Process for productions of formamides and acrylamides

Abstract

This invention relates to performance chemicals field, it discloses a novel and green process for simultaneous productions of formamides as well as mono- and multi-functional acrylamides under very mild conditions and with high efficiency. These substances are widely useful as industrial solvents or raw materials, in particular acrylamides are important olefinically-unsaturated polymerizable monomers in photo-curing materials.

Claims

1. A process for preparing compound C and compound D simultaneously, wherein the process is illustrated in equation (I), starting materials are compound A and compound B under conditions: ##STR00014## wherein in the equation (I), R.sub.1 and R.sub.2 is independently selected from the group consisting of hydrogen, linear or branched aliphatic groups containing 1-24 carbons (C.sup.1-C.sup.24) and aromatic groups containing 6-24 carbons (C.sup.6-C.sup.24); R.sub.3 and R.sub.4 is independently selected from the group consisting of hydrogen, C.sup.1-C.sup.24 aliphatic groups and C.sup.6-C.sup.24 aromatic groups; R.sub.5 is selected from the group consisting of hydrogen, methyl (CH.sub.3) and hydroxymethyl (CH.sub.2OH); R.sub.6 is selected from the group consisting of OH, H, CHO, R.sub.1, OR.sub.1, NHR.sub.1, NR.sub.1R.sub.2 and OM, wherein M is a metal cation; the conditions are two or more factors selected from the group consisting of organic base, inorganic base, catalyst, promoter, inhibitor, heat, microwave, ultrasonic wave, vacuum, pressure and solvent.

2. The process according to claim 1, wherein the compound A is prepared by equation (III) with compound E, compound F and compound G as starting compounds ##STR00015##

3. The process according to claim 1, wherein the compound B is formic acid that is prepared by the following reaction: ##STR00016##

4. The process according to claim 1, wherein the compound B is formaldehyde that is prepared by the following reaction: ##STR00017##

5. The process according to claim 1, wherein the organic base is aliphatic or aromatic amine; the inorganic base is alkaline metal, alkaline-earth metal, or hydroxide, oxide, sulfide, carbonate, carboxylate, sulfonate of transition metal; the catalyst or promoter is Lewis acidic or basic compound.

6. The process according to claim 1, wherein the inhibitor is one or compounds selected from the group consisting of phenol, phenol derivative, hydroquinone, benzoquinone, naphthoquinone, phenothiazine, phosphite, N-nitroso-N-phenylhydroxylamine aluminum salt, 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy, tri-(4-hydroxy-TEMPO) phosphate, copper chloride and copper dibuthyldithiocarbamate; the amount of the inhibitor employed is in the range of 0.01-5% molar fraction.

7. The process according to claim 6, wherein the phenol derivative is 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-methoxyphenol, dibutylhydroquinone, or pyrogallic acid.

8. The process according to claim 6, wherein the amount of inhibitor employed are in the range of 0.01-3% molar fraction.

9. The process according to claim 1, wherein the reaction temperature is in the range of 25-400 C.

10. The process according to claim 2, wherein the reaction temperature is in the range of 25-400 C.

11. The process according to claim 1, wherein the reaction pressure is in the range of 0.001-50 atm.

12. The process according to claim 2, wherein the reaction pressure is in the range of 0.001-50 atm.

13. The process according to claim 1, wherein the solvent is one or more compound selected from a group consisting of aromatic or aliphatic hydrocarbon, halogenated aromatic or aliphatic hydrocarbon, ester, alcohol, ether, nitrile, ketone, amide, sulfone, carbonate, water, super-critical carbon dioxide and ionic liquids.

14. The process according to claim 3, wherein the compound A is 1,3-dimorpholinopropan-1-one, the compound C is 4-acryloylmorpholine, and the compound D is N-formylmorpholine, the corresponding reaction equation is show as following: ##STR00018##

15. The process according to claim 3, the compound A is 3-(diethylamino)-N,N-diethylpropanamide, the compound C is N,N-diethylacrylamide, the compound D is N,N-diethyl formamide, the corresponding reaction equation is show as following: ##STR00019##

16. The process according to claim 1, wherein the compound C is one of the following structures: ##STR00020## ##STR00021##

Description

DETAILED DESCRIPTION OF THE INVENTION

Experiment 1

(1) ##STR00008##

(2) Under Argon atmosphere, a mixture of 50.0 g 1,3-dimorpholinopropan-1-one, 11.1 g formic acid, 0.5 g phenothiazine, and 200 mL xylene was charged into a flask and further heated up to 140 C. with stirring for 2 hrs, an additional portion of 11.0 g formic acid was added and the stirring was continued overnight. The crude mixture was concentrated under reduced pressure to give 45.5 g crude oil. GC analysis on the sample revealed formation of N-formylmorpholine (48.7%) and ACMO (51.8%). Fractional distillation of the crude mixture furnished the two products in pure forms.

Experiment 2

(3) ##STR00009##

(4) Under Argon atmosphere, a mixture of 40.0 g 3-(diethylamino)-N,N-diethyl-propanamide, 9.2 g formic acid, 0.4 g phenothiazine, and 170 mL xylene was charged into a flask and further heated up to 140 C. with stirring for 2 hrs, an additional portion of 9.2 g formic acid was added and the stirring was continued for 8 hrs. The crude mixture was concentrated under reduced pressure to give 52.6 g crude oil. GC analysis on the sample revealed formation of N,N-diethylformamide (46.7%) and N,N-diethyl acrylamide (49.2%). Fractional distillation of the crude mixture furnished the two products in pure forms.

Experiment 3

(5) ##STR00010##

(6) Under Argon atmosphere, a mixture of 50.0 g 1,3-dimorpholinopropan-1-one, 7.2 g paraformaldehyde, 0.5 g phenothiazine, and 200 mL xylene was charged into a flask and further heated up to 110 C. with stirring for 4 hrs, an additional portion of 7.2 g paraformaldehyde was added and the stirring was continued for 8 hrs. The crude mixture was concentrated under reduced pressure to give 42.5 g crude oil. GC analysis on the sample revealed formation of morpholinomethanol (48.9%) and ACMO (52.1%). Fractional distillation of the crude mixture furnished ACMO in pure form.

Experiment 4: One-Pot Synthesis from Acrylic Acid

(7) ##STR00011##

(8) Under Argon atmosphere, a mixture of 322.0 g morpholine and 66.3 g acrylic acid was charged into a flask and heated up to 50 C. with stirring for 0.5 hr. The reaction was further brought to 135 C. for 8 hrs. After the formed morpholine and water were removed under reduced pressure at 100 C., an additional portion of 147.4 g anhydrous morpholine was added. The mixture was heated to 135 C. and refluxed for 3 hrs, on which point the formation of 1,3-dimorpholinopropan-1-one was judged to be complete. Excess morpholine was completely removed by distillation with reduced pressure at 100 C. and further at high vacuum. The formed 203.0 g 1,3-dimorpholinopropan-1-one was directly combined with 45.2 g formic acid, 1.9 g phenothiazine, and 1 L xylene, and the resultant mixture was further heated up to 140 C. with stirring for 4 hrs, an additional portion of 46.2 g formic acid was added and the stirring was continued overnight. The crude mixture was concentrated under reduced pressure to give 198.4 g crude oil. GC analysis on the sample revealed formation of N-formylmorpholine (45.4%) and ACMO (50.6%). Fractional distillation of the crude mixture furnished the two products in pure forms.

Experiment 5: One-Pot Synthesis from Methyl Acrylate

(9) ##STR00012##

(10) Under Argon atmosphere, a mixture of 92.5 g morpholine and 0.22 g inhibitor BHT was charged into a flask, to which 37.0 g methyl acrylate was slowly added over 1 hr, followed by additional portion of 18.5 g morpholine. The mixture was heated up to 55 C. with stirring for 2 hrs, to which a mixture of 7.8 g 30% MeONa in 40 g MeOH was added over 1 hr. The reaction was brought to 75 C. with stirring for 5 hrs. Upon completion, 2.3 g concentrated H.sub.2SO.sub.4 was added. Excess MeOH and morpholine were next sequentially removed under reduced pressure. The formed 93.4 g 1,3-dimorpholinopropan-1-one was directly combined with 18.8 g formic acid, 0.84 g phenothiazine, and 450 mL xylene, and the resultant mixture was further heated up to 140 C. with stirring for 2 hrs, an additional portion of 18.1 g formic acid was added and the stirring was continued overnight. The crude mixture was concentrated under reduced pressure to give 95.6 g crude oil. GC analysis on the sample revealed formation of N-formylmorpholine (46.1%) and ACMO (51.7%). Fractional distillation of the crude mixture furnished the two products in pure forms.

Experiment 6

(11) ##STR00013##

(12) Under argon atmosphere, a mixture of prepared 5.2 g 3-(diethylamino)-1-morpholinopropan-1-one, 1.3 g formic acid, 58 mg phenothiazine, and 25 mL xylene was charged into a flask and further heated up to 140 C. with stirring for 45 mins, an additional portion of 1.2 g formic acid was added and the stirring was continued for 5 hrs. The crude mixture was concentrated under reduced pressure to give 5.1 g crude oil. GC analysis on the sample revealed formation of N,N-diethylformamide (44.8%) and ACMO (50.3%). Fractional distillation of the crude mixture furnished the two products in pure forms.

(13) The present invention has now described in detail, including the preferred embodiments thereof. However, it should be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention that fall within the scope and spirit of the invention.