tolueno

1
HO
S
O

HS

Br

HO

H
O

6
O
O

7
O

OH

O
Cl
N
N
Cl

8
O

Cl
NH
N
Cl

Cl

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tolueno

HO

S
O

Rx-ID: 33899955
Yield

95 %

Conditions & References

Example Name 17
Example 17: Transfer hydrogenolysis of phenylmethanesulfonic acidPd/ C (5 molpercent) is weighed
into a reaction flask. A solvent mixture consisting of ethanol and water (4: 1) and ammonium formate
(30 molpercent) is added, the reaction flask is capped with a rubber septa and the mixture is heated
(80 C) for 2 minutes. Formic acid (3 equivalents) and then phenylmethanesulfonic acid (1 equivalents) are added by syringe. The reaction is run for 10-40 minutes and the reaction is quenched with
brine. The product is extracted by DCM and the organic phase is dried by Na2S04. The product toluene
was analyzed by NMR and produced in 95percent yield.
With formic acid, ammonium formate, 5 palladium on charcoal in ethanol, water, T= 80 C
Patent; SAMEC, Joseph; LUNDSTEDT, Anna; SAWADJOON, Supaporn; KAT2BIZ AB C/O INTERPARES KONSULT AB; WO2012/121659; (2012); (A1) English

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tolueno

HO
S

HS

Rx-ID: 3385268
Yield

93 %

Conditions & References

With dihydrogen peroxide, methyltrioxorhenium (VII) in acetonitrile, T= 20 C

Ballistreri, Francesco P.; Tomaselli, Gaetano A.; Toscano, Rosa M.; Tetrahedron Letters; vol.
49; nb. 20; (2008); p. 3291 - 3293

92 %

With dihydrogen peroxide, trichlorophosphate in water, Time= 1.08333h, T= 80 C, Micellar solution

Bahrami, Kiumars; Khodaei, Mohammad M.; Abbasi, Jamshid; Synthesis; vol. 2012; nb. 2;
(2012); p. 316 - 322

50 %

With tetrakis(pyridine)silver(II) peroxodisulfate in acetonitrile, Time= 2h, Heating

Firouzabadi, Habib; Salehi, Peyman; Mohammadpour-Baltork, Iraj; Bulletin of the Chemical Society of Japan; vol. 65; nb. 10; (1992); p. 2878 - 2880

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tolueno

3
Br

HS

Rx-ID: 573484
Yield

96 %

Conditions & References

Stage 1: With potassium carbonate, ethanethiolic acid in methanol, Time= 0.5h, T= 20 C

Stage 2: With potassium carbonate in methanol, Time= 0.5h, T= 20 C
Han, Chien-Chung; Balakumar; Tetrahedron Letters; vol. 47; nb. 47; (2006); p. 8255 - 8258

88 %

With hydrosulfide exchange resin (from Amberlite IRA-400), triethyl amine hydrochloride in methanol,
Time= 1h, Ambient temperature
Choi; Yoon; Synthesis; nb. 4; (1995); p. 373 - 375

80 %

With 1-(2-hydroxyethyl)-4,6-diphenylpyridin-2-thione in benzene, Time= 20h, T= 20 C

Molina, P.; Alajarin, M.; Vilaplana, M. J.; Katritzky, A. R.; Tetrahedron Letters; vol. 26; nb. 4;
(1985); p. 469 - 472

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only. Reaxys and the Reaxys trademark are owned and protected by Reed
Elsevier Properties SA and used under license.

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tolueno

4
HO

Br

Rx-ID: 817410
Yield

100 %

Conditions & References

With 1,1,1,2,2,2-hexamethyldisilane, pyridinium hydrobromide perbromide in chloroform, Time=

0.5h, T= 25 C
Olah, George A.; Gupta, B. G. Balaram; Malhotra, Ripudaman; Narang, Subhash C.; Journal of
Organic Chemistry; vol. 45; nb. 9; (1980); p. 1638 - 1639

100 %

Example Title Step-II (Preparation of benzyl bromides)

General procedure: benzyl alcohols (1 mmol) in dry benzene (15 mL) and phosphorus tribromides
(0.5 mL) and stirred at room temperature to get respective benzyl bromides in quantitative yields,
usual work-up.
With phosphorus tribromide in benzene, T= 20 C
Parihar, Swati; Kumar, Amit; Chaturvedi, Amit K.; Sachan, Naresh Kumar; Luqman, Suaib;
Changkija, Bendangla; Manohar, Murli; Prakash, Om; Chanda; Khan, Feroz; Chanotiya; Shanker, Karuna; Dwivedi, Anila; Konwar, Rituraj; Negi, Arvind S.; Journal of Steroid Biochemistry and
Molecular Biology; vol. 137; (2013); p. 332 - 344

99 %

Stage 1: With 1,2,3-Benzotriazole, thionyl chloride in dichloromethane, Time= 0.0833333h

Stage 2: With potassium bromide in dichloromethane, DMFA, Time= 0.5h
Bandgar, Babasaheb P.; Bettigeri, Sampada V.; Monatshefte fur Chemie; vol. 135; nb. 10; (2004);
p. 1251 - 1255

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5/10

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tolueno

5
O

HO

Rx-ID: 601797
Yield

100 %

Conditions & References

With Triethoxysilane, potassium fluoride, Time= 36h, Product distribution

Corriu, R. J. P.; Perz, R.; Reye, C.; Tetrahedron; vol. 39; nb. 6; (1983); p. 999 - 1010

100 %

With n-butyllithium, 2,5-Dihydroanisole in tetrahydrofuran, Petroleum ether, Time= 5h, Ambient temperature, Product distribution
Hiramatsu, Mitsuo; Fujinami, Tatsuo; Sakai, Shizuyoshi; Chemistry Letters; (1982); p. 7 - 8

100 %

With sodium tetrahydroborate in methanol, dichloromethane, Time= 0.00166667h, T= 22 C, also in

other alcohols, also at other temperatures, also the reduction time required for 50percent reduction
Ward, Dale E.; Rhee, Chung K.; Canadian Journal of Chemistry; vol. 67; (1989); p. 1206 - 1211

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tolueno

H
O

Rx-ID: 11173419
Yield

99 %

Conditions & References

Example Title 4.4 Partial reduction of aromatic esters to corresponding aldehydes (Table 4)
General procedure: The following experimental procedure for the partial reduction of ethyl benzoate
to benzaldehyde is representative. A dry and argon-flushed flask, equipped with a magnetic stirring
bar and a septum, was charged with morpholine (0.18mL, 2.1mmol) and THF (10mL). After cooling
to 0C, DIBALH (2.0mL, 1.0M in hexane, 2.0mmol) was added dropwise and the mixture was stirred
for 3h at the same temperature. Ethyl benzoate (0.14g, 1.0mmol) was added slowly to the reaction
mixture, which was stirred for 10min. Then, DIBALH (1.1mL, 1.0M in hexane, 1.1mmol) was added
and the mixture was stirred for 10min again. The reaction was stopped aqueous 1N HCl (10mL) and
extracted with diethyl ether (210mL). The combined organic layers were dried over MgSO4, filtered,
and concentrated under reduced pressure. Purification of the residue by short column chromatography on silica gel using Et2O yielded benzaldehyde (106mg, 99percent).
Stage 1: With morpholine, diisobutylaluminium hydride in tetrahydrofuran, hexane, Time= 3.16667h,
T= 0 C, Inert atmosphere
Stage 2: With diisobutylaluminium hydride in tetrahydrofuran, hexane, Time= 0.166667h, T= 0 C,
Inert atmosphere
Jeon, Ah Ram; Kim, Min Eai; Park, Jae Kyo; Shin, Won Kyu; An, Duk Keun; Tetrahedron; vol.
70; nb. 29; (2014); p. 4420 - 4424

79 %

With n-butyllithium, diisobutylaluminium hydride, tert-butyl alcohol in tetrahydrofuran, hexane, T= 0

C
De Munoz, Juan M.; Alcazar, Jesus; De La Hoz, Antonio; Diaz-Ortiz, Angel; European Journal of
Organic Chemistry; nb. 2; (2012); p. 260 - 263

84 %
With sodium diisobutyl(t-butoxy)aluminum hydride in tetrahydrofuran, hexane, Time= 6h, T= 0 C
Chromat. Song, Jung In; An, Duk Keun; Chemistry Letters; vol. 36; nb. 7; (2007); p. 886 - 887

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7/10

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tolueno

O
OH

Cl
N

N
Cl

Rx-ID: 35150705
Yield

92 %

Conditions & References

Example Name 14
Example Title Ethyl benzoate (6m)
General procedure: Alcohol (2 or 5, 5.31 mmol, 1 equiv) and 2-acylpyridazin-3(2H)-ones (1k or 4,
6.37 mmol, 1.2 equiv) were placed in a capped vial without solvent or in the presence of tetrahydrofuran (5 mL, 6f and 6g) at room temperature. The resulting mixture was irradiated in aMWoven
(300Woutput,1378 kPa) at 150 C for 5 min, until 1k or 4 was consumed. The reaction was monitored
by TLC. After cooling Phenyl acetate (3) of the reaction vial, the product was extracted with dichloromethane (6 mL). The reaction mixture was filtered, and the resultant filtrate was evaporated under
reduced pressure. The resulting residue was purified further by silica gel column chromatography to
give the corresponding esters 3 and 6Ethyl benzoate (6m) Yield: 601 mg, 92percent. Colorless oil.
IR (KBr, CH2Cl2) 3064, 3032, 2982, 2936, 2903, 1717, 1599, 1450, 1391, 1366, 1308, 1272, 1171,
1107, 1069, 1024, 871, 849 cm-1. 1H NMR (300 MHz, CDCl3) 1.28 (t, 3H, J1 and J2=7.1 Hz),
4.33-4.40 (m, 2H), 7.38-7.43 (m, 2H), 7.50-7.55 (m, 1H), 8.02-8.05 (m, 2H). 13C NMR (75 MHz,
CDCl3) 14.30, 60.89, 128.29, 129.51, 130.51, 132.77, 166.56. HRMS (m/z): [M]+ calcd for
C9H10O2 150.0681. Found: 150.0685.
in tetrahydrofuran, Time= 0.0833333h, T= 150 C, p= 10336Torr , Microwave irradiation
Kim, Bo Ram; Sung, Gi Hyeon; Lee, Sang-Gyeong; Yoon, Yong Jin; Tetrahedron; vol. 69; nb.
15; (2013); p. 3234 - 3237

92 %

Example Title General Procedure for the Conversion of N-Acylpyridazin-3(2H)-ones into the Corresponding Ester
General procedure: Alcohol(1, 5.31 mmol, 1 equiv.) and 2-acylpyridazin-3(2H)-ones (2,6.37 mmol,
1.2 equiv.) were placed in a culture tube (Pyrexbrand 9825 culture tube with screw cap), sealed, and
heatedto 100 C. The resulting mixture was kept at this temperatureuntil 1 disappeared (as determined by TLC analysis). Aftercooling of the tube, dichloromethane (5-6 mL) was added tothe mixture
with stirring until the reaction mixture wasdissolved. After removing 4,5-dichloropyridazin-3(2H)-oneby filtration, the resulting filtrate was evaporated underreduced pressure. The resulting residue was
further purifiedby silica gel column chromatography to give the correspondingesters 3.
in neat (no solvent), Time= 2h, T= 100 C, Sealed tube, Green chemistry
Kim, Bo Ram; Sung, Gi Hyeon; Ryu, Ki Eun; Kim, Jeum-Jong; Yoon, Yong-Jin; Bulletin of the
Korean Chemical Society; vol. 34; nb. 11; (2013); p. 3410 - 3414

72 %

Example Title Synthesis of 5ei; General Procedure:

General procedure: To a solution of alcohol 2 (1 equiv, 2 mmol) in THF (20 mL), AlCl3 (1 equiv) was
added followed by stirring for 1 min. 2-Aroyl-4,5-dichloropyridazin-3(2H)-one 1 (1 equiv) was added
and the mixture was stirred at room temperature until the alcohol was consumed. The reaction was
quenched by the addition of H2O (20 mL), followed by stirring for 10 min at room temperature, and
then neutralized with a saturated solution of NaHCO3. After the addition of further H2O (20 mL) and
CH2Cl2 (40 mL), the resulting organic layer was separated,and H2O (10 mL) and a saturated solution
of NaCl (20 mL)were added. The organic layer was then separated and dried over anhydrous MgSO4.
The solvent was evaporated under reduced pressure and the resulting residue was applied to the top
of an open-bed silica gel column. The column was eluted with CH2Cl2 (for 5gi) or n-hexaneEtOAc
(3:1 v/v for 5eand 5f). Fractions containing the product were combined and evaporated under reduced
pressure to give the desired esters.Fractions containing 4,5-dichloropyridazin-3(2H)-one were combined and evaporated under reduced pressure to quantitatively give reusable 4,5-dichloropyridazin-3(2H)-one.
Stage 1: With AlCl3, aluminium chloride in tetrahydrofuran, Time= 0.0166667h
Stage 2: in tetrahydrofuran, Time= 0.25h, T= 20 C

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tolueno

Kim, Bo Ram; Sung, Gi Hyeon; Ryu, Ki Eun; Yoon, Hyo Jae; Lee, Sang-Gyeong; Yoon, YongJin; Synlett; vol. 25; nb. 13; (2014); p. 1909 - 1915; Art.No: ST-2014-U0361-L

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9/10

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tolueno

O
NH

N
Cl

Cl

Cl
N

Cl

N
Cl

Rx-ID: 1699242
Yield

82 %

Conditions & References

With triethylamine in dichloromethane, Time= 0.166667h, T= -10 C

Kang, Young-Jin; Chung, Hyun-A; Kim, Jeum-Jong; Yoon, Yong-Jin; Synthesis; nb. 6; (2002);
p. 733 - 738
With triethylamine in benzene, T= 50 C
Carmellino; Massolini; Pagani; Zani; Leri; Farmaco; vol. 48; nb. 10; (1993); p. 1427 - 1438

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