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All 4 posts Subject: Synthesis of dill-apiole & tetraMeO-allylbenzene Please login to post Down

Vitus_Verdegast
(Stranger)
03-05-03 04:08
No 413969
      Synthesis of dill-apiole & tetraMeO-allylbenzene
(Rated as: excellent)

SYNTHESIS OF DILL-APIOLE AND 1,2,3,4-TETRAMETHOXY-5-ALLYLBENZENE

The following is taken from J. Chem. Soc. 2, 1934, p. 1681-1684 :

A convenient method for the preparation of 1,2-dihydroxy-3,4-dimethoxybenzene (I) in quantity has now been found in the oxidation of the accessible gallacetophenone 3,4-dimethyl ether with H₂O₂ in alkaline solution, and it has been used in the synthesis of dill-apiole in the following manner. Treatment with allyl bromide in acetone in presence of K₂CO₃ yielded a monallyl ether, which underwent molecular rearrangement on heating with production of 1,2-dihydroxy-3,4-dimethoxyallylbenzene (II) (uncharacterised) as the chief product. Since migration of an allyl group under these conditions always yields an o- or a p-hydroxyallylbenzene, the production of (II) probably means that the monoallyl ether is chiefly the 2-O-allyl ether. Methylenation of (II) with CH₂I₂ and anhydrous K₂CO₃ in acetone yielded directly almost pure dill-apiole (III), characterised by the formation of monobromodill-apiole dibromide, which was directly compared (mixed mp.) with a specimen prepared from natural dill-apiole. The allyl groups in these compounds cannot occupy position 6, since the final product would then be an isomeride of dill-apiole and not dill-apiole itself, the constitution of which was definitely established by the researches of Ciamician and Silber (Ber.,1896, 29, 1799) and Thoms (Arch. Pharm., 1904, 242, 328). Dill-apiole has been isolated from dill oil (Ciamician and Silber, loc. cit.), from matico oil from the leaves of Piper augustifolium (Thoms, loc. cit.), from sea-fennel oil (Delépine, Compt. Rend., 1909, 149, 215), and from Crithmum maritimum (Francesconi and Sernagotti, Atti R. Acad. Lincei, 1913, 22, 231, 312).

Methylation of (II) with methyl sulphate and alkali readily gave 1,2,3,4-tetramethoxy-5-allylbenzene, which is apparently identical with a product isolated by Thoms (Ber., 1908, 41, 2753) from parsley oil and to which this consitution was assigned. Direct comparision of the synthetic and the natural product was not possible in this case.

As possible intermediates in the synthesis of parsley apiole the following compounds have been prepared : pyrogallol methylene ether (2,3-methylenedioxyphenol) (IV), by the direct methylenation of pyrogallol with CH₂Br₂ and K₂CO₃ in acetone; gallacetophenone-4-methyl ether, by the nuclear acylation of pyrogallol 1-monomethyl ether (Baker, Montgomery, and Smith, J. Chem. Soc., 1932, 1282); 7-methoxy-8-acetyl-2-methylchromone - this compound could not be hydrolysed to the monomethyl ether of 2,4-diacetylresorcinol. Hydrolysis of 7-methoxy-8-acetyl-2-methylchromone (Baker, this vol., p. 73) with 4% aq. NaOH at 100° gives resacetophenone, the nuclear acetyl group in position 8 having been replaced by hydrogen; 2,4-diacetylresorcinol is unaffected under these conditions, although it has been recorded that reduction of this diacetyl resorcinol by Clemmensen's method yields 4-ethylresorcinol (Rosenmund, Buchwald and Deligiannis, Arch. Pharm., 1933, 271, 344).

Experimental

Gallacetophenone 3,4-dimethyl ether
To a boiling mixture of gallacetophenone (16.8 gr; 1 mol), benzene (400 cc) and anhydrous K₂CO₃ (55 gr) was added methyl sulphate (26.5 gr, 2.05 mols) in one portion, and the whole refluxed for 6 hours with occasional shaking. After the addition of water (750 cc) and shaking, the benzene layer was separated and shaken several times with NaOH solution, and the alkaline extracts solidified. The precipitated gallacetophenone 3,4-dimethyl ether after crystallisation from MeOH had mp. 75-77° (yield, 10 gr) (for previous methods of preparation from gallacetophenone, see Perkin, J., 1895, 67, 997 ; Perkin and Wilson, J., 1903, 83,132 ; David and von Kostanecki, Ber., 1903, 36, 127).

1,2-dihydroxy-3,4-dimethoxybenzene (I)
Gallacetophenone 3,4-dimethyl ether (9.8 gr) in 10% NaOH solution (40 cc) was oxidised by the addition of a 3% solution of hydrogen peroxide (75 cc) in an atmosphere of coal gas. Considerable rise of temp occurred and the mixture darkened. After about 30 min. the solution was acidified, and extracted with ether, the extracts dried and distilled, and 1,2-dihydroxy-3,4-dimethoxybenzene obtained as a pale yellow oil (5 gr), bp.160-170/20mm.

1,2-dihydroxy-3,4-dimethoxy-5-allylbenzene (II)
To 1,2-dihydroxy-3,4-dimethoxybenzene (12 gr) and allyl bromide (8.5 gr) in acetone (25 cc) was added anhydrous K₂CO₃ (12 gr), and the mixture refluxed for 18 hours with frequent shaking. After evaporation of the acetone, the mixture was acidified with dilute H ₂SO₄ and extracted with ether, the extracts were shaken with an excess of dil. aq. NaOH, and the phenolic products precipitated from the alkaline layer by acid and again extracted with ether. After removal of the solvent the monoallyl ether was heated in an oil bath to about 165°; its temp then suddenly rose to 190°, and ,after being kept at 200° for a few minutes, it was distilled at diminished pressure. The thick oily product (4 gr), bp. 160-173°/14mm, which partly solidified was directly used in the following experiments.

Dill-apiole (1,2-methylenedioxy-3,4-dimethoxy-5-allylbenzene) (III)
Crude 1,2-dihydroxy-3,4-dimethoxy-5-allylbenzene (4 gr), CH₂I₂ (5.2 gr), acetone (25 cc) and anhydrous K₂CO₃ (3gr) were refluxed for 8 hours. After removal of the acetone and dilution, the methylenated product was extracted with ether, and the extracts shaken with dil. aq. NaOH and distilled twice under reduced pressure. The dill-apiole (1 gr) distilled as a colourless, almost odourless oil at 172-173°C/16mm.

1,2,3,4-tetramethoxy-5-allylbenzene
1,2-dihydroxy-3,4-dimethoxy-5-allylbenzene (3 gr) in MeOH (15 cc) was shaken with methyl sulphate (8 gr) and a 10% solution of KOH (60 cc), added in portions, and finally heated on the steam-bath. After addition of water ether extracted the 1,2,3,4-tetramethoxy-5-allylbenzene as an oil, which after distillation at diminished pressure (bp 145°/12mm) solidified when strongly cooled, and had an mp. of 25°

Pyrogallol methylene ether (IV)
Pyrogallol (50 gr), acetone (400 cc), Me₂Br₂ (110 gr) and anhydrous K₂CO₃ were refluxed for 30 hours, then diluted, acidified, and extracted with a large volume of ether. The ethereal extract was shaken several times with water, filtered, and shaken with aq. NaOH. The alkaline layer was acidified, extracted several times with warm light petroleum (bp. 40-60°), and yielded a semi-solid product which, after being presses on porous porcelain and recrystallised from light petroleum had an mp. 65°

"There are many things under the sun."

demorol
(Hive Bee)
05-12-03 18:22
No 432829
      Synthesis of Gallacetophenone
(Rated as: excellent)

Synthesis of Gallacetophenone (2,3,4-trihydroxyacetophenone)

Procedure

In a 250mL RB flask, fitted with a reflux condenser to which is attached a calcium chloride tube, 28g (0.21 mole) of freshly fused and finely powdered zinc chloride (Note 1) is dissolved in 38mL of glacial acetic acid by heating in an oil bath at 135–140°C. Forty grams (0.37 mole) of 95% acetic anhydride is then added to the clear, pale brown liquid, followed by the addition in one lot of 50g (0.4 mole) of distilled pyrogallol (Note 2). The mixture is heated at 140–145°C (Note 3) for 45 minutes with frequent and vigorous shaking. The unused acetic anhydride and acetic acid are removed by distilling under reduced pressure. The red-brown cake is broken up by the addition of 300mL of water with mechanical stirring for a few minutes. The mixture is cooled in ice water, filtered with suction, and washed with cold water. The crude material, 45–50g, is crystallized from 500mL of boiling water saturated with sulfur dioxide. The yield of straw-colored needles melting at 171–172°C is 36–38g (54–57% of the theoretical amount). On saturating the mother liquor with salt and cooling to 10°C, 4–5g of crude material is obtained, which on recrystallization yields 3–4g of pure material (Note 4).

Notes

1.) A good quality of zinc chloride must be used, and it is an advantage to fuse it immediately before use.

2.) Variations in the proportions of acetic acid, acetic anhydride, and zinc chloride did not result in increased yields.

3.) The temperature must be carefully regulated and must not exceed 150°C. In this preparation, as well as in the preparation of other ketones by the Nencki reaction, higher temperatures lead to the formation of a highly colored and resinous product which probably contains a little diketone.

4.) This method has been used for the preparation of other phenolic ketones such as resacetophenone, 2-acetyl-1-naphthol, 2-phenylacetyl-1-naphthol, and 2-phenylpropionyl-1-naphthol.

Reference: Organic Syntheses, CV 2, 304 (http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?rxntypeid=2&prep=CV2P0304)

I'm dreaming of the white crystals.

pHarmacist
05-13-03 12:54
      Nice!
(Rated as: insignificant)

Rhodium
(Chief Bee)
12-18-03 22:54
No 477701
User Picture       Synthesis of all Apiole Positional Isomers
(Rated as: excellent)

Methylenedioxybenzene Derivates. 27.
The Synthesis of Dimethoxy-Methylenedioxy-Allylbenzenes
Franz Dallacker
Chem. Ber. 102, 2663-2676 (1969) (https://www.rhodium.ws/pdf/apioles.dallacker.pdf)

Abstract
The synthesis of 2,3-Dimethoxy-4,5-Methylenedioxy- (Dillapiole), 2,5-Dimethoxy-3,4-Methylenedioxy- (Parsley Apiole), 4,6-Dimethoxy-2,3-Methylenedioxy-, 2,6-Dimethoxy-3,4-Methylenedioxy-, 5,6-Dimethoxy-2,3-Methylenedioxy- and 4,5-Dimethoxy-2,3-Methylenedioxy-allylbenzene is described. _{(In German)}

^{The Hive - Clandestine Chemists Without Borders}

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



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	All 4 posts		Subject: Synthesis of dill-apiole & tetraMeO-allylbenzene		Please login to post		Down


		Vitus_Verdegast (Stranger) 03-05-03 04:08 No 413969				Synthesis of dill-apiole & tetraMeO-allylbenzene (Rated as: excellent)
						SYNTHESIS OF DILL-APIOLE AND 1,2,3,4-TETRAMETHOXY-5-ALLYLBENZENE The following is taken from J. Chem. Soc. 2, 1934, p. 1681-1684 : A convenient method for the preparation of 1,2-dihydroxy-3,4-dimethoxybenzene (I) in quantity has now been found in the oxidation of the accessible gallacetophenone 3,4-dimethyl ether with H₂O₂ in alkaline solution, and it has been used in the synthesis of dill-apiole in the following manner. Treatment with allyl bromide in acetone in presence of K₂CO₃ yielded a monallyl ether, which underwent molecular rearrangement on heating with production of 1,2-dihydroxy-3,4-dimethoxyallylbenzene (II) (uncharacterised) as the chief product. Since migration of an allyl group under these conditions always yields an o- or a p-hydroxyallylbenzene, the production of (II) probably means that the monoallyl ether is chiefly the 2-O-allyl ether. Methylenation of (II) with CH₂I₂ and anhydrous K₂CO₃ in acetone yielded directly almost pure dill-apiole (III), characterised by the formation of monobromodill-apiole dibromide, which was directly compared (mixed mp.) with a specimen prepared from natural dill-apiole. The allyl groups in these compounds cannot occupy position 6, since the final product would then be an isomeride of dill-apiole and not dill-apiole itself, the constitution of which was definitely established by the researches of Ciamician and Silber (Ber.,1896, 29, 1799) and Thoms (Arch. Pharm., 1904, 242, 328). Dill-apiole has been isolated from dill oil (Ciamician and Silber, loc. cit.), from matico oil from the leaves of Piper augustifolium (Thoms, loc. cit.), from sea-fennel oil (Delépine, Compt. Rend., 1909, 149, 215), and from Crithmum maritimum (Francesconi and Sernagotti, Atti R. Acad. Lincei, 1913, 22, 231, 312). Methylation of (II) with methyl sulphate and alkali readily gave 1,2,3,4-tetramethoxy-5-allylbenzene, which is apparently identical with a product isolated by Thoms (Ber., 1908, 41, 2753) from parsley oil and to which this consitution was assigned. Direct comparision of the synthetic and the natural product was not possible in this case. As possible intermediates in the synthesis of parsley apiole the following compounds have been prepared : pyrogallol methylene ether (2,3-methylenedioxyphenol) (IV), by the direct methylenation of pyrogallol with CH₂Br₂ and K₂CO₃ in acetone; gallacetophenone-4-methyl ether, by the nuclear acylation of pyrogallol 1-monomethyl ether (Baker, Montgomery, and Smith, J. Chem. Soc., 1932, 1282); 7-methoxy-8-acetyl-2-methylchromone - this compound could not be hydrolysed to the monomethyl ether of 2,4-diacetylresorcinol. Hydrolysis of 7-methoxy-8-acetyl-2-methylchromone (Baker, this vol., p. 73) with 4% aq. NaOH at 100° gives resacetophenone, the nuclear acetyl group in position 8 having been replaced by hydrogen; 2,4-diacetylresorcinol is unaffected under these conditions, although it has been recorded that reduction of this diacetyl resorcinol by Clemmensen's method yields 4-ethylresorcinol (Rosenmund, Buchwald and Deligiannis, Arch. Pharm., 1933, 271, 344). Experimental Gallacetophenone 3,4-dimethyl ether To a boiling mixture of gallacetophenone (16.8 gr; 1 mol), benzene (400 cc) and anhydrous K₂CO₃ (55 gr) was added methyl sulphate (26.5 gr, 2.05 mols) in one portion, and the whole refluxed for 6 hours with occasional shaking. After the addition of water (750 cc) and shaking, the benzene layer was separated and shaken several times with NaOH solution, and the alkaline extracts solidified. The precipitated gallacetophenone 3,4-dimethyl ether after crystallisation from MeOH had mp. 75-77° (yield, 10 gr) (for previous methods of preparation from gallacetophenone, see Perkin, J., 1895, 67, 997 ; Perkin and Wilson, J., 1903, 83,132 ; David and von Kostanecki, Ber., 1903, 36, 127). 1,2-dihydroxy-3,4-dimethoxybenzene (I) Gallacetophenone 3,4-dimethyl ether (9.8 gr) in 10% NaOH solution (40 cc) was oxidised by the addition of a 3% solution of hydrogen peroxide (75 cc) in an atmosphere of coal gas. Considerable rise of temp occurred and the mixture darkened. After about 30 min. the solution was acidified, and extracted with ether, the extracts dried and distilled, and 1,2-dihydroxy-3,4-dimethoxybenzene obtained as a pale yellow oil (5 gr), bp.160-170/20mm. 1,2-dihydroxy-3,4-dimethoxy-5-allylbenzene (II) To 1,2-dihydroxy-3,4-dimethoxybenzene (12 gr) and allyl bromide (8.5 gr) in acetone (25 cc) was added anhydrous K₂CO₃ (12 gr), and the mixture refluxed for 18 hours with frequent shaking. After evaporation of the acetone, the mixture was acidified with dilute H ₂SO₄ and extracted with ether, the extracts were shaken with an excess of dil. aq. NaOH, and the phenolic products precipitated from the alkaline layer by acid and again extracted with ether. After removal of the solvent the monoallyl ether was heated in an oil bath to about 165°; its temp then suddenly rose to 190°, and ,after being kept at 200° for a few minutes, it was distilled at diminished pressure. The thick oily product (4 gr), bp. 160-173°/14mm, which partly solidified was directly used in the following experiments. Dill-apiole (1,2-methylenedioxy-3,4-dimethoxy-5-allylbenzene) (III) Crude 1,2-dihydroxy-3,4-dimethoxy-5-allylbenzene (4 gr), CH₂I₂ (5.2 gr), acetone (25 cc) and anhydrous K₂CO₃ (3gr) were refluxed for 8 hours. After removal of the acetone and dilution, the methylenated product was extracted with ether, and the extracts shaken with dil. aq. NaOH and distilled twice under reduced pressure. The dill-apiole (1 gr) distilled as a colourless, almost odourless oil at 172-173°C/16mm. 1,2,3,4-tetramethoxy-5-allylbenzene 1,2-dihydroxy-3,4-dimethoxy-5-allylbenzene (3 gr) in MeOH (15 cc) was shaken with methyl sulphate (8 gr) and a 10% solution of KOH (60 cc), added in portions, and finally heated on the steam-bath. After addition of water ether extracted the 1,2,3,4-tetramethoxy-5-allylbenzene as an oil, which after distillation at diminished pressure (bp 145°/12mm) solidified when strongly cooled, and had an mp. of 25° Pyrogallol methylene ether (IV) Pyrogallol (50 gr), acetone (400 cc), Me₂Br₂ (110 gr) and anhydrous K₂CO₃ were refluxed for 30 hours, then diluted, acidified, and extracted with a large volume of ether. The ethereal extract was shaken several times with water, filtered, and shaken with aq. NaOH. The alkaline layer was acidified, extracted several times with warm light petroleum (bp. 40-60°), and yielded a semi-solid product which, after being presses on porous porcelain and recrystallised from light petroleum had an mp. 65° "There are many things under the sun."



		demorol (Hive Bee) 05-12-03 18:22 No 432829				Synthesis of Gallacetophenone (Rated as: excellent)
						Synthesis of Gallacetophenone (2,3,4-trihydroxyacetophenone) Procedure In a 250mL RB flask, fitted with a reflux condenser to which is attached a calcium chloride tube, 28g (0.21 mole) of freshly fused and finely powdered zinc chloride (Note 1) is dissolved in 38mL of glacial acetic acid by heating in an oil bath at 135–140°C. Forty grams (0.37 mole) of 95% acetic anhydride is then added to the clear, pale brown liquid, followed by the addition in one lot of 50g (0.4 mole) of distilled pyrogallol (Note 2). The mixture is heated at 140–145°C (Note 3) for 45 minutes with frequent and vigorous shaking. The unused acetic anhydride and acetic acid are removed by distilling under reduced pressure. The red-brown cake is broken up by the addition of 300mL of water with mechanical stirring for a few minutes. The mixture is cooled in ice water, filtered with suction, and washed with cold water. The crude material, 45–50g, is crystallized from 500mL of boiling water saturated with sulfur dioxide. The yield of straw-colored needles melting at 171–172°C is 36–38g (54–57% of the theoretical amount). On saturating the mother liquor with salt and cooling to 10°C, 4–5g of crude material is obtained, which on recrystallization yields 3–4g of pure material (Note 4). Notes 1.) A good quality of zinc chloride must be used, and it is an advantage to fuse it immediately before use. 2.) Variations in the proportions of acetic acid, acetic anhydride, and zinc chloride did not result in increased yields. 3.) The temperature must be carefully regulated and must not exceed 150°C. In this preparation, as well as in the preparation of other ketones by the Nencki reaction, higher temperatures lead to the formation of a highly colored and resinous product which probably contains a little diketone. 4.) This method has been used for the preparation of other phenolic ketones such as resacetophenone, 2-acetyl-1-naphthol, 2-phenylacetyl-1-naphthol, and 2-phenylpropionyl-1-naphthol. Reference: Organic Syntheses, CV 2, 304 (http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?rxntypeid=2&prep=CV2P0304) I'm dreaming of the white crystals.



		pHarmacist 05-13-03 12:54				Nice! (Rated as: insignificant)



		Rhodium (Chief Bee) 12-18-03 22:54 No 477701				Synthesis of all Apiole Positional Isomers (Rated as: excellent)
						Methylenedioxybenzene Derivates. 27. The Synthesis of Dimethoxy-Methylenedioxy-Allylbenzenes Franz Dallacker Chem. Ber. 102, 2663-2676 (1969) (https://www.rhodium.ws/pdf/apioles.dallacker.pdf) Abstract The synthesis of 2,3-Dimethoxy-4,5-Methylenedioxy- (Dillapiole), 2,5-Dimethoxy-3,4-Methylenedioxy- (Parsley Apiole), 4,6-Dimethoxy-2,3-Methylenedioxy-, 2,6-Dimethoxy-3,4-Methylenedioxy-, 5,6-Dimethoxy-2,3-Methylenedioxy- and 4,5-Dimethoxy-2,3-Methylenedioxy-allylbenzene is described. _{(In German)} ^{The Hive - Clandestine Chemists Without Borders}

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