# US 4,399,075 A · Process for producing chlorinated phenoxytoluene derivatives

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- Number: US 4,399,075 A
- Document ID: US4399075A
- Status: Granted
- Kind: A
- Application number: 06/277,347
- Filed: 1981-06-25
- Granted: 1983-08-16
- Earliest claimed: 1981-06-25
- Assignees: Asahi Chemical Co., Ltd.
- Inventors: Zenichi Yoshida; Susumu Kato; Takuya Fujiki; Yasuhiro Amemiya
- Web page: https://patentgrep.com/patent/US4399075A

## CPC

- C07C 41/22: by introduction of halogens; by substitution of halogen atoms by other halogen atoms
- C07C 45/63: by introduction of halogen; by substitution of halogen atoms by other halogen atoms
- C07C 201/12: by reactions not involving the formation of nitro groups
- C07C 253/30: by reactions not involving the formation of cyano groups
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Phenoxytoluene derivative is chlorinated in a very high yield and selectivity in the presence of nitrogen-, sulfur-, phosphorus- or oxygen-containing compound which is capable of forming a charge-transfer complex with chlorine, chlorine radical or organic halogen compound, together with radical initiator and organic halogen compound.

## Claims

### Claim 1

A process for producing in high yield and high selectivity a chlorinated phenoxytoluene derivative represented by the formula ##STR23## wherein R.sup.1 and R.sub.2 are the same or different and are each hydrogen, halogen, cyano, nitro, alkyl, alkoxyl, alkoxycarbonyl, halogenoalkyl, acyl, acyloxy, aryl, aralkyl or aralkyloxy, R.sup.3 is hydrogen or chlorine, which comprises chlorinating at a temperature of 0.degree. to 150.degree. C. a phenoxytoluene derivative represented by the formula ##STR24## wherein R.sup.1 and R.sup.2 are same as above, with chlorine in an amount that provides said chlorinated phenoxytoluene derivative, in the presence of about 0.001 to 50 wt. % based on said phenoxytoluene derivative of at least one compound selected from the group consisting of nitrogen-containing compound, sulfur-containing compound, phosphorus-containing compound and oxygen-containing compound which is capable of forming a charge-transfer complex with chlorine, chlorine radical or organic halogen compound, together with about 0.001 to 20 wt. % based on said phenoxytoluene derivative of radical initiator and about 1 to 20 times the weight of said phenoxytoluene derivative of an organic halogen compound.

### Claim 2 (depends on 1)

A process as defined in claim 1 wherein the nitrogen-containing compounds are those represented by the formulae ##STR25## in which R.sup.4 to R.sup.6 are each hydrogen, alkyl having 1 to 20 carbon atoms, hydroxyalkyl having 1 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 10 carbon atoms with or without a substituent, two or three of R.sup.4 to R.sup.6 may form a ring, R.sup.7 is alkylene having 2 to 8 carbon atoms or arylene having 6 to 10 carbon atoms.

### Claim 3 (depends on 1)

A process as defined in claim 1 wherein the sulfur-containing compounds are those represented by the formulae ##STR26## R.sup.8 and R.sup.9 are each alkyl having 1 to 20 carbon atoms; cycloalkyl having 5 to 8 carbon atoms; aryl having 6 to 10 carbon atoms; heterocyclic group having nitrogen, sulfur, oxygen atom, etc, and R.sup.8 and R.sup.9 may conjointly form an alicyclic or heterocyclic ring, a is an integer of 1 to 8, A and B is R.sup.11, NR.sup.12 R.sup.13, NR.sup.12 NR.sup.12 R.sup.13, NR.sup.12 NCR.sup.12 R.sup.13, SR.sup.12, SNR.sup.12 R.sup.13, SHNR.sup.12 R.sup.13 R.sup.14 or OR.sup.14, R.sup.10 to R.sup.14 are hydrogen, alkyl having 1 to 20 carbon atoms aryl having 6 to 10 carbon atoms, alicyclic or heterocyclic ring and R.sup.12 and R.sup.13 or R.sup.12 to R.sup.14 may conjointly form a heterocyclic ring, R.sup.12 and R.sup.13 further include acyl having 1 to 20 carbon atoms with or without a substituent and R.sup.11 does not include hydrogen, A and B may conjointly form an alicyclic or heterocyclic ring, D is NR.sup.12, sulfur atom or oxygen atom, E is R.sup.15, R.sup.15 SR.sup.15, R.sup.15 SO.sub.2 R.sup.15, C(S)NHR.sup.15 NHC(S), R.sup.15 NHC(S)NHR.sup.15, R.sup.15 NR.sup.12 R.sup.15, R.sup.15 C(O)R.sup. 15 or R.sup.15 C(S)R.sup.15, b is 0 or an integer of 1 to 4 but b is 1 when D is NR.sup.12 or oxygen atom, c is 0 or 1, F is R.sup.16, CN, NR.sup.17 R.sup.18, C(O)R.sup.17, S(O)R.sup.17, C(O)OR.sup.17, C(O)NR.sup.17 R.sup.18, C(O)SR.sup.17, R.sup.19 C(O)OR.sup.17, R.sup.19 C(O)NR.sup.17 R.sup.18, R.sup.19 SR.sup.17 R.sup.19 NR.sup.17 R.sup.18, R.sup.19 C(O)R.sup.17 or HNR.sup.17 R.sup.17 R.sup.18, R.sup.16 to R.sup.18 are hydrogen; alkyl having 1 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, alicyclic or heterocyclic froup with or without a substituent; but R.sup.16 is alkyl, aryl or alicyclic group having a substituent when f is 0, R.sup.19 is alkylene having 1 to 12 carbon atoms or arylene having 6 to 10 carbon atoms with or without a substituent, G is R.sup.19, R.sup.19 C(O)R.sup.19, C(O)R.sup.19 C(O) or C(O), L is sulfur atom or NR.sup.17, d is 1 to 8, e is 1 to 50 and f is 0 or 1 to 50, and F further includes R.sup.19 OR.sup.17 and R.sup.19 OR.sup.19 OR.sup.19 when d is other than 1.

### Claim 4 (depends on 1)

A process as defined in claim 1 wherein the phosphorus-containing compounds are those represented by the formulae ##STR27## in which M, Q and T are hydrogen, halogen, R.sup.20, WR.sup.20 or NR.sup.20 R.sup.21, R.sup.20 and R.sup.21 are the same or different and are hydrogen, alkyl having 1 to 20 carbon atoms; aryl having 6 to 10 carbon atoms; amino; alicyclic or heterocyclic ring, W is oxygen atom or sulfur atom, and M and Q, or Q and T may conjointly form an alicyclic or heterocyclic ring, and at least two of M, Q and T are organic group other than hydrogen.

### Claim 5 (depends on 1)

A process as defined in claim 1 wherein the oxygen-containing compounds are those represented by the formulae ##STR28## in which R.sup.22 and R.sup.23 are each alkyl having 1 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, alicyclic or heterocyclic ring, and R.sup.22 and R.sup.23 may form an alicyclic, heterocyclic or large polyether ring, R.sup.24 and R.sup.25 are the same or different and are alkylene having 2 to 8 carbon atoms, X is oxygen atom, sulfur atom, alkoxyl, alkylamino or alkylamido, each having 1 to 20 carbon atoms and with or without a substituent, aryloxy having 6 to 10 carbon atoms, oxyalicyclic or oxyheterocyclic ring, each having or not having a substituent, Y is hydrogen, halogen, hydroxyl, mercapto, alkyl having 1 to 20 carbon atoms, carboxylalkyl having 2 to 20 carbon atoms or alkylamino having 1 to 20 carbon atoms, Z is oxygen atom or sulfur atom, g is 1 to 50, h is 0 to 25 and i is 1 to 6 but i is 2 when X is oxygen atom or sulfur atom.

### Claim 6 (depends on 1)

A process as defined in claim 1 wherein the amount is about 0.01 to 30 wt % based on the starting phenoxytoluene derivative.

### Claim 7 (depends on 1)

A process as defined in claim 1 wherein the organic halogen compounds are those represented by the formulae ##STR29## in which Hal means halogen atom, m is 0 or an integer of 1 to 3, m' is 0 or an integer of 1 to 2, m" is 0 or 1, n is an integer of 1 to 6, or chlorinated paraffin.

### Claim 8 (depends on 7)

A process as defined in claim 7 wherein the organic halogen compound is carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, chloroform, bromoform, iodoform, methylene chloride, methylene bromide, dichloroethane, trichloroethane, tetrachloroethane, tetrachloroethylene or hexachlorocyclohexane.

### Claim 9 (depends on 1)

A process as defined in claim 1 wherein the amount of 5 to 10 times the weight of the starting phenoxytoluene derivative.

### Claim 10 (depends on 1)

A process as defined in claim 1 wherein the radical initiator is an azo compound or peroxide.

### Claim 11 (depends on 10)

A process as defined in claim 10 wherein the radical initiator is azobisisobutyronitrile or benzoyl peroxide.

### Claim 12 (depends on 1)

A process as defined in claim 1 wherein the amount is about 0.01 to 15 wt % of the starting phenoxytoluene derivative.

### Claim 13 (depends on 1)

A process as defined in claim 1 wherein chlorine is blown into the reaction system in an amount of about 0.5 to 10 mole % per minute of the starting phenoxytoluene derivative.

### Claim 14 (depends on 13)

A process as defined in claim 13 wherein the amount is about 2 to 5 mole % per minute of the starting phenoxytoluene derivative.