Compounds and their uses

Abstract

The present invention relates to a series of novel indigo-type structures, alizarin-type structures and anthraquinone-type structures comprising various substituents, and methods for their synthesis. In one aspect the invention provides a dye comprising one of novel structures. Embodiments of the present invention stem from the realization that it is possible to add pendant or functional groups to certain natural compounds, particularly indigo, alizarin and anthraquinone based compounds to improve their textile dyeing properties to be competitive with fossil fuel based dyes.

Description

Compounds and Their UsesFIELD OF INVENTION

[0001] The present invention relates to the field of chemical synthesis, particularly synthesis of dyestuffs.

[0002] In one form, the invention relates to novel compounds and methods for their synthesis.

[0003] In one particular aspect the compounds of the present invention are suitable for commercial production of dyes which can be applied to textile fibres.

[0004] It will be convenient to hereinafter describe the invention in relation to chemicals for use as dyes, however it should be appreciated that the present invention is not limited to that use only and the novel chemicals disclosed herein may have other uses, particularly other industrial applications.BACKGROUND ART

[0005] It is to be appreciated that any discussion of documents, devices, acts or knowledge in this specification is included to explain the context of the present invention. Further, the discussion throughout this specification comes about due to the realisation of the inventor and / or the identification of certain related art problems by the inventor. Moreover, any discussion of material such as documents, devices, acts or knowledge in this specification is included to explain the context of the invention in terms of the inventor’s knowledge and experience and, accordingly, any such discussion should not be taken as an admission that any of the material forms part of the prior art base or the common general knowledge in the relevant art in Australia, or elsewhere, on or before the priority date of the disclosure and claims herein.

[0006] Fabric dyes are substances that chemically bond to textile fibres. The colour of a dye is dependent on its ability to absorb light within the visible region of the electromagnetic spectrum (380-750 nm), which then excites valence pi-electrons inthe dye. The fabric dye may be used in conjunction with a mordant, which is a chemical that forms a coordination compound with the dye which then attaches to a fibre to improve the fastness of the dye on the fibre.

[0007] Dyeing of fabric or natural fibres dates back to the Neolithic period. Originally, dyes were obtained from animal, vegetable or mineral sources such as roots, berries, bark, leaves, wood, fungi and lichens and were used to colour fibre based materials such as threads, yarns or fabrics that were woven or knitted. Over the centuries the processes for dyeing fabric have become more and more complex as people sought to improve the lightfastness and colourfastness properties and the ability of the dye to bind with the materials they are absorbed into.

[0008] The colour of a fabric could be an important factor in its value. For example, in ancient times isolation of a small amount of royal purple dye (6,6’-dibromoindigo) required substantial human labour and consumed tens of thousands of Murex sea snails hence the dye was an expensive and highly valued symbol of status. Abundance and scarcity also affected the dyestuff market. Scarcity of dyestuffs often occurred when dyestuff crops were spoiled or diseased, and trade routes for relevant crops could be disrupted by wars, politics, piracy, weather, and even the availability of slaves.

[0009] However, in response to these problems, large-scale demand and technological improvements, most dyes used in the modern world are synthetically produced from substances such as petrochemicals. Synthesising dyes chemicals provides superior economy of scale, consistent colour, and superior fabric fastness. Synthetic fossil fuel based dyes currently comprise over 90% of all textile dyes. They are commonly based on benzene, ethylene and napthol derivatives which are then chemically modified to contain various pendant groups that facilitate their ability to bond with natural fibres (such as cotton, linen, cashmere, wool, silk, viscose, etc) or synthetic fibres (such as polyester, nylon, elastane, acrylic, spandex etc).

[0010] The change from natural to synthetic dyes was triggered by creation of the first synthetic dye, mauvine, a purple dye which was derived from aniline in coal tar by William Henry Perkin in 1856. The colour purple was particularly desirable because ithad been used as a mark of status and prestige since ancient times. Natural purple dyes were expensive and difficult and labour-intensive to extract and many lacked chemical and colour stability, or fastness. The synthetic version produced by Perkin was an immediate commercial success. Similar success followed for other dye colours.

[0011] The discovery of mauveine started a surge in synthetic dyes and in organic chemistry in general. Other aniline based dyes followed, such as fuchsine, safranine and induline and many thousands of other synthetic dyes have since been prepared.

[0012] In decades following Perkins’ discovery, synthetic dyes virtually replaced the natural dyes that had been used by the textile industry for centuries. In the nineteenth century the coal tar industry provided most of the precursors needed for large scale industrial synthesis of the dyes. The twentieth century saw further expansion of the dye industry with precursors principally provided by the petrochemical industry. Synthetic fossil fuel based dyes currently comprise over 90% of all textile dyes. They are most commonly based on benzene, ethylene and napthol derivatives which are chemically modified to contain various pendant groups that facilitate their ability to bond with natural plant or animal-based fibres (such as cotton, linen, cashmere, wool, silk, viscose) or synthetic fibres (such as polyester, nylon, elastane, acrylic, spandex).

[0013] The conventional uses of synthetic dyes over the past 180 years have created serious threat to global environment. In particular, their presence in textile effluents has polluted the environment and their toxic and non-biodegradable nature posed serious threats to soil fertility, crop production, and human health. Furthermore, fossil fuels are an increasingly scarce resource.

[0014] For these reasons, attempts have been made to find alternative building blocks for generating sustainable textile dyes. However, some alternative plant- derived dyes like indigo have the disadvantage of consuming significant areas of arable land. Some alternative dyes are microbially produced, but they suffer the disadvantage of not being as colourfast as synthetic dyes.

[0015] Accordingly, there is still a need for natural dyes that are at least competitive with fossil fuel-based dyes in terms of economy, environmentally acceptability and functionality. There is also a need to take advantage of the additional functional properties that natural dyes have over many synthetic dyes such as antimicrobial activity, UV protection, antioxidant qualities.SUMMARY OF INVENTION

[0016] An object of the present invention is to provide novel dyes based on natural compounds.

[0017] Another object is to provide alternative building blocks for generating sustainable textile dyes.

[0018] A further object of the present invention is to alleviate at least one disadvantage associated with the related art.

[0019] It is an object of the embodiments described herein to overcome or alleviate at least one of the above noted drawbacks of related art systems or to at least provide a useful alternative to related art systems.Indigo Dyes

[0020] In a first aspect of embodiments described herein there is provided a novel indigo compound represented by Formula INI:Formula INI wherein,where X is a halide and M is Li, Na or K;, or R1 and R2 together formwhere X is a halide;R3 and R6 are chosen from -H, CH3 ,-SO3H, -SO3M, where M is Li, Na or K;X where X is halide,R4 is chosen from -H, CH3 , -SO3H, -SO3M, where M is Li, Na or K; andR5 is chosen from X where X is halide,

[0021] In a preferred embodiment, Formula INI is chosen from:SUBSTITUTE SHEET (RULE ™R1 and R2 together formR3 is chosen from -H, CH3, or -SOsNa; andR4 is chosen from - H, CH3, or -SOsNa.

[0023] Products according to the present invention may be synthesised by the reaction of a natural dye such as indigo or a natural indigo derivative with a structure having a highly reactive functional group. Suitable natural indigo derivatives include structures such as 5,5’-indigodisulphonic acid sodium salt (indigo carmine) which is derived from indigo by aromatic sulphonation. Without wishing to be bound by theory the functional group reacts with the nucleophilic functional groups of textile fibres by Michael addition, typically forming a covalent ether bond.

[0024] In a second aspect of embodiments described herein there is provided a novel indigo compound, which is the product of the reaction of indigo or an indigo derivative with vinyl sulphone or a vinyl sulphone derivative.

[0025] For example, the novel indigo compound could be the product of a reaction of indigo or an indigo derivative such as indigo carmine, leuco indigo, indigo sulphonate, indigoidine, indole, indoxyl, tyrian purple and indigo carboxylic acid with 2-haloethane sulphonyl halide such as 2-chlorethane sulphonyl chloride

[0026] In another aspect of embodiments described herein there is provided a novel indigo compound, which is the product of the reaction of indigo or an indigo derivative such as indigo carmine with a halogenated propionyl structure such as 2,3- dibromopropionyl chloride

[0027] In another aspect of embodiments described herein there is provided a novel indigo compound, which is the product of the reaction of indigo or an indigo derivative such as indigo carmine with vinyl sulphone parabase ester (2-[(4- aminophenyl)sulphonyl]ethyl hydrogen sulphate)

[0028] The novel indigo compounds of the present invention may be used in further reactions leading to further novel indigo compounds.Alizarin Dyes

[0029] In a first aspect of embodiments described herein there is provided a novel alizarin compound represented by Formula ALI:Formula ALI wherein,R1 is chosen from -OH,, where X is a halide, and Z is chosen from a halide, or an unsaturated aliphatic group, or a sulphonic acid group;where X is a halide, and Z is chosen from a halide, an unsaturated aliphatic group, or a sulphonic acid group;R3 is chosen fromalkali metal, andR4 is chosen fromis a halide.

[0030] In a preferred embodiment,R1 is chosen from -OH, -SO3CHCH2, or -SO3CH2CH2Z;R2 is chosen from -OH, -SO3CHCH2, -SO3CH2CH2Z;R3 is chosen from -H, -SO3H, or -CH2N(CH2COOH)2, andR4 is =0 where Z is chosen from a chemical structure containing a halide or an unsaturated aliphatic group.

[0031] In a particularly preferred embodiment, Formula AL1 is chosen from:

[0032] Products, according to the present invention, may be synthesised by the reaction of a natural dye such as alizarin or a natural alizarin derivative with a structure having a highly reactive functional group. Suitable natural alizarin derivatives include structures such as 3,4-dihydroxy-9,10-dihydroanthracene-2-sulphonic acid (also known as Alizarin Red S) or its alkali metal salt (such as, for example, Alizarin Red S Sodium) or 3,4-dihydroxyanthraquinin-2-yl-methylimino-diacetic acid (also known as Alizarin Complexone or Alizarin Fluorine Blue). Without wishing to be bound by theory, the functional group reacts with the nucleophilic functional groups of textile fibres by Michael addition, typically forming a covalent ether bond.

[0033] In a second aspect of the embodiments described herein, there is provided a novel alizarin compound, which is the product of the reaction of alizarin or an alizarin derivative with a vinyl sulphone derivative.

[0034] For example, the novel alizarin compound could be the product of a reaction of alizarin or an alizarin derivative with 3-halopropanesulphonyl halide such as 3- chlorpropanesulphonyl chloride

[0035] In another aspect of the embodiments described herein, there is provided a novel alizarin compound, which is the product of the reaction of alizarin or an alizarin derivative with a halotriazine, preferably chlorotriazine (cyanuric chloride).

[0036] In another aspect of embodiments described herein there is provided a novel alizarin compound, which is the product of the reaction of alizarin or an alizarin derivative with a halogenated propanoic acid such as 2,3-dibromochloropropanoic acid

[0037] In another aspect of embodiments described herein there is provided a novel alizarin compound, which is the product of the reaction of alizarin or an alizarin derivative with vinyl sulphone parabase ester (2-[(4-aminophenyl)sulphonyl]ethyl hydrogen sulphate)Anthraquinone Dyes

[0038] In a preferred embodiment the novel compound formed is of FormulaZ is chosen from an aromatic group or a heteroarene group, aliphatic group;chosen from an aromatic group, a heteroarene group or an aliphatic group and X is a halogen;R3 is chosen from -H, -OH,, -SO3H or -SO3M where M is an alkali metal;R4, R5 and R8 are independently chosen from -H or -OH;R6 is H; andR7 is -H or

[0039] In a preferred embodiment, for anthraquinone compound of Formula ANI:Cl, Br or I; and M is Li, Na or K;R3 is chosen from -H,alkali metal; andR4 to R8 are all H.

[0040] Preferably, the novel compound of Formula ANI is chosen from the following structures:

[0041] The person skilled in the art will appreciate that double bonds can be included in various positions in the ring structures. With respect to the ring structures, the carbon atoms in the chemical structure of Formula ANI are implied to be located at the corners. Hydrogen atoms attached to carbon atoms are not indicated, except to indicate an aspect of the stereochemistry of the structure - each carbon atom is considered to be associated with enough hydrogen atoms to provide the carbon atom with four bonds.

[0042] In a preferred embodiment of the present invention the sulphone is chosen from the group comprising Formula ANII:R’ is chosen fromwhere X is a halide and M is an alkali metal.

[0043] Preferably the sulphone is chosen from the group comprising 2-chlor-ethanesulphonyl halidexor ethenesulphonyl halideor vinyl sulphone (where preferably the halide is a chloride), parabase ester (vinyl sulphone base, or (2-[(4-aminophenyl)sulphonyl]ethyl hydrogen sulphate)

[0044] The novel anthraquinone compound could be, for example, the product of a reaction of an anthraquinone with n-halo based sulphonyl halide such as 2- chlorethane sulphonyl chloride

[0045] In another aspect of embodiments described herein there is provided a novel anthraquinone compound, which is the product of the reaction of an anthraquinone with vinyl sulphone parabase ester (2-[(4-aminophenyl)sulphonyl]ethyl hydrogen sulphate)

[0046] In another aspect of embodiments described herein there is provided a novel anthraquinone compound, which is the product of the reaction of an anthraquinone with a pyrimethanil derivative, or more preferably a sulphonyl substituted anilazine derivative such as sodium 2-((4-((4,6-dichloro-1 ,3,5-triazin-2- yl)amino)phenyl)sulfonyl)ethyl sulfate

[0047] In another aspect of embodiments described herein there is provided a dye comprising any one of the aforementioned novel derivatives.

[0048] In a further aspect of embodiments described herein there is provided a method of dyeing comprising the step of contacting any one of the aforementioned novel compounds with fibre to be dyed.

[0049] The fibres may be natural or synthetic and may be spun or unspun. Spun fibres may be part of a yarn that is woven, knitted or bonded into fabric. For example,the method may comprise the step of contacting one of the aforementioned novel compounds with fibres, yarn or fabric comprising silk, cotton, linen, viscose / rayon, wool, acrylic, nylon, polyester, polypropylene / olefin / polyolefin, hemp, regenerated cellulose fibres (such as products sold under the trade mark Tencel) or combinations thereof.

[0050] Other aspects and preferred forms are disclosed in the specification and / or defined in the appended claims, forming a part of the description of the invention.

[0051] In essence, embodiments of the present invention stem from the realization that it is possible to add pendant / functional groups to natural chemicals to improve their textile dyeing properties to be competitive with fossil fuel based dyes.

[0052] Advantages provided by the present invention comprise the following:• Improved binding to textile fibres, resulting in improved characteristics such as colourfastness (rub fastness, wash fastness, lightfastness etc), dye exhaustion, colour depth, hue, vibrance and evenness of dyeing.• Provision of a more eco-friendly dyeing process, saving on usage of chemicals during dyeing, usage of water usage, and wasting of time due to less post dyeing wash steps being required.

[0053] Further scope of applicability of embodiments of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the disclosure herein will become apparent to those skilled in the art from this detailed description.DETAILED DESCRIPTIONIndigo Dyes

[0054] Natural indigo is an ancient dye that has been used since at least the third millennium BC. It is derived from the Isatis tinctoria plant (also known as woad) or the leaves of the Indigofera plant by an arduous and time consuming process. Productionof indigo dye is an arduous process making it relatively expensive and time consuming to isolate from plants.

[0055] By the 19thcentury, natural indigo production could no longer meet the demands of the clothing industry as large amounts started to be consumed, for example, for the large-scale commercial production of blue jeans or blue denim. In 1865, Adolf von Baeyer, a German chemist, began working on the synthesis of indigo. His first synthesis of indigo in 1878 was from the synthetic compound isatin, and his second synthesis in 1880 was from 2-nitrobenzaldehyde. It was not until 1883 that Baeyer determined the structure of indigo. In 1905, Baeyer won the Nobel prize in chemistry for his work on organic dyes including indigo. In 1897 Hoechst and BASF patented and launched their own version of synthetic indigo.

[0056] By 1914, use of synthetic indigo had almost completely replaced the use of naturally derived indigo. Today synthetic indigo is manufactured from raw materials obtained from the petrochemical industry.

[0057] The benzene rings in indigo can be modified to give a variety of derivatives. Replacing the two NH groups of indigo with S atoms provides thioindigo, which is a deep red dye. Natural tyrian purple dye was highly prized in antiquity and was isolated from secretions of a common Mediterranean snail. In 1909 it was identified as a mixture of 6,6'-dibromoindigo (red) and 6-bromoindigo (purple) but it has never been produced on a commercial basis. The related compound 5,7,5',7'-tetrabromoindigo (Ciba blue) is, however, of commercial value.

[0058] Reaction of indigo with sulfuric acid creates a dark blue-green derivative called indigo carmine (3,3’-dioxo-2,2’-bis-indolyden-5,5’-disulphonic acid disodium salt). Indigo carmine became available in the mid-18th century and today it is used as a colorant for food, pharmaceuticals, and cosmetics.

[0059] Today, fabric such as denim is solely dyed with synthetic indigo because its colour saturation, colourfastness and purity (which affects shade consistency) are far superior to natural indigo. Denim woven from yarn dyed with natural indigo has more colour variation including a distinctive green cast. However natural dyes tend to have better functional properties (antimicrobial, UV protective, antioxidant etc) compared with synthetic dyes. The present invention combines the best features from both synthetic and natural dyes by adding the pendant / functional groups to the natural dye structure.

[0060] The present invention is based on the natural indigo-type structure which can be used as a dye, to which pendant / functional groups have been added.

[0061] In a first aspect of embodiments described herein there is provided a novel indigo compound represented by Formula INI:Formula INI wherein,a halide and M is Li, Na or K;R3 is chosen from -H, CH3 , -SO3H, -SO3M, where M is Li, Na or K; X whereX is halide,R4 is chosen from -H, CH3 , -SO3H, -SO3M, where M is Li, Na or K; andR5 is chosen from X where X is halide,Indigo Examples

[0062] The invention will be further described with reference to the following nonlimiting examples.

[0063] Preferred novel structures according to the present invention are listed in the following Tables (TABLE IN1 and TABLE IN2). The table also lists the principal reactants used to prepare the novel structures and includes a summary of the reaction steps.

[0064] TABLE IN1

[0066] The invention will be further described with reference to the following nonlimiting examples.General information with respect to synthesis

[0067] All evaporations were carried out in vacuo with a rotary evaporator. Analytical samples were dried in vacuo (1 -5 mmHg) at rt. Thin layer chromatography (TLC) was performed on silica gel plates, spots were visualized by UV light (214 and 254 nm). Purification by column and flash chromatography was carried out using silica gel (200-300 mesh). Solvent systems are reported as mixtures by volume. All NMR spectra were recorded on a Bruker 400 (400 MHz) spectrometer. 1 H chemical shifts are reported in 5 values in ppm with the deuterated solvent as the internal standard. Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, br = broad, m = multiplet), coupling constant (Hz), integration. LCMS spectra were obtained on an Agilent 1200 series 61 10 or 6120 mass spectrometer with electrospray ionization and excepted as otherwise indicated, the general LCMS condition was as follows: Waters X Bridge C18 column (50 mm x 4.6 mm x 3.5 urn), Flow Rate: 2.0 mL / min, the column temperature: 40 °C.Synthetic Routes

[0068] The following are illustrative synthetic routes for preparing the compounds listed in Table IN1 :

[0069] Synthetic route for Indigo TM-A

[0070] Synthetic route for Indigo TM-C

[0071] Synthetic route for Indigo TM-Dindigo Carmine lndigo-TM-0

[0072] Synthetic route for Indigo Carmine TM-B

[0073] Synthetic route for Indigo Carmine TM-D

[0074] Synthetic route for Indigo Carmine TM-F

[0075] Synthetic route for Indigo Carmine TM-E

[0077] Synthetic route for IN12

[0079] Synthetic route for IN14

[0080] Synthetic route for IN15

[0082] Synthetic route for IN17

[0084] Synthetic route for IN19

[0085] Synthetic route for IN20

[0087] Synthetic route for IN22Specific Examples

[0088] The following are illustrative preparations for selected compounds listed inTable IN1 :Compound IN2

[0089] Synthetic route for Indigo-TM-B

[0090] Synthetic route for lndigo-TM-B-1

[0091] A mixture of Indigo (2.62 g, 10.0 mmol) and CS2CO3 (7.80 g, 24.0 mmol) in DMF (60 mL) was stirred at 60°C for 1 hr. To the mixture was added 2- (bromomethyl)oxirane (1.37 g, 10.0 mmol), then the mixture was stirred at 80°C for 1 hr. After consumption of starting material, the mixture was diluted by water (200 mL)with stirring and filterer by suction to give a solid. The solid was washed by water and dried to give TM-B-1 (2.0 g, 62.9% yield) as blue solid.

[0092] LC-MS m / z: 319.2[M+1 ]+; LCMS purity (214 nm): 59.20%; tR = 1.514 min.

[0093] The synthesis of Indigo-TM-B

[0094] To a solution of TM-B-1 (1 .40 g, 4.40 mmol) and TEA (2.23 g, 22.0 mmol) in DCM (100 mL) was added 2-chloroethanesulfonyl chloride (1 .79 g, 1 1 .0 mmol) dropwise at room temperature, then the mixture was stirred at room temperature for 2 hr. After consumption of starting material, the mixture was concentrated under reduced pressure and purified by column chromatography on silica gel (eluting with 80% EtOAc in hexane) to give Indigo-TM-B (1 .0 g, 55% yield) as purple solid.

[0095] 1 H NMR (400 MHz, DMSO-d6) δ 7.65-7.59 (m, 4H), 7.37 (dd, J = 8.0, 4.0Hz, 2H), 7.07-7.03 (m, 2H), 6.84 (dd, J = 16.4, 10.0 Hz, 1 H), 6.20 (d, J = 16.8 Hz, 1 H), 6.15 (d, J = 10.0 Hz, 1 H), 5.14 (dd, J = 9.6, 6.0 Hz, 1 H), 4.49 (d, J = 12.0 Hz, 1 H), 4.38 (dd, J = 10.4, 6.0 Hz, 1 H), 4.23 (dd, J = 10.8, 6.4 Hz, 1 H), 3.81 (dd, J = 12.4, 4.0 Hz, 1 H).

[0096] LC-MS m / z: 409.0[M+1 ]+; LCMS purity (214 nm): 78.61 %; tR = 1 .798 minCompound IN7

[0097] Synthetic route for Indigo Carmine TM-CIndigo TM-B-1

[0099] A mixture of Indigo (2.62 g, 10.0 mmol) and CS2CO3 (7.80 g, 24.0 mmol) in DMF (60 mL) was stirred at 60°C for 1 hr. To the mixture was added 2- (bromomethyl)oxirane (1 .37 g, 10.0 mmol), then the mixture was stirred at 80°C for 1 hr. After consumption of starting material, the mixture was diluted by water (200 mL) with stirring and filterer by suction to give a solid. The solid was washed by water and dried to give TM-B-1 (2.0 g, 62.9% yield) as blue solid.

[0100] LC-MS m / z: 319.2[M+1 ]+; LCMS purity (214 nm): 59.20%; tR = 1.514 min. 1 H NMR (400 MHz, DMSO-d6) δ 12.66 (s, 1 H), 8.27-8.20 (m, 2H), 7.99-7.97 (m, 2H), 7.85 (d, J = 8.4 Hz, 1 H), 7.78 (d, J = 8.4 Hz, 1 H), 7.29 (dd, J = 16.4, 9.6 Hz, 1 H), 6.47- 6.38 (m, 2H).

[0101] LC-MS m / z: 331 .0[M+1 ]+; LCMS purity (254 nm): 97.05%; tR = 2.1 18 min.

[0102] The synthesis of Indigo-TM-B

[0103] To a solution of TM-B-1 (1 .40 g, 4.40 mmol) and TEA (2.23 g, 22.0 mmol) in DCM (100 mL) was added 2-chloroethanesulfonyl chloride (1 .79 g, 1 1 .0 mmol) dropwise at room temperature, then the mixture was stirred at room temperature for 2 hr. After consumption of starting material, the mixture was concentrated under reduced pressure and purified by column chromatography on silica gel (eluting with 80% EtOAc in hexane) to give Indigo-TM-B (1 .0 g, 55% yield) as purple solid.

[0104] 1 H NMR (400 MHz, DMSO-d6) δ 7.65-7.59 (m, 4H), 7.37 (dd, J = 8.0, 4.0 Hz, 2H), 7.07-7.03 (m, 2H), 6.84 (dd, J = 16.4, 10.0 Hz, 1 H), 6.20 (d, J = 16.8 Hz, 1 H), 6.15 (d, J = 10.0 Hz, 1 H), 5.14 (dd, J = 9.6, 6.0 Hz, 1 H), 4.49 (d, J = 12.0 Hz, 1 H), 4.38 (dd, J = 10.4, 6.0 Hz, 1 H), 4.23 (dd, J = 10.8, 6.4 Hz, 1 H), 3.81 (dd, J = 12.4, 4.0 Hz, 1 H).

[0105] LC-MS m / z: 409.0[M+1 ]+; LCMS purity (214 nm): 78.61 %; tR = 1 .798 min.

[0106] Synthetic route for Indigo Carmine

[0107] Synthetic route for Indigo Carmine TM-A

[0108] Synthetic route for lndigo-TM-B-1indigo IMB-1

[0109] A mixture of Indigo (2.62 g, 10.0 mmol) and CS2CO3 (7.80 g, 24.0 mmol) in DMF (60 mL) was stirred at 60°C for 1 hr. To the mixture was added 2- (bromomethyl)oxirane (1.37 g, 10.0 mmol), then the mixture was stirred at 80°C for 1 hr. After consumption of starting material, the mixture was diluted by water (200 mL) with stirring and filterer by suction to give a solid. The solid was washed by water and dried to give TM-B-1 (2.0 g, 62.9% yield) as blue solid.

[0110] LC-MS m / z: 319.2[M+1 ]+; LCMS purity (214 nm): 59.20%; tR = 1.514 min.

[0111] Synthesis of Indigo Carmine TM-AIndigo Carmine-B-1 Indigo Carmine-TM-A

[0112] Indigo and CS2CO3 in DMF were stirred at 60°C for 1 hr. Thereafter, 2- (bromomethyl)oxirane was added and the mixture stirred at 80°C for 1 hr. In the next step triethylamine in DCM was added with 2-chloroethanesulfonyl chloride at the solution stirred at room temperature overnight.Indigo Product TestingDyeing conditions

[0113] Dyes according to the present invention were tested on swatches of cotton griege, silk and nylon (82% mix with spandex) that had been prepared for dyeing. Theswatches were kept in contact with a solution of the dye for 60 minutes at 60°C (without the presence of salt). Antioxidant (0.1 -10wt%) and soda ash (approx. 0.3g / l) as were added to raise the pH to 10.

[0114] The dyeing solution consisted of the dye (Compound 2) at 1 % WOF (weight of fibre), that is, 1 gm dye to 100 gms fibre. The liquor (water) to fibre ratio was between 1 :10 and 1 :20. A post fixing agent was applied for 20 minutes at 55 °C.

[0115] TABLE IN2 sets out a comparison of the results of dyeing each swatch by material using synthetic indigo dye of the prior art, against swatches dyed using the above method.

[0116] The dye testing outlined above was repeated for dyeing solutions consisting of from about 0.1 % and about 20% WOF and the results were found to be substantially the same as set out in TABLE IN2. Preferably the WOF for dyeing using dyes of the present invention is 0.1 -10% WOF, more preferably 0.1 -5%WOF, even more preferably 0.1 -1 % WOF. The person skilled in the art will appreciate that the other important step is fixing, and the dyeing results were found to be similar across a range of common fixing regimes.

[0117] TABLE IN2:* Fastness scale (wash and rub) - 1 -10 from poor to excellent.** Depth of colour scale - 1 -10 from light to dark.

[0118] The appearance of wash water post-dyeing (during the 2nd wash step) shows the Compound IN2 indigo dye has improved fibre binding ability, reducing the amount of unbound dye, compared to an equivalent indigo dye of the prior art. The wash water left after dyeing the swatches with indigo dye of the prior art was more turbid with unbound dye than the wash water left after dyeing the swatches with Compound IN2 of the present invention. Compared with an equivalent indigo dye of the prior art, the indigo dye of the present invention can dye silk, nylon, wool and cotton using eco-friendly dyeing conditions and can completely remove the need to use hydrosulphite for reduction and can instead use sugar for the reduction step.Anthraquinone Dyes

[0119] Anthraquinones (also known as anthracenediones, anthraquinoids or dioxoanthracenes) are phenolic compounds. The structure is based on the 9,10- anthraquinone skeleton with carbonyl groups at the 9 and 10 positions.

[0120] Anthraquinones are naturally occurring and can be found in plants such as senna, rhubarb, fungi, lichen, bacteria and some insects. Anthraquinone itself is colourless, but introduction of electron donor groups such as hydroxy or amino groups onto the anthraquinone ring system can produce dyes ranging from red, through violet to blue and green.

[0121] The name “anthraquinone” was first used by German chemists Graebe and Liebermann in 1868 in a publication describing the chemical synthesis of the red dye alizarin from anthracene, a component of coal tar. Natural alizarin was one of the first colorants to have its structure determined, and one of the first to be synthesised and patented by Graebe and Liebermann 1868. The synthesis comprised the steps of dibromination of anthraquinone, followed by fusion with sodium hydroxide. Another much cheaper synthesis was developed in 1869 by Graebe, Liebermann and Caroand comprised the steps of treating anthraquinone with fuming sulphuric acid, followed by sodium hydroxide and potassium chlorate.

[0122] The progression to industrial production of alizarin led to further research in anthraquinone chemistry. Synthesis of anthraquinone dyes is principally based on sulphonation of anthraquinone to form anthraquinone sulphonic acid, or nitration of anthraquinone to form nitroanthraquinone.

[0123] Vinyl sulphone groups are often included in dye structures as a reactive group that bonds covalently to fibres as a so-called, “reactive hook”. The fabric fibre first dyestuffs with a [2-(sulphooxy)ethyl]sulfonyl group were patented in 1949 by Farbwerke Hoechst. From the early 1980s onwards, reactive dyes containing a monochlorotriazine anchor in addition to the vinylsulfone reactive group were produced by the dye manufacturers Sumitomo and Hoechst AG. In 1988, Ciba-Geigy introduced double anchor dyes with a combination of a vinylsulfone reactive group and a monofluorotriazine reactive group under the brand name Cibacron™.

[0124] Since then many vinylsulphone intermediates and reactive dyes have been created such as those described in Indian patent 2802 / MUM / 2009.

[0125] In a first aspect of embodiments described herein there is provided a novel compound formed by the reaction of an anthraquinone with a sulphone, preferably a vinyl sulphone.

[0126] Preferably the novel compound formed by reaction of an anthraquinone with a sulphone is of Formula ANI:Formula ANI whereinZ is chosen from an aromatic group or a heteroarene group, aliphatic group;an aromatic group, a heteroarene group, or an aliphatic group and X is a halogen;R3 is chosen from -H, -OH,, -SO3H or -SO3M where M is an alkali metal;R4, R5 and R8 are independently chosen from -H or -OH;R6 is H; andR7 is -H or

[0127] The person skilled in the art will appreciate that double bonds can be included in various positions in the ring structures. With respect to the ring structures, the carbon atoms in the chemical structure of Formula ANI are implied to be located at the corners. Hydrogen atoms attached to carbon atoms are not indicated, except to indicate an aspect of the stereochemistry of the structure - each carbon atom is considered to be associated with enough hydrogen atoms to provide the carbon atom with four bonds.

[0128] Preferably the novel compound of Formula ANI is chosen from the following structures:

[0129] Preferably the novel compound is formed by the addition of a sulphone to a solution of an anthraquinone in common solvents such as dichloromethane (DCM) and triethylamine (TEA) at zero degrees to room temperature.Anthraquinone Examples

[0130] The invention will be further described with reference to the following nonlimiting examples.

[0131] Preferred novel structures according to the present invention are listed in the following Table AN1 . The table also lists the principal reactants used to prepare the novel structures and includes a summary of the reaction steps.General information with respect to synthesis

[0133] All evaporations were carried out in vacuo with a rotary evaporator. Analytical samples were dried in vacuo (1 -5 mmHg) at rt. Thin layer chromatography (TLC) was performed on silica gel plates, spots were visualized by UV light (214 and 254 nm). Purification by column and flash chromatography was carried out using silica gel (200-300 mesh). Solvent systems are reported as mixtures by volume. All NMR spectra were recorded on a Bruker 400 (400 MHz) spectrometer.1H chemical shifts are reported in 5 values in ppm with the deuterated solvent as the internal standard. Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, br = broad, m = multiplet), coupling constant (Hz), integration. LCMS spectra were obtained on an Agilent 1200 series 61 10 or 6120 mass spectrometer with electrospray ionization and excepted as otherwise indicated, the general LCMS condition was as follows: Waters X Bridge C18 column (50 mm x 4.6 mm x 3.5 urn), Flow Rate: 2.0 mL / min, the column temperature: 40 °C.Compound AN1

[0134] Synthetic route for Alizarin-TM-AAteirm A&zariBiJMA

[0135] To a solution of Alizarin (10.0 g, 41 .62 mmol) and TEA (1 1 .6 mL, 83.25 mmol) in DCM (200 mL), 2-chloroethanesulfonyl chloride (8.14 g, 49.95 mmol) was added dropwise at 0°C. Then, the mixture was stirred at room temperature overnight. After consumption of the starting material, the mixture was concentrated under reduced pressure and purified by column chromatography on silica gel (eluting 20% EtOAc in hexane) to give Alizarin-TM-A (4.85 g, 35% yield) as a yellow solid.

[0136] 1H NMR (400 MHz, DMSO-cfe) 6 12.66 (s, 1 H), 8.27-8.20 (m, 2H), 7.99-7.97 (m, 2H), 7.85 (d, J= 8.4 Hz, 1 H), 7.78 (d, J= 8.4 Hz, 1 H), 7.29 (dd, J= 16.4, 9.6 Hz, 1 H), 6.47- 6.38 (m, 2H).

[0137] LC-MS m / z: 331 .0[M+1 ]+; LCMS purity (254 nm): 97.05%; tR = 2.1 18 min.Compound AN2

[0138] The synthesis of Alizarin-TM-B

[0139] To a solution of Alizarin (31 .32 g, 130.0 mmol) and TEA (52.62 g, 520.0 mmol) in DCM (500 mL), 2-chloroethanesulfonyl chloride (35.5 mL, 325.0 mmol) was added at 0 °C. Then, the mixture was stirred at room temperature for 2 d. After consumption of the starting material, the mixture was concentrated under reduced pressure and purified by column chromatography on silica gel (eluting 25 to 30% EtOAc in hexane) to give Alizarin- TM-B (13.7 g, 25% yield) as a yellow solid.

[0140] 1H NMR (400 MHz, CDCI3-d) δ 8.40 (d, J= 8.4 Hz, 1 H), 8.31 -8.27 (m, 2H), 7.93 (d, J= 8.4 Hz, 1 H), 7.85-7.82 (m, 2H), 7.19 (dd, J= 16.4, 10.0 Hz, 1 H), 6.88 (dd, J = 16.4, 10.0 Hz, 1 H), 6.58-6.44 (m, 2H), 6.32-6.25 (m, 2H).

[0141] LC-MS m / z: 438[M+18]+; LCMS purity (214 nm): 100%; tR = 2.097 minCompound AN7

[0142] Scheme 1 : Synthetic route for Alizarin Complexon-TM-A.Alizarin Complexon Alizarin Complexon-TM-AThe synthesis of Alizarin Complexon-TM-A

[0143] To a mixture of Alizarin Complexon (Compound 1 , 1 .0 g, 2.59 mmol) and K2CO3 (1 .43 g, 10.36 mmol) in 1 ,4-dioxane (30 mL), 2-chloroethanesulfonyl chloride (0.42 g, 2.59 mmol) was added at rt. The mixture was stirred at rt overnight. After the consumption of the starting material, the mixture was diluted with water (100 mL) and acidified with 1 mol / L HCI aqueous solution to pH 6~7 with stirring. The mixture was filtered by suction, and the yellow solid was collected and dried to give Alizarin Complexon-TM-A (240 mg, 19.4% yield).

[0144] LC-MS m / z: 473.2[M-1] +; LCMS purity (254 nm): 46.12%; tR = 1 .344 minCompound AN16

[0145] The synthesis of Alizarin Red S-TM-CAlizarin Red-S-TM-C Alizarin Red 5

[0146] To a solution of Alizarin Red S (1.0 g, 2.92 mmol) in DCM (40 mL), 2- chloroethanesulfonyl chloride (1.19 g, 7.30 mmol) and TEA (2.36 g, 23.36 mmol) was added. Then, the mixture was stirred at rt overnight. After consumption of the starting material, the mixture was evaporated under reduced pressure, diluted with water (200 mL), acidified with 1 mol / L HCI aqueous solution and extracted with EtOAc (50 mL x3). The organic extract was evaporated under reduced pressure to give Alizarin Red S-TM-C (350 mg, 23.9% yield)

[0147] LC-MS m / z: 499.0[M-1] +; LCMS purity (254 nm): 72.41 %; tR = 1 .475 minAnthraquinone Product TestingDyeing conditions

[0148] Dyes according to the present invention were tested on swatches of cotton greige, silk and nylon (82% mix with spandex) that had been prepared for dyeing. The swatches were kept in contact with a solution of the dye for 60 min at 60°C (without the presence of salt). Antioxidant (0.1 -10 wt%) and soda ash (approx. ,0.3g / L) were added to raise the pH to 10.

[0149] The dyeing solution consisted of the dye (Compound AN2) at 1 % WOF (weight of fibre), that is, 1 gm dye to 100 gms fibre. The liquor (water) to fibre ratio was between 1 :10 and 1 :20. A post fixing agent was applied for 20 minutes at 55 °C.

[0150] TABLE AN2 sets out a comparison of the results of dyeing each swatch by material using synthetic indigo dye of the prior art, against swatches dyed using the above method. Compared with an equivalent dye of the prior art, the dyes of the present invention can dye silk, nylon, wool and cotton using eco-friendly dyeing conditions and can completely remove the need to use hydrosulphite for reduction and can instead use sugar for the reduction step.

[0151] The dye testing outlined above was repeated for dyeing solutions consisting of from about 0.1 % and about 20% WOF and the results were found to be substantially the same as set out in TABLE AN2. Preferably the WOF for dyeing using dyes of the present invention is 0.1 -10% WOF, more preferably 0.1 -5%WOF, even more preferably 0.1 -1 % WOF. The person skilled in the art will appreciate that the other important step is fixing, and the dyeing results were found to be similar across a range of common fixing regimes.TABLE AN2:* Fastness scale (wash and rub) - 1 -10 from poor to excellent.** Depth of colour scale - 1 -10 from light to dark.Alizarin Dyes

[0152] Natural alizarin was one of the first colourants to have its structure determined, and one of the first to be synthesised and patented by Graebe and Liebermann 1868. The synthesis comprised the steps of dibromination of anthraquinone, followed by fusion with sodium hydroxide. Another much cheaper synthesis was developed in 1869 by Graebe, Liebermann and Caro and comprised the steps of treating anthraquinone with fuming sulphuric acid, followed by sodium hydroxide and potassium chlorate.

[0153] The present invention is based on the natural alizarin-type structure, which can be used as a dye, to which pendant / functional groups have been added.

[0154] In the past, functional groups have been added to synthetic dyes derived from coal tar or petroleum-derived compounds. For example, vinyl sulphone reactive anchors have been introduced into synthetic dyes via an aromatic or aliphatic amine. A well-known reactive anchor is vinyl sulphone parabase ester, which is aniline substituted with a [2- (sulphoxy)ethyl]sulphonyl group. The first dyes with a [2-(sulphoxy)ethyl]sulphonyl group were patented in 1949 by Farbwerke Hoechst. Vinyl sulphone parabase ester has been used as a diazo component in the preparation of azo dyes. Another known reaction is the condensation or parabase ester with a chlorine or fluorotriazine residue, which can be linked to any chromophore via a further amino group. From the 1980s onwards reactive dyes containing a monochlortriazine anchor and the vinylsulphone reactive group were produced by Sumitomo and Hoechst AG. Other substituents have been added to the aromatic ring such as hydroxy, methyl and methoxy groups.. Ortho, meta and parasubstitution by vinyl sulfone anilines have also been used.

[0155] The vinyl sulfone group can also be introduced via a primary or secondary aliphatic amine, by condensation with a halotriazine compound. For example 2-[2-(2- chlorethylsulfonyl)ethoxy]ethanamine has been used in bifunctional reactive dyes in combination with a monofluoro or monochlorotriazine hook. In 1988 Ciba-Geigy developed double anchor dyes having a combination of vinylsulphone reactive group and a monofluorotriazine reactive group.

[0156] Alizarin (madder complex) has been used as a natural textile dye for hundreds of years. Naturally derived dyes of the prior art such as alizarin are generally not as colourfast as synthetic dyes, however natural dyes tend to have better functional properties (antimicrobial, UV protective, antioxidant etc) compared with synthetic dyes. The present invention combines the best features from both synthetic and natural dyes by adding the pendant / functional groups to the natural dye structure.

[0157] In a first aspect of embodiments described herein there is provided a novel alizarin compound represented by Formula ALI:Formula ALI wherein,R1 is chosen from -OH,where X is a halide, and Z is chosen from an aliphatic group, halide, or a sulphonic acid group;where X is a halide and Z is chosen from an unsaturated aliphatic group, a halide, or a sulphonic acid group;R4 is chosen fromhalide.EXAMPLES

[0158] The invention will be further described with reference to the following nonlimiting examples.

[0159] Preferred novel structures according to the present invention are listed in the following Table AL1 . The table also lists the principal reactants used to prepare the novel structures and includes a summary of the reaction steps.

[0160] Table AL1:General information with respect to synthesis

[0161] All evaporations were conducted under a vacuum using a rotary evaporator. Analytical samples were dried under vacuum (1 -5 mmHg) at room temperature. Thin- layer chromatography (TLC) was performed on silica gel plates, and spots were visualised under UV light (214 and 254 nm). Purification by column and flash chromatography was carried out using silica gel (200-300 mesh). Solvent systems are reported as mixtures by volume. All NMR spectra were recorded on a Bruker 400 (400 MHz) spectrometer.1H chemical shifts are reported in 5 values in ppm with the deuterated solvent as the internal standard. Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, br = broad, m = multiplet), coupling constant (Hz), integration. LCMS spectra were obtained on an Agilent 1200 series 6110 or 6120 mass spectrometer with electrospray ionisation and excepted as otherwise indicated, the general LCMS conditions were as follows: Waters X Bridge C18 column (50 mm x 4.6 mm x 3.5 urn), Flow Rate: 2.0 mL / min, column temperature: 40 °C.Compound AL1

[0162] Synthetic route for Alizarin-TM-A (1 -hydroxy-9,10-dioxo-9,10-dihydro- anthracen-2-yl ethenesulfonate)

[0163] To a solution of Alizarin (1 ,2-dihydroxyanthracene-9, 10-dione, 10.0 g, 41.62 mmol) and triethylamine (TEA, 11.6 mL, 83.25 mmol) in dichloromethane (DCM, 200 mL), 2-chloroethanesulfonyl chloride (8.14 g, 49.95 mmol) was added dropwise at 0°C, followed by stirring the mixture at room temperature overnight. After the consumption of the starting material, the mixture was concentrated under reduced pressure and purified by column chromatography on silica gel (eluting with 20% ethyl acetate (EtAc) in hexane) to yield Alizarin-TM-A (1 -hydroxy-9,10-dioxo-9,10-dihydroanthracen-2-yl ethenesulfonate, 4.85 g, 35% yield) as a yellow solid.

[0164] 1H NMR (400 MHz, DMSO-cfe, 298 K) 6 12.66 (s, 1 H), 8.27-8.20 (m, 2H), 7.99-7.97 (m, 2H), 7.85 (d, J = 8.4 Hz, 1 H), 7.78 (d, J = 8.4 Hz, 1 H), 7.29 (dd, J = 16.4, 9.6 Hz, 1 H), 6.47-6.38 (m, 2H).

[0165] LC-ESI-MS (m / z): calcd. for [Ci6Hio06S] 330.02, found 331 .0[M+H]+

[0166] LCMS purity (254 nm): 97.05%; tR = 2.1 18 min.Compound AL2

[0167] Synthetic route for Alizarin-TM-B (9,10-dioxo-9,10-dihydroanthracene-1 ,2- diyl diethenesulfonate)

[0168] To a solution of Alizarin (1 ,2-dihydroxyanthracene-9, 10-dione, 31.32 g, 130.0 mmol) and EtaN (52.62 g, 520.0 mmol) in DCM (500 mL), 2-chloroethane sulfonyl chloride (35.5 mL, 325.0 mmol) was added at 0 °C, followed by stirring the mixture at room temperature for 2 days. After consumption of the starting material, the mixture was concentrated under reduced pressure and purified by column chromatography on silica gel (eluting with 25 to 30% EtAc in hexane) to yield Alizarin- TM-B (9,10-dioxo-9,10-dihydroanthracene-1 ,2-diyl diethenesulfonate, 13.7 g, 25% yield) as a yellow solid.

[0169] 1H NMR (400 MHz, CDCI3-d) 298 K) 5 8.40 (d, J = 8.4 Hz, 1 H), 8.31-8.27 (m, 2H), 7.93 (d, J= 8.4 Hz, 1 H), 7.85-7.82 (m, 2H), 7.19 (dd, J = 16.4, 10.0 Hz, 1 H), 6.88 (dd, J= 16.4, 10.0 Hz, 1 H), 6.58-6.44 (m, 2H), 6.32-6.25 (m, 2H).

[0170] LC-ESI-MS (m / z): calcd. for [C18H12O8S2] 420.00, found 438[M+18]+

[0171] LCMS purity (214 nm): 100%; tR = 2.097 minCompound AL3

[0172] Synthetic route for Alizarin-TM-C (2-((4,6-dichloro-1 ,3,5-triazin-2-yl)oxy)-1 - hydroxyanthracene-9,10-dione)

[0173] A mixture of Alizarin (1 ,2-dihydroxyanthracene-9, 10-dione, 2.40 g, 10.0 mmol) and K2CO3 (1.52 g, 1 1.0 mmol) in 1 , 4-dioxane (100 mL) was stirred at room temperature for 30 min. To the mixture, 2,4,6-trichloro-1 ,3,5-triazine (1.84 g, 10.0 mmol) was added portionwise, then the mixture was stirred at room temperature for 2 h. After consumption of the starting material, the mixture was diluted with water (300 mL), acidified with 2 mol / L HCI aqueous solution, and filtered by suction to yield a yellow solid. The yellow solid was washed with water and dried to give Alizarin-TM-C (2-((4,6-dichloro-1 ,3, 5-triazin-2-yl)oxy)-1 -hydroxyanthracene-9, 10-dione, 3.32 g, 85% yield) as a yellow solid.

[0174] LC-ESI-MS (m / z): calcd. for [C17H7CI2N3O4] 386.98, found 388.0[M+H]+

[0175] LCMS purity (254 nm): 58.03%; tR = 1 .976 minCompound AL4

[0176] Synthetic route for Alizarin-TM-D (1 ,2-bis((4,6-dichloro-1 ,3,5-triazin-2- yl)oxy)anthracene-9,10-dione)

[0177] A mixture of Alizarin (1 ,2-dihydroxyanthracene-9, 10-dione, 2.40 g, 10.0 mmol) and K2CO3 (3.04 g, 22.0 mmol) in 1 ,4-dioxane (100 mL) was stirred at room temperature for 30 min. To the mixture, 2,4,6-trichloro-1 ,3,5-triazine (3.69 g, 20.0 mmol) was added portionwise, then the mixture was stirred at room temperature overnight. After consumption of the starting material, the mixture was diluted with water (300 mL), acidified with 2 mol / L HCI aqueous solution and filtered by suction to yield a yellow solid. The yellow solid was washed with water and dried to give Alizarin- TM-D (1 ,2-bis((4,6-dichloro-1 , 3, 5-triazin-2-yl)oxy)anthracene-9, 10-dione, 3.36 g, 62.7% yield) as a yellow solid.

[0178] LC-ESI-MS (m / z): calcd. for ^oHeBrCkNeCU] 533.92, found 534.8[M+H]+

[0179] LCMS purity (254 nm): 70.55%; tR = 2.41 1 minCompound AL7

[0180] Synthetic route for Alizarin Complexon-TM-A (2,2'-((4-hydroxy-9,10-dioxo-3-((vinylsulfonyl)oxy)-9,10-dihydroanthracen-2-yl)azanediyl)diacetic acid).

[0181] To a mixture of Alizarin Complexon (Compound 1 , 1.0 g, 2.59 mmol) and K2CO3 (1.43 g, 10.36 mmol) in 1 ,4-dioxane (30 mL), 2-chloroethanesulfonyl chloride (0.42 g, 2.59 mmol) was added at room temperature, and the mixture was stirred at the same temperature overnight. After consumption of the starting material, themixture was diluted with water (100 mL) and acidified with 1 mol / L aqueous HCI solution to pH 6~7 with stirring. The mixture was filtered by suction, and the yellow solid was collected and dried to give Alizarin Complexon-TM-A (240 mg, 19.4% yield).

[0182] LC-ESI-MS m / z: calcd. for [C20H15NO10S] 461.04, found 473.2[M-1] +

[0183] LCMS purity (254 nm): 46.12%; tR = 1 .344 minCompound ALM

[0184] Synthetic route for Alizarin Red S-TM-A (sodium 3,4-bis((2- bromoacryloyl)oxy)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate).

[0185] To a solution of Alizarin-Red S (sodium 3,4-dihydroxy-9,10-dioxo-9,10- dihydroanthracene-2-sulfonate, or 3,4-dihydroxy-9,10-dihydroanthracene-2-sulphonic acid (or a salt thereof) 1 .0 g, 2.92 mmol) and 2,3-dibromopropanoyl chloride (1 .46 g, 5.84 mmol) in dichloromethane (30 mL), triethylamine (2.36 g, 23.86 mmol) was added, and the mixture was stirred at room temperature overnight. After consumption of the starting material, the mixture was evaporated, diluted with water (50 mL) and extracted with ethyl acetate (50 mL x 2). The organic extract was washed with brine (50 mL), dried over anhydrous Na2SCU, and evaporated under reduced pressure to yield Alizarin Red S-TM-A (370 mg, 21 .6% yield) as a dark purple solid.

[0186] LC-ESI-MS (m / z): calcd. for [C2oH9Br209S]- 582.83, found 584.8[M+2H]+;

[0187] LCMS purity (254 nm): 56.97%; tR = 1 .785 minCompound AL16

[0188] Synthesis of Alizarin Red S-TM-C (sodium 9,10-dioxo-3,4- bis((vinylsulfonyl)oxy)-9,10-dihydroanthracene-2-sulfonate)

[0189] To a solution of Alizarin Red S (sodium 3,4-dihydroxy-9,10-dioxo-9,10- dihydroanthracene-2-sulfonate, 1.0 g, 2.92 mmol) in dichloromethane (40 mL), 2- chloroethanesulfonyl chloride (1.19 g, 7.30 mmol) and triethylamine (2.36 g, 23.36 mmol) was added, then the mixture was stirred at room temperature overnight. After consumption of the starting material, the mixture was evaporated under reduced pressure, diluted with water (200 mL), acidified with 1 mol / L HCI aqueous solution and extracted with ethyl acetate (50 mL x3). The organic extract was evaporated under reduced pressure to give Alizarin Red S-TM-C (sodium 9,10-dioxo-3,4- bis((vinylsulfonyl)oxy)-9,10-dihydroanthracene-2-sulfonate, 350 mg, 23.9% yield) as an orange solid.

[0190] LC-ESI-MS (m / z): calcd. for [C18H11O11S3]- 498.95, found 499.0 [M-1 ]+;

[0191] LCMS purity (254 nm): 72.41 %; tR = 1.475 minAlizarin Product TestingDyeing conditions

[0192] Dyes according to the present invention were tested on swatches of cotton griege, silk and nylon (82% mix with spandex) that had been prepared for dyeing. The swatches were kept in contact with a solution of the dye for 60 min at 60 °C (without the presence of salt). Antioxidant (0.1 -10 wt%) and soda ash (approx. 0.3g / L) were added to raise the pH to 10.

[0193] The dyeing solution consisted of the dye (Compound 2) at 1 % WOF (weight of fibre), that is, 1 g dye to 100 g fibre. The liquor (water) to fibre ratio was between 1 :10 and 1 :20. A post fixing agent was applied for 20 min at 55 °C.

[0194] TABLE AL2 sets out a comparison of the results of dyeing each swatch by material using synthetic indigo dye of the prior art, against swatches dyed using the above method. Compared with an equivalent dye of the prior art, the dyes of the present invention can dye silk, nylon, wool and cotton using eco-friendly dyeing conditions and can completely remove the need to use hydrosulphite for reduction and can instead use sugar for the reduction step.

[0195] The dye testing outlined above was repeated for dyeing solutions consisting of from about 0.1 % and about 20% WOF and the results were found to be substantially the same as set out in TABLE AL2. Preferably the WOF for dyeing using dyes of the present invention is 0.1 -10% WOF, more preferably 0.1 -5% WOF, even more preferably 0.1 -1 % WOF. The person skilled in the art will appreciate that the other important step is fixing, and the dyeing results were found to be similar across a range of common fixing regimes.

[0196] TABLE AL2:Fastness scale (wash and rub) - 1 -10 from poor to excellent.Depth of colour scale - 1 -10 from light to dark.

[0197] While this invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modification(s). This application is intended to cover any variations uses or adaptations of the invention following in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth.

[0198] As the present invention may be embodied in several forms without departing from the spirit of the essential characteristics of the invention, it should be understood that the above described embodiments are not to limit the present invention unless otherwise specified, but rather should be construed broadly within the spirit and scope of the invention as defined in the appended claims. The described embodiments are to be considered in all respects as illustrative only and not restrictive.

[0199] Various modifications and equivalent arrangements are intended to be included within the spirit and scope of the invention and appended claims. Therefore, the specific embodiments are to be understood to be illustrative of the many ways in which the principles of the present invention may be practiced. In the following claims, means-plus-function clauses are intended to cover structures as performing the defined function and not only structural equivalents, but also equivalent structures.

[0200] When a Markush group or other grouping is used herein, all individual members of the group and all combinations and sub-combinations possible of the group members are intended to be individually included in the disclosure. Every combination of components described or exemplified herein can be used to practice the invention, unless otherwise stated.

[0201] Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. It will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein.

[0202] As used herein, "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of excludes any element, step, or ingredient not specified in the claim element. As used herein, "consisting essentially of does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. The broad term "comprising" is intended to encompass the narrower "consisting essentially of and the even narrower "consisting of." Thus, in any recitation herein of a phrase "comprising one or more claim element" (e.g., "comprising A), the phrase is intended to encompass the narrower, for example, "consisting essentially of A" and "consisting of A". Thus, the broader word "comprising" is intended to provide specific support in each use herein for either "consisting essentially of or "consisting of." The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.

[0203] One of ordinary skill in the art will appreciate that materials and methods, other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such materials and methods are intended to be included in this invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by examples, preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

[0204] Each of the references cited herein is incorporated by reference herein in their entirety. Such references may provide sources of materials; alternative materials, details of methods, as well as additional uses of the invention.

Claims

CLAIMSThe claims defining the invention are as follows:1 . A novel indigo compound represented by Formula INI: a novel indigo compound represented by Formula INI:where X is a halide and M is Li, Na or K;where X is a halide and M is Li, Na or K;here X is a halide;R3 and R6 are chosen from -H, -CH3, -SO3H, -SO3M, where M is Li, Na or K;X where X is halide,R4 is chosen from -H, -CH3, -SO3H, -SO3M, where M is Li, Na or K; andR5 is chosen from X where X is halide,2. An indigo compound according to claim 1 , wherein Formula IN1 is:

3. An indigo compound according to claim 1 wherein:,R1 and R2 together fR3 is chosen from -H, -CH3, or -SOsNa; andR4 is chosen from - H, -CH3, or -SOsNa.

4. A novel indigo compound of claim 1 , which is the product of the reaction of indigo or an indigo derivative with a vinyl sulphone derivative, preferably a 2- haloethanesulphonyl halide.

5. A novel indigo compound of claim 1 , which is the product of the reaction of indigo or an indigo derivative, preferably an indigo carmine with a 2- haloethanesulphonyl halide, preferably 2-chloroethanesulphonyl chloride.

6. A novel indigo compound of claim 1 , which is the product of the reaction of indigo or an indigo derivative, preferably as indigo carmine with a halogenated propionyl structure, preferably 2,3-dibromopropionyl chloride7. A novel indigo compound of claim 1 , which is the product of the reaction of which is the product of the reaction of indigo or an indigo derivative, preferably indigo carmine with vinyl sulphone parabase ester (2-[(4-aminophenyl)sulphonyl]ethyl hydrogen sulphate)8. A novel compound of Formula ANI:whereinZ is chosen from an aromatic group or a heteroarene group, aliphatic group;a halide, M is an alkali metal, Z is chosen from an aromatic group, a heteroarene group or an aliphatic group and X is a halogen;R3 is chosen from -H, -OH,, -SO3H or -SO3M where M is an alkali metal;R4, R5 and R8 are independently chosen from -H or -OH;R6 is H; and9. A novel compound according to claim 8 wherein:where Cl, Br or I; and M is Li, Na or K.R4 to R8 are all H.

10. A compound according to claim 8, wherein Formula AN1 is chosen from the group comprising:

11. A novel anthraquinone compound of claim 8 which is the product of a reaction of anthraquinone or an anthraquinone derivative with a 2-haloehane sulphonyl halide12. A novel anthraquinone compound of claim 8 which is the product of a reaction of anthraquinone or an anthraquinone derivative with vinyl sulphone parabase ester (2-[(4-aminophenyl)sulphonyl]ethyl hydrogen sulphate)13. A novel anthraquinone compound of claim 8 which is the product of a reaction of anthraquinone or an anthraquinone derivative with14. A novel anthraquinone compound of claim 8 which is the product of a reaction of anthraquinone or an anthraquinone derivative with a sulphonyl substituted anilazine derivative.

15. An alizarin compound represented by Formula ALI:Formula ALI wherein,where X is a halide, and Z is chosen from an unsaturated aliphatic group, a halide or a sulphonic acid group;where X is a halide, and Z is chosen from an unsaturated aliphatic group, a halide or a sulphonic acid group;R3 is chosen fromalkali metal, andR4 is chosen fromis a halide.

16. An alizarin compound, according to claim 15, wherein:R1 is chosen from -OH, -SO3CHCH2 or SO3CH2CH2Z;R2 is chosen from -OH, -SO3CHCH2 or SO3CH2CH2Z;R3 is chosen from -H, -SO3H, or -CH2N(CH2COOH)2, andR4 is =0 where Z is chosen from an unsaturated aliphatic group, or a sulphonic acid group.

17. An alizarin compound according to claim 15 wherein Formula ALI is chosen from the group comprising:

18. A novel alizarin compound of claim 15, which is the product of the reaction of alizarin or an alizarin derivative with a vinyl sulphone derivative, preferably n-halo based sulphonyl halide such as 3-chlorpropane sulphonyl chloride.

19. A novel alizarin compound of claim 15, which is the product of the reaction of alizarin or an alizarin derivative with a halotriazine, preferably chlorotriazine (cyanuric chloride).

20. A novel alizarin compound of claim 15, which is the product of the reaction of alizarin or an alizarin derivative with a halogenated propanoic acid such as 2,3- dibromochloropropanoic acid.21 . A novel alizarin compound of claim 15, which is the product of the reaction of alizarin or an alizarin derivative with vinyl sulphone parabase ester (2-[(4- aminophenyl)sulphonyl]ethyl hydrogen sulphate).

22. A novel alizarin compound of claim 15, which is the product of the reaction of alizarin or an alizarin derivative with23. A dye comprising a novel compound of any one of the preceding claims.

24. A method of dyeing comprising the step of contacting a novel compound of any one of claims 1 , 8 or 15 with a fibre, yarn or fabric.

25. A method according to claim 24 wherein the fibre, yarn or fabric comprises one or more of silk, cotton, linen, viscose / rayon, wool, acrylic, nylon, polyester, polypropylene / olefin / polyolefin, hemp, regenerated cellulose fibres or combinations thereof.

Images