WO2012142668A1 - Gas capture process - Google Patents

Gas capture process Download PDF

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Publication number
WO2012142668A1
WO2012142668A1 PCT/AU2012/000409 AU2012000409W WO2012142668A1 WO 2012142668 A1 WO2012142668 A1 WO 2012142668A1 AU 2012000409 W AU2012000409 W AU 2012000409W WO 2012142668 A1 WO2012142668 A1 WO 2012142668A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
represented
compound
imidazole
alkyl
Prior art date
Application number
PCT/AU2012/000409
Other languages
French (fr)
Inventor
Qi Yang
Susan N. JAMES
Mathew John Ballard
Mark Bown
Paul Feron
Graeme Douglas Puxty
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=47040973&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2012142668(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from AU2011901448A external-priority patent/AU2011901448A0/en
Application filed by Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Priority to CN201280028544.8A priority Critical patent/CN103619816B/en
Priority to AU2012245079A priority patent/AU2012245079B2/en
Priority to CA2833411A priority patent/CA2833411C/en
Priority to EP12773962.1A priority patent/EP2699546B1/en
Priority to JP2014505461A priority patent/JP6018174B2/en
Priority to US14/112,724 priority patent/US9409122B2/en
Priority to KR1020137030085A priority patent/KR20140023356A/en
Publication of WO2012142668A1 publication Critical patent/WO2012142668A1/en
Priority to ZA2013/08631A priority patent/ZA201308631B/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/56—Nitrogen atoms
    • C07D211/58—Nitrogen atoms attached in position 4
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/26—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B01D2252/20442—Cyclic amines containing a piperidine-ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • This invention relates to amines and their use in capturing carbon dioxide from gas streams. Background of the invention
  • CO 2 carbon dioxide
  • post combustion capture The process for capturing CO2 from power station and other combustion device flue gases is termed post combustion capture (PCC).
  • PCC post combustion capture
  • the C0 2 in flue gas is first separated from nitrogen and residual oxygen using a suitable solvent in an absorber.
  • the solvent is usually an aqueous basic mixture containing components that undergo a chemical reaction with acid gases such as C0 2 . It might contain amines (e.g. alkanolamines, ammonia, alkylamines) and/or inorganic salts (e.g. carbonate or phosphate).
  • the CO 2 is subsequently removed from the solvent in a process called stripping (or regeneration), thus allowing the solvent to be reused.
  • stripping or regeneration
  • the stripped C0 2 is liquefied by compression and cooling, with appropriate drying steps to prevent hydrate formation.
  • PCC in this form is applicable to a variety of stationary CO 2 sources including power stations, steel plants, cement kilns, calciners and smelters.
  • Acid gases such as carbon dioxide
  • Pressurised gas streams containing C0 2 are also produced in fuel conversion processes such as natural gas reforming and coal gasification combined with a water- gas shift conversion to produce mixtures of hydrogen and carbon dioxide. These gas streams are then suitable for pre-combustion capture of CO 2 .
  • the conventional approaches for such removal include membrane separation or amine treatment. When C0 2 is absorbed into an aqueous solution a number of reactions can occur.
  • Equation (6) is the formation of a carbamate species via a nitrogen-carbon bond formation between the amine and CO 2 . This is generally the kinetically fastest reaction of those that occur with CO 2 .
  • Equation (7) is the amine acid- base equilibrium. For polyamines the reactions of equation (6) and (7) may occur for each nitrogen atom. For sterically hindered primary or secondary amines the carbamate species is less stable than in sterically free amines which leads to enhanced formation of the bicarbonate species. For tertiary amines only the acid-base equilibrium of equation (7) occurs.
  • Monoethanolamine (MEA) is currently employed in industrial CO2 capture but has a number, of limitations, including solvent degradation due to oxidation and reaction with nitrogen and sulphur oxides, solvent losses due to high volatility and high energy requirements needed to desorb the CO2 from the C0 2 loaded MEA.
  • Some other amines used for industrial C0 2 capture have a larger C0 2 absorption capacity than MEA, but have poor rates of C0 2 capture. Slow C0 2 absorption rates are undesirable because to achieve the requisite absorption of C0 2l longer contact times between the C0 2 containing gas stream and the amine means that longer absorption columns and larger capital costs are usually required.
  • amines as sorbents in C0 2 capture may be limited by the thermal degradation and oxidation of the amines.
  • Much of the research on amine solvents for C0 2 capture is based around formulation with commercially available amines.
  • amine solvents for C0 2 capture There appears to be little study of novel amines that are designed, via amine structural modification, to match the characteristic requirement of C0 2 capture. 4-Aminopiperidine has been reported to perform well in CO2 capture (Singh et ai, 2008).
  • European patent application no 2036602 (Mitsubishi Heavy Industries, Ltd.) relates to an absorbent liquid for removing C0 2 and/or H 2 S from gas which includes compounds which are described in very general terms in the application (for example, by way of very broad general formulae).
  • the data in the application showing the CO2 absorption capacity of the compounds is quite limited.
  • the Applicants have surprisingly discovered that the compounds of the invention (as represented by formula (I) below) exhibit good molar C0 2 cyclic capacities.
  • the compounds of formula (I), which are derivatives of 4-aminopiperidine, show a higher molar CO2 cyclic capacity that that of 4-aminopiperidine itself.
  • the present invention provides a process for the capture of CO2 from gas streams, the process including contacting a C0 2 containing gas stream with a compound including: a primary or non-sterically hindered secondary amine group and at least one tertiary amine or sterically hindered secondary amine group; wherein the primary or non-sterically hindered secondary amine and the nearest tertiary or sterically hindered secondary amine group are separated by a carbon chain including 3 or 4 carbon atoms and wherein the compound is a compound of Formula (I)
  • R 1 is represented by hydrogen, C2 to Ce alkanol or Ci to C6 alkyl;
  • R 2 is represented by hydrogen, Ct to C 6 alkyl, C2 to C 6 alkanol, -(CH 2 ) n -NR6R7, -(CH 2 ) P - COOH, -(CH 2 ) p COOQ, -(CH 2 ) p -heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
  • R 3 and R 5 are independently selected from hydrogen, Ci to C 4 alkyl, C 2 to C 6 alkanol, -(CH 2 ) n -NR 8 R 9 ;
  • R 4 is represented by hydrogen, Ci to C 6 alkyl, C 2 to C 6 alkanol, -(CH 2 ) n - R6 7, -(CH 2 ) P - COOH, -(CH 2 ) p COOQ, -(CH 2 )p-S0 3 H, -(CH 2 ) p S0 3 Q, -(CH 2 )p-P0 3 H2, -(CH 2 ) p P0 3 Q s , -(CH 2 )p-heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
  • x is 0 or 1 ;
  • n 2 to 6;
  • p 1 to 6;
  • Q is hydrogen, a metal ion or R 16 R 17 R 18 R 19 N + ;
  • s 1 or 2
  • R 6 and R 7 are independently selected from hydrogen, alkyl, alkanol, alkylamine or R 6 and R 7 together with the nitrogen atom to which they are attached form a ring structure
  • R 8 and R 9 are independently selected from Ci to C 6 alkyl, C 2 to C 6 alkanol, C 2 to C 6 alkylamine, -(CH 2 ) n -NR 6 R7, -(CH 2 ) p -COOH, -(CH 2 ) P COOQ, -(CH 2 ) p -S0 3 H, -(CH 2 ) p S0 3 Q, -(CH 2 ) p -P0 3 H 2 , -(CH 2 )pP0 3 Q s , or R 8 and R 9 together with the nitrogen atom to which they are attached form a ring structure; and
  • R 16 , R 17 , R 18 and R 19 are independently selected from hydrogen or alkyl
  • R 4 when R 4 is hydrogen, R 1 and/or R 2 is not hydrogen; when R 4 is not hydrogen, R 1 and/or R 2 is hydrogen; when R 4 and R 1 are both hydrogen, R 2 is not methyl; and when R 4 and R 2 are both hydrogen, R 1 is not methyl.
  • the present invention provides a compound including: a primary or non-sterically hindered secondary amine group and at least one tertiary amine or a sterically hindered secondary amine group; wherein the primary or non-sterically hindered secondary amine group and the nearest tertiary or sterically hindered secondary amine group are separated by a carbon chain including 3 or 4 carbon atoms; and wherein the compound is a compound of Formula (I):
  • R 1 is represented by hydrogen, C2 to Ce alkanol or Ci to C6 alkyl;
  • R 2 is represented by hydrogen, d to C 6 alkyl, C 2 to C 6 alkanol, -(CH 2 )n-NR 6 R7, -(CH 2 ) P - COOH, -(CH2) p COOQ, -(CH 2 ) p -heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
  • R 3 and R 5 are independently selected from hydrogen, to C 4 alkyl, Ci to C4 alkanol, -(CH 2 ) n -NR 8 R 9 ;
  • R 4 is represented by hydrogen, d to C 6 alkyl, C 2 to C 6 alkanol, -(CH 2 ) n -NR 6 R 7 , -(CH 2 ) P - COOH, -(CH 2 )pCOOQ, -(CH 2 ) p -S0 3 H, -(CH 2 ) p S0 3 Q, -(CH 2 ) p -P0 3 H 2) -(CH 2 ) p P0 3 Qs, -(CH 2 ) p -heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
  • x is 0 or 1 ;
  • n 2 to 6;
  • p 1 to 6;
  • Q is hydrogen, a metal ion or R 16 R 17 R 18 R 19 N + ; s is 1 or 2;
  • R 6 and R 7 are independently selected from hydrogen, Ci to C 6 alkyl, C 2 to C 6 alkanol, C2 to C 6 alkylamine or R 6 and R 7 together with the nitrogen atom to which they are attached form a ring structure
  • R 8 and R 9 are independently selected from Ci to C 6 alkyl, C 2 to C 6 alkanol, C 2 to C 6 alkylamine, -(CH 2 ) n -NR 6 R 7 , -(CH 2 ) p -COOH, -(CH 2 ) p COOQ, -(CH 2 ) p -S0 3 H, -(CH 2 ) p S0 3 Q, -(CH 2 )p-P0 3 H 2 , -(CH 2 ) P P0 3 Qs, or R 8 and R 9 together with the nitrogen atom to which they are attached form a ring structure;;
  • R 14 and R 15 are independently selected from Ci to Ce alkyl, C 2 to C 6 alkanol, C 2 to C 6 alkylamine or R 14 and R 15 together with the nitrogen atom to which they are attached form a ring structure;
  • R 16 , R 17 , R 18 and R 19 are independently selected from hydrogen or alkyl
  • R 4 when R 4 is hydrogen, R 1 and/or R 2 is not hydrogen; when R 4 is not hydrogen, R 1 and/or R 2 is hydrogen; when R 4 and R are both hydrogen, R 2 is not methyl; and when R 4 and R 2 are both hydrogen, R is not methyl.
  • Figure 1 shows a flow-diagram example of a C0 2 capture apparatus that may be employed in the process of one embodiment of the present invention.
  • Figure 2 shows the C0 2 absorption and desorption of 1-ethanol-4-aminopiperidine, 1- propyl-4-aminopiperidine, 4-ethanolaminopiperidine, 4-propylaminopiperidine compared with 4-aminopiperidine.
  • Figure 3 shows the C0 2 absorption and desorption of 1-ethanol-4-aminopiperidine, 1- propyl-4-aminopiperidine, 4-ethanolaminopiperidine, 4-propylaminopiperidine, 4- aminopiperidine compared with monoethanolamine and piperazine.
  • sterically hindered secondary amine means that the substituent on the secondary amine has sufficient bulk such that a reaction between the secondary amine and CO 2 produces an unstable carbamate species.
  • alkyl means a straight or branched chain, or cyclic, saturated aliphatic group, or a combination thereof.
  • alkanol means a group where an alcohol group (-OH) is bound to a carbon atom, ie, -(CH 2 ) n OH.
  • alkylamine means a group where an alkyl group is bound to the nitrogen atom of an amine group.
  • the compounds have relatively high boiling points which may result in reduced amine evaporation during the process. The reduction in evaporation may be beneficial from cost and environmental impact perspectives.
  • the present invention provides a compound of Formula (I)
  • R 1 is represented by hydrogen, C2 to C & alkanol or C-i to C 6 alkyl;
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3l -( ⁇ 2 ) 2 ⁇ , -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH2COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole);
  • R 3 and R 5 are independently selected from hydrogen, Ci to C 4 alkyl and to C 4 alkanol;
  • R 4 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2) -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole); and
  • x is O or l ;
  • the present invention provides a compound of Formula (I) wherein: x is O or l ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -( ⁇ 2 ) 2 ⁇ , -(CH 2 ) 3 OH,
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, ⁇ (CH 2 ) 3 OH,
  • R 5 is represented by hydrogen
  • the present invention provides a compound of Formula (I) wherein:
  • x is O or f
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen
  • the present invention provides a compound of Formula (I) wherein:
  • R is represented by hydrogen;
  • R 2 is represented by hydrogen;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen, -CH 2 CH 3> -CH2CH2CH3, -(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is 0 or 1; R 1 is represented by hydrogen or Ci alkyl;
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 3 is represented by hydrogen; R 4 is represented by hydrogen; and R 5 is represented by hydrogen; with the proviso that when x is 0, R 1 is hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is 0;
  • R 1 is represented by hydrogen
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3) -(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 3 is represented by hydrogen; R 4 is represented by hydrogen; and R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is O;
  • R 1 is represented by Ci alkyl
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen
  • the present invention provides a compound of Formula (I) wherein: x is 0;
  • R 1 is represented by hydrogen
  • R 2 is represented by hydrogen
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is l;
  • R 1 is represented by hydrogen
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen
  • the present invention provides a compound of Formula (I) wherein: x is 1 ;
  • R 1 is represented by Ci alkyl
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CHa ⁇ OH, -(CH 2 )30H,
  • R 3 is represented by hydrogen; R 4 is represented by hydrogen; and R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is O;
  • R 1 is represented by Ci alkyl
  • R 2 is represented by -CH 2 CH 2 CH 3 , -CH 2 C00Na, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 ,
  • R 3 is represented by hydrogen; R 4 is represented by hydrogen; and R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is O;
  • R 1 is represented by hydrogen
  • R 2 is represented by hydrogen
  • R 3 is represented by hydrogen
  • R 4 is represented by -CH 2 CH 3l -CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 )20, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole); and
  • R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is O or l ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH 2 COOH or -(CH 2 ) 2 N(CH 3 ) 2 ;
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is 0;
  • R is represented by hydrogen;
  • R 2 is represented by -CH 2 CH 3l -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH or -(CH 2 ) 2 N(CH 3 ) 2 ;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen; and
  • R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is 0;
  • R 1 is represented by Ci alkyl
  • R 2 is represented by -CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH or -(CH 2 ) 6 OH;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen; and
  • R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is l ;
  • R 1 is represented by hydrogen
  • R 2 is represented by -CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 6 OH or -CH 2 COOH;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen; and
  • R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is 1 ;
  • R 1 is represented by Ci alkyl
  • R 2 is represented by -CH 2 CH 3 or -(CH 2 ) 2 OH
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen
  • the present invention provides a compound of Formula (I) wherein:
  • x is 0 or 1 ;
  • R 1 is represented by hydrogen
  • R 2 is represented by hydrogen
  • R 3 is represented by hydrogen
  • R 4 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH or -(CH 2 ) 6 OH; and R 5 is represented by hydrogen.
  • the present invention provides a compound of Formula (I) wherein: x is 0 or 1; R 1 is represented by hydrogen or Ci alkyl;
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 or -(CH 2 )2 (CH 3 )2;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 or -(CH 2 )2N(CH 3 ) 2 ; and R 5 is represented by hydrogen; with the proviso that when R 4 is hydrogen, R 2 is not hydrogen;
  • R 2 when R 2 is hydrogen, R 4 is not hydrogen; and when R 2 is hydrogen, R 1 is hydrogen and x is 0.
  • the present invention provides a compound of Formula (I) wherein: x is 0 or 1 ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -(CH 2 )20H, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH 2 COOH,
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -(CH 2 ) 2 OH, -(CH 2 ) 3 0H, -(CH 2 ) 6 OH, -CH 2 COOH,
  • R 5 is represented by hydrogen
  • the present invention provides a compound of Formula (I) wherein: x is 0 or 1 ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -(CH 2 ) 2 OH, -(CH 2 ) 3 OH or -(CH 2 ) 6 OH
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -(CH 2 ) 2 OH, -(CH 2 ) 3 OH or -(CH 2 ) 6 OH; and R 5 is represented by hydrogen; - with the proviso that when R 4 is hydrogen, R 2 is not hydrogen;
  • the present invention provides a compound of Formula (I) wherein: x is O or l;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -CH 2 COOH, -CH 2 COONa or -CH 2 COOK ;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen, -CH 2 COOH, -CH 2 COONa or -CH 2 COOK; and R 5 is represented by hydrogen;
  • R 2 when R 2 is hydrogen, R 4 is not hydrogen; and when R 2 is hydrogen, R 1 is hydrogen and x is 0.
  • the present invention provides a compound of Formula (I) wherein: x is 0 or 1 ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -(CH 2 ) 2 (CH 2 CH 2 )20, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5- imidazole) or -(CH 2 ) 2 (5-imidazole);
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -(CH 2 ) 2 N(CH 2 CH 2 )20, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5- imidazole) or -(CH 2 ) 2 (5-imidazole); and
  • R 5 is represented by hydrogen
  • the present invention provides a compound of Formula (I) wherein: x is 0 or 1 ; R 1 js represented by hydrogen;
  • R 2 is represented by ethyl, propyl or -(CH 2 ) 2 N(CH 3 ) 2 ;
  • R 3 is represented by hydrogen; R 4 is represented by hydrogen; and R 5 is represented by hydrogen.
  • the present invention provides a compound selected from the group consisting of:
  • the present invention provides a compound selected from the group consisting of:
  • the present invention provides a compound selected from the group consisting of:
  • the present invention provides a compound selected from the group consisting of:
  • R 1 is represented by hydrogen, C 2 to Ce alkanol or Ci to C 6 alkyl;
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3) -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH2) 2 0, -(CH 2 ) 2 N(CH 2 CH 2 )2S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole);
  • R 3 and R 5 are independently selected from hydrogen, Ci to C 4 alkyl and Ci to C 4 alkanol;
  • R 4 is represented by hydrogen-CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole); and
  • x is 0 or 1 ;
  • R 2 when R 2 is hydrogen, R 4 is not hydrogen; and when R 2 is hydrogen, R 1 is hydrogen and x is 0.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -CH 2 CH 3) -CH 2 CH 2 CH 3 , .-(CH 2 ) 2 OH, -(CH 2 ) 3 OH,
  • R 5 is represented by hydrogen; with the proviso that when R 4 is hydrogen, R 2 is not hydrogen;
  • the present invention provides a process wherein in the compound of Formula (I): x is O or l ;
  • R is represented by hydrogen or Ci alky I
  • R 2 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, - CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, - (CH 2 ) 2 N(CH 2 CH 2 )2S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole);
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I):
  • x is 0 or 1 ;
  • R 1 is represented by hydrogen
  • R 2 is represented by hydrogen
  • R 3 is represented by hydrogen
  • R 4 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, - CHzCOOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, - (CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole); and
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I):
  • x is 0 or 1 ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by -CH 2 CH 3) -CH 2 CH 2 CH 3l -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, - CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, - (CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole);
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen
  • R 1 is hydrogen
  • the present invention provides a process wherein in the compound of Formula (I):
  • x O
  • R 1 is represented by hydrogen
  • R 2 is represented by -CH 2 CH 3) -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, - CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, - (CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole);
  • R 3 is represented by hydrogen; R 4 is represented by hydrogen; and R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0;
  • R 1 is represented by C alkyl
  • R 2 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, - CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, - (CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CK 2 ) 2 (5-imidazole);
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0;
  • R 1 is represented by hydrogen
  • R 2 is represented by hydrogen
  • R 3 is represented by hydrogen
  • R 4 is represented by -CH 2 CH 3l -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, - CHzCOOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, - (CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole)and
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 1 ; R 1 is represented by hydrogen;
  • R 2 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, - CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, - (CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole);
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 1 ;
  • R 1 is represented by Ci alkyl; .
  • R 2 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, - CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, - (CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 )2(5-imidazole);
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0; R 1 is represented by Ci alkyl;
  • R 2 is represented by -CH2CH 2 CH 3l -CH 2 COONa, -CH 2 COOK, -(CH2)2 (CH 3 ) 2>
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0; R 1 ' is represented by hydrogen; R 2 is represented by hydrogen; R 3 is represented by hydrogen;
  • R 4 is represented by -CH 2 CH 3 , -CH 2 COOH, -CH 2 COONa, -CH 2 COOK, -(CH 2 ) 2 N(CH 3 ) 2 , -(CH 2 ) 2 N(CH 2 CH2)20, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5-imidazole) or -(CH 2 ) 2 (5-imidazole); and
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ;
  • R 1 is represented by hydrogen or d alkyl
  • R 2 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3l -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH 2 COOH or -(CH 2 ) 2 N(CH 3 ) 2 ;
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0;
  • R 1 is represented by hydrogen
  • R 2 is represented by -CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH or -(CH 2 ) 2 N(CH 3 ) 2 ;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen; and
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein compound of Formula (I): x is 0;
  • R 1 is represented by Ci alkyl
  • R 2 is represented by CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH or -(CH 2 ) 6 OH;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen; and
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 1;
  • R 1 is represented by hydrogen
  • R 2 is represented by -CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 6 OH or -CH 2 COOH;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen; and
  • R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is ; R 1 is represented by Ci alkyl;
  • R 2 is represented by -CH 2 CH 3 or -(CH 2 ) 2 OH; R 3 is represented by hydrogen; R 4 is represented by hydrogen; and R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I):
  • R is represented by hydrogen;
  • R 2 is represented by hydrogen;
  • ' R 3 is represented by hydrogen;
  • R 4 is represented by -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -(CH 2 ) 2 OH, -(CH 2 ) 3 OH or -(CH 2 ) 6 OH; and R 5 is represented by hydrogen.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 or -(CH 2 ) 2 N(CH 3 ) 2 ;
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -CH 2 CH 3 , -CH 2 CH 2 CH 3 or -(CH 2 ) 2 N(CH 3 ) 2 ;
  • R 5 is represented by hydrogen; with the proviso that when R 4 is hydrogen, R 2 is not hydrogen;
  • the present invention provides a process wherein in the compound of Formula (I):
  • x is 0 or 1 ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH 2 COOH, -CH 2 COONa or -CH 2 COOK ;
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 6 OH, -CH 2 COOH, -CH 2 COONa or -CH 2 COOK;
  • R 5 is represented by hydrogen
  • the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ⁇ ;
  • R 1 is represented by hydrogen or Ci alkyl
  • R 2 is represented by hydrogen, -(CH 2 ) 2 OH, -(CH 2 ). 3 OH or -(CH 2 ) 6 OH;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen, -(CH 2 ) 2 OH, -(CH 2 ) 3 OH or -(CH 2 ) 6 OH;
  • R 5 is represented by hydrogen; with the proviso that when R 4 is hydrogen, R 2 is not hydrogen;
  • R 2 when R 2 is hydrogen, R 4 is not hydrogen; and when R 2 is hydrogen, R 1 is hydrogen and x is 0.
  • the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ; R 1 is represented by hydrogen or Ci alkyl;
  • R 2 is represented by hydrogen, -CH 2 COOH, -CH 2 COONa or -CH 2 COOK ;
  • R 3 is represented by hydrogen;
  • R 4 is represented by hydrogen, -CH 2 COOH, -CH 2 COONa or -CH 2 COOK;
  • R 5 is represented by hydrogen
  • the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ;
  • R 1 is represented by hydrogen or alkyl
  • R 2 is represented by hydrogen, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, -(CH 2 ) 2 N(CH 2 CH 2 )2S, -CH 2 (5- imidazole) or -(CH 2 ) 2 (5-imidazole);
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 0, -(CH 2 ) 2 N(CH 2 CH 2 ) 2 S, -CH 2 (5- imidazole) or -(CH 2 ) 2 (5-imidazole); and
  • R 5 is represented by hydrogen
  • R 2 when R 2 is hydrogen, R 4 is not hydrogen; and when R 2 is hydrogen, R 1 is hydrogen and x is 0.
  • the present invention provides a process wherein in the compound of Formula (I): x is O o ;
  • R 1 is represented by hydrogen
  • R 2 is represented by ethyl, propyl or -(CH 2 ) 2 N(CH 3 ) 2
  • R 3 is represented by hydrogen
  • R 4 is represented by hydrogen
  • R 5 is represented by hydrogen
  • the present invention provides a process wherein in the compound of Formula (I) is selected from a group consisting of:
  • the present invention provides a process wherein in the compound of Formula (I) is selected from a group consisting of:
  • the present invention provides a process wherein in the compound of Formula (I) is selected from a group consisting of:
  • the C0 2 capture efficiency of the mixed amine solution is also better than that of 4-aminopiperidine used in a mixture with another amine.
  • the compounds described above act as promoters in mixed amine solutions. Accordingly, the cost and energy consumption of CO2 capture may be lowered by the use of a compound as described above, by itself, or in a mixture with another amine in C0 2 capture, In the process of the present invention, the compound is typically present in the form of an aqueous solution.
  • the compound may be present in the aqueous solution in an amount of from about 5 to 99 percent by weight, preferably from about 10 to 90 percent by weight, most preferably from about 15 to 75 percent by weight, based upon the total weight of the aqueous solution.
  • the compound may be present in the mixed amine solution in " an amount of from about 10 to 100 percent by weight, preferably from about 20 to 80 percent by weight, most preferably from about 30 to 70 percent by weight, based upon the total weight of the amine components.
  • the optimal amount of the compound used in the process of the present invention will depend upon the gas stream composition, outlet fluid requirement and circulation rate.
  • the process of the present invention may be carried out in conventional equipment for the removal of carbon dioxide from gas streams by reactive chemical absorption and detailed procedures are well known to the person skilled in the art. See, for example, the flow diagram of Figure 1, or Newman, S.A., Acid and Sour Gas Treating Processes, Gulf Publishing Company, Texas, 1995.
  • the equipment comprises an absorber column 2, a heat exchanger 5, a desorber column 6 and a reboiler 9.
  • Flue gas which typically comprises 1-15% C0 2 , preferably 5-15% C0 2 and more preferably 10-15% C0 2 , is optionally passed through a prescrubber and then passes through conduit 1 to the packed absorber column 2, where it is contacted with the compound of formula (I).
  • Pressure and temperature conditions in the absorber column 2 are typically 1 atm and about 40 to 60°C.
  • C0 2 -lean flue gas is released from the top of the absorber via conduit 3.
  • the C0 2 -rich solution containing the compound of formula (I) is conducted through a pipe 4 to a desorber column 6 via a heat exchanger 5. In the desorber column 6, the C0 2 -rich solution containing the compound of formula (I) is heated to reverse the absorption reaction.
  • Typical pressure and temperature conditions in the desorber are 0.4 - 15 atm and 75 to 200°C.
  • C0 2 and moisture is collected from the top of the desorber column via conduit 7.
  • the desorber column is heated by means of a reboiler 9, connected to the desorber by conduits 8 and 10.
  • the heat source of the reboiler is preferably low pressure steam at a temperature of 105-135°C, but to achieve higher temperature conditions in the stripper a higher quality steam is necessary, ie, preferably steam with a temperature 5 to 15 degrees higher than the stripper temperature.
  • the C0 2 -lean solution containing the compound of formula (I) is then conducted through a pipe 11 to the absorber 2 via the heat exchanger 5.
  • sensible heat from the C0 2 -lean solution containing the compound of formula (I) is used to heat the C0 2 -rich solution from the absorber.
  • the desorption process which regenerates the compounds of formula (I) may be carried out be any other suitable method known to the person skilled in the art, such as pressure relieving or stripping treatment.
  • the process according to the present invention may be conveniently carried out in any suitable absorber, including packed, plate or spray towers. These absorbers are interchangeable to a considerable extent although certain specific conditions may favour one over the other.
  • the process of the present invention may be carried out in either packed, plate or spray towers, or specialised towers developed to meet specific process requirements, and may contain other peripheral equipment as necessary for optimal process operation.
  • peripheral equipment may include but is not limited to an inlet gas separator, a treated gas coalescer, a solvent flash tank, a particulate filter and a carbon bed purifier.
  • the inlet gas flow rate varies according to the size of the equipment but is typically between 5 000 and 25 00 cubic metres per second.
  • the solvent circulation rate is typically between 10 and 40 cubic metres per tonne of C0 2 .
  • the operating pressure of the absorber is typically between 1 and 100 atm with lower operating pressures being typical of post-combustion CO2 capture and higher operating pressures being typical of natural gas treatment and pre-combustion C0 2 capture.
  • a gas stream containing C0 2 at or above atmospheric pressure is contacted with a compound of formula (I) at a temperature at or above ambient temperature, preferably between 30°C to 60°C, and more preferably between 35°C to 45°C to effect absorption of C0 2 from the gas stream.
  • a corrosion inhibitors, scale inhibitors, antifoam agents and/or other additives known to those in the art that may assist in the CO 2 capture process of the present invention may be employed The following examples are offered to illustrate but not to limit the present invention. Examples Example 1 Reductive Amination This method may be used for the synthesis of secondary or tertiary amine product from either (1) or (3) below.
  • the pH of the mixture was adjusted to basic ( ⁇ pH 10) by the careful addition of solid NaOH and the mixture was stirred for 15-30 min.
  • the organic phase was separated and the aqueous phase was extracted with dichloromethane (2 x 60mL).
  • the combined organic phase was washed with H 2 0 (2 x 60ml_) and dried by K 2 C0 3 or filtration through phase separation paper. Removal of the solvent under vacuum gave the product in excellent yield.
  • the amine hydrochloride salt may be used in the reaction. If the amine hydrochloride salt is used, one equivalent of triethylamine (Et 3 N) is used instead of acetic acid.
  • the amine. HCI salt may be used in the reaction.
  • amine HCf salt When the amine HCf salt was used an equivalent amount of triethylamine was added .
  • TEA.HCI salt was removed via a partition of dichloromethane-H20 followed by washing with 5% Na 2 C0 3 .
  • the organic phase was dried (phase separation paper filtration of K2CO3) and concentrated under vacuum to give the product.
  • reaction may use an alkylchloride rather than an alkylbromide. If an alkylchloride is used a small quantity of Kl was added.
  • an alkylchloride is used a small quantity of Kl was added.
  • Tien Q Pham, Ivan Greguric, Xiang Liu, Paula Berghofer, Patrice Ballantyne, Janette Chapman, Filomena Mattner, Branko Dikic, Timothy Jackson, Christian Loc'h, and Andrew Katsifis; Journal of Medicinal Chemistry, 2007, 50 (15), 3561-3572.
  • Amberlyst 15 resin was used in the Boc-deprotection.
  • the amount of resin used was calculated based on the number of amino groups in the amine molecules.
  • the ratio is 5:1 molar equivalents of resin to each amino-group in the product. Hence, this molar ratio is 10:1 in the case of diamines and 15:1 in the case of tri-amines.
  • a very slow dropwise flow rate is critical in all operations involved in resin washing or rinsing to achieve complete deprotection and quantitative or near quantitative yield.
  • the Boc-protected amine (2, 4, 5, 6 or 8) was dissolved in an amount THF that is sufficient to just cover the resin and the solution was added to the resin. The mixture was heated at gentle reflux overnight without " stirring. An aliquot of supernatant was evaporate to dryness and analyse by 1 H NMR to confirm all amine bound to resin. Resin was transferred to a glass column and drained, and then wash with 1 x bed volume of THF at a very slow flow rate.
  • the amine was released from the resin using 2M MeNH 2 /EtOH (33%, ⁇ 8M). An equal molar quantity of MeNH 2 with respect to the resin loading was used. The resin was then washed with 1 bed volume of EtOH. In the case of aminoacid derivatives, alcohol was avoided and an aqueous ⁇ 3 ⁇ ⁇ 2 0 solution (45%, ⁇ 7.6M) was used to release the amine followed by washing with H 2 0 (1 bed volume). The combined filtrates were concentrated to dryness to yield the free amine.
  • the resin was regenerated by washing with 3M HCI in MeOH/H 2 0 (1 :1) ( ⁇ 1eq with respect to resin), water (1-2 bed volumes) followed by MeOH (1 bed volume), and then dichloromethane (1 bed volume. The clean resin was finally dried under N 2 or vacuum.
  • Step 2 Metallic sodium (1.3 g, 56 mmol) was added slowly to cold MeOH (50 ml) with stirring under nitrogen.
  • the prepared mixture of NaOMe/MeOH was transferred to the hydrogenation vessel and pyridium bromide salt (11) (11.1 g, 51 mmol) obtained from the above reaction was added to the reaction mixture followed by 5% rhodium on charcoal (1.1 g, 10% w/w).
  • the reaction was processed under hydrogen atmosphere (140 psi) at 60°C overnight.
  • the reaction mixture was filtered through Celite and washed with MeOH (100 ml_).
  • the 4-(N-Boc amino)-1-piperidineethanol (13g, 53.2mmol) was treated with TFA (26mL) for 90mL
  • TFA was removed (reduced pressure) and the TFA salt was converted to the HCI salt by treatment with 20%HCI/methanol (130mL) at ambient temperature for 30min.
  • the HCI/methanol was evaporated (reduced pressure) and the residue dissolved in H 2 0 (10ml_).
  • the solution was cooled in an ice-bath and NaOH (10 , 35ml_) added to pH >10.
  • the solution was warmed to RT and stirred for 15min prior to evaporating to dryness.
  • the residue was triturated with ether/isopropanol (2:1), filtered and evaporated to dryness. The trituration process was repeated until no salt was present in the oil (5x) to yield 6.7g (87%) of an off-white solid.
  • This method provides a specific example of the method of Example 1 and the method of Example 6.
  • Triethylamine (19.2g, 190mmol) was added to a stirring solution of 4-piperidone monohydrate hydrochloride (20.0g, 131mmol) in methanol (300mL) and stirred for 5min.
  • Boc 2 0 34g, 168mmol
  • DMAP 0.4g, 3mmol
  • the solution was stirred at ambient temperature for 20h.
  • the methanol was removed under reduced pressure and the crude was dissolved in dichloromethane (100mL). The organic phase was washed with HCI (2M, 2 x 70mL) sat.
  • the 4-(2-ethanolamino)-1-Boc-piperidine (14g, 57.3mmol) was treated with TFA (28mL) • for 90mL.
  • the TFA was removed (reduced pressure) and the TFA salt was converted to the HCI salt by treatment with 20% HCl/methanol (140mL, 280mmol HCI) at ambient temperature for 30min.
  • the HCl/methanol was evaporated (reduced pressure) to yield a white solid in quantitative yield.
  • 19 F NMR (MeOD) confirmed complete conversion to the HCI salt.
  • Compounds 1 to 4 also displayed better C0 2 release in desorption ( Figure 2(b)). Compounds 1 to 3 desorbed more C0 2 (105%, 100% and 86% on a mol% basis, respectively) at moderate temperatures (90° C), than did 4-aminopiperidine (67%). Again, the desorption yield of Compound 4 could not be accurately measured due to the inability to accurately measure the C0 2 loading of the starting material.
  • MEA and Pz are commercially available amines used in industry for CO2 capture.
  • Aqueous MEA is used as a C0 2 absorber due to its attractive CO2 loading capacity in g C0 2 /g MEA whilst it's desorption is poor and high energy consumption is required.
  • Pz was claimed widely as a promoter in C0 2 absorption by amines, but our study results showed that Pz carbamate was reasonably stable at 90°C, and this limited its capacity as a promoter in CO2 capture at lower energy consumption.
  • Hydrated gas of 10% CO2 and 90% N 2 was introduced to the amine solution through a PTFE tube (0.71 mm ID, 1.78 mm OD) at a total flow rate of 50 mL/min (controlled via a Bronkhorst High-Tech El-Flow mass flow controller). The loading was processed over night (18 hours). A sample was taken for NMR analysis.
  • the concentration of MEA used in experiment was 4M. This concentration provided same total concentration of amino-groups to that of 2M diamines.
  • NMR samples were placed into a 5 mm (178 mm long, 4.24 mm ID) NMR tube to a height of 40 mm then capped, and an external standard of 1,4-dioxane in a sealed ⁇ capillary was used in 13 C NMR analysis (5c 67.18 ppm, calibrated against an external TMS/CDC solution). Relaxation times (7» of the carbon atoms in the reaction mixture were measured using the standard inversion recovery ("Null”) method. The NMR analytical interscan recycle time was chosen as equal to 5*7 . NMR spectroscopy was performed at 25°C. The molar ratio of C0 2 -loading to amine was calculated based on integration of carbonyl signals and amine aliphatic carbon signals.
  • the weight loading figure then was calculated from molar ratio results.
  • the accuracy of loadings determined in this manner was estimated to be ⁇ 3% for amine concentrations of 4 M.
  • the cyclic capacity is the calculated difference between the maximum and minimum CO2 loading in the process of absorption-desorption cycle.
  • This example provides 1 H NMR data for examples of compounds of Formula (I).

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Abstract

A process for the capture of CO2 from gas streams, the process including contacting a CO2 containing gas stream with a compound including: a primary or non-sterically hindered secondary amine group and at least one tertiary amine or sterically hindered secondary amine group; wherein the primary or non-sterically hindered secondary amine and the nearest tertiary or sterically hindered secondary amine group are separated by a carbon chain including 3 or 4 carbon atoms and wherein the compound is a compound of Formula (I).

Description

Gas capture process
Field of the invention
This invention relates to amines and their use in capturing carbon dioxide from gas streams. Background of the invention
There is growing pressure for stationary producers of greenhouse gases to dramatically reduce their atmospheric emissions. Of particular concern is the emission of carbon dioxide (CO2) into the atmosphere. One method of reducing atmospheric CO2 emissions is through its capture at a point source and subsequent storage in geological or other reservoirs.
The process for capturing CO2 from power station and other combustion device flue gases is termed post combustion capture (PCC). In post combustion capture, the C02 in flue gas is first separated from nitrogen and residual oxygen using a suitable solvent in an absorber. The solvent is usually an aqueous basic mixture containing components that undergo a chemical reaction with acid gases such as C02. It might contain amines (e.g. alkanolamines, ammonia, alkylamines) and/or inorganic salts (e.g. carbonate or phosphate). The CO2 is subsequently removed from the solvent in a process called stripping (or regeneration), thus allowing the solvent to be reused. The stripped C02 is liquefied by compression and cooling, with appropriate drying steps to prevent hydrate formation. PCC in this form is applicable to a variety of stationary CO2 sources including power stations, steel plants, cement kilns, calciners and smelters.
Acid gases, such as carbon dioxide, are also present in natural gas and other pressurised gas streams and need to be removed to meet gas quality specifications. Pressurised gas streams containing C02 are also produced in fuel conversion processes such as natural gas reforming and coal gasification combined with a water- gas shift conversion to produce mixtures of hydrogen and carbon dioxide. These gas streams are then suitable for pre-combustion capture of CO2. The conventional approaches for such removal include membrane separation or amine treatment. When C02 is absorbed into an aqueous solution a number of reactions can occur. The reactions are shown by the following equations where (1) is hydration of gaseous C02, (2) is the reaction of C02 with water to form carbonic acid, (3) is the reaction of CO2 with hydroxide to form bicarbonate and (4) and (5) are the carbonic acid-bicarbonate- carbonate acid-base equilibria.
C02(g) ■ — C02 (1)
C02 + H20 ■ K1'K1 ' H2C03 (2)
C02 + OH- , K2,K2 ' HCO3- (3)
K-2
H+ + CO3 2- - K* * HCO3- (4)
Figure imgf000003_0001
If an amine, or multiple amines, are present in solution a number of additional reactions may occur. If the amine is a sterically free primary or secondary amine such as monoethanolamine (MEA) or diethanolamine (DEA) the following reactions can occur between CO2 and each amine. Equation (6) is the formation of a carbamate species via a nitrogen-carbon bond formation between the amine and CO2. This is generally the kinetically fastest reaction of those that occur with CO2. Equation (7) is the amine acid- base equilibrium. For polyamines the reactions of equation (6) and (7) may occur for each nitrogen atom. For sterically hindered primary or secondary amines the carbamate species is less stable than in sterically free amines which leads to enhanced formation of the bicarbonate species. For tertiary amines only the acid-base equilibrium of equation (7) occurs.
CO2 + Am . K*K6 — AmCOQ- + H+ (6)
K.6
Am + H* .. 7 »x AmH+ (7) Monoethanolamine (MEA) is currently employed in industrial CO2 capture but has a number, of limitations, including solvent degradation due to oxidation and reaction with nitrogen and sulphur oxides, solvent losses due to high volatility and high energy requirements needed to desorb the CO2 from the C02 loaded MEA. Some other amines used for industrial C02 capture have a larger C02 absorption capacity than MEA, but have poor rates of C02 capture. Slow C02 absorption rates are undesirable because to achieve the requisite absorption of C02l longer contact times between the C02 containing gas stream and the amine means that longer absorption columns and larger capital costs are usually required. The use of amines as sorbents in C02 capture may be limited by the thermal degradation and oxidation of the amines. Much of the research on amine solvents for C02 capture is based around formulation with commercially available amines. There appears to be little study of novel amines that are designed, via amine structural modification, to match the characteristic requirement of C02 capture. 4-Aminopiperidine has been reported to perform well in CO2 capture (Singh et ai, 2008).
In addition, European patent application no 2036602 (Mitsubishi Heavy Industries, Ltd.) relates to an absorbent liquid for removing C02 and/or H2S from gas which includes compounds which are described in very general terms in the application (for example, by way of very broad general formulae). However, the data in the application showing the CO2 absorption capacity of the compounds is quite limited.
However, there still exists a need for a more efficient C02 capture technology or process for post combustion capture.
It is an object of the present invention to overcome or at least alleviate one or more of the problems associated with the prior art. Reference to any prior art in the specification is not, and should not be taken as, an acknowledgment or any form of suggestion that this prior art forms part of the common general knowledge in Australia or any other jurisdiction or that this prior art could reasonably be expected to be ascertained, understood and regarded as relevant by a person skilled in the art.
Summary of the invention
The Applicants have surprisingly discovered that the compounds of the invention (as represented by formula (I) below) exhibit good molar C02 cyclic capacities. The compounds of formula (I), which are derivatives of 4-aminopiperidine, show a higher molar CO2 cyclic capacity that that of 4-aminopiperidine itself.
Accordingly, in one aspect, the present invention provides a process for the capture of CO2 from gas streams, the process including contacting a C02 containing gas stream with a compound including: a primary or non-sterically hindered secondary amine group and at least one tertiary amine or sterically hindered secondary amine group; wherein the primary or non-sterically hindered secondary amine and the nearest tertiary or sterically hindered secondary amine group are separated by a carbon chain including 3 or 4 carbon atoms and wherein the compound is a compound of Formula (I)
Figure imgf000005_0001
wherein
R1 is represented by hydrogen, C2 to Ce alkanol or Ci to C6 alkyl;
R2 is represented by hydrogen, Ct to C6 alkyl, C2 to C6 alkanol, -(CH2)n-NR6R7, -(CH2)P- COOH, -(CH2)pCOOQ, -(CH2)p-heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur; R3 and R5 are independently selected from hydrogen, Ci to C4 alkyl, C2 to C6 alkanol, -(CH2)n-NR8R9;
R4 is represented by hydrogen, Ci to C6 alkyl, C2 to C6 alkanol, -(CH2)n- R6 7, -(CH2)P- COOH, -(CH2)pCOOQ, -(CH2)p-S03H, -(CH2)pS03Q, -(CH2)p-P03H2, -(CH2)pP03Qs, -(CH2)p-heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
x is 0 or 1 ;
n is 2 to 6;
p is 1 to 6;
Q is hydrogen, a metal ion or R16R17R18R19N+;
s is 1 or 2
R6 and R7 are independently selected from hydrogen, alkyl, alkanol, alkylamine or R6 and R7 together with the nitrogen atom to which they are attached form a ring structure
R8 and R9 are independently selected from Ci to C6 alkyl, C2 to C6 alkanol, C2 to C6 alkylamine, -(CH2)n-NR6R7, -(CH2)p-COOH, -(CH2)PCOOQ, -(CH2)p-S03H, -(CH2)pS03Q, -(CH2)p-P03H2, -(CH2)pP03Qs, or R8 and R9 together with the nitrogen atom to which they are attached form a ring structure; and
R16, R17, R18 and R19 are independently selected from hydrogen or alkyl;
with the proviso that when R4 is hydrogen, R1 and/or R2 is not hydrogen; when R4 is not hydrogen, R1 and/or R2 is hydrogen; when R4 and R1 are both hydrogen, R2 is not methyl; and when R4 and R2 are both hydrogen, R1 is not methyl.
In a further aspect, the present invention provides a compound including: a primary or non-sterically hindered secondary amine group and at least one tertiary amine or a sterically hindered secondary amine group; wherein the primary or non-sterically hindered secondary amine group and the nearest tertiary or sterically hindered secondary amine group are separated by a carbon chain including 3 or 4 carbon atoms; and wherein the compound is a compound of Formula (I):
Figure imgf000007_0001
wherein
R1 is represented by hydrogen, C2 to Ce alkanol or Ci to C6 alkyl;
R2 is represented by hydrogen, d to C6 alkyl, C2 to C6 alkanol, -(CH2)n-NR6R7, -(CH2)P- COOH, -(CH2)pCOOQ, -(CH2)p-heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
R3 and R5 are independently selected from hydrogen, to C4 alkyl, Ci to C4 alkanol, -(CH2)n-NR8R9 ;
R4 is represented by hydrogen, d to C6 alkyl, C2 to C6 alkanol, -(CH2)n-NR6R7, -(CH2)P- COOH, -(CH2)pCOOQ, -(CH2)p-S03H, -(CH2)pS03Q, -(CH2)p-P03H2) -(CH2)pP03Qs, -(CH2)p-heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
x is 0 or 1 ;
n is 2 to 6;
p is 1 to 6;
Q is hydrogen, a metal ion or R16R17R18R19N+; s is 1 or 2;
R6 and R7 are independently selected from hydrogen, Ci to C6 alkyl, C2 to C6 alkanol, C2 to C6 alkylamine or R6 and R7 together with the nitrogen atom to which they are attached form a ring structure
R8 and R9 are independently selected from Ci to C6 alkyl, C2 to C6 alkanol, C2 to C6 alkylamine, -(CH2)n-NR6R7, -(CH2)p-COOH, -(CH2)pCOOQ, -(CH2)p-S03H, -(CH2)pS03Q, -(CH2)p-P03H2, -(CH2)PP03Qs, or R8 and R9 together with the nitrogen atom to which they are attached form a ring structure;;
R14 and R15 are independently selected from Ci to Ce alkyl, C2 to C6 alkanol, C2 to C6 alkylamine or R14 and R15 together with the nitrogen atom to which they are attached form a ring structure; and
R16, R17, R18 and R19 are independently selected from hydrogen or alkyl;
with the proviso that when R4 is hydrogen, R1 and/or R2 is not hydrogen; when R4 is not hydrogen, R1 and/or R2 is hydrogen; when R4 and R are both hydrogen, R2 is not methyl; and when R4 and R2 are both hydrogen, R is not methyl.
Brief description of the drawings / figures
Figure 1 shows a flow-diagram example of a C02 capture apparatus that may be employed in the process of one embodiment of the present invention. Figure 2 shows the C02 absorption and desorption of 1-ethanol-4-aminopiperidine, 1- propyl-4-aminopiperidine, 4-ethanolaminopiperidine, 4-propylaminopiperidine compared with 4-aminopiperidine.
Figure 3 shows the C02 absorption and desorption of 1-ethanol-4-aminopiperidine, 1- propyl-4-aminopiperidine, 4-ethanolaminopiperidine, 4-propylaminopiperidine, 4- aminopiperidine compared with monoethanolamine and piperazine. Detailed description of the embodiments
As used herein, the term "sterically hindered secondary amine" means that the substituent on the secondary amine has sufficient bulk such that a reaction between the secondary amine and CO2 produces an unstable carbamate species. As used herein, the term "alkyl" means a straight or branched chain, or cyclic, saturated aliphatic group, or a combination thereof.
As used herein, the term "alkanol" means a group where an alcohol group (-OH) is bound to a carbon atom, ie, -(CH2)nOH.
As used herein, the term "aikylamine" means a group where an alkyl group is bound to the nitrogen atom of an amine group.
As used herein, except where the context requires otherwise, the term "comprise" and variations of the term, such as "comprising", "comprises" and "comprised", are not intended to exclude further additives, components, integers or steps.
It has surprisingly been found that the compounds used in the process of the present invention, described above, have a higher capacity for C02 absorption and good reaction rates in CO2 absorption, and higher efficiency in CO2 desorption.
In addition, the compounds have relatively high boiling points which may result in reduced amine evaporation during the process. The reduction in evaporation may be beneficial from cost and environmental impact perspectives. In one embodiment the present invention provides a compound of Formula (I)
Figure imgf000009_0001
wherein
R1 is represented by hydrogen, C2 to C& alkanol or C-i to C6 alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3l -(ΟΗ2)2ΟΗ, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 and R5 are independently selected from hydrogen, Ci to C4 alkyl and to C4 alkanol;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2) -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
x is O or l ;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a compound of Formula (I) wherein: x is O or l ;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(ΟΗ2)2ΟΗ, -(CH2)3OH,
-(CH2)6OH, -CHzCOOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, ~(CH2)3OH,
-(CH2)60H, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2) -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a compound of Formula (I) wherein:
x is O or f;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a further embodiment, the present invention provides a compound of Formula (I) wherein:
x is 0;
R is represented by hydrogen; R2 is represented by hydrogen; R3 is represented by hydrogen; R4 is represented by hydrogen, -CH2CH3> -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0 or 1; R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2 (CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen; with the proviso that when x is 0, R1 is hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0;
R1 is represented by hydrogen; R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3) -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is O;
R1 is represented by Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S) -CH2(5-imidazole) or -(CH2)2(5-imidazole); R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0;
R1 is represented by hydrogen; R2 is represented by hydrogen; R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2t
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazoie); and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is l;
R1 is represented by hydrogen;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2>
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is 1 ;
R1 is represented by Ci alkyl; R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CHa^OH, -(CH2)30H,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5.-imidazole);
R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
' In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is O;
R1 is represented by Ci alkyl;
R2 is represented by -CH2CH2CH3, -CH2C00Na, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is O;
R1 is represented by hydrogen; R2 is represented by hydrogen; R3 is represented by hydrogen; R4 is represented by -CH2CH3l -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is O or l ;
R1 is represented by hydrogen or Ci alkyl; R2 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH or -(CH2)2N(CH3)2;
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0;
R is represented by hydrogen; R2 is represented by -CH2CH3l -(CH2)2OH, -(CH2)3OH, -(CH2)6OH or -(CH2)2N(CH3)2; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0;
R1 is represented by Ci alkyl;
R2 is represented by -CH2CH3, -(CH2)2OH, -(CH2)3OH or -(CH2)6OH; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is l ;
R1 is represented by hydrogen;
R2 is represented by -CH2CH3, -(CH2)2OH, -(CH2)6OH or -CH2COOH; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen. In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is 1 ;
R1 is represented by Ci alkyl; R2 is represented by -CH2CH3 or -(CH2)2OH; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein:
x is 0 or 1 ;
R1 is represented by hydrogen; R2 is represented by hydrogen; R3 is represented by hydrogen;
R4 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH or -(CH2)6OH; and R5 is represented by hydrogen.
In a further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0 or 1; R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3 or -(CH2)2 (CH3)2; R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3 or -(CH2)2N(CH3)2; and R5 is represented by hydrogen; with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0 or 1 ;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -(CH2)20H, -(CH2)3OH, -(CH2)6OH, -CH2COOH,
-CH2COONa or -CH2COOK;
R3 is represented by hydrogen;
R4 is represented by hydrogen, -(CH2)2OH, -(CH2)30H, -(CH2)6OH, -CH2COOH,
-CH2COONa or -CH2COOK; and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0. In a further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0 or 1 ;
R1 is represented by hydrogen or Ci alkyl; R2 is represented by hydrogen, -(CH2)2OH, -(CH2)3OH or -(CH2)6OH; R3 is represented by hydrogen;
R4 is represented by hydrogen, -(CH2)2OH, -(CH2)3OH or -(CH2)6OH; and R5 is represented by hydrogen; - with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a compound of Formula (I) wherein: x is O or l;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2COOH, -CH2COONa or -CH2COOK ; R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2COOH, -CH2COONa or -CH2COOK; and R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0 or 1 ;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -(CH2)2 (CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5- imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen, -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5- imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
In a still further embodiment, the present invention provides a compound of Formula (I) wherein: x is 0 or 1 ; R1 js represented by hydrogen;
R2 is represented by ethyl, propyl or -(CH2)2N(CH3)2;
R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a further embodiment, the present invention provides a compound selected from the group consisting of:
Figure imgf000022_0001
Figure imgf000023_0001
In a further embodiment, the present invention provides a compound selected from the group consisting of:
Figure imgf000023_0002
Figure imgf000024_0001
In a further embodiment, the present invention provides a compound selected from the group consisting of:
Figure imgf000024_0002
In a further embodiment, the present invention provides a compound selected from the group consisting of:
Figure imgf000024_0003
Figure imgf000025_0001
R1 is represented by hydrogen, C2 to Ce alkanol or Ci to C6 alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3) -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 and R5 are independently selected from hydrogen, Ci to C4 alkyl and Ci to C4 alkanol;
R4 is represented by hydrogen-CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
x is 0 or 1 ;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COO , -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3) -CH2CH2CH3, .-(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen; with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is O or l ;
R is represented by hydrogen or Ci alky I;
R2 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, - CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, - (CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I):
x is 0 or 1 ;
R1 is represented by hydrogen; R2 is represented by hydrogen;
R3 is represented by hydrogen; R4 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, - CHzCOOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, - (CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I):
x is 0 or 1 ;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by -CH2CH3) -CH2CH2CH3l -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, - CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, - (CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen;
with the proviso that when x is O, R1 is hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I):
x is O;
R1 is represented by hydrogen;
R2 is represented by -CH2CH3) -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, - CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, - (CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0;
R1 is represented by C alkyl;
R2 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, - CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, - (CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CK2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0;
R1 is represented by hydrogen;
R2 is represented by hydrogen;
R3 is represented by hydrogen;
R4 is represented by -CH2CH3l -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, - CHzCOOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, - (CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole)and
R5 is represented by hydrogen. In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 1 ; R1 is represented by hydrogen;
R2 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, - CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, - (CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen; R4 is represented by hydrogen; and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 1 ;
R1 is represented by Ci alkyl; .
R2 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, - CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, - (CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen. In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0; R1 is represented by Ci alkyl;
R2 is represented by -CH2CH2CH3l -CH2COONa, -CH2COOK, -(CH2)2 (CH3)2>
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S1 -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0; R1 'is represented by hydrogen; R2 is represented by hydrogen; R3 is represented by hydrogen;
R4 is represented by -CH2CH3, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2, -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ;
R1 is represented by hydrogen or d alkyl;
R2 is represented by -CH2CH3, -CH2CH2CH3l -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH or -(CH2)2N(CH3)2;
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0;
R1 is represented by hydrogen;
R2 is represented by -CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH or -(CH2)2N(CH3)2; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein compound of Formula (I): x is 0;
R1 is represented by Ci alkyl;
R2 is represented by CH2CH3, -(CH2)2OH, -(CH2)3OH or -(CH2)6OH; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 1;
R1 is represented by hydrogen;
R2 is represented by -CH2CH3, -(CH2)2OH, -(CH2)6OH or -CH2COOH; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is ; R1 is represented by Ci alkyl;
R2 is represented by -CH2CH3 or -(CH2)2OH; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I):
x is 0;
R is represented by hydrogen; R2 is represented by hydrogen; ' R3 is represented by hydrogen;
R4 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH or -(CH2)6OH; and R5 is represented by hydrogen.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3 or -(CH2)2N(CH3)2;
R3 is represented by hydrogen; R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3 or -(CH2)2N(CH3)2; and
R5 is represented by hydrogen; with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I):
x is 0 or 1 ;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa or -CH2COOK ;
R3 is represented by hydrogen;
R4 is represented by hydrogen, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa or -CH2COOK; and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1·;
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -(CH2)2OH, -(CH2).3OH or -(CH2)6OH; R3 is represented by hydrogen; R4 is represented by hydrogen, -(CH2)2OH, -(CH2)3OH or -(CH2)6OH; and R5 is represented by hydrogen; with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ; R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2COOH, -CH2COONa or -CH2COOK ; R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2COOH, -CH2COONa or -CH2COOK; and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is 0 or 1 ;
R1 is represented by hydrogen or alkyl; R2 is represented by hydrogen, -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5- imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen, -(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5- imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and when R2 is hydrogen, R1 is hydrogen and x is 0.
In a still further embodiment, the present invention provides a process wherein in the compound of Formula (I): x is O o ;
R1 is represented by hydrogen; R2 is represented by ethyl, propyl or -(CH2)2N(CH3)2; R3 is represented by hydrogen; R4 is represented by hydrogen; and R5 is represented by hydrogen.
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I) is selected from a group consisting of:
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I) is selected from a group consisting of:
Figure imgf000039_0002
In a further embodiment, the present invention provides a process wherein in the compound of Formula (I) is selected from a group consisting of:
Figure imgf000039_0003
Figure imgf000040_0001
Figure imgf000041_0001
When a compound as described above is used in a mixture with another amine, (ie, a mixed amine solution), the C02 capture efficiency of the mixed amine solution is also better than that of 4-aminopiperidine used in a mixture with another amine. Without wishing to be bound by theory, it is thought that the compounds described above act as promoters in mixed amine solutions. Accordingly, the cost and energy consumption of CO2 capture may be lowered by the use of a compound as described above, by itself, or in a mixture with another amine in C02 capture, In the process of the present invention, the compound is typically present in the form of an aqueous solution. The compound may be present in the aqueous solution in an amount of from about 5 to 99 percent by weight, preferably from about 10 to 90 percent by weight, most preferably from about 15 to 75 percent by weight, based upon the total weight of the aqueous solution. When the compound is used in a mixture with another amine, (ie, a mixed amine solution), the compound may be present in the mixed amine solution in "an amount of from about 10 to 100 percent by weight, preferably from about 20 to 80 percent by weight, most preferably from about 30 to 70 percent by weight, based upon the total weight of the amine components. The optimal amount of the compound used in the process of the present invention will depend upon the gas stream composition, outlet fluid requirement and circulation rate. A person skilled in the art would readily be able to determine the appropriate amount of the compound to use in the process of the present invention. The process of the present invention may be carried out in conventional equipment for the removal of carbon dioxide from gas streams by reactive chemical absorption and detailed procedures are well known to the person skilled in the art. See, for example, the flow diagram of Figure 1, or Newman, S.A., Acid and Sour Gas Treating Processes, Gulf Publishing Company, Texas, 1995. In the embodiment described by Figure 1 , the equipment comprises an absorber column 2, a heat exchanger 5, a desorber column 6 and a reboiler 9. Flue gas, which typically comprises 1-15% C02, preferably 5-15% C02 and more preferably 10-15% C02, is optionally passed through a prescrubber and then passes through conduit 1 to the packed absorber column 2, where it is contacted with the compound of formula (I). Pressure and temperature conditions in the absorber column 2 are typically 1 atm and about 40 to 60°C. C02-lean flue gas is released from the top of the absorber via conduit 3. The C02-rich solution containing the compound of formula (I) is conducted through a pipe 4 to a desorber column 6 via a heat exchanger 5. In the desorber column 6, the C02-rich solution containing the compound of formula (I) is heated to reverse the absorption reaction. Typical pressure and temperature conditions in the desorber are 0.4 - 15 atm and 75 to 200°C. C02 and moisture is collected from the top of the desorber column via conduit 7. The desorber column is heated by means of a reboiler 9, connected to the desorber by conduits 8 and 10. The heat source of the reboiler is preferably low pressure steam at a temperature of 105-135°C, but to achieve higher temperature conditions in the stripper a higher quality steam is necessary, ie, preferably steam with a temperature 5 to 15 degrees higher than the stripper temperature. The C02-lean solution containing the compound of formula (I) is then conducted through a pipe 11 to the absorber 2 via the heat exchanger 5. In the heat exchanger 5, sensible heat from the C02-lean solution containing the compound of formula (I) is used to heat the C02-rich solution from the absorber. The desorption process which regenerates the compounds of formula (I) may be carried out be any other suitable method known to the person skilled in the art, such as pressure relieving or stripping treatment.
The process according to the present invention may be conveniently carried out in any suitable absorber, including packed, plate or spray towers. These absorbers are interchangeable to a considerable extent although certain specific conditions may favour one over the other.
In addition to conventional packed, plate or spray towers, specialised absorber towers have been developed to meet specific process requirements. Examples of these specific towers include impingement-plate scrubbers and turbulent contact scrubbers.
The process of the present invention may be carried out in either packed, plate or spray towers, or specialised towers developed to meet specific process requirements, and may contain other peripheral equipment as necessary for optimal process operation. Such peripheral equipment may include but is not limited to an inlet gas separator, a treated gas coalescer, a solvent flash tank, a particulate filter and a carbon bed purifier. The inlet gas flow rate varies according to the size of the equipment but is typically between 5 000 and 25 00 cubic metres per second. The solvent circulation rate is typically between 10 and 40 cubic metres per tonne of C02. The operating pressure of the absorber is typically between 1 and 100 atm with lower operating pressures being typical of post-combustion CO2 capture and higher operating pressures being typical of natural gas treatment and pre-combustion C02 capture.
In the process of the present invention, a gas stream containing C02 at or above atmospheric pressure is contacted with a compound of formula (I) at a temperature at or above ambient temperature, preferably between 30°C to 60°C, and more preferably between 35°C to 45°C to effect absorption of C02 from the gas stream. Optionally, corrosion inhibitors, scale inhibitors, antifoam agents and/or other additives known to those in the art that may assist in the CO2 capture process of the present invention may be employed The following examples are offered to illustrate but not to limit the present invention. Examples Example 1 Reductive Amination This method may be used for the synthesis of secondary or tertiary amine product from either (1) or (3) below.
Figure imgf000044_0001
(1) (2) (3) (4)
Sodium triacetoxyborohydride, Na(OAc>3BH (60 mmol) was added potionwise to a stirred solution of terf-butyl 4-oxopiperidine-1-carboxylate (1) or 1-Boc-:piperidine-4- carboxaldehyde (3) (30 mmol), acetic acid (30 mmole) and corresponding amine, RNH2 or RNHMe, (30 mmole) in dichloromethane (60 ml). The reaction was stirred under nitrogen at room temperature overnight. The reaction was then quenched by the careful addition of H20 or 1M NaOH (60 mL). The pH of the mixture was adjusted to basic (~pH 10) by the careful addition of solid NaOH and the mixture was stirred for 15-30 min. The organic phase was separated and the aqueous phase was extracted with dichloromethane (2 x 60mL). The combined organic phase was washed with H20 (2 x 60ml_) and dried by K2C03 or filtration through phase separation paper. Removal of the solvent under vacuum gave the product in excellent yield. NOTE - the amine hydrochloride salt may be used in the reaction. If the amine hydrochloride salt is used, one equivalent of triethylamine (Et3N) is used instead of acetic acid.
A detailed description of this method is provided in Ahmed F. Abdel-Magid, Kenneth G. Carson, Bruce D. Harris, Cynthia A. Maryanoff, and Rekha D'. Shah; Journal of Organic Chemistry, 1996, 61 (11) 3849-3862.
Example 2
Hvdroqenation
Figure imgf000045_0001
(3) (6)
The corresponding amine (30 mmol) was added to a solution of 1-Boc-piperidine-4- carboxaldehyde (3) (30 mmol) in EtOH (40 ml) followed by 10% Pd/C (50% in H20, 0.3 g). The reaction was processed under a hydrogen atmosphere (40 psi) at room temperature until gas uptake finished and reaction completed (-2-3 hours). The reaction mixture was filtered through celite and the filtrate was evaporated to dryness to give product (6) in excellent yield.
Note: The amine. HCI salt may be used in the reaction. When the amine HCf salt was used an equivalent amount of triethylamine was added . After the above work-up of the reaction, TEA.HCI salt was removed via a partition of dichloromethane-H20 followed by washing with 5% Na2C03. The organic phase was dried (phase separation paper filtration of K2CO3) and concentrated under vacuum to give the product.
«
A detailed description of this method is provided in WO 2007/018461. Example 3
Reductive Amination
The following synthesis of amines (5) and (4) start with amines (2) and (6). The synthesis of amine (2) is provided in Example 1 and the synthesis of amine (6) in Example 2.
Figure imgf000046_0001
(2) (5) (6) (4)
To a solution of amine (2 or 6) (30 mmole) in dichloromethane (200 mL) was added aqueous formaldehyde (37% in H2O, 12.2mL) followed by sodium triacetoxyborohydride (90 mmol) and AcOH (40 ml). The reaction mixture was stirred under N2 overnight at room temperature. The reaction was quenched by the addition of H2O or 1 M NaOH (100 mL). The pH of the mixture was adjusted to basic (~pH 10) by the careful addition of solid NaOH. The organic phase was separated and the aqueous phase was extracted with dichloromethane (2 x 60mL). The combined organic phase was washed with H2O (2 x 60mL) and dried by K2CO3 or a filtration through phase separation paper. Removal of the solvent under vacuum gave the product (5 or 4) in excellent yield.
A detailed description of this method is provided in Kazuhiro Yokoyama , Noriko Ishikawa, Susumu Igarashi, et al; Bioorganic & Medicinal Chemistry, 16 2008, 7968- 7974.
Example 4
Alkylation B
Figure imgf000047_0001
(7) (8)
Alkylbromide (49.5 mmol) was added to a stirred suspension of 4-(Boc-amino)- ' piperidine (7) (45mmol) and K2CO3 (264 mmol) in acetonitrile (450 ml). The reaction mixture was heated at reflux for 3 hours and then cooled to room temperature. K2CO3 was removed by filtration and the filtrate was concentrated under vacuum to dryness. The residue was dissolved in dichloromethane (90ml) and water (90mL) was added. The mixture was stirred and the pH of the mixture was adjusted to pH 10 with NaOH. The organic phase was separated and aqueous phase was extracted with dichloromethane (2 x 60mi_). The combined organic phase was washed with H2O (2 x 90ml) and dried by K2C03 or a filtration through phase separation paper. Removal of the solvent under vacuum gave product (8) in excellent yield.
Note: the reaction may use an alkylchloride rather than an alkylbromide. If an alkylchloride is used a small quantity of Kl was added. A detailed description of this method is provided in Tien Q. Pham, Ivan Greguric, Xiang Liu, Paula Berghofer, Patrice Ballantyne, Janette Chapman, Filomena Mattner, Branko Dikic, Timothy Jackson, Christian Loc'h, and Andrew Katsifis; Journal of Medicinal Chemistry, 2007, 50 (15), 3561-3572.
Example 5 Boc-Deprotection via ion-exchange resin
Amberlyst 15 resin was used in the Boc-deprotection. The amount of resin used was calculated based on the number of amino groups in the amine molecules. The ratio is 5:1 molar equivalents of resin to each amino-group in the product. Hence, this molar ratio is 10:1 in the case of diamines and 15:1 in the case of tri-amines. A very slow dropwise flow rate is critical in all operations involved in resin washing or rinsing to achieve complete deprotection and quantitative or near quantitative yield.
The Boc-protected amine (2, 4, 5, 6 or 8) was dissolved in an amount THF that is sufficient to just cover the resin and the solution was added to the resin. The mixture was heated at gentle reflux overnight without "stirring. An aliquot of supernatant was evaporate to dryness and analyse by 1H NMR to confirm all amine bound to resin. Resin was transferred to a glass column and drained, and then wash with 1 x bed volume of THF at a very slow flow rate.
The amine was released from the resin using 2M MeNH2/EtOH (33%, ~8M). An equal molar quantity of MeNH2 with respect to the resin loading was used. The resin was then washed with 1 bed volume of EtOH. In the case of aminoacid derivatives, alcohol was avoided and an aqueous Μβ3Ν Η20 solution (45%, ~7.6M) was used to release the amine followed by washing with H20 (1 bed volume). The combined filtrates were concentrated to dryness to yield the free amine. The resin was regenerated by washing with 3M HCI in MeOH/H20 (1 :1) (≥1eq with respect to resin), water (1-2 bed volumes) followed by MeOH (1 bed volume), and then dichloromethane (1 bed volume. The clean resin was finally dried under N2 or vacuum.
A detailed description of this method is provided in Yun-Shan Liu, Cunxiang Zhao, David E. Bergbreiter, and Daniel Romo; Journal of Organic Chemistry, 1998, 63, 3471- 3473.
Example 6
Figure imgf000048_0001
(10) (11) (12) Step 1
2-Hydroxyethylene bromide (9.1 ml, 128 mmol) was added to a solution of 4- aminopyridine (10) (10 g, 106 mmol) in toluene (260 ml). The reaction was heated at reflux for 3.5 hours with stirring and then cooled to room temperature. The formed oil became solid upon cooling. The suspension was filtered and the solid was washed with toluene. The product (11) (22.7 g) was obtained as a pale brown solid at 98% yield.
Note: An alkylchloride or an ω-hydroxy-alkyl chloride is also suitable as a replacement for the bromide compounds in this method.
Step 2 Metallic sodium (1.3 g, 56 mmol) was added slowly to cold MeOH (50 ml) with stirring under nitrogen. The prepared mixture of NaOMe/MeOH was transferred to the hydrogenation vessel and pyridium bromide salt (11) (11.1 g, 51 mmol) obtained from the above reaction was added to the reaction mixture followed by 5% rhodium on charcoal (1.1 g, 10% w/w). The reaction was processed under hydrogen atmosphere (140 psi) at 60°C overnight. The reaction mixture was filtered through Celite and washed with MeOH (100 ml_).
The filtrate was concentrated under vacuum to dryness to confirm complete recovery. The residue was redissolved in MeOH (150 ml_) and poured over Amberlyst 15 resin (106g, 50 mmol). The mixture was heated at gentle reflux without stirring overnight. The resin was transferred to a column and washed with MeOH (150 ml_). The amine was released from the resin by using 33% MeNH2/EtOH (63 mL, ~0.5mol) in EtOH (190 mL) and further washed with EtOH (150 mL). Removal of the solvent of the combined ethanolic fractions gave 5.04g of clear golden oil (69 %). Analysis of 1H and 23Na NMR showed the desired product (12) free from sodium salt. The product may also be collected by fractional distillation (collected at 122"C/1.0 mbar).
A detailed description of this method is provided in a) Gordon N. Walker, Miriam Ann Moore and Barbara N. Weaver; Journal of Organic Chemistry, 1961, 26 (8), 2740-2747; b) Tatsuya Ito, Tomomi Ikemoto, Yasushi Isogami, Hiroki Wada, Misayo Sera, Yukio Mizuno, and Mitsuhiro Wakimasu; Org. Proc. Res. Dev., 2002, 6 (3), 238-241 ; c) ASTRAZENECA AB, Patent: WO2009/35407 A1 , 2009; Location in patent: Page/Page column 10; 21.
Example 7
Synthesis of 4-amino-1 -piperidineethanol
Figure imgf000050_0001
4-(N-Boc aminoM-piperidineethanol 4-(N-Boc amino)*1-piperidine (10g, 50mmol), bromoethanol (7.1mL, lOOmmol) and K2CO3 (55.2g, 400mmol) in acetonitrile (200mL) were heated at reflux for 5h. The K2CO3 was filtered off and the acetonitrile was evaporated to dryness (reduced pressure). The resulting residue was dissolved in dichloromethane (100mL) and H2O (100mL) was added. The mixture was stirred vigorously and then the phases were allowed to separate, the pH of the aqueous phase was tested (>pH 10, adjust with potassium hydroxide if necessary). The aqueous phase was removed and extracted with dichloromethane (2 x 100mL). The combined organic phases were washed with H2O (2 x 100ml_) and sat. NaCI (lOOmL), dried over Na2S04, filtered and evaporated to dryness (reduced pressure). The product was purified by dry column vacuum chromatography (DCVC) (Pedersen et al.) eluting with methanol/dichloromethane/ethyl
^
acetate (2:9:9), to yield 7.1g of a golden oil (58% yield) which crystallised on standing to give off-white crystals. 1H IMMR (CDCI3, 400MHz) δ 4.43 (br s, 1 H), 3.58 (t, J=4.5, 2H), 3.48 (br s, 1 H), 2.90-2.78 (m, 2H), 2.51 (t, J=5.4, 2H), 2.24-2.12 (m, 2H), 1.99-1.88 (m, 2H), 1.44 (s, 9H), 1.44-1.35 (m, 2H, superimposed). 4-amino-1-piperidineethanol
The 4-(N-Boc amino)-1-piperidineethanol (13g, 53.2mmol) was treated with TFA (26mL) for 90mL The TFA was removed (reduced pressure) and the TFA salt was converted to the HCI salt by treatment with 20%HCI/methanol (130mL) at ambient temperature for 30min. The HCI/methanol was evaporated (reduced pressure) and the residue dissolved in H20 (10ml_). The solution was cooled in an ice-bath and NaOH (10 , 35ml_) added to pH >10. The solution was warmed to RT and stirred for 15min prior to evaporating to dryness. The residue was triturated with ether/isopropanol (2:1), filtered and evaporated to dryness. The trituration process was repeated until no salt was present in the oil (5x) to yield 6.7g (87%) of an off-white solid.
Example 8
Synthesis of 4-(2-ethanolamino)-piperidine
This method provides a specific example of the method of Example 1 and the method of Example 6.
Figure imgf000051_0001
1-Boc-4-piperidone
Triethylamine (19.2g, 190mmol) was added to a stirring solution of 4-piperidone monohydrate hydrochloride (20.0g, 131mmol) in methanol (300mL) and stirred for 5min. Boc20 (34g, 168mmol) was added in portions over a 5min period, followed by DMAP (0.4g, 3mmol). The solution was stirred at ambient temperature for 20h. The methanol was removed under reduced pressure and the crude was dissolved in dichloromethane (100mL). The organic phase was washed with HCI (2M, 2 x 70mL) sat. Na2C03 (70mL) and sat NaCI (50mL), dried over Na2S04, filtered and evaporated to dryness to yield 1- Boc-4-piperidone as a white solid in quantitative yield. 1H NMR (CDCI 3400m Hz) δ 3.71 (t, J=6.2Hz, 4H), 2.44 (t, J=6.2Hz, 4H), 1.49 (s, 9H).
4-(2-ethanolamino)-1-Boc-piperidine
Na(OAc)3BH (40.58g, 192mmol) was added slowly to a stirring solution of 1-Boc-4- piperidone (15.25g, 77mmol), ethanolamine (4.68g, 77mmol) and acetic acid (4.6g, 77mmol) in dichloromethane (150mL) cooled in a water bath under N2 and the solution was stirred at ambient temperature for 18h. The reaction was quenched by the careful addition of H20 (75mL) and the mixture stirred for 45min. The solution was basified to pH 10 by the careful addition of 25% NaOH (~150mL) and stirred a further 10min. The phases were allowed to separate and the organic phase was washed with H20 (150mL) and saturated NaCI (150mL), dried over Na2S04, filtered and evaporated to dryness to yield the target (17.49g, 94%) as a clear oil which crystallised on standing. 1H NMR (CDCI 3 400mHz) δ 4.02 (br s, 2H), 3.63 (tr, J=5.2Hz, 2H), 2.88-2.71 (m, 4H), 2.66-2.54 (m, 1H), 1.91-1.79 (m, 2H), 1.44 (s, 9H), 1.31-1.15 (m, 2H). 4-(2-ethanolamino)-piperidine
The 4-(2-ethanolamino)-1-Boc-piperidine (14g, 57.3mmol) was treated with TFA (28mL) • for 90mL. The TFA was removed (reduced pressure) and the TFA salt was converted to the HCI salt by treatment with 20% HCl/methanol (140mL, 280mmol HCI) at ambient temperature for 30min. The HCl/methanol was evaporated (reduced pressure) to yield a white solid in quantitative yield. 19F NMR (MeOD) confirmed complete conversion to the HCI salt.
The salt was dissolved in H20 (10mL) and cooled in an ice-bath. NaOH (10M, 35mL) was added to pH >10. The solution was warmed to RT and stirred for 15min prior to evaporating to dryness. The residue was triturated with ether/isopropanol(2:1), filtered and evaporated to dryness. The trituration process was repeated until no salt was present in the oil (5x) to yield 7.8g (95%) of a clear oil which solidified on standing. Example 9
The te|t results (shown in the accompanying figures) are a comparison of four compounds within general formula (I) with 4-aminopiperidine in terms of their C02 absorption at 40°C (Figure 2(a)) and C02 desorption at 90°C (Figure 2(b)). These absorption experiments were carried with CO2 gas (99%).
The compounds within the scope of Formula (I) used in this example are as follows:
Figure imgf000053_0001
As can be seen from the graphs shown in Figure 2(a), compounds 1 , 2 and 3 have higher capacities for C02 loading (200%, 180% and 180% on a mol% basis, respectively) than 4-aminopiperidine (155%). 4-Propylaminopiperidine (Compound 4) has a higher C02 loading in absorption than the result shown in Figure 2(a) Compound 4 formed a large quantity of bicarbonate solid during its C02 absorption, which was hot able to be measured by 13C NMR, hence, the real C02 loading was higher than that illustrated in Figure 2(a). As can be seen from Figure 2(a) compounds 1 to 4 have faster or at least similar reaction rates in absorption.
Compounds 1 to 4 also displayed better C02 release in desorption (Figure 2(b)). Compounds 1 to 3 desorbed more C02 (105%, 100% and 86% on a mol% basis, respectively) at moderate temperatures (90° C), than did 4-aminopiperidine (67%). Again, the desorption yield of Compound 4 could not be accurately measured due to the inability to accurately measure the C02 loading of the starting material.
The results above indicated that the compounds of Formula (I) may improve C02 capture capacity (C02 absorption and desorption) of known systems. The compounds exhibited a more efficient cycle of C02 absorption-desorption, which may lead to significantly lower the energy consumption in C02 capture.
These results were also compared with monoethanolamine (MEA) and piperizine (Pz) ■ for their CO2 absorption and desorption. MEA and Pz are commercially available amines used in industry for CO2 capture. Aqueous MEA is used as a C02 absorber due to its attractive CO2 loading capacity in g C02/g MEA whilst it's desorption is poor and high energy consumption is required. Pz was claimed widely as a promoter in C02 absorption by amines, but our study results showed that Pz carbamate was reasonably stable at 90°C, and this limited its capacity as a promoter in CO2 capture at lower energy consumption.
In Figure 3, CO2 absorption and desorption results for Compounds 1 to 4 and 4-amino- piperidine (2M and 1.7M in one case due to the material availability) were compared with MEA (4M) and piperazine (Pz) (2M). An MEA concentration of 4M was chosen in this comparison to match the total amine/nitrogen concentration of diamines (2x2M).
The results of C02 absorption at 4Q°C are displayed as a ratio of mole of CCVmole of amine (Figure 3(a)) and as a ratio of mole of CO2 /mole of nitrogen (Figure 3(c)). The results of desorption at 90°C are also displayed in the same two ways respectively in Figure 3(b) and Figure 3(d). Compounds 1 to 4 as a whole showed better reaction rates for C02 loading and C02 release in absorption and desorption. 1-ethanol-4- aminopiperidine (Compound 1), in particular, stood out during this comparison as shown by its highest loading in absorption and largest release of C02 in desorption. It also had the highest reaction rates in both reactions. Example 10
CO? absorption-desorption 1. Absorption
An amine solution (2M, 10 ml_) was added to a 50 ml jacketed 2-necked pear-shaped flask. The reaction solution was stirred, heated to and maintained at 40°C with a Ratek Thermoregulator thermostatted bath. The stirring speed, 900 rpm, was kept the same in all absorption and desorption experiments. A condenser was connected to the flask through a Claisen adapter, and an electronic thermometer introduced to monitor the temperature of the amine solution. Hydrated gas of 10% CO2 and 90% N2 was introduced to the amine solution through a PTFE tube (0.71 mm ID, 1.78 mm OD) at a total flow rate of 50 mL/min (controlled via a Bronkhorst High-Tech El-Flow mass flow controller). The loading was processed over night (18 hours). A sample was taken for NMR analysis.
The concentration of MEA used in experiment was 4M. This concentration provided same total concentration of amino-groups to that of 2M diamines.
2. Desorption
After the gas supply was removed, the C02-rich amine solution obtained from the above absorption was heated at a constant temperature of 90°C with a Ratek Themrioregulator thermostatted bath. Samples are taken from reaction for NMR analysis at reaction time of 2, 5, 10, 30 and 60 minutes.
3. General Method for quantitative 13C NMR analysis and data processing
NMR samples were placed into a 5 mm (178 mm long, 4.24 mm ID) NMR tube to a height of 40 mm then capped, and an external standard of 1,4-dioxane in a sealed · capillary was used in 13C NMR analysis (5c 67.18 ppm, calibrated against an external TMS/CDC solution). Relaxation times (7» of the carbon atoms in the reaction mixture were measured using the standard inversion recovery ("Null") method. The NMR analytical interscan recycle time was chosen as equal to 5*7 . NMR spectroscopy was performed at 25°C. The molar ratio of C02-loading to amine was calculated based on integration of carbonyl signals and amine aliphatic carbon signals. The weight loading figure then was calculated from molar ratio results. The accuracy of loadings determined in this manner was estimated to be ± 3% for amine concentrations of 4 M. The cyclic capacity is the calculated difference between the maximum and minimum CO2 loading in the process of absorption-desorption cycle.
4. pKa Calculations Software: SPARC Online Calculator version 4.6 - http://archemcalc.com/sparc/
Conditions: 25°C, 0 M ionic strength, aqueous solution. Table 1 - C02 sequestration in 10% C02 and 90% N2
Figure imgf000056_0001
Figure imgf000057_0001
b The pKa of any additional nitrogen in the R-group is given in brackets.
Example 10
This example provides 1H NMR data for examples of compounds of Formula (I).
Table2 1H NMR data
Figure imgf000057_0002
Figure imgf000058_0001
(CH2)2N(CH3 Ή NMR in d4- H NMR in d4- methanol methanol
3.02, 2H, d b, 5 3.00, 2H, m;
J13.1 Hz; 2.70, 2.66, 2H, t, J7.2
2H, t, J6.8 Hz; Hz; 2.55, 2H,
2.59-2.50, 2H, m; .7, 12.3 Hz, J22.l
2.43, 2H, t, J6.7 Hz; 2.47-2.42, 4H,
Hz; 2.23, 6H, s; m; 2.23, 6 H, s;
1.91-1.84, 2H, m; 1.71, 2H, d b
1.23, 2H, m. J13.0 Hz; 1.67- 1.54, 1H, m; 1.1 1,
2H. m.
References
1. Singh, P., Versteeg, G.F., Structure and activity relationships for C02 regeneration from aqueous amine-based absorbents, Process Safety Env. Prot, 2008, 86, 347-359.
2. Pedersen, D. S. and Rosenbohm, C, Synthesis, 2001 , 16, 2431-2434
It will be understood that the invention disclosed and defined in this specification extends to all alternative combinations of two or more of the individual features mentioned or evident from the1 text or drawings. All of these different combinations constitute various alternative aspects of the invention.

Claims

The claims defining the invention are as follows:
1. A process for the capture of C02 from gas streams, the process including contacting a C02 containing gas stream with a compound including:
a primary or non-sterically hindered secondary amine group and
at least one tertiary amine or sterically hindered secondary amine group;
wherein the primary or non-sterically hindered secondary amine and the nearest tertiary or sterically hindered secondary amine group are separated by a carbon chain including 3 or 4 carbon atoms and wherein the compound is a com ound of Formula (I)
Figure imgf000060_0001
wherein
R1 is represented by hydrogen, C2 to C6 alkanol or d to C6 alkyl;
R2 is represented by hydrogen, Ci to C6 alkyl, C2 to C6 alkanol, -(CH2)n-NR6R7, -(CH2)P- COOH, -(CH2)pCOOQ, -(CH2)p-heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
R3 and R5 are independently selected from hydrogen, Ci to C4 alkyl, C2 to C6 alkanol, -(CH2)n-NR8R9;
R4 is represented by hydrogen, Ci to C6 alkyl, C2 to C6 alkanol, -(CH2)n-NR6R7, -(CH2)P- COOH, -(CH2)PCOOQ, -(CH2)p-S03H, -(CH2)pS03Q, -(CH2)p-P03H2, -(CH2)pP03Qs, -(CH2)p-heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
x is O oM ;
n is 2 to 6;
p is 1 to 6;
Q is hydrogen, a metal ion or R 6R17R18R19N+; s is 1 or 2
R6 and R7 are independently selected from hydrogen, alkyl, alkanol, alkylamine or R6 and R7 together with the nitrogen atom to which they are attached form a ring structure
R8 and R9 are independently selected from d to C6 alkyl, C2 to C6 alkanol, C2 to C6 alkylamine, -(CH2)n-NR6R7, -(CH2)p-COOH, -(CH2)pCOOQ, -(CH2)P-S03H, -(CH2)pS03Q, -(CH2)p-P03H2, -(CH2)pP03Qs, or R8 and R9 together with the nitrogen atom to which they are attached form a ring structure; and
R16, R17, R18 and R19 are independently selected from hydrogen or alkyl;
with the proviso that when R4 is hydrogen, R1 and/or R2 is not hydrogen;
when R4 is not hydrogen, R and/or R2 is hydrogen;
when R4 and R1 are both hydrogen, R2 is not methyl; and
when R4 and R2 are both hydrogen, R is not methyl.
2. A process according to claim 1 wherein the compound is a compound of formula (I), wherein:
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -GH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
3. A process according to claim 2 wherein the compound is a compound of formula (I), wherein:
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH,
-(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH^ CCHzCH^S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
4. A process according to claim 2 wherein the compound is a compound of formula (I), wherein:
x is 0;
R1 is represented by hydrogen;
R2 is represented by hydrogen;
R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen.
5. A process according to claim 3 wherein the compound is a compound of formula (I), wherein: r
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH or -(CH2)2N(CH3)2; R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
6. A process according to claim 4 wherein the' compound is a compound of formula (I), wherein:
R1 is represented by hydrogen;
R2 is represented by hydrogen;
R3 is represented by hydrogen;
R4 is represented by -CH2CH3> -CH2CH2CH3) -(CH2)2OH, -(CH.2)3OH or -(CH2)6OH; and R5 is represented by hydrogen.
7. A process according to claim 2 wherein the compound is a compound of formula (I), wherein:
R is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3 or -(CH2)2N(CH3)2;
R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3 or -(CH2)2N(CH3)2; and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
8. A process according to claim 2 wherein the compound is selected from the group consisting of:
Figure imgf000064_0001
9. A process according to claim 2 wherein the compound is selected from the group consisting of:
Figure imgf000065_0001
10. A compound including:
a primary or non-sterically hindered secondary amine group and
at least one tertiary amine or a sterically hindered secondary amine group;
wherein the primary or non-sterically hindered secondary amine group and the nearest tertiary or sterically hindered secondary amine group are separated by a carbon chain including 3 or 4 carbon atoms; and
wherein the compound is a com ound of Formula (I):
Figure imgf000065_0002
wherein
R1 is represented by hydrogen, C2 to C6 alkanol or Ci to C6 alkyl;
R2 is represented by hydrogen, Ci to C6 alkyl, C2 to C6 alkanol, -(CH2)n-NR6R7, -(CH2)P- COOH, -(CH2)pCOOQ, -(CH2)pTheterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
R3 and R5 are independently selected from hydrogen, Ci to C4 alkyl, Ci to C4 alkanol, -(CH2)n-NR8R9 ;
R4 is represented by hydrogen, Ci to C6 alkyi, C2 to C6 alkanol, -(CH2)n-NR6R7, -(CH2)P- COOH, -(CH2)pCOOQ, -(CH2)p-S03H, -(CH2)pS03Q, -(CH2)p-P03H2, -(CH2)pP03Qs, -(CH2)p-heterocyclic ring containing one to four heteroatoms independently selected from nitrogen, oxygen and sulphur;
x is 0 or 1 ;
n is 2 to 6;
p is 1 to 6;
Q is hydrogen, a metal ion or R16R17R18R19N+;
s is 1 or 2;
R6 and R7 are independently selected from hydrogen, Ci to C6 alkyi, C2 to C6 alkanol, C2 to C6 alkylamine or R6 and R7 together with the nitrogen atom to which they are attached form a ring structure
R8 and R9 are independently selected from Ci to C6 alkyi, C2 to C6 alkanol, C2 to C6 alkylamine, -(CH2)n-NR6R7, -(CHzVCOOH, -(CH2)pCOOQ, -(CH2)p-S03H, -(CH2)pS03Q, -(CH2)p-P03H2, -(CH2)pP03Qs, or R8 and R9 together with the nitrogen atom to which they are attached form a ring structure;;
R 4 and R15 are independently selected from Ci to C6 alkyi, C2 to C6 alkanol, C2 to.Ce alkylamine or R14 and R15 together with the nitrogen atom to which they are attached form a ring structure; and
R16, R17, R18 and R19 are independently selected from hydrogen or alkyi;
with the proviso that when R4 is hydrogen, R and/or R2 is not hydrogen;
when R4 is not hydrogen, R1 and/or R2 is hydrogen;
when R4 and R1 are both hydrogen, R2 is not methyl; and
when R4 and R2 are both hydrogen, R is not methyl.
11. A compound according to claim 10, wherein in the compound of Formula (I) wherein: R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3) -(CH2)20H, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2 (CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
12. A process according to claim 11 wherein the compound is a compound of formula (I), wherein:
R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CH2COONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2N(CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole);
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
13. A compound according to claim 11 , wherein in the compound of Formula (I): x is 0;
R1 is represented by hydrogen; R2 is represented by hydrogen;
R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -CH2COOH, -CHzCOONa, -CH2COOK, -(CH2)2N(CH3)2,
-(CH2)2N(CH2CH2)20, -(CH2)2 (CH2CH2)2S, -CH2(5-imidazole) or -(CH2)2(5-imidazole); and
R5 is represented by hydrogen.
14. A compound according to claim 12, wherein in the compound of Formula (I): R1 is represented by hydrogen or Ci alkyl;
R2 is represented by -CH2CH3, -CH2CH2CH3l -(CH2)2OH, -(CH2)3OH, -(CH2)6OH, -GH2COOH or -(CH2)2N(CH3)2;
R3 is represented by hydrogen;
R4 is represented by hydrogen; and
R5 is represented by hydrogen.
15. A compound according to claim 13; wherein in the compound of Formula (I): R1 is represented by hydrogen;
R2 is represented by hydrogen;
R3 is represented by hydrogen;
R4 is represented by -CH2CH3, -CH2CH2CH3, -(CH2)2OH, -(CH2)3OH or -(CH2)6OH; and R5 is represented by hydrogen.
16. A compound according to claim 11 , wherein in the compound of Formula (I): R1 is represented by hydrogen or Ci alkyl;
R2 is represented by hydrogen, -CH2CH3, -CH2CH2CH3 or -(CH2)2N(CH3)2; R3 is represented by hydrogen;
R4 is represented by hydrogen, -CH2CH3> -CH2CH2CH3 or -(CH2)2N(CH3)2; and R5 is represented by hydrogen;
with the proviso that when R4 is hydrogen, R2 is not hydrogen;
when R2 is hydrogen, R4 is not hydrogen; and
when R2 is hydrogen, R1 is hydrogen and x is 0.
17. A compound according to claim 11 wherein the compound is selected from the group consisting of:
Figure imgf000069_0001
Figure imgf000069_0002
Figure imgf000069_0003
Figure imgf000070_0001
Figure imgf000070_0002
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AU2012245079B2 (en) 2013-09-05
CN103619816A (en) 2014-03-05
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AU2012245079A1 (en) 2013-01-24
US20140127103A1 (en) 2014-05-08
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