of O2, SO3, H2O2, NO2, N2O, alkyl peroxides such as tert- butylperoxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, methyl hydroperoxide, phosphomolybdic acid, peracids such as peracetic acid and persulfuric acid, or their salts such as sodium perborate and sodium percarbonate, sulfuric acid and the like, to the zone, maintaining the reaction zone at temperatures within the range of about 20-350 °C, preferably, 50-300 °C and more preferably 90-200 °C and pressures within the range of about atmospheric or below to 10,000 psig or greater, preferably, 100-5000 psig, and more preferably 500-3000 psig for times ranging from about 1 second or less to 10 hours or greater, preferably, 1 minute to 8 hours, and more preferably 10 minutes to 5 hours, in order to functionalize the alkane to a difunctional state, and thereafter hydrolyzing the difunctionalized intermediate to produce an aliphatic diol. Regioselective conditions for the production of the difunctionalized intermediate would, for example, preferably be maintained by maintaining reaction conditions, e.g. reaction temperature, residence time, and alkane conversion, such that undesired over-functionalization does not occur, selection of a stabilizing agent that adequately stabilizes the difunctionalized alkane against further functionalization, and control of the produced water concentration such that stabilized intermediates are not hydrolyzed prematurely under functionalization conditions where the produced alcohol could be further functionalized. The difunctionalized intermediate could then be easily separated by filtration from the insoluble components of the process, and by phase separation or distillation from the remaining process components. The hydrolysis reaction would typically be carried out at temperatures within the range of about 20-350 °C, preferably, 30-250 °C and more preferably 50-200 °C and pressures within the range of about ambient or below to 1000 psig, preferably, ambient to 750 psig, and more preferably ambient to 500 psig, for times ranging from about 1 second to 10 hours, preferably 1 minute to 5 hours, and more preferably 10 minutes to 1 hour.

The production of aromatic alcohols or aromatic diols would be carried out employing processes substantially similar to those employed for production of the aliphatic counterparts, employing reaction conditions (temperatures, pressures and times) and regioselectivity derived by routine experimentation from the detailed teachings provided hereinabove for each of the functionalization process. Several routes for the production of carbonyl compounds (aldehydes and or ketones) may be employed utilizing the present invention. All of the routes described hereinbelow employ the step of producing a di-functionalized intermediate (one functionalized carbon hydrogen bond of each of two hydrocarbyl groups), the process for the production of which has been described hereinabove with respect to, for example, the production of diols such as ethylene glycol from ethane. A first route for the production of carbonyls involves the formation of a vinyl ester from the di-functionalized intermediate (I) by elimination of HOX in, as schematically illustrated below, a catalyzed process.

I II III

As shown, the di-functional intermediate (I) is converted to a vinyl ester (II) (OX = an ester function, such as sulfate, trifluoroacetate, carbonate, trifluoromethanesulfonate), by elimination of HOX. This transformation may be accomplished in either a catalyzed or uncatalyzed fashion but as depicted above, is carried out in the presence of a basic catalyst. Preferred catalysts are basic or metal catalysts that are insoluble in the reaction medium. More preferably the catalysts are basic catalysts such as: sodium hydroxide; sodium hydride; butyl lithium; metal oxides such as magnesium oxide, lanthanum oxide and calcium oxide; metal alkoxides such as sodium methoxide; potassium tertiary butoxide; amines such as triethylamine; and tertiary amine functionalized ion-exchange resins such as Amberlyst™ resin. In this embodiment a vinyl ester is hydrolyzed by water to yield the carbonyl compound (III), which may be an aldehyde or a ketone, depending on the nature of R. Catalysts and conditions for this hydrolysis reaction are well known in the art. Catalysts may be soluble or insoluble in the reaction medium, preferably insoluble, and may be acids, bases, or metal complexes.

A second route to carbonyl compounds involves the initial hydrolysis of the di-functionalized intermediate (the ultimate precursor) to a mono-functional, mono-hydroxyl compound (IV) followed by subsequent molecular rearrangement, as schematically illustrated below.

I IV V III

The conversion from di-functional intermediate to mono- functional, mono-hydroxyl compound (IV) is described more fully hereinbelow with respect to the production of epoxides. In this embodiment, the intermediate mono-functional, mono-hydroxyl compound is converted to one or more carbonyl compounds (V and/or III) via a basic catalyzed reaction. This step may be conducted in a liquid, vapor, supercritical, solid or mixed phase reaction, and may be catalyzed or uncatalyzed. Preferably it is conducted as a mixed phase reaction which would enable easier separation of the carbonyl from the catalyst and unreacted ultimate precursor. For instance, the difunctional intermediate may be fed in the gas phase along with water to a solid basic catalyst such as magnesium oxide. The product would then be easily recovered by condensation and purified by distillation. Useful catalysts can include acids, bases, or metal catalysts, and preferably are selected from those which are insoluble in the reaction menstruum. More preferred catalysts are basic catalysts, and most preferred are basic catalysts selected from among: sodium hydroxide; sodium hydride; butyl lithium; metal oxides such as magnesium oxide, lanthanum oxide and calcium oxides; metal alkoxides such sodium methoxide; potassium tertiary butoxide; amines such as triethylamine; and tertiary amine functionalized ion-exchange resins such as Amberlyst™ resin.

A third route from di-functionalized intermediate to carbonyl compounds involves the hydrolysis of a di-functionalized intermediate (ultimate precursor) to a diol (VI) followed by a pinacol rearrangement, as schematically illustrated below.

I VI V III

The formation of a diol has been described heretofore. The pinacol rearrangement reaction of diols to carbonyl compounds is well known in the art. Catalysts for this reaction include conventional strong acids such as sulfuric acid, hydrochloric acid, -toluenesulfonic acid and the like. The rearrangement reaction may also be catalyzed by solid acids, such as -toluenesulfonic acid (J. Chem. Soc, Perkin Trans. I, 1989, p. 209), and heteropolymetallate acids, such as H3DPM012O40] (J. Mol. Catal., A, 107 (1996), p. 305) or acidic ion- exchange resins such as perfluorinated sulfonic acid resins. Preferred catalysts are acid catalysts which are insoluble in the reaction medium.

A fourth route to carbonyl compounds involves the conversion of a di-functional intermediate (the ultimate precursor )(I) to a mono- functional, mono-hydroxyl compound (IV), followed by elimination of H2O to a vinyl ester ( II), then hydrolysis to the carbonyl compound, as schematically illustrated below.

I IV II III

The conversion of the di-functional intermediate to the mono- functional, mono-hydroxyl compound is accomplished by partial hydrolysis. This hydrolysis may be carried out in the liquid phase, the gas phase or supercritical phase, and may be catalyzed or uncatalyzed. The process may be carried out in a batch, semi-continuous or continuous manner as desired. For example, water may be added to the di-functional intermediate as a liquid, as steam, or as a compound which liberates water under reaction conditions, such as a hydrated metal complex or an aldehyde hydrate. The di-functional intermediate and/or water may be dissolved in any appropriate solvents, such that the reaction menstruum is multiple, immiscible liquid phases. Consequently, solubility of the reagents and products in the solvent is of paramount importance such that the product mono-functional, mono-hydroxyl compound may be easily separated from at least the reagents and, more preferably, any byproducts. Suitable solvents include inorganic and organic solvents such as esters, ethers, aliphatic and aromatic hydrocarbons, ketones, silicone oils, chlorinated hydrocarbons and the like. Specific solvents that may be useful include benzene, toluene, xylenes, alkyl or polyalkyl benzenes, pentanes, hexanes, decanes, cyclohexane, diethyl ether, t-butyl methyl ether, anisole, veratrole (o-methoxyanisole), dimethoxyethane, tetraglyme (tetraethylene glycol dimethyl ether), diphenyl ether, ethyl acetate, benzyl acetate, o-dichlorobenzene, benzophenone, acetophenone and cyclohexanone. The choice of solvent is also made on the basis, among other factors, of solvent stability to reaction conditions, cost, and process operability issues. The concentration (excluding water or any optional catalyst) of the di-functional compound in the solvent is not critical and may range from about 1 weight % or less to about 99 weight % or greater. More preferred concentrations are at least about 10 weight %, and most preferred concentrations are at least about 20 weight %. More concentrated solutions are most preferred, consistent with acceptable product selectivity, since this minimizes the amount of solvent that must be recycled in a continuous process. The partial hydrolysis reaction is performed in a manner which maximizes the yield of the mono-functional, mono-hydroxyl product. It may be desirable to add water to a solution of the di-functional intermediate such that the di-functional intermediate is always at higher concentration than the water. In any case, it is important to control the stoichiometry of the reaction by controlling the molar ratio of water to di-functional intermediate. In general, mole ratios of less than 10:1 are desired. More preferred are ratios of less than 5:1, and most preferred are mole ratios of water to di-functional intermediate of less than 2:1. It should be recognized that equilibrium mixtures of di- functional intermediate, mono-functional, mono-hydroxyl compound, and di-hydroxyl compound may be formed depending on the reaction conditions chosen. Desired mono-functional, mono-hydroxyl intermediate may be separated as described hereinabove and di- functional intermediate and di-hydroxyl compound may be then re- equilibrated to generate more mono-functional, mono-hydroxyl compound and more solvent to the mono-functional, mono-hydroxyl compound may be employed.

The next step in this fourth route involves the conversion of the mono-functional, mono-hydroxyl compound to the vinyl ester. This process may be catalyzed or uncatalyzed and may be carried out in a liquid, vapor, supercritical, solid or mixed phase reaction. Preferred catalysts may be acidic, basic or metal catalysts, and more preferred catalysts are acidic materials that are insoluble in the reaction medium. Th e final step in this fourth route is the conversion of the vinyl ester to the carbonyl compound by hydrolysis with water to yield the carbonyl compound, which may be an aldehyde or a ketone, depending on the nature of R. Catalysts and conditions for this conversion are well known in the art. Catalysts are, preferably, insoluble in the reaction medium, and may be acids, bases, or metal complexes.

The chemistry for the production of oxiranes (epoxides) from, for example, C2 or higher hydrocarbyl-group containing compounds is shown schematically below (following the left branch of the reaction scheme).

A B I

Oxirane Aaridme

The process is a multiple step process in which a difunctionalized intermediate, producable as described heretofore, is partially hydrolyzed to a mono-functional, mono-hydroxyl compound by, for example, the process described above with respect to the production of carbonyl compounds, and then the mono-functional intermediate is reacted to produce the final product. It should be understood that two or more reactions in the process of producing the ultimate precursor can be accomplished in one stage or step. In an alternative embodiment of the production of the mono-functional, mono-hydroxyl compound, a portion of the di-functional intermediate may be completely hydrolyzed to diol (VI) by treatment with excess water to which is added additional di-functional intermediate such that an equilibrium mixture of diol, mono-functional, mono-hydroxyl compound (IV) and di-functional intermediate (I) is obtained (schematically illustrated below), from which the desired mono- functional, mono-hydroxyl product may be recovered and then reacted further to produce a final product.

(VI) (I) (IV)

The hydrolysis may be conducted in an uncatalyzed manner, or an appropriate catalyst may be employed. Such catalysts may be an acid, one or more Bronsted or Lewis acid or mixtures thereof, one or more basic materials, or one or more metal catalysts, or mixtures thereof. The catalyst may be solid, liquid or gaseous. Representative acid catalysts include sulfuric acid, sulfurous acid, hydrochloric acid, boron trifluoride, zinc chloride, antimony oxide, sulfonated perfluoro- ion exchange resins. Representative basic materials include sodium hydroxide, sodium carbonate, triethylamine, magnesium oxide, lanthanum oxide.

The product mono-functional, mono-hydroxyl compound may be recovered from the reaction solution before subsequent reaction in the second step, or it may be reacted in-situ to yield the epoxide. In one embodiment of the invention, a solvent to the final product is added to the reaction system and both reactions are performed in the same reactor, such that both chemical conversions are achieved in one step. Suitable solvents include dimethylsulfoxide, dimethylformamide, water, silicone oil, trioctylamine, and the like. Alternatively, the two transformations may be achieved in a plurality of reactors or reaction steps with or without intermediate isolation or purification of reaction intermediates. If it is desirable to isolate and purify the intermediate mono-functional, mono-hydroxyl compound to remove potential impurities which may influence the course of the second reaction step, or to remove any catalyst used in the first step for recycle and reuse before subjecting the reaction product from the first step to subsequent reaction to yield epoxide.

The temperature of the reaction is not critical, but is selected to achieve a commercially acceptable reaction rate. Reaction rate will depend upon the concentration of the reagents and upon the nature of any catalyst present. Reaction temperature is selected to give an acceptable reaction rate at conditions which do not decompose the reagents or products of any catalyst, whilst retaining acceptable product selectivity. Reaction temperature may be between 25°C or lower to 500°C or higher. More preferably, the reaction temperature is between 50°C and 300°C. Most preferably, it is between 75°C and 200°C.

Reaction pressures also are not critical and may be between autogenous pressure and 10,000 psig or higher, but more preferably between atmospheric pressure and 1500 psig, more preferably between atmospheric pressure and 600 psig.

The epoxide- forming reaction may be carried out in the liquid, gas, supercritical or solid phase, or in a mixed phase manner. For example, a solid catalyst may be employed to which a liquid phase solution of the mono-functional, mono-hydroxyl reagent is fed, and from which the epoxide product is covered by gas phase stripping and subsequent condensation.

The reaction may be carried out uncatalyzed or in the presence of a catalyst which may be acidic, basic or a metal catalyst. The catalyst is, preferably, insoluble in the reaction medium and most preferably is a basic catalyst selected from among sodium hydroxide, potassium hydride, sodium methoxide, magnesium oxide, lanthanum oxide, calcium oxide, tertiary amines, and resin-bound tertiary amines such as Amberlyst™ resin. The reaction conditions are not critical and are largely determined by such process considerations as achieving acceptable rates and efficiencies, catalyst performance and lifetime, and separations and operability issues. Non-limiting temperature ranges are from 25°C to 500°C, preferably from 50°C to 300°C, most preferably from 50°C to 200°C. Non-limiting pressures are from atmospheric or subatmospheric to 10,000 psig or greater, more preferably from 15 to 2000 psig, and most preferably from 50 to 600 psig.

Aziridine formation according to the process of the present invention is schematically illustrated below; again, starting from a difunctionalized intermediate (the ultimate precursor) produced, for example, as described heretofore:

I VII VIII

The reaction of the di-functional intermediate (I), to yield the aziridine (VIII) is analogous to the epoxide forming reaction described above. In this case, the di-functional intermediate is first reacted with an amine to yield the mono-functional, mono-amine compound (VII). In a second step or stage, this mono-functional intermediate is reacted to yield the aziridine. The amine employed in these reactions must be a primary amine or ammonia (Ri = H or a hydrocarbyl group which may contain heteroatoms such as C, H, O, N, P, S, halogen).

In the first step, the di-functional intermediate is reacted to yield a mono-functional, mono-amine compound (VII). This reaction may be carried out in the liquid phase, the gas phase or supercritical phase, and may be catalyzed or uncatalyzed. The process may be carried out in a batch, semi-continuous or continuous manner as desired. For example, amine may be added to the di-functional intermediate as a liquid, a vapor, or as a compound which liberates amine under reaction conditions, such as a metal amine complex or an ammonium salt. The di-functional intermediate and/or amine may be dissolved in any appropriate solvents, such that the reaction medium is multiple immiscible liquid phases, so that the product mono- functional, mono-amine compound is easily separated from at least the reagents. Suitable solvents include inorganic and organic solvents such as esters, ethers, aliphatic and aromatic hydrocarbons, ketones, silicone oils, chlorinated hydrocarbons and the like. Specific solvents that may be useful include benzene, toluene, xylenes, alkyl or polyalkyl benzenes, pentanes, hexanes, decanes, cyclohexane, diethyl ether, t-butyl methyl ether, anisole, veratrole (o-methoxyanisole), dimethoxyethane, tetraglyme (tetraethylene glycol dimethyl ether), diphenyl ether, ethyl acetate, benzyl acetate, o-dichlorobenzene, benzophenone, acetophenone, cyclohexanone. The choice of solvent is not critical and is made on the basis, among other factors, of solvent stability to reaction conditions, cost, and process operability issues. The concentration (excluding amine or any optional catalyst) of the di- functional compound in the solvent is not critical and may range from about 1 weight % or less to about 99 weight % or greater. More preferred concentrations are at least about 10 weight % and most preferred concentrations are at least about 20 weight % . More concentrated solutions are desired, consistent with acceptable product selectivity, since this minimizes the amount of solvent that must be recycled in a continuous process.

The reaction is performed in a manner which maximizes the yield of the mono-functional, mono-amine product. It may be desirable to add amine to a solution of the di-functional intermediate such that the di-functional intermediate is always at higher concentration than the amine. In any case, it is important to control the stoichiometry of the reaction by controlling the molar ratio of amine to di-functional intermediate. In general, mole ratios of less than 10:1 are desired. More preferred are ratios of less than 5:1, and most preferred are mole ratios of amine to di-functional intermediate of less than 2:1.

The aminolysis may be conducted in an uncatalyzed manner, or an appropriate catalyst may be employed. Such catalysts may be an acid, such as one or more of a Bronsted or Lewis acid or mixtures thereof, one or more basic materials, or one or more metal catalysts, or mixtures thereof. The catalysts may be solid, liquid or gaseous. Representative acid catalysts include sulfuric acid, sulfurous acid, hydrochloric acid, boron trifluoride, zinc chloride, antimony oxide, sulfonated perfluoro-ion exchange resins. Representative basic materials include sodium hydroxide, sodium carbonate, triethylamine, magnesium oxide, lanthanum oxide.

Reaction pressures also are not critical and may be between autogenous pressure and 10,000 psig or higher, but more preferably between atmospheric pressure and 1500 psig, and, most preferably, between atmospheric pressure and 600 psig.

The product mono-functional, mono-amine compound may be recovered from the reaction solution before subsequent reaction in the second step, or it may be reacted in-situ to yield the aziridine. In one embodiment of the invention, a solvent to the final product is added to the reaction system and both reactions are performed in the same reactor, such that both chemical conversions are achieved in one step. Suitable solvents include dimethyl sulfoxide, dimethyl formamide, water, silicon oil, trioctyl amine and the like. Alternatively, the two transformations may be achieved in a plurality of reactors or reaction steps with or without intermediate isolation or purification of reaction intermediates. If it is desirable to isolate and purify the intermediate mono-functional, mono-amine compound to remove potential impurities which may influence the course of the second reaction step, or to remove any catalyst used in the first step for recycle and reuse before subjecting the reaction product from the first step to subsequent reaction to yield aziridine.

The aziridine-forming reaction may be carried out in the liquid, gas, supercritical or solid phase, or in a mixed phase manner. For example, it may be advantageous to employ a solid catalyst to which a liquid phase solution of the mono-functional mono-amine reagent is fed, and from which the aziridine product is covered by gas phase stripping and subsequent condensation. The reaction may be carried out uncatalyzed or in the presence of a catalyst which may be acidic, basic or a metal catalyst. Preferably, the catalyst is a basic catalyst, which may be soluble or insoluble in the reaction medium. More preferably, the basic catalyst is insoluble in the reaction medium. Representative catalysts include sodium hydroxide, potassium hydride, sodium methoxide, magnesium oxide, lanthanum oxide, calcium oxide, tertiary amines, and resin-bound tertiary amines such as Amberlyst™ resin. The reaction conditions are not critical and are largely determined by such process considerations of achieving acceptable rates and efficiencies, catalyst performance and lifetime, and separations and operability issues. Non-limiting temperature ranges are from 25°C to 500°C, preferably from 50°C to 300°C, most preferably from 50°C to 200°C. Non-limiting pressures are from atmospheric or subatmospheric to 10,000 psig or greater, more preferably from 15 to 2000 psig, and, most preferably, from 50 to 600 psig.

The overall process, from startting material to final products, may be carried out in the vapor phase, liquid phase, supercritical phase or combinations thereof depending on the choice of reactants, reaction media, temperatures and pressures, with a mixed-phase system, to facilitate product recovery, being preferred. Further, it may be carried out as a continuous, semi-continuous or batch process. An integrated process would permit regeneration of the oxidant and in some instances of the catalyst, as well as provide certain economic advantages attributable to such factors as reactant and product throughputs and maintenance of reaction conditions at steady state over relatively long periods of time.

The reactors which may be used in the process of this invention include a fluid bed, a fixed bed, trickle bed, cyclic regenerating bed, and the like, with suitable coolants which are well known in the art. As described above, the process may be carried out in a single reactor, or multiple reactors. It may be advantageous to carry out the process in multiple reactors or reactor stages to enhance the selectivity of the reactions to the most desirable products. When a single reactor is employed, the reaction is preferably carried out in a single step wherein the hydrocarbyl group of the hydrocarbyl-containing compound to be functionalized is passed over or through a solid acid in the presence of a catalyst, and functionalized product removed therefrom for supply to the final product reaction zone. In a multiple reactor system or a multi-zone reactor, a first reactor/zone may be employed to produce a first intermediate product, such as a mono- functional intermediate and then a second or subsequent reactor/zone may be employed to produce the ultimate precursor, such as a difunctionalized intermediate used to produce, for example, glycols, carbonyls, etc. The ultimate precursor can then be further reacted to produce the desired final product.

Claims

WE CLAIM;

1. A process for producing at least one of acyclic alcohols, cyclic alcohols, acyclic glycols, cyclic glycols, carbonyls, oxiranes and aziridines, which process comprises the steps of: a) functionalizing, under regioselective conditions, only one carbon-hydrogen bond of at least one sp³ carbon atom [at a carbon - hydrogen bond] of at least one hydrocarbyl group of a starting material comprising a hydrocarbyl group containing compound to produce a functionalized hydrocarbyl group containing precursor from which a final product comprising at least one of acyclic alcohols, cyclic alcohols, acyclic glycols, cyclic glycols, carbonyls, oxiranes and aziridines can be produced; and b) reacting the functionalized hydrocarbyl group containing precursor under conditions sufficient to produce the final product.

2. The process of claim 1, wherein the functionalized carbon atom remains essentially an sp³ carbon atom until production of the final product.

3. The process of claim 1, wherein the regioselective conditions are accomplished by maintaining the functionalized hydrocarbyl group containing precursor from which the final product is produced, and any functionalized intermediate from which the functionalized hydrocarbyl group containing precursor can be produced, in a phase different from that phase in which at least one of any functionalizing reagent and catalyst that may be employed during production of the functionalized precursor is maintained during production of at least one of the precursor and intermediate.

4. The process of claim 1, wherein regioselective conditions are accomplished by employing a stabilizing agent to functionalize the carbon - hydrogen bond and essentially prevent the functionalized carbon - hydrogen bond from further functionalization before the production of the final product.

5. The process of claim 2, wherein the regioselective conditions are accomplished by employing reaction conditions during any functionalization reaction such that the functionalized carbon - hydrogen bond of the hydrocarbyl-group containing compound is essentially prevented from further functionalization prior to the production of the final product.

6. The process of claim 4, wherein the stabilizing agent comprises a stabilizing group capable of substantially protecting said functionalized carbon - hydrogen bond from further activation by reacting with the carbon - hydrogen bond to provide a functionalized compound substituted at said bond with said stabilizing group.

7. The process of claim 1, wherein the starting material is an alkane and the final product comprises glycol.

8. The process of claim 4, wherein the stabilizing agent is di- functional and one carbon - hydrogen bond of an at least two carbon atom containing hydrocarbyl group of a hydrocarbyl group-containing compound are functionalized to produce the functionalized precursor.

9. A process for the production of aliphatic and cyclic alcohols from alkanes comprising the steps of: a) functionalizing a starting material comprising acyclic or cyclic hydrocarbon by reacting the same, under regioselective conditions, with a stabilizing agent comprising an sp³ carbon atom protecting group to produce a mono-functionalized hydrocarbyl group containing precursor; and b) hydrolyzing the mono-functionalized hydrocarbyl group containing precursor to produce alcohol.

10. A process for the production of aliphatic or aromatic diol, comprising the steps of: a) functionalizing a starting material selected from a group comprising aliphatic and aromatic hydrocarbon by reacting the starting material, under regioselective conditions, with a stabilizing agent comprising an sp³ carbon atom protecting group to produce a di- functionalized hydrocarbyl group containing precursor; and b) hydrolyzing the di-functionalized hydrocarbyl group containing precursor to produce diol.

11. The process of claim 10 wherein the starting material is selected from the group of methane and ethane.

12. A process for the production of carbonyl compounds, comprising the steps of: a) functionalizing a starting material selected from a group comprising aliphatic and aromatic hydrocarbon by reacting the starting material, under regioselective conditions, with a stabilizing agent comprising an sp³ carbon atom protecting group to produce a di-ester; and b) converting the di-ester to a vinyl ester by reacting the di-ester in the presence of a basic reaction constituent; and c) hydrolyzing the vinyl ester to produce carbonyl compound.