* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Stage #1: With triethylamine; magnesium chloride In acetonitrile for 4 h; Reflux Stage #2: With hydrogenchloride In water; acetonitrileCooling with ice
13.5 g 2-allylphenol (0.1 mol) and 100 mL acetonitrile were added to a three-necked bottle, to which 6.5 g paraformaldehyde, 22 g anhydrous magnesium chloride (0.39 mol) and triethylamine (0.02 mol) were added in this order with stirring at room temperature. After refluxing for 4 hours, the reaction solution was poured into ice water, which was adjusted with aqueous HCl solution to a pH of 5. After extraction with ethyl acetate twice, drying with anhydrous sodium sulfate and concentration under reduced pressure, 11 g solid was obtained. Yield: 68percent, MS: 163 (M+1).
68%
Stage #1: With triethylamine In acetonitrile for 4 h; Reflux Stage #2: With hydrogenchloride In water; acetonitrile
Step G: Preparation of 3-allyl-2-hydroxy benzaldehyde 13.5 g 2-allylphenol (0.1 mol) and 100 mL acetonitrile were added to a three-necked bottle, to which 6.5 g paraformaldehyde, 22 g anhydrous magnesium chloride (0.39 mol) and triethylamine (0.02 mol) were added in this order with stirring at room temperature. After refluxing for 4 hours, the reaction solution was poured into ice water, which was adjusted with aqueous HCl solution to a pH of 5. After extraction with ethyl acetate twice, drying with anhydrous sodium sulfate and concentration under reduced pressure, 11 g solid was obtained. Yield: 68percent, MS: 163 (M+1).
The o-hydroxybenzaldehyde is first reacted with 3-bromopropene,To give intermediate O-A,And then under high temperature conditions for rearrangement reaction,To give 2-hydroxy-3-allylbenzaldehyde,As shown in Scheme 6,The specific preparation method is as follows: O-hydroxybenzaldehyde (290 g, 2.38 mol) was dissolved in 500 ml of DMF,K2CO3 (493 g, 3.57 mol) was added,Followed by the dropwise addition of 3-bromopropene (346 g, 2.86 mol)60 reaction 15h,Filter,The filtrate was poured into 500 mL of CH2Cl2,The organic phase was washed successively with 5percent aqueous NaOH,Saturated salt water and washed,Anhydrous Na2SO4 dried,Concentrated under reduced pressure,To give 317 g of a yellow oil,Yield 82.3percent.317 g (1.96 mol) of 2-allyloxybenzaldehyde was reacted at 200 ° C for 4 h,And distilled under reduced pressure to give 200 g of 3-allyl-2-hydroxybenzaldehyde as a yellow oil,Yield 63percent
Reference：
[1] Tetrahedron Letters, 1995, vol. 36, # 11, p. 1845 - 1848
[2] European Journal of Medicinal Chemistry, 1997, vol. 32, # 1, p. 71 - 82
[3] Archiv der Pharmazie, 2014, vol. 347, # 12, p. 936 - 949
[4] Patent: WO2010/91382, 2010, A1, . Location in patent: Page/Page column 31
[5] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2010, vol. 49, # 11, p. 1552 - 1555
[6] Patent: CN104230845, 2017, B, . Location in patent: Paragraph 0541; 0542; 0543; 0544
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[15] Organic Letters, 2017, vol. 19, # 5, p. 1008 - 1011
3
[ 1745-81-9 ]
[ 24019-66-7 ]
Yield
Reaction Conditions
Operation in experiment
68%
With magnesium chloride; triethylamine; paraformaldehyde In acetonitrile
Step G: Preparation of 3-allyl-2-hydroxy benzaldehyde 13.5 g 2-allylphenol (0.1 mol) and 100 mL acetonitrile were added to a three-necked bottle, to which 6.5 g paraformaldehyde, 22 g anhydrous magnesium chloride (0.39 mol) and triethylamine (0.02 mol) were added in this order with stirring at room temperature. After refluxing for 4 hours, the reaction solution was poured into ice water, which was adjusted with aqueous HCl solution to a pH of 5. After extraction with ethyl acetate twice, drying with anhydrous sodium sulfate and concentration under reduced pressure, 11 g solid was obtained. Yield: 68percent, MS: 163 (M+1).
With triethylamine; at 20 - 160℃; for 0.75h;Emrys Optimizer Microwave reactor;
To a solution of <strong>[24019-66-7]3-allylsalicylaldehyde</strong> (1.62 g, 10.0 mmol) in acetic anhydride (2 ml.) in a 5 ml. Emrys process vial was added Et3N (2.0 ml). The reaction was heated at 160 0C for 45 min in an Emrys Optimizer Microwave reactor then was cooled to RT. The reaction was diluted with 50 ml. of ethyl acetate, the organic layer was washed with aqueous ammonium chloride, aqueous sodium chloride, dried (Na2SO4), and concentrated. Purification of the residue by flash chromatography on silica gel (gradient elution: 5% to 30% Ethyl acetate/Hexanes) yielded the title compound (750 mg, 40%) as a colorless oil: MS (ES) m/e 186.9 (M + H)+.
10,16-diallyl-12,13,27,28-tetrahydro-14H,29H-bis[1,2,4]triazolo[4,3-f:3,4-l]dibenzo[b,p][1,18]dioxa[8,11]dithia[5,6,13,14]tetraazacyclouncosine[ No CAS ]
10,17-diallyl-5,6,12,13,14,15,21,22,28,29-decahydrobis[1,2,4]triazolo[4,3-f:3,4-l]dibenzo[b,p][1,18]dioxa[8,11]dithia[5,6,13,14]tetraazacyclodocosine[ No CAS ]
10,16-diallyl-3,23-diphenyl-12,13,27,28-tetrahydro-14H-bis[1,2,4]triazolo[4,3-f:3,4-l]dibenzo[b,p][1,18]dioxa[8,11]dithia[5,6,13,14]tetraazacyclouncosine[ No CAS ]
10,17-diallyl-3,24-diphenyl-12,13,14,15,28,29-hexahydrobis[1,2,4]triazolo[4,3-f:3,4-l]dibenzo[b,p][1,18]dioxa[8,11]dithia[5,6,13,14]tetraazacyclodocosine[ No CAS ]
10,17-diallyl-3,24-diphenyl-5,6,12,13,14,15,21,22,28,29-decahydrobis[1,2,4]triazolo[4,3-f:3,4-l]dibenzo[b,p][1,18]dioxa[8,11]dithia[5,6,13,14]tetraazacyclodocosine[ No CAS ]
10,17-diallyl-3,23-dibenzyl-12,13,27,28-tetrahydro-14H,29H-bis[1,2,4]triazolo[4,3-f:3,4-m]dibenzo[b,p][1,18]dioxa[8,11]dithia[5,6,13,14]tetraazacyclouncosine[ No CAS ]
10,17-diallyl-3,24-diphenyl-12,13,14,15,28,29-hexahydro-30H-bis[1,2,4]triazolo[4,3-f:3,4-m]dibenzo[b,q][1,19]dioxa[8,12]dithia[5,6,14,15]tetraazacyclotricosine[ No CAS ]
10,17-diallyl-3,24-dibenzyl-12,13,14,15,28,29-hexahydro-30H-bis[1,2,4]triazolo[4,3-f:3,4-m]dibenzo[b,q][1,19]dioxa[8,12]dithia[5,6,14,15]tetraazacyclotricosine[ No CAS ]
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