# US 8,772,526 B2 · Method for preparing dithiocarbamates in particular from polyols of the glycerol type

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- Number: US 8,772,526 B2
- Document ID: US8772526B2
- Status: Granted
- Kind: B2
- Application number: 13/517,335
- Filed: 2010-12-21
- Published: 2012-10-18
- Granted: 2014-07-08
- Earliest claimed: 2009-12-21
- Assignees: Centre National De La Recherche Scientifique; Universite De Poitiers
- Applicants: Francois Jerome; Rodolphe De Sousa; Joel Barrault; Yannick Pouilloux
- Inventors: Francois Jerome; Rodolphe De Sousa; Joel Barrault; Yannick Pouilloux
- Web page: https://patentgrep.com/patent/US8772526B2

## CPC

- C07C 333/20: having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07D 295/21: Radicals derived from sulfur analogues of carbonic acid
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention concerns a method for the synthesis of glycerol dithiocarbamates or bis-dithiocarbamates (GDTCs) in which a reaction medium comprising (1) a carbonate selected from diethyl carbonate, dimethyl carbonate and ethylene or propylene carbonate associated with a glycerol type polyol in the presence of a basic catalyst or (2) a cyclic carbonate comprising five ring members, in a solvent medium, is supplemented with a primary or secondary amine in the presence of carbon disulphide, and the GDTC formed is recovered. In particular, a glycerol type polyol is brought into the presence of diethyl carbonate in the presence of a catalyst, then a primary or secondary amine is added to the reaction medium in the presence of carbon disulphide, and the GDTC formed is recovered. The invention can be used for one-step synthesis of glycerol dithiocarbamates directly from glycerol as the starting material and solvent. This method involves glycerol, diethyl carbonate, carbon disulphide (CS2) and a primary or secondary amine to produce glycerol dithiocarbamates; the glycerol/NaOH phase can be recycled 6 times without a noticeable drop in yield; the ethyl acetate is also recycled after each extraction.

## Claims

### Claim 1

A method for the preparation of a glycerol dithiocarbamate (GDTC) of formula
R1—C(OH)—CH2—S—C—(S)—NR2R3 (I)
or
R′1R′2—N—C(S)—S—CH2—CH(OH)—CH2—S—C(S)—NR2R3 (I′)
or
R2R3—N—C(S)—S—CH2—CH(OH)—CH2—O—CH2—CH(OH)—CH2—S—C(S)—NR2R3 (I″)
in which
R1 represents H; a linear or branched C1-C22 alkyl radical or a C3-C16 cyclo-alkyl radical optionally substituted with one or more hydroxy, —O-alkyl, thiohydroxy or —S-alkyl groups, the chain of the alkyl radical optionally being interrupted by one or more O, N or S heteroatoms; a linear or branched C2-C22 alkenyl radical mono- or poly-unsaturated; a C2-C6 alkynyl radical; a C6-C10 aryl radical; or a C7 to C22 arylalkyl radical; and
R2 and R3, independently of each other, represent H; a linear or branched C1-C22 alkyl radical or a C3-C16 cyclo-alkyl radical optionally substituted with one or more hydroxy, —O-alkyl, thiohydroxy or —S-alkyl groups, the chain of the alkyl radical optionally being interrupted by one or more O, N or S heteroatoms; a linear or branched, mono- or poly-unsaturated C2-C22 alkenyl radical; a C2-C6 alkynyl radical; a C6-C16 aryl radical; or a C7 to C22 arylalkyl radical; or R2 and R3 together with the nitrogen atom to which they are bonded form a cycloamino group;
R′1 and R′2 have the same meanings as R2 and R3,
wherein said method comprises
implementing a reaction medium with a carbon disulphide CS2 and a primary or secondary amine NHR2R3 wherein R2 and R3 are as defined above,
said reaction medium comprising
(a) a glycerol type polyol of formula
R1—CH(OH)—CH2OH (II)
in which R1 has the same meanings as above and a carbonate selected from the group consisting of diethyl carbonate, dimethyl carbonate, ethylene carbonate and propylene carbonate in the presence of a basic catalyst, or
(b) a cyclic carbonate comprising five ring members having the following formula (IV):
wherein R1 has the same meanings as above, or
(c) a cyclic carbonate comprising five ring members of formula
in which R′1 and R′2, independently of each other, represent H; a linear or branched C1-C22 alkyl radical or a C3-C16 cyclo-alkyl radical optionally substituted with one or more hydroxy, —O-alkyl, thiohydroxy or —S-alkyl groups, the chain of the alkyl radical optionally being interrupted by one or more O, N or S heteroatoms; a linear or branched, mono- or poly-unsaturated C2-C22 alkenyl radical; a C2-C6 alkynyl radical; a C6-C16 aryl radical; or a C7 to C22 arylalkyl radical; or R′1 and R′2 together with the nitrogen atom to which they are bonded form a cycloamino group; or
(d) a cyclic polycarbonate comprising five ring members; and recovering the formed GDTC.

### Claim 2 (depends on 1)

The method according to claim 1, wherein said reaction medium comprises a glycerol type polyol of formula (II):
before supplementing with said primary or secondary amine.

### Claim 3 (depends on 1)

The method according to claim 1, wherein said reaction medium comprises a carbonate of formula (IV):

### Claim 4 (depends on 1)

The method according to claim 1, wherein the GDTC has formula (I) R1—C(OH)—CH2—S—C—(S)—NR2R3.

### Claim 5 (depends on 1)

The method according to claim 1, wherein said secondary amine is a dialkylamine.

### Claim 6 (depends on 1)

The method according to claim 1, wherein said amine is a member selected from the group consisting of diethylamine, dimethylamine, dipropylamine, diisopropylamine, piperidine, diethanolamine and aniline.

### Claim 7 (depends on 1)

The method according to claim 1, wherein said carbonate is diethyl carbonate.

### Claim 8 (depends on 1)

The method according to claim 1, wherein said glycerol type polyol is selected from glycerol, 1,2-propanediol and ethylene glycol.

### Claim 9 (depends on 1)

The method according to claim 1, wherein said catalyst is a member selected from the group consisting of KOH, NaOH, CsOH, ammonium or tetraalkylammonium hydroxide, “Amberlyst A26OH”, a rehydrated hydrotalcite and a basic ionic liquid.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the quantity of catalyst is in the range 0.2% to 20% molar.

### Claim 11 (depends on 1)

The method according to claim 1, wherein said cyclic carbonate comprising five ring members is a member selected from the group consisting of glycerol carbonate, propylene carbonate, ethylene carbonate, glycerol monocarbonate and diglycerol bis-carbonate.

### Claim 12 (depends on 1)

The method according to claim 1, wherein said reaction medium comprises a glycerol type polyol as the solvent.

### Claim 13 (depends on 12)

The method according to claim 12, wherein said glycerol type polyol is a member selected from the group consisting of glycerol, 1,-2-propanediols, ethylene glycol, diglycerol, polyglycerol and amino-propanediol.

### Claim 14 (depends on 9)

The method of claim 9, wherein said catalyst is NaOH.

### Claim 15 (depends on 1)

The method of claim 1, wherein said range is 0.5% to 10% molar.

### Claim 16 (depends on 1)

The method of claim 1, wherein the quantity of catalyst is approximately 2% molar.

### Claim 17 (depends on 1)

The method of claim 1, wherein R1 is CH2OH.

### Claim 18 (depends on 1)

The method of claim 1, wherein R2 and R3, independently of each other, represent a linear or branched C1-C12 alkyl radical.

### Claim 19 (depends on 1)

The method of claim 1, wherein R2 and R3, independently of each other, represent a linear or branched C1-C8 alkyl radical.