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All 4 posts Subject: Preparation of 1,4-diMeO-2,5-diBr-benzene Please login to post Down

Aurelius
(Hive Addict)
01-16-03 19:57
No 398778
      Preparation of 1,4-diMeO-2,5-diBr-benzene

Method for the Preparation of 1,4-dimethoxy-2,5-dibromobenzene:

Methods of Prep:

1,4-dimethoxy-2,5-dibromobenzene has been prepared by the bromination of 1,4- dimethoxybenzene in acetic acid w/o using potassium acetate(1), bromination of 3-bromo-2,6-dimethoxybenzene (3) as well as diazotization followed by sandmeyer reaction of 5-amino-2-bromo-1,4-dimethoxybenzene (3). The present procedure is a variant of direct bromination of 1,4-dimethoxybenzene in acetic acid.

Direct bromination of polyphenolic ethers w/o the use of trapping agent for hydrogen bromide usually results in poor yields. Contamination from gummy side products makes the work-up tedious. The present use of potassium acetate as trap for the HBr considerably improves the products yield (from 40% reported (2) w/o the use of the trap to 72-75% in the present procedure). The work-up is also considerably simplified. Functionalization of the aromatic nucleus by bromine in poly phenolic ethers has considerable synthetic utility since the bromine atom is amenable to SN Ar substitutions, e.g. by cyano group, useful for infoduction of side chains(2)

Defense Research Lab. (1970)

1. J. Habermann, Ber. 11: 1034 (1878); H.E. Ungnade and K. T. Zilch. JOC 16:64 (1966).
2. W. E. Noland and F. J. Baude, JOC 31, 332 (1966).
3. L. Rubenstein, JOCS 127, 1998 (1925).

foxy2
(Distinctive Doe)
01-18-03 07:15
No 399319
      1,4-dibromo-2,5-dimethoxybenzene synthesis

Post 294110 (foxy2: "2,5-dibromo-1,4-hydroquinone synthesis", Novel Discourse)

Just thought I'd add this.

GC_MS
(Hive Bee)
01-26-03 18:35
No 401633
User Picture       H2O2/HBr

There is also "Simple and practical halogenation of arenes, alkenes and alkynes with hydrohalic acid/H2O2 (or TBHP)", N B Barhate et al, Tetrahedron 55 (1999) 11127-11142. It is mentioned on Rh's site.
Standard procure: N,N-dimethyl-(2-bromo-5-methoxy)benzamide: A solution of TBHP (70% aq, 0.15 mL, 1.17 mmol) was added to a cooled mixture of HBr (48% aq, 0.20 mL, 1.17 mmol) in MeOH (5 mL) and the mixture stirred for 5 min. To this solution N,N-dimethyl(3-methoxy)benzamide (0.21 g, 1.17 mmol) was added, stirred for 30 min and then refluxed for 6 h. On completion of the reaction (TLC) the solvent was evaporated and the product taken in 5 mL water, extracted with dichloromethane (3 x 15 mL) and residue was purified by flash column chromatography over silica gel (10% EtOAc in petroleum ether) to affor pure product as thick yellow oil (0.28 g. 98%)
1,4-dimethoxybenzene can be brominated following this procedure.
- TBHP (4.0 eq), HBr (4.0 eq) -> 2,5-dibromo-1,4-dimethoxybenzene, 98% yield
- H2O2 (4.0 eq), HBr (4.0 eq) -> 2,5-dibromo-1,4-dimethoxybenzene, 99% yield
- TBHP (1.0 eq), HBr (1.0 eq) -> 2-bromo-1,4-dimethoxybenzene, 89% yield

(TBHP = tert-butylhydroperoxide, 70%)

Ave Hive, synthetisandi te salutant!

Rhodium
(Chief Bee)
10-15-04 21:50
No 536005
User Picture       Synthesis of 2-Hydroxy-5-Methoxybenzaldehyde

_{This article is referenced above in in Post 398778 (Aurelius: "Preparation of 1,4-diMeO-2,5-diBr-benzene", Novel Discourse)}

Substitution in Derivatives of Quinol Ethers
Leon Rubenstein
J. Chem. Soc. 127, 1998-2004 (1925) (https://www.rhodium.ws/pdf/4-methoxyphenol.reimer-tiemann.pdf)

Synthesis of 2-Hydroxy-5-Methoxybenzaldehyde by the Reimer-Tiemann formylation of 4-Methoxyphenol, as well as several brominations and nitration of 2,5-Dimethoxybenzaldehyde, 2-Hydroxy-5-Methoxybenzaldehyde and other derivatives.

^{The Hive - Clandestine Chemists Without Borders}

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	All 4 posts		Subject: Preparation of 1,4-diMeO-2,5-diBr-benzene		Please login to post		Down


		Aurelius (Hive Addict) 01-16-03 19:57 No 398778				Preparation of 1,4-diMeO-2,5-diBr-benzene
						Method for the Preparation of 1,4-dimethoxy-2,5-dibromobenzene: Methods of Prep: 1,4-dimethoxy-2,5-dibromobenzene has been prepared by the bromination of 1,4- dimethoxybenzene in acetic acid w/o using potassium acetate(1), bromination of 3-bromo-2,6-dimethoxybenzene (3) as well as diazotization followed by sandmeyer reaction of 5-amino-2-bromo-1,4-dimethoxybenzene (3). The present procedure is a variant of direct bromination of 1,4-dimethoxybenzene in acetic acid. Direct bromination of polyphenolic ethers w/o the use of trapping agent for hydrogen bromide usually results in poor yields. Contamination from gummy side products makes the work-up tedious. The present use of potassium acetate as trap for the HBr considerably improves the products yield (from 40% reported (2) w/o the use of the trap to 72-75% in the present procedure). The work-up is also considerably simplified. Functionalization of the aromatic nucleus by bromine in poly phenolic ethers has considerable synthetic utility since the bromine atom is amenable to SN Ar substitutions, e.g. by cyano group, useful for infoduction of side chains(2) Defense Research Lab. (1970) 1. J. Habermann, Ber. 11: 1034 (1878); H.E. Ungnade and K. T. Zilch. JOC 16:64 (1966). 2. W. E. Noland and F. J. Baude, JOC 31, 332 (1966). 3. L. Rubenstein, JOCS 127, 1998 (1925).



		foxy2 (Distinctive Doe) 01-18-03 07:15 No 399319				1,4-dibromo-2,5-dimethoxybenzene synthesis
						Post 294110 (foxy2: "2,5-dibromo-1,4-hydroquinone synthesis", Novel Discourse) Just thought I'd add this.



		GC_MS (Hive Bee) 01-26-03 18:35 No 401633				H2O2/HBr
						There is also "Simple and practical halogenation of arenes, alkenes and alkynes with hydrohalic acid/H2O2 (or TBHP)", N B Barhate et al, Tetrahedron 55 (1999) 11127-11142. It is mentioned on Rh's site. Standard procure: N,N-dimethyl-(2-bromo-5-methoxy)benzamide: A solution of TBHP (70% aq, 0.15 mL, 1.17 mmol) was added to a cooled mixture of HBr (48% aq, 0.20 mL, 1.17 mmol) in MeOH (5 mL) and the mixture stirred for 5 min. To this solution N,N-dimethyl(3-methoxy)benzamide (0.21 g, 1.17 mmol) was added, stirred for 30 min and then refluxed for 6 h. On completion of the reaction (TLC) the solvent was evaporated and the product taken in 5 mL water, extracted with dichloromethane (3 x 15 mL) and residue was purified by flash column chromatography over silica gel (10% EtOAc in petroleum ether) to affor pure product as thick yellow oil (0.28 g. 98%) 1,4-dimethoxybenzene can be brominated following this procedure. - TBHP (4.0 eq), HBr (4.0 eq) -> 2,5-dibromo-1,4-dimethoxybenzene, 98% yield - H2O2 (4.0 eq), HBr (4.0 eq) -> 2,5-dibromo-1,4-dimethoxybenzene, 99% yield - TBHP (1.0 eq), HBr (1.0 eq) -> 2-bromo-1,4-dimethoxybenzene, 89% yield (TBHP = tert-butylhydroperoxide, 70%) Ave Hive, synthetisandi te salutant!



		Rhodium (Chief Bee) 10-15-04 21:50 No 536005				Synthesis of 2-Hydroxy-5-Methoxybenzaldehyde
						_{This article is referenced above in in Post 398778 (Aurelius: "Preparation of 1,4-diMeO-2,5-diBr-benzene", Novel Discourse)} Substitution in Derivatives of Quinol Ethers Leon Rubenstein J. Chem. Soc. 127, 1998-2004 (1925) (https://www.rhodium.ws/pdf/4-methoxyphenol.reimer-tiemann.pdf) Synthesis of 2-Hydroxy-5-Methoxybenzaldehyde by the Reimer-Tiemann formylation of 4-Methoxyphenol, as well as several brominations and nitration of 2,5-Dimethoxybenzaldehyde, 2-Hydroxy-5-Methoxybenzaldehyde and other derivatives. ^{The Hive - Clandestine Chemists Without Borders}

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