AU2004205245B2 - Preservative Compounds and their Use - Google Patents

Abstract

The invention provides a compound of Formula I ~ 't 5a wherein each of R1, R1, and Rs, is a group independently selected from hydrogen, CI-C2oalkyl, C 10 C2oalkonyI, aryl, alkaryl. aralkyl, heterocyclyl, hydny, halogen, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy and alkylcarbonylmino, wherein each alkyl, alkenyl, alkyloxy, ary], akaryl, aralkyl, or heterocyclyl group present in these may be substituted with one or more groups selected from hydroxy halogen, alkyloxy, amino, alkylamino, dialkylamino, alkyloxy. nitro, carboxyl, aminocarbonyL 15 'alkyloxycarbonyl, alkynyl, alkylcarbonyloxy and alkyloarbonylamino; each of R2, R4 and R6 is a group selected from hydrogen and Ct-Czoalkyl; each ofZi, Z and 4 as a group chosen from -C(Ry7Ps)-, -C(R7R)-C(Rjo)-, -C(k7R,)-C(R.Ri)-C(Ri P-L+, -C(RRa)-C(RRi)-C(Riilty)-C itRzvC(RisRi,, and -C(R 7R-C(RRio)-C(Ru1 R4)-C(RR 1 4)-(CH2 ).-C(R5 Rs)-; each of R,. R, Rtn. Ra and Ras is a group independently selected from hydrogen, C1 Czoalkyl, CI-2oalkenyl, aryl, alkuryl, aralkyl, heterocyclyl, hydroxy, halogen, amino, alkylamino, 5 dialkylamino, alkyloxy, nitro, carboxyl, aminncarbonyl, alkyloxycarbony4, alkynyl, alkylcarbonyloxy or alkylcarbonylamino, wherein each alkyl, alkenyl, alkyloxy, aryl, alkaryl, eralkyl, or heterocyclyl group present in these may be substituted with one or more groups selected from hydroxy, halogen, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, ulkynyl, alkylcarbonyloxy and aky4carbonyumino; and each of R2 , R4. R &, i, Rio. Ru, R 14 and 10 R 16 is chosen from hydrogen and Ci-Cmalkyl and wherein not only are ZI, Z2, and Z3 the same or different but also Rp, Rg and when present R, RIo, RI], R12, R, R14, Ris, Ri& may be the same in said Zi, Z2, and Z3 or in two of those groups, or those R groups maybe different in all three Z groups; 15 Z, Z2 and Za with more than one carbon atom maybe included in the molecules such that the C atom bearing R7 is linked to that bearing R1. R3 and Rs respectively or so that it is linked to the nitrogen atom; and Ri. R2, R3, R4, Rs, R4, ZI, Z2, and Z3 are selected so that when the three rings each contain 5 to 8 membes (including the boron and nitrogen atoms), at least one ring bears a, group other than 20 hydrogen, methyl, methoxy or ethoxy. These compounds are useful in preservative compositions, especially those used in preserving wood.

Description

Regulation 3.2 AUSTRALIA PATENTS ACT, 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT ORIGINAL Name of Applicant: NEW ZEALAND FOREST RESEARCH INSTITUTE LIfMfTED Actual Inventors: ROBERT FRANICH Address for service A J PARK, Level 11, 60 Marus Clarke Street, Canberra ACT in Australia: 2601, Australia Invention Title: Preservative Compounds and their Use 'The flowing stemem is a fulil d=cription of this invention, iAcluding die bs method ofperfonning it known to me.

PRESERVATIVE COMPOUNDS AND THEIR USE TECHNICAL FIELD This invention relates to compounds useful as preservatives, preservative compositions and methods for treating articles and materials so as to assist their preservation. 5 BACKGROUND ART Preservatives havc long been used to protect items of value to mankind from biodeterioration by bacteria, fungi, insects and marine borer. The problem has been to find preservatives suitable in their preservative function by being toxic to the deteriortion-causing organisms but not to human users of the materials and to the environment Different preservatives 10 are suitable for different applications. For food preservation the requirement for low human toxicity is clearly greater than for preservation ofwood, for example. Other factors also influence the choice of preservative. These include cost, stability and leachability. Preservation of products such as wood and textiles requires a preservative with the following properties. 15 1. It must be toxic towards target organisms while being relatively harmless to mammals and the environment. 2. It must not leach out by immersion in water or exposure to rain. 3. It must be of relatively low cost and easy to handle. 4. It mum be inoffensive to users. 20 Problems of finding preservatives with all these desirable features can be illustrated by considering the problems of existing wood preservatives. No currently-used wood preservative chemical displays all the ideal features, but lack of tem can be used as a guide to the individual chemical use. For example, copper-chrome-arsenic wood preservatives used over a range of concentrations can be used to preserve wood used in 25 exterior applications, such as marine piles and exterior cladding of buildings against decaybylfungi. While copper-chrome-arenio salts are applied to wood as an aqueous solution, they undergo chemical reaction in the wood and become "fixed". While copper-chrome-arsenic is a highly 2 effective wood preservative, it has disadvantages such as high mammalian toxicity and environmental hazard. Tributyt tin oxide wood preservative is also effective in preventing decay by fungi, but can be leached from wood in small amounts sufficient to cause extreme harm to marine organisms, so cannot be used in marine applications. Organic preservatives such as 5 pentahlorophenol and creosote, while being effective, are known to present such significant health and environmental hazards that these are rarely used. Modem insecticides, such as permethrin, are effective for preserving wood againstboring insects, but-evidence is accumulating that some species are developing resistance towards permethrin, indicating that new insecticides may need to be developed for control of these resistant 10 organisms. Boron chemicals such as borax (sodium tetraboratepentahydrate), boric acid and trimethyl borate effectively control the decay of wood by most fungi and prevent damage by wood-boring insects. The disadvantages of boron compounds for wood preservation is their ready leachability from the treated wood with water. This limits the range of applications of boron-treated wood to 15 interior situations, such as internal framing of buildings. Knowledge of the mode oftoxic action for the chemicals described above remains scant Borate toxicity towards organisms is thought to be due to inhibition of gut enzymes and bacteria (in insects) and cellulolytic enzymes of fungi. No infonmation is available on the chemical environment (trigonal or tetrahedral) of the boron element necessary for biological activity. 20 A number of attempts have been made to "fix" the boron element into wood so that boron treated wood may be used in exterior applications. The literature reveals that all these attempts have been carried out empirically, by treating wood with a variety of boron chemicals and testing the treated wood for durability using accelerated decay tests. Attempts using insoluble inorganic borate salts (e.g. cupric borate) resulted in loss ofthe boron element from the treated wood on leaching with 25 water. The reason for this is that all insoluble sults have a minimal, measurable solubility and dissociate to form hydrated ions. Over time with extensive water leading, theborate ions are totally lost from the treated wood. It is an object of the invention to provide preservatives which combine low active leachability and toxicity towards target organisms without creating a significant hazard to mammals 30 and the environment or at least to provide the public with a useful choice. It is envisaged that these 3 preservatives would be useful in a number of applications including treatment of wood and other materials including textiles. DISCLOSURE OF THE INVENTION The invention relates to preservative compounds collectively known as boratranes of the structure of formula I. In a first aspect, the invention provides a method for preserving wood or textiles comprising application to the wood or textiles of a composition containing at least one compound of Formula I: Z3

R

4 00 each of R 1 , R 3 , and R 5 , is a group selected from hydrogen, CI-C 20 alkyl, Ci-C 2 0 alkenyl, aryl, alkaryl, aralkyl, heterocyclyl, hydroxy, halogen, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy or alkylcarbonylamino, wherein each alkyl, alkenyl, alkyloxy, aryl, alkaryl, aralkyl, or heterocyclyl group present in these may be substituted with one or more groups selected from hydroxy, halogen, alkyloxy, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy or alkylcarbonylamino. Each of R2, R4 and R6 is a group selected from hydrogen and C 1

-C

2 oalkyl. Each ofZI, Z 2 and Z 3 as a group chosen from

-C(R

7 Rs)

-C(R

7 Rg)-C(R 9 Rio)

-C(R

7

R

8

)-C(R

9 Rio)-C(Rj1R12)

-C(R

7 Rs)-C(R 9 Rlo)-C(R,,R 1 2

)-C(R

3 Ri 4 )-C(Ri sRi 6

)

4 -C(R-,Rs)-C(R<>Rlo)-C(Ru 1Ru)-C(Rl3R])-(CH2).-C(Rl5Ri6) Each of R 7 , R 9 , R 11 , R 13 and R 15 is a group selected from hydrogen, CI-C 2 oalkyl, C 1 2oalkenyl, aryl, alkaryl, aralkyl, heterocyclyl, hydroxy, halogen, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy or alkylcarbonylanino, wherein each alkyl, alkenyl, alkyloxy, aryl, alkaryl, aralkyl, orheterocyclyl group present in these may be substituted with one or more groups selected from hydroxy, halogen, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy or alkylcarbonylamino.Each of R 2 , R 4 , R 6 , Rs, Rio, R 12 , R 4 and R 16 is chosen from hydrogen and Cr-C 2 0 alkyl n is an integer from I to 10. Not only are Z 1 , Z 2 , and Z 3 the same or different but also R-, Rs and when present R 9 , R 0 , Ro, R 12 , RI , R 14 , R 1 5 , Ri 6 may be the same in said Z 1 , Z 2 , and Z 3 or in two of those groups, or those R groups may be different in all three Z groups. Z 1 , Z 2 and Z 3 with more than one carbon atom may be included in the molecules such that the C atom bearing R7 is linked to that bearing R], R 3 and R 5 respectively or so that it is linked to the nitrogen atom. In the compounds of Formula 1, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z 1 , Z 2 , and Z 3 are selected so that when the three rings each contain 5 to 8 members (including the boron and nitrogen atoms), at least one ring bears a group other than hydrogen, methyl, methoxy or ethoxy. Certain compounds related to the compounds of Fonula I are known: triethanolamine borate tri-n-propanolamine borate, triisopropanolamine borate. These compounds do not form part of this aspect of the invention. Those particular compounds are freely soluble in water, and have no functional groups for bonding to other molecules, to allow fixation in the wood and are readily leached from the article with water, removing the preservative action. Preferably R 2 , R 4 , R 6 , Rs and where present Rio, R 1 2 , R 14 and R 16 are each hydrogen. In a particularly preferred embodiment the compounds have FormulaII wherein Rl, R 2 , R 3 ,

R

4 ,_ R 5 , R6 and R 7 , are as defined for Formula I 5 (CH12) (cH2) 113 B

R

2 p is an integer from 0 to 2. Each of q and r is an integer fi-om I to 3. w is an integer which is 0 or 1. At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 9 (if present) is other than hydrogen, methyl, methoxy or ethoxy. Preferably at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is other than hydrogen methyl, methoxy or ethoxy. Preferably p = 1, q = 2 and r = 2. Preferably R 2 , R 4 and R 6 are hydrogen. Particularly preferred are compounds of formula III in which R 1 , R 3 , R 5 , R 7 and R 9 (if present) are (1) as defined for formula I and (2) include a group other than hydrogen, methyl, inethoxy or ethoxy, s = 0-2, t and u are each 1 or 2 and w is 0 or 1 (refer to Formula III). Preferably,

R

1 , R 3 , R 5 and R 7 include a group other than hydrogen, methyl, methoxy or ethoxy. (c2 01 . (cH2) " N (C H 2 )t R 14 O R3 Preferably R, is selected from C -C2oaIkyl,C2-C2oaIkenyl, hydroxy or CI-C2ohydroxyalkyl. These preferable selections enable the preservative to be rendered insoluble in water (with hydrophobic alkyl groups) or condensation-polynerisable (with hydroxy or hydroxyalkyl groups) to become water insoluble within the wood. Particularly preferred compounds include those in which R 1 and R 7 are both C-C 20 alkyl and s=1, t=2, u=2, w=0, R 3 is hydrogen and R 5 is hydrogen. 6 Further particularly preferred compounds include those in which s=1, t=2, u=2, w=1, R 1 ,

R

3 , R 5 and R7 are hydrogen and R 9 is Cs-C 2 oalkyl or Cs-C2oalkenyl. Another particularly preferred group of compounds of formula III are those in which R 3 and R 5 are CI 4 alkyl and one of R 7 and R 1 is hydroxy or C 1

-C

4 hydroxyalkyl. In another aspect the invention provides preservative compositions. These compositions are formulated for the preservation of wood, textiles and other materials. The preservatives comprising the compounds of the invention have a number of useful features. They are toxic towards target organisms but compared with many preservatives are relatively harmless to the environment and mammals. They also have the feature of not being liable to leach out of treated material by immersion in water or on exposure to rain or they have controlled/slow/retarded rate of leaching. The preservative compositions comprise at least one compound of formulae I, II or III. Some ofthe molecules of the invention eg those in which one or more R groups are C-C 20 alkyl are retained in the preserved material because of their hydrophobicity. Others which are less hydrophobic may be retained in the material because they contain reactive groups which allow for cross-linking or polymerisation within the preserved material. The compounds of formula I in which R 1 , R 3 and R5 are each hydroxy or hydroxyalkyl are examples of crosslinkable compounds. The compounds of formula 1 in which R1, R 3 and R 5 are all vinyl are an examples of polymerisable compounds. The hydrophobic compounds of the invention may also be formulated in a water-borne solution using emulsifiers to form a micro-emulsion. The hydrophobic compounds of the invention maybe dissolved in a light organic solvent such as is used in wood preservation practice and applied to the treated material. Industrial aliphatic white spirit is a preferred solvent for this purpose. Preferably the compound of the invention is present in an amount of between 0.1 and 30% by weight, more preferably between 0.5 and 30%. The compounds of the invention bearing alkyl chains are preferred for use in these compositions. In the case of compounds which are useful because they are crosslinkable or polymerisable, a cross-linking agent and/or polymerisation catalyst is included in the preservative composition. To delay crosslinking or polymerisation it may be necessary to delay combining the boron-containing 7 preservative and the crosslinking agent or the polymerisation catalyst until shortlybefore treatment of the material. This will depend on the stability of the particular cross-linking chemical used, Where crosslinking is desired, the preferred compounds of the invention are those containing substituent groups such as hydroxy groups or hydroxyalkyl groups wherein the substituent is readily crosslinkable. Particularly preferred are compounds of fonnula III containing one or more hydroxy or hydroxyalkyl groups. The cro sslinking agent will depend on the nature of the substituent to be crosslinked. One preferred class of crosslinkers are the hydroxymethyl and alkylhydroxymethyl melamines, eg methylmethylol melamines and butyhnethylol melamines. Trialkyl derivatives o f trimethylolmelamine are an example of a particularly preferred group of crosslinking agents for crosslinking compounds of the invention containing hydroxy groups, eg Cymel 323 resin Formula IV which is commercially available. H N N N H N N H OBu In the case of a wood treatment, the process may involve application to the surface, immersion in the treatment composition and other methods known to those skilled in the art. Vacuum and/or pressure may be used to facilitate uptake of the treatment chemicals into the substrate. The presence of at least one boron-containing compound of Formula I, II or III distinguishes the preservative compositions of the invention from those of the prior art rather than the diluent and other agents in the compositions. The preservative compositions of the invention may contain preservative compounds of formulae I, II or III in combination with other preservative 8 compounds. Preferably one or more compounds ofFormula II are used. More preferably one or more compounds of Formula III are used. While some woods are relatively resistant to biological attack, many woods in commercial use are susceptible. In a particularly preferred method of the invention, a softwood susceptible to biodeterioration is treated with a compound according to formula I. Preferably the wood is treated with a compound chosen from the preferred, or more preferred compounds of Formula II and III. The treatment of the wood may involve methods of application known to those skilled in the art of wood preservation. The compositions applied in addition to containing at least one compound of formula I, may also contain other wood preservative compounds. When the compound offormulal is crosslinkable or polymerisable, the composition applied to the wood will generally contain a crosslinking agent or apolymerisation catalyst. The method oftreatment ofthe wood mayinvolve a subsequent step to promote crosslinking or catalytic activity (eg by elevation of temperature) usually carried out by kiln drying the treated wood. In a further aspect, the invention provides a method for preserving m4e1als wood or textiles by treating them with boric acid and an alkanolamine of Formula V. 460H- R1 R-'5 t Ri\2 Z3 V -R3 HO After treatment the boric acid and alkanolamine are allowed to react, preferably by use of heating the material. Preferably in this embodiment the alkanolamine is chosen so that the sidechain(s) are hydrophobic. The treatments are dissolved in a suitable solvent and may be incorporated into the material under pressure. Heating at temperatures in the range 40'C- 1 50"C is preferred for facilitating 9 the reaction to form the boratrane compounds of the invention. Z 1 , Z 2 , Z 3 , Ri, R 2 , R 3 , R 4 , Rs and R of Formula V are defined as for Formula I, preferably selected so that each group is also defined as for the corresponding group in Formula II, most preferably also Formula III. In another aspect the invention provides a compound of Formula III wherein R 9 (ifpresent) is (1) as defined for formula I, s=1, t=2, u=2, w=O, R 3 and Rs are hydrogen and Ri and R 7 are both C 1 C 2 0alkyl. In a further aspect the invention provides a compound of Formula III wherein R 1 , R 3 , R 5 and R 7 are hydrogen, R 9 is C 2 -C2oalkyl or C 3 -C2oalkenyl, s=l, t=2, u=2 and w=l. In yet a further aspect the invention provides 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-.

boratricyclo-[3.3.3.0"'] undecane. In another aspect the invention provides a wood preservative composition comprising 3,7-dimethyl 10-decyl-2,8,9-trioxa-5-aza-I-boratricyclo-[3.3.3.0,' 5] undecane. Compounds of formula I may prepared using Reaction Scheme I: VI R O R2 Compound offornma I 2- --

B

3 or compound ofFornmula I

Z

2 -Nj OH in which one or more R groups Z3 is in protected forn, ifrnecessary, Re3 removal ofprotecting groups HO 9a Intermediate compounds of Formula VI are rfluxed in an anhydrous solvent eg toluene. The intermediate trialkanolamine derivatives of formula VI may be prepared by means known to those skilled in the art. ) - H N OCH~ 045). Bis(2brc xeryean n 0 o REDN Rt O R . R N OH OH R Reacilo Schem 2 Reaction Scheme 3 OO SN Of+ - aligcmers cet . O OH (iO DR & NHON 120 ERaction Scheme 4 01Q HOH PjH0~<.J Scem II a ~ ae * p-rran Attna 1 9 &c-eO'C Reaction SchemeS5 a .e O CM1

R

1 -R' have the same meaning as R-R 6 of Formula I or any of them may be R 2

-R

6 in protected form. Zi, Z2 and Z 3 have the same meaning as for Formula I. The compounds of formula V can be prepared in a number of ways known to those skilled in the art. Reaction schemes 2-5 show some processes preferred by the applicant. 5 BRIEF DESCRIrHON OF DRAWINGS Pig I Solid state "B NMR spectrnu ofproduct of Cross-linking of 3.7-dideoyl-l0-hydroxymethyl 2,8,9-trioxa-5-aza-1 -boratricyclo[3.3.3.0'j-undecane and 8,11-didecyl-4-hydroxyl-2,9,10-trioxa-6 aza-1-boratricyclo[4.33..0']dodecane with Cymel 323 resin. Fig 2 Solid state' 1B NMR spectrum ofproduct ofCross-linking of 3,7-dimethyl-1 0-hydroxymethyl 10 2,8,9-trioxa-5-aza-1-boratricyclo[3.3.3.0'-undecae and 8,1 1-dimethyl-4-hydroxyl-2,9,10-trioxa 6-aza--bmtricyclo(4.3.3.0,fdodecane with Cymnel 323 resin. Fig 3 Solid state "B NMR spectrum of product Cross-linking of 3,7-dimethyl-1 0-hydroxymethyl 2,8,9-trioxa-5-aza-1-boratricylo[3.3.3.0''-undecane and 8,11-didecyl-4-hydroxyl-2,9, 1 0-trioxa-6 aza-I-boratricyclo[4.3.3.0IA]dodecane from acid catalysed hydrolysis reaction (oligoner reduced) 15 with Cymel 323 resin. Fig 4 Solid state "B NMR spectrum of product of Cross-linking of 12-hydroxymethyl-2,1 0,11 trioxa-6-aza--1-boratrioyclo[4.4.3,0' ]tetraecane and 13-hydroxyl-2,10,11-trioxa-6-aza-l boratricyvlu[44.4.40A]tetradcdane with Cymel 323 'esin. BEST MODES FOR CARRYING OUT THE INVENTION 20 EXAMPLES The following Examples irtber illustrate the invention and describe the best modes of carrying out the invention. The compounds of Examples 1-9 are listed below: 12 Example 1: CHa(C4H) Example 2: CH3(CH 2 )m

CH

3 (CH2)n o m+n= 25,27,29,31,33. The hoalogues arise from the homaloguts ofthe odginal alkkte sdimerproduct HN 100. Example 3

:

(0H 2

)QCH

3 CH3(CH21 OH (CH2)CHs These two bonMmes aise from the boric add esteuiftcation of the WA lcohos. formed flnm opening the epoxide ring of glycidoL Both primary and secondary al o groupscan be estfie 13 Example 4: H and its oflgomers formed from further reaction with glycidol; OH OH and the other isomer fiMed from opening ofthe epoxide ring of glycidoL HO o NO and the oligoners formed from father reacdon of the aminoalcohol with lycidol OO - Example 5 OH and its oligomers foned from either reacdon ofthe aminoalcoholwith glycidot: 14 and the other isomen HO 0 OH and its oligomers; OH OH -HO +,, 0 Example 6is about cross-linidag reactions. Examle7:

CH

3 (CH2)9 0 15 Example S: O+ Example 9: 5 . CH 3 (CH2)s +/ In .. O EXAMPLE 1 - Synthesis of 3-octyl-4-hept4-2,10,11-trioa-6-aza--borotricyclo 10 [4.4.4.0''tetradecane 1.1 Synthesis ofA2N-bis(2-carbomethoxyethyi)amine To methyl acrylate (300g. 3.5 mol) in a Parr reactor was added, with solid carbon dioxide in acetone cooling, anhydrous liquid ammonia (500 g). The reactor was sealed, and allowed to warm to ambient tcuperature (200). The Parr reactor was attached to an orbital shaker, and the mixture 15 shaken gently for 48h. At the end of this period, the excess of ammonia was allowed to venL GCMS analysis of the crude product indicated an approximately 1:1 mixture of di-N (carbomethoxyethane), Mt m/z 189 and tri-N-(carbomethoxyethane), M t *-, m/z 275. The mixture was distilled in vacuo ( 909C, 4.10-2. torr) to give pure NN bis(carbomethoxyethy)amin, 140 g. The product showed uo.o (neat) 1740 cm-' (saturated ester), 20 'H NMR (CDCl)ppm 2.27 (t44, C3 Cib), 2.59 (t, 4H, C2 C), 3.48 (s, 6H, -OCH 3 ). "C NMR (CDCl 3 ) ppm 32.5 (C3), 39.0 (C2), 44.6 (-OCH), 172.6 (CI). MS m/2 189 (M', 0.4%), 156 (M-33, 2%), 116 (M-73, 100%), 102 (M-87, 34%), 84 (M-105, 93%), and 42(55%). 1.2 Synthesis ofnonanoyl chloride Nonanoic acid (I0g, 0.11 mol) was converted to the acyl chloride by addition of thionyl chloride 25 (27g,.23 mol) at 20C. The mixture was then heated to 40"C until evolution of sulphur dioxide and 16 hydrogen chloride has ceased. The crude acyl chloride was obtained in quantitative yield, and was characteriscd by its spectroscopic properties. Infrared spectrm 1800 cuf' 13C NMR spectrum: 13.8, 22.5, 24.9, 28.3, 28.9, 31.5, 46.9 and 173.1. 5 "J.3. Dehydrochlorination of nonanoyl chloride to heptyl kelene dimer. Ice-cold nonanoy1 chloride (25 g, 0.14 mol) was dissolved in dry diethyl ether (30 mL) treated with cold, dry tricihylamine (14.3g, 0.14 mol) over a period of 10 min. After I h, the mixture was allowed to warm to ambient temperature, and stining continued for 24 h. The triethylamine hydrochloride was then extracted from the mixture with 2% aqueous sulphuric 10 acid. The redried ether solution was then concentrated to give crudeheptyl ketene dimer (85% yield) containing 9-heptadecanone by-product (10% yield). Infrared spectrum 1873, 1725 cn. I NMR spectrum: 0.87 (s), 1.33 (broad s), 1.73 (d of t), 2.10 (d of t), 3.93 (d of t) and 4.69 (d oft). 13C NMR spectrum: 13.9, 14.0,22.3,22.4,24.5, 25.9,274,28.7,31.2,31.4, 53.7, 101.7, 145.6. 15. Mass spectrum: m/z 224 (Mt, 4% rel int). 168 (4% ret int), 139 (8% rel int). 112 (9% rel int), 98 (100% rel int), 56 (56% rel int), 1.4 Preparation ofN.Nbis(2-carbomethoxyethy)-2-heptyl-3-keto-undecamide. To ice-cold NN-bis (2-carbomethoxyethyl)amina (8.85g, 47 mmol) was added heptyl ketene dimer (13.2g, 47 mmol) and the mixture stirred well. The exothermic reaction was allowed to go to 20 completion moderated by cooling. NN-bis (2-carbomethyoxycthyi)-2-heptyl-3-keto-undecamide was obtained in quantitative yield as a viscous liquid, and was characterised by its spectroscopic Properties. Infrared specrm: 1740, 1715, 1690, 1650 cmt. 1H1 NMR spectrum: 0.86 (s), 1.33 (broad s), 2.32 (p), 2.42 (d of t) 2.47 (q), 3.48 (t), 3.62 (a), 3.67 25 (s). 17 13CNMR spectrn: 14.0,22.6,23.4, 27.7,29.0,29.1,29.3,29.4,29.5,31.7,31.8,32.2,33.0,39.3, 42.6,44.3, 51.7, 51.9, 57.7, 169.7, 171.1, 171.3, 207.2. Mass Spectrum m/z 467 (M*,2%), 188 (100%) 1.5 N.N4is(propan-3-ol)-2-heptyl-3-hydroxy-undecanamine. 5 To an ice-cold suspension of lithium aluminium hydride (6.67g, 180 mmol) was added slowly a solution of NN-bis(2-carbometboxyethyl)-2-heptyl-3-keto-undecanide (20.1g, 43 mmol) in dry diethyl ether (50 mL). The mixture was allowed to warm to ambient temperature and then-heated under reflux and in a dry nitrogen atmosphere for 24 1. Excess of lithium aluminium hydride was destroyed using aqueous sodium hydroxide solution. The product was extracted from the residue 10 using clichloromethane and the solution concentrated to give NN-bis(2-propm-3-ol)-2-heptyl-3 hydroxy-undecanamine as a viscous liquid. The compound was characterized by its spectroscopic properties. Infrared spectrum: 3200-3400, 1064 cm". 1H NIR spectrum: 0.9 (s), 1.32 (broad s), 1.72 (p), 2.3 (m), 2.83 (d of t). 3.6 (m). 15 13C NMR spectrum: 13.7,22.3,25.5, 27.5, 29.0-30.0, 31.0,39.0, 51.1, 60.1,61.0,73.8. Mass spectrn (Negative ion ammonia CI): m/z 400 (100%, M-1). Masspctrum, (TMSi derivative): m/z 617 (M+, 1% rel int) 602(2% rel int), 290 (67%re int), 174 (60% rel int) 58 (100% rel int). 1.6. 3-Ocsyl-4-heptyl-2, 10, 11-trioxa-6-ara-1-boratricyclo-[4.4.4. 0']tetradecane. 20 To N,N-bis(propan-3-ol)-2-heptyl-3-hydroxy-undm mAne (1.92 g, 4.79 mmol) in toluene (50 ml) was added boric acid (0.52g. 8.4 mmol). The mixture was heated under reflux using a Dean-Stark water separator until the theoretical yield of water was obtained. The solution was filtered from excess of boric acid and concentrated to give 3-octyl-4-hepty1-2,10,11-trioxa-aza-1 bnrtricyclo[4.4.4.0." tetradecanc (1.74g. 89% yield) as a solid, characterised by its speomoscopic 25 properties. Infrared spectrum: 1079. 1118, 1160 cm 2 18 'C NMR spectrum: 14.0,22.2,23.7,25.5-319, 54.4, 55.3, 60.2, 60.6, 73.1. "DNMR spectm: 1.73 ppm Mass spectrum: m/z 296 (35% rel int), 142 (30% rel int), 141 (100% rel int), 140 (60% rel int). Mass spectrum (negative ion anunonia Cl): n/z 426 (3% rel int), 409 (27% rel int), 468 (100% rel 5 int). EXAMPLE 2 - SynthesIs of a mixture of 3-aky1.4-alkyl.2,10,11-trioxa- 6 aza-1- boratricyclo(4.4.4.0"'tetradecmes. The Reaction scheme below snnmarises the chemistry involved.

NII

3 CHO N

OCH

3 o NH 0 00 CH30 0 0 ~jAn ,- N ;-Te - -- ~~ %.Zs? 4 :40. C ~ g i 19 Characterization of commercial alkylkerenedimer AKD 100 RN AKD 100 HN was analysed by probe mass spectrometry and was shown to comprise a mixture of C28, C30, C32, C34 and C36 homologues, with C30 the most abundant. Preparation of di.N-(carbomethoxyethy)-2-alkyl-3-ketoalkylamide. (where the alkyl group length 5 varies according to the MW ofthe original AKD homotogue) To AKD 100 HN (181g, average mw 448, 0.4mol)whichhad been melted in a round-bottomed flask was added dipwise over three hours N,N-bis(2-carbomethoxyethy1aimine (77g, 0.41 mol). The molten mixture was stirred for a further three hours, and then allowed to cool to give a viscous semi solid (256g). The crude product (flm) showed c-o 1740 (ester), 1715 (kotouc) and 1690 (amide). 10 'H NMR (CDC13) 'H NMR (CDC13)0.9 (CM), 1.3, 2.3, 2.4,2.7 (i, CHi's), 3.5 (t, CH), 3.62, 3.67 (S, OCH). ' 3 CNMR (CDCa). 14.0 alkyll CH 3 ), 44.0 to 22.5 (26 alkyl CH2), 51.7, 52.0 (OCH 3 ), 57.8 (QH), 169.5 (amide -0), 171.1, 172.3 (ester -=0), 207.2 (ketone C=O). MS (Probe, NCI,

NH

3 reactant gas). in/z 532 (M 693-161), 504 (M665- 161), 476 (M 637-161), 448 (M-609-161). Lithium aluminium hydride reduction ofdi-N-(carbomethyethyl)-2-alkyl-3-ketoalkylamide togive 15 di-N-(propan-1-ol)-N-(1.2-dialkylpropan--olamine (where the aikyl group length wries according to the MW ofthe original AKD homologue). Lithium aluminium hydride (40g, 1.5 mol based on 0.5 equivalents per ester functional group, 0.25 equivalents each for the ketone and snide functional groups and taken unjust over 2 fNld excess over theory) was added to anhydrous diethylether (2.2L) with cooling and stirring. To the LiAIH 4 slurry 20 was added the keto-amide-diester homologue mixture (200g, average MW 637, 0.32 mol) in anhydrous diethyl either (I L) and the mixture was then stirred and heated under reflux for 24h. The mixture was cooled and transferred to a large beaker. Saturated aqueous ammonium chloride solution was then cautiously added with continuous stirring until the excess of LiAlH 4 had been hydrolysed. The grey granular precipitate was fited, and the precipitate was washed with two 500 25 mL potions of ether. and the washings combined with the filtrat which was concentrated to give a viscous yellow gum (348g, 84%). The aminoulcohol showeduo.n 3 4 0 0 cmd 1 (film), with no carbonyl absorption bands present 'H NMR (CIaOD) 0.9 (alkyl C0H), 1.32,2.3,2.9,3.6 (alkyl Cfis and CH). UC NMR (CHsOD) 14-51 (C2s nd CH), 60. 61 (-CH 2 OH), 74 (-QHOH). MS (BT 70 eV, probe, TMSi derivative). n/z 757,785, 813, 841 (M 1%), 73 (100%) MS (NCI, NH 3 at 0.35 ton) 20 540, 568, 596, and 624 (M-H)~ Reaction of the alkyl aminoalcohol homologue mixture with boric acid under Dean-Starkremoval of water conditions. Preparation of 1,2-dialkyl-2,10,11-trioxa-6-aza-1 boraticyclo[4A.4Ol, tetradecane (where the alky group length varies according to the MW ofthe 5 original -AKD homologue). The homologous mixture of alkyl aminoalcohols (70& 0.12 mol) was placed in a IL flask fitted with a stirrer and a Dean Stark apparatus. Boric acid (8.0g) was added, and the mixture followed by toluene (650 iL). The mixture was stirred and heated under reflux until the theoretical volume of water was obtained. The mixture was cooled and filtered from a small quantity of unreacted boric 10 acid, and the toluene was removed under reduced pressure. The mixture of boraranes was obtained as near white semi-solid (70g, 97%). IR (film) N-wa. co ml 8.o)1160, 1120, 1080 cm' 'H NMR (CDCla) 0.9 (alkyl CH3), 1.4, 1.9, 2.4, 2.7, 2.8 (alkyl CH2s and CM. ' 3 C NMR (CDC1h) 14 (alkyl LH3), 19-40 (alkyl C-as and CH), 54, 55, and 56 (N-CH2s), 60, 61, 73 (OCH 2 s and O-CHR), " 1 B NMR (CDCl,)1.7:ppm. MS (NC!, NH, at 0.35 torr, probe) mz 566,594,622,650 (M+NH3y, 5%, 15 548, 576, 604, 632 (M-H), 100%. EXAMPLE 3: SynthesIs and Charactersation of 3,7-didecyl-10-hydroxymethyl-2,89 trioxa-5-aza-1-boratricyclo[3.3.3.0'f-undecane and 8,11-didecyl-4-hydroxyl2,9,0-trioxa-6 aza 1-boratrileyelo[4.3.3.0 3 'dodecane Stei One: Ring Opening of 1,2-epoxydodecane with 3-amino-1,2-propanadial 20 In a 250ml round bottom flask was placed 3-amino-1,2-propanediol (11.56 & 0.12 mol), and a magnetic stirrer. 1,2-epoxydodecane (4 5 .42g, 0.25 mol), and toluene-4-sulphonic acid (4 crystals) were then added from a dropping funnel with stiring and heating to 120'C using an oil bath. The actionn mixhn was allowed to stir for two weeks, and was then left to cool to room temperature. The mixture yielded 54.41 g of a waxy liquid, of which 54% byweight was found to be NN 25 bis(dodecan-2-ol)-N-(propmne-2,3-diol)emine, using a back calculation from the boric acid esterification reaction, in step two. FT-IR (neat): 3200-3500cm- 1 (polymeric OH stretch), 2954 cma. CH3,. 2912 cml. CH 2 , 2852 cm',CH2. 1464 cm-b.CHa. 21 1376 cm716 CH 3 , 1341 =n1 CH wag, 1072 cm v (C-O)2" alcohol, 1040 cm-lv (C-0) 1" alcohol, 874 cm-'NR 3 bend, 721 cuff CH 2 rocking mode. 'H NMR (THF-da): - 8 1.10 (s, 6H, -CH3), 1.50 (s, 24H, CH2 window), 2.50-2.90 5 (m,4H,CH beta to central N atom, alkyl), 3.60-4.00 (m, 4H CH beta to central N atom, non alkyl), 4.50 (, 2H, fRee OH). t3 C NMR CI -da): 8 15.4 (CH), alkyl CHI), 24.3, 27.4, 31.1, 31.4, 31.7, 33.6, 37.0 (all CI, alkyl CR 2 ). 62.0 (Clii, alpha to 10 alcohol). 65.0 (CHz alpha to central nitrogen atom), 66.4 (CH2, CH2 10 alpha to central nitrogen atom, non alkyl) 69.5, 70.2, 71.3. 72.2, (all CH, CH beta to central N atom). FAB-MS (FAB(+), C, 15 keV); [M + H+, m/z - 460 (100%). [(M + H) - H 2 O]*, m/z = 442 (14%). [(M + H) - 2H 2 0r, m/z -424 (3%). 15 [(M + H) - CH(OH)CH2 1 OH]*, /z - 398 (23%). {R-CH(OH)CH2NCH2CH(OH)CH2(OH) + H]', m/z - 288 (78%) [R-CH2NCH 2 + H]*. m/z =226 (181%) (M'+ H]+* m/z=276 (15%) 20 ES-MS (ES (+I), Cone Voltage [M + Na]*, =/z - 482.0 (20%) 60 V) [M + H]+, m/2= 460.1 (100%) [(M -H20)+ H]*, m/z= 442.4 (2%) [IM + H]+, m/z 276.2(30%) 22 [M* + H) - H20], w/z = 258.1 (35%) {(M'+ H) - 2H20]', m/z - 239.9 (3%) where M = N-(dodecan-2-ol)-N-(propmne-2,3-diol)amine, and R = CoH2i. Step Two; Boric Acid Estericaon Reaction. 5 The reaction mixture f-rom step one (54.41 g) was dissolved in 700 ml of toluene in a 1 L round bottom flask wid boric acid (7.33 g, 0.12 mol), assuming that the reaction mixture from step one was all NN-bis(dodecan-2-ol)-N-(propan-2,3-diol)amline, was added, along with toluene-4-sulphonic acid (4 crystals). The reaction mixture was heated to reflux with string and the water created by the reaction was removed azeotropically, using a Dean and Stark apparatus. After four hours the 10 reaction was complete. The reactionmixture was then allowed to col to room temperature, and was filtered to remove the unreacted boric acid. The toluene was removed at reduced pressure, to yield a waxy yellow solid. The waxy yellow solid was dissolved in hot ThF/hexane 1:1 and stored in a freezer for 24 hours. After freezing for 24 hours, a white solid was collected by filtration. The white solid was stored over silica gel, in a desiccator for 24 hours, to remove residual solvent, yield 30.12 15 g, 54%, MP =75"C. FT-IR (CHCL 3 ); 3200-3500 cmut (polymeric OH stretch), 2956 cm-' -% CH,. 2934 c=7 v. CHR2, 2911 cm"' u, CH 2 . 2849 an- u, CH 2 , 1468 cm' 6. CH 3 , 1378 nf' S. CH, 1343 cn' CH wag, 1257 cm' N-Cipstretching, 1102 cm~' N->B transannular dative 20 bond, 884 cmd NR3 bend, 755 cm"1 and 721 cm~' CEa rocking modes. H NMR (THF-da): 8 1.10 (d, S, -CH3), 1.30-1.90 (s. 2611, CH 2 window), 2.45-3.05 (m, IH), 3.10-3.30 (i, 1H), 3.30-3.90 (i, 4H), 3.90-4.60 (m, 211), protons around N-+B transannular dative bond. 25 "CNMR(THF-d.): 5 15.2 (CH3, alkyl-CH3), 24.3, 27.6, 27.9, 31.1, 31.4, 31.7, 33.7, 36.0, 38.1 (all CH 2 , alkyl-CH 2 ), 63.1, 64.3, 64.5, 64.8, 67.1, 67.4, 68.3,68.6.68.7,69.5,70.6 (all CH 2 . alpha to central nitrogen atom, 23 alpha to baron coordinated 0 atoms, alpha to free OH), 72.3, 73.4, 73.6,74.5,75.3,75.7,76.2,77.3, 77.8,78.8 (all CH, beta to central nitrogen atom, bonded to fre. OH). "B NMR (solid state) Single broad peak centred at 17.9 ppm. 5 1 B NMR (ITHF, solution state): 298 K 15.9 ppm 13.3.3.0] ring system 10.5 ppm [4.3.3.0] ring system 333 K 15.9 ppm [3.3.3.0] ring system 10.2 ppm [4.3.3.0} ring system FAB-MS (FAB (+), Cs, IS keV): 10 [M+ H]*m/z=468 (100%) [M + HI* m/z = 460 (81%) [M + H] t m/z =276 (45%) [(M+ H) - 2H2O n/z -240 (37%) ES-MS (ES(+), Cone Voltage =60 V): 15 [M + H]'m/z - 467.8 (20%) [M' + H]+ m/z = 460.2 (60%), present from the equilibrium set up between the boron compounds and the trinikmnolamine precursor. 20 (M* + H]+ m/z = 276.1 (25%) [(M*- H2 0 ) + Hf' m/z -257.S (5%) [(M*- 1-2Q - CH3)+HJ+m/z=232.8 (3%) 24 (M* - H20 - (-CH2-CH3)) + Hlt m/z= 219.0 (27%). where M' = NN-bis(dodecan-2-al)-N-(propane-2,3-diol)amine, and M* = N-(dodecan-2-ol)-N (propone-2,3-dio1)amin EXAMPLE 4: Synthesis and Chmaeterisation of 3,7,dimethyl-10-hydroxymethyl-2A9 trioxa-5-aa-l-boratrieylo3.33.0"]uudeeane and 8,11-dimethyl-4-hydroxyl-2,9,10-trioxa-5 aza-1-boratricyclo[4.3.3.0ldodeCane in mixture with higher molecular weight oligomers. Step One; Ring Opening of 2,3-epoxypropan-1-ol with N.N-bis(propan-2-ol)amine 10 NN-bis(propan-2-ol)amine (111.29 & 0.84 nol), was dissolved in 200 i ofmethanol, along with toluene-4-sulphonic acid (4 crystals), in a 500 ml three neck Bask. The reaction mixture was then equilibrated to -8 to -10"C using an ice-salt bath. 2,3-Epoxypropan-1-ol (61.91 g. 0.84 mol) was dissolved in 150 ml of methanol, and was added to the reaction mixture from a dropping funnel, over a two hour period with stirring at -8 to -10"C. The reaction mixture was then allowed to come to 15 room temperature and stining was continued for 24 hours. After 24 hours, the methanol was removed at reduced pressure to yield 164.85 g (95%), of NN bia(propan-2-ol)-N-(popane-2,3-diol)emiue as a lime green liquid, which three months after synthesis showed signs of solidification. PT-IR (neat): 3200-3500 cm"' (polymeric OH stretch), 2968 cm' uu CH 3 , 2932 20 cni' u. CH 2 , 2884 cm- ' i CH 2 , 2832 crr' v, CH 2 , 1460 cni' u

CH

3 , 1375 cm-' u, CH 3 , 1336 cnf' CH wag, 1257 cn' N-Ca, stretching, 1132 cun' C-0-C antisymmnetric stretching in ethers, 1058 en 1 f u (C-O) 1" alcohol, 957 cmf' and 940 cnT' NR3 bending modes. 25 'H NMR (CDgOD): 61.25 (in, 3K, diastereoisomeric CH 3 's),2.35-2.85 (Um, 3), 3.40 (s, 1 E), 3.50-3.65 (i, IN), 3.70-4.00 (n, 21), protons alpha and beta to the central nitrogen atom, and protons bonded to free OH groups, 4.95 (a, 211, free OH). 25 "C NMR (CDOD): 6 21.1, 21.3, 21.4, 217 (all CH 3 , diastereoisomeric CH 3 's), 60.3, 61.1 (CH2, alphato free O), 65.3,65.7, 65.9, 66.0,66.4 (all CH 2 , alpha to the central nitrogen atom), 66.6,67.1, 67.7,70.9,71.7,72.0 (all CH, CH bonded to free OH, and beta to central nitrogen atom). 5 FAB-MS (FAB (+), Cs, 15 keV): [M+ H]+m/z -208 (100%) [(M + CH2CH(OH)CH2(O)) + H]' m/z - 282 (2%) [(M - CH2CH(OH)CH2(OH)) + H]f 10 rn/z 134 (3%) ES-MS (ES (+), Cone Voltage -60 V): [M + H]* m/z -208.1 (100%) [(M - H20)+ H+m/z= 189.9 (50%) [(M -2H20)+ H]+m/z= 172.0 (12%) 15 [(M-CH(OR)H2OH)) + -3 m/z = 145.9 (4%) [(M + CH2CH(OH)CH2(OH)) + H]r m/z=282.1 (50%) [(M + CH2CH(OH)CH2(OH)) - H20) + ] 20 m/z=264.1 (5%) [(M + CH2CH(OH)CH 2

(OH)-CH(OH)CH

2 OH)) + H]* m/z 230.1 (5%) 26 [(M + 2CH2CH(OH)CH2(OH)) + H]* m/z = 356.2 (27%) [(M + 3CH2CH(OH)CH2(OH)) + H]* m/z - 430,2 (10%) 5 [M* + H]+m/z = 133.8 (20%) [(M* - H20)+ HJ+m/z - 115.8 (35%)] where M= NN-bis(propan-2-ol)-N-{propan-2,3-diol)amine and M - NN-bis(propan-2-ol)amine. Step Two: ora Acid Esterifcation Reaction ofN.N-bis(propan-2-o)-N-(propane-2,3-diol)amine and Oligomers 10 NN-bis(propan-2-ol)-N-(propane-2,3-diol)amine and oligomers (10.46g 0.05 mCI), based on the molecular weight ofNN-bis(propan-2-ol)-N-(propane-2,3-diol)amine, toluene-4-sulphonic acid (4 crystals), and borie acid (3.16 g, 0.05 mol), were placed in a250 ml round bottom flask with200 ml of butan-1 -ol. The reaction mixture was then heated to reflux with stirring, and the water produced by the reaction was removed azeotropically, using a Dean and Stark apparatus, (1.80 ml of the 15 expected 2.73 ml of water was collected). The production of water was slow and took 60 hours. The reaction mixture was allowed to cool to room temperature, and no boric acid was observed. The butan-1-ol was removed at reduced pressure to yield a viscous yellow liquid, which was stoied over silica gel in a desiccator for 24 hours, to remove residual butan-1-ol, yield 10.76 & quantitative. FT-UR (neat): 3200-3500 cm' polymerie OH stretch,2967 cma CH, 2932 cm-' 20 v, CH 2 , 2873 cm~' o, CH 3 , 1476 cm'a 8. CH3, 1380 cf' S, CHa, 1258 cm1 N-Cwtz stretch, 1091-1145 cm' N-tB transmnnular dative bond, 915 cm'. 876 cm, and 817 cm' NR, banding modes. 'H NMR (THF-ds): 51.10 (t,4H, diastcreoisomeric CHs's), 1.30-1.80(mi6H), 2.70-3.40 25 (m, 6H), protons around the N-+B transannular dative bond, 3.75 (t, 27 free OH), 4.10-4.70 (m, 2H), protons around theN-->B transannular dative bond. 3 C NMR(THF-ds): 8 15.9, 20.9,21.1,21.2,21.3, 21.5,21.8,22.1,22.2.22.9,23.1,23.6, 23.9, 24.4, 24.7 (all CH 3 , diastercoisomeric CHj's), 37.A (CH 2 , N 5 CH 2 ), 60.7 (CH2, CH2OH), 63.8 (CH 2 , CH 2 OH), 64.4, 65.0, 65.3, 65.4, 65.6, 65.8, 66.6 (al1 CH 2 , CH 2 0H), 69.1, 69.3, 69.7, 70.0, 70.3, 70.9,72.2,72.8,74.3,74.4,75,3,76.1,77.6,79.3 (all CH, CH-OH). "B NMR THF): 298 K 15.3 ppm[3.3.3.0] ring system 10 9.6 ppm[4.3.3.0) ring system 333 K 15.4 ppm[3.3.3.0] ring system 9.6 ppm[4.3.3.0] ring system 20.1 ppm small shoulder due to B(OBu)/HkBO FABMS (MAB ( Cs, 15 keV): 1+ .[M+ ]m/z - 216 (100%) [M - H 2 0) + H+ n/z = 198 (32%) [(M - CH(OH)) + H] n/z = 184 (27%) [(M - CH20H-CH 3 ) + H]* m/z -170 (20%) [(M - CHaCH(OH)) + Hf m/z - 156 (22%) 20 mfz =142 (55%). (M - O x 3 + H * OH n/zn= 140 (70%). [(M-83)+H)+m/za =133(90%). 28 Step Three: Acid Catalysed Hydrolysis of Oligomers N,N-bis(propan-2-ol)-N-(propane-2,3-diol)amine and oligomers (84.39 g, 0.41 mol), based on the 5 molecular weight ofNN-bis(propan-2-ol)-N-(propane-2,3-diol)amine were dissolved in 300 ml of distilled water, in a 1 L round bottom flask. Orthophosphoric acid (272.42 g, 2.45 mol) was added, and the reactieinmixture was heated to reflux with stirring for 36 bours. After 36 hours, the reaction mixture was allowed to cool to room temperature, before a 10% by weight NaOH solution was used to adjust the pH of the reaction mixture to 7-7.2 (pH paper). The solvent (mostly water), was then 10 removed at reduced pressure to yield a viscous orange liquid, and white sodium phosphates. The viscous orange liquid was dissolved in methanol, and allowed to stand overnight to precipitate any remaining phosphates. The methanol solution was then filtered twice and the methanol was removed at reduced pressure to yield 82.28 g of a dark orange liquid (trialkanolamine and glycol from hydrolysis). The dark orange liquid was the chromatographed, using a DOWEX 5OW-X8 ion 15 exchange resin in the H T form. The column was first eluted with distilled water to remove any residual sodium phosphates and the glycol from hydrolysis, and the second elution with a 10% by weight NH 3 solution to remove the trialnolanmine product frmn the resin. The NH 3 solution was removed at reduced pressure, to yield 54.61g, 65%, of a dark orange liquid. FT-IR (neat); 3200-3500 cm*' (polymeric OH stretch), 29j cm? v. C%.

20 2931 cm'' u. CH 2 , 2831 cm' . CH 2 , 1461 cm-' 5, CH, 1375 cni' 6, CH 3 , 1336 cm-' CH wag, 1285 cm"' N-C, 1 * stretching, 1133 cm 1 C-0-C aUtisymmetric stretching in ethers, 1066 cm' u (C-O) 10 alcohol, 95$ cm~' and 839 cm7 Na bending modes. 'H NMR (CD 2 OD); 8 1.35 (m, 4H, diastereoisomeric CHgs), 2.60-3.00 (bn, 4H, CH 25 bonded to free OH, diastereoisomeric CH 3 1 s and beta to the central nitrogen atom), 3.60-4.40 (m, 4H, CH bonded to free OH, CH20H and beta to the central nitrogen atom), 5.00 (s, 2H, free OH). 29 1C NMR (CDQ3D); 8 21.9, 22.1, 22.2, 22.5, 22.6, 22.7 (all CH3, diastereoisomeric

CH,

1 s), 57.8,58.1,60.6 (all CH 2 , alpha to the central nitrogen atom), 64.8,65.2,65.4,65.7,66.4,66.6,66.7 (all CH21, bonded to free OH), 67.3, 67.7, 67.9, 68.4, 68.7 (all CH, bonded to free OH, 5 . . - diastereoisomerio.CH,'s and beta to the central nitrogen atom), 71.6 72.0, 72.4 (all CH, bonded to free OH, CH2OH and beta to the central nitrogen atom). FAB-MS (FAB (t), Cst 15 keV): [M + Hf m/z -208 (100%) 10 ES-MS (BS (+) Cone Voltage - 60 V): (M + H]+m/z= 208 (100%) [(M -CH2CH(OH)CH2OH) + H]+ m/z - 133.9 (100%) [(M-CH2CH(OH)CH20H-H20)+ H)+ 15 m/z - 115.8 (2%a) whore M=N,Nrbisproane-2-ol)-N-(propane-2,3-diol)&mine Step Four: Boric Acid Estenfication Reaction ofNN-bis(propan-2-ol)-N-(propane 2,3-doI)amlne N.N-bis(propan-2-ol)-N-(propane-2,3-diol)amine (19.70 g. 0.095 mol), tolueno-4-sulphonic acid(4 20 crystals), and boric acid (5.88 g 0.095 mol), were placed in a 500 ml round bottom flask, along with 350 ml-of toluene. The reaction was then heated to reflux, with stirring. The water produced by the reaction was removed azotropically, using a Dean and Stark apparatus. The reaction mixture was thon allowed to cool to room temperature and a red-brown substance solidified, the toluene was decanted and the red brown substance was dissolved in methanol, filtered, and the methanol removed 25 atreduced pressure to yield a red-brown liquid. Residual methanol and toluene wereremovedunder a nitrogen atmosphere, followed by storage over silica gel in a desiccator for24 bours, yield 14.89g, 30 73%. Attempted recrystallisadons from ethanol, ethanol/petroleum spirit, and hexane/dichloromethane proved unsuccessfil. FT-IR (neat): 3200-3500 cm-E (polymeric OH stretch), 2971 cm~' . CH3. 2931 cm- u. CH2, 2872 cm-' u. CH2, 1467 cu 5. CH3, 5 1383 cmE 8, CHI, 1257 cm^' N-Cupg totching, 1079-1145 cm-l N-+B trmnsannular dative bond, 914 cm', 874 cmP, and 818 cm-P NRJ bending modes. 'H NMR (THF-da): S 1.10-1.40 (m.23 H, diastereoisomeric CHI's)2.35-3.20 (m, 14H). 3.20-3.90 (m, 291), 3.90-4.60 (m, 13H), 5.55 (t, 21, free OH), 10 protons surrounding the N-)B ftnsannular dative bond. 1C NMR (THF-d): 8 20.8, 21.2, 21.6, 21.9, 22.1, 22.2, 22.8, 23.56, 23.61, 23.8, 24.4, 24.6 (all CH3, dinstereoisomeric CHI's), 56.3 (CH 2 , CH2 bonded to free OH), 61.0,61.3, 63.5 (all CH 2 , CH2's bonded to free OH), 65.3, 65.7,65.9,66.1,67.2, 67.4,67.8 (all CH 2 , CH2's alpha to the central 15 nitrogen atom, bonded to free OH), 69.8 (CH, CH bonded to diastercoisomeric CH3, beta to the central nitrogen atom), 70.1 (CH2, CH2OH), 72.1 (CH, CH-OH), 72.5 (CH2, CH 2 OH), 72. 74.2,74.3, 75.1, 76.0, 77.9, 79.4 (all CH, CH-OH). "B NMR (solution state, THF): 298K 14.7 ppm [3.3.3.0] ring system 20 9.6 ppm [4.3.3.0) ring system 333K 14.6 ppm [3.3.3.0] ring system 9.3 ppm [4.3.3.0] ring system FAB-MS (FAB (+), C', 15 keV): [M+ Hf m/z= 216 (100%) 31 [M* + 1)f m/z = 208 (30%). from the equilibrium set up between the boron compounds and the trialkanolamine precursor Where M products and M'= NN-bis(propan-2-ol)~N-(propane 2,3-diol)amine. 5 EXAMPLE 5: Synthesis and Characterlsation of 12-hydroxymethyl-21O,11-iaxa-6-aza-1 boratrieyelo[4A.3.0O"'tetradeeane (5) and 13-hydroxyl-2,10,11-trioxa-6-aZa-1 boratrlcycloF4.4.4.0ltetradecane Step One: Reduction of NN-bis(2-carbmethoxyethyl)amine to NN-bisoropan-3 ol)amine 10 Absolute ethanol was dried from the magnesium ethylate, and stored over molecular sieves (Linde type 4A) prior to use. To a 1 L three neck flask, equipped with a reflux condenser, mechanical stirrer, and a nitrogen atmosphere, was added 800 ml of dry ethanol and NN-bis(2-carbmethoxyethyl)amine (48.21 , 0.26 mol). The reaction mixture was then cooled to 0-44C using an ice/water bath, before dry ethanol 15 washed sodium metal (70.16 g., 3.05 mol) was added in large pieces with stirring. A vigorous reaction occurred which was controlled using an ice/water bath. After 45 minutes, the reaction had subsided and the reaction mixture was heated to reflux with stirring. The reaction mixture was allowed to reflux with stirring for 24 hours. After 24 hours, the rcacticaimixtuc had turned yellow colour. The reaction mixture was allowed to cool to room temperature and was diluted with 500 ml 20 of distilled water. The ethanol was then distilled, vacuum was applied via a water aspirator to remove the last ofthe ethanol. The pH of the reaction mixture was then adjusted to 7 using 5 mol L' 1 HCl, the pH was monitored with a pH meter. The water was then removed at reduced pressure, to yield a yellow-orange liquid and solid NaCL. The yellow-orange liquid was dissolved in methanol, and filtered twice to remove any remaining NaCi. The methanol was then removed at reduced 25 pressure, to yield (44.50g) of a yellow orange liquid, which was azeotropicallydried with toluene, to yield NN-bis (propan-3-ol)amine, 30.3g, 88%.. FT-IR (neat); 2500-3500 cmo' polymeric OH stretch, 1583 cmi' OH bmncing vibration, 1207 cmo' C-N stretching vibration, 1062 cm" C-0 stretch, 1* alcohol, 839 cm-' HNR 2 bending mode. 32 'H NMR (CD 3 (OD): 8 1.75 (p, CH 2 , 2.35 (m, CH 2 alpha to NH group, 2.95 (ra CRz alpha to the OH group), 3,55 (t, HNR2), 4.85 (s, free OH). "C NMR (CD 3 DD); 6 27.8, 29.7 (CH2, 33.4, (CH 2 ,. N-CH2), 34.5 (CH 2 , N-CU 2 ), 38.8 (CH2, N-CH2), 40.4 (CH2, CR2011). GCMS (70 eV, El. OAc 5 derivative): Retention time = 37.13 minutes Area percent - 99% m/z 259 (M* 1%), 244 (M* -CHa, 10%) 216 (M-' - COCH 3 , 6%) 10 199 (M -CH3COOH, 2%) 184 (M* - CH3COOH - CH 3 , 12%) 172 (M* - 87, 8%). 156 (M.+- 103, 21%) 140 (M*- - 119, 16%) 130 (M 4 ' - 129, 100%) 15 113 (M" - 146, 10%) 101 (M - 158,27%),70 (M- 189,39%) FAB-MS (FAB (+), Cs*, 15 keV): [M + H]"m/z = 134 (100%)

[M-H

3 O*M/z= 115 (55%) 20 ES-MS (ES (+), Cone Voltage - 6V): [M+ H]m/z= 134.5 (100%) [(M - H20) + H]+ m/z -116.5 (30%) 33 Where M N,N-bis(propan-3-ol)anine 0 Step Tw: Ring Opening of 2,3-epoxypropan-t-I with N,N-bis(propan-3-oI)amlne N,N-bis(propan-3-ol)unine (17.10 g 0.13 mol) and tolucne-4-sulphonic acid (4 crystals), were dissolved in 200 ml of methanol in a 500 r three neck flask. Thereaction mixture was equilibrated 5 to -8 to -10C, using an ice/saltbath. 2,3-Epoxypropan-1-ol (9.51 g, 0.13 mol) dissolvedin 100ml of methanol was then added from a dropping fnel to the reaction mixture with stirring. The reaction mixture was allowed to warm up to room temperature and was stirred for 24 hours. After 24 hours the etinol was then removed at reduced pressure, to yield 25,81 , 97% of a red-orange liquid. 10 FT-IR (neat): 3200-3500 crn polymeric OH stretch, 2946 cm7' . CH 2 , 1402 cn- N-CH 2 bending mode, 1198 ca' C-N stretching mode, 1108 cm* C-0 stretch, 2" alcohol, 926 cf' and 854 cm- 1

NR

3 bending modes. 'H NMR (CDjOD): 8 1.65-1.90 (m, 6H), 2.25-2.50 (m, 6H), 2.80-3.20 (m, 16), 15 3.30-3.60 (m, 26H), protons alpha and beta to the central nitrogen atom, protons bonded to free OH groups, 4.80 (s, 2H, free OH). "C NMR (CDOD): 8 27.7,28.4,29.7 (all CH2, beta to OH and beta to the central nitrogeinatomh) 31.7, 33.4(CH 2 ,NCH), 52.0,52.6,53.0,53.3 20 (all CH2, CH20H), 56.7,57.9,59.5,60.1,60.4,60.7, (all CH2,

CH

2 OH), 64.3,65.5 (CH 2 , CH 2 QH), 66.5,73.8 (CH, CH-OH). FAB-MS (FAB (+), Cs, 15 keV): [M+ HrYm/z=208 (100%) [(M + CH2CH(OH)CH2(OH)) + H)* 25 ma/z=282 (18%) [(M - CH2CH(OH)CH2(oH) - H20) + H]* 34 m/z = 115 (53%) ES-MS (ES (+), Cone Voltage =60 V): [[M + H] m/z -208.5 (100%) [(M + CH2CH(OH)CH2(OH))+ H]* 5 mzn - 282.5 (22%) [(M - H2o)+ ]+m/z - 190.5 (10%) [(M - 2H20) + H]+ m/z = 172.5 (8%) [(M- CH2(OH)CH2OH) + Hr m/z= 146.5 (18%) 10 [(M - CH2CH(OH)CH2OH) + HJ* m/z = 134.4 (20%) [(M - CH2CH(OH)CH2OH - H20) + H] 4 m/z - 116.5 (10%) Where M =N,N-bis(propan-3-ol)-N-(propane-2,3-dioi)amine Step 3: Boric Acit Esrerilcadon Reaction of NN-bis(propan-3-o)-N-propane-2,3-diol)amine N,N-bis(propan-3-ol)-N-(propmne-2,3-diol)amine (5.02 g, 0.024 mol), toluene-4-sulphonic acid (4 crystals) and boric acid (1.51 & 0.024 mol), were placed in a250 ml roundbottom flask, with 200 ml of butan-1-ol The rmation mixture was then heated to refha with stining and the water produced 20 by the reaction was removed azeotropically, using a Dean and Stark apparatus. The production of water was slow and took 60 hours, (0.75 ml of the expected 1.31 ml of water was collected). The reaction mixture was allowed to cool to room temperaur No boric acid was observed. The butan 1-ol was removed at reduced pressure, to yield an orange liquid which was stored under vacun over silica gel in a desiccator for 24 hours to remove residual butanol. yield 4.7 g, 91%. 35 FT-JR (neat): 3200-3500 cm' polymeric OH stretch, 2935 cm 4 u. CH2, 2875 cif iii CH2, 1581 em" OH bendingmode, 1462 cm' CH 2 scissor, 1383 cm- 1 8 (CH), 1250 cm- 1 C-N stretching vibration, 1102 c=71 N->B transannular dative bond, 963 cm-E' and 850 cm-I NR 3 bending 5 . ' '- . modes.

'H NMR (IHF-da): 5 1.20 (t, 31, CH 3 frombutan--1-ol or tributyl borate) 1.30-1.90 (w, 9H), 2.00 (s, SH), protons around the N->B transannular dative bond, 3.00-3.50 (s, 40H, free OH), 3.50-4.25 (n, 22H), 4.35 (4, 2H), protons around the N-+B transannular dative bond. 10 'C NMR (THF-dg): 5 15.4 (CH. from residual butan-1-ol or tributyl borate), 21.4, 25.9,26.3 (CHz,N-CH2-rCH2-0), 62.9,63.2, (CH 2 , CH 2 OH), 71.9 (CH, CH-OH). "B NMR (solution state THF): 298 K 5.3 ppm[4.4.3.0] ring system 3.4 ppm [4.4.4.0} ring system 15 333 K 5.4 ppm [4.4.3.0] ring system 3.6 ppm (4.4.4.0J ring system FAB-MS (FAB (+), Cs*, 15 keV): (M t H]i m/z= 216 (100%) [(M - 82)+ H]* m/z= 134 (35%) 20 [(M - H2O) t H]*m/z -198 (10%) [(M - CH(OH) + H]* nz = 184 (8%) [(M - CH2OH - CH)+ Hm/Z -170 (5%) + ' o * " m/z=1 4 2 (15%). 36 EXAMPLE 6 Cross-Llnklng Reactions of Boratranes S In this Example boratranes of Examples 3-5 are reacted with Cymel 323 (sec Formula IV) in a suitable solvent (in the presence of toluean-4-sulphonic acid, catalyst) to produce a condensation polymer. Two moles ofboratranes for each mole of Cymel 323 were used. The resulting polymers have the repeating units shown in Formulae VII and VI where the R groups indicate boratrane molecules inced to the polymer through these hydroxy substituents. 10 OR > OR .N N N N NH H .N Y N AvyNN VII N N N;Z, N Nyr N on OR OR R = Brairanc 15 Reaction One: Crss-inkng of 3,7-didecyl-J0-hydroxymethyl-2,8,9-trioxa-5-aza-l boraricyclo[33.3,0' 2 ]-undecane and 8, 11-didecyl-4-hydroxy-2,9, 10-zrioxa-6 aza-i-boraricyclo[4.3.3.D"]dodecane with Cymel 323 resin. To a 250m1 round bottom flask was added 3,7-didecyl-l0-hydroxymethyI-2,8,9-trioxa-s-aza-1 20 bortricyclo[3.3.3.0'jundecane (1) and 8,11-didecyl-4-hydroxy1-2,9,10-trioxa-6-aza-l boratricyclo[4.3.3.0'Adodecae (2) (1.62 g 3.5 mmol), Cymel 323 (0.67g 1.7 mmol, a commercially available crosslinking chemical), toune-4-sulphanic acid (4 crystals) and 200 ml of toluene, the last portion of the Cymel 323 had to be solubilised with 10 ml of obloroform. The reaction mixture was then heated to reflu with stirring for 24 hours. After 24 hours the reaction 25 mixture was allowed to cool to room temperature and the toluene was removed at reduced pressure, 37 the waxy white solid produced was then dried in a vacuum oven at 105"C for 24 hours, to yield 3.61 g of a powdery white solid. "B NMR (solid state): 1.60 ppm[4.3.3-0] ring system 5.00 ypm[3.3.3.03 ring system 5 (see Figure 1) Reaction Two: Cross-linking of 3,7-dimethyl-10-hydroxymethyl-2,9-trioxa-S-aa.1 boratricyclo[3.3.3.0 t' -undecane and 8.i-dlimethyl-4-hydroxyl-2,9,10 trioxa-5-aza-1-borafricyclo[4.3.3.0']dodecane To a 250m1 conical flask was added 3,7-dimethyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l 10 boratricyclo{3.3.3.0' 5 undecane (3) and 8,11-dimethyl-4-hydroxyl-2,9-10-trioxa-6-aza-l boratricyclo[4.3.3,0''']dodecane (4) (1.46 g, 6.8 mmol), Cymel 323 (1.31 g, 3.4 mmol), toluene-4 sulphonic acid (4 crystals), and 200 ml of water, the last of the Cymel 323 had to be solubilised with 10 ml of ethanol. The reaction mixture was then stirred at room temperature for 24 hours, the reaction mixture was then dried in a vacuum oven at 105"C for 24 hours, to yield 2.20 g of clear 15 glassy solid. "B NMR (solid state): 11.3 ppm Polymeric boron (<5%totalB signal) 6.2 ppm [3.3.3.0] ring system 20 2.0 ppm [4.3.3.0] ring system (see Figure 2) Reaction Thr: Cross-linking of 3,7-dimethyl-1 O-hydroxymethyl-2.8.9-trioxa-.Saa-1 borazricyclo[3.3.3. O' 4 -undeane and 8.11-dimethyl-4-hydroryl-2.910-trioxa-6-aza-1boratricyclof4.3.3.O' 6 ]dodecanefrom acid catalysed hydrolysis reaction (oligomer-reduced) with Cymel 323 resin To a 250 ml conical flask was added 3 ,7-dimethyl-10-hydoxyl-2,8,9-trioxa-5-aza-1 boranicyclo[3.3.3.0 '9]udecane (3), and 8,11-dimethyl-4-hydroxyl-2,9,10-trioxa-6-aza-l 5 boratricyclo[4.3.3.0 1 "dodecane (4) (1.37 p, 6.4 mmol), Cymel 323 (1,23 S, 3.2 tumol), tolune4 sulphonic acid (4 crystals), and 200 ml ofwater, 10 ml of ethanol was added to solubilisa the last of the Cymel 323. The reaction mixturewas then stirred at room temperature for 24 hours, the reaction mixture was then dried in a vacuum oven at 105"C for 24 hours, to yield 2.03 g of a light brown solid. 10 "B NMR (solid slate): 11.5 ppm Polymeric boron (<5% total B signal) 6.3 ppm (3.3.3.0] ring system 1.6 ppm (4.3.3.0] ring system (see Figure 3) 15 Reaction Four: Cross-linking of 12-hydroymethyl-2,10, 1J-rrixa-6-aza-1 boratriyclo[4.4.3. 0"]Jteradecane and 13-hydroxyl-2, 10, 11-trioxa-6-aza-1 b6raricyo[.4.4.0"]tetradecane with Cymel -323 resin .To a 250 ml conical flask was added 12-hydroxy-2,10,l -trioxa-6-aza-1-bora tricyclo[4.4.3.0]tetradecane (5) and 13-hydroxyl-2,l0,11 -trioxa-6-aza-l-boratricyclo 20 [4,4.4.0'']tetradecane (6) (0.52 g, 2.4 mmol), Cyrnel 323 (0.47 g, 1.2 mmol), toluene-4-sulphonic acid (4 crystals), and 200 =r of water, the last ofthe Cymel 323 had to be solubilised with 10 ml of ethanol. The reaction mixture was stirred at room temperature for24hours, the reaction mixture was then dried in a vacuum oven at 105T for 24 hours, to yield 038 g of an orange solid. B NMR (solid state): 8.5 ppm 25 Polymeric boron (<5% total B signal) 1.7 ppm 39 [4.4.4.0] ring system (see Figure 4) Summary of Cross-liUng reactions From these results, it is evident that the six boratranes can be crosslinked with the Cynel 323 resin, 5 to produce polymers containing different boron chemical environments, which arc not caused by hydrolysis of the boratranes to boric acid. The solid state "B NMR chemical shifIs observed can be assigned as follows. Borrnce Ring System 6("B)(ppm)soIid state (1) [3.3.3.0] 5.0 (2) [4.3.3.01 1.6 (3) [3.3.3.01 6.2 (4) [43.3.o] 2.0 (6 [4.4.4.0 -1.7 The spectra of some of the polymerised boratranes showed a signal at 11.3-11.5 ppm which is not 10 dut to hydrolysis to boric acid, but is more likely to be due to an unexpected chemical environment within the polymer. Preliminary"BNMR experiments indicate that exposure of these polymers to water for 24 hours does not cause appreciable hydrolysis of the polymers. 40 EXAMPLE 7 Preparation of 3,7,dimethyl-10-decyl-2,,9-trioxa-5-aza-1-boratricyclo-[3.33.0lundecane. MO 0 H o H+H OH H O 4 0 3 110 3 ----- D Reaction Schedule: Synthesis of di-N-(propan-2-ol)-N-(dodecan-2-ol)-mnine (the amino-alcohol, 5 C12/AM)and 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-l-boratricyclo-[3.3.3.0 15 ]-undeeane (C12/S555/B).

Method: Step 1: Preparation ofdi-N-(propan-2-ol)-N-(ddean-2-ol)-amine. Commetcial diisoprpanolamin containing 10% water (4.615 kg) was added to a 50 litre QVF 10 reaction flask with an attached Dean Stark apparatus and was dried by azeotroping with toluene (10 litres). The anhydrous diisopropanolamine (4.193 kg, 31.475 mol) was warmed to -60*C and 1,2 epoxydodecane (5.801 kg, 31.475 mol) was allowed slowly through a dropping flnnel with thorough stirring. The reaction mixture was maintained at -60"C and stirred for a further hour after all the epoxide had bew added. The product di-N-(propan-2-ol)-N-(dodeca-2-ol)-amie, was kept in 15 toluene for the next step, A sample of the product was TMS-derivatised by heated with Bis Trimethylsilyl acetamide in pyridine and was characterized by direct insertion probe wnass spectscopy. 41

(CH

3

)

a SIO -OSI(CHal Di-N-(propan-2-ol)-N-(dodecan-2-o')-amino tis -trimethylailylether (baW-534) Mass Spectrum (70 eV, DIP, El) 534 (M" 0.2%6), 518 (M*- 15-1, 4.6%), 417 (M+,- 117,35%), 416 (M"- 117-1, 100%), 392 (Mt 141-1, 0.8%, 291 (M*-243,18%), 290 (M*- 243-1,M"-127 5 117), 72%), 284 (M"- 117(x2)-15-1, 1.0%), 17 4 (M"- 243-117, 1.5%) Step 2: Freparation of 3.7-dimethyl-)0-d Il-2,8,9-arloxa-5-aza--boratricyclo-[3.30 -)t undecane (C12/555/B). To bis isopropanol dodecan-2-ol amine (- 10kg) was added toluene (20 1), boric acid (1.95 kg) and p-toluene sulphonic acid (2.7 g). The reaction mi ture was refluxed with thorough stirring until the 10 theoreticalyield ofwaterwas collected inthDein Starkapparatus. Theboratrane + toluene product was kept at 50"C and drained from the base a the reaction vessel into a steel bucket. The steel bucket was kept at 50"C to prevent crystalisatio of the boratrune, Portions of the reaction product were transferred to 2 litre round bottom flasks and toluene was removed by evaporation under reduced pressure The boratrane was crystalised in glass beakers and the small amount of residual 15 solvent evaporated in the fumehood.Yield 10.2 Cg. "B NMR (64.2 MHz, CH 3 CON(CH3)a) 15.

3 65 ppm Mass Spectrum (70 eV, DIP, EI) 325 (M", 1.0%), 310 (M"-1 5,2.5%), 281 (M*-44, 4.8%), 184 ("-141,100%) 154(M'-141-15(x2)orM' 113-58,41%), 140(M"-27-58, 11.8%) 42 EXAMPLE S Preparation of 2,10,11-trioxa-6-aza-1-borotricyclo[4A4.5.0'pentadecane. 0 ( I ~3 (C-)1804a 5~ Method: wrn 10 Step L. Addition of NN-bis(2-carbomethoxyethyl)amtne to succinic anhydride. N,N-bis(2-carbomethoxyethyl)amine (9.5g 0.05 mol) was added dropwise with stining to succinic anhydride (5g, 0.05 mol) in dry toluene (50 mL). When all the amine had been added, the mixtmre was stirred for a further 2h, and then allowed to cool. The intermediate amidedester-acid, N,N-bis(2-carbomethoxycthyl)-3-carboxypropionamide, was 15 -recovered in -uantitativc yield (14.5g) as a semicrystalline mass. IR' m 3600, 1740, 1700, 1680 om 'H NMR (CH 3 OD) ppm 2.4, 2.7 (m, CH 2 ), 3.60, 3.66 (s, OCH3), 11.0 (CO2H) "C NMR (CH3OD) ppm 32.0. 38.0, 39.2, 40.1, 44.6,49.2, 162.2, 168.4, 172.6 MS (El) m/z 289 (M*;3%), 188 (100%) 20 Step 2: Methylation of N,N-bis(2-carbomethozyethyl)-3-carboxypropfonamide with dimethyl sulphate. The intermediate diester-acid-amide (12g, 0.042mol) was dissolvediamethanol (100 mL) and to the solution was added sodium hydroxide (1.75g, 0.043 mol). To the solution was added dropwise with stirring diethyl snlphate (5.3g 0.043 mol). 'A the end of the.addition, the solutioiVwas heated 43 under reflux for two hours, cooled and the solution filtered from sodium sulphate. The product, N,N-bis(2-carbomethoxythyl)-3-carbomethoxypropionamide, was isolated as a gummy liquid (11.7g, 90%), characterised by its spectroscopic properties. Ilum= 1740, 1680 cmut 5 'H NMR (CDC13) ppm 2.4, 2.7 (m, CH2), 3.60, 3.64, 3.66 (OCH 3 ) "C NMR (CDC1i) ppm 33.0, 38.0, 39.3. 40.1, 44.6, 46.4, 49.1, 162.3, 171.1, 172.6 MS (EI) m/z 303 (M*, 12%, 188 (100%) Step 3: Reduction of the triester-amide, NN-bls(2-carbomethoxyethy)-3 carbomerhoxypropionamide, with lithium aluminium hydride. 10 The triester-amide (12.7g, 0.042 mol) dissolved in dry diethyl ether (250 mL) was added dropwise to a stirred mixture of lithium aluminium hydride (5.7 g) in dietbyl ether (200 mL). The mixture was heated under reflux and under a blanket of nitrogen for 24h. The mixture was cooled, and the excess of lithium aluminium hydride was destroyed by cautious addition of saturated aqueous anmonium chloride. The granular precipitate was filtered, and the filtrate concentrated to give an oil. The 15 precipitate was extracted with tetrahydrafuran using a soxhlet apparatus to give further oil. The two extracts were combined to give NN-bis(3-hydroxypropyl)-4-hydroxybutylamine (73g, 85%), characterised by its spectroscopic properties. IRua (film) 3600 em' 'H NMR ppm (CH30D) ppm 1.77 (m, CH2), 2.4 (m, CH 2 ), 2.94 (m, CH7), 5.55 20 (OH, exch with D20) 'C NMR (CH3OD) ppm 20.2,27.7, 29.8, 33.3, 24.4. 34.6, 39,0, 40.6 MS (TMSI ether) mtz 421 (M, 2%), 331 (m-90, 55%), 73 (100%) Step 4: Reaction ofNNbig(3-hydroxypropy)4-hydroxyburylamine with boricacid wuerDean-Stark water removal conditions. 25 NN-bis(3-hydroxyprpy)4-hydmxybutylamine (7.0g. 0.034mol) and boric acid (2.2g. 0.035 mol) were added to toluene (150 mL) together with a catalytic amount of toluene-p-sulphonic acid (10 44 mg). The mixture was stirred and heated under reflux using a Dean-Stark water separation apparatus. After the theoretical quantity of water (0.6 mL) had been collected, the solution was cooled and the solution filtered from a small quantity of insoluble material (residual boric acid) and then concentated to dryness using the rotary evaporator. The product, was a crystalline solid, mp 5 232-235 0 C. IRo. 2950, 2875. 1005 cm~'. 'H NMR (CDCI 3 ) ppm 1.9 (m, N-CH2), 4.1 (m, N-CH2), 5.2 (in, O-CH 2 ). "C NMR (CDC1,) ppm 23.7, 55.0, 55.2, 612 "B NMR (CDCIa) ppm 3.7 10 MS m/z 213 (M+, 33%). 155 (M-C 3 HO, 45%), 154 (M-CH.F0, 100%), 141 (M-C 4 HO, 10%) EXAMPLE 9: Preparation of 14-(dodee-2-en-1-yly-2,10,11-trioxa-6-aza-1-borotriyelo [4.4.5.0"] pentadeane. 15 0 G4 20 45 Method: Step 1: A addition of N.N-bis(2-carbomethoxyerhypaamine to dodec-2-en-1-yi succinic anhydride. To stirred, neat dodec-2-en-1-y1 succinic unhydride (I1.25g, 0.042 mol) was added dropwise NN bis(2-carbomethoxyethyl)amine (8.0g, 0.0 42 mol), Tbe exothennicreaction was allowed to prcced. 5 and then the mixture allowed to cool. After stirring for 4h, the crude product, N,N-bis(2 carbomeoxythy)-2(2-arboxyethyl)-tetrado.4-eamide (19.25g) was obtained as a pale-yellow liquid chamcterised from its spectroscopic properties. (Note: this reaction can also produce NN bis(2-carbomethoxythyl)-2-carboxymthyi-pentdeO-5-enamide by nucleophilic attack of the nitrogen atom of the aminodiester at the alternate carbonyl group of the alkenylsuccinic nhydride. 10 See also results of Step 4 of this synthesis. Only one example is given here as an illustration of the method). Muto 1740.1700,1680,1630 cn 1 'H NMR (CDCI,) ppm 0.9 (CH 3 ), 1.22 (m, CH 2 ), 2.5, 2.9 (mi, CH 2 ), 3.62, 3.66 (s, OCH3), 5.5 (in, CH=CH). 15 "C NMIR (CDCI,)ppm 15.5. 24.4,26.8,31.0, 31.4, 32.9, 33.4, 36.9, 39.2,39.4,44.6,49.1, 121.6, 123.4, 162.3, 166.8, 172.8. MS m/z 455 (Mt 5%), 188 (100%), 167 (C, 2

H

2 ). Step 2: Methylation of NN-bis(2-carbomethoryethyl)-3-arbrymethyl-tetradec-4-enamide with dimethyl sulphate. 20 The intermediate diester-acid-amide (15g, 0.033 mol) was dissolved in methanol (150 mL) and to the solution was added sodium hydroxide (1.35g, 0.033 mol). To the solution was added dropwise with stirring dimethyl sulphate (4.2g, 0.033 mol). At the end of the addition, the solution was heated under reflux for two hours, cooled and the solution filtered from sodium sulphate. The product, N,N-bis(2-carbontboxyethyl)-3-carbonethoxymethyl-tetadec-4-eaWMde, was isolatedasagunmy 25 liquid (12.8g. 85%). characterised by its spectroscopic properties. IRum 1740, 1680, 1630 cm-1 46 'H NMR (CDCI,) ppm 0.9 (CH3), 1.20 (ma, CH 2 ),2.5,3.0 (m, CH 2 ), 3.62,3.63,3.66 (s, OCH3), 5.5 (i, CH=CH) "C NMR (CDC 3 ) ppm 15.5,24.4, 26.8, 31.0, 31.4,32.9, 33.4, 36.9, 39.2, 39.4,44.6,46.8, 49.1, 121.6, 123.4. 166.4, 166.8, 172.8. 5 MS m/z 469 (M; 2%), 188 (100%), 167 (CnHt2, 5%) Step 3: Reduction ofNN-bi(e with lithium aluniium hydride The triester-amide (12.5g, 0.027 mol) dissolved in dry diethyl ether (250 mL) was added dropwise to a stirred mixture of lithium aluminium hydride (2.7g) in diethyl ether (250 mL). The mixture was 10 heated under reflux and under a blanket ofnitrogen for 24h. The mixture was cooled, and the excess of lithium aluminium hydride was destroyed by cautious addition of saturated aqeous ammonium chloride. The granular precipitate was filtered, and the filtrate concentrated to give NN-bis(3 hydroxypropy).-2-hydroxyethy-tetrdec-4naine (8.6& 85%) as an oil, characterised by its spectroscopic properties. 15 IR u= (film) 3600 cm' 'H NMR ppm (CH 3 OD) ppm 0.9 (CH), 1.75 (m, CH 2 ), 2.4, 2.8 (m, CH2), 5.5 (m, CH-CH), 6.4 (OH, exch. with D2O). "C NMR (CH 1 OD) ppm 15.5, 24.3,26.7,31.0,31.3, 32.9, 33.5,37.0,39.3,39.5,42.8,43.4,44.0, 44.6,46.8,49.1, 121.6,123.4. 20 MS (TMSi ether) m/z 587 (M+., 2%), 497 (M-90, 33%), 167 (Cj2Hn' 5%), 75 (75%), 73 (100% 6). Step 4. Preparadon of 14.-dodec-2-en.1-y)-2,10,11-triax-6-aza-1-borotricyco [4.4.5. 0'JpePtadecane To NN-bis(3-hyoxypropy1)-2-hydroxyethyl-tetradec-4.namine (7.5g, 0.02 mol) in toluene and toluenep-sulphonic acid (10 mg) was added boric acid (1 A& 0.023 mol) and themixture stirred and 25 heated under retux for 5 h when the theoretical volume ofwater (0.4 mL) had been recovered. The crude product was filtered and concentrated under reduced pressure to give 14-(dodeo-2-en-1-yl) 2,10,1 1-trioxa-6-aza-1-borotricyclo-[4.4.5.0"]pentadeCae as an oiL 47 The "B NMR spectrum also suggested that 13-(dodec-2--en-1-y)-2,10,11-trioxa-6-azaborotricyclo-[4.4.5.01jpentadecane might have also been formed from the alternative minoalcohol, since the spcotnn showed two equal intensity signals at 2.8 and 3.7 ppr The boratrame products were characterised by the spectroscopic properties, 5 IRumax2950, 2875, 1105 cm UH NMR (CDCl)ppm 0.9((CH3), 1.77, 1.9(m, CH2),2.4,2.8,4.0,5.1 (m, CH2), 5.5(m, CH-CH). "C NMR (CDMl,) ppm 15.5, 23.7, 26.7, 31.0, 31.3, 32.9. 33.5, 37.0,393, 39.5, 42.8.43.4, 44.0, 44.6,46.8,49.1. 55.0, 55.2,61.1, 121.6,123.4. "B NMR (CDCl,) ppm 2.8,3.7 10 MS m/2 379 (M* 25%), 321 (M-C 3

H

6 0, 45%), 320 (M-C3H20, 100%), 167 (CaHfn*, 2%). ADDENDUM TO EXAMPLES 1-9 - SPECTROSCOPIC TECHNIQURS 'This addcndum describes the spectroscopic techniques used in Examples 1-8. NMR spectra. All solution state spectra were obtained on a Bruker AC-200 NMR spectrometer at 25*C(298 K) or6O*C (333 K) using either a5 mm dual probe for'H and 1 C or a 10mmbroad-band 15 probe for "B. Samples were dissolved in a suitable solvent viz CDCs, acetone-d6, DMSO-d6, H0, CDO, THF, or THF-ds. The one dimensional spectra, were obtained and processed using the standardNZFRI acquisition parameters that are summaised in the following tables (Tables 1 and 2). Nucleus Frequency Delay 90* Pulse Data Size (MHz) (s p)(Hz) 1H 200.13 1 7.9 16 "C 50.33 2 13.6 32 "B 64.20 2 25.3 4 Table 1: Standard NZFRI NMR spectral acquisition parameters (solution state) 48 cuurAUtrLi ug.LarE . Nucleus Line Broadening Reference Acquisition (0.0 ppm) Sequence 'H 0.1 TMS ZG _1.0 TMS Powgate "B 1.0 BPOEt Powgate Table 2: Stanard NZFRJ NMR. spectral acquisition parameters (solution state) TS - tetramethylsilane ZG = single pulse experiment 5 BF 3 0Ft - boron uifluoride etherate Powgate powergated 'H decoupling experiment All solid state spectra, were obtained on a Broker AC-200 NMR spectrometer at 25"C using a solid state probe. Samples were typically ground to a fine powder using a pestle and mortar, and were packed into a sample rotor. The spectra ware obtained and processed, using the standard NZFRI 10 acquisition parameters, that are aumrnarised in the following tables (Tables 3 and 4). Nucleus Frequency Delay 9Q" Pulse Data Size (MHz) (s) (RS-) (Hz) BEt 64.20 2 4.5 4 Table 3 Standard NZFRI NMR spectral acquisition parameters (solid state) 49 CUU4AUri-F uLOrM rnum Nucleus Line Broadening Reference Acquisition (0.) ppm) Sequence 11 D.0

BP

1 QBt HPDEC Table 4 Standard NZFRI NMR spectral acquisition parameters (solid state) HPDEC = high power decoupling 5 Mass spectra. All EI mass spectra, were obtained on a Hewlett-Packard 5985 integrated GCMS system, operating under I ionisation conditions. Typical injection procedures involved a sample volume of I pL, at I mg mr' concentration, in a suitable solvent (CH 2 C12). The ionising energy was set at 70 eV, with the ion source at 200C for El. All GCMS samples were rnm on a Hewlett Packard 5890 gas chrmatograph, utilising a 25 m Ultra-2 10 (HP5) capillary column. The standard operating conditions are summnaiased below. Normal Injection: Inj Port A- 250"C, det A- 250*Cion source=200"C, cobn head pressure= 10psi, temperate program: initial temperatr of40*C fqr 2 minutes, followed by a temperature gradientprogrm of5* per minute up to 300PC (total run time 64 minutes). 15 The di and trialkanolamines were TMS or OAo derivatised, prior to analysis, to increase their volatility. The TMS derivatising procedure used was as follows: to a 10mg sample oftriarannlamine, 50 ml of pyridine, followed by 100 ml of BSA (Bis Trimetbyluilyl Acezamide) was added. The mixture was then heated for 45 mins, while dry nitrogen was blown over the sample to remove the solvent The 20 derivatised tialkanolamine was then made up to the appropriate concentration in dichloromethane for DIP (direct insertion probe) mass spectrometry. 50 L.UU-autbU' .L.IR WO1 The OAC derivatising procedure used was as follows: To a 10 mg sample of the di or trialkanolamine was added 50 ml of pyridine and 50 ml of acetic anhydride. The mixture was then heated to 60"C, with stirring for two hours. After this time, water was added to quench the reaction. The reaction mixture was then extracted with CHzC12, washed with saturated NaHCo, I mol L' HC, saturated 5 NuHo.o diied with MgSO 4 , and the C2C12 was removed at reduced pressure: Residual solvent was then blown away using dry nitrogen. The derivatised di or trialknoluamine, was then made up to the appropriate concentration in CH2C12 for GCMS. All fast atom Bombardment mass spectra, were obtained on a VG70-250S double focusingmagntic sector mass spectrometer, operating under (+) ionisation conditions. Typical sample preparation 10 involved dissolution of a di or trialkanolainie in glycerollethanol, or aboratrane in tetramethylene sulphone/THF, or tetramethylene sulphone/ethanol prior to probe injection. The ion source used was a cesium atom gun, and the ionisation energy was set at +15 keV for (+) ion spectra. All electrospray mass spectra, were obtained on a VG Platform U electospray mass spectrometer, operating under (+) ionisation conditions. Typical sample preparation involved dissolving the di or 15 trialkanolamine in MaCN/Water 1:1 at an appropriate concentration, prior to injection. The ion source used, was a corona discharge and the cone voltage was set at 30 V or 60 V. Infra-red spectra. All infta-red spectra were obtained on a Digilab FTS-60 FT-IR spectrometer. Samples, were typically run as neat films between KBr discs or as solutions in CHiCLt. The spectral range was between 400.4000 cm 20 EXAMPLE 10: Fungicidal Toxicity Trials Samples of the atranes were prepared for fungitoxicity trials. These trials test the compounds f'ungiidal activity towards basidiomycetes, a group that contains the larger and more important wood destroying figi. 51 10.1 Method The experimental procedure involved dipping gas sterilised filter paper (a suitable cellulose medium) with the fungicidal treatment solutions, then inoculating the treated filtered papers in the centre with an antibipti, assay disc, inoculated with Coniophora pweana. Controls involving the solvents dichloromethane (Trial One), chloroform ('rial Twb) and water'were also tested. The papers were then transferred to Petri dishes, which were incubated for two weeks at 22"C in polyethylene bags to prevent drying. The extent of growth, or colony diagneter (cm) of Cputeana on the treated filtered papers was tUen measured. The MIC value was then determined. Effectively, this. is the concentration level required to prevent wood-rotting basidiomycetes from grwing. Three separate 10 trials were carried out. 10.2 Trial One Three compounds were tested, at six different concentrations, to determine the minimum inhibitory concentration (MIC) value for each compound. The compounds were tri-n-propanolamine borate, boric acid, and 3-octyl-4-heptyl-2,10,11-trioxa-6-aza-l-boratricyclo[4.4.4.0]tebadecane 15 (OHTABT). The results are shown in Table 5. Table 5 Treatment Concentration 1 (mm)Average MIC value - (%w/v) Growth (%BAE) . Boric Acid 0.01 63 0.3% 0.03 65 0.10 50 0.30 0 1.00 0 3.00 0 OHTABT 0.093 85 0.93% 0.280 70 0.930 0 2.800 0 9.300 0 28.000 0 52 Tri-n- 0.032 59 >9.6% propanolamine 0.096 62 borate 0.320 53 0.960 51 3.200 53 9.600 16 H20 control 100.00 43 CHZCI 100.00 41 Concentrations and MIC values were expressed as % boric acid equivalents (ie the concentrations shown are those of the boric acid that would be released if the boron-contaning compound was stoichometrically hydrolysed to give boric acid). 5 10.3 Trial Two Four samples were tested, to determine the minimum inhibitory concentration (MIC) value for each sample. The four treatments were: Treatment 1. 3,7-didecyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-1..boratricyclo[3.3.3.0']undecae and 8,1 1-didecyl-4-hydroxyl-2,9,1 0-trioxa-6-aza-1-boratricyclo[4.3.3.0'dodecanO 10 (Example 3). Treatment 2. 3,7-dimethyl-L-hydroxymethyl2,8,9-trioxa-5-ezad boratricyclo[3.3.3.0f)undecmne and, 8,1 1-dimethyl-4-hydroxyl-2,9, 10-trioxa-5-aza 1-boratricyclo[4.3.3.0'] dodecane, in mixture with higher molecular weight oligomers (Example 4). 15 Treatment 3. 3,7-dimethyl-10-bydroxymethyl-2,8.9-trioxa-5-aza-l boratricyclo[3.3.3.0'fxundecane, and 8,1 1-dimethyl-4-hydroxyl-2,9,10-trioxa-5-aza 1-boratricyclo[4.3.3.0"] dodecane not containing higher molecular weight oligomem (Example 4). Treatment 4. 12-hydroxymethyl-2,1011-trioxa-6-aza-1-boratricyclo[4.4.3.D"Itetradecane, and 20 13-hydroxyl-2,10,11-trioxa6-aza-1--boracyclo[4.4.4.0'ite1- (Example 5). 53 The results are shown in Table 6 Table 6 - Treatment Concentration Average Growth h C -value ( w/v) (mM) . (% w/v) (% BAB) 1 0.10 25 0.25% BAE 0.25 0 0.50 0 - 0.75 0 1.00 0 2 0.10 17 0.25% BAE 0.25 0 0.50 0 0.75 0 1.00 0 3 0.10 0 _0.1% BAE 0.25 0 0.50 0 0.75 0 1.00 0 4 0.10 32 0.25% BAR 0.25 0 0.50 0 0.75 0. 1.00- 0 Water 84 Chloroform 84 BAE = boric acid equivalent 5 The results indicate that the alkyl-, hydroxyalkyl 1- and hydroxy-substituted boratraes tested have strong fungicidal activity. Trial Three 'The [4,4,5,0't boratranes of Examples £ and 9 were submitted to a rapid filter paper assay. The results are shown in table 7. 54 Table 7 Treatment- Concentration Colony growth'- MIC value %wv (mm) A E) . Compound 1 0.11 70 0.99% .. 0.34 66 1.10 50 3.40 0 11.0 0 'Compound 2 0.14 80 >0.22 0.42 50 <0.69 1.40 10 4.20 0 14.0 0 'Compound 1: 2,10,11-trioxa-6-aza-l-borotricyclo[4.4.5.0'Jpcntmdecane 5 'Compound 2: Mixture of l4-(dodec-2-e.1-yl)-2,10,l 1-trioxa-6-aza-1-borotricyclo [4.4.5.0"'pentadecane and 13-(dodec-2-en-1-yl)-2,10,11 -trioxa-6-aza--borotricyclo [4.4.5.0"pentadecane. EXAMPLE 1lThe determInation of efficacy of 3,7-dimethyl-10-decyl-28,9-triona-5-aza-1 10 boratriyelo-[3.33.0 ndecane (C12/555/B) and 12-diafly-2,10,11-ftriox-6 aza---boratricyel-44.401j tetradeene (C231666/B) as permanent wood preservatives against wood-decaying fungi. 55 In this Example the above two compounds were tested as potential permanent wood preservatives using a laboratory decay test. Blocks of wood of dimensions 35x35x7mn were treated by vacuum impregnation with the two preservatives. The blocks were of either Radiata Pine or European Beech, 5 Each compound was tested at a number of retentions. For each of these ten were exposed to each test fimuas, and six were subjected to chemical analysis. Each treatment retention was made up to 500g using chloroform to give percentage retention expressed as weight/weight. A set ofuntreated controls and a set ofsolvent blanks with ten replicates each were included in each 10 test. C 12/555/B was tested at concentrations of0.5%V, 1.0%, 1.5%, 2.0%, 2.5% and 3.0%. C23/666/B was tested at 2.0%, 4.0% and 6.0%. The test fungi were Tyromyces palustris, Poria placenta, Glecophyllum trabeum, Coniophora pateana, Trametes lilacino-gilva and Coriolus versicolor. T liliacino-gilva is a white rot fungs of 15 economic importance in Australia. The T palustris strain used was that specified in Japanese JIS A9302 standard laboratory decay test. The stains of the other four fungi used were those specified for ENl3 tests. The blocks were weighed initially then treated with the test compounds at respecdve retentions, reweighed after each treatment and were subsequently transferred into air-tight containers and 20 allowed "to fix" for two weeks following the protocol for a laboratory decay test. Following the fixation period, the blocks were resaturated in distilled water in preparation for the fburteen (14) days leaching cycle. The first five blocks from a set often replicates to be exposed to a test fungus were leached according to EN 84 standard procedure. Once resaturated the blocks were leached in nine (9) times their volume of distilled water. The water in the leaching container was 25 changed on every altemate day for two weeks; Upon completion of the leaching cycle, the blocks were air-dried on racts for one week after which both the leached and non-leached blocks, the untreated controls and solvent blank blocks were placed in the 12% Equilibrium Moisture Content (EMC) room for at least another week before weighing (weight before exposure to the test fungi). The blocks were then packaged and sterilised by exposure to otbylene oxide gas, after which they 56 were transferred aseptically into prepared Sutter jars. The Sutter jars contained 2% malt agar and had an active growth of the test fungi inoculated two weeks prior to the placement of the blocks in thejars. A perspex mat was placed sandwiched between the imngi growing on malt agar and the test block to prevent contact of the block with the media. The blocks were exposed to the test fungi at 5 27C for six weeks. After six weeks, the blocks wem removed from incubation, brushed carefully to remove any adhering mycelium and placed on racks to air-dry for at least one week. Once air-dried, they were returned to the EMC room for another week, after which all ofthe blocks were weighed (weight after exposure to the test fungi) and percent weight losses calculated. 10 Tables 7-12 show the results. A weight loss of greater than 2.00% ofa test block due to wood decay by the test tingi indicates the chemical modification treatment used would not provide suitable protection when used in an outdoor exposure situation. Data is included for chiorofun controls. In addition to the untreated controls, treatments with boric acid were included for some of the tests. The results show that C12/555/B was effective at preventing weight loss of radiata pine blocks 15 exposed to Tpalustris, Pplacenta, G trabeum and Cputmana. It was also effective with beech blocks exposed to Tlilacino-gilva and C versicolor. It was effective at almost every concentration tested in all the tests with unleached blocks. With leached blocks the lower concentrations used were not effective, but retentions of 3.0% (or less) were effective in each of the tests except for preventing weight loss due to Coriphd veradoalor in beech blocks. C23/666/B was tested f'r prevention of 20 weight loss in radiata pine blocks exposed to Tpalustris, G trabeum and Cputeana. In all cases it was effective in the unleached blocks but was ineffective in leached blocks except at the highest concentration used (6.0% retention) for G trabeum. This result presumably reflects leaching of Compound B from the wood or hydrolysis of it. It is noted that as expected boric acid was effective where tested in unleached blocks, but not in leached blocks. 57 TABLE 7 - Mean Percent Weight Loss of Radiata Pine Blocks Exposed to Tpalustris %Weight Loss %Weight Loss (Range in Brackets) (Range in Brackets) Retention Chemical Leahed Unleached 0.5% C12/555/B 26.08 0 .(14.83-30.59) (0-0.40) 1.0% 14.76 0 (7.94-28.98) 1.5% 728 0 (0-17.45) 2.0% 0 0 2.5% 0 0 3.0% " 0 0 2.0% C23/6661 20.65 0 _______________ _______________ (19.16-31.05) _________ 4.0% " 15.31 0 (4.10-22.91). 6.0%" 13.68 0. (7.53-20.07) Chloroform 15.65 14.70 (10.86-21.69) (10.24-18.58) Untreated 20.79 11.54 (17.77-24.23) (5.93-17.32) 58 Table 8 - Mean Percent Weight Loss of Radiata Pine Blocks Exposed to Pplacmnta %Wlefght Loss %Weight Loss Rante in Brackets Range in Brackets Retention Chemical Leached Unleached. 0.5% C121555/B 17.74 0 (10.82-22.49) 1.0%" 5.00 0 (0-8.23) 1.5% 1.38 0 (0-5.11) 2.0% 0 0 2.5% 0 3.0% " 0 0 Chloroform 22.83 25.34 (16.95-35.12) (21.35-33.70) Untreated 21.66 23.87 (16.52-31.22) (13.47-28.34) Table 9 - Mean Percent Weight Loss of Rudiata Pine Blocks Exposed to G trabeum % Weight Loss % Weight Loss (Range in Brackets) (Range in Brackcts) Retention Chemical Leached Unleached 0.5% C12/555/B 25.31 0 ______________(20.51-31.00) 1.0% " 3,02 0 (0-10.11) 1.5% " 0 0 2.0%. * 0 - 0 59 2.5% U00 3.0 _________0 0 2.0%o C23/666/B 4.71 -0 _____ ____ _____ ___ _____ ____ __ g.11--900) _ _ _ _ _ _ _ _ 4.0% II 2.15 0 _____ ____ ____ _____ ____ ____ (0-5.74 6.0% -N 0 0 14% Chlorofbrin 24.76 23.09 ____________ ____________(9.80-28.47) .-- (18.13-298.72) Untreated 21.15 20.68 __________________________(15.15-27.43) (15.47-23.156 . Table 10 - Mean Percent Weight Loss of Radista Pine Blocks Exposed to Cpweana % Weight Loss % Weight Loss __________ (Rage. in Bracts) Rag in Brackets) Retention Chemical Leached Unleached 0.5 . . C12f555/8 33.67. 0.66 _____________(25.96-38.48) (0-3.96) 1.00H 23.830 ____ ____ ____ ___ ____ ____ ____ ___ (13.64-31.82) _ _ _ _ _ _ _ _ _ 1.5% ~ 117.90 0 ______________(14.65-27-31) 2.6a3.75 0 2.0% N ~~(0-10.32) ________ 2.5% 1.67 0 _____ _____ _____ (0. 12-3.09) _ _ _ _ _ _ _ _ 3.0% 0 0 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ (M-40) _ _ _ _ 2.%C23/6661B 17.80 0 (14.62-24.18) 60 4.0% 16.59 0 _____________ ______________ 10.40-22.79) 6.0% 11.41 0 0.2% Bori&-Acid 29.98' 0 _______________ _______________(26._47-3,78) ________ 0.40/ Booric Acid 26.17 0 ______________22.52-34.07) 0.6% Boric Add 26.81 0 __________________ (22.17-31.39)__________ Chloroftirm 29-66 30.67 _____________ _____________20,02-34.70) (27.50-35,04) Untreated 26.20 3034 ____________ ____________(21.76-29.19 GL.4-35) Table 11I- Mean Percent Weigh Loss of Beech Block Exposed to Trates Wiacinotibv % Weight Loss % Weight Loss Retention ChmclLeached Unleanhed 1.00/ C12/555/B 19.56 0 ________________(19.17-19-93) _________ 1.5% 18.08 10 ______________ ______________(16.83-19.5,5) ________ 2.0&8110 (1.79310L) 2.5% 0 3.0% 100 61 Chloroform 20.28 6.78 Untwned . 12.37 . 7.72. _____________ ______________(1.33-24.80) (0,10-23-82) Table 12 - Mean Percent Weight Loss of Bech Blocks Exposed to C veicolor Weight Loss 10/ Weight Loss ___________ ___________ Rang in Bresg (Range in Brakets Retention Chemical Leached Unleached 1.0% C12/5551B 24.73 2.41 (21.57-28.53) (0-1 1.OS) 1.5% 301:2 0 _______________(24.98-36.92) ________ 2.0%6 21.83 0 (9.86-29.55) 2.5% 29.r7 0 (27.80-31.78) 3.0% 34.09 0 __________________ (31.39-38.65) _________ 2.0%A C23/666/B 30.58 0 _____________________________(27.88&35.31) ________ 4.00/ 21.85 0 _____ ____ _____ _ __ _____ ____ ____ (0-29.89) _ _ _ _ _ _ _ _ _ 0.2%/ Boric Acid 30.22 0 ________________ (26.34-36.73) ________ 0.4% Boric Acid 26.94 0 (25.08-29.15) 62 0.6% Boric Acid 25.57 0 ____ ___ ____ ___ ____ ___ ____ ___ (21.68-28.85) Chloroform 35.03 31.09 (31.50-39.25) (25.65-40.20) Coltiol (untreated) 34.94 34-14 (31.19-38.56) (31.76-36.84) EXAMPLE .2 Wood Treatment Compositions The compounds of Examples 1 and 2 are dissolved in industrial white spirit (eg Pegasol) to give boric acid equivalent of 0.1-0.8%. The compounds of Examples 3-6 arc dissolved in water to 5 achieve the same boric acid equivalents. These compositions also include toluene-4-sulphonic acid and the crosslinker Cymel 323. Frequently the latter two are added shortly prior to use of the compositions to avoid premature crosslinking. See Table 13 for specific compositions. Table 13 Composition I 3--Otyl-4-heptyl-2.101 1-trioxa-6-aza-1-boratricyclo [444.0']tetrdecane 6,6g Pegasol 1s 1OOOml. M(BAE)0.1% 2 3-Octyl-4-heptyl-2,10,1 1-trioxa-6-aa-1-boratricyclo [4.4.4.OlJtetradecane 26-4g Pegasol qS 10 O0mI (BAB) - 04% 3 3-Octyl-4-heptyl-2,10,11-trioxa-6-aza-l-boratricyclo [4.4.4.0Atetradecane 52.8g Pegasol qa 1000ml (BAE)- 0.8% 4 3-alkyl-4-aoky--2,1 0,1 1-trioxa-6-aza-14ratricyclo [4.4.4.0']tetrdecanes (Example 3) 9.5g Pegasol qS I 000ml (BAE)= 0.1% 63 5 3-alkyl-4-alkyl--2,10,1 1-trioxa-6-aza-1-boratricYclo [4.4.4.01f]tetradecanes (Example 3) 38.1g Pegasol q 1000iml (BAE) - 0.4% 6 . 3-ulkyl-4--ayl--2,1 1trioxa-6-azasl-boratricyclo [4.4:4.0]tetrdecaneCs (Example 3) 76.1g Pegasol qs 1000m] (BAE) - 0.8% 7 Product of Example 4 7.5g Cymel 323 3.lg Toluene-4-sulphonic acid 15mg Water qs 1 000ml OBE) - 0.41% 8 Product of Example 4 30.2g Cymnel 323 12.4g Tolune-4-sulphonic acid 15mg Water qs 1000ml (BAE) = 0.4% 9 Product of Exmple 4 60.2g Cymol 323 24.8g Toluene4-sulphoniC acid 15 mg Water qs 1000ml (BAE) = 0.8% 10 Product of Example.5 (step 2) 3.5g dymel 323 3.g Toluene-4-sulphonic acid 10 mg Water qa 1000ml (BAE) =0. 1%1 12 Product of Example 5 (step 2) 13.9g Cymel 323 12.5g Toluene-4-sulpbanio acid 10 mg Water qs 1000ml (BAB) =0.4% 12 Product of Example 5 (step 2) 27.8g Cyme 323 25.0g Toluene-4-sulphonic ci 10 mg Water qs 1000ml (AE) = 0.8% 13 Product of Example 5 (step 4) 3.5g Cymel 323 3.lg Tolucne-4-sulphonic acid 12 mg Water 1000 mI (BAE)=0.1% 14 Produc of Example 5 (stop 4) 13.

9 8 Cymel 323 12.5g Toluens-4-sulphonic acid 12 zng Water 1000 ml - (BAB)=4OA% 15 Product of Example 5 (step 4) 27.8g Cymel 323 25.Og Toluene-4-sulphonic acid 12 mg Water 1000 ml (BAE) = 0.8% 16 Product of Example 6 3.5g Cymel 323 3.lg Toluene-4-sulphonic acid 12 mg Water 1000 ml S(BAB) 0.1% 17 Product of Example 6 13.9g Cyme1 323 12.5g Toluene-4--sulphonic acid 12 mg Water 1000 ml (BAB) - 0.4%Y 18 Product of Example 6 27.8g Cymel 323 25.0g Toluene-4-sulphonin acid 12 mg Water 1000 ml (BAE) = 0.8% EXAMPLE 13- Treatment of Wood 13.1 Treatment of Wood - Method A Method A is useful for treating wood with compositions 1-6. 5 Dried wood (kiln-dried) is placed in a vaotmn/pressure vessel, and the wood is evacuated to -85kPa. The wood treatment solution is allowed to fill the vessel, collapsing the vacuum. 65 Pressure may be applied to 1400kPa to complete the wood impregnation. The wood is removed from the treatment vessel, and the solvent removed by passive evaporation or by vacuum. 13.2 Method B This method is suitable for water based compositions 7-18. 5 Dried wood (kiln-dried) is placed in a vacuum/pressurevessel, and the woodis evacuatedto -85kPa. The wood treatment solution is allowed to fill the vessel, collapsing the vacuum. Pressure may be applied to 1400kPa to complete the wood impregnation. The treated wood is transferred to a wood drying kiln and is dried to give after reconditioning, a final moisture content of about 12%/. During 10 the stage of drying to constant weight, the crosslinking chemical bonds to the boron-containing molecule forming a higher molecular weight polymer which is insoluble in water. EXAMPLE 14 In-itu preparation of compounds in wood matrix. This Example illustrates the method of wood preservation in which the desired compound in the 15 wood is prepared from the compound starting materials, boric acid and the alkanolamine. . The compound 3,7-dimethyl-10 decyl-2,8,9-tri-5-aza--boratricyclo3.3.3.0-undcCde [1] may be prepared in wood matrix using the the following procedure. - Boric acid (6.2g, 0.1 mol) was dissolved in water-industrial tetruhydrofuran (9:1. 2.1) and to the solution was added N-(2-decyl-2-hydroxyethyl)-NN-bis(2methyl-2-hydroxythyl)-amine [2) (32.5g, 20 0.1 mol) and roluene-p-sulphonic acid (100 mg). A clear solution was obtained. The " 1 B NMR spectrum showed a signal at 20 ppm indicative ofberic acid. The solution was used to treat air-dired radiata pine sapwood blocks (50x25x 20 0 mm) using a standard vacuum (-85 kPa) and pressure (1400 kPa) sequence. The blocks were then transferred to an oven at 10 0C and dried to constant weight. The treated wood material produced was analysed 25 using solid phase (CP/MAS) "B NMR spectroscopy which showed a strong signal at 4.5 ppm, together with lesser signals at -1.5 ppm and -8,5 ppm. The signal at 4.5 ppm is indicative of the formation of the desired boratrane [] in situ within the wood matrix. 66 Thus, it is not necessary (although may be desirable for some bomrmne wood preservatives) to prepare the desired compound prior to wood treatment, as the chemical process of esterification of boric acid with the desired alkanolamine may be carried out within the wood matrix itself 5 (1]1 10 Throughout the specification, unless the context required otherwise, the word "comprise or variations such as "comprises" or "comprising", will be understood to implythe inclusion ofa stated integer or group of integers but not the exclusion of any other integer or group of integers. 15 Aspects of the invention have been described by way of example only and it should be appreciated that modifications end additions may be made thereto without departing from the scope of the invention. 67

Claims (19)

1. 2. A method as claimed in claim 1, wherein the composition comprises at least one compound of Formula II 69 (ClB)P (CH)r 5 N C R6 (II) wherein p is an integer flom 0 to 2; each of q and r is an integer from 1 to 3; w is an integer which is 0 or 1; and wherein (1) R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 9 (if present) are as defined in claim I and (2) at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 9 (if present) is other than hydrogen, methyl, methoxy or ethoxy; to the wood or textiles.
2. 3. A method as claimed in claim I wherein the composition comprises at least one compound of Formula III 9 NC' (CK12) t 0 '1 wherein R 1 , R 3 , R 5 , R 7 and R 9 (if present) are (1) as defined in claim 1 and (2) include a group other than hydrogen, methyl, methoxy or ethoxy, s = 0-2, t and u are each I or 2 and w is 0 or 1; to the wood or textiles. 70
3. 4. A method as claimed in any one of claims 1 to 3 wherein at least one of R 1 , R3, R 5 and R 7 of formula III includes a group other than hydrogen, methyl methoxy or ethoxy.
4. 5. A method as claimed in claim 3 wherein RI is selected from C-C 2 0alkyl, C 2 C 2 o alkenyl, hydroxy or C-C 2 0hydroxyalkyl
5. 6. A method as claimed in claim 3 wherein R, and R 7 of formula III are both Ce C 2 oalkyl and s=1, t=2, u=2, w=0, R 3 is hydrogen and R 5 is hydrogen.
6. 7. A method as claimed in claim 3 wherein for formula III, s=l, t=2, u=2, w=l, R 1 , R3, R5 and R7 are hydrogen and R9 is C-C 2 0alkyl or CS-C 2 oalkenyl.
7. 8. A. method as claimed in claim 7 wherein R3 and R 5 are C14alkyl and one of R7 and Ri is hydroxy or C-C 4 hydroxyalkyl.
8. 9. A method as claimed in any one of claims I to 8 wherein the compound has a hydroxy group or a hydroxyalkyl group and the wood or textiles are also treated with a hydroxymethyl or alkylhydroxymethyl melamine to crosslink the compound.
9. 10. A method as claimed in any one of claims 1 to 8 wherein the compound has a reactive group allowing polymerisation of the compound and the wood or textiles are also treated with a polymerisation catalyst to polymerise the compound.
10. 11. A method for preserving wood or textiles comprising application of boric acid and an alkanolamine of Formula V: R6 011 R Z2-N OH V Z 3 R 4 71 wherein Z 1 , Z 2 , Z 3 , R 1 , R2, R3, R 4 , R5 and R 6 are as defined in claim 1; and allowing the boric acid and the alkanolanine to react to form a compound of claim 1 in the treated material.
11. 12. Wood treated with at least one compound of formula I, II or III as described in any one of claims 1 to 3 wherein the compound(s) is present in an amount of between 0. 1 and 30% by weight.
12. 13. A compound of Formula III 9 c1I.Q S jiOW R o a P, 33 0 wherein R9 (if present) is (1) as defined for formula I in claim 1, s=1, t=2, u=2, w=0, R3 and R5 are hydrogen and R, and R7 are both Cl-C 2 0alkyl.
13. 14. A compound of Formula III Nr= (CH') t R 3, wherein R1, R3, R5 and R 7 are hydrogen, R 9 is C 2 -C 20 alkyl or C 3 -C 2 oalkenyl, s=1, t=2, u=2 and w= 1. 72
14. 15. A composition including the compound as claimed in claim 13 or claim 14 formulated in an aqueous solution using emulsifiers to form a microemulsion.
15. 16. 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-1-boratricyclo-[3.3.3.0' ,] undecane. 17 A wood preservative composition comprising 3.7-dimethyl-10-decyl-2,8,9 trioxa-5-aza- 1 -boratricyclo- [3.3.3.0,',5] undecane.
16. 18. A method as claimed in any one of claims 1-11 wherein the composition is applied to wood.
17. 19. A compound as claimed in any one of claims 13,14 and 16, substantially as hereinbefore described with reference to the Examples.
18. 20. A wood preservative composition as claimed in any one of claims 12, 15 and 16, substantially as hereinbefore described with reference to the Examples.
19. 21. A method as claimed in any one of claims 1-11, substantially as hereinbefore described with reference to the Examples. NEW ZEALAND FOREST RESEARCH INSTITUTE LIMITED Patent attorneys for the applicant AJ PARK 73