# US 9,518,039 B2 · Polymer-fixed derivatives of dithiolane or dithiane

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- Number: US 9,518,039 B2
- Document ID: US9518039B2
- Status: Granted
- Kind: B2
- Application number: 15/023,801
- Filed: 2014-09-23
- Published: 2016-08-11
- Granted: 2016-12-13
- Earliest claimed: 2013-09-27
- Assignees: Karlsruher Institut Fuer Technologie
- Applicants: Karlsruher Institut Fuer Technologie
- Inventors: Nicole Jung; Simone Graessle; Stefan Braese
- Web page: https://patentgrep.com/patent/US9518039B2

## CPC

- C07D 339/06: having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
- C07D 235/18: with aryl radicals directly attached in position 2
- C07D 339/08: Six-membered rings
- C07D 409/04: directly linked by a ring-member-to-ring-member bond
- C07F 5/022: {without C-boron linkages}
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Derivatives of 1,3-dithianes and 1,3-dithiolanes of the general formula 1a or salts thereof of the general formula 1b where P=polymeric support, m=1 or 2, Z is an organic linker or X=inorganic or organic anion, processes for preparation thereof and use thereof.

## Claims

### Claim 1

A derivative of a 1,3-dithiane or 1,3-dithiolane of general formula 1a
or a salt thereof of general formula 1b
wherein
P=polymeric support,
m=1 or 2,
Z=organic linker of any length which binds the dithiolane/dithiane unit of general formula of 1a via a double bond or binds the dithiolane/dithiane unit of general formula of 1b via a single bond to the polymeric support P,
X=inorganic or organic anion.

### Claim 2 (depends on 1)

The derivative of claim 1, wherein Z is selected from:
—CH2—Y—(CH2)n—CH2—, —CH2—Y—(CH2)n—CH═,
—CH2—Y—CO—(CH2)n—CH2—, —CH2—Y—CO—(CH2)n—CH═,
—CH2—NH—C6H4—Y—(CH2)n—CH2— or —CH2—NH—C6H4—Y—(CH2)n—CH═,
where
Y═NH or O, and
n=0 to 10.

### Claim 3 (depends on 1)

The derivative of claim 1, wherein Z is selected from:
—CH2—Y—(CH2)n—CH2—, —CH2—Y—(CH2)n—CH═,
—CH2—Y—CO—(CH2)n—CH2—, or —CH2—Y—CO—(CH2)n—CH═,
where
Y═NH or O, and
n=0 to 10.

### Claim 4 (depends on 2)

The derivative of claim 2, wherein n=1 or 2.

### Claim 5 (depends on 3)

The derivative of claim 3, wherein n=1 or 2.

### Claim 6 (depends on 1)

The derivative of claim 1, wherein X is selected from Br−, Cl−, Br3−, ClO4, HCl2, BF4−, or CF3SO3−.

### Claim 7 (depends on 1)

The derivative of claim 1, wherein X is selected from BF4− and CF3SO3−.

### Claim 8 (depends on 1)

The derivative of claim 1, wherein P is selected from one or more of polystyrene, polypropylene, polyethylene, polyethylene terephthalate, silica, or cellulose.

### Claim 9 (depends on 1)

The derivative of claim 1, wherein P represents polystyrene.

### Claim 10 (depends on 5)

The derivative of claim 5, wherein P represents polystyrene and X is selected from BF4− and CF3SO3−.

### Claim 11 (depends on 1)

The derivative of claim 1, namely one or more of the following:

### Claim 12 (depends on 1)

A process for preparing a derivative of claim 1, wherein the process comprises or consists of
(a) providing a polymeric support with pendant functional groups,
(b) reacting the functional groups in the polymeric support with a chain extender,
(c) optionally, modifying the functional groups of the chain-extended product resulting from (b),
(d) reacting the product resulting from (b) or (c) with optionally substituted aliphatic or aromatic dithio compounds having one or two carbon atoms between the sulfur atoms, and
(e) optionally, working up the product resulting from (d)
(e1) to afford a corresponding dithiolanylium salt/dithianylium salt (1b),
or
(e2) to afford a ylidene-dithiolane/dithiane (1a).

### Claim 13 (depends on 1)

A process for preparing a derivative of claim 1 of formula (1b), wherein the process comprises or consists of
(a) providing polystyrene with pendant —CH2—NH2 groups,
(b) reacting the product of (a) with succinic anhydride in dimethylformamide and/or triethylamine and in the presence of 4-(dimethylamino)pyridine to result in a carboxylic acid,
(c) reacting the carboxylic acid of (b) with thionyl chloride to afford the acid chloride,
(d) reacting the acid chloride of (c) with 1,2-dithioethane or 1,3-dithiopropane in the presence of HBF4 in diethyl ether, and
(e) optionally, working up the product of (d) by removing the solvent and washing the remaining resin, followed by drying the resin.

### Claim 14 (depends on 1)

A process for preparing a derivative of claim 1 of formula (1b), wherein the process comprises or consists of
(a) providing polystyrene with pendant —CH2—NH2 groups,
(b) reacting the product of (a) with adipoyl dichloride in dimethylformamide and/or triethylamine and in the presence of 4-(dimethylamino)pyridine (DMAP),
(d) reacting the product of (b) with 1,2-dithioethane or 1,3-dithiopropane in the presence of HBF4 in diethyl ether, and
(e) optionally working up the product of (d) by removing the solvent and washing the remaining resin, followed by drying the resin.