IL27076A - Production of n-substituted amides - Google Patents

Description

Production of amides 2 relates to the production of amides in which the to the reaction medium in which it is Hereinafter said amides will be referred to for short as More specifically the invention relates to the production of amides by reaction between a and an olefin or a secondary or tertiary a selected from the secondary alcohols and tertiary alcohols be referred to some instances for short as or the acceptor Percentages herein are expressed by weight otherwise Where the nitrile starting material contains more than one nitrile group the product will contain a ponding number of The reaction a nitrile and an acceptor compound to produce an amide is Sitter and 4045 According to this known a nitrile interacts with an acceptor compound in the presence of concentrated sulphuric After hydrolysis and neutralization the resulting aside is separated from the reaction mixture by A difficulty inherent in this process is the problem of disposal of the spent sulphuric A further inherent dif iculty is encountered in eases where either the olefin or the nitrile Includes an or other radical which may react with concentrated sulphuric acid to form a sulphonlc acid undergo In accordance with the invention there is provided a process for the production of an which comprises the steps of reacting an acceptor being an a secondary alcohol or tertiary with a nltrile in the presence of an acidic being sulphuric phosphoric acid or a partial eater of phoric acid and reacting the product of Step with a compound having the general in which represents a hydrocarbon radical or an inertly substituted hydrocarbon radical provided the substituent is other than OH or and may represent a hydrogen atom when said acidic compound is phosphoric acid or a partial ester and in which X represents oxygen or sulphur provided that where phosphoric acid or a partial ester thereof used as the acidic the acceptor compound If desired the reaction mixture may be further if desired the reaction mixture may be diluted with water and an amide recovered from the reaction In accordance with one embodiment of the invention there is provided a process wherein does not represent a hydrogen but said compound in step has the general formula in which represents a hydrocarbon radical or an inertly substituted hydrocarbon radical and X is as de ined in the preceding paragraph and wherein at least one having the general formula 4 or which is as defined A is as defined below and X is as defined in the preceding paragraph a salt of said ester is separately recovered from the reaction a mixture comprising an amide and at least one ester or a salt thereof as defined above may be recovered as the final It was surprising to discover in accordance with one embodiment of the invention that in the reaction mixture resulting from the reaction of an acceptor compound with a either in the presence of sulphuric phosphoric acid or a partial ester of phosphoric the mixture reacts very rapidly with the compound to produce mono derivatives of the acid This was not to be expected since when pure sulphuric or phosphoric acid or a partial of phosphoric acid is reacted with a compound of any reaction occurs only very if at This is illustrated by the Test after Example 22 The overall process scheme can be illustrated in the case of an olefin as the acceptor compound as 5 in which A represents a a hydrocarbon radical or an inertly substituted hydrocarbon represents inertly a hydrogen a hydrocarbon radical or hydrocarbon radical and represents a hydrocarbon radical inertly or hydrocarbon It is seen that in addition to the amide the process can provide substituted sulphuric or phoric acid derivatives which may be for as lubricant components in corrosion resisting in leather tanning and as larvaecidee or as and as components in plastics to impart fire resistance and plasticity amides may be useful additives to and intermediates in the production of synthetic gents and surface active and also as thickening agents for paints and since both akl phosphoric or sulphuric acid and amides are generally surface active emulsifiers or the mixture as produced directly by an embodiment of the process according to the or the mixtures remaining after partial separate recovery of the also be useful for these If the resulting amide can be hydrolysed into an amine and a free which hydrolysis proceeds according to the following S i f 6 It is thus seen that the result of the overall reaction in this case is a transfer of the nitrogen atom the nitrile to the acceptor compound in other an In accordance with a further embodiment of the the acceptor compound is reacted in step with the nitrile under coonrdiatipoanrsiianlwehsitchertohfe compound is liquid and in the presence of phosphoric whose concentration at least by the reaction product rom step is hydrolysed i and an substituted amide is recovered from the sed reaction Where in a process according to the invention either the acceptor compound or the nitrile comprises an aromatic radical the use of phosphoric aoid or a partial ester thereof is Where phosphoric acid or a partial ester thereof is used and the acceptor compound is under normal atmospheric conditions the case of a olefin faction can be achieved by cooling or by using elevated Where the aoid used in a process according to the invention is sulphuric the use of the acceptor compound in liquid form is The reaction temperature may vary between wide limits depending on the nature of the The molar ratios between the acceptor the nitrile and the phosphoric or sulphuric acid may vary 7 within wide in particular since in some cases the nitrlle also serve as solvent for the reaction the molar ratios in the process according to the invention should preferably be so selected that the yield of the aside calculated on either the acceptor or the nitrlle should not be below in a process according to the phosphoric acid is used and operation ia at ambient the molar ratio of acid to should at least be to produce good for only molar equivalents are used at ambient the yield of the product is usually approximately based on either of the reactants yields than with this reaction ratio can be achieved by operating at elevated temperature or in a more acidic When the molar ratio of phosphoric acid to nitrlle is at least and operation is at ambient the yields are generally and based on either the acceptor or She phosphoric acid can be recovered from the process in the form of ammoniumalkali metal which are valuable fertiliser The nitr compound may each aliphatic or aromatic and chosen from a large Some of are listed in the following 7a in which R Acceptor in situ from a metal Gyclohexanol 2 6 4 2 The reacta t used in step to produce the substituted phosphoric or sulphuric aoid ean be or substituted secondary or tertiary alcohol or phenol or thio the reaction is very rapid and so that esters of inorganic acid difficult to pare by other means derivatives phosphoric can be obtained in this It is sometimes convenient although not necessary to use a solvent or diluent other than a reagent of the action these may for carbox lic such as acetic or Alternativel it is possible to operate in the presence of exeeee nltrile the reaction mixture otherwise too viscous for effective if the introduction of additional is The is illustrated by the following Examples to which it is not g of g of phosphoric and 50 ee of 100 acetic acid were mixed at atmospheric pressure in a glass vessel surmounted by a acetone condenser while 12 g of was introduced at ambient She reaction mixture was then poured into 200 g of ater and neutralised with acetamlde was extracted with 5 x 50 ee of ether from which it was recovered in a yield based on half the quantity of and ia a pure state by evaporation of the The spectrum of product was identical to that of pure Example 2 1 was repeated in all respects except that the quantity phosphoric acid taken was me yield of pure amide was thereby increased to Bxample When the reaction described Example 2 was repeated in the presence of ee of the yield of acetamlde was essentially ed of g of phoephoric 20 of acetic aeid and 10 ee of contained in a rocking autoclave were heated at The product was worked ae in Example 1 and yielded of pure 56 g of leeeutene wae added under a reflux condeneer into a mixture of ee of aeetonitrlle and g of product was worked up as Example 1 yielding on the quantity of of the pure ee of dry aeetonitrlle wae added to g of solution wae poured a eixty ee pressure tube whieh wae cooled a aeetone Liquid 10 ee wae added to the cold the tube eloeed a pressure and shaken at ambient temperature for two The leeeutene was then removed by lla ion at ambient temperature and atmoepherle pressure for Anhydrous methyl 25 ee was added ami the mixture shaken for one and a half hour at poured fifty of neutralised with fhe netural solution was extracted w th 5 x ee a ter drying and evaporation of the this extras yielded g f 19 The aqueous was with 120 and thereafter found to contain mole of monomethyl phoephoric acid in addition to unreaeted The overall yield baaed on half the amount of initially preeent was of both amide and monoalkyl phoephorio Other experiments in essentially the manner are described in mole Example Hydroxy Compound 100 Olefin 7 alcohol 8 Phenol N 9 alcohol N n 10 alcohol n 11 mercaptan N 12 oxide M N 15 Methyl alcohol M later Based on half the amount of 4 was used Based on the total amount of present was used the presence of glacial AcOH 12 A mixture made from g of 20 ml dry aoetonitrile and 10 ml of a ml glass pressure tube at ambient was shaken two The vieccus mixture which was obtained was mixed with 30 ml of absolute ethyl alcohol and shaken for another half an water was then added and the solution neutralised with The neutral aqueous solution was extracted with ether and the aqueous phase after passed over a exchange resin in the hydrogen form IE was found by chromatography to consist of a mixture of sulfuric and ethyl sulfuric The ether after yielded g of being compound was found to contai and An mixture of and methyl phosphoric mole of eac essentially free of phosphoric was reacted at a glass twenty ml of dry and 10 ml of After two the excess was removed and twenty ml of absolute methyl alcohol was added and the heating continued for one a half hours at After the solution was poured over neutralised and extracted with The ether extract g of aoe identified by its and by comparing its to that of The residual aqueous analysed by paper chromatograph shoved that both the and phosphoric acids had the molar ratio of the acids had changed to a ratio la respect of methyl Example 21 quantities of a After neutralisation and extraction with a crystalline product was recovered the extract was that of aerylaalde is reported to be Example 22 was substituted in Example The ether extract after a crystalline solid that of hexyl acrlamide is reported to be As specified pure phosphoric acid not readily react with a compound and X are as defined This illustrated by the following 23 g of phosphoric with twenty ml of anhydrous methyl The solution was stirred at ambient temperature for two diluted with water and found by analysis to consist of phosphoric acid methyl phosphoric acids and mixtures of aerylonitrile egrelohexanol were with a five molar of and with for one hour at After a crystalline product was recovered a quantitative yield on the amount of either or solid product was identified by being Ita spectrum vaa to that of pure mixtures of aerylonitrile and propaaol mixed h a fire molar oxeoaa of 100 and with for one hour at After neutralisation and extraotion with an organic compound was Its Reported for A mixture of 4 g of 5 g of and fifty of ethylene glyool refluxod for four The product was distilled at atmospheric pressure through a fractionating column and the collected produet was found by speetral analysis to contain primary By gas the compound was found to be over fhe piorate of the produet molted at while the reported value for the piorate of la insufficientOCRQuality

Claims (39)

- 15 - 27076/2 CLAI

1. A process for the produetion of an N-substituted amide (as hereinbefore defined), which comprises the steps of (a) reacting an acceptor compound, being an olefin, a secondary alGOhol or a tertiary alcohol, with a nitrile in the presence of an acidic compound, being sulphuric acid, phosphoric acid or a partial ester of phosphoric acid, and (b) reacting the product step (a) with a compound having the general formula R'XH in which R' represents a hydrocarbon radical or an inertly substituted hydrocarbon radical provided the substituent is other than OH or SH and may represent a hydrogen atom when said acidic compound is phosphoric acid or a partial ester thereof, and in which X represents oxygen or sulphur provided that where phosphoric acid or a partial ester thereof is used as the acidic compound, the acceptor compound is liquid, whereby there is produced an N-substituted amide.

2. A process according to Claim 1, wherein an if-substltuted amide is recovered from the reaction mixture.

3. A process according to Claim 1 or 2, wherein the reaction mixture is neutralised.

4. A process according to Claim 1, 2 or 3» wherein the reaction mixture is diluted with water.

5. A process according to any one of Claims 1 to 4, wherein R' does not represent a hydrogen atom, but said compound used in step (b) has the general formula - 16 - 27076/2 R* *XH In which R' ' represents a hydrocarbon radical or an Inertly substituted hydrocarbon radical and X is as defined in Claim 1 and wherein at least one este , having the general formula Ε· ·Α2 Ρ0? or Ε··ΗΧ80¾ in which R' ' is as defined above, A represents a hydrogen atom, a hydrocarbon radical or an inertly substituted hydrocarbon radical and X is as defined in Claim 1» and/or a salt of said ester is separately recovered from the reaction mixture.

6. A process according to Claim 5» wherein a mixture comprising an N-subatituted amide and at least one ester or salt thereof, as defined in Claim 5, is recovered froa the reaction mixture.

7. A process according to Claim 1, wherein the acceptor compound is reacted in step (a) with the nitrile wider conditions in which the acceptor compound is liquid and in the presence of phosphoric acid or a partial ester of phosphoric acid, whose concentration is at least 70 by weight, the reaction product from step (a) is hydrolysed in step (b) and an -substituted amide is recovered from the hydrolysed reaction mixture·

8. A process according to any one of the preceding claims, wherein phosphoric acid or a partial ester of phosphoric acid is used as the acidic compound and the ratio - 17 - 27076/2 of acidic compound to nitrile la at least 2:1.

9. A process according; to any one of the preceding claims, wherein the mixture for the reaction between the acceptor compound and the nitrile comprises a solvent therefor.

10. A process according to any one of the preceding r claims, wherein phosphoric acid is used as the acidic compound and wherein the reaction mixture is neutralised and thereafter an ammonium or alkali metal salt of phosphoric acid is recovered from the reaction mixture.

11. A process aeoordiag to any one of Claims 1 to 5 and 7 to 10, which further comprises the additional step of hydrolysing the N-substituted amide thereby to obtain a free carboxylic acid and an amine.

12. A process, substantially as described in foregoing Example 1.

13. A process* substantially as described in foregoing Example 2.

14. · A process, substantially as described in foregoing Example 3·

15. A process» substantially as d scribed in foregoing Example 4.

16. A process substantially as described in foregoing Example 5.

17. A process, substantially as described in foregoing Example 6. - 18 - 27076/2

18. A process, substantially as described in foregoing Example 7.

19. A process, substantially as described In foregoing Example 8.

20. A process, substantially as described In foregoing Example 9.

21. A process, substantially as described in foregoing Example 10.

22. A process, substantially as described in foregoing Example 11.

23. 3. A process, substantially as described in foregoing Example 12.

24. A process, substantially as described in foregoing Example 13.

25. A process, substantially as described in foregoing Example 14.

26. A process, substantially as described in foregoing Example 15.

27. A process, substantially as described i foregoing Example 16.

28. A process, substantially as described in foregoing Example 17·

29. A process, substantially as described in foregoing Example 18. - 19 27076/2

30. A process, substantially as described in foregoing Example 19.

31. A process* substantially as described in foregoing Example 20.

32. A process, substantially as described in foregoing Exaxiple 21.

33. A process, substantially as described in foregoing Example 22.

34. A process, substantially as described in foregoing Example 24.

35.. A process, substantially as described in foregoing Example 25.

36. A process, substantially as described in foregoing Example 26.

37. An If-substltuted aaide whenever produced b the process of any one of Clalme 1 to 10 and 12 to 35*

38. An ester having the general formula K««Al2xw3 or R^H SO, 3 in which E" is as defined in Claim 5» A is as defined in Claim 5 and X is as defined in Claim 1, and/or a salt of said eater, whenever produced by the process of any one of Claims 1 to 5, 17 to 23» 26 to 28, 30 and 31 or any one of Claims 6, 8, 9, 10 or 11 when appended to Claim 5. - 20 - 27076/2

39. A ffilxture whenever produoed by the process of Claim 6 or any one of Claims 8, 9 or 10 when appended to Claim 6. 40· An amine whenever produced by the process of Claim 11 or 36. MC/rb