Method for the manufacture of new amine

Abstract

The present invention relates to a process and compositions for the manufacture of amines. In particular, a process for the manufacture of diamines comprising the steps of (a) contacting a nitrile compound having the formula (I) with an amine compound having the formula RdHN-Rc in the presence of a metal catalyst under hydrogen pressure.

Description

FIELD OF THE INVENTION

[0001] The field of invention concerns a method to manufacture new amines. BACKGROUND OF THE INVENTION

[0002] The invention is a new process and compositions for the manufacture of amines. The scope of the amines prepared according to the new method comprise 5 amines of formula 1: Ra Rc ' Rb ^A^ ^Rd Formula 1 where Ra and Rb are independently aliphatic groups or Ra and Rb are cycloaliphatic or Ra and Rb are together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom (N, O or S) and where A is an aliphatic group or a 10 cycloaliphatic ring, Rc is aliphatic, cycloaliphatic, cycloalkyl or alkoxyalkyl group or tertiary amino alkyl and Rd is a hydrogen atom or methyl group.

[0003] The most preferred compounds have the structure shown in Formula 2: ,-R1                    R4 :       N-----(CH2)x+1----N---(CH2)y---O---R3 Formula 2 wherein R1 and R2 are independently C1-9 aliphatic groups and preferably R1 and R2 are 15 independently C1-3 aliphatic groups or R1 = H and R2 = C1-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring and where x =1 or 2 and preferably 2 and where R3 is a C1-9 aliphatic linear or branched or cycloaliphatic, R4 is H or methyl and y = 2 or 3. SUBSTITUTE SHEET (RULE 26)

[0004] US11745137 discloses several methods for the synthesis of amines which is defined according to the general Formula I: r^rWl’-nh........4V wherein R1 and R2 independently is aliphatic, cycloaliphatic, or R1 and R2 together with the nitrogen to which they are attached form a heterocyclic ring. L1 is aliphatic, cycloaliphatic, or L1 and R1 together with the nitrogen to which they are attached form a heterocyclic ring and R3 is aliphatic, cycloaliphatic, cycloalkyl-alkyl, or alkoxy-alkyl.

[0005] According to US11745137, compound of Formula I can be made in diverse ways. One such way involves a two-step reaction. The first reaction can be summarized according to the general scheme A: 1                       2                                          3 in which R1 and R2 independently is aliphatic, cycloaliphatic, or R1 and R2 together with the nitrogen to which they are attached form a heterocyclic ring. L1 is aliphatic, cycloaliphatic, or L1 and R1 together with the nitrogen to which they are attached form a heterocyclic ring and R3is aliphatic, cycloaliphatic, cycloalkylalkyl, or alkoxyalkyl such that R4 and the carbon to which it is attached together form R3 as defined above for formula I. The acid reactant denoted as 1 above could be activated for reaction in the presence of a suitable solvent and reacted with amine 2 to form amide 3. The recommended activating agents might be any reagent able to facilitate acid coupling with an amine. Among the activating agents mentioned included boric acid, a carbodiimide reagent like DCC (N, N’-dicyclohexylcarbodimide) optionally used in combination with hydroxybenzotriazole, bis-(2-oxo-3-oxazolidinyl)phosphinic chloride, thionyl chloride, mesyl chloride, tosyl chloride or their combination. Non-limiting examples of solvents include aprotic solvents such as toluene, chlorinated solvents such as chloroform, dichloromethane, dimethylformamide (DMF), tetrahydrofuran (THF) or their combinations. In some embodiments the reaction might be conducted with the removal of water such as by using a drying agent or an azeotropic water removal. The second step is shown according to the general scheme B: where amine 3 is reacted with reducing agent 4 to form the diamine 5. A variety of reducing agents can be used such as lithium aluminum hydride, borane dimethyl sulfide, borane-THF or lithium borohydride. The reduction can be conducted in a suitable solvent such as THF, methanol, ether, or a combination thereof. The temperature of the reaction can range from room temperature to the refluxing temperature of the solvent.

[0006] Example 1 in US11745137 disclosed a preparation procedure according to general scheme A and B shown above to make specifically N-(2-ethoxyethyl)-3-morpholinopropan-1-amine. The experimental procedure consists of contacting 2-ethoxy acetic acid (200 mmol), 3-morpholinopropane-1-amine (200 mmol) and 0.5% boric acid and heat the mixture to reflux in toluene with azeotropic removal of water until no more water is produced. The reaction was cooled down to room temperature washed with aqueous base, dried, and evaporated to yield the corresponding amine which was then reduced with lithium aluminum hydride (200 mmol) in refluxing THF to give N-(2-ethoxyethyl)-3-morpholinopropan-1-amine after purification. This is illustrated in the following reaction sequence: N-(2-ethoxyethyl)-3-morpholinopropan-l -amine

[0007] Thus, this method requires the formation of an amide that needs the constant withdraw of water from the reaction media by virtue of an azeotropic distillation using toluene. The amide produced in this way requires full reduction with lithium aluminum hydride which is known to react violently even with small amounts of water causing the risk of a potential explosion particularly if the water produced in the first step is not fully removed. In addition, plant storage of large-scale quantities of LiAIH4 is not an option because in addition to its strong reactivity, the material is also shock sensitive and could explode during its handing. Finally, the mehod also requires solid contaminated waste containing lithium / aluminum salts that need to be treated and disposed. Hence, due to the multiple risks this method seems suitable for small scale lab preparation but not large-scale tonne production.

[0008] Another way involves a reaction that can be summarized according to the general scheme C: 6                    2                                       7 wherein R5 is hydrogen or alkyl such as C1-6alkyl, C1-4alkyl, ethyl, or methyl. The carbonyl compound 6 is reacted with amine 2 and a reducing agent to form amine 7. Examples of reducing agents that can be used include borohydrides such as sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride or lithum borohydride or by catalytic reduction such as by hydrogen with palladium, nickel, ruthenium, and platinum on carbon. The reaction can be performed in one step such as by reductive alkylation or in two sequential steps where the amine is allowed to react with the carbonyl compound to form an imine before being contacted with a reducing agent. Suitable solvents include alcohols such as methanol, ethanol, or isopropanol, toluene, THF, acetonitrile or a combination thereof.

[0009] Example 2 in US11745137 disclosed a preparation procedure according to general scheme A and B shown above to make N-isobutyl-3-morpholinopropan-1-amine. The experimental procedure consists of contacting 3-aminopropylmorpholine (53.5 g, 370 mmol) with isobutylaldehyde (31.6 g, 438 mmol) in 300 ml of methanol until the reaction was completed. Upon cooling to about 0°C sodium borohydride (15.44g, 408 mmol) was added in small portions and when the addition was completed the reaction was warmed up to room temperature. The mixture was placed under rotary evaporation to remove methanol and the white slurry dissolved in 100 ml of aqueous 10M KOH and by extracting the aqueous layer with methylene chloride. The organic layer was further washed with 10M solution of KOH followed by a wash with distilled water and then dried over magnesium sulfate, filtered, and evaporated. Distillation of the desired product under reduced pressure gave a yield of about 53 %. This is illustrated in the following reaction sequence:

[0010] Thus, this method requires the formation of an imine that requires reduction with sodium borohydride which is known to release flammable gases which might ignite spontaneously specially because water is produced during the condensation of 3-aminopropylmorpholine with isobutylaldehyde. In addition, plant storage of large scale quantities of NaBH4 is not a viable option because in addition to its strong reactivity, the material could ignite causing a fire and explosion if exposed to adventitious moisture. Finally, this method also requires solid contaminated waste containing lithium / boron salts that need to be treated and disposed. Hence, due to the multiple risks this method seems suitable for small scale lab preparation but not large scale tonne production.

[0011] Another way involves a reaction that can be summarized according to the general scheme D: 8                   2 Amine 2 is treated with compound 8 to form compound 3. Typically, amine 2 is provided in excess, such as two times, three times, four times or five times or more excess with respect to compound 8 to facilitate the formation of compound 3 to drive the reaction to completion and to limit the formation of tertiary amine. X in scheme D is a suitable leaving group such as halogen (chloro or bromo) methylate or tosylate. The reaction might be performed neat without any solvent or alternatively using a solvent in the presence (or absence) of additional base. Examples of solvents include chlorinated solvents such as chloroform or dichloromethane, toluene, acetonitrile, DMF, THF, pyridine or a combination thereof. Suitable bases include any base that can facilitate the reaction such as trialkylamines, pyridine or inorganic bases such as potassium carbonate. The reaction mixture might optionally be contacted with aqueous base to remove excess of amine and / or neutralize any salt of the product that might have formed. The reaction might be performed at a suitable temperature to drive the reaction such as from 20°C to 120°C or more or to a reflux temperature of the solvent(s).

[0012] Example 3 in US11745137 disclosed a preparation procedure according to general scheme D shown above to make N-(2-ethoxyethyl)-3-morpholinopropan-1-amine. The experimental procedure consists of contacting 3-aminopropylmorpholine (307 g, 2.13 mol) that was heated to a temperature of about 80°C with 2-bromo-ethylether (116 g, 0.739 mol) that was added dropwise to the neat amine. The reaction temperature increased to about 110°C, and it was maintained until complete addition. After stirring overnight, the excess amine was distilled under reduced pressure. The residue was poured on 250 ml chloroform chilled on ice and washed with 10M KOH aqueous solution followed by distilled water. The organic layer was separated and the aqueous layer washed with chloroform followed by combining all the chloroform fractions which were dried with Na2SO4, filtered, and evaporated. The amine was distilled under reduced pressure with a yield of 55 %. 80° C

[0013] Thus, this method requires the reaction of 3-aminopropylmorpholine with 2-bromoethyl ether a flammable substance that requires storage at low temperatures to prevent its exposure to sources of ignition. Furthermore, the procedure of isolation using chloroform is not suitable in large scale due to the challenges that involve the toxicity associated with chloroform including the risk of cancer of the bladder and gastrointestinal track due to accidental release or exposure. Hence, due to the multiple risks this method seems suitable for small scale lab preparation but not large scale tonne production.

[0014] Synthesis of polyamines have also been described using homogeneous and heterogeneous catalysts. Several publications describe the formation of amine mixtures which in some cases are able to produce, at least partially, secondary amine mixtures from nitrile precursors under hydrogen reduction conditions.

[0015] Vishwas G. Chandrashekhar, Wolfgang Baumann, Matthias Beller, and Rajenahally V. Jagadeesh; Science (2022), 376(6600), pp. 1433-1441 teaches the use of nickel-based homogeneous catalyst able to promote amine-nitrile coupling with the purpose of making various potential pharmaceutical intermediates using specific poly-phosphine ligands. The homogeneous nickel catalyst system provides for an efficient reductive cross coupling of nitriles with ammonia and amines allowing for the synthesis of various primary, secondary, and tertiary amines relevant to drug manufacturing. Although, it is technically and conceptually sound, the difficulty of such homogeneous systems will prove difficult to bring to large multiton and kiloton scale due to the cost and complexity of the chemical structure of the catalyst. Nevertheless, the paper illustrates that transiton metals having the proper coordination environment can be useful in providing efficient amine-nitrile coupling with the purpose of making secondary or tertiary amines with high yield and selectivity.

[0016] Greenfield, Harold; l&EC Product Research and Development, (1967), 6(2), pp. 142-144; relates to the performance of various metal catalysts including nickel, cobalt, platinum, palladium, rhodium, and ruthenium which were tested when butyronitrile was hydrogenated in methanol to give butylamine, dibutylamine, and tributylamine. The results confirm the potential utility of metal catalysts such as Pd and Pt to make secondary and tertiary amine. However, the data shown under the conditions of the study favors the formation of the tertiary amine even under low conversions. Conditions for the formation of the secondary amine seems more favorable when using Rh and Ru catalysts. Rh-catalyst in the presence of ammonia also seems to significantly favor the formation of dibutylamine. When using Pd-catalyst, the tertiary amine (tributylamine) is almost the exclusive product even in the presence of ammonia which tends to favor the formation of the primary amine when using other catalyst such as Ni. Based on these studies, it is reasonable to conclude under the conditions of the study that the reduction of alkyl-nitriles by palladium catalyst seems to favor the formation of tertiary amines (>90%) while secondary amines are present as impurities (<10 %).

[0017] Liam McMillana, Lauren F. Gilpina, Justin Baker, Colin Brennan, Alan Hall, David T. Lundie, David Lennon; Journal of Molecular Catalysis A: Chemical, (2016), 411, pp. 239-246 relates to the liquid phase hydrogenation of aromatic nitriles, benzonitrile, benzyl cyanide, 3-phenyl propionitrile and cinnamonitrile over supported Pd on carbon. Form this study, it is interesting to note the formation of the secondary amine N-benzyl-2-phenethylamine (C6H5CH2CH2-NH-CH2C6H5) via the cross-coupling of intermediate with phenethylamine, or possibly of phenethyimine (C6H5CH2CH = NH) with benzylamine while no symmetrical secondary amine products were observed. This observation combined with the absence of benzylamine or phenethyimine in the liquid phase serves as proof that the coupling reactions that lead to formation of the secondary amine must be catalyst mediated on the surface of the support. Because of the relative low concentrations of the secondary amine relative to the main product (toluene) one can also conclude that carbon is not a suitable support for amine-nitrile cross-coupling.

[0018] Krupka, Jiri; Pasek, Josef; Navratilova, Marketa Collection of Czechoslovak Chemical Communications (2000), 65(11), pp. 1805-1819; describes the hydrogenation of 3-(dimethylamino)propionitrile over several metal catalysts including palladium but also ruthenium on alumina and platinum on carbon. Comparative examples show the performance of palladium-black as well as palladium metal supported on various materials such as carbon, alumina and silico-alumina using 3-(dimethylamino)-propionitrile (DMAPN) as substrate. In all cases, DMAPN can react under hydrogen pressure and at about 80-120°C to give complex mixture of product of which tris[3-(dimethylamino)propyl] amine is the main one. Significant amount of by-products are also observed due to the retro-Michael addition of DMAPN, despite the high pKa (pKa = 10.7) of DMA and high affitinity for acrylonitrile, leading to the formation of free acrylonitrile and dimethylamine in further detriment of the overall yield of the main secondary-amine product N,N-bis[3-(dimethylamino)propyl]amine (BDMAPA). Several conclusions are withdrawn from these studies. The main product obtained using the various palladium catalysts were TDMAPA and BDMAPA with higher yields for TDMAPA. Other byproduct contents were reduced with the most active catalysts. Thus, the overall yield of TDMAPA and BDMAPA increases relative to other products when using palladium supported on alumina. Palladium supported on carbon (Pd / C) was found is not a suitable catalyst converting DMAPN to the corresponding nitrile-coupling products BDMAPA and TDMAPA. According to the study, the most suitable catalysts able to provide the best overall yield of BDMAPA and TDMAPA are the palladium supported on alumina (Pd / AI2O3) with various loading typically ranging from 5 to 10 wt.%. The overall performance of the various palladium catalyst was found to be according to the following ranking: Pd-black « 5% Pd / C < 2% Pd / SiO2-AI2O3 < 0.56% Pd / AI2O3 < 5% Pd / AI2O3 (20 m2 / gcat) < 10% Pd / AI2O3 < 5% Pd / AI2O3 (150 m2 / gcat). Thus, 5% Pd / AI2O3 catalyst possesses a significantly much higher activity than the 5% Pd / C. Other catalysts such as 5 wt.% Ru / AI2O3 exhibited the lowest activity with DMAPA, the primary amine, being the main product. This study also teaches that 5 wt.% Pt / C showed a comparable activity to 5 wt.% Pd / C with DMAPA also being the main product. Addition of ammonia helps reducing the by-product improving the overall yield of BDMAPA and TDMAPA, but the concentration of the byproducts is still significant and about 20 % even when using a large % of ammonia and about 33 wt. % based on total mass of DMAPA and NH3.

[0019] Consistent with these observations, US5101975 discloses a process for the preparation of BDMAPA and TDMAPA also using Pd supported on y-alumina. In this case, using DMAPN as substrate favors the formation of TDMAPA (48%) over BDMAPA (32%). Thus, BDMAPA is not the preferred compound. Another drawback of the process is the need of Pd / y-alumina which is more costly than Pd / C because recycling of palladium metal from the support is much more difficult than in the case of Pd / C catalyst where the metal is simply recovered by combustion of the support. A strategy for increasing the concentration of BDMAPA in the product mixture is via hydrogenation of DMAPN in the presence of DMAPA in a 1 / 1 molar ratio which leads to the formation of higher yield of BDMAPA (81.5%) and lower yield of TDMAPA (3.8 %). The amount of byproduct is not disclosed but it is assumed to correspond to the rest of the composition and about 14.7% in part due to trans-cyanoethylation between DMA and DMAPA even though DMA is a stronger base (pKa 10.7) than DMAPA (pKa 9.7). This strategy works for making BDMAPA because the nitrile (DMAPN) is the precursor of the amine (DMAPA). However, this will not work for cases of molecules where the nitrile-precursor is different than the amine precursor.

[0020] P F Butskus, Russ. Chern. Rev.’ (1961), 30, pp 583-598 describes cyanoethylation reactions of multiple substrates and their properties. It also describes the reversibility of the cyaoethylation reaction particularly under heat, under distillation conditions and in the presence of cyanoethylated compounds in the presence of other acrylonitrile acceptors. For example, by heating DMAPN in the presence of piperidine can lead to the formation of about 30% 2-cyanoethylpiperidine. In this case, the transfer of acrylonitrile from one substrate (dimethylamine, DMA) to another (piperidine) seems feasible because piperidine is a stronger base (pKa 11.2) than DMA (pKa 10.7) and the extend of trans-cyanoethylation is likely to be more extensive as the difference in basicity increases for cases that are structurally similar or related. This is supported by the fact that, for example, some p-alkoxypropionitriles can be used as cyanoethylating agents. For example, p-methoxypropionitrile can be used to cyanoethylate ammonia, dimethylamine, dibutylamine, piperidine, morpholine and other similar amines. All these cases have been studied and reported in the literature and the trans-cyanoethylated products were isolated and characterized. Thus, trans-cyanoethylations can occur when nitrile precursors made via Michael addition of acrylonitrile to amine-1 are put in contact with amine-2 that has higher affinity for acrylonitrile than the amine-1 used to build nitrile-molecule. Thus, it would be expected that substantial number of by-products would be formed if the amines used in the process have different affinities for acrylonitrile. In general, primary amines have higher affinity for acrylonitrile than secondary amines as evidenced, for example, by the exotherm observed when acrylonitrile is added to primary amines. In the case of secondary amines, the exotherm is much milder and the reaction may require heating or a catalyst to proceed.

[0021] Thus, there is a need for new methods and proceses to make amines of Formula 2 using chemicals and raw materials that are amenable to large scale processes as to minimize or completely remove the risk of: a) explosion from shock sensitive materials, b) fire and explosion due to exothermic reactions caused by adventitious moisture, c) exposure to highly reactive and pyrophoric substances carrying the risk of serious injuries or death (for example, from using LiAIH4 or NaBH4), d) exposure to highly toxic material carrying risk of cancer and death due to accidental release; e) fire and explosion due to highly flammable materials that require storage under cold to prevent an industrial accident; f) disposal of toxic solid waste that requires energy and cost to completely remove the risks before discharge. There is also a need for a process to make amines of Formula 2 such that by-product formation due to transcyanoethylation and by-product formation is minimized. Furthermore, there is also a need for a process to make amines of Formula 2 such that the catalyst can be recycled with ease to minimize cost and avoid depletion of precious metals.

[0022] Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention. BRIEF SUMMARY OF THE INVENTION

[0023] The present invention relates to a new process for the manufacture of amines.

[0024] The scope of the amines prepared according to the new method comprise amines of formula 1: Ra i r ' Rb           ^Rd Formula 1 where Ra and Rb are independently aliphatic groups or Ra and Rb are cycloaliphatic or Ra and Rb are together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom (N, O or S) and where A is an aliphatic group or a cycloaliphatic ring, Rc is aliphatic, cycloaliphatic, cycloalkyl or alkoxyalkyl group or tertiary amino alkyl and Rd is a hydrogen atom or methyl group.

[0025] However, the most preferred compounds have the structure shown in Formula 2: r ; N-----(CH2)x+1----N---(CH2)y---O---R3 R2           Formula? wherein R1 and R2 are independently C1-9 aliphatic groups and preferably R1 and R2 are independently C1-3 aliphatic groups or R1 = H and R2 = C1-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring and where x =1 or 2 and preferably 2 and where R3 is a C1-9 aliphatic linear or branched or cycloaliphatic, R4 is H or methyl and y = 2 or 3.

[0026] In some embodiments, one or more of the following conditions may apply: a) at least one of R1 and R2 is branched alkyl or cycloalkyl; b) R1 is cycloaliphatic; c) R1 and R2 together with the nitrogen to which they are attached, forms a heterocyclic ring; d) al least one of R1 and R2 is not linear alkyl; e) R3 is a C1-9 aliphatic linear or branched or cycloaliphatic R4 is H and y = 2 or 3.

[0027] The instant invention solves some problems associated with conventional processes to make amines comprising compounds of Formula 2. The instant invention provides processes and methods using chemicals and raw materials that are amenable to large scale production as to minimize or completely remove the risk of: a) explosion from shock sensitive materials, b) fire and explosion due to exothermic reactions caused by adventitious moisture, c) exposure to highly reactive and pyrophoric substances carrying the risk of serious injuries or death (for example, from using LiAIH4 or NaBH4), d) exposure to highly toxic material carrying risk of cancer and death due to accidental release; e) fire and explosion due to highly flammable materials that require storage under cold to prevent an industrial accident; f) disposal of toxic solid waste that requires energy and cost to completely remove the risks before discharge. There is also a need for a process to make amines of Formula 2 such that by-product formation due to transcyanoethylation and by-product formation is minimized. Furthermore, there is also a need for a process to make amines of Formula 2 such that the catalyst can be recycled with ease to minimize cost and avoid depletion of precious metals.

[0028] The instant invention provides a process using heterogeneous catalysts under hydrogen reduction conditions. These catalysts can be re-used in multiple cycles either under batch or semi-batch conditions and upon completion of the useful life the metal catalyst can be recovered and recycled. Of particular importance is the finding of the high yields produced when the selection of amines and nitriles disclosed are used with Pd supported on various carbonaceous materials. Prior art results indicates that Pd catalyst supported on carbonaceous materials such as activated carbon is highly ineffective for the nitrile-amine coupling reaction. Also, the use of Pd supported on alumina provided high yields of the secondary amine even though it typically favors preferentially the formation of the tertiary amines.

[0029] The processes and methods to make amines comprising Formula 2 provided by the invention allow the scale production of these products to be used in multiple applications.

[0030] In one exemplary embodiment, the present invention provides new chemical compositions comprising amines of Formula 2.

[0031] Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention. BRIEF SUMMARY OF THE INVENTION

[0032] The NMR spectrum analysis of product mixture from Example 2 and discussed in Example 3 is shown in Fig. 1. DEFINITIONS

[0033] The following definition is provided in order to aid those skilled in the art in understanding the detailed description of the present invention. pphp - parts by weight per hundred weight parts polyol. DETAILED DESCRIPTION OF THE INVENTION

[0034] The invention is a new process and compositions for the manufacture of amines. The scope of the amines prepared according to the new method comprise amines of formula 1: Ra Rc ' Rb K ^Rd Formula 1 where Ra and Rb are independently aliphatic groups or Ra and Rb are cycloaliphatic or Ra and Rb are together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom (N, O or S) and where A is an aliphatic group or a cycloaliphatic ring, Rc is aliphatic, cycloaliphatic, cycloalkyl or alkoxyalkyl group or tertiary amino alkyl and Rd is hydrogen atom or methyl group.

[0035] Most preferred compounds have the structure shown below for Formula 2: z \ r ; N-----(CH2)x+1----N---(CH2)y---O---R3 R2           Formula? wherein R1 and R2 are independently C1-9aliphatic groups; preferably R1 and R2 are independently C1-3 aliphatic groups or R1 = H and R2 = C1-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring and where x =1 or 2 and preferably 2 and where R3 is a C1-9 aliphatic linear or branched or cycloaliphatic, R4 is H or methyl and y = 2 or 3.

[0036] The present invention provides new methods and proceses to make amine compositions comprising amines of Formula 2 using chemicals and raw materials that are amenable to large scale processes as to minimize or completely remove the risk of: a) explosion from shock sensitive materials, b) fire and explosion due to exothermic reactions cause by adventitious moisture, c) exposure to highly reactive and pyrophoric substances carrying the risk of serious injuries or death (for example, from using LiAIH4 or NaBH4), d) exposure to highly toxic material carrying risk of cancer and death due to accidental release; e) fire and explosion due to highly flammable materials that require storage under cold to prevent an industrial accident; f) disposal of toxic solid waste that requires energy and cost to completely remove the risks before discharge. Also, the process of the present invention to make amines of Formula 2 avoids by-product formation by minimizing trans-cyanoethylation between amine precursors. Furthermore, there is also a need for a process to make amines of Formula 2 such that the metal catalyst can be recycled with ease to minimize cost and avoid depletion of precious metals.

[0037] These processes and methods comprise contacting selected nitriles with selected amines as shown in the following equation for compounds comprising amines of Formula 1: Equation 1 H2 / Catalyst -NH3 Formula 1 Nitrile           Amine where Ra and Rb are independently aliphatic groups or Ra and Rb are cycloaliphatic or Ra and Rb are together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom (N, O or S) and where A is an aliphatic group or a cycloaliphatic ring, Rc is aliphatic, cycloaliphatic, cycloalkyl or alkoxyalkyl group or tertiary amino alkyl and Rd is hydrogen atom or methyl group.

[0038] The most preferred compounds are made according with equation 2: ,,R1                                                                            ,.R1                    R4 •'  \                                                  Cat        \               | ; N----(CH2)X--CN + R3—O—(CH2)y—NH2 + 2 H2 ----:      N----(CH2)X+1---N--(CH2)y---O--R3 + NH3 r2           Formula 2 wherein R1 and R2 are independently C1-9 aliphatic groups and preferably R1 and R2 are independently C1-3 aliphatic groups or R1 = H and R2 = C1-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring having or not an additional heteroatom (N, O or S) and where x =1 or 2 and preferably 2 and where R3 is a C1.9 aliphatic linear or branched or cycloaliphatic, R4 is H or methyl and y = 2 or 3. Process

[0039] These processes and methods comprise contacting selected nitriles with selected amines in the presence of a metal catalyst under hydrogen pressure. In one embodiment, the procedure comprises suspending a supported metal catalyst in a heel of selected amines in a reactor equipped with a mechanical stirrer, feeding lines as needed and a hydrogen supply. The supported metal catalyst is suspended in the selected amines heel and the sealed reactor is purged with an inert gas such as nitrogen. The temperature of the suspension is progressively increased from ambient temperature or close to ambient temperature (20-40°C) to about 70 °C to 150°C and preferably to about 80-120°C. The reactor is then pressurized with hydrogen gas. The hydrogen pressure will depend on the materials of construction and pressure rating of the equipment and typically a suitable hydrogen pressure is from about 15 psig to about 2000 psig and preferably from about 40 psig to about 1000 psig and more preferably from about 60 psig to about 900 psig and even more preferably from 80 to 800 psig to complete the reduction of the metal catalyst. The time for the complete reduction of the metal catalyst to its active state depends on the type of metal employed but typically is about 20-60 minutes. The specific nitrile is fed into the mechanically stirred suspension where the catalyst suspended in selected amines will mix with the nitrile in a semi-batch manner to facilitate the reaction of the amine with the nitrile to the corresponding imine which gets hydrogenated to an amine mixture comprising amines of Formula 2. The reaction is continued until no more hydrogen uptake is observed which indicates the end of the chemical reaction. The reactor is allowed to cool down to room temperature and upon venting of gases (excess hydrogen and ammonia), the reactor might optionally be filled with hydrogen to keep the catalyst active for the next use. The product comprising amines of Formula 2 is collected after filtration of the catalyst.

[0040] Alternatively, and for the selected amines and nitriles of this disclosure, it is possible to conduct the reaction in a batch manner. In one embodiment, the procedure comprises suspending a supported metal catalyst in a heel which is a mixture of the specific amine and the specific nitrile in a reactor equipped with a mechanical stirrer, feeding lines as needed and a hydrogen supply. The supported metal catalyst is suspended in the amine / nitrile mixture heel and the sealed reactor is purged with an inert gas such as nitrogen. The temperature of the suspension is progressively increased from ambient temperature or close to ambient temperature (20-40°C) to about 70 °C to 150°C and preferably to about 80-120°C and preferably to about 80-120°C. The reactor is then pressurized with hydrogen gas. The hydrogen pressure will depend on the materials of construction and pressure rating of the equipment and typically a suitable hydrogen pressure is from about 15 psig to about 2000 psig and preferably from about 40 psig to about 1000 psig and more preferably from about 60 psig to about 900 psig and even more preferably from 80 to 800 psig to complete the reduction of the metal catalyst. The time for the complete reduction of the metal catalyst to its active state depends on the type of metal employed but typically is about 20-60 minutes. The reaction is continued until no more hydrogen uptake is observed which indicates the end of the chemical reaction. The reactor is allowed to cool down to room temperature and upon venting of gases (excess hydrogen and ammonia), the reactor might optionally be filled with hydrogen to keep the catalyst active for the next use. The product comprising amines of Formula 2 is collected after filtration of the catalyst.

[0041] One aspect of the invention relates to a process for the manufacture of diamines comprising the steps of (a) contacting a nitrile compound having the formula ,--”Ra ' Rb T=N with an amine compound having the formula RdHN----Rc jn the presence of a metal catalyst under hydrogen pressure, wherein Ra and Rb are independently aliphatic groups, or Ra and Rb are cycloaliphatic, or Ra and Rb together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom selected from the group consisting of nitrogen, oxygen, or sulfur, and A is an aliphatic group or a cycloaliphatic ring, and wherein Rc is an aliphatic, cycloaliphatic, cycloalkyl or alkoxyalkyl group and Rd is a hydrogen atom or methyl group.

[0042] In a preferred embodiment of the process, the nitrile compound is a compound .-R1 I N----(CH2)X---CN having the formula '' R2 and the amine compound is an amino-ether compound having the formula R3—o—(CH2)y—NH2 wherein R1 and R2 are independently Ci-9 aliphatic groups or R1 = H and R2 = Ci-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring having or not an additional heteroatom selected from the group consisting of nitrogen, oxygen, or sulfur, and where x =1 or 2 and where R3 is a Ci. 9 aliphatic linear or branched or cycloaliphatic, and y = 2 or 3. In another preferred embodiment, R1 and R2 are independently C1-3aliphatic groups. In a further preferred embodiment, x = 2. Selected Nitriles

[0043] Preferable nitriles have the formula: ,,R1 I N----(CH2)X—cn R2

[0044] wherein R1 and R2 are independently C1-9 aliphatic groups and preferably R1 and R2 are independently C1-3 aliphatic groups or R1 = H and R2 = C1-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring and where x =1 or 2 and preferably 2.

[0045] Most preferred examples of nitriles that can be used in the process comprise N-(2-cyanoethyl)-morpholine, N,N-dimethylaminopropionitrile (DMAPN), N-(2-cyanoethyl)-piperidine, N-(2-cyanoethyl)-imidazole, N-(2-cyanoethyl)-N’-methyl-piperidine, N-(2-cyanoethyl)-N,N-dicyclopropyl-amine, N-(2-cyanoethyl)-N,N-dimethylcyclopropyl-amine, N-(2-cyanoethyl)-pyrrolidine, N-(2-cyanoethyl)-N-cyclopropyl-amine, N-(2-cyanoethyl)-N-methylcyclopropyl-amine, N-(2-cyanoethyl)-N-ethyl-amine, N-(2-cyanoethyl)-N-isopropyl-amine, N-(2-cyanoethyl)-N-propyl-amine, N-(2-cyanoethyl)-N-butyl-amine, N-(2-cyanoethyl)-N-isobutyl-amine, N-(2-cyanoethyl)-N-(sec-butyl)-amine, N-(2-cyanoethyl)-N-(tert-butyl)-amine, N-(2-cyanoethyl)-N-(n-pentyl)-amine, N-(2-cyanoethyl)-N-(n-iso-pentyl)-amine, N-(2-cyanoethyl)-N-(n-tert-pentyl)-amine, N-(2-cyanoethyl)-N-(n-neopentyl)-amine, N-(2-cyanoethyl)-N-(n-sec-pentyl)-amine, N-(2-cyanoethyl)-N-(3-pentyl)-amine, N-(2-cyanoethyl)-N-(sec-isopentyl)-amine, N-(2-cyanoethyl)-N-(1 -hexyl)-amine, N-(2-cyanoethyl)-N-(2-hexyl)-amine, N-(2-cyanoethyl)-N-(3-hexyl)-amine, N-(2-cyanoethyl)-N-(iso-hexyl)-amine, N-(2-cyanoethyl)-N-(4-methylpent-1 -yl)-amine, N-(2-cyanoethyl)-N-(4-methylpent-2-yl)-amine, N-(2-cyanoethyl)-N-(2-methylpent-1-yl)-amine, N-(2-cyanoethyl)-N-(3,3-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N-(3,3-dimethylbut-2-yl)-amine, N-(2-cyanoethyl)-N-(2,2-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N-(cyclohexyl)-amine, N-(2-cyanoethyl)-N-(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanoethyl)-N-(1,3-dimethylbutyl)-amine, N-(2-cyanoethyl)-N-(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanoethyl)-N-(1,3-dimethylbutyl)-amine, N-(2-cyanoethyl)-N-methyl-N-cyclopropyl-amine, N-(2-cyanoethyl)-N-methyl-N-methylcyclopropyl-amine, N-(2-cyanoethyl)-N-methyl-N-isopropyl-amine, N-(2-cyanoethyl)-N-methyl-N-propyl-amine, N- (2-cyanoethyl)-N-methyl-N-butyl-amme, N-(2-cyanoethyl)-N-methyl-N-isobutyl-amme, N-(2-cyanoethyl)-N-methyl-N-(sec-butyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(tert-butyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-iso-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-tert-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-neopentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-sec-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(sec-isopentyl)-amine, N-(2-cyanoethyl)-N-(1-hexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(2-hexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3-hexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(iso-hexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(4-methylpent-1 -yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(4-methylpent-2-yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(2-methylpent-1 -yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3,3-dimethylbut-1 -yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3,3-dimethylbut-2-yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(2,2-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(cyclohexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(1,3-dimethylbutyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanoethyl)-N-methyl-N-(1,3-dimethylbutyl)-amine and the like.

[0046] Less preferred nitriles comprise N-(2-cyanoethyl)-N,N-diethyl-amine, N-(2-cyanoethyl)-N,N-diisopropyl-amine, N-(2-cyanoethyl)-N,N-dipropyl-amine, N-(2-cyanoethyl)-N,N-dibutyl-amine, N-(2-cyanoethyl)-N,N-diisobutyl-amine, N-(2-cyanoethyl)-N,N-di(sec-butyl)-amine, N-(2-cyanoethyl)-N,N-di(tert-butyl)-amine, N-(2-cyanoethyl)-N,N-di(n-pentyl)-amine, N-(2-cyanoethyl)-N,N-di(n-iso-pentyl)-amine, N-(2-cyanoethyl)-N,N-di(n-tertpentyl)-amine, N-(2-cyanoethyl)-N,N-di(n-neopentyl)-amine, N-(2-cyanoethyl)-N,N-di(n-secpentyl)-amine, N-(2-cyanoethyl)-N,N-di(3-pentyl)-amine, N-(2-cyanoethyl)-N,N-di(sec-isopentyl)-amine, N-(2-cyanoethyl)-N,N-di(1-hexyl)-amine, N-(2-cyanoethyl)-N,N-di(2-hexyl)-amine, N-(2-cyanoethyl)-N,N-di(3-hexyl)-amine, N-(2-cyanoethyl)-N,N-di(iso-hexyl)-amine, N-(2-cyanoethyl)-N,N-di(4-methylpent-1-yl)-amine, N-(2-cyanoethyl)-N,N-di(4-methylpent-2-yl)-amine, N-(2-cyanoethyl)-N,N-di(2-methylpent-1 -yl)-amine, N-(2-cyanoethyl)-N,N-di(3,3-dimethylbut-1 -yl)-amine, N-(2-cyanoethyl)-N,N-di(3,3-dimethylbut-2-yl)-amine, N-(2-cyanoethyl)-N,N-di(2,2-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N,N-di(cyclohexyl)-amine, N-(2-cyanoethyl)-N,N-di(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanoethyl)-N,N-di(1,3-dimethylbutyl)-amine, N-(2-cyanoethyl)-N,N-di(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanoethyl)-N,N-di(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-morpholine, N-(2-cyanomethyl)-piperidine, N-(2-cyanomethyl)-imidazole, N-(2-cyanomethyl)-N’-methyl-piperidine, N-(2-cyanomethyl)-N,N-dicyclopropyl-amine, N-(2-cyanomethyl)-N,N-dimethylcyclopropyl-amine, N-(2- cyanomethyl)-pyrrohdme, N-(2-cyanomethyl)-N,N-diisopropyl-amme, N-(2-cyanomethyl)-N,N-dipropyl-amine, N-(2-cyanomethyl)-N,N-dibutyl-amine, N-(2-cyanomethyl)-N,N-diisobutyl-amine, N-(2-cyanomethyl)-N,N-di(sec-butyl)-amine, N-(2-cyanomethyl)-N,N-di(tert-butyl)-amine, N-(2-cyanomethyl)-N,N-di(n-pentyl)-amine, N-(2-cyanomethyl)-N,N-di(n-iso-pentyl)-amine, N-(2-cyanomethyl)-N,N-di(n-tertpentyl)-amine, N-(2-cyanomethyl)-N,N-di(n-neopentyl)-amine, N-(2-cyanomethyl)-N,N-di(n-secpentyl)-amine, N-(2-cyanomethyl)-N,N-di(3-pentyl)-amine, N-(2-cyanomethyl)-N,N-di(sec-isopentyl)-amine, N-(2-cyanomethyl)-N,N-di(1 -hexyl)-amine, N-(2-cyanomethyl)-N,N-di(2-hexyl)-amine, N-(2-cyanomethyl)-N,N-di(3-hexyl)-amine, N-(2-cyanomethyl)-N,N-di(iso-hexyl)-amine, N-(2-cyanomethyl)-N,N-di(4-methylpent-1 -yl)-amine, N-(2-cyanomethyl)-N,N-di(4-methylpent-2-yl)-amine, N-(2-cyanomethyl)-N,N-di(2-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N,N-di(3,3-dimethylbut-1-yl)-amine, N-(2-cyanomethyl)-N,N-di(3,3-dimethylbut-2-yl)-amine, N-(2-cyanomethyl)-N,N-di(2,2-dimethylbut-1 -yl)-amine, N-(2-cyanomethyl)-N,N-di(cyclohexyl)-amine, N-(2-cyanomethyl)-N,N-di(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanomethyl)-N,N-di(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-N,N-di(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanomethyl)-N,N-di(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-N-cyclopropyl-amine, N-(2-cyanomethyl)-N-methylcyclopropyl-amine, N-(2-cyanomethyl)-N-isopropyl-amine, N-(2-cyanomethyl)-N-propyl-amine, N-(2-cyanomethyl)-N-butyl-amine, N-(2-cyanomethyl)-N-isobutyl-amine, N-(2-cyanomethyl)-N-(sec-butyl)-amine, N-(2-cyanomethyl)-N-(tert-butyl)-amine, N-(2-cyanomethyl)-N-(n-pentyl)-amine, N-(2-cyanomethyl)-N-(n-iso-pentyl)-amine, N-(2-cyanomethyl)-N-(n-tert-pentyl)-amine, N-(2-cyanomethyl)-N-(n-neopentyl)-amine, N-(2-cyanomethyl)-N-(n-sec-pentyl)-amine, N-(2-cyanomethyl)-N-(3-pentyl)-amine, N-(2-cyanomethyl)-N-(sec-isopentyl)-amine, N-(2-cyanomethyl)-N-(1 -hexyl)-amine, N-(2-cyanomethyl)-N-(2-hexyl)-amine, N-(2-cyanomethyl)-N-(3-hexyl)-amine, N-(2-cyanomethyl)-N-(iso-hexyl)-amine, N-(2-cyanomethyl)-N-(4-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N-(4-methylpent-2-yl)-amine, N-(2-cyanomethyl)-N-(2-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N-(3,3-dimethylbut-1 -yl)-amine, N-(2-cyanomethyl)-N-(3,3-dimethylbut-2-yl)-amine, N-(2-cyanomethyl)-N-(2,2-dimethylbut-1 -yl)-amine, N-(2-cyanomethyl)-N-(cyclohexyl)-amine, N-(2-cyanomethyl)-N-(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanomethyl)-N-(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-N-(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanomethyl)-N-methyl-N-cyclopropyl-amine, N-(2-cyanomethyl)-N-methyl-N-methylcyclopropyl-amine, N-(2-cyanomethyl)-N-methyl-N-isopropyl-amine, N-(2-cyanomethyl)-N-methyl-N-propyl-amine, N-(2-cyanomethyl)-N-methyl-N-butyl-amine, N-(2-cyanomethyl)-N-methyl-N-isobutyl-amine, N-(2- cyanomethyl)-N-methyl-N-(sec-butyl)-amme, N-(2-cyanomethyl)-N-methyl-N-(tert-butyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-iso-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-tert-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-neopentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-sec-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(sec-isopentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(1-hexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(2-hexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3-hexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(iso-hexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(4-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(4-methylpent-2-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(2-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3,3-dimethylbut-1-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3,3-dimethylbut-2-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(2,2-dimethylbut-1 -yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(cyclohexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanomethyl)-N-methyl-N-(1,3-dimethylbutyl)-amine and the like.

[0047] In one preferred embodiment, the nitrile is selected from the group consisting of N-(2-cyanoethyl)-morpholine, N,N-dimethylaminopropionitrile (DMAPN), N-(2-cyanoethyl)-N-methyl-N-isopropyl-amine, N-(2-cyanoethyl)-imidazole, N-(2-cyanoethyl)-N-(cyclohexyl)-amine, and N-(2-cyanoethyl)-N-methyl-N-(cyclohexyl)-amine. Specific Amino-Ethers

[0048] Preferred amines are more specifically amino-ethers that can be used in the process include those of formula: R3-O-(CH2)y-NH2 where R3 is a C1-9 aliphatic linear or branched or cycloaliphatic and y = 2 or 3. Specific examples comprise methoxyethyl-1 -amine, 2-ethoxyethyl-1-amine, 2-(n-propoxy)ethyl-1-amine, 2-(isopropoxy)ethyl-1-amine, 2-(n-butoxy)ethyl-1-amine, 2-(iso-butoxy)ethyl-1-amine, 2-(sec-butoxy)ethyl-1-amine, 2-(t-butoxy)ethyl-1-amine, 2-(n-pentoxy)ethyl-1-amine, 2-(n-isopentoxy)ethyl-1-amine, 2-(tert-pentoxy)ethyl-1-amine, 2-(neo-pentoxy)ethyl-1 -amine, 2-(n-isopentoxy)ethyl-1 -amine, 2-(sec-isopentoxy)ethyl-1 -amine, 2-(3-pentoxy)ethyl-1-amine, 2-(n-hexoxy)ethyl-1-amine, 2-(2-hexoxy)ethyl-1-amine, 2-(3-hexoxy)ethyl-1-amine, 2-(iso-hexoxy)ethyl-1-amine, 2-(4-methylpent-1-yloxy)ethyl-1-amine, 2-(4-methylpent-2-yloxy)ethyl-1-amine, 2-(2-methylpent-1-yloxy)ethyl-1-amine, 2-(3,3-dimethylbut-1 -yloxy)ethyl-1 -amine, 2-(3,3-dimethylbut-2-yloxy)ethyl-1 -amine, 2-(2,2 dimethylbut-1-yloxy)ethyl-1-amme, 2-heptoxyethyl-1-amine, 2-octooxyethyl-1-amine, 2-(2-ethylhexyloxy)-1-amine, 3-methoxypropyl-1-amine, 3-ethoxypropyl-1-amine, 3-propoxypropyl-1-amine, 3-butoxypropyl-1-amine, 3-pentoxypropyl-1-amine, 3-hexoxypropyl-1-amine, 3-heptoxypropyl-1-amine, 3-octoxypropyl-1-amine, 3-(2-ethylhexyloxy)propyl-1-amine and the like.

[0049] In one preferred embodiment, the amine is selected from the group consisting of 2-ethoxyethyl-1-amine, 3-methoxypropyl-1-amine, and 3-ethoxypropyl-1-amine. Products Made by the Process

[0050] Preferred products made by the process comprise compounds according to the formula 2: ,-R1                   R4 :' \                     I , :       N-----(CH2)x+i----N---(CH2)y---O---R3 Formula 2 where R1, R2, R3, R4, x and y are the same as defined above.

[0051] Preferred examples of products made according to equation 2 comprise N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (shown below), / \ O             l\T \ / H N-(2-ethoxyethyl)-3-morpholinopropan-l-amine N-(2-(n-propoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(isopropoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(n-butoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(iso-butoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(sec-butoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(t-butoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(n-pentoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(tert-pentoxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(neo-pentoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(sec-isopentoxyl)-3-morpholinopropan-1-amine, N-(2-(3-pentoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(n-hexoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(2-hexoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(3-hexoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(iso-hexoxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-morpholinopropan-1 -amine, N-(2-(2-methylpent-1-yloxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(3,3- dimethylbut-1-yloxy)ethyl)-3-morphohnopropan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-morpholinopropan-1-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-morpholinopropan-1-amine, N-(2-heptoxyethyl)-3-morpholinopropan-1-amine, N-(2-octooxyethyl)-3-morpholinopropan-1-amine, N-(2-ethylhexyloxy)-3-morpholinopropan-1-amine, N-(2-ethoxyethyl)-3-(imidazolyl)propan-1-amine (shown below), N-(2-ethoxyethyl)-3-(imidazolyl)propan-l-amine N-(2-(n-propoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(isopropoxy)ethyl)-3-(imidazolyl)propan-l-amine, N-(2-(n-butoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(iso-butoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(sec-butoxy)ethyl)-3-(imidazolyl)propan-l-amine, N-(2-(t-butoxy)ethyl)-3-(imidazolyl)propan-1 -amine, N-(2-(n-pentoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-(imidazolyl)propan-l-amine, N-(2-(tert-pentoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(neo-pentoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-(imidazolyl)propan-l-amine, N-(2-(sec-isopentoxyl)ethyl)-3-(imidazolyl)propan-1 -amine, N-(2-(3-pentoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(n-hexoxy)ethyl)-3-(imidazolyl)propan-l-amine, N-(2-(2-hexoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(3-hexoxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(iso-hexoxy)ethyl)-3-(imidazolyl)propan-l-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-(imidazolyl)propan-1 -amine, N-(2-(2-methylpent-1-yloxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(3,3-dimethylbut-1-yloxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-(imidazolyl)propan-l-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-(imidazolyl)propan-1-amine, N-(2-heptoxyethyl)-3-(imidazolyl)propan-1 -amine, N-(2-octoxyethyl)-3-(imidazolyl)propan-l-amine, N-(2-ethylhexyloxy)-3-(imidazolyl)propan-1-amine, N-(3-ethoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-propoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-butoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-pentoxypropyl)-3-(imidazolyl)propan-l-amine, N-(3-hexoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-heptoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-octoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-(2-ethylhexyloxy)propyl)-3-(imidazolyl)propan-1 -amine, N-(2-ethoxyethyl)-3-(pyrrolidinyl)propan-l-amine (shown below), N-(2-ethoxyethyl)-3-(pyrrolidinyl)propan-l-amine N-(2-(n-propoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(isopropoxy)ethyl)-3-(pyrrolidinyl)propan-l-amine, N-(2-(n-butoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(iso-butoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(sec-butoxy)ethyl)-3-(pyrrolidinyl)propan-l-amine, N-(2-(t-butoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(n-pentoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-(pyrrolidinyl)propan-l-amine, N-(2-(tert-pentoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(neo-pentoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-(pyrrolidinyl)propan-l-amine, N-(2-(sec-isopentoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(3-pentoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(n-hexoxy)ethyl)-3-(pyrrolidinyl)propan-l-amine, N-(2-(2-hexoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(3-hexoxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(iso-hexoxy)ethyl)-3-(pyrrolidinyl)propan-l-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-(pyrrolidinyl)propan-1 -amine, N-(2-(2-methylpent-1-yloxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(3,3-dimethylbut-1-yloxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-(pyrrolidinyl)propan-l-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-heptoxyethyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-octoxyethyl)-3-(pyrrolidinyl)propan-l-amine, N-(2-ethylhexyloxy)-3-(pyrrolidinyl)propan-1-amine, N-(3-ethoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-propoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-butoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-pentoxypropyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-hexoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-heptoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-octoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(2-ethylhexyloxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-propoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(isopropoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-butoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1 -amine, N-(2-(iso-butoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(sec-butoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(t-butoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-pentoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1 -amine, N-(2-(tert-pentoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(neo-pentoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-(N’-isopropyl-N’- methyl)propan-1-amine, N-(2-(sec-isopentoxy)ethyl)-3-(N -isopropyl-N -methyl)propan-1-amine, N-(2-(3-pentoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-hexoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(2-hexoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(3-hexoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(iso-hexoxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(4-methylpent-1 -yloxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1 -amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(2-methylpent-1-yloxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(3,3-dimethylbut-1-yloxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-heptoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-octoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-ethylhexyloxy)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-ethoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-propoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-butoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-pentoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-hexoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-heptoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-l-amine, N-(3-octoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(2-ethylhexyloxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-ethoxyethyl)-3-(imidazolyl)propan-1-amine

[0052] Other preferred examples of products made according to equation 2 comprise N-(3-ethoxypropyl)-3-morpholinopropan-1 -amine (shown below), N-(3-ethoxypropyl)-3-morpholinopropan-l-amine N-(3-(n-propoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(isopropoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(n-butoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(iso-butoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(sec-butoxy)propyl)-3-morpholinopropan-1 -amine, N-(3-(t-butoxy)propyl)-3-morpholinopropan-1 -amine, N-(3-(n-pentoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(n-isopentoxy)propyl)-3-morpholinopropan-1 -amine, N-(3-(tert-pentoxy)propyl)-3-morpholinopropan-1 -amine, N-(3-(neo-pentoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(sec-isopentoxypropyl)-3-morpholinopropan-1-amine, N-(3-(3-pentoxy)propyl)-3-morpholinopropan-1-amine, N-(3- (n-hexoxy)propyl)-3-morphohnopropan-1-amine, N-(3-(2-hexoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(3-hexoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(iso-hexoxy)propyl)-3-morpholinopropan-1-amine, N-(3-(4-methylpent-1-yloxy)propyl)-3-morpholinopropan-1-amine, N-(3-(4-methylpent-2-yloxy)propyl)-3-morpholinopropan-1-amine, N-(3-(2-methylpent-1-yloxy)propyl)-3-morpholinopropan-1-amine, N-(3-(3,3-dimethylbut-1-yloxy)propyl)-3-morpholinopropan-1-amine, N-(3-(3,3-dimethylbut-2-yloxy)propyl)-3-morpholinopropan-1 -amine, N-(3-(2,2-dimethylbut-1 -yloxy)propyl)-3-morpholinopropan-1-amine, N-(3-heptoxypropyl)-3-morpholinopropan-1-amine, N-(3-octooxypropyl)-3-morpholinopropan-1-amine, N-(3-hexyloxypropyl)-3-morpholinopropan-1 -amine, N-(3-ethoxypropyl)-3-morpholinopropan-1 -amine, N-(3-propoxypropyl)-3-morpholinopropan-1-amine, N-(3-butoxypropyl)-3-morpholinopropan-1-amine, N-(3-pentoxypropyl)-3-morpholinopropan-1-amine, N-(3-hexoxypropyl)-3-morpholinopropan-1-amine, N-(3-heptoxypropyl)-3-morpholinopropan-1-amine, N-(3-octoxypropyl)-3-morpholinopropan-1 -amine, N-(3-(2-ethylhexyloxy)propyl)-3-morpholinopropan-1 -amine, N-(3-(3-propylhexyloxy)propyl)-3-morpholinopropan-1-amine, N-(3-ethoxypropyl)-3-(imidazolyl)propan-l-amine (shown below), N-(3-ethoxypropyl)-3-(imidazolyl)propan-l -amine N-(3-(n-propoxy)propxy)-3-(imidazolyl)propan-1-amine, N-(3-(isopropoxy)propyl)-3-(imidazolyl)propan-l-amine, N-(3-(n-butoxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(iso-butoxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(sec-butoxy)propyl)-3-(imidazolyl)propan-l-amine, N-(3-(t-butoxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(n-pentoxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(n-isopentoxy)propyl)-3-(imidazolyl)propan-l-amine, N-(3-(tert-pentoxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(neo-pentoxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(n-isopentoxy)propyl)-3-(imidazolyl)propan-l-amine, N-(3-(sec-isopentoxyl)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(3-pentoxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(n-hexoxy)propyl)-3-(imidazolyl)propan-l-amine, N-(3-(2-hexoxy)propyl)-3-(imidazolyl)propan-1 -amine, N-(3-(3-hexoxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(iso-hexoxy)propyl)-3-(imidazolyl)propan-l-amine, N-(3-(4-methylpent-1-yloxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(4-methylpent-2-yloxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(2-methylpent-1-yloxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(3,3-dimethylbut-1-yloxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-(3,3-dimethylbut-2-yloxy)propyl)-3- (imidazolyl)propan-l-amine, N-(3-(2,2-dimethylbut-1-yloxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-heptoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-octoxypropyl)-3-(imidazolyl)propan-l-amine, N-(2-propylhexyloxy)-3-(imidazolyl)propan-1-amine, N-(3-ethoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-propoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-butoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-pentoxypropyl)-3-(imidazolyl)propan-l-amine, N-(3-hexoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-heptoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-octoxypropyl)-3-(imidazolyl)propan-1-amine, N-(3-(2-propylhexyloxy)propyl)-3-(imidazolyl)propan-1-amine, N-(3-ethoxypropyl)-3-(pyrrolidinyl)propan-1-amine (shown below), N-(3-ethoxyproyl)-3-(pyrrolidinyl)propan-l-amine N-(3-(n-propoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(isopropoxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-(n-butoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(iso-butoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(sec-butoxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-(t-butoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(n-pentoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(n-isopentoxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-(tert-pentoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(neo-pentoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(n-isopentoxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-(sec-isopentoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(3-pentoxy)propyl)-3-(pyrrolidinyl)propan-1 -amine, N-(3-(n-hexoxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-(2-hexoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(3-hexoxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(iso-hexoxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-(4-methylpent-1-yloxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(4-methylpent-2-yloxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(2-methylpent-1-yloxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(3,3-dimethylbut-1-yloxy)propyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-(3,3-dimethylbut-2-yloxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-(2,2-dimethylbut-1-yloxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-heptoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-octoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-propylhexyloxy)-3-(pyrrolidinyl)propan-l-amine, N-(3-ethoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-propoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-butoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-pentoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3-hexoxypropyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-heptoxypropyl)-3-(pyrrolidinyl)propan-1-amine, N-(3- octoxypropyl)-3-(pyrrohdmyl)propan-1-amine, N-(3-(2-propylhexyloxy)propyl)-3-(pyrrolidinyl)propan-l-amine, N-(3-ethoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(n-propoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(isopropoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(n-butoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-l-amine, N-(3-(iso-butoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(sec-butoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(t-butoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(n-pentoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(n-isopentoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-l-amine, N-(3-(tert-pentoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(neo-pentoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(n-isopentoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(sec-isopentoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(3-pentoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-l-amine, N-(3-(n-hexoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(2-hexoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(3-hexoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1 -amine, N-(3-(iso-hexoxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(4-methylpent-1-yloxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(4-methylpent-2-yloxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(2-methylpent-1-yloxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(3,3-dimethylbut-1-yloxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(3,3-dimethylbut-2-yloxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(2,2-dimethylbut-1-yloxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-heptoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-octoxypropyl)-3-(N’-isopropyl-N’- methyl)propan-1-amine, N-(3-propylhexyloxy)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-ethoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-propoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-butoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-pentoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-hexoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-heptoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-l-amine, N-(3-octoxypropyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(2-ethylhexyloxy)propyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-ethoxypropyl)-3-(imidazolyl)propan-1-amine and the like.

[0053] In one preferred embodiment, the process is a process for the manufacture of N-(2-ethoxyethyl)-3-morpholinopropan-1-amine comprising the steps of (a) contacting N- (2-cyanoethyl)-morphohne with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

[0054] In another preferred embodiment, the process is a process for the manufacture of N-(2-ethoxypropyl)-3-morpholinopropan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-morpholine with 3-ethoxypropyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

[0055] In another preferred embodiment, the process is a process for the manufacture of N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-N-methyl-N-isopropyl-amine with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

[0056] In another preferred embodiment, the process is a process for the manufacture of N-(2-ethoxyethyl)-3-(imidazolyl)propan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-imidazole with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

[0057] In another preferred embodiment, the process is a process for the manufacture of N-(2-ethoxyethyl)-3-(cyclohexyl)propan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-N-(cyclohexyl)-amine with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

[0058] In another preferred embodiment, the process is a process for the manufacture of N-(2-ethoxyethyl)-3-(N’-cyclohexyl-N’-methyl)propan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-N-methyl-N-(cyclohexyl)-amine with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure. Secondary Products and New Compositions Made by the Process: New Compositions

[0059] New chemical compositions shown in Formula 3 are made as byproducts of the process: (CH2)x+1--N---(CH2)y---o—R3 Formula 3 where R1, R2, R3, x and y are the same as defined above.

[0060] The side products compounds are made according with equation 3: R1 \                                                 Cat 2 :     / N---(CH2)x--CN + R3—O—(CH2)y—nh2 + h2 7^ R2 R1 R2 -4—N (CH2)y—o—R3 ^2 Formula 3 where R1, R2, R3, x and y are the same as defined above. Equation 3 occurs sequentially with compounds of formula 2 being the intermediates in the process. Thus, compound of formula 3 can be made by reacting the selected amines with compound of formula 2 according to the equation 4: Ri R2 N---(CH2)X+1—N_(CH2)y—O—R' Formula 2 Cat +H2 N----(CH2)X---CN -----! '                     -nh3 R2 R2 N---(CH2)x+1-— N--(CH2)y--O—R: -^2 Formula 3

[0061] Preferred examples of products made according to equation 3 comprise N-(2-ethoxyethyl)-bis(3-morpholinopropan)-1-amine (shown below), N-(2-ethoxyethyl)-bis(3-morpholinopropan)-l-amine N-(2-(n-propoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(isopropoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(n-butoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(iso-butoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(sec-butoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(t-butoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(n-pentoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(n-isopentoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(tert-pentoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(neo-pentoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(n-isopentoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(sec-isopentoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(3-pentoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(n-hexoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(2-hexoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(3-hexoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(iso-hexoxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(4-methylpent-2-yloxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(2-methylpent-1-yloxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(3,3-dimethylbut-1-yloxy)ethyl)-bis(3-morpholinopropan-1-amine), N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-bis(3-morpholinopropan)-1-amine, N-(2-heptoxyethyl)-bis(3- morphohnopropan)-1 -amine, N-(2-octoxyethyl)-bis(3-morphohnopropan)-1-amine, N-(2-ethylhexyloxy)-bis(3-morpholinopropan)-1-amine, N-(3-ethoxypropyl)-bis(3- morpholinopropan)-1-amine, N-(3-propoxypropyl)-bis(3-morpholinopropan)-1-amine, N-(3-butoxypropyl)-bis(3-morpholinopropan)-1-amine, N-(3-pentoxypropyl)-bis(3- morpholinopropan)-1-amine, N-(3-hexoxypropyl)-bis(3-morpholinopropan)-1-amine, N-(3-heptoxypropyl)-bis(3-morpholinopropan)-1-amine, N-(3-octoxypropyl)-bis(3- morpholinopropan)-1-amine, N-(3-(2-ethylhexyloxy)propyl)-bis(3-morpholinopropan)-1-amine, N-(2-ethoxyethyl)-bis(3-(pyrrolidinyl)propan)-1-amine (shown below), N-(2-ethoxyethyl)-bis(3 -(pyrrolidinyl)propan)-1 -amine N-(2-(n-propoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(isopropoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(n-butoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(iso-butoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(sec-butoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(t-butoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(n-pentoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(tert-pentoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(neo-pentoxy)ethyl)-3-bis(pyrrolidinyl)propan-1 -amine, N-(2-(n-isopentoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(sec-isopentoxyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(3-pentoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(n-hexoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(2-hexoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(3-hexoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(iso-hexoxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(2-methylpent-1-yloxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(3,3-dimethylbut-1-yloxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-heptoxyethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-octooxyethyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-ethylhexyloxy)-3-bis(pyrrolidinyl)propan-1-amine, N-(3-ethoxypropyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(3-propoxypropyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(3-butoxypropyl)-3- bis(pyrrohdinyl)propan-1-amine, N-(3-pentoxypropyl)-3-bis(pyrrohdinyl)propan-1-amine, N-(3-hexoxypropyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(3-heptoxypropyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(3-octoxypropyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(3-(2-ethylhexyloxy)propyl)-3-bis(pyrrolidinyl)propan-1-amine, N-(2-ethoxyethyl)-3-bis(imidazolyl)-1-amine (shown below), N-(2-ethoxyethyl)-bis(imidazolyl)-1 -amine N-(2-(n-propoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(isopropoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(n-butoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(iso-butoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(sec-butoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(t-butoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(n-pentoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(tert-pentoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(neo-pentoxy)ethyl)-3-bis(imidazolyl)propan-1 -amine, N-(2-(n-isopentoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(sec-isopentoxyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(3-pentoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(n-hexoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(2-hexoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(3-hexoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(iso-hexoxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(2-methylpent-1-yloxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(3,3-dimethylbut-1-yloxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-heptoxyethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-octooxyethyl)-3-bis(imidazolyl)propan-1-amine, N-(2-ethylhexyloxy)-3-bis(imidazolyl)propan-1-amine, N-(3-ethoxypropyl)-3-bis(imidazolyl)propan-1-amine, N-(3-propoxypropyl)-3-bis(imidazolyl)propan-1-amine, N-(3-butoxypropyl)-3-bis(imidazolyl)propan-1-amine, N-(3-pentoxypropyl)-3-bis(imidazolyl)propan-1-amine, N-(3-hexoxypropyl)-3-bis(imidazolyl)propan-1-amine, N-(3-heptoxypropyl)-3-bis(imidazolyl)propan-1-amine, N-(3-octoxypropyl)-3-bis(imidazolyl)propan-1-amine, N-(3-(2-ethylhexyloxy)propyl)-3-bis(imidazolyl)propan-1-amine, N-(2-ethoxyethyl)-3-bis(N’- isopropyl-N -methyl)propan-1 -amine, N-(2-(n-propoxy)ethyl)-3-bis(N -isopropyl-N -methyl)propan-1-amine, N-(2-(isopropoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-butoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(iso-butoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(sec-butoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(t-butoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-pentoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(tert-pentoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(neo-pentoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(n-isopentoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1 -amine, N-(2-(sec-isopentoxyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(3-pentoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1 -amine, N-(2-(n-hexoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(2-hexoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(3-hexoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(iso-hexoxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(4-methylpent-1-yloxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(4-methylpent-2-yloxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(2-methylpent-1-yloxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(3,3-dimethylbut-1-yloxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(3,3-dimethylbut-2-yloxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-(2,2-dimethylbut-1-yloxy)ethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-heptoxyethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-octooxyethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-ethylhexyloxy)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-ethoxypropyl)-3-bis(N’-isopropyl-N’-methyl)propan1-amine, N-(3-propoxypropyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-butoxypropyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-pentoxypropyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-hexoxypropyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-heptoxypropyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-octoxypropyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(3-(2-ethylhexyloxy)propyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-ethoxyethyl)-3-bis(N’-isopropyl-N’-methyl)propan-1-amine, N-(2-ethoxyethyl)-3-bis(imidazolyl)propan-1-amine and the like. Catalysts Used in the Process.

[0062] Preferred examples of metal catalysts either dispersed on a solid support or as neat metal catalyst include, but are not limited to, Pt, Pd, Rh, Ru, Ni, Cu or Co, and the like, or any combination thereof. However, the preferred catalysts are Pd, Pt and Ni and more preferred are Pd and Pt and most preferred Pd. The catalyst can be used as neat metal catalyst or dispersed on a solid support but more preferably it is used dispersed on a solid support.

[0063] Different supports can be used such as carbon or oxidic supports.

[0064] The carbon support is typically activated carbon having porous structures of various sizes and shapes including micropores (< 2 nm width), mesopores (2 and 50 nm width) and macropores (width > 50 nm). Activated carbons have large surface area per unit mass making them ideal supports for metal catalyst dispersions. The surface area and pore volumes of activated carbons vary in a wide range depending on the raw materials and process used for its manufacture. The amount of material adsorbed can be very large because of the large surface of activated carbon. The Brunauer-Emmett-Teller (BET) area (internal area) is determined by measuring the gas adsorbed (typically N2) at a given pressure. Activated carbons typically have a BET area ranging from 800 to 1500 m2 Zg.

[0065] The oxidic support of the metal catalyst used in accordance with the invention comprise silica, alumina, titania, chromia, zirconia and metal oxides such as zinc oxide, magnesium oxide, calcium oxide, barium oxide as well as metal carbonates.

[0066] Supported catalysts contain the catalytically active metal in an amount of about 5% to 70% by weight, preferably about 5% to about 50% by weight and preferably about 5% to 30% by weight, and more preferably about 5% to 20% by weight all based on the total weight of the hydrogenation catalyst. A suitable example is a commercially available palladium on alumina catalyst having 5 wt. % palladium on alumina. Another suitable example is a commercially available palladium on alumina catalyst having 15 wt. % palladium on alumina. Alumina and silico-aluminates are preferred oxidic supports. In addition to unavoidable impurities, the support such as an alumina based support, may also comprise other additives to a certain extent. For example, other inorganic oxides such as oxides of metals of group IA, IIIB, IVB, IIIA and IVA of the Periodic Table of the Elements may be present in the alumina support, especially silicon dioxide, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide, sodium oxide and / or calcium oxide. The maximum content in the support of such oxides other than alumina is dependent upon the oxide actually present, but can be determined in the individual case with reference to the X-ray diffractogram of the hydrogenation catalyst, since a change in the structure is accompanied by a significant change in the X-ray diffractogram. The content of such oxides other than alumina is below 50% by weight, preferably below 30% by weight, more preferably below 10% by weight. The purity of the alumina is preferably higher than 50%.

[0067] The metal catalyst can be dispersed at various loadings on a given support but typically contains from about 1.0 wt. % to about 30 wt. %, from about 3.0 wt. % to about 20 wt. %; from about 5.0 wt.% to about 15.0 wt. %.

[0068] In the case of alumina-based catalysts the Pd or Pt loadings ranges from 1.015.0 wt. %, preferably 1.0-10 wt. % and more preferably 1.0-5.0 wt. %. Most preferred catalyst is a dispersion of about 2.0 wt. % to about 5.0 wt. % on alumina.

[0069] In the case of carbon-based catalysts the Pd or Pt loadings ranges from 1.0-20 wt. %, prefereably 1.0-15 wt. % and also prefereably 2.0-15 wt. % and also preferably 5.0 wt.% to 15 wt.%. Most prefer catalysts are Pd dispersed on carbon ranging from 5.0 wt.% to about 15 wt.%.

[0070] The catalyst quantity that is dispensed in the reaction process depends on the speed of reaction desired and on the wt. % of metal dispersed on a given support. For example, if 5.0 wt. % Pd on carbon catalyst is used then a suitable wt. % of catalyst to be used based on the total amount of amine and nitrile reactants can range from 0.05% to about 15%, more preferably from 0.1 to about 10 %, more preferably from 0.5 % to about 5.0 %, and more preferably 1.0 % to about 3 %.

[0071] In some cases, the catalyst used in accordance with the invention additionally comprises at least one promoter. For example, it may comprise further metals of group VIII, IB and I IB of the Periodic Table of the Elements (Cu, Ag, Au, Zn, Cd, Hg).

[0072] In some cases, the metal catalyst might be an unsupported metal catalyst such as Raney cobalt or Raney nickel. The metals may be present in pure metallic form, but also in the form of compounds, for example in the form of metal oxides. Under the operating conditions of the process they are present in the form of metals of metal hydrides. The conversion of any oxides to metals or metal hydrides can be effected in the manner known to those skilled in the art and before the catalyst is used in a hydrogenation process where pre-reduction might be required. Solvents Used in the Process

[0073] Examples of optional solvents that can be used include but are not limited to water and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, 2-ethylhexanol and the like. Other optional solvents include ethers such as diethylether, petroleum ether (ligroine), tetrahydrofuran, glycerin, glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycols, etc. Any solvent that does not interfere with the reaction shown in equation 2 that makes compounds of formula 2 is a suitable solvent. By “does not interfere” it is meant a solvent that does not poison the catalyst, which does not change the composition of the amines provided by the processs comprising Formula 2 and that it provides an advantage to the overall process relative to the solvent-free process.

[0074] The tertiary amine comprising compounds according to Formula 2 can have at least one secondary amine functionality in which case equation 2 requires that R4 is hydrogen atom with all the other substituents as defined above. ,.-Ri                                                                          ,.-R(                    R4 ■'  \                                                  Cat        \               | ; N---(CH2)X--CN + R3—O—(CH2)y—NHR4+ 2 H2 ----1 N---(CH2)X+1---N--(CH2)y--O--R3 + NH3 Formula 2 Compounds according to Formula 2 can have no secondary amine group in which case equation 2 requires that R4 is methyl group with R1, R2, R3, x and y as defined above. ,.-R,                                                                          ,.-R(                    R4 ■' \                                            Cat f \             | ; N---(CH2)x--CN + R3—o—(CH2)y—NHR4+ 2 H2 ----:      N---(CH2)X+1---N--(CH2)y--O--R3 + NH3 Formula 2

[0075] Tertiary amines comprising compounds of Formula 2 where R4 is a methyl group can also be conveniently prepared in two step reactions using formaldehyde (FA) and a catalyst as follows: Step 1: R3—O—(CH2)y—NH2 + 2H2 + NH3 Step 2: R\ / N----(CH2)x+i----N---(CH2)y---O---R3 R2 ,-R^              CH3 :      / N----(CH2)x+1----N---(CH2)y---O---R3 R2

[0076] The composition comprising compounds as defined in Formula 2 can also be acid blocked with an acid including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acids or any other organic or inorganic acid. Examples of carboxylic acids include mono-acids, di-acids or poly-acids with or without isocyanate reactive groups. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid and the like. An acid blocked catalyst can be obtained by known methods using conventional equipment.

[0077] The amines of the present invention can further comprise blends with materials such as carboxylate salts in any amount. Illustrative examples of alkali metal, alkaline earth metal, and quaternary ammonium carboxylate salts include, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate, 2-hydroxypropyltrimethylammonium octoate solution, and the like, or any combination thereof.

[0078] It is also within the scope of the amine composition of this invention to include mixtures or combinations of more than one amine composition as defined in Formula 2. Additionally, the amines or the novel compositions of the present invention can also further comprise blends with other amines known in the art.

[0079] The term “contact product” is used herein to describe compositions wherein the components are contacted together in any order, in any manner, and for any length of time. For example, the components can be contacted by blending or mixing. Further, contacting of any component can occur in the presence or absence of any other component of the compositions or foam formulations described herein. Combining additional amines components can be done by any method known to one of skill in the art. For example, in one aspect of the present invention, amine compositions can be prepared by combining or contacting the amine composition as defined in Formula 2 with at least one tertiary amine having or not at least one functional group (hydroxyl OH, primary amine NH2, secondary amine group =NH, amide -CONH2, substituted amide - CONHR with R = C1-C6 alkyl group, urea -NHCONH2) and optionally with an alkali metal carboxylate salt. This typically occurs in solution form.

[0080] While compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components or steps.

[0081] Another aspect of the present invention provides a compound having the formula ,'R1                     R4 / \                I , :       N----(CH2)x+i---N (CH2)y O—R3 '■■■■ R^ wherein R1 and R2 are independently C1-9 aliphatic groups or R1 = H and R2 = C1-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring having or not an additional heteroatom selected from the group consisting of nitrogen, oxygen or sulfur, and where x =1 or 2 and where R3 is a C1-9 aliphatic linear or branched or cycloaliphatic, R4 is H or methyl and y = 2 or 3.

[0082] In a preferred embodiment, the compound is N-(2-ethoxypropyl)-3-morpholinopropan-1 -amine.

[0083] In another preferred embodiment, the compound is N-(2-ethoxyethyl)-3-(1H-imidazol-1-yl)propan-1-amine.

[0084] In another preferred embodiment, the compound is N-(2-ethoxyethyl)-3-(pyrrolidin-1 -yl)propan-1 -amine.

[0085] In another preferred embodiment, the compound is N’-(2-ethoxyethyl)-N’”,N’”-dimethylpropane-1,3-diamine.

[0086] In another preferred embodiment, the compound is N-(2-ethoxyethyl)-3-(N”-methyl-piperazine)propan-1-amine.

[0087] In another preferred embodiment, the compound is N-(2-ethoxyethyl)-3-(N’-cyclohexyl)propan-1 -amine.

[0088] In another preferred embodiment, the compound is N-(2-ethoxyethyl)-3-(N’-cyclohexyl-N’-methyl)propan-1-amine.

[0089] In another preferred embodiment, the compound is N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine. EXAMPLES

[0090] These Examples are provided to demonstrate certain aspects of the invention and shall not limit the scope of the claims appended hereto.

[0091] EXAMPLE 1 Synthesis of N-(2-Cyanoethyl)-Morpholine Morpholine (607 g, 8 mol) and water (140 g) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. Then the steel reactor is sealed and purged with nitrogen for three times. The temperature of the reactor is increased to 50°C and acrylonitrile (553 mL, 446 g, 8.4 mol) is then charged into the reactor from a high pressure syringe pump at a speed sufficient to keep the reactor temperature at 50°C or slighthly below (~ 4 hours feeding time) while stirring at about 1000 rpm. Upon completion of addition, hold the reaction temperature at 50°C for 2 hours before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under vacuum. N-(2-cyanoethyl)-morpholine is collected with an approximate yield of 99 % yield and 100% purity based on GC analysis.

[0092] EXAMPLE 2 (inventive) Synthesis of N-(2-ethoxyethyl)-3-morpholinopropan-1-amine using excess ethoxyethylamine (Amine / Nitrile Molar Ratio = 3 / 1)—Semi-Batch Ethoxyethylamine (99 g, 1.11 mol), isopropanol (100 g, 127 ml) and 5% Pd / C (3.3 g, 50 wt. % in water) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. N-(2-cyanoethyl)-morpholine (52 g, 0.37 mol) is charged into the high-pressure syringe pump. Heat the reactor to 80°C and adjust the hydrogen pressure to be at 800 psi. Dispense N-(2-cyanoethyl)-morpholine solution from the pump into the reaction over about 4.5 hours under mechanical stirring (1000 rpm) and held for an additional 4 hours at temperature until the hydrogen uptake is stopped. After cooling down to room temperature, the reactor is then vented and all volatiles are removed on rotary evaporator under reduced pressure, and about 100 ml of a yellow liquid containing N-(2-ethoxyethyl)-3-morphohnopropan-1-amine (89 % by GC analysis) which was purified by distillation (overhead temperature 102°C-78°C @ 0.8 torr).

[0093] EXAMPLE 3 (inventive) Analysis of Product Mixture from Example 2 The sample distilled in Example 2 was analyzed by 13C NMR confirming the chemical structure. 13C NMR: The sample was dissolved in chloroform-d with chromium acetylacetonate added as a relaxation agent. The NMR experiment was performed at ambient temperature employing the Bruker Avance III 500 FT-NMR spectrometer equipped with a 10 mm BBO probe. Quantitative 13C NMR data was acquired using inverse-gated decoupling, a 30° pulse, and a 6 second relaxation delay. The chemical shift scale was referenced to the solvent peak. The NMR spectrum analysis is shown in Fig. 1.

[0094] EXAMPLE 4 (inventive) Synthesis of N-(2-ethoxyethyl)-3-morpholinopropan-1-amine using stoichiometric amount ofethoxyethylamine(Amine / Nitrile Molar Ratio = 1 / 1)—Semi-Batch Ethoxyethylamine (99 g, 1.11 mol), isopropanol (100 g, 127 ml) and 15% Pd / C (9.9 g, 50 wt. % in water) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. N-(2-cyanoethyl)-morpholine (156 g, 1.1 mol) is charged into the high-pressure syringe pump. Heat the reactor to 80°C and adjust the hydrogen pressure to be at 800 psi. Dispense N-(2-cyanoethyl)-morpholine solution from the pump into the reaction over about 4.5 hours under mechanical stirring (1000 rpm) and held for an additional 4 hours at temperature until the hydrogen uptake is stopped. After cooling down to room temperature, the reactor is then vented and all volatiles are removed on rotary evaporator under reduced pressure, and about 250 ml of a yellow liquid containing N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (72 % by GC analysis) which was purified by distillation (overhead temperature 102°C-78°C @ 0.8 torr). In this case, new compound 3 described in example 3 [N-(2-ethoxyethyl)-bis(3-morpholinopropan)-1-amine; MW = 343] is made in about 20 % yield.

[0095] EXAMPLE 5 (inventive) Synthesis of N-(2-ethoxyethyl)-3-morpholinopropan-1-amine using various reactant ratios and metal catalysts The following table shows the results of various catalyst and experimental conditions to make N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) using batch or semibatch procedure. Based on this data, palladium catalyst was most effective and better than Ra-Ni or Pt. Both 15 wt. % and 5 wt. % load of palladium metal on carbon were effective in making compounds 1 when the molar ratio of amine / nitrile was from 1 / 1 to 3 / 1 with the yield being at higher concentrations of the amine. Although product 1 can be made in a wide ranges of temperature from 40-140°C; better yield are obtained when temperature is about 80°C and / or within the range of 70-90°C. Thus, it clear from comparing semi-batch run# 3 at 80°C (72 % yield) vs. run # 7 (64 % yield) that carrying out the process at 80°C produce better yield of 1. When using Pd / C the selectivity towards compound 1 increases when the amine / nitrile ratio is increased from 1 to 3 while the selectivity towards compound 3 decreases under these conditions. Pt / C was not as effective as palladium in producing N-(2-ethoxyethyl)-3-morpholinopropan-1-amine even at higher temperatures producing compound 1 in about 29 % yield. Pt / C also increases the formation of AP-morpholine (3-aminopropyl morpholine). When using Pd / AI2O3 as catalyst, best results are obtained when the amine / nitrile ratio is closed to stochiometric and about 1 to 1 yielding EEMPA at about 75 % yield. Using excess amine does not improve the yield but rather decreases the overall yield to about 68 % with the formation of significant amounts of AP-morpholine. Finally, Ra-Ni can produce product 1 in a low yield making primarily AP-morpholine. Thus, optimum process conditions comprise: a) temperature in the range 40-80°C and preferably 60-80°C; b) Preferred catalyst is Pd with a loading on the support in the range from 3 wt. % to about 20 wt. % and preferably from 5 wt. % to 15 wt. %; c) Preferred supports are carbon and alumina and most preferred carbon; d) amine / nitrile ratio from 1 / 1 to 3 / 1 is preferred when the support is a carbonaceous support and amine / nitrile ration of about 1 / 1 is preferred when the support in a metal-oxide support such as alumina; e) Hydrogen pressure from about 50-800 psi and preferably from 60 to 100 psi; f) Process can be run batch or semi-batch with similar yields. Exp # Catalyst Process Type Amine / Nitrile Molar Ratio Temperature ("C) Hydrogen Pressure (psi) iiiiiiiji (%> 2 (%) 3 (%) AP-Morpholine 1 5% Pd / C Semi-Batch 3 to 1 80 800 86 2 2.5 2.1 2 15% Pd / C Semi-Batch 3 to 1 80 800 89 1.0 4.7 1.2 3 15% Pd / C Semi-Batch 1 to 1 80 800 72 2.9 19 0.6 4 5% Pt / C Semi-Batch 1 to 1 80-140 800 29 2.7 0.3 2.9 5 5%Pd / AI2O3 Semi-Batch 1 to 1 80 800 75 4.4 17 0.6 6 5%Pd / AI2O3 Semi-Batch 3 to 1 80-100 800 68 4.4 2.2 6.6 7 15% Pd / C Semi-Batch 1 to 1 100 800 64 2.4 21 0.3 8 15% Pd / C Batch 3 to 1 60-80 800 91 1.1 5.1 0.3 9 15% Pd / C Batch 1 to 1 40-80 100 72 3.1 20 0.3 10 Raney-Ni Batch 1 to 1 40-80 800 30.2 19 0.4 48.5

[0096] EXAMPLE 6 (inventive, new compound) Synthesis of N-(2-ethoxypropyl)-3-morpholinopropan-1-amine (Amine / Nitrile Molar Ratio = 3 / 1)—Semi-Batch 5 3-Ethoxypropylamine (156.7 g, 1.519 mol), IPA (9.5 g) and 15% Pd / C (4.9 g, ~50% wet) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. N-(2-cyanoethyl)-morpholine (70.8 g, 0.505 mol) is charged into the high-pressure syringe pump. Heat the reactor to 80°C and adjust the hydrogen pressure to be 10 at 800 psi. Charge N-(2-cyanoethyl)-morpholine solution from the pump into the reaction at a speed of 19.4 mL / hour until the hydrogen uptake is stopped after 3.5 hours. Then the reaction is held at the same condition for 2 hour before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 120 g of the final 15 product is collected as a mixture of material containing 91 % N-(2-ethoxypropyl)-3-morpholinopropan-1-amine which is purified by distillation.

[0097] EXAMPLE 7 (inventive, new compound) Synthesis of N-(2-ethoxypropyl)-3-morpholinopropan-1-amine (Amine / Nitrile Molar Ratio = 3 / 1)—Batch 3-Ethoxypropylamine (156.7 g, 1.519 mol), N-(2-cyanoethyl)-morpholine (70.1 g, 0.500 mol), IPA (100.1 g) and 15% Pd / C (4.88 g, ~50% wet) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil. The reactor was heated to 80°C and adjust the hydrogen pressure to be at 800 psi. The reaction was continued until the hydrogen uptake is stopped after 2.5 hours. Then the reaction is held at the same condition for 0.5 hour before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 128 g of the final product is collected as a mixture of material containing 90 % N-(2-ethoxypropyl)-3-morpholinopropan-1-amine which is purified by distillation.

[0098] EXAMPLE 8 (inventive, new compound) Synthesis of N-(2-ethoxypropyl)-3-morpholinopropan-1-amine (Amine / Nitrile Molar Ratio = 3 / 1)—Batch 3-Ethoxypropylamine (156.7 g, 1.519 mol), N-(2-cyanoethyl)-morpholine (70.1 g, 0.500 mol), IPA (100.1 g) and 15% Pd / C (4.84 g, ~50% wet) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle and cooling coil. The reactor pressure was adjusted to be at 800 psi, and the reactor was heated to 40°C. The reaction temperature was adjusted in 10°C increments to maintain the hydrogen uptake. The reaction continued until the hydrogen uptake is stopped after 3.25 hours where the final reaction temperature was 80°C. Then the reaction is held at the final condition for 0.75 hour before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 127 g of the final product is collected as a mixture of material containing 91.7 % N-(2-ethoxypropyl)-3-morpholinopropan-1-amine which is purified by distillation.

[0099] EXAMPLE 9 Synthesis of N-2-cyanoethyl-imidazole Imidazole (339.7 g, 4.1 mol) and water (60 g) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. Then the steel reactor is sealed and purged with nitrogen for three times. The temperature of the reactor is increased to 50°C and stir for 30min to help dissolve all the imidazole. Acrylonitrile (229.4 g, 4.3 mol) is then charged into the reactor from a high pressure syringe pump over a period of two hours while maintaining the reactor temperature between 60-80°C. Upon completion of addition, hold the reaction temperature at 75°C for 2.5-3.0 hours before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under vacuum. N-(2-cyanoethyl)-imidazole is collected in 99.5% yield and 100% purity based on GC analysis.

[00100] EXAMPLE 10 (inventive, new compound) Synthesis of N-(2-ethoxyethyl)-3-(1 H-imidazol-1 -yl)propan-1 -amine (Amine / Nitrile Molar Ratio = 3 / 1)—Batch 2-Ethoxyethylamine (133.8 g, 1.501 mol), 3-(1 H-imidazol-1-yl)-propane-nitrile (aqueous solution, 75.4 g, 0.498 mol), IPA (99.8 g) and 15% Pd / C (4.03 g, ~50% wet) are charged into a stainless-steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. The reactor pressure was adjusted to be at 800 psi, and the reactor was heated to 40°C. The reaction temperature was adjusted in 10°C increments to maintain the hydrogen uptake. The reaction continued until the hydrogen uptake is stopped after 3 hours where the final reaction temperature was 80°C. Then the reaction is held at the final condition for 2 hours before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 102 g of the final product is collected as a mixture of material containing 90 % N-(2-ethoxyethyl)-3-(1 H-imidazol-1-yl)propan-1-amine which is purified by distillation.

[00101] EXAMPLE 11 Synthesis of N-2-cyanoethyl-pyrrolidine Pyrrolidine (300 g, 4.22 mol) and water (60 g) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. Then the steel reactor is sealed and purged with nitrogen for three times. Acrylonitrile (290 mL) is then charged into the reactor from a high pressure syringe pump at a speed of 100mL / hour while maintaining the reactor temperature at 50°C. Upon completion of addition, hold the reaction temperature at 50 C for 2 hours before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under vacuum. N-(2-cyanoethyl)-pyrrolidinyl is collected in 98.5% yield and 100% purity based on GC analysis.

[00102] EXAMPLE 12 (inventive, new compound) Synthesis of N-(2-ethoxyethyl)-3-(pyrrolidin-1 -yl)propan-1 -amine (Amine / Nitrile Molar Ratio = 3 / 1)—Batch 2-Ethoxyethylamine (133.7 g, 1.500 mol), 3-(pyrrolidin-1 -yl)propanenitrile (62.1 g, 0.500 mol), IPA (101.4 g) and 15% Pd / C (4.01 g, ~50% wet) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle and a cooling coil. The reactor pressure was adjusted to be at 800 psi, and the reactor was heated to 40°C. The reaction temperature was adjusted in 10°C increments to maintain the hydrogen uptake. The reaction continued until the hydrogen uptake is stopped after 5 hours where the final reaction temperature was 80°C. Then the reaction is held at the final condition for 1 hours before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 102 g of the final product is collected as a mixture of material containing 84 % N-(2-ethoxyethyl)-3-(pyrrolidin-1-yl)propan-1-amine which is purified by distillation.

[00103] EXAMPLE 13 (inventive, new compound) Synthesis of N’-(2-ethoxyethyl)-N”’,N”’-dimethylpropane-1,3-diamine (Amine / Nitrile Molar Ratio = 3 / 1)—Batch 2-Ethoxyethylamine (160.45 g, 1.800 mol), 3-(dimethylamino)propane nitrile (58.9 g, 0.600 mol), IPA (101.2 g) and 15% Pd / C (4.27 g, ~50% wet) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. The reactor pressure was adjusted to be at 800 psi, and the reactor was heated to 40°C. The reaction temperature was adjusted in 10°C increments to maintain the hydrogen uptake. The reaction continued until the hydrogen uptake is stopped after 5 hours where the final reaction temperature was 80°C. Then the reaction is held at the final condition for 0.5 hours before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 95 g of the final product is collected as a mixture of material containing 93 % N’-(2-ethoxyethyl)-N”’,N”’-dimethylpropane-1,3-diamine which is purified by distillation.

[00104] EXAMPLE 14 Synthesis of N-(2-cyanoethyl)-N’-methyl-piperazine N-methyl-piperazine (250.6 g, 2.5 mol) and 5 g of water are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. Then the steel reactor is sealed and purged with nitrogen for three times. The temperature of the reactor is increased to 40°C and acrylonitrile (138.3 g, 2.6 mol) is then charged into the reactor from a high pressure syringe pump at a speed sufficient to keep the reactor temperature at 40-80°C or slighthly below (~ 1.5 hours feeding time) while stirring at about 1000 rpm. Upon completion of addition, hold the reaction temperature at 75°C for 3 hours before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under vacuum. N-(2-cyanoethyl)-N’-methylpiperazine is collected with an approximate yield of 99.5 % yield and 100% purity based on GC analysis.

[00105] EXAMPLE 15 (inventive, new compound) Synthesis of N-(2-ethoxyethyl)-3-(N’’-methyl-piperazine)propan-1-amine using excess ethoxyethylamine Ethoxyethylamine (133.7 g, 1.5 mol), isopropanol (100 g, 127 ml), N-(2-cyanoethyl)-N’-methyl-piperazine (76.6 g, 0.50 mol) and 5% Pd / C (4.58 g, 50 wt. % in water) was charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle and a cooling coil. The reactor pressure was adjusted to be at 800 psi, and the reactor was heated to 40°C while stirring at 1000 rpm. The reaction temperature was adjusted in 10°C increments to maintain the hydrogen uptake. The reaction continued until the hydrogen uptake is stopped after 3.25 hours where the final reaction temperature was 80°C. Then the reaction is held at the final condition for 0.75 hour before the heating is shut down. After cooling down to room temperature, the reactor was vented and all volatiles were removed on rotary evaporator under reduced pressure to give about 114 g of a yellow liquid containing N-(2-ethoxyethyl)-3-(N -methyl-piperazme)propan-1-amine (90.2 % by GC analysis) which was purified by distillation.

[00106] EXAMPLE 16 (inventive, new compound) Synthesis of N-(2-ethoxyethyl)-3-(N’-cyclohexyl)propan-1-amine Step-1: Cyclohexylamine (271.5 g, 2.48 mol) and 30 g of water are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle, cooling coil and a high pressure syringe pump connected with stainless steel feeding lines. Then the steel reactor is sealed and purged with nitrogen for three times. The temperature of the reactor is kept at ambient temperature 25°C and acrylonitrile (136.9 g, 2.6 mol) is charged into the reactor from a high pressure syringe pump at a speed sufficient to keep the reactor temperature at 60°C or slighthly below (~ 40 minutes feeding time) while stirring at about 1000 rpm. Upon completion of addition, hold the reaction temperature at 60-65°C for 3 hours before the heating is shut down. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under vacuum. N-(2-cyanoethyl)-N-cyclohexylamine is collected with an approximate yield of 99.5 % yield and 100% purity based on GC analysis.

[00107] Step-2: Ethoxyethylamine (133.7 g, 1.5 mol), isopropanol (100 g, 127 ml), N-(2-cyanoethyl)-N-cyclohexyl-amine (81.3 g, 0.50 mol) made in step-1 and 5% Pd / C (4.6 g, 50 wt. % in water) was charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle and a cooling coil. The reactor was purged with nitrogen and then with hydrogen. The reactor pressure was adjusted to be at 800 psi and the reactor was heated to 40°C while stirring at 1000 rpm. The reaction temperature was adjusted in 10°C increments to maintain the hydrogen uptake. The reaction continued until the hydrogen uptake is stopped after 3.25 hours where the final reaction temperature was 80°C. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 115 g of the final product is collected as a mixture of material containing 89.5 % N-(2-ethoxyethyl)-3-(cyclohexyl)propan-l-amine which is purified by distillation.

[00108] EXAMPLE 17 (prophetic, new compound) Synthesis of N-(2-ethoxyethyl)-3-(N’-cyclohexyl-N’-methyl)propan-1-amine Ethoxyethylamine (112 g, 1.26 mol), N-(2-cyanoethyl)-N-methyl-N-cyclohexyl-amine (209 g, 1.26), water (11.3 g) and 5% Pd / C (9.0 g) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle and cooling coil. The reactor is purged with nitrogen and then with hydrogen. The reactor pressure is adjusted to be at 800 psi and the reactor is heated to 40°C while stirring at 1000 rpm. The reaction temperature is adjusted in 10°C increments to maintain the hydrogen uptake. The reaction continued until the hydrogen uptake is stopped after about 5 hours where the final reaction temperature was 80°C. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 300 g of the final product is collected as a mixture of material containing 90 % N-(2-ethoxyethyl)-3-(N’-cyclohexyl-N’-methyl)propan-1-amine which is purified by distillation.

[00109] EXAMPLE 18 (prophetic, new compound) Synthesis of N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine Ethoxyethylamine (112 g, 1.26 mol), N-(2-cyanoethyl)-N-isopropyl-N-methylamine (158.8 g, 1.26), water (11.3 g) and 5% Pd / AI2O3 (9.0 g) are charged into a stainless steel reactor equipped with mechanical stirrer, heating mantle and a cooling coil. The reactor is purged with nitrogen and then with hydrogen. The reactor pressure is adjusted to be at 800 psi and the reactor is heated to 40°C while stirring at 1000 rpm. The reaction temperature is adjusted in 10°C increments to maintain the hydrogen uptake. The reaction continued until the hydrogen uptake is stopped after about 5 hours where the final reaction temperature was 80°C. The reactor is then vented after cooling to room temperature. All volatiles are removed on rotary evaporator under reduced pressure, and about 240 g of the final product is collected as a mixture of material containing 90 % N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine which is purified by distillation.

Claims

1. A process for the manufacture of diamines comprising the steps of (a) contacting a ,-'"Ranitrile compound having the formula Rb A^=Nwith an amine compound having the formula RdHN----Rc jn the presence of a metal catalyst under hydrogen pressure, wherein Ra and Rb are independently aliphatic groups, or Ra and Rb are cycloaliphatic, or Ra and Rb together with the N-atom and the dotted curved line form a heterocyclic ring having or not an additional heteroatom selected from the group consisting of nitrogen, oxygen, or sulfur, and A is an aliphatic group or a cycloaliphatic ring, and wherein Rc is an aliphatic, cycloaliphatic, cycloalkyl or alkoxyalkyl group and Rd is a hydrogen atom or methyl group.

2. The process of claim 1 wherein the nitrile compound is a compound having the ^R1I N----(CH2)X---CNformula '' R2and the amine compound is an amino-ether compound having the formulaR3—O—(CH2)y—NH2wherein R1 and R2 are independently Ci-9aliphatic groups or R1 = H and R2 = Ci-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring having or not an additional heteroatom selected from the group consisting of nitrogen, oxygen, or sulfur, and where x =1 or 2 and where R3 is a C1-9 aliphatic linear or branched or cycloaliphatic, and y = 2 or 3.

3. The process of claim 2 wherein R1 and R2 are independently C1-3 aliphatic groups.

4. The process of claim 2 or 3 wherein x = 2.

5. The process of any of the preceding claims wherein the nitrile is selected from the group consisting of N-(2-cyanoethyl)-morpholine, N-(2-cyanoethyl)-piperidine, N-(2-cyanoethyl)-imidazole, N-(2-cyanoethyl)-N’-methyl-piperidine, N-(2-cyanoethyl)-N,N-dicyclopropyl-amine, N-(2-cyanoethyl)-N,N-dimethylcyclopropyl-amme, N-(2-cyanoethyl)-pyrrolidine, N-(2-cyanoethyl)-N-cyclopropyl-amine, N-(2-cyanoethyl)-N-methylcyclopropyl-amine, N-(2-cyanoethyl)-N-ethyl-amine, N-(2-cyanoethyl)-N-isopropyl-amine, N-(2-cyanoethyl)-N-propyl-amine, N-(2-cyanoethyl)-N-butyl-amine, N-(2-cyanoethyl)-N-isobutyl-amine, N-(2-cyanoethyl)-N-(sec-butyl)-amine, N-(2-cyanoethyl)-N-(tert-butyl)-amine, N-(2-cyanoethyl)-N-(n-pentyl)-amine, N-(2-cyanoethyl)-N-(n-iso-pentyl)-amine, N-(2-cyanoethyl)-N-(n-tert-pentyl)-amine, N-(2-cyanoethyl)-N-(n-neopentyl)-amine, N-(2-cyanoethyl)-N-(n-sec-pentyl)-amine, N-(2-cyanoethyl)-N-(3-pentyl)-amine, N-(2-cyanoethyl)-N-(sec-isopentyl)-amine, N-(2-cyanoethyl)-N-(1 -hexyl)-amine, N-(2-cyanoethyl)-N-(2-hexyl)-amine, N-(2-cyanoethyl)-N-(3-hexyl)-amine, N-(2-cyanoethyl)-N-(iso-hexyl)-amine, N-(2-cyanoethyl)-N-(4-methylpent-1-yl)-amine, N-(2-cyanoethyl)-N-(4-methylpent-2-yl)-amine, N-(2-cyanoethyl)-N-(2-methylpent-1 -yl)-amine, N-(2-cyanoethyl)-N-(3,3-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N-(3,3-dimethylbut-2-yl)-amine, N-(2-cyanoethyl)-N-(2,2-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N-(cyclohexyl)-amine, N-(2-cyanoethyl)-N-(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanoethyl)-N-(1,3-dimethylbutyl)-amine, N-(2-cyanoethyl)-N-(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanoethyl)-N-(1,3-dimethylbutyl)-amine, N-(2-cyanoethyl)-N-methyl-N-cyclopropyl-amine, N-(2-cyanoethyl)-N-methyl-N-methylcyclopropyl-amine, N-(2-cyanoethyl)-N-methyl-N-isopropyl-amine, N-(2-cyanoethyl)-N-methyl-N-propyl-amine, N-(2-cyanoethyl)-N-methyl-N-butyl-amine, N-(2-cyanoethyl)-N-methyl-N-isobutyl-amine, N-(2-cyanoethyl)-N-methyl-N-(sec-butyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(tert-butyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-iso-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-tert-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-neopentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(n-sec-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3-pentyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(sec-isopentyl)-amine, N-(2-cyanoethyl)-N-(1-hexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(2-hexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3-hexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(iso-hexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(4-methylpent-1-yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(4-methylpent-2-yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(2-methylpent-1 -yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3,3-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3,3-dimethylbut-2-yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(2,2-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N-methyl-N-(cyclohexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(1,3-dimethylbutyl)-amine, N-(2-cyanoethyl)-N-methyl-N-(3,5,5-trimethyl-cyclohexyl-2-ene)-amme, N-(2-cyanoethyl)-N-methyl-N-(1,3-dimethylbutyl)-amine and the like.

6. The process of any of claims 1 -4 wherein the nitrile is selected from the group consisting of N-(2-cyanoethyl)-N,N-diethyl-amine, N-(2-cyanoethyl)-N,N-diisopropyl-amine, N-(2-cyanoethyl)-N,N-dipropyl-amine, N-(2-cyanoethyl)-N,N-dibutyl-amine, N-(2-cyanoethyl)-N,N-diisobutyl-amine, N-(2-cyanoethyl)-N,N-di(sec-butyl)-amine, N-(2-cyanoethyl)-N,N-di(tert-butyl)-amine, N-(2-cyanoethyl)-N,N-di(n-pentyl)-amine, N-(2-cyanoethyl)-N,N-di(n-iso-pentyl)-amine, N-(2-cyanoethyl)-N,N-di(n-tertpentyl)-amine, N-(2-cyanoethyl)-N,N-di(n-neopentyl)-amine, N-(2-cyanoethyl)-N,N-di(n-secpentyl)-amine, N-(2-cyanoethyl)-N,N-di(3-pentyl)-amine, N-(2-cyanoethyl)-N,N-di(sec-isopentyl)-amine, N-(2-cyanoethyl)-N,N-di(1-hexyl)-amine, N-(2-cyanoethyl)-N,N-di(2-hexyl)-amine, N-(2-cyanoethyl)-N,N-di(3-hexyl)-amine, N-(2-cyanoethyl)-N,N-di(iso-hexyl)-amine, N-(2-cyanoethyl)-N,N-di(4-methylpent-1-yl)-amine, N-(2-cyanoethyl)-N,N-di(4-methylpent-2-yl)-amine, N-(2-cyanoethyl)-N,N-di(2-methylpent-1-yl)-amine, N-(2-cyanoethyl)-N,N-di(3,3-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N,N-di(3,3-dimethylbut-2-yl)-amine, N-(2-cyanoethyl)-N,N-di(2,2-dimethylbut-1-yl)-amine, N-(2-cyanoethyl)-N,N-di(cyclohexyl)-amine, N-(2-cyanoethyl)-N,N-di(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanoethyl)-N,N-di(1,3-dimethylbutyl)-amine, N-(2-cyanoethyl)-N,N-di(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanoethyl)-N,N-di(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-morpholine, N-(2-cyanomethyl)-piperidine, N-(2-cyanomethyl)-imidazole, N-(2-cyanomethyl)-N’-methyl-piperidine, N-(2-cyanomethyl)-N,N-dicyclopropyl-amine, N-(2-cyanomethyl)-N,N-dimethylcyclopropyl-amine, N-(2-cyanomethyl)-pyrrolidine, N-(2-cyanomethyl)-N,N-diisopropyl-amine, N-(2-cyanomethyl)-N,N-dipropyl-amine, N-(2-cyanomethyl)-N,N-dibutyl-amine, N-(2-cyanomethyl)-N,N-diisobutyl-amine, N-(2-cyanomethyl)-N,N-di(sec-butyl)-amine, N-(2-cyanomethyl)-N,N-di(tert-butyl)-amine, N-(2-cyanomethyl)-N,N-di(n-pentyl)-amine, N-(2-cyanomethyl)-N,N-di(n-iso-pentyl)-amine, N-(2-cyanomethyl)-N,N-di(n-tertpentyl)-amine, N-(2-cyanomethyl)-N,N-di(n-neopentyl)-amine, N-(2-cyanomethyl)-N,N-di(n-secpentyl)-amine, N-(2-cyanomethyl)-N,N-di(3-pentyl)-amine, N-(2-cyanomethyl)-N,N-di(sec-isopentyl)-amine, N-(2-cyanomethyl)-N,N-di(1 -hexyl)-amine, N-(2-cyanomethyl)-N,N-di(2-hexyl)-amine, N-(2-cyanomethyl)-N,N-di(3-hexyl)-amine, N-(2-cyanomethyl)-N,N-di(iso-hexyl)-amine, N-(2-cyanomethyl)-N,N-di(4-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N,N-di(4-methylpent-2-yl)-amine, N-(2-cyanomethyl)-N,N-di(2-methylpent-1 -yl)-amine, N-(2-cyanomethyl)-N,N-di(3,3-dimethylbut-1-yl)-amme, N-(2-cyanomethyl)-N,N-di(3,3-dimethylbut-2-yl)-amine, N-(2-cyanomethyl)-N,N-di(2,2-dimethylbut-1-yl)-amine, N-(2-cyanomethyl)-N,N-di(cyclohexyl)-amine, N-(2-cyanomethyl)-N,N-di(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanomethyl)-N,N-di(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-N,N-di(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanomethyl)-N,N-di(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-N-cyclopropyl-amine, N-(2-cyanomethyl)-N-methylcyclopropyl-amine, N-(2-cyanomethyl)-N-isopropyl-amine, N-(2-cyanomethyl)-N-propyl-amine, N-(2-cyanomethyl)-N-butyl-amine, N-(2-cyanomethyl)-N-isobutyl-amine, N-(2-cyanomethyl)-N-(sec-butyl)-amine, N-(2-cyanomethyl)-N-(tert-butyl)-amine, N-(2-cyanomethyl)-N-(n-pentyl)-amine, N-(2-cyanomethyl)-N-(n-iso-pentyl)-amine, N-(2-cyanomethyl)-N-(n-tert-pentyl)-amine, N-(2-cyanomethyl)-N-(n-neopentyl)-amine, N-(2-cyanomethyl)-N-(n-sec-pentyl)-amine, N-(2-cyanomethyl)-N-(3-pentyl)-amine, N-(2-cyanomethyl)-N-(sec-isopentyl)-amine, N-(2-cyanomethyl)-N-(1-hexyl)-amine, N-(2-cyanomethyl)-N-(2-hexyl)-amine, N-(2-cyanomethyl)-N-(3-hexyl)-amine, N-(2-cyanomethyl)-N-(iso-hexyl)-amine, N-(2-cyanomethyl)-N-(4-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N-(4-methylpent-2-yl)-amine, N-(2-cyanomethyl)-N-(2-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N-(3,3-dimethylbut-1-yl)-amine, N-(2-cyanomethyl)-N-(3,3-dimethylbut-2-yl)-amine, N-(2-cyanomethyl)-N-(2,2-dimethylbut-1-yl)-amine, N-(2-cyanomethyl)-N-(cyclohexyl)-amine, N-(2-cyanomethyl)-N-(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanomethyl)-N-(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-N-(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanomethyl)-N-methyl-N-cyclopropyl-amine, N-(2-cyanomethyl)-N-methyl-N-methylcyclopropyl-amine, N-(2-cyanomethyl)-N-methyl-N-isopropyl-amine, N-(2-cyanomethyl)-N-methyl-N-propyl-amine, N-(2-cyanomethyl)-N-methyl-N-butyl-amine, N-(2-cyanomethyl)-N-methyl-N-isobutyl-amine, N-(2-cyanomethyl)-N-methyl-N-(sec-butyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(tert-butyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-iso-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-tert-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-neopentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(n-sec-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3-pentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(sec-isopentyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(1-hexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(2-hexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3-hexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(iso-hexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(4-methylpent-1-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(4-methylpent-2-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(2-methylpent-1-yl)-amine,N-(2-cyanomethyl)-N-methyl-N-(3,3-dimethylbut-1-yl)-amme, N-(2-cyanomethyl)-N-methyl-N-(3,3-dimethylbut-2-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(2,2-dimethylbut-1-yl)-amine, N-(2-cyanomethyl)-N-methyl-N-(cyclohexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3,3,5-trimethylcyclohexyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(1,3-dimethylbutyl)-amine, N-(2-cyanomethyl)-N-methyl-N-(3,5,5-trimethyl-cyclohexyl-2-ene)-amine, N-(2-cyanomethyl)-N-methyl-N-(1,3-dimethylbutyl)-amine and the like.

7. The process of any of claims 1 -5 wherein the nitrile is selected from the group consisting of N-(2-cyanoethyl)-morpholine, N,N-dimethylaminopropionitrile, N-(2-cyanoethyl)-N-methyl-N-isopropyl-amine, N-(2-cyanoethyl)-imidazole, N-(2-cyanoethyl)-N-(cyclohexyl)-amine, and N-(2-cyanoethyl)-N-methyl-N-(cyclohexyl)-amine.

8. The process of any of the preceding claims wherein the amine is selected from the group consisting of methoxyethyl-1 -amine, 2-ethoxyethyl-1-amine, 2-(n-propoxy)ethyl-1-amine, 2-(isopropoxy)ethyl-1-amine, 2-(n-butoxy)ethyl-1-amine, 2-(iso-butoxy)ethyl-1-amine, 2-(sec-butoxy)ethyl-1-amine, 2-(t-butoxy)ethyl-1-amine, 2-(n-pentoxy)ethyl-1 -amine, 2-(n-isopentoxy)ethyl-1 -amine, 2-(tert-pentoxy)ethyl-1 -amine, 2-(neo-pentoxy)ethyl-1-amine, 2-(n-isopentoxy)ethyl-1-amine, 2-(sec-isopentoxy)ethyl-1-amine, 2-(3-pentoxy)ethyl-1-amine, 2-(n-hexoxy)ethyl-1-amine, 2-(2-hexoxy)ethyl-1-amine, 2-(3-hexoxy)ethyl-1-amine, 2-(iso-hexoxy)ethyl-1-amine, 2-(4-methylpent-1-yloxy)ethyl-1-amine, 2-(4-methylpent-2-yloxy)ethyl-1-amine, 2-(2-methylpent-1-yloxy)ethyl-1-amine, 2-(3,3-dimethylbut-1-yloxy)ethyl-1 -amine, 2-(3,3-dimethylbut-2-yloxy)ethyl-1-amine, 2-(2,2-dimethylbut-1-yloxy)ethyl-1 -amine, 2-heptoxyethyl-1-amine, 2-octooxyethyl-1-amine, 2-(2-ethylhexyloxy)-1-amine, 3-methoxypropyl-1-amine, 3-ethoxypropyl-1-amine, 3-propoxypropyl-1-amine, 3-butoxypropyl-1-amine, 3-pentoxypropyl-1-amine, 3-hexoxypropyl-1-amine, 3-heptoxypropyl-1-amine, 3-octoxypropyl-1-amine, 3-(2-ethylhexyloxy)propyl-1-amine and the like.

9. The process of any of the preceding claims wherein the amine is selected from the group consisting of 2-ethoxyethyl-1-amine, 3-methoxypropyl-1-amine, and 3-ethoxypropyl-1 -amine.

10. The process of any of the preceding claims for the manufacture of N-(2-ethoxyethyl)-3-morpholinopropan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-morpholine with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

11. The process of any of the preceding claims for the manufacture of N-(2-ethoxypropyl)-3-morpholinopropan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-morpholine with 3-ethoxypropyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

12. The process of any of the preceding claims for the manufacture of N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-N-methyl-N-isopropyl-amine with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

13. The process of any of the preceding claims for the manufacture of N-(2-ethoxyethyl)-3-(imidazolyl)propan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-imidazole with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

14. The process of any of the preceding claims for the manufacture of N-(2-ethoxyethyl)-3-(cyclohexyl)propan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-N-(cyclohexyl)-amine with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

15. The process of any of the preceding claims for the manufacture of N-(2-ethoxyethyl)-3-(N’-cyclohexyl-N’-methyl)propan-1-amine comprising the steps of (a) contacting N-(2-cyanoethyl)-N-methyl-N-(cyclohexyl)-amine with 2-ethoxyethyl-1-amine in the presence of Pd / AI2O3 or Pd / C under hydrogen pressure.

16. A compound having the formula”'R\ I:      N----(CH2)x+i---N---(CH2)y---0—R3R2wherein R1 and R2 are independently Ci-9 aliphatic groups or R1 = H and R2 = Ci-9 aliphatic or cycloaliphatic or R1 and R2 are, together with the N-atom and the dotted curved line, a heterocyclic ring having or not an additional heteroatom selected from the group consisting of nitrogen, oxygen or sulfur, and where x =1 or 2 and where R3 is a Ci-9 aliphatic linear or branched or cycloaliphatic, R4 is H or methyl and y = 2 or 3.

17. The compound of claim 17 wherein the compound is N-(2-ethoxypropyl)-3-morpholinopropan-1 -amine.

18. The compound of claim 17 wherein the compound is N-(2-ethoxyethyl)-3-(1 H-imidazol-1-yl)propan-1-amine.

19. The compound of claim 17 wherein the compound is N-(2-ethoxyethyl)-3-(pyrrolidin-1 -yl)propan-1 -amine.

20. The compound of claim 17 wherein the compound is N’-(2-ethoxyethyl)-N”’,N”’-dimethylpropane-1,3-diamine.

21. The compound of claim 17 wherein the compound is N-(2-ethoxyethyl)-3-(N”-methyl-piperazine)propan-1-amine.

22. The compound of claim 17 wherein the compound is N-(2-ethoxyethyl)-3-(N’-cyclohexyl)propan-1 -amine.

23. The compound of claim 17 wherein the compound is N-(2-ethoxyethyl)-3-(N’-cyclohexyl-N’-methyl)propan-1-amine.

24. The compound of claim 17 wherein the compound is N-(2-ethoxyethyl)-3-(N’-isopropyl-N’-methyl)propan-1-amine.

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