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All 8 posts Subject: Novel syntheses related to asarone Please login to post Down

GC_MS
(Hive Addict)
12-28-03 13:47
No 479459
User Picture       Novel syntheses related to asarone
(Rated as: excellent)

The following post is the translation of an interesting article from México:

New synthetic route for the preparation of potentially hypocholesterolemic analogs of alpha-asarone.
Determination of E/Z isomer content in natural and synthetic mixtures of alpha-asarone and its analogs. Munoz, Heber; Diaz, Francisco; Sanchez, Adrian; Barajas, Marcelino; Labarrios, Fernando; Tamariz, Joaquin. Acta Mexicana de Ciencia y Tecnologia(41), 51-62 (1993) (https://www.rhodium.ws/pdf/asarone.nueva.ruta.pdf)

Its translation has been requested by Rh, but it does not contain a procedure to convert eugenol into asarone (although you may find one via diazotation), Nevertheless, it contains some interesting chemistry. I sticked to the experimental part. It is advised to check the original article for structure drawings, references and/or IR, NMR, TLC, MS data. According to Post 436354 (Rhodium: "Archive of "Wanted References" Volume 1", Novel Discourse), the article has been provided by java. Muchas gracias, amigo wink

1,2-Dimethoxy-4-(2-propenyl)benzene (11)

There slowly and simultaneously was added 7.7 g dimethyl sulfate (0.061 mol) and aqueous NaOH (2.44 g NaOH in 10 mL water) to 10 g eugenol (10) (0.061 mol), which was warmed up to 60°C. Care should be taken that the reaction mixture does not exceed 60°C. The mixture is stirred for another hour, after which the oleaginous phase separated. It yielded, after distillation, 9.55 g (88%) 11; bp 151-153°C/37 mmHg (lit ²² bp 125°C/14 mmHg).

4,5-Dimethoxy-2-(2-propenyl)nitrobenzene (12)

A mixture of 6.05 g (0.034 mol) of 11 and 25.4 g (0.423 mol) of GAA was cooled down to 5°C, after which there was added 4 mL (0.1 mol) concentrated nitric acid drop by drop. The mixture was stirred at the same temperature for another 20 min. It was subsequently poured on ice, which resulted in the precipitation of a yellow substance. It was filtered and washed with water (3 x 5 mL), dried in vacuo and recrystallized from hexane, yielding 5.46 g (72%) of 12 as yellow needle-shaped crystals; mp 41-42°C (lit ²³ mp 44°C).

(E)-4,5-dimethoxy-2-(1-propenyl)nitrobenzene (3a)

Metallic sodium (1.5 g, 0.065 mol) was dissolved in 100 mL anhydrous MeOH. Subsequently, 10 g (0.045 mol) of 12 was added, after which the reaction mixture was stirred for another 8 h at 25°C. The precipitated product was removed via vacuum filtration and recrystallized from hexane, yielding 9.2 g (92%) of 3a as yellow crystals.

(E)-1-Amino-4,5-dimethoxy-2-(1-propenyl)benzene (3b)

3.0 g (13.4 mmol) of 3a was dissolved in boiling MeOH, after which a solution of 10 g (0.057 mol) NaHSO₃ in 50 mL was added. This mixture was refluxed for 4 h. The solvent was evaporated and the residue taken up into 100 mL MeOH and boiled for 5 mins. Insoluble salts were removed by filtration, while the filtrate was concentrated in vacuo and recrystallized from ethyl acetate, yielding 2.15 g (83%) of 3b as orange crystals that darken under the influence of light; mp 93-94°C (lit ¹² mp 94-96°C).

(E)-1-Amino-4,5-dimethoxy-2-(2-propenyl)benzene (13)

To a solution of 1.0 g (4.48 mmol) of 12 in 13 mL MeOH (at room temperature), there was slowly added a solution of 14.0 g NaHSO₃ in 50 mL of water. The mixture was stirred at 25°C for another 8 hr. The suspension was filtered and the solids washed with 150 mL MeOH. The filtrates were combined and the solvent evaporated under reduced pressure. The residue was purified via column chromatography (20 g silica gel, hexane/ethyl acetate 9:1), yielding 0.57 g (66%) of 13 as a coffee-coloured viscous liquid.

1-Acetamido-4,5-dimethoxy-2-(2-propenyl)benzene (14)

A mixture of 0.1 g (0.52 mmol) of 13 and 0.5 mL (5.3 mmol) acetic anhydride was stirred at ambient temperature for 5 h. There subsequently was added 10 mL of water, after which the mixture was extracted with DCM (3 x 20 mL). The organic phase was dried over anhydrous sodium sulfate and the solvent stripped off under reduced pressure. The residue was dissolved in a mixture of water/MeOH (3:2, 25 mL), decolourized with charcoal and filtered. The filtrate was extracted with DCM (3 x 30 mL) and the organic phase dried over anhydrous sodium sulfate. This yielded 0.109 g (90%) of 14 as clear coffee-coloured crystals after evaporation of the solvent; mp 122-123°C (lit ²³ 126-127°C).

5,6-Dimethoxy-2-methylindole (15)

A suspension of 0.26 g PdCl₂(CH₃CN)₂ (0.1 mmol) in dry THF (3.5 mL) was prepared under a nitrogen atmosphere. The mixture was stirred at room temperature for 2 h, after which 0.1 g dry triethylamine (0.99 mmol) was added and the resulting mixture stirred for a further 1.5 h. There were two more additions of triethylamine (0.1 g, 0.99 mmol) followed by stirring at 25°C for 1.5 h. Subsequently, the mixture was filtered and the filtrate reduced in volume under reduced pressure. The residue was purified via column chromatography (30 g silica gel, hexane/ethyl acetate 9:1), yielding 0.067 g (35%) of 15 as yellow crystals; mp 86-87°C (lit ¹⁴ 88-89°C).

1,2,4-Triacetoxybenzene (20)

To a mixture of 12 g (0.12 mol) concentrated sulfuric acid and 180 g (1.76 mol) acetic anhydride, there was added 19 (60 g, 0.55 mol) in small portions and with vigorous stirring. The temperature is increased and should be maintained between 40-50°C till the end of the reaction. The reaction mixture is allowed to cool down to room temperature, after which it is poured in 750 mL cold water. The mixture is cooled down to 10°C and the white precipitate is filtered off. This yields 117.6 g (84%) of 20 as white crystals after recrystallization from EtOH and drying in vacuo; mp 96-97°C (lit ²⁴ 96-97°C).

1,2,4-Trimethoxybenzene (21)

To a mixture of 28.5 mL (38 g, 0.3 mol) dimethyl sulfate and 40 mL MeOH, there was added 25.2 g (0.1 mol) of 20. Vacuum was applied (30 mmHg) and the reaction mixture temperature cooled down to 5°C. Aqueous NaOH (24 g NaOH in 50 mL water) was added to the mixture while the reaction mixture temperature did not exceed 20°C. When all solution was added, the vacuum was relieved and the mixture warmed to 60°C for 1h after which the reaction was allowed to rest for another 12 h. Two phases were formed upon the addition of 50 mL water. The mixture was extracted with ether (3 x 50 mL) and the organic phase dried over anhydrour sodium sulfate. Evaporation of the solvent yielded a residue, which on distillation under reduced pressure gave 10.51 g (62%) of 21; bp 115-120°C/5 mmHg.

Asaraldehyde (16a)

To a precooled mixture of POCl₃ (12 mL, 18.39 g, 0.12 mol) and dry DMF (11 mL), there was slowly added a solution of 20 g 21 (0.12 mol) in 4 mL DMF. The mixture was stirred and cooled on an ice bath during the addiction. Subsequently, the mixture was warmed to 95°C during 4.5 h. It was then cooled down to 25°C and added to 100 mL of an ethyl acetate/water mixture. This caused a creamy coloured precipitate to fall out, which was filtered and recrystallized from EtOH to yield 11.9 g (51%) of 16a as white crystals; mp 112-113°C (lit ²⁵ 114°C).

(Z)-1,2,4-trimethoxy-5-(1-propenyl)benzene (2)

A 25 mL glass recipient sealed with a septum was charged with 0.177 g (5.5 mmol) NaH (75% solution), which was washed with 2 x 2 mL hexane. Under a nitrogen atmosphere, 2.7 mL DMSO was introduced and the suspension warmed up to 80°C for 45 min with vigorous stirring. At 0°C, there was added 1.52 g (4.15 mmol) of ethyltriphenylphosphonium bromide in 4.2 mL DMSO and the mixture stirred at room temperature for 40 min. There subsequently was added at 25°C 0.12 g (0.61 mmol) of 16a and the mixture stirred for 2 days. The solution was whased with brine (25 mL) and extracted with ethyl acetate (3 x 15 mL). the organic phase was dried over anhydrous sodium sulfate and the solvent evaporated in vacuo. The residue was purified by column chromatography (30 g Florisil, hexane/ethyl acetate 8:2), yielding 0.018 g (14%) of a mixture of 1/2 (52:48) as a coffee-coloured oil.

Veratraldehyde (23)

To a boiling solution of 182 g (1.2 mol) of 22 in 450 mL water, there was added preheated aqueous NaOH (72 g NaOH in 360 mL water). The mixture was heated and 189 g (1.5 mol) dimethyl sulfate was drop-wise added. The mixture was further warmed for 45 min and another 39 g (30 mL, 0.31 mol) dimethyl sulfate was added. After 10 min, there was successively added aqueous NaOH (12 g NaOH in 60 mL water) and 30 mL dimethyl sulfate. This was repeated twice, finally followed by the addition of 75 g NaOH in 150 mL water. The reaction mixture is warmed for an additional 20 min and allowed to cool down to 25°C, after which is extracted with ether (3 x 50 mL). The combined ether extracts were dried over anhydrous sodium sulfate and the solvent removed in vacuo, yielding a dense oil that is further purified by distillation. This gave 181.49 g (91%, lit ¹⁹ 82-87%) of 23 (bp 153°C/8 mmHg) as a white solid; mp 45-46°C (lit ¹⁹ 45-46°C).

6-Nitroveratraldehyde (16b)

A 1 L glass recipient covered with aluminium foil was charged with 350 mL (7.77 mol) HNO₃ and brought to a temperature of 15°C (water bath) (careful! 16b is photosensitive). Subsequently, there slowly was added 70 g (0.42 mol) of finely crushed 23, care being taken that the temperature remained 18-22°C. The mixture was stirred for 10 min and poured in a glass recipient containing 4 L of water under vigorous stirring. After 15 min, a precipitate started to fall out which was filtered in the absence of light, and washed with cold water (2 L). It was dried at ambient temperature and protected from light for 15 days. The solid substance is recrystallized twice from EtOH, yielding 56.94 g (64%) of 16b; mp 129-131°C (lit ²⁶ 129-131°C).

Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".

sYnThOmAtIc
(Hive Addict)
01-02-04 05:57
No 480186
      Why would you want asarone?

Why would you want asarone from eugenol when you can make asaronaldehyde from eugenol??? That puts you a lil closer to the end product right?

Or is it that you were hoping to find a new route for eugenol->asaronaldehyde?

GC_MS
(Hive Addict)
01-02-04 08:32
No 480194
User Picture       It depends on which synthetic route you ...

It depends on which synthetic route you prefer. Henry condensation of asaraldehyde or via the pseudonitrosite of asarone.

Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".

methymouse
(Stranger)
01-14-04 16:04
No 482376
      Vanillin

Furthermore, asaronaldehyde can be prepared more easily from vanillin. See this synthesis (https://www.rhodium.ws/chemistry/tma2.vanillin.html) of 2-bromo 4,5-dimethoxy benzaldehyde.

I've got the kind of toys you've never seen
Manmade and a bit obscene

Rhodium
(Chief Bee)
01-14-04 21:27
No 482418
User Picture       I need to add the following info to that doc

That is an untested synthesis which might be troublesome. See the following posts:

Post 465752 (Rhodium: "6-Bromo- to 6-Methoxy-piperonylic acid", Novel Discourse)
Post 471601 (Rhodium: "Indirect 6-Methoxylation of Veratraldehyde", Methods Discourse)

^{The Hive - Clandestine Chemists Without Borders}

Rhodium
(Chief Bee)
01-14-04 22:43
No 482433
User Picture       But...? They depict more reactions...

GC_MS or any other spanish-speaking bee; what is their reference for the reactions depicted on page 53 and 58?

I have BTW uploaded this document to my page: https://www.rhodium.ws/chemistry/asarone.analogs.html

^{The Hive - Clandestine Chemists Without Borders}

GC_MS
(Hive Addict)
01-14-04 23:29
No 482440
User Picture       Experimental

That synthesis was not explained in the experimental part of this publication. It is published in another article (cf reference 11). It discusses the total synthesis of asarone starting from 1,2,4-trimethoxybenzene. The latter can be synthesize rather easily via Thiele-Winter of p-benzoquinone (90% yield and also described in this text) followed by methylation with DMS (60% obtainable, I know from experience).

The idea is to react 1,2,4-trimethoxybenzene with propionic acid anhydride using iodine as a catalyst (Post 413289 (GC_MS: "Acylation of alkyl aryl ethers with I2 as catalyst", Novel Discourse)). The thus obtained propiophenone is reduced to the corresponding alcohol with NaBH4, which in turn is dehydrated with Ac2O/NaOAc. This yields asarone.

The experimental details are described in reference 11, which should be archived in one of my maps.

Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".

Rhodium
(Chief Bee)
01-14-04 23:33
No 482443
User Picture       Ref #11

Ahaa! Then I hereby signal my interest to have that one posted! wink

^{The Hive - Clandestine Chemists Without Borders}

	https://the-hive.archive.erowid.org	the-hive@erowid.org



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	All 8 posts		Subject: Novel syntheses related to asarone		Please login to post		Down


		GC_MS (Hive Addict) 12-28-03 13:47 No 479459				Novel syntheses related to asarone (Rated as: excellent)
						The following post is the translation of an interesting article from México: New synthetic route for the preparation of potentially hypocholesterolemic analogs of alpha-asarone. Determination of E/Z isomer content in natural and synthetic mixtures of alpha-asarone and its analogs. Munoz, Heber; Diaz, Francisco; Sanchez, Adrian; Barajas, Marcelino; Labarrios, Fernando; Tamariz, Joaquin. Acta Mexicana de Ciencia y Tecnologia(41), 51-62 (1993) (https://www.rhodium.ws/pdf/asarone.nueva.ruta.pdf) Its translation has been requested by Rh, but it does not contain a procedure to convert eugenol into asarone (although you may find one via diazotation), Nevertheless, it contains some interesting chemistry. I sticked to the experimental part. It is advised to check the original article for structure drawings, references and/or IR, NMR, TLC, MS data. According to Post 436354 (Rhodium: "Archive of "Wanted References" Volume 1", Novel Discourse), the article has been provided by java. Muchas gracias, amigo 1,2-Dimethoxy-4-(2-propenyl)benzene (11) There slowly and simultaneously was added 7.7 g dimethyl sulfate (0.061 mol) and aqueous NaOH (2.44 g NaOH in 10 mL water) to 10 g eugenol (10) (0.061 mol), which was warmed up to 60°C. Care should be taken that the reaction mixture does not exceed 60°C. The mixture is stirred for another hour, after which the oleaginous phase separated. It yielded, after distillation, 9.55 g (88%) 11; bp 151-153°C/37 mmHg (lit ²² bp 125°C/14 mmHg). 4,5-Dimethoxy-2-(2-propenyl)nitrobenzene (12) A mixture of 6.05 g (0.034 mol) of 11 and 25.4 g (0.423 mol) of GAA was cooled down to 5°C, after which there was added 4 mL (0.1 mol) concentrated nitric acid drop by drop. The mixture was stirred at the same temperature for another 20 min. It was subsequently poured on ice, which resulted in the precipitation of a yellow substance. It was filtered and washed with water (3 x 5 mL), dried in vacuo and recrystallized from hexane, yielding 5.46 g (72%) of 12 as yellow needle-shaped crystals; mp 41-42°C (lit ²³ mp 44°C). (E)-4,5-dimethoxy-2-(1-propenyl)nitrobenzene (3a) Metallic sodium (1.5 g, 0.065 mol) was dissolved in 100 mL anhydrous MeOH. Subsequently, 10 g (0.045 mol) of 12 was added, after which the reaction mixture was stirred for another 8 h at 25°C. The precipitated product was removed via vacuum filtration and recrystallized from hexane, yielding 9.2 g (92%) of 3a as yellow crystals. (E)-1-Amino-4,5-dimethoxy-2-(1-propenyl)benzene (3b) 3.0 g (13.4 mmol) of 3a was dissolved in boiling MeOH, after which a solution of 10 g (0.057 mol) NaHSO₃ in 50 mL was added. This mixture was refluxed for 4 h. The solvent was evaporated and the residue taken up into 100 mL MeOH and boiled for 5 mins. Insoluble salts were removed by filtration, while the filtrate was concentrated in vacuo and recrystallized from ethyl acetate, yielding 2.15 g (83%) of 3b as orange crystals that darken under the influence of light; mp 93-94°C (lit ¹² mp 94-96°C). (E)-1-Amino-4,5-dimethoxy-2-(2-propenyl)benzene (13) To a solution of 1.0 g (4.48 mmol) of 12 in 13 mL MeOH (at room temperature), there was slowly added a solution of 14.0 g NaHSO₃ in 50 mL of water. The mixture was stirred at 25°C for another 8 hr. The suspension was filtered and the solids washed with 150 mL MeOH. The filtrates were combined and the solvent evaporated under reduced pressure. The residue was purified via column chromatography (20 g silica gel, hexane/ethyl acetate 9:1), yielding 0.57 g (66%) of 13 as a coffee-coloured viscous liquid. 1-Acetamido-4,5-dimethoxy-2-(2-propenyl)benzene (14) A mixture of 0.1 g (0.52 mmol) of 13 and 0.5 mL (5.3 mmol) acetic anhydride was stirred at ambient temperature for 5 h. There subsequently was added 10 mL of water, after which the mixture was extracted with DCM (3 x 20 mL). The organic phase was dried over anhydrous sodium sulfate and the solvent stripped off under reduced pressure. The residue was dissolved in a mixture of water/MeOH (3:2, 25 mL), decolourized with charcoal and filtered. The filtrate was extracted with DCM (3 x 30 mL) and the organic phase dried over anhydrous sodium sulfate. This yielded 0.109 g (90%) of 14 as clear coffee-coloured crystals after evaporation of the solvent; mp 122-123°C (lit ²³ 126-127°C). 5,6-Dimethoxy-2-methylindole (15) A suspension of 0.26 g PdCl₂(CH₃CN)₂ (0.1 mmol) in dry THF (3.5 mL) was prepared under a nitrogen atmosphere. The mixture was stirred at room temperature for 2 h, after which 0.1 g dry triethylamine (0.99 mmol) was added and the resulting mixture stirred for a further 1.5 h. There were two more additions of triethylamine (0.1 g, 0.99 mmol) followed by stirring at 25°C for 1.5 h. Subsequently, the mixture was filtered and the filtrate reduced in volume under reduced pressure. The residue was purified via column chromatography (30 g silica gel, hexane/ethyl acetate 9:1), yielding 0.067 g (35%) of 15 as yellow crystals; mp 86-87°C (lit ¹⁴ 88-89°C). 1,2,4-Triacetoxybenzene (20) To a mixture of 12 g (0.12 mol) concentrated sulfuric acid and 180 g (1.76 mol) acetic anhydride, there was added 19 (60 g, 0.55 mol) in small portions and with vigorous stirring. The temperature is increased and should be maintained between 40-50°C till the end of the reaction. The reaction mixture is allowed to cool down to room temperature, after which it is poured in 750 mL cold water. The mixture is cooled down to 10°C and the white precipitate is filtered off. This yields 117.6 g (84%) of 20 as white crystals after recrystallization from EtOH and drying in vacuo; mp 96-97°C (lit ²⁴ 96-97°C). 1,2,4-Trimethoxybenzene (21) To a mixture of 28.5 mL (38 g, 0.3 mol) dimethyl sulfate and 40 mL MeOH, there was added 25.2 g (0.1 mol) of 20. Vacuum was applied (30 mmHg) and the reaction mixture temperature cooled down to 5°C. Aqueous NaOH (24 g NaOH in 50 mL water) was added to the mixture while the reaction mixture temperature did not exceed 20°C. When all solution was added, the vacuum was relieved and the mixture warmed to 60°C for 1h after which the reaction was allowed to rest for another 12 h. Two phases were formed upon the addition of 50 mL water. The mixture was extracted with ether (3 x 50 mL) and the organic phase dried over anhydrour sodium sulfate. Evaporation of the solvent yielded a residue, which on distillation under reduced pressure gave 10.51 g (62%) of 21; bp 115-120°C/5 mmHg. Asaraldehyde (16a) To a precooled mixture of POCl₃ (12 mL, 18.39 g, 0.12 mol) and dry DMF (11 mL), there was slowly added a solution of 20 g 21 (0.12 mol) in 4 mL DMF. The mixture was stirred and cooled on an ice bath during the addiction. Subsequently, the mixture was warmed to 95°C during 4.5 h. It was then cooled down to 25°C and added to 100 mL of an ethyl acetate/water mixture. This caused a creamy coloured precipitate to fall out, which was filtered and recrystallized from EtOH to yield 11.9 g (51%) of 16a as white crystals; mp 112-113°C (lit ²⁵ 114°C). (Z)-1,2,4-trimethoxy-5-(1-propenyl)benzene (2) A 25 mL glass recipient sealed with a septum was charged with 0.177 g (5.5 mmol) NaH (75% solution), which was washed with 2 x 2 mL hexane. Under a nitrogen atmosphere, 2.7 mL DMSO was introduced and the suspension warmed up to 80°C for 45 min with vigorous stirring. At 0°C, there was added 1.52 g (4.15 mmol) of ethyltriphenylphosphonium bromide in 4.2 mL DMSO and the mixture stirred at room temperature for 40 min. There subsequently was added at 25°C 0.12 g (0.61 mmol) of 16a and the mixture stirred for 2 days. The solution was whased with brine (25 mL) and extracted with ethyl acetate (3 x 15 mL). the organic phase was dried over anhydrous sodium sulfate and the solvent evaporated in vacuo. The residue was purified by column chromatography (30 g Florisil, hexane/ethyl acetate 8:2), yielding 0.018 g (14%) of a mixture of 1/2 (52:48) as a coffee-coloured oil. Veratraldehyde (23) To a boiling solution of 182 g (1.2 mol) of 22 in 450 mL water, there was added preheated aqueous NaOH (72 g NaOH in 360 mL water). The mixture was heated and 189 g (1.5 mol) dimethyl sulfate was drop-wise added. The mixture was further warmed for 45 min and another 39 g (30 mL, 0.31 mol) dimethyl sulfate was added. After 10 min, there was successively added aqueous NaOH (12 g NaOH in 60 mL water) and 30 mL dimethyl sulfate. This was repeated twice, finally followed by the addition of 75 g NaOH in 150 mL water. The reaction mixture is warmed for an additional 20 min and allowed to cool down to 25°C, after which is extracted with ether (3 x 50 mL). The combined ether extracts were dried over anhydrous sodium sulfate and the solvent removed in vacuo, yielding a dense oil that is further purified by distillation. This gave 181.49 g (91%, lit ¹⁹ 82-87%) of 23 (bp 153°C/8 mmHg) as a white solid; mp 45-46°C (lit ¹⁹ 45-46°C). 6-Nitroveratraldehyde (16b) A 1 L glass recipient covered with aluminium foil was charged with 350 mL (7.77 mol) HNO₃ and brought to a temperature of 15°C (water bath) (careful! 16b is photosensitive). Subsequently, there slowly was added 70 g (0.42 mol) of finely crushed 23, care being taken that the temperature remained 18-22°C. The mixture was stirred for 10 min and poured in a glass recipient containing 4 L of water under vigorous stirring. After 15 min, a precipitate started to fall out which was filtered in the absence of light, and washed with cold water (2 L). It was dried at ambient temperature and protected from light for 15 days. The solid substance is recrystallized twice from EtOH, yielding 56.94 g (64%) of 16b; mp 129-131°C (lit ²⁶ 129-131°C). Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".



		sYnThOmAtIc (Hive Addict) 01-02-04 05:57 No 480186				Why would you want asarone?
						Why would you want asarone from eugenol when you can make asaronaldehyde from eugenol??? That puts you a lil closer to the end product right? Or is it that you were hoping to find a new route for eugenol->asaronaldehyde?



		GC_MS (Hive Addict) 01-02-04 08:32 No 480194				It depends on which synthetic route you ...
						It depends on which synthetic route you prefer. Henry condensation of asaraldehyde or via the pseudonitrosite of asarone. Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".



		methymouse (Stranger) 01-14-04 16:04 No 482376				Vanillin
						Furthermore, asaronaldehyde can be prepared more easily from vanillin. See this synthesis (https://www.rhodium.ws/chemistry/tma2.vanillin.html) of 2-bromo 4,5-dimethoxy benzaldehyde. I've got the kind of toys you've never seen Manmade and a bit obscene



		Rhodium (Chief Bee) 01-14-04 21:27 No 482418				I need to add the following info to that doc
						That is an untested synthesis which might be troublesome. See the following posts: Post 465752 (Rhodium: "6-Bromo- to 6-Methoxy-piperonylic acid", Novel Discourse) Post 471601 (Rhodium: "Indirect 6-Methoxylation of Veratraldehyde", Methods Discourse) ^{The Hive - Clandestine Chemists Without Borders}



		Rhodium (Chief Bee) 01-14-04 22:43 No 482433				But...? They depict more reactions...
						GC_MS or any other spanish-speaking bee; what is their reference for the reactions depicted on page 53 and 58? I have BTW uploaded this document to my page: https://www.rhodium.ws/chemistry/asarone.analogs.html ^{The Hive - Clandestine Chemists Without Borders}



		GC_MS (Hive Addict) 01-14-04 23:29 No 482440				Experimental
						That synthesis was not explained in the experimental part of this publication. It is published in another article (cf reference 11). It discusses the total synthesis of asarone starting from 1,2,4-trimethoxybenzene. The latter can be synthesize rather easily via Thiele-Winter of p-benzoquinone (90% yield and also described in this text) followed by methylation with DMS (60% obtainable, I know from experience). The idea is to react 1,2,4-trimethoxybenzene with propionic acid anhydride using iodine as a catalyst (Post 413289 (GC_MS: "Acylation of alkyl aryl ethers with I2 as catalyst", Novel Discourse)). The thus obtained propiophenone is reduced to the corresponding alcohol with NaBH4, which in turn is dehydrated with Ac2O/NaOAc. This yields asarone. The experimental details are described in reference 11, which should be archived in one of my maps. Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".



		Rhodium (Chief Bee) 01-14-04 23:33 No 482443				Ref #11
						Ahaa! Then I hereby signal my interest to have that one posted! ^{The Hive - Clandestine Chemists Without Borders}

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