Name: 10049-21-5|Sodium Phosphate Monobasic hydrate|99%
Brand: Ambeed
SKU: A809930
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1
[ 10049-21-5 ]
3α-acetylthioandrostane-6,17-dione [ No CAS ]
3α-mercapto-6-methyleneandrostane-17-one [ No CAS ]
3α-acetylthio-6-methyleneandrostane-17-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35%; 35%		To a stirred solution of 3alpha-acetylthioandrostane-6,17-dione (Prepn. 78, 600 mg) in THF (8 niL) cooled at -50 C, a solution of ylide prepared from methyltriphenylphosphonium bromide (1.47 g) in THF dry (8 mL) at -50 C and potassium tert-butoxide (484 mg ), was added. After 2 h the temperature was raised to room temperature. The mixture was quenched by addition of 5% NaH2PU4 aqueous solution and extracted with EtOAc (2 x 60 mL). The combined organic extracts were washed with 5% NaH2PO4 aqueous solution, brine, dried over Na2SO4, and evaporated to dryness. The residue was purified by flash chromatography (n-hexane/EtOAc 9/1) to give 3alpha-acetylthio-6- methyleneandrostan-17-one (210 mg, 35 % yield) and 3alpha-mercapto-6- methyleneandrostan-17-one (208 mg, 35 % yield). 1H-NMR (300 MHz, DMSO-dbeta, ppm from TMS): 3alpha-acetylthio-6-methyleneandrostane-17- one: delta 4.73 (IH, m), 4.39 (IH, m), 3.96 (IH, m), 2.44-0.84 (2OH, m), 2.29(3H, s), 0.75 (3H, s), 0.66 (3H, s); 3alpha-mercapto-6-methyleneandrostane- 17-one: delta 4.73 (IH, m), 4.38 (IH, m), 3.57 (IH, m), 2.52 (IH, d), 2.45- 0.95 (2OH, m), 0.76 (3H, s), 0.63 (3H, s).

Reference： [1]Patent: WO2007/118832,2007,A2 .Location in patent: Page/Page column 171-172

2
[ 10049-21-5 ]
[ 130551-92-7 ]
[ 98-59-9 ]
1,3-oxazol-2-ylmethyl 4-methylbenzenesulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
28%	With n-butyllithium; In tetrahydrofuran; hexane;	C. 1,3-Oxazol-2-ylmethyl 4-methylbenzenesulfonate To a solution of <strong>[130551-92-7]1,3-<strong>[130551-92-7]oxazol-2-ylmethanol</strong></strong> (0.77 g, 7.77 mmol) in THF (15 ml) was added dropwise 2.5 M solution of n-BuLi in hexane (4.7 ml, 11.7 mmol) at -78 C. under nitrogen atmosphere and the reaction mixture was stirred for 30 min at the same temperature. Then to the mixture was added dropwise a solution of p-toluenesulfonyl chloride (1.48 g, 7.77 mmol) in TBF (5 ml)-78 C., and the mixture was stirred for 1 h at the same temperature. The mixture was poured into saturated aqueous solution of sodium dihydrogenphosphate and the whole was extracted with EtOAc (10 ml*2). The combined organic layers were washed with brine (10 ml), dried over MgSO4, and concentrated in vacuo. The residue was purified by column chromatography (SiO2, EtOAc/hexane=1/3) to give 550 mg of the titled compound (28%). 1H-NMR (CDCl3) delta 7.81 (d, J=8.1 Hz, 2H), 7.63 (d, J=0.8 Hz, 1H), 7.35 (d, J=8.1 Hz, 2H), 7.08 (d, J=0.8 Hz, 1H), 5.12 (s, 2H), 2.45 (s, 3H).

Reference： [1]Patent: US2002/42421,2002,A1

3
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 513-35-9 ]
[ 18450-27-6 ]
[ 441800-93-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	In water; tert-butyl alcohol;	EXAMPLE 105B 2-(ethoxycarbonyl)-1H-indole-3-carboxylic Acid A solution of Example 105A (500 mg, 2.3 mmol) in tert-butanol (48 mL) and 2-methyl-2-butene (11.5 mL) at room temperature was treated with a solution of sodium chlorite (1.9 g, 21.1 mmol) and sodium dihydrogenphosphate (1.9 g, 15.9 mmol) in water (19 mL), stirred for 18 hours, and concentrated. The concentrate was diluted with water and extracted twice with hexanes. The aqueous phase was adjusted to pH 3 with 1N HCl and extracted three times with ethyl acetate. The combined ethyl acetate extracts were dried (Na2SO4), filtered, and concentrated to provide the desired product (530 mg, 99%). MS (ESI) m/e 234 (M+H)+, 251 (M+NH4)+, 256 (M+Na)+, 232 (M-H)-.

Reference： [1]Patent: US2002/91148,2002,A1

4
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 146137-79-3 ]
[ 146328-87-2 ]

Yield	Reaction Conditions	Operation in experiment
	With dihydrogen peroxide; sodium sulfite; In water; acetonitrile;	PREPARATION 88(2) To a solution of <strong>[146137-79-3]5-cyano-2-fluorobenzaldehyde</strong> (145 mg) in acetonitrile (2 mL) were added a sodium dihydrogenphosphate aqueous solution (23 mg in 1 mL water) and 30percent hydrogen peroxide (0.09 mL). To the resulting mixture was added dropwise a sodium chlorite aqueous solution (126mg in 1 mL water) for an hour at 0° C. The mixture was stirred for an hour at ambient temperature, then a small amount of sodium sulfite was added. The mixture was diluted with ethyl acetate and washed successively with 1N-hydrochloric acid and brine. The organic layer was dried over sodium sulfate and evaporated in vacuo. The residue was triturated with diisopropyl ether to give 5-cyano-2-fluorobenzoic acid (137 mg) as a solid substance. NMR (DMSO-d6, delta): 7.29 (1H, t, J=9 Hz), 7.83 (1H, m), 8.32 (1H, dd, J=2, 7 Hz); Mass m/z: 164 (M+-1).

Reference： [1]Patent: US6384080,2002,B1

5
[ 10049-21-5 ]
[ 61273-84-5 ]
[ 295319-07-2 ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium cyanoborohydride; In methanol; acetone;	C. 6-Methoxy-2-(methylethyl)-1-[4-(phenylmethoxy)benzyl]-1,2,3,4-tetrahydroisoquinoline To a mixture of 6-methoxy-1-[4-(phenylmethoxy)benzyl]-1,2,3,4-tetrahydroisoquinoline (0.36 g, 1 mmol), acetone (3 mL), and <strong>[10049-21-5]sodium dihydrogenphosphate</strong> (0.4 g) in methanol (5 mL) was added sodium cyanoborohydride (0.5 g, 8 mmol). After 48 hours, the reaction was quenched with water and extracted with CH2Cl2. The organic layer was dried over MgSO4, filtered, and concentrated to give the title compound (0.321 g, 80% yield): ES-MS (m/z) 402 [M+H]+.

Reference： [1]Patent: US6436923,2002,B1

6
[ 10049-21-5 ]
[ 79099-07-3 ]
[ 1730-25-2 ]
[ 203662-51-5 ]

Yield	Reaction Conditions	Operation in experiment
	In diethyl ether;	Example 270 4-Allyl-1-(tert-butoxycarbonyl)piperidin-4-ol Into a solution of 4.98 g of 1-(tert-butoxycarbonyl)-4-piperidone in diethyl ether (150 ml) was dropped at 0 C. in a nitrogen atmosphere 30 ml of a 1.0 M solution of allylmagnesium bromide in diethyl ether and the resulting mixture was stirred for 3 hours. Then the reaction mixture was poured into an aqueous solution of sodium dihydrogenphosphate and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with n-hexane/ethyl acetate) to thereby give 4.12 g of the title compound as a white solid. 1H-NMR(CDCl3) delta ppm: 1.45(s, 9H), 1.54(m, 4H), 2.23(br.d, J=7 Hz, 2H), 3.15(br.s, 2H), 3.80(br.s, 2H), 5.15(ddt, J=1, 2, 16 Hz, 1H), 5.21(ddt, J=1, 2, 10 Hz, 1H), 5.86(ddt, J=7, 10, 16 Hz, 1H)

Reference： [1]Patent: US6518423,2003,B1

7
[ 10049-21-5 ]
[ 7790-86-5 ]
[ 203661-55-6 ]
[ 15469-97-3 ]
[ 203655-46-3 ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium; sodium chloride; In tetrahydrofuran; hexane; ethyl acetate;	(10-Methoxymethyl-10H-pyrazino[2,3-b][1,4]benzothiazin-8-yl)-[1-(triphenylmethyl)imidazol-2-yl]methanol 50 ml of a solution of 1.32 g of 1-(triphenylmethyl)imidazole in dry tetrahydrofuran was ice-cooled in a nitrogen atmosphere. After adding 2.8 ml of a 1.6 M solution of n-butyllithium in hexane, the resulting mixture was stirred for 2 hours. Then the reaction mixture was cooled to -78° C. After adding 1.23 g of cerium (III) chloride, the reaction mixture was stirred for 30 minutes. Further, 40 ml of a solution of 0.546 g of (10-methoxymethyl-10H-pyrazino[2,3-b][1,4]benzothiazin-8-yl)carbaldehyde in dry tetrahydrofuran was dropped thereinto. Then the reaction mixture was brought back to room temperature and distributed into an aqueous solution of sodium dihydrogenphosphate and ethyl acetate. After filtering off the inorganic matters, the aqueous layer was extracted with ethyl acetate, washed successively with water and a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate followed by filtration. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (eluted with dichloromethane/methanol) to thereby give 716 mg of the title compound as a yellow solid. 1H-NMR(CDCl3) delta ppm: 2.84(d, J=8 Hz, 1H), 3.44(s, 3H), 4.98(d, J=8 Hz, 1H), 5.07(d, J=9 Hz, 1H), 5.19(d, J=9 Hz, 1H), 6.40(dd, J=2, 8 Hz, 1H), 6.68(d, J=8 Hz, 1H), 6.77(d, J=2 Hz, 1H), 6.78(d, J=2 Hz, 1H), 7.09-7.12(m, 7H), 7.23-7.26(m, 9H), 7.82(s, 2H)

Reference： [1]Patent: US6518423,2003,B1

8
[ 10049-21-5 ]
potassium terbutylate [ No CAS ]
[ 117294-21-0 ]
[ 1253-46-9 ]
[ 214746-44-8 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene;	Preparation 7 Methyl 4-[(8-Bromo-3,4-dihydro-2-naphthalenyl)methyl]benzoate 1.77 g of potassium terbutylate was added at 20 C. to a suspension containing 7.37 g of [[4-(methoxycarbonyl)phenyl]methyl]triphenyl-phosphonium bromide and 60 ml of anhydrous toluene. Agitation was carried out for 45 minutes and 2.25 g of 8-bromo-3,4-dihydro-2-(1H)-naphthalenone dissolved in 12 ml of toluene was added. The reaction medium was heated to 75~80 C. for 4 hours and 30 minutes, and then maintained at 20 C. for 18 hours. A dilute solution of sodium acid phosphate was added and extraction was carried out with toluene. The organic phases were dried over magnesium sulfate, concentrated and 10 g of product was obtained which is chromatographed on silica eluding with a heptane/isopropyl ether mixture 8-2. In this way 1.85 g of sought product was obtained.

Reference： [1]Patent: US6555709,2003,B1

9
[ 10049-21-5 ]
1-(N,N-dimethylamino)-3-(4-fluorophenyl)-2-(4-methylthiophenyl)prop-1-en-3-one [ No CAS ]
[ 107-91-5 ]
[ 181811-68-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	In methanol; N,N-dimethyl-formamide;	Step 2 Preparation of 1,2-dihydro-6-(4-fluorophenyl)-5-[4-(methylthio)phenyl]-2-oxo-pyridine-3-carbonitrile A solution of 26.1 g of 1-(N,N-dimethylamino)-3-(4-fluorophenyl)-2-[4-(methylthio)phenyl]prop-1-en-3-one (Step 1), 200 ml of dry DMF, 7.2 g (8.6 mMol) of the cyanoacetamide and 8 ml methanol was transferred to a dropping funnel. This solution was added dropwise to a slurry of 4.0 g of sodium hydride in 100 ml of DMF in a 3-necked round bottom flask with a magnetic stirrer and cooled with an ice bath. The temperature reached to 25 C. After complete addition of the reactants the mixture was heated to 80 C. for 4 hours, cooled and poured into one liter of 1M NaH2 PO4 to give an insoluble yellow solid which was washed with water and air dried to yield 24.5 g of a yellow powder (95%).

Reference： [1]Patent: US5916905,1999,A

10
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 189092-64-6 ]
N-(2-t-butyl-5-carbamoylphenyl)-3-(4-carboxy-2-methoxyphenyl)octanamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With dimethyl sulfoxide; In water;	EXAMPLE 112 N-(2-t-Butyl-5-carbamoylphenyl)-3-(4-carboxy-2-methoxyphenyl)octanamide (Compound No. 302) A solution of 650 mg (7.19 mmol) of sodium chlorite in 7 ml of water was added dropwise over a period of 15 minutes to a solution of 1.44 g (3.18 mmol) of N-(2-t-butyl-5-carbamoylphenyl)-3-(4-formyl-2-methoxyphenyl)octanamide (prepared as described in Example 110) in a mixture of 15 ml of dimethyl sulfoxide and a 1M aqueous solution of <strong>[10049-21-5]sodium dihydrogenphosphate</strong>, and the resulting mixture was stirred for 4.5 hours. At the end of this time, the reaction mixture was acidified with 1N aqueous hydrochloric acid, and methylene chloride was added thereto to separate out crystals, which were collected by filtration. The crystals were washed with water and then with ethyl acetate to give 1.32 g (yield 89%) of the title compound as a powdery substance, melting at 204-206 C. (from methylene chloride). Nuclear Magnetic Resonance Spectrum (270 MHz; CDCl3 -Hexadeuterated dimethyl sulfoxide) delta ppm: 0.83 (3H, triplet, J=6 Hz);

Reference： [1]Patent: US5880147,1999,A

11
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 513-35-9 ]
3-(1,1-Dimethylheptyl)-4-methoxybenzaldehyde [ No CAS ]
3-(1,1-dimethylheptyl)-4-methoxybenzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With hydrogenchloride; sodium hydroxide; In water; tert-butyl alcohol;	PREPARATIVE EXAMPLE 7 3-(1,1-Dimethylheptyl)-4-methoxybenzaldehyde (13 g, 49.5 mmol), t-butanol (65 ml) and 2-methyl-2-butene (35.2 ml, 332 mmol) were mixed, and to this solution was added dropwise a solution prepared by mixing sodium chlorite (7.37 g, 64.4 mmol), <strong>[10049-21-5]sodium dihydrogenphosphate</strong> (7.73 g, 64.4 mmol) and water (50 ml). The mixture was stirred at room temperature for 12 hours. A 1N sodium hydroxide solution (100 ml) was added, and t-butanol was evaporated under reduced pressure. Conc. hydrochloric acid was added to make the mixture acidic. The aqueous layer was extracted 3 times with ethyl acetate (150 ml). The organic layers were combined, washed with saturated brine (100 ml), and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by column chromatography (n-hexane/ethyl acetate=5/1-2/1) to give 3-(1,1-dimethylheptyl)-4-methoxybenzoic acid (10.7 g, 77%) as colorless crystals. 1 H-NMR (CDCl3)delta: 7.98(1H, d, J=2.15 Hz), 7.97(1H, dd, J=9.12, 2.15 Hz), 6.89(1H, d, J=9.12 Hz), 3.89(3H, s), 1.83-1.74(2H, m), 1.36(6H, s), 1.24-1.10(6H, m), 1.00-0.94(2H, m), 0.83(3H, t, J=6.49 Hz). FABMS (m/z): 279[M+ H+ ] (65), 261(70), 193(100).

Reference： [1]Patent: US6017919,2000,A

12
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 513-35-9 ]
[ 194359-81-4 ]
1-bromo-4-pentyloxynaphthalene-2-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With hydrogenchloride; sodium hydroxide; In water; tert-butyl alcohol;	PREPARATIVE EXAMPLE 16 1-Bromo-4-pentyloxynaphthalene-2-carbaldehyde (0.77 g, 2.4 mmol), t-butanol (4.8 ml) and 2-methyl-2-butene (1.71 ml, 16.1 mmol) were mixed, and a solution prepared by mixing sodium chlorite (360 mg, 3.12 mmol), <strong>[10049-21-5]sodium dihydrogenphosphate</strong> (374 mg, 3.12 mmol) and water (2.4 ml) was added dropwise. The mixture was stirred at room temperature for 16.5 hours. A 1N aqueous sodium hydroxide solution (5 ml) was added, and t-butanol was evaporated under reduced pressure. Conc. hydrochloric acid was added to make the mixture acidic. Saturated saturated brine (5 ml) was added, and the aqueous layer was extracted 3 times with ethyl acetate (10 ml). The organic layer was dried over anhydrous magnesium sulfate, and the drying agent was filtered off. The filtrate was concentrated under reduced pressure. The obtained residue was recrystallized from ethyl acetate to give 1-bromo-4-pentyloxynaphthalene-2-carboxylic acid (619 mg, 76%) as pale-yellow crystals. 1 H-NMR (CDCl3)delta: 8.47(1H, d, J=8.4 Hz), 8.33(1H, d, J=8.4 Hz), 7.72-7.58(2H, m), 7.24(1H, s), 4.18(2H, t, J=6.48 Hz), 1.62-1.37(6H, m), 0.97(3H, t, J=7.2 Hz). FABMS (m/z): 338[M+ H+ ] (90), 339(70), 268(50).

Reference： [1]Patent: US6017919,2000,A

13
[ 10049-21-5 ]
[ 513-35-9 ]
ethyl (+/-)-3-[4-hydroxy-1-butyl]-5H-dibenzo[a,d]cycloheptene-10-acetate [ No CAS ]
Ethyl (+/-)-3-[3-carboxy-1-propyl]-5H-dibenzo [a,d]cycloheptene-10-acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With NaClO2; In dichloromethane; water; ethyl acetate;	e Ethyl (+-)-3-[3-carboxy-1-propyl]-5H-dibenzo [a,d]cycloheptene-10-acetate A solution of ethyl (+-)-3-[4-hydroxy-1-butyl]-5H-dibenzo[a,d]cycloheptene-10-acetate (342.4 mg, 0.97 mmole) in anhydrous CH2 Cl2 (19 mL) was cooled to 0 C. under argon, and 2,2,6,6-tetramethyloxopiperidinium chloride (J. Org. Chem. 1985, 50, 1332-1334; 260 mg, 1.36 mmole) was added in one portion. The reaction was stirred at 0 C. for 1 hr, then 2-methyl-2-butene (1.2 mL, 11 64 mmole) was added, followed by a cold (0 C.) solution of NaClO2 (0.88 g, 7.76 mmole) and NaH2 PO4 (0.90 g, 6.50 mmole) in H2 O (26 mL). After 10 min, the reaction was diluted with EtOAc (100 mL) and the layers were separated. The organic layer was washed sequentially with cold 1.0 N HCl (10 mL) and saturated brine (20 mL), dried (MgSO4), and concentrated. Silica gel chromatography (gradient: 1:1 EtOAc/CHCl3 then 9:9:2 EtOAc/CHCl3 /EtOH) gave impure title compound. Rechromatography on silica gel (7:3:0.1 toluene/EtOAc/AcOH) gave the pure title compound (233.7 mg, 66%): TLC (1:1 EtOAc/CHCl3) Rf 0.46; 1 H NMR (400 MHz, CDCl3) delta 7.05-7.22 (m, 4 H), 6.92-7.05 (m, 3 H), 4.34 (d, J=15.0 Hz, 1 H), 4.10-4.25 (m, 2 H), 3.80-3.90 (m, 2 H), 3.33 (dd, J=15.1, 4.1 Hz, 1 H), 2.95 (dd, J=15.1, 9.4 Hz, 1 H), 2.48-2.60 (m, 4 H), 2.48-2.60 (m, 4 H), 2.37 (t, J=7.4 Hz, 2 H), 1.87-2.00 (m, 2 H), 1.27 (t, J=7.2 Hz, 3 H); MS (ES) m/e 389 (M+Na)+, 367 (M+H)+.

Reference： [1]Patent: US6008213,1999,A

14
[ 10049-21-5 ]
[ 5292-43-3 ]
[ 111-46-6 ]
[ 149299-82-1 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hexamethyldisilazane In tetrahydrofuran	a Preparation of succinimidyl 8-carboxy-3,6-dioxaoctyl-2-benzoylthioacetyl)glycylglycylglycinate a) Preparation of tert-butyl 8-hydroxy-3,6-dioxaoctanoate. A solution of 53 g of 2-hydroxyethyl ether (0.5 mol) in 200 mL of tetrahydrofuran was prepared, and the solution cooled in an ice-water bath. The solution was placed under a slow stream of argon. Sodium bis(trimethylsilyl)amide (125 mL, 0.125 mol, 1M in tetrahydrofuran) was added dropwise over a 30 minute period. The mixture was stirred an additional 30 minutes, then 24.4 g of tert-butyl 2-bromoacetate (0.125 mol) was added. The mixture was then stirred for 1 hour. The ice-water bath was removed, and the mixture transferred to a separatory funnel using 250 mL of 1M NaH2 PO4. The mixture was extracted with ethyl acetate (3*150 mL). The combined extracts were dried over sodium sulfate, filtered, and the solvent removed by rotary evaporator to give a clear yellow liquid. The liquid was purified by chromatography using 500 mL of silica gel and eluding with ethyl acetate/hexanes 1:1. The product was isolated as a clear, gold liquid. Obtained 5.49 g TLC Rf 0.50 (EtOAc). NMR (DMSO-d6) δ 1.42 (s, 9H), 3.42 and 3.54 (m, 8H), 3.98 (s, 2H).
	With sodium hexamethyldisilazane In tetrahydrofuran	II.a a) a) Preparation of tert-butyl 8-hydroxy -3,6- dioxaoctanoate A solution of 53 g of 2-hydroxyethyl ether (0.5 mol) in 200 mL of tetrahydrofuran was prepared, and the solution cooled in an ice-water bath. The solution was placed under a slow stream of argon. Sodium bis(trimethylsilyl)amide (125 mL, 0.125 mol, 1 M in tetrahydrofuran) was added dropwise over a 30 minute period. The mixture was stirred an additional 30 minutes, then 24.4 g of tert-butyl 2-bromoacetate (0.125 mol) was added. The mixture was then stirred for 1 hour. The ice-water bath was removed, and the mixture transferred to a separatory funnel using 250 mL of 1 M NaH2 PO4. The mixture was extracted with ethyl acetate (3*150 mL). The combined extracts were dried over sodium sulfate, filtered, and the solvent removed by rotary evaporator to give a clear yellow liquid. The liquid was purified by chromatography using 500 mL of silica gel and eluding with ethyl acetate/hexanes 1:1. The product was isolated as a clear, gold liquid. Obtained 5.49 g TLC Rf 0.50 (EtOAc). NMR (DMSO-d6)δ 1.42 (s, 9H), 3.42 and 3.54 (m, 8H), 3.98 (s, 2H).

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - US5185433, 1993, A
[2]Current Patent Assignee: JOHNSON & JOHNSON INC - US5162505, 1992, A

15
[ 10049-21-5 ]
NaHPO₄ [ No CAS ]
Na₂ S₂ O₄ [ No CAS ]
[ 182193-03-9 ]
2-(3,4-difluorophenyl)-2-methyl-oxirane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With m-chloroperoxybenzoic acid; In dichloromethane; water;	c. 2-(3,4-Difluorophenyl)-2-methyl-oxirane To a biphasic solution of 1,2-difluoro-4-isopropenyl-benzene (0.81 g, 5.1 mmol) in CH2 Cl2 (50 mL) and 50 mL of phosphate buffer (made by dissolving 0.3 g of NaHPO4 and 0.35 g of NaH2 PO4 in 50 mL water, pH=8) at 0 C., was added a solution of 3-chloroperoxybenzoic acid (approx. 75% solid, 3.32 g, 10.2 mmol) via a dropping funnel fitted with a cotton plug dropwise in two batches. The solution was stirred at room temperature overnight. It was extracted with CH2 Cl2, washed with sat. Na2 S2 O4 solution followed by water. The organic layer was finally washed with sat. NaHCO3, separated, dried over Na2 SO4, filtered and solvent was removed in vacuo. 2-(3,4-Difluorophenyl)-2-methyl-oxirane was obtained as a pale yellow oil (0.65 g, 74% yield). It was used in the next step without purification.

Reference： [1]Patent: US6159990,2000,A

16
[ 10049-21-5 ]
[ 97-65-4 ]
Citraconic anhydride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	In 5,5-dimethyl-1,3-cyclohexadiene;	EXAMPLE 1 Synthesis of Citraconic Anhydride In a one liter reaction vessel equipped with a thermometer, a mechanical stirrer and a Dean Stark Trap with reflux-condensor, 500 grams of itaconic acid and 10 grams of NaH2 PO4 were suspended in 450 ml of Shell Ondina oil. The suspension was warmed very rapidly with an oil bath to 180 C. Upon heating the itaconic acid dissolved/melted and a clear solution was formed from which the water separates. At the end of the water distillation 10-30 ml of xylene was added. When the theoretical amount of water was distilled off, the mixture was cooled and the vessel was equipped with a vacuum distillation set-up. The xylene was then distilled off at 100 C. and 500 mbar and subsequently the citraconic anhydride was distilled off at 100 C. and 20 mbar. The citraconic anhydride was obtained as a colorless liquid in a 79% yield.

Reference： [1]Patent: US5329022,1994,A

17
[ 5050-41-9 ]
[ 10049-21-5 ]
[ 154464-88-7 ]
[ 104-15-4 ]
9-(2-(N-pyrrolidinyl)ethoxy)-3-oxo-spiro[5.5]undecane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate In tetrahydrofuran; water; ethylene glycol; ethyl acetate; benzene	2 9-(2-(N-pyrrolidinyl)ethoxy)-3-oxo-spiro[5.5]undecane II-b Preparation 2 9-(2-(N-pyrrolidinyl)ethoxy)-3-oxo-spiro[5.5]undecane II-b A mixture of 2.00 g of 9-hydroxy-3-oxo-spiro[5.5]undecane (II-a, Prep. 1), 3 ml of ethylene glycol and 0.020 g of p-toluensulfonic acid in 100 ml of benzene was refluxed in a Dean-Stark apparatus, under nitrogen atmosphere, for 2 hrs. The reaction mixture was then cooled to room temperature, diluted with ethyl acetate, washed with disodium hydrogen phosphate (5% water solution), dried over anhydrous sodium sulfate and evaporated in vacuum. The residue (2.30 g), N-(2-chloroethyl)pyrrolidine (2.75 g) and sodium hydride (0.830 g; 60 dispersion in oil) in 20 ml of anhydrous tetrahydrofuran were stirred under argon atmosphere at reflux temperature for 2.5 hrs in a Dean-Stark apparatus, and part of the distilled solvent collected, to the point of making the reaction a pasty stirrable mixture. The mixture was cooled to room temperature, sodium dihydrogenphosphate (5% water solution) and ethyl acetate were added and the organic layer was separated and thoroughly extracted with 1N HCl. The collected aqueous layers were made basic with 5% sodium carbonate and extracted with ethyl acetate to give, after workup, 2.5 g of a brown-yellow oil which was purified by flash chromatography (SiO2; chloroform/methanol 90/10) to give 1.80 g of pure title compound (II-b) as an amorphous white solid. TLC: Rf=0.28 (SiO2 plates, chloroform/methanol 90/10). 1 H-NMR (300 MHz, CDCl3, ppm from TMS): 3.62 (2H, t), 3.30 (1H, hept), 2.78 (2H, t), 2.70-2.55 (4H, m), 2.40-2.30 (4H, dd), 1.90-1.2 (16H, m).

Reference： [1]Current Patent Assignee: ALFASIGMA GROUP - US5444082, 1995, A

18
[ 67-47-0 ]
[ 10049-21-5 ]
[ 75-36-5 ]
[ 10551-58-3 ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine In dichloromethane	7 STAGE A: 5-(acetyloxy) methyl-2-furancarboxaldehyde STAGE A: 5-(acetyloxy) methyl-2-furancarboxaldehyde 10.05 cm3 of acetyl chloride is added at 5° C. to a solution containing 16.2 g of 5-(hydroxy methyl) 2-furan-carboxaldehyde and 200 cm3 of methylene chloride. Then 11.4 cm3 of pyridine and 50 cm3 of methylene chloride are added. The reaction mixture is maintained under agitation for 3 hours at 20° C. It is then treated with an aqueous solution of sodium acid phosphate and extracted with methylene chloride, followed by drying and concentrating. After chromatography on silica eluding with a hexane--ethyl acetate mixture (7-3), 19.35 g of desired product is obtained.

Reference： [1]Current Patent Assignee: SANOFI - US5340835, 1994, A

19
[ 10049-21-5 ]
2-(iso-butyryl)-amino-3-methylbenzamide [ No CAS ]
[ 71381-27-6 ]

Yield	Reaction Conditions	Operation in experiment
76%	With sodium hydroxide; In methanol; water;	Step B Preparation of 8-methyl-2-iso-propylquinazolin-4-one 5N Sodium hydroxide solution (0.56 mL, 0.0028 mol) was added to a mixture of 2-(iso-butyryl)amino-3-methylbenzamide (0.62 g, 0.0028 mol) in methanol (6 mL) and water (14 mL) at room temperature. The mixture was heated at reflux for 1 hr. then cooled to room temperature and acidified with 2N hydrochloric acid solution. Saturated <strong>[10049-21-5]sodium dihydrogen orthophosphate</strong> solution was added and the mixture extracted with methylene chloride (4 times). The combined organic phase was washed with water, brine, dried (magnesium sulfate) and the solvent removed in vacuo to leave 8-methyl-2-iso-propylquinazolin-4-one (0.43 g, 76%) identical with the material isolated in step A.

Reference： [1]Patent: US5401745,1995,A

20
[ 123-91-1 ]
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 513-35-9 ]
[ 5059-30-3 ]
[ 54778-20-0 ]
[ 83894-17-1 ]

Yield	Reaction Conditions	Operation in experiment
	In hexane; water; ethyl acetate; acetone	K Compound 133 of Table 1 Compound 133 of Table 1 A mechanically stirred suspension of 15 g (83.5 mmol) of 2-chloroindole-3-carboxaldehyde [XXVI: R1 =R3 =H, X=Cl] (Schule, et al., Arch, Pharm. [Weinheim] 1972;305:523-533), 84 mL of 2-methyl-2-butene, and 200 mL of p-dioxane in an ice bath was treated with a solution of 40 g each of sodium chlorite and sodium dihydrogen phosphate monohydrate in 200 mL of water. The biphasic mixture was then stirred vigorously at 25° C. for 3.5 hours. An additional 16 g each of solid sodium chlorite and sodium dihydrogen phosphate monohydrate was added and the mixture was stirred for another 3.5 hours. The mixture was diluted with 350 mL of ethyl acetate and 200 mL of water. The layers were separated and the aqueous phase was extracted with 300 mL of ethyl acetate. The combined organic extracts were extracted with cold 2% aqueous NaOH (3*200 mL). The basic extracts were combined and acidified to pH 4 with 6N aqueous HCl. The precipitated solids were collected by filtration, washed well with water, and air dried overnight. The solids were dissolved in 150 mL of hot acetone and the solution was treated with 65 mL of hexane. After storage at 3° C. for 20 hours, the solids were collected by filtration, washed with cold acetone, and dried to leave 7.71 g of pure 2-chloroindole-3-carboxylic acid [XXVII: R1 =R3 =H, X=Cl] as an off-white solid; mp 181.5° C. (dec). Further processing of the filtrate as above afforded 2.41 g of a second crop; mp 179.5° C. (dec). Total yield 10.12 g (62%). The acid chloride of 2-chloroindole-3-carboxylic acid [XXVII: R1 =R3 =H, X=Cl] was made via SOCl2 as described above.

Reference： [1]Current Patent Assignee: PFIZER INC - US5464861, 1995, A

21
[ 98-10-2 ]
[ 10049-21-5 ]
[ 530-62-1 ]
5,7-Dimethyl-2-ethyl-3-[[4-[1-phenyl-2-(phenylsulfonylaminocarbonyl)ethyl]phenyl]methyl]-3H-imidazol[4,5-b]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	With 1,8-diazabicyclo[5.4.0]undec-7-ene; In tetrahydrofuran; water;	EXAMPLE 55 5,7-Dimethyl-2-ethyl-3-[[4-[1-phenyl -2-(phenylsulfonylaminocarbonyl)ethyl]phenyl]methyl]-3H-imidazo[4,5-b]pyridine To a mixture of 0.3 g (0.69 mmol) of the compound obtained in example 9 in 13 mL of tetrahydrofuran was added 0.111 g (0.69 mmol) of 1,1'-carbonyldiimidazole and the mixture was heated at reflux for 3 hr. Next, it was allowed to cool and a mixture consisting of 0.133 g (0.87 mmol) of benzenesulfonamide and 1.29 mL (0.87 mmol) of DBU was added. The resulting mixture was heated at 40 C. overnight, and was then allowed to cool and concentrated. The residue was taken up in water and was acidifed with 10% NaH2 PO4 solution (pH=5). The resulting solution was then extracted with chloroform and ethyl acetate. The combined organic phases were dried and the solvents were removed to afford a crude product. This was purified by chromatography on silica gel (chloroform-methanol, 2%), to give the title compound of the example (yield: 42%). mp=81-86 C.; 1 H-NMR (80 MHz, CDCl3) delta (TMS): 1.21 (t, J=7.2 Hz, 3H, CH3), 2.53 (s, 3H, CH3), 2.55 (s, 3H, CH3), 2.59 (q, J=7.2 Hz, 2H, CH2), 2.77 (d, J=7.2 Hz, 2H, CH2), 3.4 (broad signal 1H, COOH), 4.37 (t, J=7.2 Hz, 1H, CH), 5.34 (s, 2H, CH2), 7.0-7.2 (m, 15H, Ar). Analysis Calcd for C32 H32 N4 O3 S.1.5H2 O: C 66.30%, H 6.09%, N 9.66%, S 5.53%. Found: C 66.15%, H 5.81%, N 9.90%, S 6.08%.

Reference： [1]Patent: US5554624,1996,A

22
[ 10049-21-5 ]
[ 171744-39-1 ]
[ 3483-12-3 ]
[ 173590-74-4 ]

Yield	Reaction Conditions	Operation in experiment
	With formic acid; In N-methyl-acetamide;	EXAMPLE 6 2-Thio-N-(4-sulfamoylphenyl)benzamide 2,2'-Dithiobis (4'-sulfamoyl)benzanilide (0.1 g, 0.2 mmol) was dissolved in 4 mL of dimethylformamide and 1.6 mL of 2.7% NaH2 PO4. Dithiothreitol (0.1 g, 0.7 mmol) was added, and the mixture was allowed to stir for 0.5 hours. Formic acid (10 mL 10% aqueous) was added to precipitate the product, which was collected by filtration, washed with water and diethyl ether to yield 72 mg of 2-thio-N-(4-sulfamoylphenyl)benzamide, mp 230-231 C.; NMR (DMSO-d6): delta10.7 (s, 1H), 7.9-7.7 (m, 4H), 7.6 (d, 1H), 7.5 (d, 1H), 7.4 (m, 1H), 7.3-7.2 (m, 3H).
	With formic acid; In N-methyl-acetamide;	EXAMPLE 6 2-Thio-N-(4-sulfamoylphenyl)benzamide 2,2'-Dithiobis(4'-sulfamoyl)benzanilide (0.1 g, 0.2 mmol) was dissolved in 4 mL of dimethylformamide and 1.6 mL of 2.7% NaH2 PO4. Dithiothreitol (0.1 g, 0.7 mmol) was added, and the mixture was allowed to stir for 0.5 hours. Formic acid (10 mL 10% aqueous) was added to precipitate the product, which was collected by filtration, washed with water and diethyl ether to yield 72 mg of 2-thio-N-(4-sulfamoylphenyl)benzamide, mp 230-231 C.; NMR (DMSO-d6): delta10.7 (s, 1H), 7.9-7.7 (m, 4H), 7.6 (d, 1H), 7.5 (d, 1H), 7.4 (m, 1H), 7.3-7.2 (m, 3H).

Reference： [1]Patent: US5463122,1995,A
[2]Patent: US5734081,1998,A

23
[ 10049-21-5 ]
[ 171744-41-5 ]
[ 3483-12-3 ]
5-Acetylamino-2-thiobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In N-methyl-acetamide; water;	EXAMPLE 10 5-Acetylamino-2-thiobenzamide 2,2'-Dithiobis-5-(acetamidobenzamide) from Example 9 (80 mg, 0.2 mmol) was partially dissolved in 3 mL of dimethylformamide and 1.5 mL 2.7% NaH2 PO4. A homogeneous solution was realized with the addition of dithiothreitol (0.1 g, 0.7 mmol) and after 20 minutes, 10 mL of 10% acetic acid was added. The solvents were removed in vacuo, the residue slurried in water, and the solid removed by filtration to yield 22 mg of the title compound, mp 148-149 C.; NMR (DMSO-d6): delta10.0 (s, 1H), 7.9 (s, 1H), 7.7 (s, 1H), 7.5 (m, 2H), 7.3 (d, 1H), 5.2 (s, 1H), 2.0 (s,3H).
	With acetic acid; In N-methyl-acetamide; water;	EXAMPLE 10 5-Acetylamino-2-thiobenzamide 2,2'-Dithiobis-5-(acetamidobenzamide) from Example 9 (80 mg, 0.2 mmol) was partially dissolved in 3 mL of dimethylformamide and 1.5 mL 2.7% NaH2 PO4. A homogeneous solution was realized with the addition of dithiothreitol (0.1 g, 0.7 mmol) and after 20 minutes, 10 mL of 10% acetic acid was added. The solvents were removed in vacuo, the residue slurried in water, and the solid removed by filtration to yield 22 mg of the title compound, mp 148-149 C.; NMR (DMSO-d6): delta10.0 (s, 1H), 7.9 (s, 1H), 7.7 (s, 1H), 7.5 (m, 2H), 7.3 (d, 1H), 5.2 (s, 1H), 2.0 (s,3H).

Reference： [1]Patent: US5463122,1995,A
[2]Patent: US5734081,1998,A

24
[ 10049-21-5 ]
[ 142070-81-3 ]
[ 60-29-7 ]
[ 142794-95-4 ]

Yield	Reaction Conditions	Operation in experiment
0.130 g (30.2%)	With H2;palladium-carbon; In tetrahydrofuran;	Step C Sodium (4R,5S,6S)-3-[[[p-carbamoylphenyl)thio]methyl]thio]-6-[1'(R)-hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo-[3.2.0]hept-2-ene-2-carboxylate (Ix) STR94 A solution of p-nitrobenzyl (4R,5S,6S)-3-[[[(p-carbamoylphenyl)thio]methyl]thio]]-6-[1'(R)-hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (0.543 g, 1 mmol) in tetrahydrofuran (40 mL) was added to a mixture of Et2 O (40 mL) and 0.1M NaH2 PO4 /NaOH buffer solution (pH:7.0, 20 mL). The mixture was subjected to hydrogenolysis over 10% Pd/C catalyst (0.543 g) at 40 psi H2 for 3 h. Then the catalyst was filtered off and the filtrate extracted with Et2 O. The aqueous phase was chromatographed on reversed phase silica gel being, eluted with 0-10% CH3 CN/water. The pertinent fractions were combined and lyophilized to afford 0.130 g (30.2%) of the title compound. IR (nujol) numax: 1740 (beta-lactam), 1660 (--CONH2), 1590 cm-1 (--CO2 --); 1 H NMR (D2 O, 200 MHz) delta: 7.77 (2H, d, aromatic-H), 7.61 (2H, d, aromatic-H), 4.37 (2H, ABq, --CH2 S--), 4.19 (1H, m, H-1'), 3.87 (1H, dd, J=2.35Hz, 9.19, H-5), 3.36 (1H, dd, J=2.46, 6.07Hz, H-6), 3.56 (1H, m, H-4), 1.26 (3H, d, J=6.33Hz, 1'-CH3), 1.12 ppm (3H, d, J =7.24 Hz, 4-CH3).

Reference： [1]Patent: US5116833,1992,A

25
[ 10049-21-5 ]
[ 142070-64-2 ]
[ 75-05-8 ]
[ 142794-77-2 ]

Yield	Reaction Conditions	Operation in experiment
47%	With H2;palladium-carbon; In tetrahydrofuran;	Step B Sodium (5R,6S)-6-[1'(R)-1-hydroxyethyl]-3-[[[(pyridin-2-yl)thio]methyl]thio]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (Ie) STR43 A solution of p-nitrobenzyl (5R,6S)-6-[1'(R)-hydroxyethyl]-3-[[[(pyridin-2-yl)thio]methyl]thio]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (880 mg, 1.82 mmol) in THF (50 mL), ether (50 mL) and a 0.05M, pH 7.0 NaH2 PO4 /NaOH buffer solution (80 mL, 4 mmol) was subjected to hydrogenolysis at 45 psi H2 for 1 h at 15 C., using 10% Pd/C (880 mg) as catalyst. The catalyst was removed by filtration and washed with H2 O (25 mL). The organic phase was extracted with H2 O (220 mL). The aqueous phases were combined, washed with ether (225 mL) and passed through a C18 muBondaPak reversed phase column (75 g of the packing material; the column eluted first with H2 O followed successively by 2%, 5% and 8% CH3 CN/H2 O) to give the title material (320 mg, 47%); purity: 99.9% (as checked by HPLC); T1/2 19 h (pH 7.4). UV lambdaH2Omax 298 (16,100), 246 (9,950); IR (Nujol) numax:3600-3400 (OH); 1760 and 1595 cm-1 (C=O); 1 H NMR (D20, 200 MHz) delta: 8.46-8.42 (1H, m, pyridine-H), 7.81-7.73 (1H, m, pyridine-H), 7.50, 7.46 (1H, d, J=8.1 Hz, pyridine H), 7.32-7.25 (1H, m, pyridine H), 4.59, 4.52, 4.50, 4.43 (2H, ABq, J=13.9 Hz, SCH2 S), 4.25-4.12 (2H, m, H-1' and H-5), 3.39 (1H, dd, J=2.6 Hz, J=5.9 Hz, H-6), 3.43, 3.38, 3.34, 3.29, 3.25, 3.21, 3.16, 3.12 (2H, m, CH2 -4), 1.285 ppm (3H, d, J=6.4 Hz, CH3).

Reference： [1]Patent: US5116833,1992,A

26
[ 10049-21-5 ]
[ 142070-76-6 ]
[ 142794-93-2 ]

Yield	Reaction Conditions	Operation in experiment
0.339 g (29%)	With H2;palladium-carbon; In tetrahydrofuran; water;	Step B Sodium (4R,5S,6S)-6-[1'(R)-hydroxyethyl]-3-[[[[(furan-2-yl)-methyl]thio]methyl]thio]-4-methyl-7-oxo-1-azabicyclo-[3.2.0]hept-2-ene-2-carboxylate (Iu) STR83 A solution of p-nitrobenzyl (4R,5B,6S)-6-[1'(R)-hydroxyethyl]-3-[[[[(furan-2-yl)methyl]thio]methyl]thio]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (1.512 g, 3.0 mmol) in a mixture of ether (30 mL) and tetrahydrofuran (30 mL) was added to 60 mL of pH 7.0, 0.1M NaH2 PO4 /NaOH buffer solution. The resulting mixture was subjected to hydrogenolysis over 10% Pd/C catalyst (1.512 g) at 42 psi H2 for 3 h. The catalyst was removed by filtration over a pad of Celite and washed with ether (30 mL) and the pH 7.0 buffer solution (30 mL). The aqueous phase was separated from the organic phase and chromatographed on reversed phase silica gel, eluted with 5-20% acetonitrile in water; the pertinent fractions were pooled and lyophilized. The solid thus obtained was rechromatographed on reversed phase silica gel, eluted with acetonitrile/water (12/88); the pertinent fractions were once again pooled and lyophilized to afford 0.339 g (29%) of the title product as a white powder. IR (KBr) numax: 1599 (--CO2 --), 1750 cm-1 (beta-lactam);

Reference： [1]Patent: US5116833,1992,A

27
[ 10049-21-5 ]
2N-isopropanol [ No CAS ]
Na 2 SO₄ [ No CAS ]
[ 4385-48-2 ]
[ 5770-59-2 ]

Yield	Reaction Conditions	Operation in experiment
	With diisobutylaluminium hydride In toluene	6 EXAMPLE 6 A molar solution of DIBAH in toluene (73 ml) is added dropwise to a stirred solution of 1,4-benzodioxan-2-one (8.9 g) in dry toluene (100 ml), cooled at -70° C. during 40 minutes. Stirring at this temperature is continued for 15 minutes, then the excess reagent is destroyed by adding 2N-isopropanol in toluene (75 ml), under stirring, at -70°÷-60° C. The mixture is warmed at room temperature and treated with 30% NaH2 PO4 aqueous solution (6 ml) and 25 g of anhydrous Na 2 SO4, for 4 hours, under stirring. The inorganic material is filtered out and the elude is evaporated to dryness to give 8.2 g of 2-hydroxy-1,4-benzodioxan.

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG - US4798898, 1989, A

28
ammonium vanadate [ No CAS ]
[ 10049-21-5 ]
[ 60345-96-2 ]
[ 127-68-4 ]
[ 70917-17-8 ]

Yield	Reaction Conditions	Operation in experiment
	In N-methyl-acetamide; water;	EXAMPLE 1 780 Parts of dimethylformamide, 48 parts of milled sodium dihydrogen phosphate (monohydrate) and 355 parts of 1,4-diaminoanthraquinone-2-carboxylic acid methyl ester are heated to 55 C. and 81.5 parts of sodium cyanide are introduced in 2 portions with an interval of 15 minutes. The temperature rises to 65 C. The mixture is stirred until a thin layer chromatogram indicates that no starting material is left. For the dehydrogenation, a solution of 216 parts of primary sodium dihydrogen phosphate, 84 parts of sodium m-nitrobenzenesulfonate and 0.1 part of ammonium vanadate in 2,160 parts of water is added to the reaction mixture. The mixture is then stirred for 1 hour at 65-70 C. after which it is heated for 1 hour at 70-90 C. The dye is then filtered off, washed with warm water and dried. 334 parts of 1,4-diamino-2-cyano-anthraquinone-3-carboxylic acid methyl ester are obtained; melting point 215-218 C.

Reference： [1]Patent: US4181668,1980,A

29
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 513-35-9 ]
[ 198904-53-9 ]
4-(1,3-Thiazol-2-yl)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	In tetrahydrofuran; water; tert-butyl alcohol;	8.15(2H,d,J=8.2Hz), 10.07(1H,s) A mixture of <strong>[198904-53-9]4-(2-thiazolyl)benzaldehyde</strong> (4.6 g, 24 mmol), sodium chlorite (5.5 g, 61 mmols), sodium dihydrogenphosphate (3.2 g, 27 mmols), 2-methyl-2-butene (8.6 g, 120 mmols), tert-butanol (40 ml), tetrahydrofuran (40 ml) and water (20 ml) was stirred at room temperature for 3 hours. The mixture was poured into 1 N hydrochloric acid, and the precipitate formed was taken out through filtration and dried. Thus was obtained a solid of 4-(2-thiazolyl)benzoic acid (4.0 g, 79 %). 1H-NMR (DMSO-d6) delta: 7.89(1H,m), 8.00-8.06(5H,m)

Reference： [1]Patent: EP1123918,2001,A1

30
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 429666-54-6 ]
[ 513-35-9 ]
[ 429666-56-8 ]

Yield	Reaction Conditions	Operation in experiment
67%	With hydrogenchloride; In tetrahydrofuran; methanol; dichloromethane; water; ethyl acetate; tert-butyl alcohol;	(4) 3-t-Butyldiphenylsilyloxy-1-(4-carboxyl-1,3-thiazol-2-yl)azetidine To a solution of 3-t-butyldiphenylsilyloxy-1-(4-formyl-1,3-thiazol-2-yl)azetidine (3.5 g, 8.28 mmol) (obtained as described in Reference Example 2(3)) in anhydrous methylene chloride (21 ml) were added t-butanol (105 ml) and a solution of 2M 2-methyl-2-butene in tetrahydrofuran (41.4 ml), followed by dropwise addition of a solution of sodium chlorite (1.88 g, 16.6 mmol) and <strong>[10049-21-5]sodium dihydrogenphosphate</strong> (1.99 g, 16.6 mmol) in water (21 ml) in an ice bath and the mixture was stirred for 1 hour. After checking the completion of the reaction, to the reaction mixture was added 1 M hydrochloric acid to a pH of from 2 to 3. The resulting mixture was extracted with ethyl acetate. The organic layer was separated, washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on a silica gel column using ethyl acetate ? 5% methanol in ethyl acetate as the eluant to afford 3-t-butyldiphenylsilyloxy-1-(4-carboxyl-1,3-thiazol-2-yl)azetidine (2.34 g, yield 67%) as a brown syrup. 1H-NMR (400 MHz, CDCl3): delta (ppm) 7.62-7.56 (4H, m), 7.50 (1H, s), 7.49-7.36 (6H, m), 4.81-4.72 (1H, m), 4.16-4.08 (2H, m), 4.04 (2H, dd, J=9.5, 5.1Hz), 2.00 (1H, br s), 1.07 (9H, s).

Reference： [1]Patent: EP1340757,2003,A1

31
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 513-35-9 ]
[ 429673-09-6 ]
[ 429666-56-8 ]

Yield	Reaction Conditions	Operation in experiment
59%	With hydrogenchloride; In tetrahydrofuran; dichloromethane; water; tert-butyl alcohol;	(11) 3-t-Butyldiphenylsilyloxy-1-(4-carboxyl-2-yl)azetidine To a solution of 3-t-butyldiphenylsilyloxy-1-(4-formyl-1,3-oxazol-2-yl)azetidine (3.09 g, 7.60 mmol) (obtained as described in Reference Example 70(10)) in anhydrous methylene chloride (18 ml) were added t-butanol (93 ml) and a solution of 2 M 2-methyl-2-butene in tetrahydrofuran (5.70 ml, 11.4 mmol), followed by dropwise addition of a solution of sodium chlorite (1.72 g, 15.2 mmol) and <strong>[10049-21-5]sodium dihydrogenphosphate</strong> (1.82 g, 15.2 mmol) in water (18 ml) in an ice bath, and the mixture was stirred for 1 hour. After checking the completior of the reaction to the reaction mixture was added 1 M hydrochloric acid to a pH of from 2 to 3. The resulting mixture was extracted with ethyl acetate. The organic layer was separated, washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on a silica gel column using methylene chloride and methylene chloride (9:1) as the eluant to afford 3-t-butyldiphenylsilyloxy-1-(4-carboxyl-1,3-thiazol-2-yl)azetidine (1.90 g, yield 59%) as a brown solid. Mass spectrum (FAB+): m/z: 423 [M+H]+

Reference： [1]Patent: EP1340757,2003,A1

32
[ 10049-21-5 ]
[ 132927-09-4 ]
[ 448-36-2 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium; In water; dimethyl sulfoxide;	Production Example 21d) 3.0 g of <strong>[132927-09-4]2-methoxy-4-(trifluoromethyl)benzaldehyde</strong> was dissolved in 50 ml dimethyl sulfoxide and an aqueous solution (20 ml) of 1.6 g sodium dihydrogenphosphate, followed by adding dropwise an aqueous solution (30 ml) of 8.0 g sodium chloritethereinto. After stirring at room temperature for 3 days, water was added thereto, followed by extracting with ethyl acetate. The extract was washed with brine, dried over anhydrous magnesium sulfate and the solvent was evaporated. The residue was subjected to silica gel column chromatography, to give 0.8 g of 2-methoxy-4-(trifluoromethyl)benzoic acid as a colorless solid from fractions eluted with hexane-ethyl acetate (3:7).1H-NMR(CDCl3) δ: 4.14 (s, 3H) 7.29(s,1H) 7.41(d,J=8Hz,1H) 8.30(d,J=8Hz,1H)

Reference： [1]Patent: EP1216980,2002,A1

33
[ 437711-24-5 ]
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 437711-25-6 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; In water; acetonitrile;	Step B Preparation of 1-(2-Chlorophenyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxylic Acid To a suspension containing the title compound of Step A (43.2 g, 138 mmol) in acetonitrile (415 mL) was added sodium dihydrogenphosphate monohydrate (92.4 g, 669 mmol) over about 0.25 h. After stirring at room temperature for 0.5 h, the mixture was cooled to about 5 C. and a solution containing sodium chlorite (181.7 g, 2.0 mmol) in 430 mL of water was added dropwise over 1 h while keeping the reaction temperature at less than 10 C. [Note: an aqueous sodium hydroxide scrubber was attached to scrub an evolving yellow off-gas.] Following completion of addition the suspension was stirred at 5 C. for about 1 h, at 25 C. overnight, then acidified to pH=1 by dropwise addition of concentrated hydrochloric acid (150 mL), then extracted with ethyl acetate (1500 mL, then 2250 mL). The combined ethyl acetate extracts were added dropwise to an aqueous sodium metasufite solution (228.5 g in 1.05 L water) at a reaction temperature of less than 20 C. The suspension was partitioned and the aqueous layer extracted with ethyl acetate (2*100 mL). The organic layers were combined, dried over magnesium sulfate and evaporated under reduced pressure. The residue was triturated with hexane:diethyl ethert (99:1, 100 mL) to yield 32.9 g of the title compound as a solid. 1H NMR (DMSO-D6): delta 13.9 (bs, 1H), 7.7(m,5H).

Reference： [1]Patent: US2004/63738,2004,A1

34
[ 10049-21-5 ]
Graham salt [ No CAS ]

Reference： [1]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 103, page 369 - 371
[2]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 103, page 369 - 371
[3],1947,p. 14
[4]Seifen, Oele, Fette, Wachse,1949,vol. 75,p. 533 - 535
[5],1940,vol. 21,p. 107 - 113
[6],1940,vol. 21,p. 107 - 113
    C. II,1940,p. 2358
[7]Angewandte Chemie,1965,vol. 77,p. 1056 - 1066
[8]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 103, page 369 - 371
[9]Przemysl Chemiczny,1957,vol. 13,p. 599 - 602
[10]Industrial and Engineering Chemistry,1942,vol. 34,p. 13 - 19
[11]Fette, Seifen, Anstrichmittel,1956,vol. 58,p. 81 - 87
[12]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 103, page 369 - 371
[13],1957,vol. 2,p. 706 - 713
[14]Przemysl Chemiczny,1957,vol. 13,p. 599 - 602
[15]Chimie et Industrie (Paris),1948,vol. 60,p. 541 - 549
[16]Chimie et Industrie (Paris),1952,vol. 68,p. 771 - 778
[17]Chemiker-Zeitung,1937,vol. 61,p. 793 - 795
[18]Industrial and Engineering Chemistry,1942,vol. 34,p. 13 - 19
[19],1938,vol. 16,p. 129 - 135
[20]Industrie Chimique (Paris),1950,vol. 37,p. 267 - 278
[21]Chemiker-Zeitung,1934,vol. 58,p. 677 - 680
[22]Zeitschrift fur Anorganische und Allgemeine Chemie,
    Zeitschrift fuer Anorganische und Allgemeine Chemie,1955,vol. 281,p. 262 - 283
[23]Journal of the American Chemical Society,1936,vol. 58,p. 1877 - 1877
[24]Journal of the American Chemical Society,1949,vol. 71,p. 207 - 209
[25]Zeitschrift fur Anorganische und Allgemeine Chemie,
    Zeitschrift fuer Anorganische und Allgemeine Chemie,1943,vol. 251,p. 213 - 220
[26]Journal of the American Chemical Society,1949,vol. 71,p. 207 - 209
[27],1935,vol. 2,p. 539 - 542
    C. A.,1935,p. 7728
[28]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.4, 127, page 1640 - 1643
[29],1938,vol. 32,p. 212 - 216
[30]Patent: JP1261,1962,
    Chem.Abstr.,1963,vol. 58

35
[ 10049-21-5 ]
disodium pyrophoshate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In neat (no solvent); at 210℃;Inert atmosphere;	General procedure: The TGA measurements for SDP (Fig. 3) indicated that SDP undergoes a two-stage dehydration. The first stage occurred at 210 C with a weight loss of 8%, and the second stage was dehydration at 340 C with a 15% overall weightloss. This result is in agreement with the findings by Li and Tang[18] that SDP decomposes when heated, producing disodium dihydrogen pyrophosphate, Na2H2P2O7, at 210 C with a 7.5% weight loss, followed by a second stage of decomposition between 223 C and 352 C, producing NaPO3 with a 14.9% overall weightloss.

Reference： [1]Journal of Thermal Analysis and Calorimetry,2006,vol. 86,p. 475 - 478
[2]Patent: DE342207,1921,
[3]Russian Journal of Inorganic Chemistry,1989,vol. 34,p. 659 - 662
Russ. J. Inorg. Chem. (Transl. of Zh. Neorg. Khim.),1989,vol. 34,p. 1170 - 1174
[4],1833,vol. 123,p. 253 - 253
[5]Annalen der Physik,1834,vol. 32,p. 33 - 33
[6]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: MVol., 337, page 915 - 917
[7]Journal of Alloys and Compounds,2017,vol. 690,p. 896 - 902

36
disodium hydrogenphosphate [ No CAS ]
[ 10049-21-5 ]
[ 62-54-4 ]
octacalcium phosphate pentahydrate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In water mixed dropwis at pH=5, stirred at 60°C for 3 h; XRD, SEM;
	In water pptd. by dropping 0.04 M soln. of Ca salt into soln. of na salts mixt.; stirred at 60°C and pH 5; ppt. washed (disd. H2O), dried at 37°C; detd. by SEM, TEM, SAED;

Reference： [1]Bigi, Adriana; Boanini, Elisa; Walsh, Dominic; Mann, Stephen [Angewandte Chemie - International Edition, 2002, vol. 41, # 12, p. 2163 - 2166]
[2]Arellano-Jiménez; García-García; Reyes-Gasga [Journal of Physics and Chemistry of Solids, 2009, vol. 70, # 2, p. 390 - 395]

37
[ 10049-21-5 ]
silver nitrate [ No CAS ]
silver orthophosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In water; glycerol;	General procedure: To a 100 ml glass beaker ~ 15.2 ml of deionized water were added followed by slow addition of ~ 0.8g Laponite XLG powder to the water under stirring. Over the next 30 minutes, the stirred contents transformed to a clear gel. The beaker was tared and glycerol (~ 2.0g) was added which caused the viscosity of the gel to briefly increase. The glycerol was stirred into the gel which did not seem to affect its clarity. Next, ~ 1.0 ml of warm 0.1M monosodium cyanurate solution was added and mixed into the gel to uniformity. The gel had gained a shade of opacity though it remained mostly clear. Finally, as before ~ 1.0 ml silver nitrate solution (0.1M) was added in roughly 3 equal aliquots to the gel. Upon completion of silver salt solution, we noticed slight increase in the opacity though it was much less than when hydroxyethyl cellulose was used as thickener in the example above. Over next few days we observed that the opacity decreased making the gel look practically clear. Though, the gel was thixotropic, it was practically transparent, smooth to feel and readily spreadable. The pH of the gel was ~ 7.
		In a typical procedure, DMF (5mL) and water (15mL) were mixed together to form a transparent solution. Then, 15mmoL of urea and 3mmoL of silver nitrate (AgNO3) were successively added under stirring for 10min at room temperature. Subsequently, a solution of sodium dihydrogen phosphate (NaH2PO4) (1.5mmoL, 10mL) was added dropwise. After stirring for 1h, the obtained precipitate was separated by centrifuge and washed with ethanol and distilled water for several times, respectively. Finally, the product was dried in a vacuum oven at 60C for 12h
		All the chemicals were purchased from Shanghai Reagent Company. All the chemicals and solvents were used without further purification. The pristine Ag3PO4 samples were prepared by an ion-exchange method. In a typical synthesis, 0.02 mol NaH2PO4 and 0.06 mol CH3COOAg or AgNO3 were dissolved in 100 mL of distilled water, respectively. The above solutions were mixed under constant stirring for 30 min. The as-obtained yellow precipitates were washed and kept in an oven at 60 C for 3 h. After that, the dried samples (named as AP-C or AP-N) were calcined in a muffle furnace at 200, 400 and 700 C in air for 4 h. The resultant samples are denoted as A200-C, A400-C and A700-C, or A200-N, A400-N and A700-N, respectively.

	In water; at 20℃; for 4h;	Ag3PO4/TiO2 composites were synthesized employing a simplemethod described in detail elsewhere [5]. In brief, an appropriateamount of P25 TiO2(e.g., 1.60 g for the sample containing 75% TiO2)was dispersed in 50 mL distilled water and sonicated for 15 min.After sonication, 3.06 g of AgNO3were added and the solution wasleft under stirring for 15 min. Then, 1.91 g of NaH2PO4dissolved in50 mL distilled water, were dropwise added into the solution, whichwas stirred for 240 min at room temperature. The as preparedAg3PO4/TiO2composites were filtered off, washed with water andethanol and dried in an oven at 60C for 12 h. Pure Ag3PO4wasprepared using the same method but in the absence of TiO2.
		Ag3PO4 powder utilized in this article was synthesized by the facileion-exchange method. First, 20 mL 0.5M AgNO3 solution was added to50 mL ultrapure water with a pipette. Then, the solution was vigorouslystirred for 1 h under dark. And then, 20 mL 0.5M NaH2PO4 solutionwas introduced dropwise with a syringe pump for 4 h with continuouslyvigorously stirring. The resultant precipitates were collected and washedwith ultra-pure water and ethanol for three times. Finally, theobtained precipitates were dried under 60 C in oven overnight. Thedried samples were subsequently milled into fine powders with amortar and pestle. Obtained golden-yellow powders were denoted asAPO.

Reference： [1]Bulletin of the Chemical Society of Japan,1983,vol. 56,p. 877 - 880
[2]Chemical Communications,2013,vol. 49,p. 5498 - 5500
[3]RSC Advances,2014,vol. 4,p. 37220 - 37230
[4]Patent: WO2014/179353,2014,A1 .Location in patent: Page/Page column 35
[5]Catalysis Communications,2016,vol. 77,p. 55 - 59
[6]Journal of Alloys and Compounds,2016,vol. 680,p. 436 - 445
[7]RSC Advances,2016,vol. 6,p. 85962 - 85969
[8]Catalysis Today,2017,vol. 280,p. 99 - 107
[9]Catalysis science and technology,2016,vol. 6,p. 4116 - 4123
[10]Catalysis Today,2019,vol. 335,p. 565 - 573
[11]Journal of Alloys and Compounds,2020,vol. 840

38
[ 86119-84-8 ]
[ 7647-14-5 ]
[ 10049-21-5 ]

Yield	Reaction Conditions	Operation in experiment
	With amberlite IR120; In water; at 20℃; under 760.051 Torr;pH Ca. 1.6;Flow reactor;	Step 0: The column was filled with resin particles for the apparent volume of 22 mL.Then, it was completed with pure water in order to facilitate the contact of reactants withresin particles during exchange process. The cationic exchange capacity of the columnwas 29.8 mEq. The same resin sample was used for all the tests in this report.? Step 1: The resin in the column was in the protonated form (R-SO3-H). For the firstsynthesis step (Equation (3)), 340 mL of NaCl (100 mM) passed through the column atthe liquid flow rate of 2-20 mL min-1, followed by rinsing with 50 mL of water.? Step 2: The resin was now saturated with sodium cations (R-SO3-Na). For the secondsynthesis step (Equation (4)), 340 mL of H3PO4 (100 mM) passed through the column atthe same liquid flow rate as for the first synthesis step (2-20 mL). The column was alsorinsed with 50 mL of water.? Step 3: To regenerate the column, 340 mL of HCl (100 mM) was pumped through thecolumn at the flow rate of 2 mL min-1. This quantity of HCl was largely sufficient foracidifying the quantity of resin present in the column. Then, the column was rinsed with50 mL of water following the regeneration

Reference： [1]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 88, page 341 - 344
[2]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 88, page 341 - 344
[3]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 88, page 341 - 344
[4]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 88, page 341 - 344
[5]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: Na: SVol.1, 88, page 341 - 344
[6]Phosphorus, Sulfur and Silicon and the Related Elements,2015,vol. 190,p. 1743 - 1748
[7]Patent: DE650258,1933,
[8]Patent: DE547882,1928,
[9]Patent: FR720577,1932,
C. I,1932,p. 2983
[10]Patent: FR35834,1930,
[11]Patent: FR659360,1928,

39
[ 10049-21-5 ]
[ 62-54-4 ]
brushite [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With chitosan In water chitosan-coated glass substrate transferred into soln. of polyaspartic acid and calcium acetate, then NaH2PO4 soln. added and mixt. was kept at 18°C for (few min - several h); substrate washed with water and dried at room temp.; XRD;

Reference： [1]Shi, Yi; Zhang, Yahong; Yang, Wuli; Tang, Yi [Chemical Communications, 2009, # 4, p. 442 - 444]

40
[ 10049-21-5 ]
sodium metaphosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In melt; at 300 - 900℃;	A sodium phosphate glass in the system Na2O-P2O5 was prepared by the conventional melt quenching technique from NaH2PO4 as starting material. A quantity of the chemical component was first heated at 300C for 1h for the purpose of excluding water, and then it was melted in an electric furnace at 900C for 2h in platinum crucible so that a homogeneously melt was obtained. The melt was then cast into a steel mould, the glass was annealed at 300C and was cooled slowly at room temperature.

Reference： [1]Journal of Alloys and Compounds,2013,vol. 577,p. 543 - 549

41
[ 7758-19-2 ]
[ 10049-21-5 ]
[ 513-35-9 ]
[ 15971-29-6 ]
[ 13041-62-8 ]

Yield	Reaction Conditions	Operation in experiment
55%	In water; tert-butyl alcohol;	Example 20 Preparation of 4-methoxy-1-naphthoic acid 2. 4-Methoxy-1-naphthaldehyde (10g, 53.72mmol) was dissolved in t-butanol (75ml) and 2-methyl-2-butene (35ml) was added at room temperature. A solution of sodium chlorite (7.99g, 70.63mmol) and sodium dihydrogen orthophosphate (9.15g, 76,27mmol) in water (50ml) was added dropwise. The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo and the residue was washed with a solution of 2MHCl (100ml) and the solid was filtered and washed with dichloromethane (100ml) and water (100ml) and dried in vacuo. The solid was recrystallised from methanol to give 5.95g (55%) of 4-methoxy-1-naphthoic acid 2 as cream crystals.

Reference： [1]Patent: EP2698385,2014,A1 .Location in patent: Page/Page column

42
[ 10049-21-5 ]
[ 7646-78-8 ]
tin(IV) phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With nitric acid; In water; at 20℃; for 1h;pH 0 - 1;	A simple and ambient sol-gel method was used for the synthesis of styrene-tin(IV) phosphate nanocomposite ion exchanger (ST/TPNC). The synthesis of nanocomposite ion exchanger has been carried out in two stages. In the first stage, inorganic precipitates of tin (IV) phosphate (TP) were prepared by mixing sodium dihydrogen phosphate (0.1 M) and tin (IV) chloride (0.1 M) in 1:1 volume ratio with constantstirring at room temperature. 1 M HNO3 was added to maintain the pH of the mixture solution between 0 and 1. The resultant slurry containing the precipitates of tin(IV) phosphate was stirred for 1 h.

Reference： [1]Journal of Alloys and Compounds,2014,vol. 606,p. 105 - 111

43
[ 10049-21-5 ]
bismuth (III) nitrate pentahydrate [ No CAS ]
bismuth phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In ethylene glycol; at 160℃; for 16h;Autoclave;	General procedure: All chemicals were purchased from Sinopharm Chemical Reagent Co., Ltd. (China), which were used as received without further purification. BiPO4/BiOBr composites were synthesized via a facile one-pot solvothermal method. In a typical process, the precursor solution was prepared by dissolving 4 mmol of Bi(NO3)3?5H2O and appropriate stoichiometric amount of cetyl triethylammnoniumbromide (CTAB) and NaH2PO4 into 70 ml of ethylene glycol (EG). After stirring for 30 min, the resultant precursor solution was transferred into a 100 ml Teflon-lined stainless steel autoclave. The autoclave was sealed and maintained at 160 C for 16 h and allowed to cool down to room temperature naturally. The precipitate was washed with absolute ethanol and distilled water for three times, respectively, and dried at 80 C in air. According to the above process,a series of BiPO4/BiOBr photocatalysts with the different molar ratios were prepared by adjusting the concentrations of PO43- and Cl- ions.The prepared samples were denoted as x% BiPO4, where x refers to the molar ratio of BiPO4 (x = 5%, 10% and 20%). For comparison, pure BiPO4 and BiOBr were also prepared using the same method except the absence of CTAB or NaH2PO4
	In ethylene glycol; at 160℃; for 16.5h;Autoclave;	In a typical process, the precursor solution was prepared by dissolving2 mmol Bi(NO3)35H2O and an appropriate stoichiometric amount ofNaH2PO4 in 35 mL of ethylene glycol. After stirring for 30 min, theresulting precursor solution was transferred into a 50-mL Teflon-linedstainless steel autoclave. The autoclave was sealed and maintained at160 C for 16 h, before allowing to cool to room temperature naturally.The precipitate was washed with absolute ethanol and distilled water forthree times, and then dried at 80 C in air.

Reference： [1]Materials Research Bulletin,2015,vol. 63,p. 187 - 193
[2]Journal of Physics and Chemistry of Solids,2018,vol. 113,p. 142 - 150

44
[ 10049-21-5 ]
[ 143-19-1 ]
iron(II) chloride [ No CAS ]
sodium iron phosphate [ No CAS ]

Reference： [1]Journal of Materials Chemistry A,2015,vol. 3,p. 8265 - 8271

45
[ 10049-21-5 ]
[ 143-19-1 ]
[ 555-36-2 ]
O₄P^(3-)*Na⁽¹⁺⁾*Fe⁽²⁺⁾ [ No CAS ]

Reference： [1]Journal of Materials Chemistry A,2015,vol. 3,p. 8265 - 8271

46
[ 10049-21-5 ]
bismuth (III) nitrate pentahydrate [ No CAS ]
bismuth(III) phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		All chemicals were purchased fromSinopharm Chemical Reagent Co., Ltd. (China), which were used as received without further purification. BiPO4/BiOBr composites were synthesized via a facile one-pot solvothermal method. In a typical process, the precursor solution was prepared by dissolving 4mmol of Bi(NO3)3.5H2O and appropriate stoichiometric amount of cetyltriethylammnoniumbromide (CTAB) and NaH2PO4 into 70 ml of ethylene glycol (EG). After stirring for 30 min, the resultant precursor solution was transferred into a 100ml Teflon-lined stainless steel autoclave. The autoclave was sealed and maintained at 160 C for 16 h and allowed to cool down to room temperature naturally. The precipitate was washed with absolute ethanol and distilled water for three times, respectively, and dried at 80 C in air. According to the above process, a series ofBiPO4/BiOBr photocatalysts with the different molar ratios were prepared by adjusting the concentrations of PO43- andCl- ions. The prepared samples were denoted as x% BiPO4, where x refers to the molar ratio of BiPO4 (x = 5%,10% and 20%). For comparison, pure BiPO4 and BiOBr were also prepared using the same method except the absence of CTAB or NaH2PO4.
	In water; at 70℃; for 2h;Sonication;	General procedure: In a typical synthesis, Bi (NO3)3.5H2O (4.85 g) and [HMIM]H2PO4 (1.85 g) or NaH2PO4 (0.6 g) were placed in a beaker.Deionized water (100 mL) was added to above solution; the mixture was magnetically stirred to form a homogeneous solution. The reaction of mixture was carried out under ultrasound at 70C for 2 h. The white precipitate was separated by centrifugalization, washed several times with distilled water and ethanol, and dried at 90C for 6 h. The samples denoted as IL-BiPO4 and Na-BiPO4 represent the samples prepared in the presence of [HMIM] H2PO4 and NaH2PO4.

Reference： [1]Materials Research Bulletin,2015,vol. 63,p. 187 - 193
[2]RSC Advances,2015,vol. 5,p. 100625 - 100632
[3]Inorganic and Nano-Metal Chemistry,2017,vol. 47,p. 1328 - 1333

47
[ 10049-21-5 ]
silver nitrate [ No CAS ]
silver orthophosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		AgNO3 (6.2 g) was dissolved in deionized water (20 mL) and the ammonia solution (0.1 mol L-1) was added drop wisely to the above solution to form a transparent silver-ammino complex. The Tollens? reagent (0.15 mol L-1) was prepared after the silver-ammino complex being diverted into a volumetric flask (250 mL). The NaH2PO4 solution (5 mL, 0.05 mol L-1) was added into a clean beaker with 40 mL deionized water which 0.02 g of polyacryl-amide (PAM) was dissolved in. The Tollens? reagent (5 mL) was introduced into the above beaker by a microliter syringe (The measuring range was 10 mL) under different conditions via photocontrol. These conditions included dark field, visible light, ultraviolet light and monochromatic light sources (yellow, green,red). These monochromatic lights were produced by optical grating transformed from a tungsten lamp (15 W). The products were collected after centrifugalization and washed with deionized water and alcohol for several times, respectively. Finally, the products were kept in the absolute ethyl alcohol.
		General procedure: Ag3PO4/diatomite was synthesized by a simple hydrothermal method. 0.419 g of fine diatomite was dispersed in 50 ml distilled water and magnetically stirred for 2 hours to obtain a uniform suspension. 30 ml 0.4 mol/L AgNO3 aqueous solution was dropwise added to the above suspension to obtain a homogeneous suspension. After magnetic stirring for 30 min, the positive Ag+ ions would electrostatically assembled on the surface of the negative charged diatomite. Then, 20 ml of 0.21 mol/L NaH2PO4 aqueous solution was dropwise added to the above suspension under vigorous magnetic stirring under dark conditions, and the reaction was continued for 10 min. The yellow precipitate of Ag3PO4/diatomite was collected by centrifugation and then was washed with deionized water and ethanol for three times. Finally, the precipitate was transferred to a 50 ml high pressure reaction kettle with a certain amount of deionized water to achieve the appropriate filling degree. The reactor is placed in a vacuum drying oven heated at 140C for 15 h. After the natural cooling to room temperature, the sediment was separated by ethanol washing centrifuge. The samples were dried in a vacuum drying oven at 80C for 6 h. The Ag3PO4 sample was prepared under the same condition without adding of diatomite.

Reference： [1]Materials Research Bulletin,2014,vol. 60,p. 783 - 793
[2]Journal of Alloys and Compounds,2019,vol. 775,p. 845 - 852

48
[ 10049-21-5 ]
[ 1186-10-3 ]
[ 557-34-6 ]
3Zn⁽²⁺⁾*1.5O₄P^(3-)*0.5HO₄P^(2-)*1.5Na⁽¹⁺⁾*C₃H₆BrO₃P^(2-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%		The mixture of the diethyl 3-bromopropylphosphonate(5 mmol), 8 mL of concentrated hydrochloric acid (36%) and25 mL of acetic acid was stirred at 80C for 24 h, followed bycooling down and evaporating under reduced pressure as wellas neutralizing. Sodium dihydrogen phosphate (1.56 g, 10 mmol)in 8 mL of deionized water and zinc acetate (3.29 g, 15 mmol)in 10 mL of deionized water were added while gradually raisingthe temperature to 66C. And then the mixture was retaining for72 h and laying for another 18 h at room temperature. The whitepowder zinc phosphonates were obtained by filtering, washingthoroughly with deionized water and drying in vacuum. Yield:92.0%. Found: C, 5.65; H, 0.92. Calc. for C3H6O11P3BrNa2Zn3: C,5.70; H, 0.95%.

Reference： [1]Journal of Molecular Catalysis A: Chemical,2016,vol. 416,p. 147 - 153

49
[ 10049-21-5 ]
calcium(II) nitrate tetrahydrate [ No CAS ]
[ 1310-73-2 ]
hydroxy-apatite [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	In water; at 80℃; for 3h;pH 5;	General procedure: All reagents were ACS-reagent grade. Distilled water was used for the preparation of solutions. The procedure for the preparation of CaApOH is as follows: samples of 1.2g Ca(NO3)2·4H2O, 0.5g Na3PO4, and 0.04g NaOH were placed in the bottom of a 125mL Erlenmeyer flask equipped with a standard taper joint bearing a condenser with a thermometer inserted in the condenser and held slightly above the bottom of the flask (but in the solution) by a thin slice of suction tubing at the top of the condenser. The flask was placed on a heating/stir plate and 50mL of distilled water was added. The solution was stirred magnetically and heated to 80C for approximately 3h. The pH was measured, but not adjusted, at the beginning and at the end of the 3h of digestion using Hydrion pH 1.0-12.0 paper. [In order to determine the effect of pH, the pH was adjusted with 3 M NaOH for some samples at the beginning and during digestion.] Stirring was then discontinued and the solution was allowed to cool and settle overnight. The precipitate was suction filtered in a medium porosity glass filter crucible and washed 5 times with a total of about 150mL of distilled water. The precipitate was dried in a vacuum drying oven at 110 C for at least 4h and then ground with a mortar and pestle and stored in a closed, parafilmed vial.

Reference： [1]Polyhedron,2017,vol. 127,p. 403 - 409

50
[ 10049-21-5 ]
[ 6047-25-2 ]
Iron phosphate hydroxide hydrate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With nitric acid In water at 220℃; for 6h; Autoclave; High pressure;	2.2. Synthesis Iron phosphate hydroxide hydrate (Fe1.19(PO4)(OH)0.57(H2O)0.43) was prepared by hydrothermal reaction. First,2.0 mmol sodium dihydrogen phosphate (NaH2PO4.2H2O, Aldrich)and 2.0 mmol iron(II) oxalate dihydrate (FeC2O4.2H2O, Aldrich)were dissolved in 60 mL distilled water with 1.5 ml nitric acid(HNO3, Aldrich).The reaction mixture was then sealed into a125 mL Teflon-lined stainless steel autoclave, heated at 220 C for6 hours and cooled to room temperature. After reaction, theresulting light yellow powder was poured through afilter paper ina buchner funnel, washed with distilled water and dried in vacuumat 120 C for 10 hours. Samples with carbon black addition wereprepared using the same synthesis procedure by adding the carbonblack (Alfa Aesar) in the reaction mixture. The amounts of carbonwere 2.77, 5.55 and 8.32 mmol, respectively.

Reference： [1]Karegeya, Claude; Mahmoud, Abdelfattah; Cloots, Rudi; Vertruyen, Bénédicte; Boschini, Frédéric [Electrochimica Acta, 2017, vol. 250, p. 49 - 58]

51
tantalum(V) oxide [ No CAS ]
[ 1633-05-2 ]
[ 10049-21-5 ]
[ 497-19-8 ]
tridecasodium distrontium ditantalum nonaphosphate [ No CAS ]