GB2322129A

GB2322129A - Polyazabicyclic compounds

Info

Publication number: GB2322129A
Application number: GB9802985A
Authority: GB
Inventors: Leonardo Guglielmetti; Martin Studer; Frank Bachmann; Josef Dannacher; Beat Freiermuth
Original assignee: Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: BASF Schweiz AG
Priority date: 1997-02-13
Filing date: 1998-02-13
Publication date: 1998-08-19
Also published as: GB9802985D0; GB9702978D0

Abstract

Compounds having the formula: in which the bonds denoted # represent either a single or a double bond; R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, amino, nitro, cyano, sulfo or sulfonamido; R 1 is hydrogen or C 1 -C 4 alkyl; Z is C 2 -C 6 alkylene; and n is 0 or 1; as well as salts and metal complexes thereof are novel compounds. The new metal complexes are useful as bleach catalysts. Intermediates of formula

Description

Compounds The present invention relates to new compounds, in particular to new polyazabicyclic compounds; to processes for their production; to new metal complexes of the new polyazabicyclic compounds; and to the use of the new metal complexes as bleach catalysts.

The present invention provides new compounds having the formula:

in which R is hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, amino, nitro, cyano, sulfo or sulfonamido; R1 is hydrogen or C1-C4allyl; Z is C2-C6alkylene; and n is O or 1; as well as salts thereof. The bonds denoted represent either a single or a double bond.

-C,-C4alkyl groups R or R1 include methyl, ethyl, n-propyl, isopropyl and n-butyl, with methyl being preferred.

C1-C4alkoxy groups R include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy, with methoxy being preferred.

When R is halogen, it is preferably fluorine, chlorine, bromine or iodine, especially chlorine.

C2-C6alkylene groups Z include ethylene, n-propylene, methylethylene, n-butylene, n pentylene and n-hexylene, ethylene groups being preferred.

Salts of the compounds of formula (1) are preferably mineral acid salts such as hydrochloride, nitrate, sulfate and phosphate salts.

When n is 1, preferred compounds according to the present invention are those having the formula:

in which each of the bonds denoted ~ preferably represents a single bond and R and R, have their previous significance; as well as salts thereof.

When n is 0, preferred compounds according to the present invention are those having the formula:

in which each of the bonds denoted ~ preferably represents a single bond and R and R1 have their previous significance; as well as salts thereof.

The compounds of formula (2) are especially preferred. The preferred compound of formula (2) is 3,6,9,15-tetrakis(methyl)-3,6,9,15-tetraazabicyclot9.3.1]pentadecane as well as the tetrahydrochloride salt thereof.

The compounds of formula (1) may be produced, for example, in a first process by a) firstly conducting a cyclisation reaction by reacting a compound having the formula:

in which R has its previous significance and Y is a leaving group; with a compound having the formula:

in which Z and n have their previous significance and X is hydrogen or an amine protecting group, to obtain a compound having the formula:

in which R, Z, X and n have their previous significance; and then b) when R1 is a C1-C4alkyl group, reacting the compound of formula (6) with an alkylating agent which is capable of converting each of the groups N-X into an N-C1-C4alkyl group, to produce a compound of formula (1).

The leaving group Y in the reactant of formula (4) may be, e.g., a hydroxy, a chloro-, a bromo-, a mesyloxy-, a tosyloxy- or a C1-C4alkoxycarbonyl group. Each of the NH2- groups in the reactant of formula (5) is preferably in a protected form, for example it may be protected, prior to reaction with the compound of formula (4), by converting the respective hydrogen groups X into an amine protecting group, for example, a tosylate or trifluoroacetate group.

After the reaction of the compound of formula (4) with the compound of formula (5), the protecting groups X in formula (6) are removed prior to the reaction of the compound of formula (6) with the alkylating agent. The methods of removing such protecting groups X are well known. For example, if the protecting group X is a tosylate group, this may be removed, e.g., by treating the protected compound of formula (6) with a mineral acid, with an alkali metal in liquid ammonia, with HBr and phenol or with lithiumaluminium hydride.

The alkylation of the compound of formula (6) may be conducted, e.g., by reacting the compound of formula (6) with a C1-C4alkyl halide, a C,-C4alkyl sulfate, a C1-C4 alkanol or, preferably in the case of a methylation of a compound of formula (6), with formaldehyde in the presence of formic acid (Leuckart-Wallach reaction).

Finally, if desired, a compound of formula (1) in which one or more bonds denoted ~ are double bonds may be converted into a partly or fully saturated counterpart, for example by hydrogenation. The hydrogenation may be conducted, for example in an atmosphere of hydrogen over a catalyst such as Raney nickel.

The starting materials of formula (4) and (5) are known compounds which can be produced by known methods.

In a modification of this first process, the compounds of formula (1) in which one or more bonds denoted ~ are single bonds may be produced by reacting a compound having the formula:

in which R and Y have their previous significance; with a compound having the formula (5) to obtain a compound having the formula:

in which Z, X and n have their previous significance; and then b) when R1 is a O1-C4alkyl group, removing the protecting groups X and reacting the compound of formula (6A) in which X is hydrogen with an alkylating agent which is capable of converting each of the groups N-H into an N-C1-C4alkyl group, to produce a compound of formula (1).

Some of the starting materials of formula (4A) are known compounds and may be produced by methods which are known per se. For example, the compound of formula (4A) in which R is hydrogen and Y is hydroxy is a known compound and may be obtained by the hydrogenation of pyridine-2,6-dimethanol, or by the hydrogenation of pyridine-2,6dicarboxylic acid or the dimethyl ester thereof. On the other hand, the compounds of formula (4A) in which Y is a tosyloxy group are new compounds and, as such, form a further aspect of the present invention.

The compounds of formula (1) are capable of forming complexes with heavy metals, in particular manganese in the oxidation numbers 11, III, IV and/or V; copper in the oxidation numbers I and/or ll; cobalt in the oxidation number il and/or Ill; zinc in the oxidation number ll; iron in the oxidation numbers 11, Ill and IV; vanadium in the oxidation numbers Ill, IV and V; and titanium in the oxidation numbers Ill and IV. Such metal complexes form a further aspect of the present invention.

The new metal complexes according to the present invention may be produced by known methods, e.g. by methods described in US-4,655,785.

The new metal complexes are excellent bleach catalysts in combination with peroxy compounds and provide enhanced bleach effects at low wash temperatures (e.g. at 15 to 40 C.).

Accordingly, the present invention provides a fabric bleaching composition comprising a) a peroxy compound; and b) 0.005 to 0.05%, by weight of a metal complex according to the present invention.

The peroxy component a) of the fabric bleaching compositions of the present invention may be hydrogen peroxide, a compound which liberates hydrogen peroxide, a peroxyacid, a peroxyacid bleach precursor or a mixture thereof.

Compounds which liberate hydrogen peroxide are well known and include, e.g., inorganic compounds such as alkali metal peroxides, -perborates, -percarbonates, -perphosphates and -persulfates and organic compounds such as peroxylauric acid, peroxybenzoic acid, 1,1 2-diperoxydodecanoic acid, diperoxyisophthalic acid and urea peroxide, as well as mixtures thereof. Sodium percarbonate and sodium perborate, in particular sodium perborate monohydrate, are preferred.

Peroxyacid compounds and peroxyacid bleach precursors are also well known and a summary of references describing them is provided in the above-mentioned US-A-5114606.

Examples of peroxyacid bleach precursors include benz(4H )-1 ,3-oxazi n-4-one derivatives, especially substituted 2-phenyl-benz(4H)-1,3-oxazin- 4-one 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulfophenyl carbonate chloride (SPCC) N-octyl, N, N-dimethyl-N 1 0-carbophenoxy decyl ammonium chloride (ODC) 3-(N,N,N-trimethyl ammonium) propyl sodium 4-sulfophenyl carboxylate N,N,N-trimethyl ammonium toluyloxy benzene sulfonate sodium-4-benzoyloxy benzene sulfonate (SBOBS) N, N,N',N'-tetraacetyl ethylene diamine (TAED) sodium-1 -methyl-2-benzoyloxy benzene-4-sulfonate sodium-4-methyl-3-benzoyloxy benzoate and sodium nonanoyloxybenzene sulfonate (NOBS).

The substituted 2-phenyl-benz(4H)-1 ,3-oxazin-4-one, NOBS and TAED precursors are preferred.

Preferably, the amount of the peroxy compound in the fabric bleaching composition according to the invention ranges from 0.5 to 50%, especially from 2 to 20% by weight, based on the total weight of the composition.

The fabric bleaching compositions of the present invention preferably also comprises a surfactant and a detergent builder component.

The surfactant component is preferably an anionic surfactant, a nonionic surfactant or a mixture thereof and is preferably present in an amount of 5 to 50%, especially 5 to 25% by weight, based on the total weight of the fabric bleaching composition.

The anionic surfactant component may be, e.g., a sulphate, sulphonate or carboxytate surfactant, or a mixture of these.

Preferred sulphates are alkyl sulphates having 12-22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxy sulphates having 10-20 carbon atoms in the alkyl radical.

Preferred sulphonates include alkyl benzene sulphonates having 9-15 carbon atoms in the alkyl radical.

In each case, the cation is preferably an alkali metal, especially sodium.

Preferred carboxylates are alkali metal sarcosinates of formula R-CO(R')CH2COOM' in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is Ci C4 alkyl and M1 is alkali metal.

The nonionic surfactant component may be, e.g., a condensate of ethylene oxide with a Og C15 primary alcohol having 3-8 moles of ethylene oxide per mole.

The detergent builder component is preferably present in an amount of 5 to 80%, especially 10 to 60% by weight, based on the total weight of the fabric bleaching composition.lt may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.

Preferred silicates are crystalline layered sodium silicates of the formula NaHSimO2m+1pH2O or Na2SimO2m+,.pH2O in which m is a number from 1.9 to 4 and p is O to 20.

Preferred aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.

Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.

Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.

Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.

The fabric bleaching compositions of the invention preferably also contain one or more agents capable of binding metal ions, preferably manganese, in particular an aminocarboxylate, an aminophosphonate, a polyamine or a mixture of these. Examples of am inocarboxylates include ethylenediaminetetraacetate, N-hydroxy ethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethyl enetetraaminehexaacetate, diethylenetriaminepentaacetate, ethylenediaminedisuccinate, especially the S,S isomer, and ethanoldiglycine, each in their acid forms or as the respective alkali metal, ammonium or substituted ammonium salts, as well as mixtures thereof. Examples of aminophosphonates include diethylenetriaminepentamethylene phosphonic acid and salts thereof. Examples of polyamines are, e.g., diethylenetriamine, pentamethyldiethylenetriamine, 1,1',7,7'tetramethyl-4-hydroxymethyl-diethylenetriamine and 1 ,4,4'-trimethyl-1 '-hydroxymethyl- ethylenediamine. Most preferred agents capable of binding the complexing metal are diethylenetriami nepentamethylene phosphonic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid and salts thereof, and diethylenetriamine.

The agent capable of binding metal ions is generally present in an amount of 0.1 to 10%, preferably from 0.1 to 3% by weight, based on the weight of the fabric bleaching composition.

The fabric bleaching compositions of the invention may contain, in addition to the components already mentioned, one or more of fluorescent whitening agents, such as a bis triazinylamino-stilbene < Iisulphonic acid, a bis-triazolyl-stilbene-disulphonic acid, a bis-styrylbiphenyl, a bis-benzofuranylbiphenyt, a bis-benzoxalyl derivative, a bis-benzimidazolyl derivative, a coumarine derivative or a pyrazoline derivative; soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; enzymes, such as proteases, cellulases, lipases, oxidases and amylases; photobleaching agents; pigments; and/or shading agents. These constituents should, of course, be stable to the bleaching system employed.

A particularly preferred fabric bleaching composition co-additive is a polymer known to be useful in preventing the transfer of labile dyes between fabrics during the washing cycle.

Preferred examples of such polymers are polyvinyl pyrrolidones, optionally modified by the inclusion of an anionic or cationic substituent, especially those having a molecular weight in the range from 5000 to 60,000, in particular from 10,00 to 50,000. Preferably, such polymer is used in an amount ranging from 0.05 to 5%, preferably 0.2-1.7% by weight, based on the weight of the detergent.

The formulation of the fabric bleaching compositions of the invention may be conducted by any conventional technique.

The fabric bleaching composition may be formulated as a solid; or as a non-aqueous liquid fabric bleaching composition, containing not more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in GB-A2158454.

Preferably, the fabric bleaching composition is in powder or granulate form.

Such powder or granulate forms may be produced by firstly forming a base powder by spraydrying an aqueous slurry containing all the said components, apart from the components a) and b); then adding the components a) and b) by dry-blending them into the base powder. In a further process, the component b) may be added to an aqueous slurry containing the surfactant and builder components. followed by spray-drying the slurry prior to dry-blending component a) into the mixture. In a still further process, a nonionic component is not present, or is only partly present in an aqueous slurry containing anionic surfactant and builder components; component b) is incorporated into the nonionic surfactant component, which is then added to the spray-dried base powder; and finally component a) is dry-blended into the mixture.

The present invention also comprises a bleaching and/or cleaning process comprising contacting a fabric to be bleached and/or cleaned with an effective amount of a fabric bleaching composition according to the present invention. Preferably the amount of the fabric bleaching composition used is such that the amount of metal complex compound b) provides from 0.001 to 100 ppm, preferably from 0.01 to 20 ppm of complexing metal in the bleaching and/or cleaning bath.

The following Examples further illustrate the present invention.

Example 1 A) Production of 3,6,9-tris(p-tolylsulfonyl)-3,6,9,1 5-tetraazabicyclo[9.3.1 ]pentadeca- 1(15)11,1 3-triene having the formula:

The compound of formula (101 ) is a known compound and is produced according to the procedure described in Example 1a of EP-A24 352 218, except that the macrocyclisation described therein is conducted using 2,6-bis(p-tolylsulfonylmethyl)pyridine instead of 2,6bis(chloromethyl)pyridine.

B) Production of 3,6,9,1 5-tetraS7sbicyclot9.3.1 ]pentadeca-1(15),1 1,1 3-triene-trihydrochloride having the formula:

The parent free amine of the compound of formula (102) is a known compound and is produced according to the procedure described in Example 1b of EP-A2-0 352 218. The compound of formula (102) is obtained by de-tosylation of the compound of formula (101) using conc. sulfuric acid at elevated temperature, and then precipitating the de-tosylated free amine as the tri-hydrochloride using hydrochloric acid.

C) Production of 3,6,9,1 5-tetrnazabicyclot9.3. I ]pentadecane-tetrahydrochloride having the formula:

1.18 g of the compound of formula (102) are dissolved in 12 ml of distilled water and are treated with 0.6 g of 5% Rh/C. The resulting solution is stirred ovemight at 25"C. in an atmosphere of hydrogen and at a pressure of 3 bar. After completion of the hydrogenation, the catalyst is filtered off and the filtrate is concentrated and dried under high vacuum. 1.22 g (91% of theory) of the compound of formula (103) are obtained as a yellow powder. NMR analysis of the compound gives: 13C NMR (D20) & 23.5, 28.1(6-ring CH2), 51.1, 45.4, 46.1(12-ring CH2), 53.2CH) C11H24N4 x 4HCI (358.19).

D) Production of 3,6,9,1 5-tetrakis(methyl)-3,3,9, 1 5-tetraazabicyclo[9 .3.1 ipentadecane- tetrahydrochloride having the formula:

1.08 g of the tetrahydrochloride compound of formula (103) are dissolved in 3 ml of distilled water to give a clear yellowish solution. With cooling, 4 ml of 50% aqueous sodium hydroxide solution are added, whereupon a light-yellow suspension is formed. The solid material, the free amine derived from the tetrahydrochloride compound of formula (103), is filtered off and sucked dry. With cooling, 0.98 g of the moist free amine is added to 8 ml of formic acid. To the clear colourless solution so obtained, there are added 6.4 ml of formaldehyde, over 30 minutes at 5"C. The reaction mixture is then heated for 40 hours under reflux. The resulting clear yellow solution is diluted with 5 ml of water. The pH of the diluted solution is adjusted to 11 by the addition of 50% aqueous sodium hydroxide solution, with cooling. The aqueous alkaline solution is then extracted three times with dichloromethane, using 15 ml of dichloromethane for each extraction. The resulting organic phases are combined, dried over anhydrous sodium sulfate, concentrated and dried under high vacuum. 620 g of crude product are obtained which are dissolved in 2 ml of conc. hydrochloric acid, with cooling. On addition of ethanol, a solid product is precipitated and this is filtered off and washed with icecold ethanol. The washed solid is dissolved in distilled water and the solution is filtered and lyophilised. In this way, 295 mg (21% theory) of the compound of formula (104) are obtained as a colourless solid having the following NMR analysis: 13C NMR (D2O) S13.1, 22.1(6-ring CH2), 53.0, 53.5, 58.6 (12-ring CH2), 40.6, 44.1, 46.7(H3), 59.1 LCH) C15H32N4 x 4HCI (414.29).

Example 2 A) The compound of formula (104) as obtained in Example 1 D) is converted into its manganese salt by preparing a solution of the compound of formula (104) in methanol and then adding to this solution, at 25"C., the stoichiometric amount of Mn(ClO4)2 dissolved in methanol. The formation of the metal complex is monitored spectrometrically.

B) The bleach-promoting action of the manganese complex obtained in part A) is determined as follows. Using a Linitest device, each of the beakers is filled with 80 ml of test liquid, 2.5 g of tea-stained cotton and 7.5 g of white cotton, as ballast. The test liquid contains H202 (8.6 mmol/l)and the manganese complex obtained in part A) (5 x 106 mol/l) dissolved in borax buffer (0.03 mmol/pH 10). The test liquid is heated to 400 C. and held at this temperature for 30 minutes. The brightness value of the tea-stained cotton is determined, before and after treatment, using an ICS SF 500 spectrophotometer. The results obtained show that the manganese complex obtained in part A) exerts a bleach-promoting effect.

Example 3

5 g of 2,6-piperidine-dimethanol, which is obtained in known manner by the hydrogenation of pyridine-2,6-dimethanol, are suspended in 40 ml of tetrahydrofuran. To this suspension are added 6.7 g of powdered potassium hydroxide and the mixture is cooled to -5 C. Into this mixture there are then added, dropwise, at -5 C., over 1 hour, a solution of 19.5 g of toluene sulfonyl chloride dissolved in 50 ml of tetrahydrofuran. The mixture is stirred for 5 hours at O"C. and then for 8 hours at 20"C. The solution is filtered and the separated residue is washed with tetrahydrofuran. The filtrate is concentrated. 19 g of crude material are obtained which are purified by column chromatography (eluate: toluene/ethyl acetate/ethanol 50:5:5).

The yield of the compound of formula (401), as a colourless oil, is 1.5 g (47% of theory).

The compound of formula (401) has the following NMR analysis: 1H NMR (CDC13): 6= 1.00,1.28,1.50,1.79 (m, 6H, CH2), 2.45 (s, 3H, Ts-CH3), 2.86 (m, 2H, CH), 3.80, 3.95 (m, each 2H, CH2OH), 7.36, 7.78 (m, each 4H, Ts-H); 13C NMR (CDCl3) 6= 24.4 (Ts-CH3), 25.7, 30.0 (CH2), 76.3 (CH2O), 130.7, 132.8 (tert. arom.

C), 135.4,147.8 (quat. arom. C).

C21H27NO6S2 (452.6).

Example 4 Preparation of 3,10,1 6-Triazabicyclo[1 0.3.1 ]-hexadecane-triene-dihydrobromide

5 g (9.48 mmol) 3,10-Bis(p-tolylsulfonyl)-3,10,16-triazabicyclo[10.3.1]-hexadecane- triene (known compound, prepared according to K. Krakowiak, Pol. J. Chem. (1986) 60, 277) are treated with a mixture of HBr (47 %) and acetic acid (vol. ratio 6:4). The reaction mixture is heated under reflux with stirring for 48 hours. After cooling to room temperature, the solution is evaporated in vacuo. The residue is taken up in 20 ml of water and 50 ml of diethyl ether are added. A white solid precipitates which is filtered, washed with diethyl ether and dried in vacuo to give a slightly brownish powder, m.p. 260 "C (dec.), Yield: 3.25 g (90 %).

NMR (D20): 8 = 22.2, 23.9, 46.9, 49.5 (CH2), 124.2, 140.0 (Aryl-C, tert.) 151.1 (Aryl C, quart.) C13H23Br2N3 (381.16).

Example 5 Preparation of 3,8,1 4-Triazabicyclo [8.3.1 ]-tetradecane-triene-dihydrobromide

5 g (10.0 mmol) of the known compound 3,8-Bis(p-tolylsulfonyl)-3,8,14 triazabicyclot8.3.1]-tetradecane-triene are reacted and worked-up as described in Example 4. Yield: 3.3 9 (92 %), brownish powder, m. p. 280 "C (dec.), NMR (D2O): 6 = 21.0, 43.4, 48.9 (CH2), 48.9 (CH), 124.3, 140.3 (Aryl-C, tert.), 149.6 (Aryl-C, quart.).

C,1H1gBr2N3 (353.1).

ExamDle 6 Preparation of 3,10,16-Triazabicyclo[10.3.1]-hexadecane-trihydrobromide

7.11 9 (18.36 mmol) 3,10,16-Triazabicyclo[10.3.1]-hexadecane-triene- dihydrobromide are reacted with 5 % Rh/C and worked-up as described for compound of formula (103) to give 6.3 g (91 %) of a slightly yellow powder.

NMR (D20) 6 = 23.4, 24.5, 29.7, 46.4, 50.2 (CH2), 52.5 (CH).

C13H33Br3N3 (371.4).

Example 7 Preparation of 3,10,1 6-Tris(methyl)-3, 10,1 6-triazabicyclo [10.3.1]-hexadecane- trihydrochloride

2 g (5.38 mmol) of 3,10,16-Triazabicyclo[10.3.1]-hexadecane-trihydrobromide are reacted and worked-up as described for compound of formula (104), and 1.1 g (55 %) of a colourless solid are obtained.

NMR (D2O) 6 = 24.0, 24.4, 28.8 (CH2), 43.0 (CH3), 50.7 (CH), 55.3, 61.5 (CH2), MS m/z = 269 (M- 3 HCl)+ C16H33C13N3 (376.8) The above compound is converted into its manganese salt as described in Example 2 and its bleach promoting action is confirmed in the same manner described in Example 2.

Claims

Claims.

1. A compound having the formula:

in which the bonds denoted --- represent either a single or a double bond; R is hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, amino, nitro, cyano, sulfo or sulfonamido; R1 is hydrogen or C1-C4alkyl; Z is C2-C6alkylene; and n is 0 or 1; as well as salts thereof..

2. A compound according to claim 1 in which R is hydrogen, methyl, methoxy, chlorine, amino, nitro, cyano, sulfo or sulfonamido; R1 is hydrogen or methyl; Z is ethylene; and n is 0 or 1.

3. A compound according to claim 1 having the formula:

in which R and R1 are as defined in claim 1; as well as salts thereof.

4. A compound according to claim 3 in which each of the bonds denoted ~ represents a single bond.

5. A compound according to claim 1 having the formula:

in which R and R1 are as defined in claim 1; as well as salts thereof.

6. A compound according to claim 5 in which each of the bonds denoted ~ represents a single bond.

7. 3,6,9,1 5-tetrakis(methyl)-3,6,9, 1 5-tetraazabicyclo[9.3.1 ]pentadecane or the tetrahydrochloride salt thereof.

8. A process for the production of a compound of formula (1) comprising a) firstly conducting a cyclisation reaction by reacting a compound having the formula:

in which R is as defined in claim 1 and Y is a leaving group; with a compound having the formula:

in which Z and n are as defined in claim 1 and X is hydrogen or an amine protecting group, to obtain a compound having the formula:

in which R, Z and n are as defined in claim and X has its previous significance; and then b) when R1 is a O1C4alkyl group, reacting the compound of formula (6) with an alkylating agent which is capable of converting each of the groups N-X into an N-C1-C4alkyl group, to produce a compound of formula (1).

9. A process according to claim 8 in which the leaving group Y in the reactant of formula (4) is a hydroxy, chloro-, a bromo-, a mesyloxy-, a tosyloxy- or a C1-C4alkoxycarbonyl group.

10. A process according to claim 8 in which each group X is an amine protecting group.

11. A process according to claim 9 in which each group X is a tosylate or trifluoroacetate group.

12. A process according to any of claims 8 to 11 in which, after the reaction of the compound of formula (4) with the compound of formula (5), the protecting groups X in formula (6) are removed prior to the reaction of the compound of formula (6) with the alkylating agent.

13. A process according to claim 12 in which the protecting group X is a tosylate group and this is removed by treating the protected compound of formula (6) with a mineral acid, with an alkali metal in liquid ammonia, with HBr and phenol or with lithiumaluminium hydride.

14. A process according to any of claims 8 to 13 in which the alkylation of the compound of formula (6) is conducted by reacting the compound of formula (6) with a Ct-C4alkyl halide, a C1-C4alkyl sulfate, a C1-C4 alkanol or, in the case of a methylation of a compound of formula (6), with ethylene oxide in the presence of formic acid (Leuckart-Wallach reaction).

15. A process according to any of claims 8 to 14 in which a compound of formula (1) in which one or more bonds denoted ~ are double bonds are converted into a partly or fully saturated counterpart.

16. A process according to claim 15 in which one or more of the double bonds are converted by hydrogenation.

17. A process according to claim 16 in which the hydrogenation is conducted in an atmosphere of hydrogen over a catalyst.

18. A process for the production of a compound of formula (1) in which one or more bonds denoted - - are single bonds, comprising reacting a compound having the formula:

in which R is as defined in claim 1 and Y is as defined in claim 8; with a compound having the formula (5) to obtain a compound having the formula:

in which Z and n are as defined in claim 1 and X is as defined in claim 8; and then b) when R1 is a Cl-C4alkyl group, removing the protecting groups X and reacting the compound of formula (6A) in which X is hydrogen with an alkylating agent which is capable of converting each of the groups N-H into an N-C1-C4alkyl group, to produce a compound of formula (1).

19. A complex of a compound of formula (1) with a metal selected from manganese in the oxidation numbers 11, III, IV and/or V; copper in the oxidation numbers I and/or II; cobalt in the oxidation number Il and/or Ill; zinc in the oxidation number II; iron in the oxidation numbers 11, Ill and IV; vanadium in the oxidation numbers Ill, IV and V; and titanium in the oxidation numbers lil and IV.

20. A fabric bleaching composition comprising a) a peroxy compound; and b) 0.005 to 0.05%, by weight of a metal complex according to claim 19.

21. A composition according to claim 20 in which the peroxy component a) is hydrogen peroxide, a compound which liberates hydrogen peroxide, a peroxyacid, a peroxyacid bleach precursor or a mixture thereof.

22 A composition according to claim 21 in which the compound which liberates hydrogen peroxide is an alkali metal peroxide, -perborate, -percarbonate, -perphosphate or -persulfate; peroxylau ric acid, peroxybenzoic acid, diperoxyisophthalic acid, 1,1 2-diperoxydodecanedioic acid or urea peroxide; or a mixture thereof.

23. A composition according to claim 21 in which the compound which liberates hydrogen peroxide is sodium percarbonate or sodium perborate.

24. A composition according to claim 21 in which the peroxyacid bleach precursor is a benz(4H)-1,3-oxazin-4-one derivative 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulfophenyl carbonate chloride (SPCC) N-octyl,N , N-dimethyl-N1 0-carbophenoxy decyl ammonium chloride (ODC) 3-(N,N,N-trimethyl ammonium) propyl sodium 4-sulfophenyl carboxylate N,N,N-trimethyl ammonium toluyloxy benzene sulfonate sodium-4-benzoyloxy benzene sulfonate (SBOBS) N,N,N',N'-tetraacetyl ethylene diamine (TAED) sodium-l -methyl-2-benzoyloxy benzene4-sulfonate sodium-4-methyl-3-benzoyloxy benzoate and sodium nonanoyloxybenzene sulfonate (NOBS).

25. A composition according to claim 21 in which the peroxyacid bleach precursor is a substituted 2-phenyl-benz(4H)-1 ,3-oxazin4-one, sodium nonanoyloxybenzene sulfonate or N,N,N',N'-tetraacetyl ethylene diamine.

26. A composition according to any of claims 20 to 25 in which the amount of the peroxy compound is 0.5 to 50% by weight, based on the total weight of the composition.

27. A composition according to claim 26 in which the amount of the peroxy compound is 2 to 20% by weight, based on the total weight of the composition.

28. A composition according to any of claims 20 to 27 which also comprises a surfactant and a detergent builder.

29. A composition according to claim 28 comprising 5-50% of an anionic surfactant and/or a nonionic surfactant.

30. A composition according to claim 29 comprising 5-25% of an anionic surfactant and/or a nonionic surfactant.

31. A composition according to claim 29 or 30 in which the anionic surfactant is a sulfate, sulfonate or carboxylate surfactant, or a mixture thereof.

32. A composition according to claim 29 or 30 in which the nonionic surfactant is a condensate of ethylene oxide with a C9-C15 primary alcohol having 3-8 moles of ethylene oxide per mole.

33. A composition according to claim 28 comprising 5-80% of a detergent builder.

34. A composition according to claim 33 comprising 10-60% of a detergent builder.

35. A composition according to claim 33 or 34 in which the detergent builder is an alkali metal phosphate; a carbonate or bicarbonate; a silicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; an aminoalkylene poly (alkylene phosphonate); or a mixture of these.

36. A composition according to any of claims 20 to 35 in which one or more agents capable of binding metal ions are present.

37. A composition according to claim 36 in which the agent capable of binding metal ions is an aminocarboxylate, an aminophosphonate, a polyamine or a mixture of these.

38. A composition according to claim 37 in which the agent capable of binding metal ions is diethylenetriaminepentamethylene phosphonic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid or a salt thereof, or diethylenetriamine.

39. A composition according to any of claims 36 to 38 in which the agent capable of binding metal ions is present in an amount of 0.1 to 10%, based on the weight of the fabric bleaching composition.

40. A composition according to any of claims 20 to 39 in which a protease, cellulase, lipase, oxidase or amylase enzyme is present.

41. A composition according to any of claims 20 to 40 which is in powder or granulate form.

42. A composition according to any of claims 20 to 40 which is in liquid form and contains 05% water.

43. A composition according to claim 42 which is in liquid form and contains 0-1% water.

44. A process for the production of a composition as claimed in claim 43 in which the components are mixed in dry form.

45. A process for the production of a composition as claimed in claim 41 in which a base powder is produced by spray-drying an aqueous slurry which contains all the components, apart from the components a) and b); then adding the components a) and b) by dry-blending them into the base powder.

46. A process for the production of a composition as claimed in claim 41 in which the component b) is added to an aqueous slurry containing the surfactant and builder components, followed by spray-drying the slurry prior to dry-blending component a) into the mixture.

47. A process for the production of a composition as claimed in claim 41 in which a nonionic surfactant component is not present, or is only partly present in an aqueous slurry containing anionic surfactant and builder components; component b) is incorporated into the nonionic surfactant component, which is then added to the spray-dried base powder; and finally component a) is dry-blended into the mixture.

48. A bleaching and/or cleaning process comprising contacting a fabric to be bleached and/or cleaned with an effective amount of a fabric bleaching composition according to any of claims 20 to 43.

49. A process according to claim 48 in which the amount of the fabric bleaching composition used is such that the amount of the complexing metal, compound b), provides from 0.001 to 100 ppm of the complexing metal in the bleaching and/or cleaning bath.

50. A process according to claim 49 in which the amount of the fabric bleaching composition used is such that the amount of the complexing metal, compound b), provides from 0.01 to 20 ppm of the complexing metal in the bleaching and/or cleaning bath.

51. A compound having the formula:

In which R is as defined in claim 1 and Y1 is a tosyloxy group.

52. 2,6-Bis(p-toluenesulfonyloxymethyl)piperidine.