nickel(2+);diacetate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The nickel hydroxide (line 50) is transferred to the nickel acetate production system tank (n) where it is dissolved in acetic acid (line 49, 1:1 ratio to dry nickel solids) and 100% wt acetic acid (line 51) are added to produce the final product nickel acetate tetrahydrate (line 52). The reaction is shown below: 2H2O+Ni(OH)2+2CH3COOH→Ni(CH3COO)2.4H2O

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Add nickel (II) acetate tetrahydrate (24.8 gms. 10 mmol) to a stirred solution of kanamycin A (9.7 gms., 20 mmol) in dimethylsulfoxide (400 ml.). Stir at room temperature for 30 minutes, then to the resulting nickel (II) salt complex thereby formed add N-benzyloxycarbonyloxyphthalimide (13.0-15.6 gms., 44-52.6 mmol) in dimethylsulfoxide (70 ml.) over a 10 minute period. Stir at room temperature for one hour, then pour the reaction mixture into ether (2500 ml.) and shake one minute. Allow the oil to settle and decant the supernatant dimethylsulfoxide ether. Repeat this procedure two more times using 1500 ml. and 1000 ml., respectively, of ether. Dissolve the resultant gummy residue in methanol (1000 ml.) and concentrated ammonium hydroxide (50 ml.). Bubble hydrogen sulfide through the solution and separate the resultant precipitate of nickel (II) sulfide through a pad of Celite and wash the residue with methanol. Stir the combined filtrate and methanol wash with Amberlite IRA-401S (OH⃝) ion exchange resin (300 gms.), filter off the resin and evaporate the filtrate in vacuo. Triturate the resultant gummy residue with a 50:50 mixture of acetonitrile:ether and filter the resultant white solid to obtain 3,6'-di-N-benzyloxycarbonylkanamycin A; yield 12.5 gms. (83.5% theory); [α]D26 +78° (c, 4.84 in 50% aqueous methanol). Analysis Calculated for: C34H48O15N4.H2O; C, 56.2; H, 6.75; N, 6.94%. Found: C, 51.02; H, 6.26; N, 6.85%. E. Treat each of the following aminoglycosides with a mixture of cupric acetate hydrate and nickel (II) acetate tetrahydrate or with cobalt (II) acetate tetrahydrate or with cadmium (II) acetate dihydrate according to the procedures of Examples 11A through 11D, respectively.

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 23.8 g (0.1 mol) of nickel acetate was added to 500 ml of ethyl cellosolve and stirred. The mixture was heated to 50° C., and 30.2 g (0.2 mol) of N-methyl-anthranilic acid was gradually added. The mixture was subjected to reaction for 2 hours at about 130° C. under refluxing and then dispersed in 2 liters of water. After 1 hour, the dispersion was subjected to filtration and the precipitate was washed with water until neutrality. The precipitate was then dried at 90° C. to obtain about 29 g of pale blue powder. The mixture was subjected to reaction for 2 hours at about 130° C. under refluxing the dispersion was subjected to filtration the precipitate was washed with water until neutrality The precipitate was then dried at 90° C.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The nickel acetate is added to the octaethylporphyrin solution; the mixture which results is refluxed for about 24 hours until the electronic spectrum of the reaction mixture indicates that chelation is complete. The reaction mixture is then concentrated to 7 mL and allowed to cool to room temperature of about 22°. Product which precipitates is recovered by filtration, dissolved in a mixed solvent composed of 5 mL dichloromethane and 2 mL methanol, and recrystallized, yielding Ni octaethylporphyrin. the mixture which results is refluxed for about 24 hours until the electronic spectrum of the reaction mixture The reaction mixture is then concentrated to 7 mL Product which precipitates is recovered by filtration dissolved in a mixed solvent recrystallized

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-(Tetrahydropyran-2-yloxy)-4-decyne (15) (0.5 g, 2.1 mmol), prepared according to Example 13, was hydrogenated in ethanol (20 ml) over P2-Ni, formed from nickel acetate (75 mg) deactivated with ethylenediamine (0.2 ml) for 4 hr. After chromatography on silica gel, the product (16) (0.43 g) was obtained in 85% yield. GC (Rt): starting material 15, 22.18 min, 0.4%; desired product 16 21.59 min, 97.9%; the 4E isomer of 16, 21.75 min, 1.7%. 1H NMR (200 MHz ) δ: 5.37 (m, 2H, CH=CH-4, 5), 4.58 (m, 1H, CH-2'), 3.60 (m, 4H, CH2 -1, 6'); 2.12 (M, 2H, CH2 -6); 2.04 (m, 2H, CH2 -3); 1.16 (tt, 2H, J=6.8, 6.8, 7.0, 7.0 Hz, CH2 -2), 1.4-1.9 (m, 6H, CH2 -3', 4', 5'), 1.29 (m, 6H, CH2 -7, 8, 9); 0.88 (t, 3H, J=7.0 Hz, CH3). IR (CCl4, cm-1) 3007, 1653, 1201, 1138, 1120 1034. MS [FAB, m/z(%)] 239 (M+ -1), 85 (100).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The nickel acetate is added to the octaethylporphyrin solution; the mixture which results is refluxed for about 24 hours until the electronic spectrum of the reaction mixture indicates that chelation is complete. The reaction mixture is then concentrated to 7 mL and allowed to cool to room temperature of about 22°. Product which precipitates is recovered by filtration, dissolved in a mixed solvent composed of 5 mL dichloromethane and 2 mL methanol, and recrystallized, yielding Ni octaethylporphyrin. the mixture which results is refluxed for about 24 hours until the electronic spectrum of the reaction mixture The reaction mixture is then concentrated to 7 mL Product which precipitates is recovered by filtration dissolved in a mixed solvent recrystallized

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-(Tetrahydropyran-2-yloxy)-4-decyne (15) (0.5 g, 2.1 mmol), prepared according to Example 13, was hydrogenated in ethanol (20 ml) over P2-Ni, formed from nickel acetate (75 mg) deactivated with ethylenediamine (0.2 ml) for 4 hr. After chromatography on silica gel, the product (16) (0.43 g) was obtained in 85% yield. GC (Rt): starting material 15, 22.18 min, 0.4%; desired product 16 21.59 min, 97.9%; the 4E isomer of 16, 21.75 min, 1.7%. 1H NMR (200 MHz ) δ: 5.37 (m, 2H, CH=CH-4, 5), 4.58 (m, 1H, CH-2'), 3.60 (m, 4H, CH2 -1, 6'); 2.12 (M, 2H, CH2 -6); 2.04 (m, 2H, CH2 -3); 1.16 (tt, 2H, J=6.8, 6.8, 7.0, 7.0 Hz, CH2 -2), 1.4-1.9 (m, 6H, CH2 -3', 4', 5'), 1.29 (m, 6H, CH2 -7, 8, 9); 0.88 (t, 3H, J=7.0 Hz, CH3). IR (CCl4, cm-1) 3007, 1653, 1201, 1138, 1120 1034. MS [FAB, m/z(%)] 239 (M+ -1), 85 (100).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Add nickel (II) acetate tetrahydrate (24.8 gms., 10 mmol) to a stirred solution of kanamycin A (9.7 gms., 20 mmol) in dimethylsulfoxide (400 ml.). Stir at room temperature for 30 minutes, then to the resulting nickel (II) salt complex thereby formed add N-benzyloxycarbonyloxyphthalimide (13.0-15.6 gms., 44-52.6 mmol) in dimethylsulfoxide (70 ml.) over a 10 minute period. Stir at room temperature for one hour, then pour the reaction mixture into ether (2500 ml.) and shake one minute. Allow the oil to settle and decant the supernatant dimethylsulfoxide ether. Repeat this procedure two more times using 1500 ml. and 1000 ml., respectively, of ether. Dissolve the resultant gummy residue in methanol (1000 ml.) and concentrated ammonium hydroxide (50 ml.). Bubble hydrogen sulfide through the solution and separate the resultant precipitate of nickel (II) sulfide through a pad of Celite and wash the residue with methanol. Stir the combined filtrate and methanol wash with Amberlite IRA-401S (OH⃝) ion exchange resin (300 gms.), filter off the resin and evaporate the filtrate in vacuo. Triturate the resultant gummy residue with a 50:50 mixture of acetonitrile:ether and filter the resultant white solid to obtain 3,6'-di-N-benzyloxycarbonylkanamycin A; yield 12.5 gms. (83.5% theory); [α]D26 + 78° (c, 4.84 in 50% aqueous methanol). Analysis Calculated for: C34H48O15N4.H 2 O; C, 56.2; H, 6.75; N, 6.94%. Found: C, 51.02; H, 6.26; N, 6.85%.

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Nickel (II) oleate is prepared by mixing 2.48 g of nickel acetate and 5.64 g of oleic acid with stirring for about one hour. The mixture is heated to about 150° C. to evaporate the acetic acid and form a transparent liquid of nickel (II) oleate. Nickel (II) oleate can also be prepared by mixing 2.57 g of nickel acetylacetonate and 5.64 g of oleic acid with stirring. The mixture is then heated to evaporate the acetylacetonate and form a transparent liquid of nickel (II) oleate. Nickel (II) oleate is prepared to evaporate the acetic acid

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1 mole of nickel (II) acetate and 6 moles of imidazole were heated to 100° C. in a stirred reactor with thorough mixing at 200 to 400 rpm for 5 to 10 minutes to obtain a complex of hexa (imidazole) nickel (II) acetate with a 97.5% yield, based on the metal salt. with thorough mixing at 200 to 400 rpm for 5 to 10 minutes

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The nickel acetate is added to the octaethylporphyrin solution; the mixture which results is refluxed for about 24 hours until the electronic spectrum of the reaction mixture indicates that chelation is complete. The reaction mixture is then concentrated to 7 mL and allowed to cool to room temperature of about 22°. Product which precipitates is recovered by filtration, dissolved in a mixed solvent composed of 5 mL dichloromethane and 2 mL methanol, and recrystallized, yielding Ni octaethylporphyrin. the mixture which results is refluxed for about 24 hours until the electronic spectrum of the reaction mixture The reaction mixture is then concentrated to 7 mL Product which precipitates is recovered by filtration dissolved in a mixed solvent recrystallized

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-(Tetrahydropyran-2-yloxy)-4-decyne (15) (0.5 g, 2.1 mmol), prepared according to Example 13, was hydrogenated in ethanol (20 ml) over P2-Ni, formed from nickel acetate (75 mg) deactivated with ethylenediamine (0.2 ml) for 4 hr. After chromatography on silica gel, the product (16) (0.43 g) was obtained in 85% yield. GC (Rt): starting material 15, 22.18 min, 0.4%; desired product 16 21.59 min, 97.9%; the 4E isomer of 16, 21.75 min, 1.7%. 1H NMR (200 MHz ) δ: 5.37 (m, 2H, CH=CH-4, 5), 4.58 (m, 1H, CH-2'), 3.60 (m, 4H, CH2 -1, 6'); 2.12 (M, 2H, CH2 -6); 2.04 (m, 2H, CH2 -3); 1.16 (tt, 2H, J=6.8, 6.8, 7.0, 7.0 Hz, CH2 -2), 1.4-1.9 (m, 6H, CH2 -3', 4', 5'), 1.29 (m, 6H, CH2 -7, 8, 9); 0.88 (t, 3H, J=7.0 Hz, CH3). IR (CCl4, cm-1) 3007, 1653, 1201, 1138, 1120 1034. MS [FAB, m/z(%)] 239 (M+ -1), 85 (100).