# US 8,541,611 B2 · Bifunctional phenyl iso(thio)cyanates, processes and intermediates products for their preparation

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- Number: US 8,541,611 B2
- Document ID: US8541611B2
- Status: Granted
- Kind: B2
- Application number: 13/535,544
- Filed: 2012-06-28
- Published: 2012-10-25
- Granted: 2013-09-24
- Earliest claimed: 2010-09-21
- Assignees: BASF SE
- Applicants: Gerhard Hamprecht; Michael Puhl; Bernd Wolf; Norbert Götz; Michael Keil; Robert Reinhard; Ingo Sagasser; Werner Seitz
- Inventors: Gerhard Hamprecht; Michael Puhl; Bernd Wolf; Norbert Götz; Michael Keil; Robert Reinhard; Ingo Sagasser; Werner Seitz
- Web page: https://patentgrep.com/patent/US8541611B2

## CPC

- C07D 213/76: to which a second hetero atom is attached (nitro radicals C07D213/61)
- C07C 303/34: of amides of sulfuric acids
- C07C 307/06: having nitrogen atoms of the sulfamide groups bound to acyclic carbon atoms
- C07C 331/28: having isothiocyanate groups bound to carbon atoms of six-membered aromatic rings
- C07D 207/20: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D 211/18: with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D 211/70: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D 295/26: Sulfur atoms
- C07D 307/52: Radicals substituted by nitrogen atoms not forming part of a nitro radical
- C07D 319/06: not condensed with other rings
- C07D 333/20: by nitrogen atoms (nitro, nitroso radicals C07D333/12)
- C07C 2601/14: The ring being saturated
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A process for preparing phenyl iso(thio)cyanates of the formula I in which a compound of the formula II or its HCl adduct is reacted with a phosgenating agent where W is oxygen or sulfur and Ar and A are as defined in claim 1 is described. Moreover, the invention relates to the use of the phenyl iso(thio)cyanates for preparing crop protection agents.

## Claims

### Claim 1

A phenyl iso(thio)cyanate of formula I,
where:
W is oxygen or sulfur,
Ar is phenyl which may be mono- or polysubstituted by the following groups: hydrogen, halogen, C1-C4-haloalkyl or cyano, and
A is a radical derived from a primary or secondary amine or is NH2,

### Claim 2

A phenyl iso(thio)cyanate of formula Ia,
wherein:
W is oxygen or sulfur,
A is a radical derived from a primary or secondary amine or is NH2, and
Ra is fluorine, chlorine or cyano, Rc is hydrogen, fluorine or chlorine and Rb and Rd are each hydrogen.

### Claim 3 (depends on 2)

A phenyl iso(thio)cyanate of the formula Ia as defined in claim 2, wherein A is a radical of the formula NR1R2 where
R1 and R2 independently of one another represent hydrogen, C1-C10-alkyl, C2-C10-alkenyl or C2-C10-alkynyl which may be unsubstituted or substituted by one of the following radicals:
C1-C4-alkoxy, C1-C4-alkylthio, CN, NO2, formyl, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C3-C10-cycloalkyl, 3- to 8-membered heterocyclyl having one, two or three heteroatoms selected from the group consisting of O, S, N and a group NR6 (where R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl), phenyl, which may have 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl, C1-C4-alkyloxycarbonyl, trifluoromethylsulfonyl, C1-C3-alkylamino, C1-C3-dialkylamino, formyl, nitro and cyano, C1-C10-haloalkyl, C2-C10-haloalkenyl, C2-C10-haloalkynyl, C3-C8-cycloalkyl, C3-C10-cycloalkenyl, 3- to 8-membered heterocyclyl having one to three heteroatoms selected from the group consisting of O, S, N and a group NR6, wherein R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl), phenyl or naphthyl, where C3-C8-cycloalkyl, C3-C10-cycloalkenyl, 3- to 8-membered heterocyclyl, phenyl and naphthyl may have 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl, C1-C4-alkyloxycarbonyl, trifluoromethylsulfonyl, formyl, C1-C3-alkylamino, C1-C3-dialkylamino, phenoxy, nitro and cyano, or
R1 and R2 together with the nitrogen atom to which they are attached form a saturated or partially unsaturated 5- to 8-membered nitrogen heterocycle which may be substituted by C1i-C4-alkyl, C1-C4-alkoxy and/or C1-C4-haloalkyl and may have one or two carbonyl groups, thiocarbonyl groups and/or one or two further heteroatoms selected from the group consisting of O, S, N and a group NR6, wherein R6 is as defined above, as ring members.

### Claim 4 (depends on 3)

A phenyl iso(thio)cyanate of formula Ia in claim 3, wherein R1 and R2 independently of one another are hydrogen, C1-C6-alkyl which is optionally substituted by a substituent selected from the group consisting of halogen, cyano, C1-C4-alkoxy, C1-C4-alkoxycarbonyl, C1-C4-alkylthio, C3-C8-cycloalkyl, furyl, thienyl, 1,3-dioxolanyl, phenyl which for its part is optionally substituted by halogen or C1-C4-alkoxy, C2-C6-alkenyl, C2-C6- alkynyl, C3-C8-cycloalkyl or phenyl which is optionally substituted by 1 or 2 substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-fluoroalkyl, C1-C4-alkoxy, C1-C4-alkoxycarbonyl, nitro and C1-C3-dialkylamino, naphthyl or pyridyl or
R1 and R2 together with the nitrogen atom to which they are attached form a five-, six-or seven-membered saturated or unsaturated nitrogen heterocycle which may optionally contain a further heteroatom selected from the group consisting of N, a group NR6 (where R6 is as defined above) and O as ring member and/or which may be substituted by one, two or three substituents selected from the group consisting of C1-C4-alkyl and C4-C4-haloalkyl.

### Claim 5 (depends on 1)

A process for preparing the phenyl iso(thio)cyanate of claim 1 which comprises reacting a compound of formula II,
where the variables Ar and A are as defined above or its HCl adduct, with phosgene, thiophosgene or diphosgene.

### Claim 6 (depends on 5)

The process of claim 5, wherein the HCl adduct of the compound of formula II is used.

### Claim 7 (depends on 5)

The process of claim 5, wherein from 0.9 to 2 molar equivalents of phosgene, thiophosgene or diphosgene are used, based on the moles of the compound of formula II.

### Claim 8 (depends on 5)

The process of claim 5, wherein the reaction of the HCl adduct of the compound of formula II is carried out in the presence of activated carbon.

### Claim 9 (depends on 2)

A process for preparing the phenyl iso(thio)cyanate of claim 2, wherein a compound of the formula IIa
wherein:
Ra, Rb, Rc and Rd independently of one another are hydrogen, halogen, C1-C4-haloalkyl or cyano, and
A is a radical derived from a primary or secondary amine or is NH2
or its HCl adduct is reacted with phosgene, thiophosgene or diphosgene, giving a compound of the formula Ia
where the variables Ra, Rb, Rc, Rd, A are as defined above and W is oxygen or sulfur.

### Claim 10 (depends on 5)

The process of claim 5, wherein the radical A in formula I is NR1R2,
where:
R1 and R2 independently of one another represent hydrogen, C1-C10-alkyl, C2-C10-alkenyl or C2-C10-alkynyl which may be unsubstituted or substituted by one of the following radicals: C1-C4-alkoxy, C1-C4-alkylthio, CN, NO2, formyl, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, C1-C4-alkylsulfinyl C1-C4-alkylsulfonyl, C3-C10-cycloalkyl, 3- to 8-membered heterocyclyl having one, two or three heteroatoms selected from the group consisting of O, S, N and a group NR6(where R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl), phenyl, which may have 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl, C1-C4-alkyloxycarbonyl, trifluoromethylsulfonyl, C1-C3-alkylamino, C1-C3-dialkylamino, formyl, nitro and cyano,C0-C10-haloalkyl, C2-C10-haloalkenyl, C2-C10-haloalkynyl, C3-C8-cycloalkyl, C3-C10-cycloalkenyl, 3- to 8-membered heterocyclyl having one to three heteroatoms selected from the group consisting of O, S, N and a group NR6 (where R6 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl), phenyl or naphthyl, wherein the C3-C8-cycloalkyl, C3-C10-cycloalkenyl, 3- to 8-membered heterocyclyl, phenyl and naphthyl may have 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl, C1-C4-alkyloxycarbonyl, trifluoromethylsulfonyl, formyl, C1-C3-alkylamino, C1-C3-dialkylamino, phenoxy, nitro and cyano, or
R1 and R2 together with the nitrogen atom to which they are attached form a saturated or partially unsaturated 5- to 8-membered nitrogen heterocycle which may be substituted by C1-C4-alkyl, C1-C4-alkoxy and/or C1-C4-haloalkyl and may have one or two carbonyl groups, thiocarbonyl groups and/or one or two further heteroatoms selected from the group consisting of O, S, N and a group NR6,wherein R6 is as defined above, as ring members.

### Claim 11 (depends on 5)

The process of claim 5, wherein the compound of formula II is prepared by the following steps:
i) reacting an aroyl compound of the formula III
in which the variable Ar is as defined above and X is halogen, OH or C1-C4-alkoxy with a sulfamic acid amide of the formula IV,
where A is as defined above and
ii) reducing N-aroylsulfamic acid amide, obtained in step (i), of the formula V
where Ar and A are as defined above, giving a compound of the formula II.

### Claim 12 (depends on 11)

The process of claim 11, wherein in step (ii) the reduction is carried out in the presence of catalytic amounts of transition metals or transition metal compounds.

### Claim 13 (depends on 11)

The process of claim 11, wherein in step (ii) the reduction is carried out in the presence of iron and at least one C1-C4-carboxylic acid.

### Claim 14 (depends on 11)

A process of claim 11, wherein in step (ii) the reduction is carried out in the presence of Raney nickel and hydrogen.