NZ514356A - Boratrane compounds and their use as wood preservatives - Google Patents

Abstract

A Boratrane compounds of formula (I) and their use as wood preservatives are disclosed, wherein the variables shown in formula (I) are as defined in the specification. 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-1-borabicyclo-[3.3.3.01,5]undecane is a particular example of the boratrane compounds that are disclosed herein.

Description

51A 356 NEW ZEALAND PATENTS ACT 1953 No: 514356 Date: 21 September 2001 COMPLETE SPECIFICATION PRESERVATIVE COMPOUNDS AND THEIR USE We, NEW ZEALAND FOREST RESEARCH INSTITUTE LIMITED, Sala Street, Rotoraa, New Zealand, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: (followed by page la) INTELLECTUAL PROPERTY OFFICE OF N.Z. 2 3 dec 2002 RSGBiySD Version ! > ? 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.

BACKGROUND ART Preservatives have long been used to protect items of value to mankind from biodeterioration by bacteria, fungi, insects and marine borers. The problem has been to find preservatives suitable in their preservative function by being toxic to the deterioration-causing organisms but not to human users of the materials and to the environment. Different preservatives^are suitable for different applications. For food preservation the requirement for low human toxicity is clearly greater than for preservation of wood, 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. 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 must be inoffensive to users. 1Q 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 them 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 exterior applications, such as marine piles and exterior cladding of buildings against decay by fungi. While copper-chrome-arsenic 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-effective wood preservative, it has disadvantages such as high mammalian toxicity and environmental hazard. Tributyl 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 pentachlorophenol and creosote, while being effective, are known to present such significant health and environmental hazards that these are rarely used.

Modern insecticides, such as permethrin, are effective for preserving wood against boring 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 organisms.

Boron chemicals such as borax (sodium tetraborate pentahydrate), 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 interior situations, such as internal framing of buildings. 2 Knowledge of the mode of toxic 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 information is available on the chemical environment (trigonal or tetrahedral) of the boron element necessary for biological activity.

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 of the boron element from the treated wood on leaching with water. The reason for this is that all insoluble salts have a minimal, measurable solubility and dissociate to form hydrated ions. Over time with extensive water leaching, the borate ions are totally lost from the treated wood.

It is an object of the invention to provide preservatives which combine low active teachability and toxicity towards target organisms without creating a significant hazard to mammals and the environment or at least to provide the public with a useful choice. It is envisaged that these preservatives would be useful in a number of applications including treatment of wood and other materials including textiles. 3 DISCLOSURE OF THE INVENTION In one aspect the invention provides preservative compounds collectively known as boratranes of the structure of formula I: each of R,, R3, and Rj, is a group selected from hydrogen, C,-C20alkyl, Q-Qoalkenyl, 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 C1-C2oalkyl. Each of Z2 and Z3 as a group chosen from -CiRrRs)- -C(R7R8)-C(R9R10)--C(R7R8)-C(RgRio)-C(Ri 1R12)- -C(R7R8)-C(R9Rio)-C(RilRi2)-C(Rl3Rl4)-C(Ri5Ri6)- -C(R7R8)-C(R9R1o)-C(R11R12)-C(R13Ri4)-(CH2)n-C(R15R16)- Each of R7, R9i Rn, R13 and R15 is a group selected torn hydrogen, Ci-C2oalkyl, C^alkenyl, aryl, alkaryl, aralkyl, heterocyclyf, 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, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy or alkylcarbonylamino.Each of R2, R4, R6, Re, R10, R12. R14 and R16 is chosen from hydrogen and CrC20alkyl. n is an integer from 1 to 10.

Not only are Zu Z2, and Z3 the same or different but also R7, R8 and when present R9, Rio> R11, R12, R13, R14. R15. R16 may be the same in said Z1, Z2, and Z3 or in two of those groups, or those R groups may be different in all three Z groups. Z2 and Z3 with more than one carbon atom may be included in the molecules such that the C atom bearing R7 is linked to that bearing R1, R3 and R5 respectively or so that it is linked to the nitrogen atom.

In the compounds of Formula I, R,, R2, R3, R4, R5, R6, Z,, Z2, and Z3 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 Formula 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.

In a particularly preferred embodiment the compounds have Formula II wherein R,, R2, R3, R4, R5, Rg and R7, are as defined for Formula I.

Preferably R2, R4, Re, Rg and where present R10, R12, R14 and R16 are each hydrogen.

R7' R 6 p is an integer from 0 to 2. Each of q and r is an integer from 1 to 3. w is an integer which is 0 or 1. At least one of R2, R3, R4, R5. R6, R7 and R9 (if present) is other than hydrogen, methyl, methoxy or ethoxy. Preferably at least one of R^ R2, R3, R4, R5, R6 and R7 is other than hydrogen methyl, methoxy or ethoxy.

Preferably p = 1, q = 2 and r = 2.

Preferably R2, R4 and Re are hydrogen.

Particularly preferred are compounds of formula III in which R^ R3l R5, R7 and R9 (if present) are (1) as defined for formula I and (2) include a group other than hydrogen, methyl, methoxy or ethoxy, s = 0-2, t and u are each 1 or 2 and w is 0 or 1 (refer to Formula III). Preferably, R1t R3, R5 and R7 include a group other than hydrogen, methyl, methoxy or ethoxy. 7 Preferably Rt is selected from C fC 2(^lkyl,C fC 2(^Ikenyl, hydroxy or C TC hydroxyalkyl. These preferable selections enable the preservative to be rendered insoluble in water (with hydrophobic alkyl groups) or condensation-polymerisable (with hydroxy or hydroxyalkyl groups) to become water insoluble within the wood.

Particularly preferred compounds include those in which R, and R7 are both C,-C2aalkyl and s=l, t=2, u=2, w=0, R3 is hydrogen and Rj is hydrogen.

Further particularly preferred compounds include those in which s=l, t=2, u=2, w=l, R,, R3, Rg and R7 are hydrogen and R, is Cg-C20alkyl or Cg-C20alkenyl.

Another particularly preferred group of compounds of formula III are those in which R3 and R5 are CI 4aIkyl and one of R7 and Rj is hydroxy or C,-C4 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 HI. Some of the molecules of the invention eg those in which one or more R groups are Ci-C20 alkyl are retained in the preserved material because of their hydrophobicity. 8 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„ R3 and Rs are each hydroxy or hydroxyalkyl are examples of crosslinkable compounds. The compounds of formula I in which R„ R3 and Rj 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 may be 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 preservative and the crosslinking agent or the polymerisation catalyst until shortly before 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 formula III containing one or more hydroxy or hydroxyalkyl groups. The crosslinking 9 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 butylmethylol melamines.

Trialkyl derivatives of 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.

BuCK -OBu n-yy-n r Br R ^ 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 in in combination with other preservative compounds. Preferably one or more compounds of Formula II are used. More preferably one or more compounds of Formula III are used.

In another aspect, the invention provides a method for preserving materials by application of a composition containing at least one compound according to Formula I, II or III. Preferred materials for the practice of the invention include wood and textiles.

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 HI. 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 of formula I is crosslinkable or polymerisable, the composition applied to the wood will generally contain a crosslinking agent or a polymerisation catalyst. The method of treatment of the wood may involve 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 materials by treating them with boric acid and an alkanolamine of Formula V. v z2-n oh z3 11 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-150°C is preferred for facilitating the reaction to form the boratrane compounds of the invention. Z„ Z2, Z3, R,, R2, R3, R4, Rs and R6 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 IH.

Compounds of formula I may prepared using Reaction Scheme I: Compound of formula I or compound ofFonnuk I in which one or more R groups is in protected form, if necessary, removal of protecting groups VI Intermediate compounds of Formula VI are refluxed 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. 12 - Uf' JCF cy NH3 + o och3 (i) och3 A j. (i) \ AKD -0 \ \ \ r och- Bis(2-caromstix)x>e!hyl)arrire "5 >- (iii) LiAfflU oh A Reaction Scheme 2 (2a Reaction Scheme 3 NH OH OH o -OH (i) nTSP^MtOH hck 6 OH N Y OK OH * oligomers NH, OH ♦ (i) OH f -■ ~£,Ort iw°c NH y OH OH OH CH,0 NH (i) °CH' Na dry . refo? OH | } <?f>CKy -C I I 'i-i-i p—7~S,i>H T f*SSlA~Jt( ire 'to'C Reaction Scheme 5 HO HO nb Rj'-R^' have the same meaning as R,-!^ of Formula I or any of them may be R, -1^ in protected form. Z„ Z2 and Z3 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.

BRIEF DESCRIPTION OF DRAWINGS Fig 1 Solid state nB NMR spectrum of product of Cross-linking of 3,7-didecyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.01'5]-undecane and 8,ll-didecyl-4-hydroxyl-2,9,10-trioxa-6-aza-l-boratricyclo[4.3.3.01,6]dodecane with Cymel 323 resin.

Fig 2 Solid state nB NMR spectrum of product of Cross-linking of 3,7-dimethyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricycIo[3.3.3.01,s]-undecane and 8,ll-dimethyl-4-hydroxyl-2,9,10-trioxa-6-aza-l-boratricyclo[4.3.3.01,6]dodecane with Cymnel 323 resin.

Fig 3 Solid state nB NMR spectrum of product Cross-linking of 3,7-dimethyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.0l's]-undecane and 8,ll-didecyl-4-hydroxyl-2,9,10-trioxa-6-aza-l-boratricyclo[4.3.3.0!'6]dodecane from acid catalysed hydrolysis reaction (oligomer reduced) with Cymel 323 resin.

Fig 4 Solid state nB NMR spectrum of product of Cross-linking of 12-hydroxymethyl-2,10,11-trioxa-6-aza-l-boratricyclo[4.4.3.01,6]tetradecane and 13-hydroxyl-2,10,ll-trioxa-6-aza-l-boratricyclo[4.4.4.01,6]tetradecane with Cymel 323 resin. 13 BEST MODES FOR CARRYING OUT THE INVENTION EXAMPLES The following Examples further illustrate the invention and describe the best modes of carrying out the invention.

The compounds of Examples 1-9 are listed below: Example 1: CH3(CH2)6- CH3(CH2)f Example 2: CH3(CH2)m CH3(CH2)n m+n= 25,27,29,31,33. The homologues arise from the homologues of the original alkyl ketene dimer product HN 100.

(CH2)9CH3 (CH2)9CH3 (CH2)9CH3 These two boratranes arise from the boric acid esterification of the aminoalcohols formed from opening the epoxide ring of glycidol. Both primary and secondary akohol groups can be esterified 14 Example 4: and its oligomers formed from further reaction with glycidol; and the other isomer formed from opening of the epoxide ring of glycidol: and the oligomers formed from further reaction of the aminoalcohol with glycidolj OH QH HO^ ^0.

Example 5: and its oligomers formed from further reaction of the aminoalcoholwith glycidol; OH and the other isomer; and its oligomers; OH OH HO^ JL O' Example 6 is about cross-linking reactions. Example 7: CH3(CH2)9 16 Example 8: Example 9: EXAMPLE 1 - Synthesis of 3-octyl-4-heptyl-2,10,ll-trioxa-6-aza-l-borotricyclo-[4.4.4.01,6]tetradecane 1.1 Synthesis of N,N-bis(2-carbomethoxyethyl)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 temperature (20°C). The Parr reactor was attached to an orbital shaker, and the mixture shaken gently for 48h. At the end of this period, the excess of ammonia was allowed to vent. GCMS analysis of the crude product indicated an approximately 1:1 mixture of di-N-(carbomethoxyethane), M+ m/z 189 and tri-N-(carbomethoxyethane), M+ , m/z 275.

The mixture was distilled in vacuo ( 90°C, 4.10"2 torr) to give pure N,N-bis(carbomethoxyethyl)amine, 140 g. The product showed vc=G (neat) 1740 cm'1 (saturated ester), 'H NMR (CDC13) ppm 2.27 (t, 4H, C3 CH2), 2.59 (t, 4H, C2 CH2), 3.48 17 (s, 6H, -OCH3). ,3C NMR (CDCI3) ppm 32.5 (C3), 39.0 (C2), 44.6 (-OCH3), 172.6 (CI). MS m/z 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 of nonanoyl chloride Nonanoic acid (lOg, 0.11 mol) was converted to the acyl chloride by addition of thionyl chloride (27g, .23 mol) at 20°C. The mixture was then heated to 40°C until evolution of sulphur dioxide and hydrogen chloride has ceased. The crude acyl chloride was obtained in quantitative yield, and was characterised by its spectroscopic properties.

Infrared spectrum 1800 cm-1 13C NMR spectrum: 13.8,22.5, 24.9,28.3, 28.9,31.5,46.9 and 173.1. 1.3. Dehydrochlorination of nonanoyl chloride to heptyl ketene dimer.

Ice-cold nonanoyl chloride (25 g, 0.14 mol) was dissolved in dry diethyl ether (30 mL) treated with cold, dry triethylamine (14.3g, 0.14 mol) over a period of 10 min. After 1 h, the mixture was allowed to warm to ambient temperature, and stirring continued for 24 h.

The triethylamine hydrochloride was then extracted from the mixture with 2% aqueous sulphuric acid. The redried ether solution was then concentrated to give crude heptyl ketene dimer (85% yield) containing 9-heptadecanone by-product (10% yield). 18 Infrared spectrum 1873,1725 cm '. 1 NMR spectrum: 0.87 (s), 1.33 (broad s), 1.73 (d oft), 2.10 (d oft), 3.93 (d oft) and 4.69 (d oft). 13C NMR spectrum: 13.9,14.0,22.3, 22.4, 24.5,25.9, 27.4, 28.7,31.2,31.4,53.7,101.7,145.6.

Mass spectrum: m/z 224 (M+, 4% rel int), 168 (4% rel int), 139 (8% rel int), 112 (9% rel int), 98 (100% rel int), 56 (56% rel int). 1.4 Preparation of N,N-bis(2-carbomethoxyethyl)-2-heptvI-3-keto-undecamide.

To ice-cold N,N-bis (2-carbomethoxyethyl)amine (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 completion moderated by cooling. N,N-bis (2-carbomethyoxyethyl)-2-heptyl-3-keto-undecamide was obtained in quantitative yield as a viscous liquid, and was characterised by its spectroscopic properties.

Infrared spectrum: 1740,1715,1690,1650 cm"1. 1H NMR spectrum: 0.86 (s), 1.33 (broad s), 2.32 (p), 2.42 (d oft), 2.47 (q), 3.48 (t), 3.62 (s), 3.67 (s). 13C NMR spectrum: 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. 19 Mass Spectrum m/z 467 (M+,2%), 188 (100%) 1.5 N,N-bis(propan-3-ol)-2-heptyl-3-hydroxy-undecanamine.

To an ice-cold suspension of lithium aluminium hydride (6.67g, 180 mmol) was added slowly a solution of N,N-bis(2-carbomethoxyethyl)-2-heptyl-3-keto-undecamide (20. lg, 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 h. Excess of lithium aluminium hydride was destroyed using aqueous sodium hydroxide solution. The product was extracted from the residue using dichloromethane and the solution concentrated to give N,N-bis(2-propan-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"1. 1H NMR spectrum: 0.9 (s), 1.32 (broad s), 1.72 (p), 2.3 (m), 2.83 (d of t), 3.6 (m). 13C NMR spectrum: 13.7,223,25.5, 27.5, 29.0-30.0, 31.0,39.0,51.1, 60.1,61.0,73.8.

Mass spectrum (Negative ion ammonia CI): m/z 400 (100%, M-l).

Mass spectrum (TMSi derivative): m/z 617 (M+, 1% rel int) 602 (2% rel int), 290 (67% rel int), 174 (60% rel int) 58 (100% rel int). 1.6. 3-Octyl-4-heptyl-2,10,ll-trioxa-6-aza-l-boratricyclo-[4.4.4.0l's]tetradecane.

To N,N-bis(propan-3-ol)-2-heptyl-3-hydroxy-undecanamine (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-heptyI-2,10,11-trioxa-6-aza-l-boratricyclo[4.4.4.0.''6]tetradecane (1.74g, 89% yield) as a solid, characterised by its spectroscopic properties.

Infrared spectrum: 1079,1118,1160 cm"1 13C NMR spectrum: 14.0,22.2, 23.7,25.5-31.9,54.4, 55.3,60.2,60.6, 73.1. nB NMR spectrum: 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 ammonia CI): m/z 426 (3% rel int), 409 (27% rel int), 408 (100% rel int). 21 EXAMPLE 2 - Synthesis of a mixture of 3-aIkyl-4-alkyl-2,10,ll-trioxa-6-aza-l-boratricyclo[4.4.4.01,6]tetradecanes.

The Reaction scheme below summarises the chemistry involved.

OCH, NH3 CH30 OCHa CH3O OCH, UAIH4 reduction H3BO3 — >■ Dean-Stark water removal Aminoalcohol 22 Characterisation of commercial alkylketenedimer AKD100 HN.

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-(carbomethoxyethyl)-2-alkyl-3-ketoalkylamide. (where the alkyl group length varies according to the MW of the original AKD homologue) To AKD 100 HN (181g, average mw 448,0.4mol) which had been melted in a round-bottomed flask was added dropwise over three hours N,N-bis(2-carbomethoxyethyl)amine (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 (film) showed vc=0 1740 (ester), 1715 (ketone) and 1690 (amide).

'H NMR (CDC13) 'H NMR (CDC13) 0.9 (CH3), 1.3, 2.3, 2.4,2.7 (m, CH2's), 3.5 (t, CH), 3.62,3.67 (s, OCH3). 13CNMR (CDC13). 14.0 (alkyl £H3), 44.0 to 22.5 (26 alkyl £H2), 51.7,52.0 (0£H3), 57.8 (CH), 169.5 (amide £=0), 171.1,172.3 (ester £=0), 207.2 (ketone £=0). MS (Probe, NCI, NH3 reactant gas), m/z 532 (M 693-161), 504 (M 665- 161), 476 (M 637-161), 448 (M 609-161).

Lithium aluminium hydride reduction of di-N-(carbomethoxyethyl)-2-alkyl-3-ketoalkylamide to give di-N-(propan-l-ol)-N-(l,2-dialkylpropan-l-ol)amine (where the alkyl group length varies according to the MW of the 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 amide functional groups and taken in just over 2 fold excess over theory) was added to anhydrous diethylether (2.2L) with cooling and stirring. To the LiAlH4 slurry was added the keto-amide-diester homologue mixture (200g, average MW 637,0.32 mol) in anhydrous diethyl either (1L) and the mixture was then stirred and heated under reflux for 24h. 23 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 LiAlH4 had been hydrolysed. The grey granular precipitate was filtered, and the precipitate was washed with two 500 mL portions of ether, and the washings combined with the filtrate which was concentrated to give a viscous yellow gum (148g, 84%). The aminoalcohol showed Vo_H3400 cm"1 (film), with no carbonyl absorption bands present. !H NMR (CH3OD) 0.9 (alkyl CH,), 1.32, 2.3, 2.9,3.6 (alkyl CH2s and CH). 13C NMR (CH3OD) 14-51 (CH2s and CH), 60,61 (-CH2OH), 74 (-CHOH). MS (EI, 70 eV, probe, TMSi derivative), m/z 757,785,813,841 (M+, 1%), 73 (100%) MS (NCI, NH3 at 0.35 torr) 540,568,596, and 624 (M-H) Reaction of the alkyl aminoalcohol homologue mixture with boric acid under Dean-Stark removal of water conditions. Preparation of l,2-dialkyl-2,10,ll-trioxa-6-aza-l- boratricyclo[4,4,4,0''6]tetradecane {where the alkyl group length varies according to the MW of the original AKD homologue).

The homologous mixture of alkyl aminoalcohols (70g, 0.12 mol) was placed in a 1L flask fitted with a stirrer and a Dean Stark apparatus. Boric acid (8.0g) was added, and the mixture followed by toluene (650 mL). 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 acid, and the toluene was removed under reduced pressure. The mixture of boratranes was obtained as near white semi-solid (70g, 97%). IR (film) b_O)1160, 1120,1080 cm"1 NMR (CDC13) 0.9 (alkyl CH3), 1.4,1.9,2.4,2.7, 2.8 (alkyl CH2s and CH). 13C NMR (CDC13) 14 (alkyl CH3), 19-40 (alkyl CH2s and CH), 54,55, and 56 (N-CH2s), 60, 61,73 (0-CH2s and O-CHR). "B NMR (CDCI3) 1.7 ppm. MS (NCI, NH3 at 0.35 torr, probe) m/z 566, 594, 622,650 (M+NH3), 5%, 548, 576, 604, 632 (M-H), 100%. 24 EXAMPLE 3: Synthesis and Characterisation of 3,7-didecyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.01,5]-undecane and 8,ll-didecyI-4-hydroxyl-2,9,10-trioxa-6-aza l-boratricyclo[4.3.3.01,6]dodecane Step One: Ring Opening of 1,2-epoxydodecane with 3-amino-l,2-propanedioI In a 250ml round bottom flask was placed 3-amino-l,2-propanediol (11.56 g, 0.12 mol), and a magnetic stirrer. 1,2-epoxydodecane (45.42g, 0.25 mol), and toluene-4-sulphonic acid (4 crystals) were then added from a dropping funnel with stirring and heating to 120°C using an oil bath. The reaction mixture 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% by weight was found to be N,N-bis(dodecan-2-ol)-N-(propane-2,3-diol)amine, using a back calculation from the boric acid esterification reaction, in step two.

FT-IR (neat): 3200-3500cm"1 (polymeric OH stretch), 2954 cm"'i)as CH3. 2912 cm"'uJS CH2, 2852 cm 'usCH2,1464 cm-16asCH3. 1376 cm'S, CH3,1341 cm1 CH wag, 1072 cm1 v (C-O)20 alcohol, 1040 em 'v (C-O) 1° alcohol, 874 cm"'NR3 bend, 721 cm"1 CH2 rocking mode.

*H NMR (THF-d8): 5 1.10 (s, 6H, -CH3), 1.50 (s, 24H, CH2 window), 2.50-2.90 (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 (s, 2H, free OH). 13C NMR (THF-dg): 815.4 (CH3, alkyl CH3), 24.3,27.4,31.1,31.4,31.7,33.6,37.0 (all CH2, alkyl CH2), 62.0 (CH2, alpha to 1° alcohol), 65.0 (CH2 alpha to central nitrogen atom), 66.4 (CH2, CH2 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(+), Cs+, 15 keV): [M + H]+, m/z = 460 (100%).

[(M + H) - H20]+, m/z = 442 (14%).

[(M + H) - 2H20]+, m/z = 424 (3%).

[(M + H) - CH(OH)CH2OH]+, m/z = 398 (23%).

[R-CH(OH)CH2NCH2CH(OH)CH2(OH) + H]+, m/z = 288 (78%) [R-CH2NCH2 + H]+, m/z = 226 (18%) [M* + H]+, m/z = 276 (15%) ES-MS (ES (+), Cone Voltage [M + Na]+, m/z = 482.0 (20%) = 60 V) [M + H]+, m/z = 460.1 (100%) [(M - H20) + H]+, m/z = 442.4 (2%) [M* + H]+, m/z = 276.2 (30%) [M* + H) - H20]+, m/z = 258.1 (35%) 26 [(M* + H) - 2H20]+, m/z = 239.9 (3%) where M* = N-(dodecan-2-oI)-N-(propane-2,3-diol)amine, and R = C10H21.

Step Two: Boric Acid Esterification Reaction.

The reaction mixture from step one (54.41 g) was dissolved in 700 ml of toluene in a 1 L round bottom flask and boric acid (7.33 g, 0.12 mol), assuming that the reaction mixture from step one was all N,N-bis(dodecan-2-ol)-N-(propane-2y3-diol)amine, was added, along with toluene-4-sulphonic acid (4 crystals). The reaction mixture was heated to reflux with stirring and the water created by the reaction was removed azeotropically, using a Dean and Stark apparatus. After four hours the reaction was complete. The reaction mixture was then allowed to cool 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 g, 54%, MP = 75°C.

FT-IR (CHClj): 3200-3500 cm1 (polymeric OH stretch), 2956 cm1 uas CH3. 2934 cm* uas CH2, 2911 cm1 uas CH2, 2849 cm1 us CH2, 1468 cm1 5as CH3, 1378 cm1 6S CH3,1343 cm1 CH wag, 1257 cm'1 N-Caliphstretching, 1102 "'cm N-B transannular dative bond, 27 884 cm"1 NR3 bend, 755 cm"1 and 721 cm'1 CH2 rocking modes.

NMR (THF-d8): 51.10 (d, 5H, -CH3), 1.30-1.90 (s, 26H, CH2 window), 2.45-3.05 (m, 1H), 3.10-3.30 (m, 1H), 3.30-3.90 (m, 4H), 3.90-4.60 (m, 2H), protons around N -B transannular dative bond. ,3C NMR (THF-dg): 615.2 (CH3, alkyI-CH3), 24.3,27.6,27.9,31.1,31.4,31.7,33.7,36.0, 38.1 (all CH2, alkyl-CH,), 63.1, 64.3, 64.5, 64.8, 67.1, 67.4, 68.3, 68.6, 68.7, 69.5, 70.6 (all CH2, alpha to central nitrogen atom, alpha to boron coordinated O 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 free OH). nB NMR (solid state) Single broad peak centred at 17.9 ppm. nB NMR (THF, solution state): 298 K 15.9 ppm [3.3.3.0] 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, 15 keV): [M + H]+ m/z = 468 (100%) [M + H]+ m/z = 460 (81%) [M + H]+ m/z = 276 (45%) [(M + H) - 2H20]+ m/z = 240 (37%) ES-MS (ES(+), Cone Voltage = 60 V): 28 [M + HJ+ m/z = 467.8 (20%) IM' + H]+ m/z = 460.2 (60%), present from the equilibrium set up between the boron compounds and the trialkanolamine precursor.

[M* + H]+ m/z = 276.1 (25%) [(M* - H20) + H]+ m/z = 257.8 (5%) [(M* - H20 - CH3) + H]+ m/z = 232.8 (3%) |(M* - H20 - (-CH2-CH3)) + H]+ m/z = 219.0 (27%). where M' = N,N-bis(dodecan-2-ol)-N-(propane-2,3-diol)amine, and M* = N-(dodecan-2-ol)-N-(propane-2,3-dioI)amine 29 EXAMPLE 4: Synthesis and Characterisation of 3,7,dimethyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.01,5]undecane and 8,ll-dimethyl-4-hydroxyl-2,9,10-trioxa-5-aza-l-boratricyclo[4.3.3.0''6]dodecane in mixture with higher molecular weight oligomers.

Step One: Ring Opening of 2,3-epoxypropan-l-oI with N,N-bis(propan-2-ol)amine N,N-bis(propan-2-ol)amine (111.29 g, 0.84 mol), was dissolved in 200 ml of methanol, along with toluene-4-sulphonic acid (4 crystals), in a 500 ml three neck flask. The reaction mixture was then equilibrated to -8 to -10°C using an ice-salt bath. 2,3-Epoxypropan-l-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 room temperature and stirring was continued for 24 hours.

After 24 hours, the methanol was removed at reduced pressure to yield 164.85 g (95%), of N,N-bis(propan-2-ol)-N-(propane-2,3-diol)amine as a lime green liquid, which three months after synthesis showed signs of solidification.

FT-IR (neat): 3200-3500 cm"1 (polymeric OH stretch), 2968 cm? uas CH3, 2932 cm1 vas CH2,2884 cm1 uas CH* 2832 cm1 us CH* 1460 cm 1 uas CH* 1375 cm"1 us CH3,1336 cm"1 CH wag, 1257 cm"1 N-Ca,iph stretching, 1132 cm'1 C-O-C antisymmetric stretching in ethers, 1058 cm1 u (C-O) 1° alcohol, 957 cm"1 and 940 cm"1 NR3 bending modes.

!H NMR (CD3OD): 61.25 (m, 3H, diastereoisomeric CH3's), 2.35-2.85 (m, 3H), 3.40 (s, 1H), 3.50-3.65 (m, 1H), 3.70-4.00 (m, 2H), protons alpha and beta to the central nitrogen atom, and protons bonded to free OH groups, 4.95 (s, 2H, free OH). 13C NMR (CD3OD): 6 21.1,213,21.4,21.7 (all CH, diastereoisomeric CH3*s), 60.3,61.1 (CH2, alpha to free OH), 65.1,65.7,65.9, 66.0,66.4 (all CH2, 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).

FAB-MS (FAB (+), Cs+, 15 keV): [M + H]+ m/z = 208 (100%) [(M + CH2CH(OH)CH2(OH)) + H]+ m/z = 282 (2%) [(M - CH2CH(OH)CH2(OH)) + H]+ m/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%) [(M-CH(OH)CH2OH)) + H]+ m/z = 145.9 (4%) [(M + CH2CH(OH)CH2(OH)) + H]+ 31 m/z = 282.1 (50%) [(M + CH2CH(OH)CH2(OH)) - H20) + H]+ m/z = 264.1 (5%) [(M + CH2CH(OH)CH2(OH)-CH(OH)CH2OH)) + H]+ m/z = 230.1 (5%) [(M + 2CH2CH(OH)CH2(OH)) + H]+ m/z = 356.2 (27%) [(M + 3CH2CH(OH)CH2(OH)) + H]+ m/z = 430.2 (10%) [M* + H]+ m/z = 133.8 (20%) [(M* - H20) + H]+ m/z = 115.8 (35%)] where M = N,N-bis(propan-2-ol)-N-(propan-2,3-diol)amine and M* = N,N-bis(propan-2-ol)amine. 32 Step Two: Boric Acid Esterification Reaction of N,N-bis(propan-2-oI)-N-(propane- 2,3-diol)amine and Oligomers N,N-bis(propan-2-ol)-N-(propane-2,3-diol)amine and oligomers (10.46g, 0.05 mol), based on the molecular weight of N,N-bis(propan-2-oI)-N-(propane-2,3-diol)amine, toluene-4-sulphonic acid (4 crystals), and boric acid (3.16 g, 0.05 mol), were placed in a 250 ml round bottom flask with 200 ml of butan-l-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 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-l-ol was removed at reduced pressure to yield a viscous yellow liquid, which was stored over silica gel in a desiccator for 24 hours, to remove residual butan-l-ol, yield 10.76 g, quantitative.

FT-IR (neat): 3200-3500 cm"' polymeric OH stretch, 2967 cm"1 CH3,2932 cm"1 v)as CH2,2873 cm'1 usCH„ 1476 cm'S^CH, 1380 cm16 SCH, 1258 cm'1 N-Caliph stretch, 1091-1145 cm"1 N-B transannular dative bond, 915 cm'1,876 cm"1, and 817 cm"1 NR3 bending modes.

!H NMR (THF-dg): 6 1.10 (t, 4H, diastereoisomeric CH3's), 1.30-1.80 (m, 6H), 2.70-3.40 (m, 6H), protons around the N-»B transannular dative bond, 3.75 (t, free OH), 4.10-4.70 (m, 2H), protons around the N-B transannular dative bond. ,3C NMR (THF-d8): 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 CH3, diastereoisomeric CH3's), 37.4 (CH2, N- CH2), 60.7 (CH2, CH2OH), 63.8 (CH2, CH2OH), 64.4,65.0, 65.3, 65.4, 65.6,65.8,66.6 (all CH2, CH2OH), 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). 33 UB NMR (THF): 298 K 15.3 ppm[3.3.3.0] ring system 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(0Bu)3/H3B03 FAB-MS (FAB (+), Cs, 15 keV): [M + H]+ m/z = 216 (100%) [(M - H20) + H]+ m/z = 198 (32%) [(M - CH(OH)) + H]+ m/z = 184 (27%) [(M - CH2OH-CH3) + H]+ m/z = 170 (20%) [(M - CH2CH(OH)) + H]+ m/z = 156 (22%) KM- —G) hi m/z = i42 (55%).

X OH ((M - | ) + H]+ 0H m/z = 140(70%).

((M - 83) + H] + m/z = 133 (90%).

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 molecular weight of N,N-bis(propan-2-ol)-N-(propane-2,3-diol)amine were dissolved in 300 ml of distilled water, in a 1L round bottom flask. Orthophosphoric acid (272.42 g, 2.45 mol) was added, and the reaction mixture was heated to reflux with stirring for 36 hours. 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 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 34 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 50W-X8 ion exchange resin in the IT 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 NH3 solution to remove the trialkanolamine product from the resin. The NH3 solution was removed at reduced pressure, to yield 54.61g, 65%, of a dark orange liquid.

FT-IR (neat): 3200-3500 cm"1 (polymeric OH stretch), 2968 cm"1 uas CH3. 2931 cm1 uas CH2,2831 cm1 us CH2,1461 cm1 6as CH3,1375 cm"1 8S CH3, 1336 cm'1 CH wag, 1285 cm'1 N-CaUph stretching, 1133 cm"1 C-O-C antisymmetric stretching in ethers, 1066 cm"11> (C-O) 1° alcohol, 955 cm"1 and 839 cm"1 NR3 bending modes.

'H NMR (CD3OD): 8 1.35 (m, 4H, diastereoisomeric CH3's), 2.60-3.00 (m, 4H, CH bonded to free OH, diastereoisomeric CH3's and beta to the central nitrogen atom), 3.60-4.40 (m, 4H, CH bonded to free OH, CH2OH and beta to the central nitrogen atom), 5.00 (s, 2H, free OH). 13C NMR (CD3OD): 6 21.9, 22.1, 22.2, 22.5, 22.6, 22.7 (all CH3, diastereoisomeric CH3's), 57.8, 58.1, 60.6 (all CH2, alpha to the central nitrogen atom), 64.8, 65.2, 65.4, 65.7, 66.4, 66.6, 66.7 (all CH2, bonded to free OH), 67.3, 67.7, 67.9, 68.4, 68.7 (all CH, bonded to free OH, diastereoisomeric CH3'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 (+), Cs+, 15 keV): [M + H]+ m/z = 208 (100%) ES-MS (ES (+) Cone Voltage = 60 V): [M + H]+ m/z = 208 (100%) [(M -CH2CH(OH)CH2OH) + H]+ m/z = 133.9 (100%) [(M-CH2CH(0H)CH20H-H20) + H]+ m/z = 115.8 (2%) where M = N,N-bis(propane-2-ol)-N-(propane-2r3-diol)amine Step Four: Boric Acid Esterification Reaction of N,N-bis(propan-2-ol)-N-(propane- 2,3-diol)amine N,N-bis(propan-2-ol)-N-(propane-2,3-diol)amine (19.70 g, 0.095 mol), toluene-4-sulphonic acid (4 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 azeotropically, using a Dean and Stark apparatus. The reaction mixture was then 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 at reduced pressure to yield a red-brown liquid. Residual methanol and toluene were removed under a nitrogen atmosphere, followed by storage over silica gel in a desiccator for 24 hours, yield 14.89 g, 73%. Attempted recrystallisations from ethanol, ethanol/petroleum spirit, and hexane/dichloromethane proved unsuccessful. 36 FT-IR (neat): 3200-3500 cm"1 (polymeric OH stretch), 2971 cm"1 uas CH3. 2931 cm"1 uas CH2,2872 cm"1 us CH2, 1467 cm"1 8as CH3, 1383 cm"1 6S CH3, 1257 cm"1 N-Caliph stretching, 1079-1145 cm"1 N-B transannular dative bond, 914 cm"1, 874 cm"1, and 818 cm"1 NR3 bending modes.

'H NMR (THF-d8): 81.10-1.40 (m, 23 H, diastereoisomeric CH3's) 2.35-3.20 (m, 14H), 3.20-3.90 (m, 29H), 3.90-4.60 (m, 13H), 5.55 (t, 2H, free OH), protons surrounding the N-B transannular dative bond. 13C NMR (THF-d8): 820.8,21.2,21.6,21.9,22.1,22.2,22.8,23.56,23.61,23.8,24.4,24.6 (all CH3, diastereoisomeric CH3's), 56.3 (CH2, CH2 bonded to free OH), 61.0, 61.3, 63.5 (all CH2, CHj's bonded to free OH), 65.3, 65.7,65.9,66.1,67.2,67.4,67.8 (all CH2, CH2's alpha to the central nitrogen atom, bonded to free OH), 69.8 (CH, CH bonded to diastereoisomeric CH3, beta to the central nitrogen atom), 70.1 (CH2, CH2OH), 72.1 (CH, CH-OH), 72.5 (CH, CH2OH), 72.7,74.2, 74.3,75.1, 76.0,77.9, 79.4 (all CH, CH-OH).

UB NMR (solution state, THF): 298K 14.7 ppm [3.3.3.0] ring system 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 (+), Cs+, 15 keV): [M + H]+ m/z = 216 (100%) 37 [M* + Hf m/z = 208 (30%), from the equilibrium set up between the boron compounds and the trialkanolamine precursor Where M = products and M* = N,N-bis(propan-2-ol)-N-(propane 2,3-diol)amine. 38 EXAMPLE 5: Synthesis and Characterisation of 12-hydroxymethyI-2,10,ll-trioxa-6-aza-l-boratricyclo[4.4.3.01,6]tetradecane (5) and 13-hydroxyl-2,10,ll-trioxa-6-aza-l-boratricycIo[4.4.4.01,6]tetradecane Step One: Reduction of N,N-bis(2-carbmethoxyethyl)amine to N,N-bis(propan-3- ol)amine 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 N,N-bis(2-carbmethoxyethyl)amine (48.21 g, 0.26 mol). The reaction mixture was then cooled to 0-4°C using an ice/water bath, before dry ethanol 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 reaction mixture had turned a yellow colour. The reaction mixture was allowed to cool to room temperature and was diluted with 500 ml of distilled water. The ethanol was then distilled, vacuum was applied via a water aspirator to remove the last of the ethanol. The pH of the reaction mixture was then adjusted to 7 using 5 mol L HC1, 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 NaCl. The methanol was then removed at reduced pressure, to yield (44.50g) of a yellow orange liquid, which was azeotropically dried with toluene, to yield N,N-bis (propan-3-oI)amine, 30.3g, 88%..

FT-IR (neat): 2500-3500 cm"1 polymeric OH stretch, 1583 cm"1 OH bending 39 vibration, 1207 cm"1 C-N stretching vibration, 1062 cm"1 C-O stretch, 1° alcohol, 839 cm"1 HNR2 bending mode.

'H NMR (CDjOD): 6 1.75 (p, CH2, 2.35 (m, CH2 alpha to NH group, 2.95 (m, CH2 alpha to the OH group), 3.55 (t, HNR2), 4.85 (s, free OH). 13C NMR (CDjOD): 5 27.8, 29.7 (CH2,33.4, (CH2, N-CH2), 34.5 (CH2, N-CH2), 38.8 (CH2, N-CH2), 40.4 (CH2, CHjOH).

GCMS (70 eV, EI, OAc-derivative): Retention time = 37.13 minutes Area percent = 99% m/z 259 (M'+, 1%), 244 (M + -CH3,10%) 216 (M'+ - COCH3, 6%) v 199 (M'+ - CH3COOH, 2%) 184 (M'+ - CH3COOH - CH3,12%) 172 (M'+ - 87, 8%), 156 (M + - 103,21%) 140 (M'+ - 119,16%) 130 (M'+ - 129,100%) 113 (M'+ -146,10%) 101 (M'+ - 158,27%), 70 (M + - 189,39%) 40 FAB-MS (FAB (+), Cs+, 15 keV): [M + H]= m/z = 134 (100%) [M - H30+]+ m/z = 115 (55%) ES-MS (ES (+), Cone Voltage = 60V): [M + H]+ m/z = 134.5 (100%) [(M - H20) + H]+ m/z = 116.5 (30%) Where M = N,N-bis(propan-3-ol)amine Step Two: Ring Opening of 2,3-epoxypropan-l-ol with N,N-bis(propan-3-ol)amine N,N-bis(propan-3-ol)amine (17.10 g, 0.13 mol) and toluene-4-sulphonic acid (4 crystals), were dissolved in 200 ml of methanol in a 500 ml three neck flask. The reaction mixture was equilibrated to -8 to -10°C, using an ice/salt bath. 2,3-Epoxypropan-l-ol (9.51 g, 0.13 mol) dissolved in 100 ml of methanol was then added from a dropping funnel 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 methanol was then removed at reduced pressure, to yield 25.81 g, 97% of a red-orange liquid.

FT-IR (neat): 3200-3500 cm'1 polymeric OH stretch, 2946 cm"1 uas CH2, 1402 cm"1 N-CH2 bending mode, 1198 cm"1 C-N stretching mode, 1108 cm"1 C-O stretch, 2° alcohol, 926 cm"1 and 854 cm"1 NR3 bending modes.

•H NMR (CDjOD): 6 1.65-1.90 (m, 6H), 2.25-2.50 (m, 6H), 2.80-3.20 (m, 16H), 3.30-3.60 (m, 26H), protons alpha and beta to the central 41 nitrogen atom, protons bonded to free OH groups, 4.80 (s, 2H, free OH). 13C NMR (CDjOD): 8 27.7,28.4,29.7 (all CH^ beta to OH and beta to the central nitrogen atom) 31.7,33.4 (CH2, N-CHJ, 52.0,52.6,53.0,53.3 (all CH2, CH2OH), 56.7,57.9, 59.5, 60.1, 60.4, 60.7, (all CH2, CH2OH), 64.3,65.5 (CH* CH2OH), 66.5,73.8 (CH, CH-OH).

FAB-MS (FAB (+), Cs+, 15 keV): [M + H]= m/z = 208 (100%) [(M + CH2CH(OH)CH2(OH)) + H]+ m/z = 282 (18%) [(M - CH2CH(OH)CH2(OH) - H20) + H]+ m/z = 115 (53%) ES-MS (ES (+), Cone Voltage = 60 V): [[M + H]+ m/z = 208.5 (100%) [(M + CH2CH(OH)CH2(OH)) + H]+ m/z = 282.5 (22%) [(M - H20) + H]+ m/z = 190.5 (10%) [(M - 2H20) + H]+ m/z = 172.5 (8%) 42 [(M- CH2(OH)CH2OH) + H]+ m/z = 146.5 (18%) [(M - CH2CH(OH)CH2OH) + H]+ m/z = 134.4 (20%) [(M - CH2CH(OH)CH2OH - H20) + H]+ m/z = 116.5 (10%) Where M = N,N-bis(propan-3-ol)-N-(propane-2,3-diol)amine Step 3: Boric Acid Esterification Reaction of N,N-bis(propan-3-ol)-N-(propane-2,3-diol)amine N,N-bis(propan-3-ol)-N-(propane-2,3-diol)amine (5.02 g, 0.024 mol), toluene-4-sulphonic acid (4 crystals) and boric acid (1.51 g, 0.024 mol), were placed in a 250 ml round bottom flask, with 200 ml of butan-l-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. 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 temperature. No boric acid was observed. The butan-l-ol was removed at reduced pressure, to yield an orange liquid which was stored under vacuum over silica gel in a desiccator for 24 hours to remove residual butanol, yield 4.76 g, 91%.

FT-IR (neat): 3200-3500 cm'1 polymeric OH stretch, 2935 cm"1 uas CH2, 2875 cm"1 uas CH2,1581 cm'1 OH bending mode, 1462 cm"1 CH2 scissor, 1383 43 cm"1 8 (CH), 1250 cm"1 C-N stretching vibration, 1102 cm"1 N-B transannular dative bond, 963 cm"1 and 850 cm"1 NR3 bending modes.

'H NMR (THF-dg): 61.20 (t, 3H, CH3 from butan-l-ol or tributyl borate) 1.30-1.90 (m, 9H), 2.00 (s, 5H), protons around the N-B transannular dative bond, 3.00-3.50 (s, 40H, free OH), 3.50-4.25 (m, 22H), 4.35 (q, 2H), protons around the N~B transannular dative bond. 13C NMR (THF-dg): 8 15.4 (CH3, from residual butan-l-ol or tributyl borate), 21.4, .9, 26.3 (CH2,N-CH2-CH2-CH2-0), 62.9,63.2, (CH2, CH2OH), 71.9 (CH, CH-OH).

UB NMR (solution state THF): 298 K 5.3 ppm[4.4.3.0] ring system 3.4 ppm [4.4.4.0] ring system 333 K 5.4 ppm [4.4.3.0] ring system 3.6 ppm [4.4.4.0] ring system FAB-MS (FAB (+), Cs+, 15 keV): [M + H]+ m/z = 216 (100%) [(M - 82) + H]+ m/z = 134 (35%) [(M - H20) + H]+ m/z = 198 (10%) [(M - CH(OH) + H]+ m/z = 184 (8%) [(M - CH2OH - CH3) + H]+ m/z = 170 (5%) OH ( (M HI m/z =142 (15%). 44 Example 6 Cross-Linking Reactions of Boratranes In this Example boratranes of Examples 3-5 are reacted with Cymel 323 (see Formula IV) in a suitable solvent (in the presence of toluene-4-sulphonic acid, catalyst) to produce a condensation polymer. Two moles of boratranes for each mole of Cymel 323 were used. The resulting polymers have the repeating units shown in Formulae VII and VIII where the R groups indicate boratrane molecules linked to the polymer through these hydroxy substituents.

To a 250ml round bottom flask was added 3,7-didecyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.01,s]undecane (1) and 8,ll-didecyl-4-hydroxyl-2,9,10-trioxa-6-aza-l-boratricyclo[4.3.3.01,6]dodecane (2) (1.62 g, 3.5 mmol), Cymel 323 (0.67g, 1.7 mmol, a commercially available crosslinking chemical), toluene-4-sulphonic acid (4 crystals), and 200 ml of toluene, the last portion of the Cymel 323 had to be solubilised with 10 ml of chloroform. The reaction mixture was then heated to reflux with stirring for 24 hours. After 24 hours the reaction mixture was allowed to cool to room temperature and the toluene was removed at reduced pressure, 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. nB NMR (solid state): 1.60 ppm[4.3.3.0] ring system OR OR OR R = Boratrane Reaction One: Cross-linking of 3,7-didecyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.01,s]-undecane and 8,ll-didecyl-4-hydroxyl-2,9,10-trioxa-6-aza-l-boratricyclo[4.3.3.0I,6]dodecane with Cymel 323 resin. 45 .00 ppm[3.3.3.0] ring system (see Figure 1) Reaction Two: Cross-linking of 3,7-dimethyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.0I,s]-undecane and 8,1 l-dimethyI-4-hydroxyl-2,9,10-trioxa-5-aza-l-boratricyclo[4.3.3.01,6]dodecane To a 250ml conical flask was added 3,7-dimethyI-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.01,s]undecane (3) and 8,ll-dimethyl-4-hydroxyl-2,9-10-trioxa-6-aza-l-boratricyclo[4.3.3.0I,6]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 glassy solid.

UB NMR (solid state): 11.3 ppm Polymeric boron (<5% total B signal) 6.2 ppm [3.3.3.0] ring system 2.0 ppm [4.3.3.0] ring system (see Figure 2) Reaction Three: Cross-linking of 3,7-dimethyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.01,s]-undecane and 8,1 l-dimethyl-4-hydroxyl-2,9,10-trioxa-6-aza-l-boratricyclo[4.3.3.01,6]dodecane from acid catalysed hydrolysis reaction (oligomer-reduced) with Cymel 323 resin 46 To a 250 ml conical flask was added 3,7-dimethyI-10-hydroxyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.0''5]undecane (3) and 8,ll-dimethyl-4-hydroxyl-2,9,10-trioxa-6-aza-l-boratricyclo[4.3.3.01,6]dodecane (4) (1.37 g, 6.4 mmol), Cymel 323 (1.23 g, 3.2 mmol), toluene-4-sulphonic acid (4 crystals), and 200 ml of water, 10 ml of ethanol was added to solubilise the last of the Cymel 323. 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 2.03 g of a light brown solid. nB NMR (solid state): 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) Reaction Four: Cross-linking of 12-hydroxymethyl-2,10,ll-trioxa-6-aza-l-boratricyclo[4.4.3.0I,6]tetradecane and 13-hydroxyl-2,10,ll-trioxa-6-aza-l-boratricyclo[4.4.4.01,6]tetradecane with Cymel 323 resin To a 250 ml conical flask was added 12-hydroxy-2,10,ll-trioxa-6-aza-l-bora tricyclo[4.4.3.0!'6]tetradecane (5) and 13-hydroxyl-2,10,ll-trioxa-6-aza-l-boratricyclo [4.4.4.01,6]tetradecane (6) (0.52 g, 2.4 mmol), Cymel 323 (0.47 g, 1.2 mmol), toluene-4-suIphonic 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 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 0.78 g of an orange solid. nB NMR (solid state): 8.5 ppm Polymeric boron (<5% total B signal) 1.7 ppm [4.4.4.0] ring system 47 (see Figure 4) Summary of Cross-linking reactions From these results, it is evident that the six boratranes can be crosslinked with the Cymel 323 resin, to produce polymers containing different boron chemical environments, which are not caused by hydrolysis of the boratranes to boric acid. The solid state nB NMR chemical shifts observed can be assigned as follows.

Boratrane Ring System 6(nB)(ppm)solid state (1) [3.3.3.01 .0 (2) [4.3.3.0] 1.6 (3) [3.3.3.01 6.2 (4) [4.3.3.01 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 due to hydrolysis to boric acid, but is more likely to be due to an unexpected chemical environment within the polymer. Preliminary nB NMR experiments indicate that exposure of these polymers to water for 24 hours does not cause appreciable hydrolysis of the polymers. 48 EXAMPLE 7 Preparation of 3,7,dimethyl-10-decyl-2,8,9-trioxa-5-aza-l-boratricyclo-[3.3.3.01,5]undecane.

Reaction Schedule: Synthesis of di-N-(propan-2-ol)-N-(dodecan-2-ol)-amine (the amino-alcohol, C12/AM)and 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-l-boratricyclo-[3.3.3.01,s]-undecane (C12/555/B).

Method: Step 1: Preparation of di-N-(propan-2-ol)-N-(dodecan-2-ol)-amine.

Commercial diisopropanolamine containing 10% water (4.615 kg) was added to a 50 litre QVF reaction flask with an attached Dean Stark apparatus and was dried by azeotroping with toluene 49 (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 funnel with thorough stirring. The reaction mixture was maintained at ~60°C and stirred for a further hour after all the epoxide had been added. The product, di-N-(propan-2-ol)-N-(dodecan-2-ol)-amine, was kept in toluene for the next step.

A sample of the product was TMS-derivatised by heated with Bis Trimethylsilyl acetamide in pyridine and was characterised by direct insertion probe mass spectroscopy.

Di-N-(propan-2-oI)-N-(dodecan-2-ol)-amine tris-trimethylsilylether (MW 534) Mass Spectrum (70 eV, DIP, EI) 534 (M**, 0.2%), 518 (M**- 15-1,4.6%), 417 (M+*- 117,35%), 416 (MT- 117-1,100%), 392 (M**- 141-1, 0.8%), 291 (M+*- 243,18%), 290 (M4*- 243-1, M^-127-117), 72%), 284 (MP*- 117(x2)-15-l, 1.0%), 174 (M*"- 243-117,1.5%) Step 2: Preparation of 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-l-boratricyclo-[3.3.3.0''5]-undecane (C12/555/B).

To bis isopropanol dodecan-2-ol amine (~ 10kg) was added toluene (20 1), boric acid (1.95 kg) and />-toluene sulphonic acid (2.7 g). The reaction mixture was refluxed with thorough stirring until the theoretical yield of water was collected in the Dean Stark apparatus. The boratrane + toluene product was kept at 50°C and drained from the base of the reaction vessel into a steel 50 bucket. The steel bucket was kept at 50°C to prevent crystalisation of the boratrane. 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 solvent evaporated in the fumehood.Yield 10.2 Kg. nB NMR (64.2 MHz, CH,CON(CH,)2) 15.365 ppm Mass Spectrum (70 eV, DIP, EI) 325 (M+\ 1.0%), 310 (M^-15,2.5%), 281 (M^-44,4.8%), 184 (M4*-141,100%), 154 (M+*-141-15(x2) or M4"-! 13-58,41%), 140 (M^-l27-58,11.8%) 51 EXAMPLE 8 Preparation of 2,10,ll-trioxa-6-aza-l-borotricyclo[4.4.5.0 jpentadecane.

P + HN CH, Ck ,-N O OH Ck ,N 2 (CH3)2S04 NaOH O 0CH3 LiALH4 H3B03 DearrStark water removal OCH, OH OH Method: Step 1. Addition of N,N-bis(2-carbomethoxyethyl)amine to succinic anhydride.

N,N-bis(2-carbomethoxyethyl)amine (9.5g, 0.05 mol) was added dropwise with stirring to succinic anhydride (5g, 0.05 mol) in dry toluene (50 mL). When all the amine had been added, the mixture was stirred for a further 2h, and then allowed to cool.

The intermediate amide-diester-acid, N,N-bis(2-carbomethoxyethyl)-3-carboxypropionamide, was recovered in quantitative yield (14.5g) as a semicrystalline mass.

IRumax 3600,1740,1700,1680 cm1 'H NMR (CH3OD) ppm 2.4,2.7 (m, CH2), 3.60,3.66 (s, OCH3), 11.0 (C02H) 13C NMR (CH3OD) ppm 32.0,38.0,39.2,40.1, 44.6,49.2,162.2,168.4,172.6 MS (EI) m/z 289 (M+53%), 188 (100%) 52 Step 2: Methylation of N,N-bis(2-carbomethoxyethyl)-3-carboxypropionamide with dimethyl sulphate.

The intermediate diester-acid-amide (12g, 0.042 mol) was dissolved in methanol (100 mL) and to the solution was added sodium hydroxide (1.75g, 0.043 mol). To the solution was added dropwise with stirring dimethyl sulphate (5.3g, 0.043 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-carbomethoxyethyI)-3-carbomethoxypropionamide, was isolated as a gummy liquid (11.7g, 90%), characterised by its spectroscopic properties.

IRumax 1740,1680 cm1 *H NMR (CDC13) ppm 2.4,2.7 (m, CH2), 3.60,3.64,3.66 (OCH3) 13C NMR (CDCI3) 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, N,N-bis(2-carbomethoxyethyI)-3-carbomethoxypropionamide, with lithium aluminium hydride.

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 diethyl 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 ammonium chloride. The granular precipitate was filtered, and the filtrate concentrated to give an oil. The precipitate was extracted with tetrahydrofuran using a soxhlet apparatus to give further oil. The two extracts were combined to give N,N-bis(3-hydroxypropyl)-4-hydroxybutylamine (7.3g, 85%), characterised by its spectroscopic properties.

IRu^ (film) 3600 cm1 53 *H NMR ppm (CH3OD) ppm 1.77 (m, CH2), 2.4 (m, CH2), 2.94 (m, CH2), 5.55 (OH, exch with DzO) 13C NMR (CH3OD) ppm 20.2, 27.7, 29.8,33.3, 24.4,34.6,39.0, 40.6 MS (TMSi ether) m/z 421 (M+, 2%), 331 (m-90, 55%), 73 (100%) Step 4: Reaction of N,N-bis(3-hydroxypropyI)4-hydroxybutylamine with boric acid under Dean-Stark water removal conditions.

N,N-bis(3-hydroxypropyl)4-hydroxybutylamine (7.0g, 0.034 mol) 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 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 concentrated to dryness using the rotary evaporator. The product, was a crystalline solid, mp 232-235°C.

IRumax 2950,2875,1005 cm1.

II NMR (CDClj) ppm 1.9 (m, N-CH2), 4.1 (m, N-CH2), 5.2 (m, 0-CH2). 13C NMR (CDCI3) ppm 23.7, 55.0,55.2,61.2 nB NMR (CDClj) ppm 3.7 MS m/z 213 (M+, 33%), 155 (M-C3H60, 45%), 154 (M-C3H70,100%), 141 (M-C4HgO, 10%) 54 EXAMPLE 9: Preparation of 14-(dodec-2-en-l-yl)-2,10,ll-trioxa-6-aza-l-borotricycIo-[4.4.5.016]pentadecane.

CHalCH^ H3BO3 DearrStark water removal CH3(CH2)8 Method: Step 1: Addition of N,N-bis(2-carbomethoxyethyl)amine to dodec-2-en-l-yl succinic anhydride.

To stirred, neat dodec-2-en-l-yl succinic anhydride (11.25g, 0.042 mol) was added dropwise N,N-bis(2-carbomethoxyethyl)amine (8.0g, 0.042 mol). The exothermic reaction was allowed to proceed, and then the mixture allowed to cool. After stirring for 4h, the crude product, N,N-bis(2-carbomethoxyethyl)-2(2-carboxyethyl)-tetradec-4-enamide (19.25g) was obtained as a pale-yellow liquid characterised from its spectroscopic properties. (Note: this reaction can also produce N,N-bis(2-carbomethoxyethyl)-2-carboxymethyl-pentadec-5-enamide by nucleophilic attack of the nitrogen atom of the aminodiester at the alternate carbonyl group of the alkenylsuccinic anhydride. See also results of Step 4 of this synthesis. Only one example is given here as an illustration of the method).

IRu^ 1740,1700,1680,1630 cm1 55 'H NMR (CDClj) ppm 0.9 (CH3), 1.22 (m, CH2), 2.5, 2.9 (m, CH2), 3.62,3.66 (s, OCH3), 5.5 (m, CH=CH). 13C NMR (CDClj)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 (M+ , 5%), 188 (100%), 167 (C,^4).

Step 2: Methylation of N,N-bis(2-carbomethoxyethyl)-3-carboxymethyl-tetradec-4-enamide with dimethyl sulphate.

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-carbomethoxyethyl)-3-carbomethoxymethyl-tetradec-4-enamide, was isolated as a gummy liquid (12.8g, 85%), characterised by its spectroscopic properties.

IRUjnaj 1740,1680,1630 cm-1 H NMR (CDClj) ppm 0.9 (CH3), 1.20 (m, CH2), 2.5,3.0 (m, CH2), 3.62,3.63,3.66 (s, OCH3), 5.5 (m, CH=CH) 13C NMR (CDC13) 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 MS m/z 469 (M+"; 2%), 188 (100%), 167 (C12H23+, 5%) Step 3: Reduction of N,N-bis(2-carbomethoxyethyl)-3-carbomethoxymethyI-tetradec-4-enamide with lithium aluminium hydride 56 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 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 ammonium chloride. The granular precipitate was filtered, and the filtrate concentrated to give N,N-bis(3-hydroxypropyl)-2-hydroxyethyl-tetradec-4-enamine (8.6g, 85%) as an oil, characterised by its spectroscopic properties.

IR i)mai (film) 3600 cm"1 H NMR ppm (CHjOD) ppm 0.9 (CH3), 1.75 (m, CH2), 2.4,2.8 (m, CH2), 5.5 (m, CH=CH), 6.4 (OH, exch. with D20).

"C NMR (CH3OD) 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.

MS (TMSi ether) m/z 587 (M+., 2%), 497 (M-90,33%), 167 (C,2H23+, 5%), 75 (75%), 73 (100%).

Step 4. Preparation of 14-(dodec-2-en-l-yl)-2,10,ll-trioxa-6-aza-l-borotricyclo-[4.4.5.0,6]pentadecane.

To N,N-bis(3-hydroxypropyl)-2-hydroxyethyl-tetradec-4-enamine (7.5g, 0.02 mol) in toluene and toluene p-sulphonic acid (10 mg) was added boric acid (1.4 g, 0.023 mol) and the mixture stirred and heated under reflux for 5 h when the theoretical volume of water (0.4 mL) had been recovered. The crude product was filtered and concentrated under reduced pressure to give 14-(dodec-2-en-l-yl)-2,10,ll-trioxa-6-aza-l-borotricyclo-[4.4.5.016]pentadecane as an oil.

The nB NMR spectrum also suggested that 13-(dodec-2-en-l-yl)-2,10,ll-trioxa-6-aza-l-borotricyclo-[4.4.5.016]pentadecane might have also been formed from the alternative 57 aminoalcohol, since the spectrum showed two equal intensity signals at 2.8 and 3.7 ppm. The boratrane products were characterised by the spectroscopic properties.

IR umax 2950, 2875,1105 cm1 IH NMR (CDClj) 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). 13C NMR (CDClj) ppm 15.5, 23.7,26.7,31.0,31.3,32.9,33.5,37.0,39.3,39.5,42.8, 43.4,44.0, 44.6, 46.8,49.1, 55.0, 55.2, 61.1,121.6,123.4.

"B NMR (CDClj) ppm 2.8,3.7 MS m/z 379 (M+; 25%), 321 (M-C3H60, 45%), 320 (M-C3H70,100%), 167 (C12H23+, 2%).

ADDENDUM TO EXAMPLES 1-9 - SPECTROSCOPIC TECHNIQUES This addendum 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) or 60°C (333 K) using either a 5 mm dual probe for *H and 13C or a 10 mm broad-band probe for nB. Samples were dissolved in a suitable solvent, viz CDClj, acetone-d6, DMSO-d6, H20, CD3OH, THF, or THF-dg. The one dimensional spectra, were obtained and processed using the standard NZFRI acquisition parameters that are summarised in the following tables (Tables 1 and 2).

Nucleus Frequency Delay 90° Pulse Data Size (MHz) (s) (Us) (Hz) SH 200.13 1 7.9 16 I3C 50.33 2 13.6 32 nB 64.20 2 .3 4 58 Table 1: Standard NZFRI NMR spectral acquisition parameters (solution state) Nucleus Line Broadening Reference (0.0 ppm) Acquisition Sequence 'H 0.1 TMS ZG 13C 1.0 TMS Powgate UB 1.0 BFjOEt Powgate Table 2: Standard NZFRI NMR spectral acquisition parameters (solution state) TMS = tetramethylsilane ZG — single pulse experiment BF3OEt = boron trifluoride etherate Powgate = powergated 'H decoupling experiment All solid state spectra, were obtained on a Bruker 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 were obtained and processed, using the standard NZFRI acquisition parameters, that are summarised in the following tables (Tables 3 and 4).

Nucleus Frequency Delay 90° Pulse Data Size (MHz) (s) ftis) (Hz) "B 64.20 2 4.5 4 Table 3 Standard NZFRI NMR spectral acquisition parameters (solid state) Nucleus Line Broadening Reference (0.0 ppm) Acquisition Sequence "B 1.0 BF3OEt HPDEC Table 4 Standard NZFRI NMR spectral acquisition parameters (solid state) HPDEC = high power decoupling 59 Mass spectra. All EI mass spectra, were obtained on a Hewlett-Packard 5985 integrated GCMS system, operating under EI ionisation conditions. Typical injection procedures involved a sample volume of 1 jiL, at 1 mg ml"1 concentration, in a suitable solvent (CHjCy. The ionising energy was set at 70 eV, with the ion source at 200°C for EI.

All GCMS samples were run on a Hewlett Packard 5890 gas chromatograph, utilising a 25 m Ultra-2 (HP5) capillary column. The standard operating conditions are summarised below.

Normal Injection: Inj Port A = 250°C, det A = 250°C, ion source = 200°C, column head pressure = 10 psi, temperature program: initial temperature of 40°C for 2 minutes, followed by a temperature gradient program of 5° per minute up to 300°C (total run time = 64 minutes).

The di and trialkanolamines were TMS or OAc derivatised, prior to analysis, to increase their volatility.

The TMS derivatising procedure used was as follows: to a lOmg sample of trialkanolamine, 50 ml of pyridine, followed by 100 ml of BSA (Bis Trimethylsilyl Acetamide) was added. The mixture was then heated for 45 mins. while dry nitrogen was blown over the sample to remove the solvent. The derivatised trialkanolamine was then made up to the appropriate concentration in dichloromethane for DIP (direct insertion probe) mass spectrometry.

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 CH2C12, washed with saturated NaHCOj, 1 mol L'1 HC1, saturated NaHCOs, dried with MgS04, and the CH2C12 was removed at reduced 60 pressure. Residual solvent was then blown away using dry nitrogen. The derivatised di or trialkanolamine, 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 focusing magnetic sector mass spectrometer, operating under (+) ionisation conditions. Typical sample preparation involved dissolution of a di or trialkanolamine in glycerol/ethanol, or a boratrane 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 II electrospray mass spectrometer, operating under (+) ionisation conditions. Typical sample preparation involved dissolving the di or trialkanolamine in MeCN/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 infra-red spectra were obtained on a Digilab FTS-60 FT-ER spectrometer. Samples, were typically run as neat films between KBr discs or as solutions in CHC13. The spectral range was between 400-4000 cm"1. 61 EXAMPLE 10: Fungicidal Toxicity Trials Samples of the atranes were prepared for fungitoxicity trials. These trials test the compounds fungicidal activity towards basidiomycetes, a group that contains the larger and more important wood destroying fungi. .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 antibiotic assay disc, inoculated with Coniophora puteana. Controls involving the solvents dichloromethane (Trial One), chloroform (Trial Two) 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 diameter (cm) of C puteana on the treated filtered papers was then measured. The MIC value was then determined. Effectively, this is the concentration level required to prevent wood-rotting basidiomycetes from growing. Three separate trials were carried out. .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,ll-trioxa-6-aza-l-boratricyclo[4.4.4.0I,6]tetradecane (OHTABT). The results are shown in Table 5.

Table 5 Treatment Concentration (mm)Average MIC value (% w/v) Growth (% BAE) 62 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 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 CH,C1, 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-containing compound was stoichometrically hydrolysed to give boric acid). .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-l-boratricyclo[3.3.3.0,,5]undecane and 8,ll-didecyl-4-hydroxyl-2,9,10-trioxa-6-aza-l-boratricyclo[4.3.3.01,6]dodecane (Example 3).

Treatment 2. 3,7-dimethyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.0''sjundecaneand,8,ll-dimethyl-4-hydroxyl-2,9,10-trioxa-5-aza-l-boratricyclo[4.3.3.01,6] dodecane, in mixture with higher molecular weight oligomers (Example 4). 63 Treatment 3. 3,7-dimethyl-10-hydroxymethyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.3.3.01,s]undecane,and8,ll-dimethyl-4-hydroxyI-2,9,10-trioxa-5-aza-l-boratricyclo[4.3.3.01,6] dodecane not containing higher molecular weight oligomers (Example 4).

Treatment 4. 12-hydroxymethyl-2,10,ll-trioxa-6-aza-l-boratricyclo[4.4.3.01,6]tetradecane, and 13-hydroxyl-2,10,ll-trioxa-6-aza-l-boratricyclo[4.4.4.01,6]tetradecane (Example ).

The results are shown in Table 6 Table 6 Treatment Concentration Average Growth MIC value (% w/v) (mm) (% w/v) (% BAE) 1 0.10 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% BAE 0.25 0 0.50 0 0.75 0 1.00 0 Water 84 Chloroform 84 BAE = boric acid equivalent The results indicate that the alkyl-, hydroxyalkyl 1- and hydroxy-substituted boratranes tested have strong fungicidal activity. 64 Trial Three The [4,4,5,01,6] boratranes of Examples 8 and 9 were submitted to a rapid filter paper assay. The results are shown in table 7.

Table 7 Treatment Concentration % wv Colony growth (mm) MIC value (%BAE) '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 4.20 0 14.0 0 Compound 1: 2,10,ll-trioxa-6-aza-l-borotricycIo[4.4.5.016]pentadecane Compound 2: Mixture of 14-(dodec-2-en-l-yl)-2,10,ll-trioxa-6-aza-l-borotricyclo-[4.4.5.016]pentadecane and 13-(dodec-2-en-l-yl)-2,10,ll-trioxa-6-aza-l-borotricyclo-[4.4.5.0 ]pentadecane. 65 EXAMPLE 11 The determination of efficacy of 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-l-boratricyclo-[3.3.3.0,,5]undecane (C12/555/B) and l,2-dialkyl-2,10,ll-trioxa-6-aza-l-boratricyclo-[4.4.4.01'6] tetradecane (C23/666/B) as permanent wood preservatives against wood-decaying fungi.

In this Example the above two compounds were tested as potential permanent wood preservatives using a laboratory decay test.

Blocks of wood of dimensions 35x35x7mm were treated by vacuum impregnation with the two preservatives. The blocks were of either Radiata Pine or European Beech.

Each compound was tested at a number of retentions. For each of these ten were exposed to each test fungus, 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 of untreated controls and a set of solvent blanks with ten replicates each were included in each test.

C12/555/B was tested at concentrations of 0.5%, 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 Tyromycespalustris, Poria placenta, Gleeophyllum trabeum, Coniophora puteana, Trametes lilacino-gilva and Coriolus versicolor. T liliacino-gilva is a white rot fungus of economic importance in Australia. The Tpalustris 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 EN113 tests. 66 The blocks were weighed initially then treated with the test compounds at respective retentions, reweighed after each treatment and were subsequently transferred into air-tight containers and 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 fourteen (14) days leaching cycle. The first five blocks from a set of ten 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 changed on every alternate day for two weeks. Upon completion of the leaching cycle, the blocks were air-dried on racks 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 ethylene oxide gas, after which they 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 the jars. A perspex mat was placed sandwiched between the fungi 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 27°C for six weeks.

After six weeks, the blocks were 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 of the blocks were weighed (weight after exposure to the test fungi) and percent weight losses calculated.

Tables 7-12 show the results. A weight loss of greater than 2.00% of a test block due to wood decay by the test fungi indicates the chemical modification treatment used would not provide suitable protection when used in an outdoor exposure situation. Data is included for chloroform controls. In addition to the untreated controls, treatments with boric acid were included for some of the tests. 67 The results show that C12/555/B was effective at preventing weight loss of radiata pine blocks exposed to Tpalustris, Pplacenta, G trabeum and Cputeana. It was also effective with beech blocks exposed to T lilacino-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 Coriolus versicolor in beech blocks. C23/666/B was tested for prevention of 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.

TABLE 7 - Mean Percent Weight Loss of Radiata Pine Blocks Exposed to Tpalustris % Weight Loss (Range in Brackets) %Weight Loss (Range in Brackets) Retention Chemical Leached Unleached 0.5% C12/555/B 26.08 (14.83-30.59) 0 (0-0.40) 1.0% ff 14.76 (7.94-28.98) 0 1.5% I! 7.28 (0-17.45) 0 2.0% ff 0 0 2.5% ff 0 0 3.0% If 0 0 2.0% C23/666/B .65 (19.16-31.05) 0 4.0% If .31 (4.10-22.91) 0 6.0% If 13.68 (7.53-20.07) 0 68 Chloroform .65 (10.86-21.69) 14.70 (10.24-18.58) Untreated .79 (17.77-24.23) 11.54 (5.93-17.32) Table 8 - Mean Percent Weight Loss of Radiata Pine Blocks Exposed to P placenta % Weight Loss Range in Brackets %Weight Loss Range in Brackets Retention Chemical Leached Unleached 0.5% C12/555/B 17.74 (10.82-22.49) 0 1.0% ff .00 (0-8.23) 0 1.5% ff 1.38 (0-5.11) 0 2.0% ff 0 0 2.5% ff 0 0 3.0% ff 0 0 Chloroform 22.83 (16.95-35.12) .34 (21.35-33.70) Untreated 21.66 (16.52-31.22) 23.87 (13.47-28.34) Table 9 - Mean Percent Weight Loss of Radiata Pine Blocks Exposed to G trabeum % Weight Loss (Range in Brackets) % Weight Loss (Range in Brackets) Retention Chemical Leached Unleached 0.5% C12/555/B .81 (20.51-31.00) 0 1.0% ff 3.02 (0-10.11) 0 1.5% ff 0 0 2.0% ff 0 0 2.5% ff 0 0 3.0% ff 0 0 2.0% C23/666/B 4.71 C2.ll-9.00") 0 69 4.0% ff 2.15 (0-5.74) 0 6.0% ff 0 0 14% Chloroform 24.76 (19.80-28.47) 23.09 (18.13-28.72) Untreated 21.15 (15.15-27.43) .68 (15.47-23.56) Table 10 - Mean Percent Weight Loss of Radiata Pine Blocks Exposed to Cputeana % Weight Loss (Range in Brackets) % Weight Loss (Range in Brackets) Retention Chemical Leached Unleached 0.5% C12/555/B 33.67 (25.96-38.48) 0.66 (0-3.96) 1.0% ff 23.83 (13.64-31.82) 0 1.5% ff 17.90 (14.65-27.31) 0 2.0% ff 3.75 (0-10.32) 0 2.5% ff 1.67 (0.12-3.09) 0 3.0% ff 0 (0-0.40) 0 2.0% C23/666/B 17.80 (14.62-24.18) 0 4.0% ff 16.59 (10.40-22.79) 0 6.0% ff 11.41 (1.19-22.97) 0 0.2% Boric Acid 29.98 (26.47-33.78) 0 0.4% Boric Acid 26.17 (22.52-34.07) 0 0.6% Boric Acid 26.81 (22.17-31.39) 0 Chloroform 29.66 (20.02-34.70) .67 (27.50-35.04) Untreated 26.20 (21.76-29.19) .34 (23.14-35.16) 70 Table 11 - Mean Percent Weight Loss of Beech Block Exposed to Trametes lilacinogilva % Weight Loss (Range in Brackets) % Weight Loss (Range in Brackets) Retention Chemical Leached Unleached 1.0% C12/555/B 19.56 (19.17-19.93) 0 1.5% II 18.08 (16.83-19.55) 0 2.0% tf 8.11 (1.79-13.06) 0 2.5% If 0 0 3.0% II 0 0 Chloroform .28 (14.61-23.25) 6.78 (0-18.44) Untreated 12.37 (1.33-24.80) 7.72 (0.10-23.82) Table 12 - Mean Percent Weight Loss of Beech Blocks Exposed to C versicolor % Weight Loss (Range in Brackets) % Weight Loss (Range in Brackets) Retention Chemical Leached Unleached 1.0% C12/555/B 24.73 (21.57-28.53) 2.41 (0-11.05) 1.5% If .92 (24.98-36.92) 0 2.0% II 21.83 (9.86-29.55) 0 2.5% II 29.87 (27.80-31.78) 0 3.0% If 34.09 (31.39-38.65) 0 2.0% C23/666/B .58 (27.88-35.31) 0 4.0% II 21.85 (0-29.89) 0 0.2% Boric Acid .22 (26.34-36.73) 0 0.4% Boric Acid 26.94 C25.08-29.15) 0 71 0.6% Boric Acid .57 (21.68-28.85) 0 Chloroform .03 (31.50-39.25) 31.09 (25.65-40.20) Control (untreated) 34.94 (31.19-38.56) 34.14 (31.76-36.84) 72 EXAMPLE 12 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 are dissolved in water to achieve the same boric acid equivalents. These compositions also include toluene-4-suIphonic 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 1 3-Octyl-4-heptyl-2,10,ll-trioxa-6-aza-l-boratricyclo [4.4.4.01,6]tetradecane 6.6g Pegasol qs 1000ml (BAE) = 0.1% 2 3-Octyl-4-heptyl-2,10,ll-trioxa-6-aza-l-boratricyclo [4.4.4.01,6]tetradecane 26.4g Pegasol qs 1000ml (BAE) = 0.4% 3 3-C)ctyl-4-heptyl-2,10,ll-trioxa-6-aza-l-boratricyclo [4.4.4.01,6]tetradecane 52.8g Pegasol qs 1000ml (BAE) = 0.8% 4 3-alkyl-4-alkyl-2,10,ll-trioxa-6-aza-l-boratricyclo [4.4.4.01,6]tetradecanes (Example 3) 9.5g Pegasol qs 1000ml (BAE) = 0.1% 3-alkyl-4-alkyl-2,10,ll-trioxa-6-aza-l-boratricyclo [4.4.4.0''6]tetradecanes (Example 3) 38.1g Pegasol qs 1000ml (BAE) = 0.4% 6 3-alkyI-4-alkyl-2,10,ll-trioxa-6-aza-l-boratricyclo [4.4.4.01,6]tetradecanes (Example 3) 76.1g Pegasol qs 1000ml (BAE) = 0.8% 7 Product of Example 4 7.5g Cymel 323 3.1g Toluene-4-sulphonic acid 15mg Water qs 1000ml (BAE) = 0.1% 8 Product of Example 4 30.1g Cymel 323 12.4g Toluene-4-sulphonic acid 15mg Water qs 1000ml (BAE) = 0.4% 73 9 Product of Example 4 60.2g Cymel 323 24.8g Toluene-4-sulphonic acid 15 mg Water qs 1000ml (BAE) = 0.8% Product of Example 5 (step 2) 3.5g Cymel 323 3.1g Toluene-4-sulphonic acid 10 mg Water qs 1000ml (BAE) = 0.1% 11 Product of Example 5 (step 2) 13.9g Cymel 323 12.5g Toluene-4-sulphonic acid 10 mg Water qs 1000ml (BAE) = 0.4% 12 Product of Example 5 (step 2) 27.8g Cymel 323 25.0g Toluene-4-sulphonic acid 10 mg Water qs 1000ml (BAE) = 0.8% 13 Product of Example 5 (step 4) 3.5g Cymel 323 3.1g Toluene-4-sulphonic acid 12 mg Water 1000 ml (BAE) = 0.1% 14 Product of Example 5 (step 4) 13.9g Cymel 323 12.5g Tolueue-4-sulphonic acid 12 mg Water 1000 ml (BAE) = 0.4% Product of Example 5 (step 4) 27.8g Cymel 323 25.0g Toluene-4-sulphonic acid 12 mg Water 1000 ml (BAE) = 0.8% 16 Product of Example 6 3.5g Cymel 323 3.1g Toluene-4-sulphonic acid 12 mg Water 1000 ml (BAE) = 0.1% 17 Product of Example 6 13.9g Cymel 323 12.5g Toluene-4-sulphonic acid 12 mg Water 1000 ml (BAE) = 0.4% 18 Product of Example 6 27.8g Cymel 323 25.0g Toluene-4-sulphonic acid 12 mg Water 1000 ml (BAE) = 0.8% 74 Example 13 - Treatment of Wood 13.1 Treatment of Wood - Method A Method A is useful for treating wood with compositions 1-6.

Dried wood (kiln-dried) is placed in a vacuum/pressure vessel, and the wood is evacuated to -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 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.

Dried wood (kiln-dried) is placed in a vacuum/pressure vessel, and the wood is evacuated to -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 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. 75 EXAMPLE 14 In-situ preparation of compounds in wood matrix.

This Example illustrates the method of wood preservation in which the desired compound in the wood is prepared from the compound starting materials, boric acid and the alkanolamine.

The compound 3,7-dimethyl-10 decyl-2,8,9-trioxa-5-aza-l-boratricyclo[3.33.01,5]-undecane [1] may be prepared in wood matrix using the the following procedure.

Boric acid (6.2g, 0.1 mol) was dissolved in water-industrial tetrahydrofuran (9:1,2.1L) and to the solution was added N-(2-decyl-2-hydroxyethyl)-N,N-bis(2-methyl-2-hydroxyethyl)-amine [2] (32.5g, 0.1 mol) and toluene-p-sulphonic acid (100 mg). A clear solution was obtained. The nB NMR spectrum showed a signal at 20 ppm indicative of boric acid.

The solution was used to treat air-dired radiata pine sapwood blocks (50x25x200 mm) using a standard vacuum (-85 kPa) and pressure (1400 kPa) sequence. The blocks were then transferred to an oven at 100°C and dried to constant weight. The treated wood material produced was analysed 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 [1] in situ within the wood matrix.

Thus, it is not necessary (although may be desirable for some boratrane 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.

CH CH [1] [2] 76 Aspects of the invention have been described by way of example only and it should be appreciated that modifications and additions may be made thereto without departing from the scope of the invention. 77

Claims (29)

WHAT WE CLAIM IS:

1. A compound of formula I: wherein each of Ri, R3, and R5, is a group independently selected from hydrogen, CrC2oalkyl, C-i-C2oalkenyl, aryl, alkaryl, aralkyl, heterocyclyl, hydroxy, halogen, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy and alkylcarbonylamino, wherein each alkyl, alkenyl, alkyloxy, aryl, 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, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy and alkylcarbonylamino; 78 each of R2, R4 and R6 is a group selected from hydrogen and Ci-C2oalkyl; each of Zi, Z2 and Z3 as a group chosen from -C(R7R8)-, -C(R7R8)-C(R9Rio)-, -C(R7R8)-C(RgRio)-C(RiiRi2)-. -C(R7R8)-C(R9R1o)-C(R11R12)-C(R13Ri4rC(R15Ri6)-, and -C(R7R8)-C(R9Rio)-C(RiiRi2)-C(Ri3Ri4)-(CH2)n-C(Ri5Ri6)-; each of R7, Rg, Rn, R13 and R15 is a group independently selected from hydrogen, Ci-C2oalkyl, Cr2oalkenyl, 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, amino, alkylamino, dialkylamino, alkyloxy, nitro, carboxyl, aminocarbonyl, alkyloxycarbonyl, alkynyl, alkylcarbonyloxy and alkylcarbonylamino; and each of R2, R4, R6. Rs. R10. R121 R-I4 and R16 is chosen from hydrogen and Ci-C2oalkyl; and wherein not only are Z1, Z2, and Z3 the same or different but also R7, Rs and when present Rg, R10, Rn, R12. R-i3> Ru, R15. R16 may be the same in said Z-t, Z2, and Z3 or in two of those groups, or those R groups may be different in all three Z groups; Zi, Z2 and Z3 with more than one carbon atom may be included in the molecules such that the C atom bearing R7 is linked to that bearing R1, R3 and R5 respectively or so that it is linked to the nitrogen atom; and Ri, R2, R3, R4, R5, R6. Z-i, Z2, and Z3 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.

2. A compound as claimed in claim 1 wherein R2, R4, R6, Rs and where present R10, Ri2, R14 and R16 are each hydrogen.

3. A compound as claimed of Formula II: II 80 wherein p is an integer from 0 to 2; each of q and r is an integer from 1 to 3; w is an integer which is 0 or 1; at least one of Ri, R2, R3, R4, R5, R6. R7 and R9 (if present) is other than hydrogen, methyl, methoxy or ethoxy.

4. A compound as claimed in claim 3 wherein at least one of Ri, R2, R3, R4, R5, R6 and R7 is other than hydrogen methyl, methoxy or ethoxy.

5. A compound as claimed in claim 4 wherein p = 1, q = 2 and r = 2.

6. A compound as claimed in claim 4 wherein R2, R4 and R6 are hydrogen.

7. A compound of formula III; wherein Ri, R3, R5, R7 and Rg (if present) are (1) as defined for formula I and (2) include a group other than hydrogen, methyl, methoxy or ethoxy, s = 0-2, t and u are each 1 or 2 and w is 0 or 1. 81

8. A compound as claimed in claim 7 wherein at least one of Ri, R3, R5 and R7 includes a group other than hydrogen, methyl methoxy or ethoxy.

9. A compound as claimed in claim 8 wherein Ri is selected from C-i-C2oalkyl, C2-C2oalkenyl, hydroxy or Ci-C2ohydroxyalkyl.

10. A compound as claimed in claim 8 wherein Ri and R7 are both Ci-C2oalkyl and s=1, t=2, u=2, w=0, R3 is hydrogen and R5 is hydrogen.

11. A compound as claimed in claim 7 wherein s=1, t=2, u=2, w=1, Ri, R3, R5 and R7 are hydrogen and Rg is C8-C20alkyl or C8-C2oalkenyl.

12. A compound as claimed in claim 8 wherein R3 and R5 are Ci^alkyl and one of R7 and Ri is hydroxy or C1-C4 hydroxyalkyl.

13. A wood preservative composition including a compound as claimed in claim 1.

14. A wood preservative composition including a compound as claimed in claim 3.

15. A wood preservative composition including a compound as claimed in claim 7.

16. A composition comprising a compound as claimed in claim 10 or claim 11 formulated in an aqueous solution using emulsifiers to form a microemulsion. 82 INTELLECTUAL PRO.^TfY OFFICE OF N.Z. - b JUL 20% received

17. A composition as claimed in any one of claims 13-16 wherein the compound is present in an amount of between 0.1 and 30% by weight.

18. A method for preserving wood or textiles comprising application of a composition containing at least one compound as claimed in any one of claims 1-12 to the wood or textiles.

19. A method as claimed in claim 18 wherein the compound has a i hydroxy group or a hydroxyalkyl group and the wood or textiles are also treated with a hydroxymethyl or alkylhydroxymethyl melamine to crosslink the compound.

20. A method as claimed in claim 18 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.

21. A composition as claimed in claim 13 wherein the compound has a reactive group allowing polymerisation of the compound, wherein the composition further comprises a polymerisation agent effective for polymerising the compound.

22. A composition as claimed in claim 13 wherein the compound has a substituent group which is hydroxyl or hydroxyalkyl group, wherein the composition further comprises a crosslinker effective for crosslinking the compound by reacting with hydroxy: groups. INTELLECTUAL PROr^TY OFFICE OF N.Z. - 6 JUL 2ES1! nrr.5l¥SB

23. A method of producing a compound as claimed in claim 1 comprising refluxing a compound of the formula VI in an anhydrous solvent in the presence of boric acid, wherein R'i, R2, R3, R4, R5, R'6 have the meaning of R1 to R6 in claim 1 or are R-i to Re in protected form; VI , Ri r5 \ Z,— Z2-N noh Z3 R3 H0 R4 and if necessary, removing any protecting group to obtain a compound of claim 1.

24. 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-1-boratricyclo-[3.3.3.01,5] undecane

25. A wood preservative composition comprising 3,7-dimethyl-10-decyl-2,8,9-trioxa-5-aza-1 -boratricyclo-[3.3.3.0,1,5J undecane

26. A compound as claimed in any one of claims 1-12, substantially as hereinbefore described with reference to the Examples.

27. A wood preservative composition as claimed in any one of claims 13-17, 21 and 22, substantially as hereinbefore described with reference to the Examples.

28. A method as claimed in any one of claims 18-20, substantially as hereinbefore described with reference to the Examples.

29. A method as claimed in claim 23, substantially as hereinbefore described with reference to the Examples. end of claims 85