WO2012088182A2

WO2012088182A2 - 2,4,5-triaminothiophenols and related compounds

Info

Publication number: WO2012088182A2
Application number: PCT/US2011/066297
Authority: WO
Inventors: Rajiv Dhawan; Joachim C. Ritter; David J. Rodini
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2010-12-20
Filing date: 2011-12-20
Publication date: 2012-06-28
Also published as: WO2012088182A3

Abstract

New triaminothiophenol compositions and related compounds are disclosed, as are processes for their preparation and for the preparation of novel salts and diacid complexes from such compounds. Polymers prepared from these compositions can be made into high strength fiber, film, and tape and are useful in applications such as protective apparel, aircraft, automotive components, personal electronics, and sports equipment.

Description

TITLE

2,4, 5-TRIAMINOTHIOPHENOLS AND RELATED COMPOUNDS

FIELD OF DISCLOSURE

The disclosure relates to new compositions based on 2 , , 5-triaminothiophenols, which are then used in the manufacture of high-performance heterocyclic aromatic polymers.

BACKGROUND

Aromatic amines and phenols are useful as monomers for high performance polymers such as aramid polymers and polybenzarenazoles . The structure of the specific monomer used greatly impacts polymer

properties such as tenacity, solubility, and also the rheological behavior of the polymer during processing such as spinning. It is thought that replacing highly symmetric monomers that are currently used (e.g., 2, 3, 5, 6-tetraaminopyridine) with asymmetric monomers would increase the solubility of the corresponding polymers and the ease with which they are processed., However, such monomers are often difficult to

synthesize or are unknown and have not been

synthesized .

There is a need for a commercially viable process to produce high purity asymmetric monomers that can be used in the production of high performance polymers such as aramid polymers and heterocyclic aromatic polymers.

DESCRIPTION

The following description is exemplary and explanatory only and is not restrictive of the invention, as defined in the appended claims.

The disclosures herein include processes fo the preparation of triaminothiophenols and related compounds. Novel compositions of matter are also disclosed .

In the context of this disclosure, a number of terms shall be utilized.

As used herein, the term "free base," as applied to a triaminothiophenol, is used to denote a triaminothiophenol compound per se, for example, Formula (I)

to distinguish it from the acid salt of a

triaminothiophenol or a complex of the

triaminothiophenol with a diacid.

As used herein, the term "triaminothiophenol salt" or "[specific triaminothiophenol name or formula reference] salt," e.g., "Formula (II) salt" or "TATHIO salt" where TATHIO means 2, , 5-triaminothiophenol, denotes a compound formed by reaction of a

triaminothiophenol with "n" equivalents of an acid ("A") such as HC1, acetic acid, H₂S0₄, or H₃PO . One example of a triaminothiophenol salt is TATHIO- 2HC1 (n=2, A=HC1) . The salt may also be a hydrate; one such example is TATHIO · 3HC1 · xH₂0. The acid name may also be incorporated into the name of the salt, so that, e.g., TATHIO · nHCl can be referred to as "2,4,5- triaminothiophenol hydrochloride salt" or "TATHIO hydrochloride." Where n is known, it can be

incorporated as well; for example, TATHIO- 3HC1 can also be referred to as "2 , , 5-triaminothiophenol

trihydrochloride salt" or "TATHIO trihydrochloride . "

As used herein, the term "triaminothiophenol complex" or "[specific triaminothiophenol name] [diacid source name] complex denotes a compound formed by reaction of a triaminothiophenol with a diacid source. Where the complex is to be used as a monomer in a polymerization,, it can also be referred to as a

"monomer complex." One example of a triaminothiophenol complex is TATHIO · TA, wherein "TATHIO" is 2,4,5- triaminothiophenol and "TA" is terephthalic acid.

As used herein the term "diacid source" refers to the diacid HOOC-Q-COOH itself, a disodium salt of HOOC-Q-COOH, a dipotassium salt of HOOC-Q-COOH, or mixtures thereof, wherein Q is a C& to C20

substituted or unsubstituted monocyclic or polycyclic aromatic nucleus.

As used herein, the term "XYTA" denotes 2-X-

5-Y-terephthalic acid, where X and Y are each

independently selected from the group consisting of H, OH, SH, SO₃H, methyl, ethyl, F, CI, and Br. One example is 2, 5-dihydroxyterephthalic acid ("DHTA") , in which X=Y=OH. The disodium or dipotassium salt of the XYTA diacid can be represented by the term "M₂XYTA" where M is Na or K.

As used herein, the term "oleum" denotes fuming sulfuric acid, which is anhydrous and is formed by dissolving excess sulfur trioxide (SO3) into sulfuric acid.

As used herein, the term "weak base" denotes a base having a base dissociation constant (also referred to as "ionization constant") K_b that is less than 1 at 25°C. Some examples are acetate ion CH3COO^", ammonia, and bicarbonate ion, HCO₃ ^" .

As used herein, the term "net yield" of P denotes the actual, in-hand yield, i.e., the

theoretical maximum yield minus losses incurred in the course of activities such as isolating, handling, drying, and the like.

As used herein, the term "purity" denotes what percentage of an in-hand, isolated sample is actually the specified substance.

As used herein, the term "alkyl" is used to denote a univalent group derived from an alkane by removing a hydrogen atom from any carbon atom: -C_nH?.n i i where n ≥ 1; as used herein, the term "alkyl" includes both substituted and unsubstituted groups.

As used herein, the term "aryl" is used to denote a univalent group whose free bonding site is to a carbon atom of an aromatic ring; as used herein, the term "aryl" includes both substituted and unsubstituted groups. An example is the "phenyl" group, i.e.", the CeHs radical shown below:

As used herein, the term "aralkyl" denotes a alkyl group which bears an aryl group; as used herein, the term "aralkyl" includes both substituted and unsubstituted groups. One such example is the benzyl group, i.e., the C7H7 radical shown below,

As used herein, the term "alkaryl" denotes an aryl group which bears an alkyl group; as used herein, the term "alkaryl" includes both substituted and unsubstituted groups. One example of an alkaryl group is the 4-methylphenyl radical, C7H7, shown below:

As used herein, the term "heteroaryl" denotes a univalent group derived from a heteroarene by removing a hydrogen atom from any ring atom; as used herein, the term "heteroaryl" includes both substituted and unsubstituted groups. A heteroarene is a

heterocyclic compound formally derived from an arene by replacement of one or more methine (-C=) and/or vinylene (-CH=CH-) groups by trivalent or divalent heteroatoms respectively in such a way as to retain its aromaticity .

In one embodiment of this invention, new compositions represented by the structures of Formulas (I), (II), (III), and (IV) below are provided.

In other embodiments of this invention, processes are provided to prepare the compositions represented by Formulas (I) through (IV) .

In Formulas (I) through (IV),

R¹ and R² are each independently H, alkyl, aryl, alkaryl, or aralkyl;

R³ and R are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;

R^A and R⁶ are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;

R' and R⁸ are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;

R⁹ is a Ci to C32 alkyl group; a C₆ to C₃₀ aryl, alkaryl, or aralkyl group; or a Ce to C_j0 heteroaryl group;

n is 1 to 10;

A is an acid, e.g., HC1, acetic acid, H₂S0₄, or H3PO4; and

Q is a Ce to C20 substituted or unsubstituted monocyclic or polycyclic aromatic nucleus.

In one embodiment of the composition represented by Formula (III), R¹, R² , R³,

R⁵, R^G, R⁷, and R⁸ are each H and R^¾ is t-butyl, as shown in Formula (V) .

V

This compound is 5- (t-butylthio) -1, 2, 4-triaminobenzene.

In another embodiment, a process is provided for preparing compositions of Formula (I), wherein each of R^J, R^1*', R^s, R⁶ and R^s is H, represented by Formula (VI)

VI

by

(a) monoaminating a_. composition of Formula (VII) ,

VII

wherein each Z is independently CI or Br, by heating a suspension of the composition of Formula (VII) in solvent to a temperature in the range of about 60°C to about 140°C and contacting it with an aqueous solution of at least 2.0 equivalents HNR⁷R⁸ to produce a composition of Formula (VIII)

VIII

(b) reacting the composition of Formula (VIII) with NaSR^y to produce the composition represented by Formula (III)

III

hydrogenating the composition produced in step (b) in water with hydrogen at a pressure in the range of about 10 to about 1000 psi (about 0.069 MPa to about 6.89 Pa) and a temperature in the range of about 50°C to about 100°C for sufficient time to consume about 5.9 to 6.5 mol equivalents of hydrogen, thereby producing a suspension comprising the composition represented by Formula (IX) ;

IX

contacting the suspension produced in step (c) with an aqueous solution with a concentration of at least 20 wt% HC1, and optionally a reducing agent, and heating at temperature between about 60°C and about 120°C for a time sufficient to convert the composition represented by Formula (IX) to the composition represented by Formula (X) where n=2 or 3;

and

contacting the composition of Formula (X) produced in step (d) with base, thereby producing the composition of Formula (VI) .

In another embodiment, a process is provided for preparing compositions of Formula (IX), comprising the steps (a), (b) , and (c) above, then steps (dl) and (el) : (dl) contacting the suspension produced in step (c) with about 1-2 equivalents of HC1, and filtering the resulting solution; and

(el) adding base to the solution to raise its pH above about 7, thereby precipitating the Formula (IX) free base.

For synthesis of the hydrochloride salt of the

composition of Formula (IX), the Formula (IX) free base is subsequently added to 5 equivalents of HC1 (34% in water) and the resulting trihydrochloride is filtered and washed with concentrated aqueous HC1.

The composition represented by Formula (VII) may be prepared by nitration of the corresponding dihalobenzene according to the method described in copending U.S. Patent Application 12/335,959, which is hereby incorporated by reference in its entirety for all purposes; by admixing a dihalobenzene represented by the structure of Formula (XI) ,

XI wherein each Z is independently CI or Br, with nitric acid, sulfuric acid, and oleum or S0₃, to form a reaction mixture that is characterized by (i) a concentration of nitric acid therein that is in the range of about 2.0 to about 2.3 moles per mole of dihalobenzene; (ii) a concentration of S0₃ therein that is in the range of about 1 to about 3 moles per mole of dihalobenzene; (iii) a concentration of dihalobenzene therein that is in the range of about 12 to about 24 weight percent; and (iv) a temperature of up to about 120°C; and stirring the reaction mixture at a

temperature in the range of about -10°C to about 70°C to form a dihalodinxtrobenzene product represented by the structure of Formula (VII) . In an embodiment, each Z is CI and R¹ and R' are each H; i.e., the compound of Formula (VII) is 1 , 3-dichloro-4 , 6-dinitrobenzene and the Formula (XI) dihalobenzene is 1 , 3-dichlorobenzene, which is commercially available.

The monoamination of the dihalodinitrobenzene can be carried out as described in copending U.S.

Patent Application 61/288,436. In step (al), a suspension of the composition of Formula (VII) in solvent is heated to a temperature in the range of about 60°C to about 140°C, preferably about 100°C to about 135°C, and more preferably about 130°C, to dissolve the composition of Formula (VII) in a solvent. A suitable solvent is an organic solvent inert to the reaction such as an aliphatic dihydric alcohol, such as ethylene glycol ("glycol") . The resulting solution is contacted at that temperature with an aqueous solution of HNR'R^s for approximately two to four hours close to ambient pressure; the HNR R^R solution is fed as it is consumed, as indicated by any convenient analytical technique (e.g., pH monitoring or measuring the- flow rate of HNR⁷R⁸ in the gas phase above the reaction mixture) . In one embodiment, the compound represented by Formula (VIII) is l-amino-3-chloro- , 6- dinitrobenzene (i.e., R¹, R², R⁷, and R^s are each H and Z is CI). At least 2.00, preferably about 2.03 to about 2.07, equivalents of HNR⁷R⁸ are required. At reaction completion, the composition of Formula (VIII) thereby produced can be directly isolated from the reaction mixture since it is only sparingly soluble in suitable solvents such as glycol at temperatures below 50°C; impurities remain in solution, and net yields of 85% have been found at greater than 98% purity for 1- amino-3-chloro- , 6-dinitrobenzene specifically.

The l-amino-3-halo- , 6-dinitrobenzene composition of Formula (VIII) is filtered, typically at about 60°C, and washed with solvent. It can then be thiolated (step (b) ) by NaSR⁹. This is done by slurrying the l-amino-3-halo-4 , 6-dinitrobenzene with methanol and adding to the slurry a solution of the thiol R⁹SH in about one to about two equivalents of aqueous base (e.g., NaOH) , thereby producing the thiolated composition represented by Formula (III) .

This thiolated composition can be isolated and subsequently contacted with a reducing agent (e.g., Zn in acetic acid) or it can be directly reduced without isolation to form the triaminothiophenol represented by Formula (IX). Generally, the thiolated composition produced in step (b) is then hydrogenated as a slurry in water. Examples of suitable

hydrogenation catalysts include without limitation Pd/C and Pt/C and mixtures thereof, optionally containing other metals from Groups VIII through X such as Fe . The groups are as described in the Periodic Table in Advanced Inorganic Chemistry by F. A. Cotton and G. Wilkinson, Interscience New York, 2nd Ed. (1966) . Of these, Pt/C, and Pd/C, e.g., 10% Pt/C and 10% Pd/C, are preferred. The catalyst is typically used in the amount of about 0.5 to about 5.0 wt% metal based on the composition represented by Formula (III) .

The hydrogenation reactor is purged with nitrogen and then hydrogen. Deaerated water is then added to the reactor. The aqueous suspension is contacted with hydrogen to form a reaction mixture at a pressure in the range of about 10 to about 1000 psi (about 0.069 MPa to about 6.89 MPa) and a temperature in the range of about 50°C to about 100°C. Reaction continues for a time sufficient to consume about 5.9 to 6.5 mol equivalents of hydrogen, thereby producing a suspension comprising the composition represented by Formula (IX) . The time required depends on the details of the specific set up but is typically about 2 to 3

IX The resulting suspension is cooled to about 25°C to about 45°C and about 1 to about 2 equivalents of HCl are added, typically as an aqueous solution with a concentration of at least 20 wt% HCl, and a reducing agent (e.g., SnCl2, or Sn powder). The reaction mixture so produced is heated at a temperature between about 60°C and about 120°C, in one embodiment between about 80°C and about 120°C, for a time sufficient to produce the composition of Formula (II) where n=2 or 3 and A=HC1, i.e., the dihydrochloride salt or

trihydrochloride salt of 2, 4, 5-triaminothiophenol . . The resulting reaction mixture is filtered, typically at a temperature in the range of about 60°C to about 80°C, to remove the spent hydrogenation catalyst.

Base (e.g., NaOH or KOH) can be to adjust the pH to a value above about 7, thereby precipitating the TATHIO free base. The TATHIO free base can then be isolated by filtration, washed, and dried if so desired.

To produce high-purity salts represented by Formula (XII) ("Formula (XII) salt"),

XII

wherein n is 1 to 10 and A is an acid, e.g., HCl, can be converted to the free base (i.e., the

composition of Formula (IX) wherein R⁸ is H) or to novel aromatic diacid complex of the free base with a diacid source, the complex represented by Formula (IV) ,

IV being of high enough purity for use in making a high molecular weight polymer material for producing high- performance fibers. The salt may also be a hydrate. In one embodiment, n is 2 to 4. In one embodiment, to prepare the Formula (XII) salt, the composition of Formula (IX) having R⁸=H is prepared as described above, slurried in water, and contacted with an acid to form and precipitate the Formula (XII) salt. The mixture containing the precipitated Formula (XII) salt is then cooled to about 5°C to about 15°C, stirred, and filtered. The Formula (XII) salt is then washed. It may be washed with deaerated aqueous acid, such as HC1 (33%) and then optionally with deaerated ethanol or methanol to produce a wet cake material.

Whether aqueous acid or cold water is used as a wash, it may be possible to eliminate the ethanol or methanol wash and dry directly from aqueous wet cake o simply use the wet cake in subsequent processing. It is likely that in a commercial process one would only wash with HCl_aq and, if desired, dry directly.

The resulting wet cake material (Formula (XII) salt) can be used in subsequent processing without drying or can be dried, for example at a pressure less than 400 Torr and a temperature of about 30 ° C to about 50 ° C , under a stream of Ny. . The dried product is preferably kept under nitrogen.

In another embodiment, a process is provided for preparing novel complexes of Formula (IV),

IV

wherein Q is a Ce. to C?₀ substituted or unsubstituted monocyclic or polycyclic aromatic nucleus.

Examples of Q include without limitation:

1 , 4-phenylene (Cr,H-,)

2 , 5-dihydroxy-l, 4-phenylene (C6H₄O₂)

1, 4-naphthylene (Ci₀H₆) ,

1, 5-naphthylene (CioH₆),

2, 6-naphthylene (Ci₀H₆) ,

, 4 ' -biphenyl diradical (Ci2H₈) ,

iphenyl ether diradical (OCi₂H₃0)

1, 5-dihydroxy-2, 6-naphthylene (C₁₀H₆O₂) .

One or more heteroatoms (such as N, O, S) may be present in the ring(s) of Q, for example, as shown below:

2, 5-pyridylene (C₅H₃N) In one embodiment, Q is represented by the structure of Formula (XIII)

wherein X and Y are each independently selected from the group consisting of H, OH, SH, S0₃H, methyl, ethyl, F, CI, and Br. Preferably, X=Y=OH (i.e., the diacid is 2, 5-dihydroxyterephthalic acid) or X=Y=H (i.e., the diacid is terephthalic acid) . When X=Y=H, the diacid is referred to as "XYTA" .

The complexes disclosed herein are formed from the reaction of the free base (Formula (IX) having R⁸=H) or Formula (XII) salt with a diacid source. In one embodiment ("Option A"), the Formula (XII) salt is precipitated and washed as described above, then slurried with water. Weak base (e.g., NaHCCb or KHCO3) , sufficient to neutralize the reaction mixture, and a diacid source are then added to the slurry to form and precipitate the complex, Formula (IV) . As used herein the term "diacid source" refers to the diacid HOOC-Q- COOH itself, the salt a disodium salt of HOOC-Q-COOH, a dipotassium salt of HOOC-Q-COOH, or mixtures thereof.

Alternatively ("Option B") , the reaction mixture containing the composition of Formula (IX) (with R⁸ = H) can be combined directly with the base and the diacid source to form and precipitate the complex of Formula (IV) . In another alternative

("Option C"), filtered free base (Formula (IX) with R^£< = H) can be dissolved in about 1 -2 equivalents of acid (e.g., HC1 ) and the solution so produced contacted with the base and the diacid source to form the complex of Formula (IV) .

In the complex described by Formula (IV), it is important that the ratio of the free base (Formula (IX) with R^fi = H) to the diacid source be 1 : 1 . This allows the production of high molecular weight polymer from the complex and high strength fiber from the polymer. In some instances, the use of a strong base such as aqueous sodium hydroxide or aqueous potassium hydroxide in the Option A, B, or C process can cause the free base to diacid ratio in the complexes so produced to deviate from 1 : 1 . In such cases, a preferred process is to dissolve the Formula (XII) salt in water and contact that solution with the diacid source in an aqueous solution of a weak base such as NaHC0₃ or KHC0₃. This process can be performed under mild conditions, e.g., from ambient temperatures to about 50°C. The ratio of equivalents of the Formula (XII) salt to equivalents of diacid source is between and optionally including any two of the following ratios: 1.00:1.00, 1.025:1.00, 1.05:1.00, 1.075:1.00, 1.10:1.00; 1.20:1:00, 1.30:1.00, 1.40:1.00, and

1.50:1.00. In one embodiment, the ratio is from

1.025:1.00 to 1.10:1.00.

Various designs are possible for combining the Formula (XII) salt with the diacid source and aqueous base to produce the complex. For example, the base and the diacid source are most conveniently added as a single solution. In other embodiments, the Formula (II) salt in an acid solution could be introduced into a vessel containing a basic diacid source solution, or the diacid source stream could be fed into the vessel containing the Formula (XII) salt in an acid solution. Which design is best for a specific situation will be evident to one of skill in the art.

The Formula (IV) complex is recovered from the reaction mixture by filtration at a temperature in of the range of about 5°C to about 50°C, preferably about 10°C to about 15°C, and washed with water and methanol, typically at a temperature in the range of about 15°C to about 40°C, and then dried. The washed and dried Formula ( III) · complex is kept under nitrogen to protect it from oxygen. It is of high enough quality and purity to produce polymer of high enough molecular weight to make high performance fibers.

The Option A embodiment discussed above can produce higher purity Formula (III) complex than

Options B or C. On the other hand, Options B and C have fewer steps, generate less waste and also require less acid (e.g. , HC1) and base (e.g. , NaHC0₃ or KHCO3) , thus lessening raw material and handling costs. All disclosed embodiments produce polymer grade material suitable for the manufacture of high-performance fibers .

Oxygen is excluded throughout all steps of the processes of making the free base, the Formula (XII) salt, and the Formula (IV) complex. Deaerated water and deaerated acid are used. A small amount of a reducing agent (e.g., about 0.5% tin powder) is optionally added to one or more of aqueous suspensions or aqueous solutions containing the triaminothiophenol free base, the Formula (XII) salt, or the Formula (IV) complex during the process to reduce impurities caused by oxidation and to prevent further impurity formation by that route.

All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly

understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control .

Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein. Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.

When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as

specifically disclosing all . ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end- point referred to.

As used herein, the terms "comprises,"

"comprising," "includes," "including," "containing," "characterized by," "has," "having" or any other variation thereof, are intended to cover a nonexclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or

apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present) , A is false (or not present) and B is true (or present) , and both A and B are true (or present) .

Use of "a" or "an" are employed to describe elements and components of the invention. This is done merely for convenience and to give a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

The materials, methods, and examples herein are illustrative only and, except as specifically stated, are not intended to be limiting.

EXAMPLES

The present invention is further defined in the following examples. It should be understood that these examples, while indicating preferred embodiments of the invention, are given by way of illustration only. From the above discussion and these examples, one skilled in the art can ascertain the essential characteristics of this invention, and without

departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various uses and conditions.

All water used was deaerated and de-ionized water.

The Examples were carried out under exclusion of oxygen. The meaning of abbreviations is as follows: "ACDNB" means l-chloro-3-amino-4 , 6-dinitrobenzene, "DADNB" means 1 , 3-diamino-4 , 6-dinitrobenzene, "DCDNB" means 1, 3-dichloro-4, 6-dinitrobenzene, "DHTA" means 2 , 5-dihydroxyterephthalic acid, "equiv" means

equivalent (s) , "g" means gram(s), "Ή-NMR" means proton nuclear magnetic resonance spectroscopy, "h" means hour(s), "K₂DHTA" means the dipotassium salt of 2,5- dihydroxyterephthalic acid, "M" means molar, "mL" means milliliter (s) , "min" means minutes, "mmol" means millimole (s) , "mol" means mole(s), "MPa" means

megapascals, "psi" means pounds per square inch, "t- BuSH" means t-butylthiol , and "wt" means weight.

DCDNB was prepared as described in U.S. Patent Application Number 12/335,959.

t-butylthiol (99% purity) and Darco® G-60

activated carbon were obtained from Sigma-Aldrich (Milwaukee, Wisconsin, USA) Example 1. Preparation of ACDNB from DCDNB

A degassed solution of wet 1 , 3-dichloro- , 6- dinitrobenzene (329 g, 24% water) in ethylene glycol under nitrogen (1 kg) was heated to 130 °C. Ammonium hydroxide (28% aqueous NH₃, 2.32 mol) was added over a- period of approximately 2 h such that the desired product was exclusively formed. After addition was complete, the reaction was allowed to cool to room temperature and the precipitate was collected via suction filtration. The filter cake was washed sparingly with water and was used as is for the next step. The final yield was 233 g, of which 6% was water leaving a dry weight of 219 g (95% yield) . The purity was >91% with the main impurity (8.6%) being DADNB. H NMR (d6 DMSO) : 8.79 ppm (s, 1H) ; 8.27 ppm (b, 2H) ; 7.22 (s, 1H) .

Example 2. Preparation of 1- (t-butylthio) -3-amino-4 , 6- dinitrobenzene from ACDNB

To a solution of NaOH (35.48 g) in 300 g water was slowly added t-BuSH (80 g) . The resultant sodium salt was then added dropwise to a solution of ACDNB (200 g of which 6% is water) in 900 g ethanol under N₂ over a period of 1.5 h. After stirring overnight, the reaction mixture was then filtered and subsequently washed with water (200 mL) followed by displacement washing with 1% NaOH solution (200 mL) , water (200 mL) , and methanol (400 mL) to give a yellow solid. The final yield was 195 g, of which 1.6% was water leaving a dry weight of 192 g (84% yield) . The purity was >90% with the main impurity (9%) being DADNB. ⁿH NMR (d6 DMSO) : 8.73 ppm (s, 1H) ; 8.24 ppm (b, 2H) ; 7.27 (s, 1H) ; 1.48 (s, 9H) .

Example 3. Preparation of 5- (t-butylthio) -1, 2, 4- triaminobenzene from 1 - (t-butylthio) -3-amino-4 , 6- dinitrobenzene

A I L stirred Hastelloy autoclave was charged with 92 g of 1- (t-butylthio) -3-amino-4, 6-dinitrobenzene (containing 1.6% water) and 5 g of 5% Pt/C (dry basis, 50% water) . The autoclave was purged 10 times with _? and 5 times with H₂ at 90 psi (0.62 MPa) .

Subsequently, 500 mL of deaerated water (purged with N₂ overnight) were added and the mixture was pressurized at 60°C to 300 psi (2.07 MPa) for 30 min, at which point the temperature was increased to 90 °C. After another hour, the pressure was increased to 500 psi (3.45 MPa) and hydrogenation was continued for an additional two hours for an approximate uptake of 2.01 moles of ¾ (6 equiv) . The excess hydrogen was released and the autoclave was cooled to 40°C and purged twice with Ν·,, after which 80 g of deaerated HCl,_lt, (36.3%, by titration) and 0.5 g SnCl_? were added. The mixture was stirred for five minutes at 40 °C, then passed through a metal CUNO filter to remove catalyst. The autoclave was rinsed with 30 mL of deaerated water. The solution was directly charged into a purged 2 L vessel.

Darco© G-60 activated carbon powder (7 g) was then added to the reaction mixture, stirred overnight and then filtered through a bed of celite. Approximately 1 g Sn powder was added to the filtrate, stirred

overnight and filtered to remove the Sn. The mixture was then brought to pH 13 by slowly adding aqueous sodium hydroxide (40 wt %) . The free base was isolated by vacuum filtration, yielding 152.48 g of a yellow solid (of which 60% was water) to give an 87% recovery. The free base wet cake was then added slowly to 238 g cold HC1 with stirring. After stirring for an

additional 2 h, the tri-hydrochloride salt was isolated by filtration and washed sparingly with cold HC1. The yield was 42.57 g (of which 14% was water) giving an isolated yield of 39% (the rest of the salt was kept in solution to be recycled in subsequent runs) and a purity of >98%. Example 4. Preparation of TATHIO · 3HC1 from 5-(t- butylthio) -1,2, 4-triaminobenzene

To a 500 mL vessel containing 35 g (of which 14% was water) of 5- (t-butylthio) -1, 2, 4-triaminobenzene was added 10 equiv 34% HC1 (100 g) . The vented system was then heated to 80 °C overnight, and another 5 equiv 34% HC1 was added the next day. Heating was continued for another 20 h and after cooling to room temperature the solution was filtered and washed sparingly with cold concentrated HC1. The off-white solid was collected as a wet cake and used as in further studies. The final yield was 19.77 g of which 12% was water, leaving a dry weight of 17.47 g (71% yield) with a purity of >98%. ^lH NMR (D₂0) : 7.45 ppm (s, 1H) ; 7.17 (s, 1H) .

Example 5. Preparation of TATHIO- DHTA from TATHIO -3HC1 solution

6.06 g of K₂DHTA (22.08 mmol) along with 2.69 g of sodium bicarbonate (32.02 mmol) was added to a reaction vessel. This was followed by the addition of 75 g of deaerated water and heating to 75°C. About 33.75 g of 0.18 M TATHIO · 3HC1 salt solution (24.3 mmol) made as described in Example 3 was added to another reaction vessel. The hot solution of K_ZDHTA was subsequently added dropwise into the TATHIO- 3HC1 salt solution at room temperature, with fast stirring, over a period of 10 minutes, which resulted in precipitation of a light brown solid. This mixture was then cooled to room temperature, with stirring, for 1.5 hours. The mixture was subsequently filtered and washed with ethanol (50 mL) . The solid beige product was allowed to dry for 18 hours under vacuum. H-NMR analysis revealed the TATHIO : DHTA ratio as being (1.00:1.01) .

Ή-NMR analysis revealed the TATHIO · T ratio as being (1.00:1.01) .

It is to be appreciated that certain features of the invention which are, for clarity, described above and below in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further,

reference to values stated in ranges include each and every value within that range.

Claims

The Claims of CL4895, 4896, 4903, and 4843 are combined in this application.

What is claimed is:

1. A composition represented by the structure of Formula (IV)

IV wherein R¹, R², and R⁷ are each independently H, alkyl, aryl, aralkyl, or alkaryl; R⁹ is a Ci to Ζ_ΛΛ alkyl group, a C₆ to C aryl, aralkyl, or alkaryl group, or a C<-_; to C 0 heteroaryl group; and Q is a Ci to C₂o substituted or unsubstituted monocyclic or

polycyclic aromatic nucleus.

2. The composition of claim 1 wherein Q is selected from the group consisting of:

1, -phenylene (CeH-j)

2 , 5-dihydroxy-l , 4 -phenylene (C_r,H

1 , -naphthylene (Ci₀H_s) /

1 , 5-naphthylene (Ci₀H₆) /

2 , 6-naphthylene (CioHr,) /

4 , 4 ' -biphenyl diradical (Ci₂H₈) ,

, 4 ' -biphenyl ether diradical (OC^HsO) ,

1, 5-dihydroxy-2 , 6-naphthylene (C_!(jH₆0;>) , and

2, 5-pyridylene (C₅H₃N) .

3. The composition of claim 1 wherein R⁵ is t-butyl or benzyl .

4. The composition of claim 1 wherein R⁹ is benzyl.

5. The composition of claim 1 wherein Q is

represented by the structure of Formula (XI)

XI

wherein X and Y are each independently selected rom the group consisting of H, OH, SH, S0₃H, methyl, thyl, F, CI, and Br.

6. The composition of claim 5 wherein X=Y=OH or X=Y=H.

7. The composition of claim 6 wherein R¹, R², and R⁷ are each H.

8. The composition of claim 7 wherein R⁹ is t-butyl or benzyl.

9. A process comprising the steps:

(a) providing an aqueous solution of a composition represented by Formula (II)

II

wherein R' , R², and R⁷ are each independently H, alkyl, or aryl R^B is H; n is a number from 2 to 4; and A is an acid selected from the group consisting of HCL, H2SO₄, H3PO₄, and acetic acid;

(b) contacting the solution with a diacid source and an aqueous solution of a weak base, thereby forming and precipitating the complex represented by Formula (IV)

wherein the diacid source is HOOC-Q-COOH, the salt a disodium salt of HOOC-Q-COOH, a dipotassium salt of HOOC-Q-COOH, or mixtures thereof; and wherein Q is a C₆ to C₂o substituted or unsubstituted monocyclic or polycyclic aromatic nucleus.

10. The process of claim 9 wherein the base in step (b) is NaHCC or KHC0₃.

11. The process of claim 9 wherein the ratio of equivalents of the composition represented by Formula (II) to equivalents of the diacid source is from

1.0:1.0 to 1.5:1.0.

12. The process of claim 11 wherein the ratio of equivalents of the composition represented by Formula (IV) to equivalents of the diacid source is from

1.025:1.0 to 1.10:1.00.

13. The process of claim 9 wherein R¹ , R^?, and R^; are each H; n is 2 to 3; and A is HCL.

14. The process of claim 9 wherein Q is selected from the group consisting of:

1 , 4-phenylene (Cr_>H))

2, 5-dihydroxy-l , 4-phenylene (CeH₄

1 , 4-naphthylene (ΟιοΗβ) ,

2, 6-naphthylene (Ci₀H₆) ,

4 , 4 ' -biphenyl diradical (Ci₂H₈) ,

'-biphenyl ether diradical (OCj₂H₈0)

1, 5-dihydroxy-2 , 6-naphthylene (CioH_c0₂)

2, 5-pyridylene (C₅H₃N)

15. The process of claim 9 wherein Q is represented by the structure of Formula (XIII)

wherein X and Y are each independently selected from the group consisting of H, OH, SH, S<¾H, methyl, ethyl, F, CI, and Br.

16. The process of claim 15 wherein X=Y=OH or X=Y=H.

17. A process comprising preparing a mixture of the composition of claim 1, P₂0^ and polyphosphor ic acid, and tin metal powder or iron metal powder; and stirring and heating the mixture to polymerize the composition of claim 1 .

From CL4896

18 . A composition represented by the structure of Formula (III)

III

wherein

R¹ and R⁸ are each independently H, alkyl, aryl, aralkyl, or alkaryl;

R⁷ and R^s are each independently H, alkyl, aryl, aralkyl, or alkaryl or may be joined to form an aliphatic ring structure; and

R^s is a Ci to C_3? alkyl group; a C₆ to C₃₀ aryl, aralkyl, or alkaryl group; or a C₆ to C₃o heteroaryl group.

19 . The composition of claim 18 wherein R¹ , R², R^;, and R⁸ are each H.

20 . The composition of claim 18 wherein R¹, R², R⁷, and R⁸ are each independently a C₁-C4 alkyl group.

2 1 . The composition of claim 18 wherein R^J is t-butyl.

22 . The composition of claim 18 wherein R^c' is benzyl.

23 . A composition represented by the structure of Formula (I)

wherein

R¹ and R² are each independently H, alkyl, aryl, alkaryl, or aralkyl;

R³ and R⁴ are each independently H, a^'lkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;

R⁵ and R⁶ are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;

R⁷ and R⁸ are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;

R^¾ is a C) to C32 alkyl group; a C₆ to C30 aryl, alkaryl, or aralkyl group; or a C₆ to C30 heteroaryl group .

24. The composition of claim 23 wherein R⁹ is t-butyl and R¹, R², R³, R⁴' R⁵' R⁶' R⁷, and R⁸ are each H.

25. The composition of claim 23 wherein R⁹ is benzyl and R¹, R^z, R³, R^4* R⁵' R⁶' R⁷, and R⁸ are each H.

26. A composition represented by the structure of Formula (II)

II

wherein R¹ , R², R⁷ and R^s are defined as in claim 1; n is a number from 1 to 10; and A is an acid selected from the group consisting of HC1, H_?SO,s,

and acetic acid.

27. The composition of claim 26 wherein R¹, R², and R' are each H, A is HC1, R^s is t-butyl, and n is 2 to 4.

6c. The composition of claim 4 wherein R¹ , R², and R⁷ are each H, A is HC1, R⁹ is benzyl, and n is 2 to 4.

28. A process comprising the steps:

(a) monoaminating a composition of Formula (VII),

VII

wherein each Z is independently CI or Br, by heating a suspension of the composition of Formula (VII) in solvent to a temperature in the range of about 60 °C to about 140°C and contacting it with an aqueous solution of at least 2.0 equivalents HNR'R⁸ to produce a

composition of Formula (VIII)

VIII

(b) reacting the composition of Formula (VIII) with NaSR⁹ to produce the composition represented by Formula (III) ;

III

(c) hydrogenating the composition produced in step (b) in water with hydrogen at a pressure in the range of about 10 to about 1000 psi (about 0.069 MPa to about 6.89 MPa) and a temperature in the range of about 50°C to about 100°C for sufficient time to consume about 5.9 to 6.5 mol equivalents of hydrogen, thereby producing a suspension comprising the composition represented by Formula (IX) ;

IX

(d) contacting the suspension produced in step

(c) with an aqueous solution with a concentration of at least 20 wt% HC1, and optionally a reducing agent, and heating at a temperature between about 60°C and about 120°C for a time sufficient to convert the composition represented by Formula (IX) to the composition represented by Formula (X) where n=2 or 3;

and

(e) contacting the composition of Formula (X) produced in step (d) with base, thereby producing the composition of Formula (VI)

wherein

R¹ and R² are each independently H, alkyl, aryl, alkaryl, or aralkyl;

R' and R^B are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure; and

R⁹ is a Ci to C3z alkyl group; a C6 to C30 aryl, alkaryl, or aralkyl group; or a C to C30 heteroaryl group.

29. The process of claim 23, wherein the temperature in step (d) is between about 80°C and about 120°C.

30. The process of claim 23, wherein R¹, R^Z, R-', and R⁸ and R² are each H.

31. The process of claim 23, wherein R⁹ is t-butyl or benzyl .

32. The process of claim 23, wherein the reducing agent in step (d) is Sn or SnCl_z.

33. The process of claim 23, further comprising adding the composition represented by Formula (VI) to 5 equivalents of HC1 (34% in water), thereby producing the composition represented by Formula (X) wherein n=2 or 3;

X

filtering the Formula (X) composition and washing it with concentrated aqueous HC1.

34. A process comprising the steps:

(a) monoaminating a composition of Formula (VII) ,

VII

wherein each Z is independently CI or Br, by heating a suspension of the composition of Formula (VII) in solvent to a temperature in the range of about 60°C to about 140°C and contacting it with an aqueous solution of at least 2.0 equivalents HNR 'R" to produce a

composition of Formula (VIII)

VIII

(b) reacting the composition of Formula (VIII) with NaSR^s to produce the composition represented by Formula (III) ;

III

(c) hydrogenating the composition produced in step (b) in water with hydrogen at a pressure in the range of about 10 to about 1000 psi (about 0.069 MPa to about 6.89 MPa) and a temperature in the range of about 50°C to about 100°C for sufficient time to consume about 5.9 to 6.5 mol equivalents of hydrogen, thereby producing a suspension comprising the composition represented

by Formula (IX) ; ^iX

(d) contacting the suspension produced in step (c) with about 1-2 equivalents of HC1, and filtering the resulting solution; and

(e) adding base to the solution to raise its pH above about 7, thereby precipitating the Formula (IX) free base.

The process of claim 34, wherein R¹, R^z, R⁷, and R^e R² are each H.

The process of claim 34, wherein R⁹ is t-butyl or benzyl .

37. The process of claim 34, wherein the reducing agent in step (d) is Sn or SnCl_?.

38. The process of claim 34, further comprising adding the composition represented by Formula (IX) to 5 equivalents of HC1 (34% in water) , thereby producing the composition represented by Formula (XII) wherein A is HC1 and n is 2 or 3;

XII

filtering the Formula (XII) composition and washing it with concentrated aqueous HC1.