1. 2,5-Dimethoxy-4-methylbenzaldehyde

Page 1

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Reactions (20)

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Substances (4)

Citations (23)

Conditions

References

1

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Rx-ID: 1999746 Find similar reactions

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With tin(IV) chloride

1.) CH2Cl2, 0 deg C, 1 h, 2.) CH2Cl2, a) 0 deg C, 30 min, b) RT, 1 h; Yield given. Multistep reaction;

2

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Kretzschmann, H.; Meier, H.

Journal fuer Praktische Chemie/Chemiker-Zeitung, 1994 , vol. 336, # 3 p. 247 - 254 Title/Abstract Full Text Show Details


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Rx-ID: 2067251 Find similar reactions

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With hydrogenchloride; aluminium trichloride; sulfuric acid

1) tetrachloroethane, 8 h, 65-70 deg C 2) overnight, room temperature 3) steam distillation; Yield given. Multistep reaction;

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Malesani, Giorgio; Galiano, Fabio; Ferlin, Maria Grazia; Masiero, Sergio

Journal of Heterocyclic Chemistry, 1980 , vol. 17, p. 563 - 569 Title/Abstract Full Text Show Details

3

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With selenium(IV) oxide

Rx-ID: 4305568 Find similar reactions

Sayigh,A.A.R. et al.

Journal of the Chemical Society, 1964 , p. 3482 - 3484 Full Text View citing articles Show Details

4

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Rx-ID: 4323550 Find similar reactions

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86%

Stage #1: N-methyl-N-phenylformamide With phosphoryl chloride

T=20°C; 0.833333 h; Inert atmosphere; Stage #2: 2-methyl-1,4-dimethoxybenzene T=70°C; 1 h; Inert atmosphere;

Miyawaki, Akari; Kikuchi, Daisuke; Niki, Masu; Manabe, Yuki; Kanematsu, Makoto; Yokoe, Hiromasa; Yoshida, Masahiro; Shishido, Kozo

Journal of Organic Chemistry, 2012 , vol. 77, # 18 p. 8231 - 8243 Title/Abstract Full Text View citing articles Show Details

67%

Stage #1: N-methyl-N-phenylformamide With phosphoryl chloride

T=20°C; 0.666667 h; Stage #2: 2-methyl-1,4-dimethoxybenzene T=50°C; 6 h; Stage #3: With sodium acetate; sodium hydrogensulfite

more than 3 stages; Hide Experimental Procedure

Bignon, Eric; Bras, Jean Pierre; De Cointet, Paul; Despeyroux, Pierre; Frehel, Daniel; Gully, Danielle

Patent: US2004/43995 A1, 2004 ; Location in patent: Page 12 ; Title/Abstract Full Text Show Details

A.a:Preparation of the Syntetic Intermediates; A. Preparation of the Acids 1 (Variants); 2,5-Dimethoxy-4-methylbenzoic Acid (Compound A.1); a) 2,5-Dimethoxy-4-methylbenzaldehyde After stirring a mixture of 8.5 mi of N-methyifor maniiide (0.068 moi) and 6.3 mi of phosphorus oxytrichio ride (0.068 moi) at room temperature for 40 minutes, 17.8 g of 2,5-dimethoxytoiuene (0.117 moi) are introduced. The reaction mixture is heated for 6 hours at 500 C. and then, after returning to a temperature of 20 C., it is hydroiysed with 100 mi of aqueous 10percent sodium acetate soiution, extracted twice with diethyi ether and concentrated. The residue is taken up in aqueous sodium hydrogen suiphite soiution and extracted twice with diethyi ether. The aqueous phase is basied (pH=12) in order to give white crystais; m.p.=83 C.; yieid=67percent. (i) POCl3, (ii) /BRN= 2045336/; Multistep reaction;

Standridge; Howell; Gylys; et al.

Journal of Medicinal Chemistry, 1976 , vol. 19, # 12 p. 1400 - 1404


Title/Abstract Full Text View citing articles Show Details

Hide Details

With phosphoryl chloride

T=0 - 80°C; 1 h; Hide Experimental Procedure

Mohr, Peter; Nettekoven, Matthias; Plancher, Jean-Marc; Richter, Hans; Roche, Olivier; Takahashi, Tadakatsu; Taylor, Sven

Patent: US2009/29976 A1, 2009 ; Location in patent: Page/Page column 22 ; Title/Abstract Full Text Show Details

11.1:2,5-Dimethoxy-4-methyl-benzaldehyde

Step 1 2,5-Dimethoxy-4-methyl-benzaldehyde To a solution of 2,5-dimethoxytoluene (4.66 g, 30.6 mmol) in 60 mL of N-methyl-N-phenyl-formamide was added at 0° C. POCl3 (8.41 mL, 3 eq.), and the mixture was heated for 60 Min. to 80° C. After cooling, the reaction mixture was poured onto crashed ice, twofold extracted with AcOEt, washed with water, dried over sodium sulfate, and evaporated to dryness. Flash chromatography (SiO2, hexane/AcOEt=9/1) afforded 4.153 g of the title compound as off-white solid. MS (ISP): 181.3 [M+H]+.

Stage #1: N-methyl-N-phenylformamide With phosphoryl chloride

T=20°C; 4 h; Stage #2: 2-methyl-1,4-dimethoxybenzene T=70°C; 2 h; Hide Experimental Procedure

Title/Abstract Full Text Show Details

1.a:

Preparation 1; 2,5-Dimethoxy-4-methylbenzoic acid (Compound XII); a) 2,5-Dimethoxy-4-methylbenzaldehyde; 280 ml of phosphorus oxide trichloride are admixed with 212 ml of N-methylformanilide. After 4 hours at room temperature, 110 g of 2,5-dimethoxytoluene are added and the reaction mixture is brought to 70° C. for 2 hours. The reaction mixture is poured dropwise onto ice. The precipitate obtained is filtered, taken up in dichloromethane and decanted. The organic phase is dried over anhydrous sodium sulphate and the solvents are evaporated under reduced pressure. This gives 116 g of yellow crystals; m.p.=83° C.

5

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Rx-ID: 5214044 Find similar reactions

Bignon, Eric; Csikos, Eva; Frehel, Daniel; Gonczi, Csaba; Heja, Gergley; Morvai, Miklos; Podanyi, Benjamin; Schlovicsko Varkonyine, Erika

Patent: US2004/19091 A1, 2004 ; Location in patent: Page/Page column 6 ;

85.9%

With phosphoryl chloride

T=80°C; 8 h; Hide Experimental Procedure

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NOVARTIS AG; BECKWITH, Rohan Eric, John; BRITO, Luis; DECHRISTOPHER, Brian, Addison; GAMBER, Gabriel, Grant; GEALL, Andrew; ZABAWA, Thomas

Patent: WO2016/37053 A1, 2016 ; Location in patent: Page/Page column 81 ; Title/Abstract Full Text Show Details

14:2,5-dimethoxy-4-methylbenzaldehyde

Phosphorous oxychloride (12.5 mL) was slowly added to 2,5-dimethoxy-toluene (5 g, 3.3 mmol) in 10 mL DMF. The reaction was stirred at room temperature for 4 h then heated to 80 °C for 4 h. Then the reaction was poured into ice water and filtered. The filtrate was collected, dried over sodium sulfate and concentrated under reduced pressure to provide 5.1 g (85.9percent) of the desired product as a pale yellow solid. TLC: Rf = 0.4 (EtOAc: Hexane, 1 :9), UV active.

80%

With phosphoryl chloride in 1,2-DICHLOROETHANE

T=80°C; Vilsmeier-Haack formylation; 12 h;

Mehta, Goverdhan; Khan, Tabrez Babu; Sunil Kumar

Tetrahedron Letters, 2010 , vol. 51, # 39 p. 5116 - 5119 Title/Abstract Full Text View citing articles Show Details

With phosphoryl chloride

T=60°C; Formylation; 24 h;

Tomatsu, Ayumi; Takemura, Syunji; Hashimoto, Kimiko; Nakata, Masaya

Synlett, 1999 , # 9 p. 1474 - 1476 Title/Abstract Full Text View citing articles Show Details


6

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7

Lewin et al.

Organic Preparations and Procedures International, 1978 , vol. 10, p. 201,203 Full Text Show Details

Upjohn Co.

Patent: FR1415670 , 1961 ; Chem.Abstr., 1966 , vol. 64, # 5002 Full Text Show Details

Staab et al.

Chemische Berichte, 1977 , vol. 110, p. 3351,3355 Full Text Show Details

Nakao et al.

Sankyo Kenkyusho Nenpo, 1970 , vol. 22, p. 90 Chem.Abstr., vol. 75, # 5400p Full Text Show Details

Schulgin

Patent: SU509216 , 1977 ; Ref. Zh., Khim., 1979 , vol. 11, # N156P Full Text Show Details

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8

Rx-ID: 7023705 Find similar reactions

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Multi-step reaction with 2 steps 1: 82 percent / potassium hydroxide / methanol / 8 h / steam distillation 2: 1) HCl, aluminium chloride 2) aqueous H2SO4 / 1) tetrachloroethane, 8 h, 65-70 deg C 2) overnight, room temperature 3) steam distillation View Scheme

Rx-ID: 21364071 Find similar reactions

Malesani, Giorgio; Galiano, Fabio; Ferlin, Maria Grazia; Masiero, Sergio

Journal of Heterocyclic Chemistry, 1980 , vol. 17, p. 563 - 569 Title/Abstract Full Text Show Details


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Rx-ID: 25339854 Find similar reactions

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Shulgin; Alexander T.

Patent: US4034113 A1, 1977 ;

in water

Hide Experimental Procedure

Title/Abstract Full Text Show Details

2:EXAMPLE 2 STR6

EXAMPLE 2 STR6 A solution of 40 ml. phosphorous oxychloride (POCl3) and 45 ml. of N-methylformanilide is allowed to stand at ambient temperature for 50 minutes. There is then added 15.2 g. of 2,5-dimethoxytoluene and the resulting solution is heated on the steam bath for 140 minutes. The extremely dark viscous reaction mixture is added to 2 liters of water, and allowed to stir for several hours to complete the hydrolysis of the reaction intermediates. The solid product is removed by filtration, and after washing with water and air-drying yields 16.6 g of reddish crumbly crystals. This solid product is extracted with 2*125 ml. of boiling hexane, which on cooling deposits 12.1 g. of pale cream-colored crystals. Recrystallization from boiling hexane, yields a brilliant white product 2,5-dimethoxy-4-methylbenzaldehyde.

9

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Rx-ID: 33671723 Find similar reactions

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With potassium carbonate in acetone

T=25°C; 20 h;

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Ravi Kumar; Behera, Manoranjan; Raghavulu; Jaya Shree; Yennam, Satyanarayana

Tetrahedron Letters, 2012 , vol. 53, # 32 p. 4108 - 4113 Title/Abstract Full Text View citing articles Show Details

10

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Formanilid 6, POCl3, 2,5-Dimethoxytoluol;

Rx-ID: 7192412 Find similar reactions

Matin,S.B. et al.

Journal of Medicinal Chemistry, 1974 , vol. 17, p. 877 - 882 Full Text View citing articles Show Details


11

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Rx-ID: 4323553 Find similar reactions

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Zweig,J.S.; Castagnoli,N.

Journal of Medicinal Chemistry, 1977 , vol. 20, p. 414 - 421 Full Text View citing articles Show Details

(i) POCl3, (ii) /BRN= 2331801/; Multistep reaction;

12

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Multi-step reaction with 5 steps 1: (i) SOCl2, (ii) /BRN= 1098229/ 2: LiAlD4 / tetrahydrofuran 3: PBr3 / CCl4

4: LiAlD4 / tetrahydrofuran 5: (i) POCl3, (ii) /BRN= 2331801/ View Scheme

Rx-ID: 22650687 Find similar reactions

Zweig,J.S.; Castagnoli,N.

Journal of Medicinal Chemistry, 1977 , vol. 20, p. 414 - 421 Full Text View citing articles Show Details

13

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Multi-step reaction with 3 steps 1: PBr3 / CCl4

2: LiAlD4 / tetrahydrofuran 3: (i) POCl3, (ii) /BRN= 2331801/ View Scheme

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Rx-ID: 22653813 Find similar reactions

Zweig,J.S.; Castagnoli,N.

Journal of Medicinal Chemistry, 1977 , vol. 20, p. 414 - 421 Full Text View citing articles Show Details


14

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Multi-step reaction with 2 steps 1: LiAlD4 / tetrahydrofuran 2: (i) POCl3, (ii) /BRN= 2331801/ View Scheme

Rx-ID: 22653833 Find similar reactions

Zweig,J.S.; Castagnoli,N.

Journal of Medicinal Chemistry, 1977 , vol. 20, p. 414 - 421 Full Text View citing articles Show Details

15

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Multi-step reaction with 6 steps 1: (i) Mg, EtI, Et2O, (ii) /BRN= 1900390/ 2: (i) SOCl2, (ii) /BRN= 1098229/ 3: LiAlD4 / tetrahydrofuran 4: PBr3 / CCl4

5: LiAlD4 / tetrahydrofuran 6: (i) POCl3, (ii) /BRN= 2331801/ View Scheme

Rx-ID: 22655733 Find similar reactions

Zweig,J.S.; Castagnoli,N.

Journal of Medicinal Chemistry, 1977 , vol. 20, p. 414 - 421 Full Text View citing articles Show Details

16

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3: LiAlD / tetrahydrofuran

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Rx-ID: 22659251 Find similar reactions Zweig,J.S.; Castagnoli,N.

Journal of Medicinal Chemistry, 1977 , vol. 20, p. 414 - 421 Full Text View citing articles Show Details


4

4: (i) POCl3, (ii) /BRN= 2331801/ View Scheme

17

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Rx-ID: 7206943 Find similar reactions

Toluol 13-d6, Methylformamid, POCl3, Formylierung;

Weinkam et al.

Analytical Chemistry, 1976 , vol. 48, p. 203,204 Full Text Show Details

entspr. Toluolderivat, HCN, AlCl3;

Fentiman; Foltz

Journal of Labelled Compounds and Radiopharmaceuticals, 1976 , vol. 12, p. 69,74 Full Text Show Details

18

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Rx-ID: 11147013 Find similar reactions

87%

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With titanium tetrachloride in dichloromethane

T=20°C; 0.25 h;

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Shaikh, Ajam C.; Wang, Yu-Yun; Chen, Chinpiao

Journal of Labelled Compounds and Radiopharmaceuticals, 2007 , vol. 50, # 7 p. 660 - 665 Title/Abstract Full Text View citing articles Show Details

19

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Rx-ID: 11418883 Find similar reactions


Multi-step reaction with 2 steps 1: 96 percent / KOH; Bu4NBr / 96 h / 55 °C 2: 87 percent / TiCl4 / CH2Cl2 / 0.25 h / 20 °C View Scheme

Shaikh, Ajam C.; Wang, Yu-Yun; Chen, Chinpiao

Journal of Labelled Compounds and Radiopharmaceuticals, 2007 , vol. 50, # 7 p. 660 - 665 Title/Abstract Full Text View citing articles Show Details

A

B

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20

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A: 20% B: 55%

With cobalt (III) fluoride in acetonitrile

T=20°C; Oxidation; Demethylation; 0.416667 h;

Tomatsu, Ayumi; Takemura, Syunji; Hashimoto, Kimiko; Nakata, Masaya

Synlett, 1999 , # 9 p. 1474 - 1476 Title/Abstract Full Text View citing articles Show Details


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