# US 10,870,620 B1 · Radioactive carbon-14-labeled 2,2′-(((4-((4-14C chlorobenzyl)oxy)-3-methoxyphenyl)methylene)bis(2-hydroxyethyl)dithioacetal, preparation method and applications there of

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,870,620 B1
- Document ID: US10870620B1
- Status: Granted
- Kind: B1
- Application number: 16/935,727
- Filed: 2020-07-22
- Granted: 2020-12-22
- Earliest claimed: 2019-07-23
- Assignees: Zhejiang University
- Applicants: Zhejiang University
- Inventors: Wang Haiyan; Lu Yuhui; Ye Qingfu
- Web page: https://patentgrep.com/patent/US10870620B1

## CPC

- C07C 323/16: the carbon skeleton containing six-membered aromatic rings
- C07B 59/001: {Acyclic or carbocyclic compounds}
- C07C 17/16: of hydroxyl groups
- C07C 29/147: of carboxylic acids or derivatives thereof
- C07C 319/20: by reactions not involving the formation of sulfide groups
- G01T 5/00: Recording of movements or tracks of particles (spark chambers H01J47/00); Processing or analysis of such tracks
- C07B 2200/05: Isotopically modified compounds, e.g. labelled
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- G01T: MEASUREMENT OF NUCLEAR OR X-RADIATION (radiation analysis of materials, mass spectrometry G01N23/00; tubes for determining the presence, intensity, density or energy of radiation or particles H01J47/00)

## Abstract

The present disclosure provides a radioactive carbon-14 labeled XCLSBM in the structure of Formula 4 and its preparation method and applications. A 14C labeled raw material is used to synthesize a 14C-labeled XCLSBM, and a method for synthesizing a trace 14C-labeled marker of 14C-labeled XCLSBM is established, which avoids high-temperature, high-pressure reactions and the production process is safe with a low synthesis cost. The radioactive carbon-14 labeled XCLSBM can be used to trace the migration and transformation, metabolic degradation, absorption and enrichment of XCLSBM in environment and living bodies, for providing technical supports for comprehensive evaluation of the ecological safety of XCLSBM.

## Claims

### Claim 1

A radioactive carbon-14-labeled XCLSBM, characterized in that the chemical name is 2,2′-(((4-(4-14C chlorobenzyl)oxy)-3-methoxyphenyl)methylene)bis (2-hydroxyethyl) dithioacetal, the structural formula is shown as Formula 4:
wherein the asterisk represents the position of the carbon-14 mark.

### Claim 2 (depends on 1)

A method for preparing the radioactive carbon-14 labeled XCLSBM of claim 1, characterized in that comprising the following steps:
1) using p-chlorobenzoyl[14C] formic acid of Formula 1 as a radioactive raw material, adding tetrahydrofuran and a red aluminum-containing toluene solution to obtain p-chlorobenzoyl[14C] methanol of Formula 2 through a reduction reaction;
2) the p-chlorobenzoyl[14C] methanol of Formula 2 is brominated with phosphorus tribromide to obtain a p-chlorobenzoyl[14C] methyl bromide of Formula 3;
3) the p-chlorobenzoyl[14C] methyl bromide of Formula 3 is reacted with bis(2-hydroxyethyl) dithioacetal-containing vanillin under alkaline conditions through an electrophilic substitution reaction to obtain the target labeled crude product of Formula 4, which is then purified by a reversed-phase high-performance liquid chromatography to give the radioactive carbon-14 labeled XCLSBM of Formula 4,
and the bis(2-hydroxyethyl) dithioacetal-containing vanillin has the following structure:

### Claim 3 (depends on 2)

The method for preparing the radioactive carbon-14 labeled XCLSBM of claim 2, characterized in that in step 1), the ratio of the amount of p-chlorobenzoyl[14C] formic acid to the red aluminum-containing toluene solution is 0.78 mmol: 1.5˜3 mL.

### Claim 4 (depends on 2)

The method for preparing the radioactive carbon-14 labeled XCLSBM of claim 2, characterized in that in step 1), the reduction reaction conditions are that reacting at 15˜35° C. for 12˜20 hrs.

### Claim 5 (depends on 2)

The method for preparing the radioactive carbon-14 labeled XCLSBM of claim 2, characterized in that in step 2), the molar ratio of phosphorus tribromide to p-chlorobenzoyl[14C] methanol of Formula 2 is 1:2˜4.

### Claim 6 (depends on 2)

The method for preparing the radioactive carbon-14 labeled XCLSBM of claim 2, characterized in that in step 2), the bromination reaction between p-chlorobenzoyl[14C] methanol of Formula 2 and phosphorus tribromide specifically comprising the steps of:
adding p-chlorobenzoyl[14C] methanol to a reactor, performing an atmosphere replacement with nitrogen, injecting dichloromethane thereto, then adding dimethylformamide in dropwise; after cooling down by an ice salt bath, adding dichlorosulfoxide, followed by raising the temperature to 15˜35° C. to carry out the chlorination reaction for 2˜4 hrs; after completing the chlorination reaction, adding water to quench the reaction, extracting with dichloromethane, combining organic phases, adding phosphorus tribromide, reacting with phosphorus tribromide, drying with anhydrous magnesium sulfate, then filtering and carrying out a rotary evaporation under reduced pressure to obtain p-chlorobenzoyl[14C] methyl bromide of Formula 3.

### Claim 7 (depends on 2)

The method for preparing the radioactive carbon-14 labeled XCLSBM of claim 2, characterized in that in step 3), the alkaline condition is established by using potassium hydroxide.

### Claim 8 (depends on 7)

The method for preparing the radioactive carbon-14 labeled XCLSBM of claim 7, characterized in that in step 3), the molar ratio of p-chlorobenzoyl[14C] methyl bromide of Formula 3, bis(2-hydroxyethyl) dithioacetal-containing vanillin and potassium hydroxide is 1:0.8˜1.2:0.8˜1.2.

### Claim 9 (depends on 2)

The method for preparing the radioactive carbon-14 labeled XCLSBM of claim 2, characterized in that in step 3), the purification by the reversed-phase high-performance liquid chromatography applies a petroleum ether-ethyl acetate system with a volume ratio of 20:1˜4:1 to perform the column chromatography purification.

### Claim 10 (depends on 1)

A method of tracing and tracking the XCLSBM in an environment utilizing the radioactive carbon-14 labeled XCLSBM of claim 1.