Supported alkoxylated organotin reactant, preparation and use for heterogeneous-phase synthesis of tetrazoles

Abstract

A supported alkoxylated organotin reactant, to the process for preparing same, to the use of such a reactant as a catalyst for heterogeneous-phase organic synthesis, and also to a process for heterogeneous-phase synthesis of 5-substituted or 1,5-disubstituted tetrazoles using such a reactant.

Claims

1. A method of heterogeneous-phase synthesis of tetrazoles, comprising carrying out said synthesis with an alkoxylated organotin compound as a catalyst, said alkoxylated organotin compound having the following formula (I): ##STR00027## in which: Sup represents a macromolecular solid support; Z represents a linkage between the macromolecular solid support Sup and the tin atom, Z being selected from the groups of the following formulas (Z-1) to (Z-6): ##STR00028## in which: n and m, independently of one another, are integers in the range from 2 to 24, o and p, independently of one another, are integers in the range from 2 to 24, q is an integer in the range from 1 to 24, R.sup.2 and R.sup.3, independently of one another, represent a linear C.sub.1-C.sub.24 alkyl radical, a branched or cyclic C.sub.3-C.sub.24 alkyl radical, linear C.sub.2-C.sub.24 alkenyl, branched or cyclic C.sub.3-C.sub.24 alkenyl, aryl or aralkyl.

2. The method as claimed in claim 1, wherein the synthesis is that of 5-substituted or 1,5-disubstituted tetrazoles.

3. A method of heterogeneous-phase synthesis of 5-substituted tetrazoles of the following formulas (XIIIa) and (XIIIb): ##STR00029## in which: R.sup.6 represents a linear C.sub.1-C.sub.24 alkyl, branched or cyclic C.sub.3-C.sub.24 alkyl, aryl, aralkyl or heteroaryl radical, substituted or unsubstituted; R.sup.5 represents a hydrogen atom or a protective group, wherein said method comprises: 1) at least one first step consisting of reacting, in an organic solvent, under inert atmosphere and at a temperature greater than or equal to 110° C., a nitrile of the following formula (VIII):
R.sup.6—CN  (VIII) in which R.sup.6 has the same meaning as that stated above for the compounds of formula (XIIIa) and (XIIIb), with a tin compound of the following formula (X): ##STR00030## in which: Sup represents a macromolecular solid support, Z represents a linkage between the macromolecular solid support Sup and the tin atom, Z being selected from the groups of the following formulas (Z-1) to (Z-6): ##STR00031## in which: n and m, independently of one another, are integers in the range from 2 to 24, o and p, independently of one another, are integers in the range from 1 to 24, q is an integer in the range from 1 to 24, R.sup.1, R.sup.2 and R.sup.3, independently of one another, represent a linear C.sub.1-C.sub.24 alkyl radical, a branched or cyclic C.sub.3-C.sub.24 alkyl radical, linear C.sub.2-C.sub.24 alkenyl, branched or cyclic C.sub.3-C.sub.24 alkenyl, aryl or aralkyl, said reactant of formula (X) being generated in situ by reaction of the corresponding alkoxylated organotin reactant of formula (I): ##STR00032## and a trialkylsilyl compound of the following formula (IX): ##STR00033## in which the radicals R.sup.7, R.sup.8 and R.sup.9, which may be identical or different, represent a linear C.sub.1-C.sub.12 alkyl radical or a branched or cyclic C.sub.3-C.sub.12 alkyl radical, to obtain a tetrazole of the following formula (XIIa) or (XIIb): ##STR00034## in which R.sup.6 has the same meaning as in formula (VIII) above and R.sup.7, R.sup.8 and R.sup.9 have the same meaning as in formula (IX) above, after a reaction of exchange of the stannyl tetrazoles of the following formulas (XIa) or (XIb): ##STR00035## in which the radicals R.sup.1, R.sup.2 and R.sup.6 have the same meanings as those stated above for the compounds of formulas (X) and (VIII) respectively, with the compound of formula (IX), and 2) at least one second step consisting: i) either of hydrolyzing the compound of formulas (XIIa) or (XIIb) obtained above in step 1) in an acid medium, to obtain a compound of formulas (XIIIa) or (XIIIb) as defined above in which R.sup.5 is a hydrogen atom, or ii) to obtain a compound of formula (XIIIa) or (XIIIb) in which R.sup.5 is different from a hydrogen atom, of reacting said compound of formula (XIIa) or (XIIb) obtained above in step 1) with a halide of the following formula (XIV):
X′—R.sup.5  (XIV) in which X′ is a halogen atom selected from chlorine and bromine and iodine and R.sup.5 is a protective group, to obtain a compound of formulas (XIIIa) or (XIIIb) in which R.sup.5 is a protective group.

4. The method as claimed in claim 3, wherein the compound of formula (I) is used in an amount ranging from 0.05 mol % to 15 mol %.

5. The method as claimed in claim 3, wherein the first step is carried out at a temperature in the range from 130 to 140° C.

6. The method as claimed in claim 3, wherein the organic solvent is selected from dimethylformamide, dibutyl ether, diglyme, triglyme and xylenes.

7. The method as claimed in claim 3, wherein the duration of the first step varies from 30 min to 20 hours.

8. The method as claimed in claim 3, wherein during the second step, hydrolysis of the compounds of formulas (XIIa) or (XIIb) in an acid medium is carried out by adding an acid selected from hydrochloric acid, sulfuric acid and trifluoroacetic acid to the reaction mixture.

9. Method for heterogeneous-phase synthesis of a tetrazole, said method comprising the steps of synthesis employing an alkoxylated organotin compound of formula (I): ##STR00036## in which: Sup represents a macromolecular solid support; Z represents a linkage between the macromolecular solid support Sup and the tin atom, Z being selected from the groups of the following formulas (Z-1) to (Z-6): ##STR00037## in which: n and m, independently of one another, are integers in the range from 2 to 24, o and p, independently of one another, are integers in the range from 1 to 24, q is an integer in the range from 1 to 24, R.sup.1, R.sup.2 and R.sup.3, independently of one another, represent a linear C.sub.1-C.sub.24 alkyl radical, a branched or cyclic C.sub.3-C.sub.24 alkyl radical, linear C.sub.2-C.sub.24 alkenyl, branched or cyclic C.sub.3-C.sub.24 alkenyl, aryl or aralkyl, as a catalyst, wherein the tetrazole is selected from 5-phenyl-1H-tetrazole, 5-(4-methylphenyl)-1H-tetrazole, 5(4-methoxyphenyl)-1H-tetrazole, 5-(3-methoxyphenyl)-1H-tetrazole, 5-(4-nitrophenyl)-1H-tetrazole, 4-(1H-tetrazol-5-yl)benzoic acid, 5-(3-chlorophenyl)1H-tetrazole, 5-(4-chlorophenyl)-1H-tetrazole, 5-(4-hydroxyphenyl)-1H-tetrazole, 5-(3-trifluoromethylphenyl)-1H-tetrazole, 5-naphthyl-1H-tetrazole, 5-butyl-1H tetrazole, 5-octyl-1H-tetrazole, 5-(2-bromophenyl)-1H-tetrazole and 5-biphenyl-2yl-1H-tetrazole.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows the method of the present invention represented by reaction scheme 1;

(2) FIG. 2 shows reaction scheme 2; and

(3) FIG. 3 shows reaction scheme 3.

EXAMPLES

(4) Raw materials used in the examples given below: Chemicals: dimethyldichlorotin (CAS: 753-73-1), phenylmagnesium bromide (3.0 M in diethyl ether, diethyl ether, CAS: 100-58-3), lithium and aluminum hydride (CAS: 16853-85-3), diisopropylamine (CAS: 108-18-9), butyllithium (CAS: 109-72-8), tetrahydrofuran (CAS: 109-99-9), ethanol (CAS: 64-17-5), methanol (CAS: 67-56-1), hydrochloric acid (CAS: 7647-01-0), sodium chloride (7647-14-5), diiodine (CAS: 7553-56-2), sodium thiosulfate (CAS: 7772-98-7), diethyl ether (60-29-7), sodium sulfate (7487-88-9), sodium hydroxide (CAS: 1310-73-2), dimethyl carbonate (CAS: 616-38-6), these chemicals all marketed by the company Aldrich. Crosslinked polystyrene beads, sold under the trade name Amberlite® XE 305 by the company Rohm and Haas or under the trade name PL-PS/DVB MP Resin by the company Polymer Laboratories;

Examples 1 to 12: Synthesis of 1H-Tetrazoles Substituted in Position 5 with an Aromatic Group

(5) In this example, 1H-tetrazoles substituted in position 5 with a substituted or unsubstituted phenyl group were prepared according to the following general reaction scheme:

(6) ##STR00011##

(7) consisting of reacting a catalyst of formula (I) (catalytic amount) with a trialkylsilyl nitride of formula (IX) and the nitrile of formula (VIII) corresponding to the tetrazole of formula (XIII) that we wish to obtain, under inert atmosphere under reflux in the organic solvent (n-butyl ether (Bu.sub.2O)) for about 16 hours.

(8) In situ, the catalyst of formula (I) reacts with the trialkylsilyl nitride of formula (IX) to give the corresponding reactive species of formula (X) (supported tin nitride) which will react with the nitrile of formula (VIII) used according to a reaction of cycloaddition to give the corresponding intermediate of formula (XI). The latter, in the presence of a second molecule of trialkylsilyl nitride of formula (IX), makes it possible on the one hand to regenerate the reactive species of formula (X) and on the other hand to release the product of the reaction in the form of a silylated tetrazole of formula (XII). After an acid treatment and then a basic treatment, the expected final tetrazole of formula (XIII) is easily obtained by aqueous phase crystallization and filtration.

(9) The supported catalyst used in these examples is a catalyst of formula (I) with Z-1 for linkage in which n=4 and R.sup.1=R.sup.2=R.sup.3=CH.sub.3, and in which the insoluble solid support is polystyrene crosslinked with divinylbenzene.

(10) It was synthesized according to reaction schemes 2 and 3 presented in the appended FIGS. 2 and 3 respectively:

1) Preparation of dimethyldiphenyltin 2

(11) 80.5 mmol of dimethyldichlorotin 1 (Me.sub.2SnCl.sub.2) in 120 mL anhydrous tetrahydrofuran (THF) was added dropwise and under argon to 70 mL of a solution of phenylmagnesium bromide (PhMgBr) at 2.3 M (161 mmol, 2 equivalents) in ethanol. The reaction mixture was heated at 80° C. for 3 hours and the reaction was monitored by thin-layer chromatography (TLC) to detect complete disappearance of the starting reactants. The reaction mixture was then hydrolyzed with 1M hydrochloric acid (HCl) (80 mL) and the aqueous phase was extracted with diethyl ether (3×150 mL). The organic phases were washed with NaCl (400 mL), dried over MgSO.sub.4 and concentrated under vacuum. The residue was purified by silica gel chromatography and the expected compound 2 was obtained in the form of a colorless oil at a yield of 94%.

(12) .sup.1H NMR (300 MHz, CDCl.sub.3) δ=0.51 (6H, s, .sup.2J.sup.117/119.sub.Sn-H=56.6/58.8); 7.3-7.6 (10H, m) ppm.

(13) .sup.13C NMR (300 MHz, CDCl.sub.3) δ=−9.7 (.sup.1J.sub.Sn-C=363); 128.6; 128.9; 136.6 (.sup.2J.sub.Sn-C=36); 141 ppm.

(14) .sup.119Sn NMR (300 MHz, CDCl.sub.3) δ=−58.6 ppm.

2) Preparation of dimethylphenyltin iodide 3

(15) A solution of iodine (3.19 g, 12.6 mmol, 1.02 eq.) in methanol (0.3M, 21 mL), was added in darkness, under argon and at room temperature, to a solution of 12.4 mmol of dimethyldiphenyltin 2 in methanol (0.3 M, 21 mL). The reaction mixture was stirred for 18 hours at room temperature and partially concentrated under vacuum. The resultant mixture was then diluted with a saturated aqueous solution of Na.sub.2S.sub.2O.sub.3 and the aqueous phase was extracted with diethyl ether (3×200 mL). The organic phases were then washed with NaCl (300 mL), dried over MgSO.sub.4 and concentrated under vacuum. The iodobenzene remaining in the resultant residue was distilled (boiling point at 0.68 mbar: 21.9° C.) and the expected compound 3 was obtained without any additional purification in the form of a yellow oil at a yield of 44%.

(16) .sup.1H NMR (300 MHz, CDCl.sub.3) δ=1.05 (6H, s, .sup.2J.sup.117/119.sub.SnH=55.4/58), 7.34-7.5 (3H, m), 7.6 (2H, d, .sup.3J=7.6) ppm.

(17) .sup.119Sn NMR (300 MHz, CDCl.sub.3) δ=−17 ppm.

3) Preparation of dimethylphenyltin hydride 4 (Me2SnPhH)

(18) 17.6 mmol of compound 3 obtained above in the preceding step was added dropwise, at 0° C. under argon, to a suspension of 44.1 mmol of lithium aluminum hydride (LiAlH.sub.4) (2.5 eq.) in 75 mL of ethanol. The reaction mixture was stirred for 2 hours at 0° C. in darkness and then hydrolyzed with 15 mL of water. The aqueous phase was extracted with diethyl ether (3×50 mL) and the organic phases were washed with a saturated solution of NaCl (40 mL), dried over MgSO.sub.4 and concentrated under vacuum. Compound 4 was obtained in the form of a colorless oil at a yield of 76%.

(19) .sup.1H NMR (300 MHz, C.sub.6D.sub.6) δ=0.39 (6H, s, .sup.2J.sub.Sn-H=56), 5.66 (1H, s, .sup.1J.sup.117/119.sub.SnH=11725/1810, SnH), 7.39 (3H, m), 7.62 (2H, d, .sup.3J=7.3) ppm.

(20) .sup.13C NMR (300 MHz, C.sub.6D.sub.6) δ=−11 (.sup.2J.sub.Sn-C=351); 129.3; 137.3 (.sup.2J.sub.Sn-C=38.5), 137.8; 140 ppm.

(21) .sup.119Sn NMR (300 MHz, C.sub.6D.sub.6) δ=−121 ppm.

4) Preparation of poly[4-(dimethylphenylstannyl)butyl]styrene 7

(22) 27.7 mmol of compound 4 obtained above in the preceding step was added slowly, at 0° C. and under argon, to a solution of 30.5 mmol of lithium diisopropylamide (LDA) in anhydrous THF. The resultant mixture 5 was stirred for 1 hour at 0° C., then 7.4 g of polymer 6 in the dry state was added. The mixture was left to return to room temperature, then it was stirred for 18 hours. The resulting polymer was washed successively with 60 mL of a mixture of THF and water (1:1; v:v), 6×60 mL of THF, 4×60 mL of absolute ethanol before being dried under vacuum (0.5 mbar) at 60° C. for 5 hours. Polymer 7 was obtained in the form of a white resin (9.5 g).

(23) .sup.119Sn NMR MAS δ=−33 ppm.

5) Preparation of poly[4-(iododimethylstannyl)butyl]styrene 8

(24) 10.0 g of polymer 7 obtained above in the preceding step was added to a solution of iodine (3.81 g, 15.0 mmol) in 50 mL of absolute ethanol. The resultant mixture was stirred at 60° C. for 18 hours in darkness. The polymer was then washed successively with 60 mL of a mixture of THF/saturated aqueous solution of Na.sub.2S.sub.2O.sub.3 (1:1; v:v), 6×60 mL of THF, 4×60 mL of absolute ethanol before being dried under vacuum (0.5 mbar) at 60° C. for 5 hours. Polymer 8 was obtained in the form of a pale yellow resin.

(25) .sup.119Sn NMR MAS δ=+49 ppm.

6) Preparation of Compound 9 (Reactant of Formula (I))

(26) A 4 M solution of soda (2.36 mL, 9.5 mmol, 4 eq.) in an ethanol/water mixture (1:1; v:v) was added to a solution of 2 g (2.36 mmol) of polymer 8 obtained above in the preceding step in 10 mL of absolute ethanol. The reaction mixture was stirred at room temperature for 36 hours. The insoluble matter was washed successively with 4×30 mL of water, then 7×30 mL of ethanol before being dried under vacuum (0.5 mbar) at 60° C. for 5 hours. The resulting polymer was then put in a round-bottomed flask, to which 2 mL of dimethyl carbonate was then added. The reaction mixture was stirred for 18 hours at 90° C. After filtration, the expected reactant of formula (I) (compound 9) was washed with 70 mL of THF, and then with 70 mL of ethanol before being dried under vacuum (0.5 mbar) at 60° C. for 5 hours.

(27) .sup.119Sn NMR MAS δ=+110 ppm.

(28) The synthesis of the various tetrazoles was then carried out as follows:

(29) A two-necked flask equipped with a condenser was charged with the nitrile of formula (VIII) (1.0 mmol) corresponding to the expected tetrazole of formula (XIII), the reactant of formula (I) as prepared as indicated above (100 mg, 0.1 mmol) as well as (CH.sub.3).sub.3SiN.sub.3 (trimethylsilyl nitride (IX)) (0.2 mL, 1.5 mmol) in 2.5 mL of Bu.sub.2O under inert atmosphere. The reaction mixture was heated under reflux under inert atmosphere for 16 hours and was then diluted in petroleum ether (10 mL) and treated with a 1M solution of NaOH (10 mL). The residual polymer was then filtered and washed successively with 1M NaOH (5 mL), THF (5 mL) and then petroleum ether (5 mL). The filtrate was recovered and the aqueous phase was separated and then acidified with HCl to pH 1 at 0° C. in order to crystallize the expected tetrazole of formula (XIII). The crystals were then filtered and dried under vacuum.

(30) Table 1 below presents the various tetrazoles of formula (I) synthesized, as well as the yield of the reaction:

(31) TABLE-US-00001 TABLE 1 Yield of product Example Tetrazole of formula (VII) isolated (%)  1   5-phenyl-1H-tetrazole 95  2   5-(4-methylphenyl)-1H-tetrazole 91  3   5-(4-methoxyphenyl)-1H-tetrazole 89  4   5-(3-methoxyphenyl)-1H-tetrazole 78  5   5-(4-nitrophenyl)-1H-tetrazole 90  6   4-(1H-tetrazol-5-yl)benzoic acid 81  7   5-(3-chlorophenyl)-1H-tetrazole 83  8   5-(4-chlorophenyl)-1H-tetrazole 86  9 0   5-(4-hydroxyphenyl)-1H-tetrazole 82 10   5-(3-trifluoromethylphenyl)-1H-tetrazole 87 11   5-(2-bromophenyl)-1H-tetrazole 72 12   5-biphenyl-2-yl-1H-tetrazole 63

Characterization of the Compounds

5-phenyl-1H-tetrazole (Ex. 1)

(32) White solid, Melting point: 210-211° C.;

(33) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=8.02-7.98 (m, 2H), 7.58-7.54 (m, 3H), ppm;

(34) .sup.13C NMR (75 MHz, d.sub.6-DMSO): δ=155.8; 131.6; 129.8; 127.3; 124.7 ppm

5-(4-methylphenyl)-1H-tetrazole (Ex. 2)

(35) White solid; Melting point.=246-248° C.

(36) IR (KBr)=3100-2200 (Br), 1614, 1569, 1504, 1163, 1055, 1028, 823, 744 cm.sup.−1

(37) .sup.1H NMR (300 MHz, d.sub.6-DMSO): 7.92 ppm (d, J=8.0 Hz, 2H); 7.41 (d, J=8.0 Hz, 2H); 2.39 (s, 3H) ppm.

(38) .sup.13C NMR (100 MHz, d.sub.6-DMSO): 155.0; 141.0; 129.8; 126.8; 121.2; 21.0 ppm.

5-(4-methoxyphenyl)-1H-tetrazole (Ex. 3)

(39) White solid; Melting point: 231-233° C.

(40) IR (KBr): 3200-2300 (Br), 1298, 1184, 1035, 750 cm.sup.−1

(41) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=7.96 (d, J=9.0 Hz, 2H), 7.15 (d, J=9.0 Hz, 2H), 3.85 (s, 3H) ppm;

(42) .sup.13C NMR (100 MHz, d.sub.6-DMSO): 161.3; 154.6; 128.5; 116.2; 114.7; 55.4 ppm

5-(3-methoxyphenyl)-1H-tetrazole (Ex. 4)

(43) White solid

(44) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=7.64-7.50 (m, 2H), 7.53 (t, J=7.5 Hz, 1H), 7.17 (ddd, J=1.5 Hz, J=3 Hz, J=9 Hz, 1H)

(45) .sup.1H NMR (75 MHz, d.sub.6-DMSO): δ=159.7; 130.7; 125.3; 119.1; 117.01; 112.1; 55.4 ppm.

5-(4-nitrophenyl)-1H-tetrazole (Ex. 5)

(46) White solid, Melting point=218-220° C.

(47) IR (KBr): 3500-2400 (Br), 1604, 1531, 1488, 1338, 1311, 993, 867, 854 cm.sup.−1;

(48) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=8.45 ppm (d, J=9.0 Hz, 2H); 8.30 (d, J=9.0 Hz, 2H);

(49) .sup.13C NMR (75 MHz, d.sub.6-DMSO): δ=155.6; 148.8; 130.7; 128.3; 124.6 ppm.

4-(1H-tetrazol-5-yl)benzoic acid (Ex. 6)

(50) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=13.1 (s broad, 1H); 8.1 ppm (m, 4H); 3.3 (s broad, 1H)

(51) .sup.13C NMR (75 MHz, d.sub.6-DMSO): δ=166.6; 155.3; 132.9; 130.2; 128.2; 127.1

5-(3-chlorophenyl)-1H-tetrazole (Ex. 7)

(52) .sup.1H NMR (300 MHz, d.sub.6-DMSO): 8.07-8.02 (m, 1H); 7.66-7.64 (m, 1H), 7.7-7.6 (m, 2H)

(53) .sup.13C NMR (75 MHz, d.sub.6-DMSO): 154.8; 133.9; 131.4; 130.9; 126.5; 126.4; 125.6

5-(4-chlorophenyl)-1H-tetrazole (Ex. 8)

(54) White solid; Melting point: 252-254° C.;

(55) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=8.07 (d, J=8.8 Hz, 2H); 7.70 (d, J=8.8 Hz, 2H);

(56) .sup.13C NMR (75 MHz, d.sub.6-DMSO): δ=155.3; 136.3; 129.9; 129.0; 123.6.

5-(4-hydroxyphenyl)-1H-tetrazole (Ex. 9)

(57) White solid, Melting point: 236-238° C.;

(58) IR (KBr): 3600-3200 (Br), 1616, 1515, 1471, 1282, 1247, 1080, 995, 842 cm.sup.−1;

(59) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=10.18 (Br s, 1H); 7.86 (d, J=8.5 Hz, 2H); 6.95 (d, J=8.5 Hz, 2H) ppm

(60) .sup.13C NMR (75 MHz, d.sub.6-DMSO): δ=160.0; 154.8; 128.7; 116.2; 114.6 ppm.

5-(4-trifluoromethylphenyl)-1H-tetrazole (Ex 10)

(61) .sup.1H NMR (300 MHz, d.sub.6-DMSO): 8.35 (2H, m), 7.9 (1H, m), 7.85 (1H, m)

(62) .sup.13C NMR (75 MHz, d.sub.6-DMSO): 152.9; 128.5 (q, J=1.2 Hz); 128.5; 127.8 (q, J=32 Hz); 125.4 (q, J=3.8 Hz); 123.0; 121.3 (q, J=277 Hz); 121.0 (q, J=4.0 Hz).

5-(2-bromophenyl)-1H-tetrazole (Ex. 11)

(63) White solid, melting point: 179-180° C.;

(64) .sup.1H NMR (300 MHz, d.sup.6-DMSO): 7.5-7.6 (m, 2H); 7.7 (dd, J=7.5; J=2, 1H);

(65) .sup.13C NMR (100 MHz, d.sup.6-DMSO): 121.6; 126.3; 128.1; 131.9; 132.5; 133.4; 154.5.

5-biphenyl-2-yl-1H-tetrazole (Ex. 12)

(66) White solid, melting point: 142-143° C.;

(67) .sup.1H NMR (300 MHz, d.sup.6-DMSO): 7.1 (m, 2H); 7.31 (m, 3H); 7.58 (m, 2H); 7.69 (m, 2H);

(68) .sup.13C NMR (100 MHz, d.sup.6-DMSO): 123.4; 127.4; 127.5; 127.7; 128.2; 128.7; 130.5 (2C), 131.0; 139.2; 141.5.

Example 13: Preparation of 5-naphthyl-1H-tetrazole

(69) ##STR00024##

(70) In this example, 5-naphthyl-1H-tetrazole was prepared starting from the corresponding nitrile of formula (VIII) according to the protocol used above for the compounds in examples 1 to 12. 5-Naphthyl-1H-tetrazole was obtained in the form of a white solid at a yield of 85%.

(71) Melting point: 205-206° C.;

(72) IR (KBr): 3200-2200 (Br), 3060, 1566, 1417, 1249, 1085, 1020, 825, 759 cm.sup.−1;

(73) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=8.57-8.54 (m, 1H), 8.21-8.18 (m, 1H); 8.11-8.08 (m, 1H); 8.00-7.98 (m, 1H); 7.74-7.63 (m, 3H);

(74) .sup.13C NMR (75 MHz, d.sub.6-DMSO): δ=133.3; 131.4; 129.9; 128.6; 128.3; 127.6; 126.7; 125.3; 125.1; 121.5; 114.4.

Example 14: Preparation of 5-butyl-1H-tetrazole

(75) ##STR00025##

(76) In this example, 5-butyl-1H-tetrazole was prepared starting from the corresponding nitrile of formula (VIII) according to the protocol used above for the compounds in examples 1 to 12. 5-Butyl-1H-tetrazole was obtained in the form of a white solid at a yield of 50%.

(77) .sup.1H NMR (300 MHz, d.sub.6-DMSO): δ=2.87 (t, J=7.5 Hz, 2H); 1.68 (m, 2H); 1.33 (m, 2H); 0.9 (t, J=7.5 Hz, 3H).

(78) .sup.13C NMR (75 MHz, d.sub.6-DMSO): δ=155.9; 29.0; 22.3; 21.4; 13.4.

Example 15: Preparation of 5-octyl-1H-tetrazole

(79) ##STR00026##

(80) In this example, 5-octyl-1H-tetrazole was prepared starting from the corresponding nitrile of formula (VIII) according to the protocol used above for the compounds in examples 1 to 12. 5-Octyl-1H-tetrazole was obtained in the form of a pale yellow solid at a yield of 42%.

(81) .sup.1H NMR (300 MHz, d.sub.6-DMSO): 2.85; (t, J=7.5 Hz, 2H); 1.68 (m, 2H); 1.26 (m, 10H); 0.85 (m, 3H).

(82) .sup.13C NMR (75 MHz, d.sub.6-DMSO): 155.9; 31.1; 28.4; 28.3; 27.0; 22.6; 22.0; 13.9.