4-(N,N-dimethylamino)butyraldehyde dimethyl acetal [CAS 19718-92-4; InChIKey WDZKKBDOGYBYBG-UHFFFAOY

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2016-02-23 21h:33m:32s (EST)

O

O

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O

N

O

O

N

Cl O

O

Rx-ID: 22878996 View in Reaxys 1/4 Yield 71 %

Conditions & References 1 : Preparation of the Grignard reagent and the compound of the formula-I wherein [RAPOS;] [=R2 =R3=ME] Into a 2L four-necked round bottom flask was charged magnesium turnings (25gr) under N2 atmosphere. Benzene [(50ML),] the above benzene solution [(50ML),] trimethyl orthoformate (20gr), and a small crystal of iodine were added into the flask and heated to reflux temperature. Within 15-20min of reflux, vigorous reaction took place indicating the initiation of Grignard reaction. Remaining quantity of the benzene solution [(600ML)] and trimethyl orthoformate of the [FORMULA-XVII] where [R3] = R5 = Me (119gr) were taken into two separate addition funnels and added to the reaction mass at reflux temperature over a period of [3-4] hrs. After the addition, the reaction mass was maintained at reflux for another 2hrs and cooled to [25°C.] The reaction mass was filtered over a celite pad and washed the cake with [100ML] of benzene. Benzene was removed from the reaction mass by ordinary distillation keeping a 20cm vigroux column.

Excess trimethyl orthoformate was distilled under mild vaccum keeping the mass below [80°C.] Finally, the residue was distilled under vaccum to afford [100GR] (71percent) [OF 4- (N,] N-dimethylamino) butyraldehyde dimethyl acetal as a colorless liquid. B. p.: [80-85°C/15-20MM).]

With iodine, magnesium in benzene, Time= 5.25 - 6.33333h, Heating / reflux Patent; NATCO PHARMA LIMITED; WO2003/101931; (2003); (A2) English View in Reaxys

60 %

2 : Preparation of the Grignard reagent and the compound of the [FORMULA-I WHEREIN] [= R2 = R3 = ME] Into a 2L four-necked round bottom flask was charged magnesium turnings (25gr), toluene [(50ML),] the above toluene solution [(50ML),] trimethyl orthoformate (20gr), and a small crystal of iodine under nitrogen atmosphere at [25°C.] The contents were slowly heated to [75-80°C.] After maintaining for about 20 min, a vigorous reaction took place indicating the initiation of Grignard reaction. Remaining quantity of the toluene solution [(600ML)] and trimethyl orthoformate of the formula-XVII where [R3] = [R5] = Me [(119GR)] were taken into two separate addition funnels and added to the reaction mass at [75-80°C] over a period of 3-4 hrs. After the addition, the reaction mass was maintained at 75- [80°C] for another 2hrs and cooled to [25°C.] The reaction mass was filtered over a celite pad and washed the cake with [100ML] of toluene. Toluene was removed from the reaction mass by ordinary distillation keeping a 20cm vigroux column. Excess trimethyl orthoformate was distilled under mild vaccum keeping the mass below [80°C.] Finally, the residue was distilled under vaccum to afford 85gr (60percent) of 4- (N, N- dimethylamino) butyraldehyde dimethyl acetal as a colorless liquid. B. p.: [80-85°C/15-] 20mm).

With iodine, magnesium in toluene, Time= 5.33333 - 6.33333h, T= 25 - 80 °C Patent; NATCO PHARMA LIMITED; WO2003/101931; (2003); (A2) English View in Reaxys

53 %

3 : Preparation of the Grignard reagent and the compound of the formula-I wherein [=RT =R3 =ME] Into a 2L four-necked round bottom flask were charged magnesium turnings [(18GR),] THF [(50ML),] the above THF solution [(SOGR),] trimethyl orthoformate (lOgr), and a small crystal of iodine under nitrogen atmosphere at [25°C.] The contents were slowly heated to reflux temperature. After maintaining for about 20 min at reflux a vigorous reaction took place indicating the initiation of Grignard reaction. Remaining quantity of the THF solution [(550GR)] and trimethyl orthoformate of the formula-XVII where [R3= R5] = Me (90gr) were taken into two separate addition funnels and added to the reaction mass at [75-80°C] over a period of 3-4 hrs. After the addition, the reaction mass was maintained at reflux for another 2hrs and cooled to [25°C.] The reaction mass was filtered over a celite pad and washed the cake with 100ml of THF. THF was removed from the reaction mass by ordinary distillation keeping a 20cm vigroux column. Excess trimethyl orthoformate was distilled under mild vaccum keeping the mass [BELOW 80°C.] Finally, the residue was distilled under vaccum to afford 75gr (53percent) of [4- (N,] N-dimethylamino) butyraldehyde dimethyl acetal as a colorless liquid. B. p.: [80-85°C/15-20MM).]

With iodine, magnesium in tetrahydrofuran, Time= 5.33333 - 6.33333h, T= 25 - 80 °C , Heating / reflux Patent; NATCO PHARMA LIMITED; WO2003/101931; (2003); (A2) English View in Reaxys 1 : Example 1; 4,4-Dimethyl amino butyraldehyde dimethyl acetal 100GMS (0. 66MOL) OF CHLORO bromo propane was taken in 100RNL OF CYCLOHEXANE and 125gms of 42percent caustic soda lye was added at 20-25°C. The mass was stirred for 60min at 25-30 °C and 100GMS of 40percent DIMETHYLAMINE was added. The mass was stirred for 24 hours at 25-30 °C, checked for the absence of chloro bromo

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propane (limit 5percent). 200ML of cyclohexane was added and organic layer was separated and dried with sodium sulfate. The organic layer was used for next stage without isolation/purification. 25gms of magnesium turnings and 70ML OF TRIMETHYLORTHO FORMATE was taken in a well-dried flask which was equipped with an addition funnel, thermometer socket and reflux condenser. The reaction mass was heated to 65-70 °C and the above organic layer was added in 4 hours. The reaction mixture was stirred for 2 hours at 65-70 °C and cooled to 25-30°C. The mass was filtered and filtrate was stripped off solvent under reduced pressure. The product was distilled under 10-15MMLHG at 145-150 ° C to get 28gms of the >90percent pure (GC) 4, 4-DIMETHYLAMINO butyraldehyde dimethyl acetal, which can be used straight away for the next stage; With magnesium in cyclohexane, Time= 6h, T= 65 - 70 °C Patent; POTLURI, Ramesh, Babu; HARIHARAKRISHNAN, Venkata, Subramanian; TADIMALLA, Venkata, Srihari; KODALI, Hari, Prasad; GOTTIMUKKALA, Venkata, Mallaparaju; WO2004/99141; (2004); (A1) English View in Reaxys

O

O

NH 2

N

I O

O

Rx-ID: 11110206 View in Reaxys 2/4 Yield

Conditions & References

53 %

With potassium carbonate in methanol, Time= 5h, T= 60 °C Hassan, Maizom; Morimoto, Sachiko; Murakami, Hiroyuki; Ichiyanagi, Tsuyoshi; Mori, Nobuhiro; Bioscience, Biotechnology and Biochemistry; vol. 71; nb. 6; (2007); p. 1439 - 1446 View in Reaxys

O

O

Cl

N H

O

N O

Rx-ID: 3288376 View in Reaxys 3/4 Yield

Conditions & References

87 %

in water, 1.) r.t., 15 min, 2.) 62 deg C, 1 h Chen; Senanayake; Bill; Larsen; Verhoeven; Reider; Journal of Organic Chemistry; vol. 59; nb. 13; (1994); p. 3738 - 3741 View in Reaxys

O

N O

Rx-ID: 7167772 View in Reaxys 4/4 Yield

Conditions & References Patent; Takahara; Yoshida; JP6809529; (1966); ; vol. 69; nb. 107070z; (1968) View in Reaxys

Copyright © 2016 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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