Process for producing chlorinated phenoxytoluene derivatives

This invention relates to a process for producing chlorinated phenoxytoluene derivatives in high yields and selectivities by chlorinating a methyl group on a side chain of phenoxytoluene derivatives. The chlorinated phenoxytoluene derivatives of this invention include both phenoxybenzyl chlorides and phenoxybenzal chlorides. These chlorinated phenoxytoluene derivatives are easily converted by hydrolysis to phenoxybenzyl alcohol derivatives or phenoxybenzaldehyde derivatives. Especially, m-phenoxybenzyl alcohol or m-phenoxybenzaldehyde is an important intermediate of agricultural chemicals and insecticides. Various processes have heretofore been reported for producing phenoxybenzyl alcohols and phenoxybenzaldehydes.
For example, several patents have already been filed on processes for producing chlorinated phenoxytoluene derivatives by chlorinating methyl group in a side chain of phenoxytoluene derivatives, which processes are deemed to be preferable industrically.
1. Japanese Published Examined Patent Application (Kokoku) Nos. 10,228/1976 and 45,573/1976 (U.S. Pat. No. 4,014,940) discloses a method of chlorinating directly m-phenoxytoluene with use of phosphorus halogenide at a high temperature of more than 220.degree. C. This method, however, has an disadvantage of accompanying a reaction operation at a high temperature and consumption of a lot of energy. Moreover, in this process, selectivities are low in both phenoxybenzyl chlorides and phenoxybenzal chlorides and especially low in phenoxybenzal chlorides.
2. Japanese Published Unexamined Patent Application (Kokai) No. 95,623/1977 (U.S. Pat. No. 4,085,147) discloses the preparation of a mixture of m-phenoxybenzyl chloride and m-phenoxybenzal chloride by chlorinating m-phenoxytoluene with chlorine in carbon tetrachloride in the presence of a radical initiator. This process gives the contemplated products in rather low selectivities. Especially, selectivity of phenoxybenzal chloride is very low with accompanying a production of a lot of nuclear-chlorinated products.
3. Japanese Kokai No. 40,732/1978 (U.S. Pat. No. 4,108,904) describes halogenation of m-phenoxytoluene by use of sulfuryl chloride, chlorine or bromine as a halogenating agent in carbon tetrachloride. The process is carried out with use of a free radical initiator or a strong incandescent light source. However, selectivities are rather low in both m-phenoxybenzyl chloride and m-phenoxybenzal chloride and especially very low in m-phenoxybenzal chloride.
4. Japanese Kokai No. 46,929/1978 (U.S. Pat. No. 4,146,737) discloses a method of chlorinating m-phenoxytoluene on the side chain in carbon tetrachloride with use of sulfuryl chloride as a halogenating agent in the presence of a radical initiator. In this method, the contemplated products are obtained in rather low selectivities and m-phenoxybenzal chloride in very low selectivity.
5. Japanese Kokai No. 103,433/1978 (DT-OS No. 27 07 232) shows a halogenation of m-phenoxytoluene on the side chain in carbon tetrachloride with chlorine or bromine as a halogenating agent by use of ultraviolet rays. In this process, selectivities are also low. When phenoxybenzal halide is obtained in a rather high selectivity, a highly chlorinated trichloride derivatives are produced in a large amount.
6. Japanese Kokai No. 92,928/1979 (U.K. patent application No. 2,010,837 describes a process for preparing m-phenoxybenzyl chloride, which comprises reacting m-phenoxytoluene with chlorine in the presence of a sulphur-containing catalyst without using a radical initiator and at a temperature which is, or is equivalent to, 200.degree. to 280.degree. C. at atmospheric pressure. However, selectivity of m-phenoxybenzyl chloride is rather low and that of m-phenoxybenzal chloride is extremely low.
It is generally known that, in the chlorination of aromatic compounds, electrophilic substitution reactions in the benzene ring proceed in competition with radical substitution reactions on the side chain. This occurs also in the chlorination of phenoxytoluene derivatives. For example, in U.S. Pat. No. 4,085,147, it is shown that a lot of nuclear-chlorinated products are formed together with side chain-chlorinated products.
Further, phenoxybenzal chloride derivatives are converted to phenoxyphenyl trichloromethane derivatives with a progress of chlorination. Accordingly, it is necessary to restrict the formation of the trichloride derivatives simultaneously with the restriction of the chlorination in benzene ring in order to obtain phenoxybenzal chloride derivatives in an high yield and high selectivity.
An object of this invention is to provide a method of chlorinating a phenoxytoluene derivative on the side chain in an extremely high yield and high selectivity.
An object of this invention is to provide a method of chlorination of a phenoxytoluene derivative with accompanying a very small formation of nuclear-chlorinated products and phenoxyphenyl trichloromethane derivatives.
Another object of this invention is to provide a method of chlorinating a phenoxytoluene derivative in which each of phenoxybenzyl chloride and phenoxybenzal chloride derivative is obtained in a very high yield and high selectivity.
These and other objects of the invention will become apparent from the following description.
The present invention provides a process for preparing a chlorinated phenoxytoluene derivative represented by the formula ##STR1## wherein R.sup.1 and R.sup.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, characterized by chlorinating with chlorine a phenoxytoluene derivative represented by the formula ##STR2## wherein R.sup.1 and R.sup.2 are same as above, in the presence 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 radical initiator and organic halogen compound.
According to this invention, both of phenoxybenzyl chloride derivatives and phenoxybenzal chloride derivatives are prepared in an extremely high yield and high selectivity compared with the afore-mentioned conventional processes. Nuclear-chlorinated products and phenoxyphenyl trichloromethane derivatives, by-products, are restricted in an amount of usually less than 2 to 3%, respectively. These findings are quite novel which are not seen in conventional processes.
The chlorinated phenoxytoluene derivatives obtained by the present process are represented by the formula (1). In the groups R.sup.1 to R.sup.2, preferable examples of halogen are chlorine and bromine. Preferable examples of alkyl are those having 1 to 4 carbon atoms such as methyl, ethyl and butyl. Examples of preferable alkoxyl are those having 1 to 4 carbon atoms such as methoxy and propoxy. Examples of alkoxycarbonyl are those having 2 to 5 carbon atoms such as methoxycarbonyl and butoxycarbonyl. Halogenoalkyl has preferably 1 to 4 carbon atoms and includes for example chloromethyl and bromoethyl. Preferable examples of the group acyl both in acyl and acyloxy are those having 2 to 8 carbon atoms such as acetyl, propionyl, benzoyl and toluoyl. Examples of preferable aryl are those having 6 to 9 carbon atoms such as phenyl, tolyl and xylyl. Preferable examples of the group aralkyl both in aralkyl and aralkyloxy are those having 7 to 10 carbon atoms such as benzyl, phenylethyl and phenylpropyl.
Nitrogen-containing compounds useful in this invention are a wide variety of compounds represented by the following formulae. ##STR3## Preferable examples of R.sup.4 to R.sup.6 are hydrogen; alkyl having 1 to 20 carbon atoms such as methyl, butyl, octyl, dodecyl, hexadecyl, stearyl, etc; hydroxyalkyl having 1 to 10 carbon atoms such as hydroxymethyl, hydroxypropyl, hydroxyheptyl, etc; cycloalkyl having 5 to 8 carbon atoms such as cyclohexyl, cycloheptyl etc; aryl having 6 to 10 carbon atoms with or without a substituent such as phenyl, tolyl, ethylphenyl, chlorophenyl, trichlorophenyl, bromophenyl, etc. Two or three of R.sup.4 to R.sup.6 may form a ring.
Preferable examples of R.sup.7 are alkylene having 2 to 8 carbon atoms such as ethylene, propylene, hexamethylene, etc; arylene having 6 to 10 carbon atoms such as phenylene, tolylene, dimethylphenylene, chlorophenylene, etc.
Examples of preferable nitrogen-containing compounds are triethylamine, isobutylamine, 1-methylpentylamine, di-n-octylamine, n-dodecylamine, n-hexadecylamine, stearylamine, diethanolamine, cyclohexylamine, aniline, N,N-diethylaniline, 2,4,5-trichloroaniline, p-toluidine, hexamethylenediamine, p-phenylenediamine, succinimide, piperidine, pyridine, quinoline, 2-imidazoline, ethyleneimine, hexamethylenetetramine, 3,5-di-n-heptyl-1,2,4-triazole, 2,4-di-(4-pyridyl)-6-methyl-s-triazine, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,4-diazabicyclo(2,2,2)octane, etc.
Useful sulfur-containing compounds of the invention are represented by the following formulae. ##STR4## Preferable examples of R.sup.8 and R.sup.9 are 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. Further 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 group 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. In the above, as the groups alkyl, cycloalkyl, aryl, alkylene and arylene, the same are usable as those described in the nitrogen-containing compounds. As the acyl group in the definition of the above A and B, acetyl, butyryl, stearoyl, benzoyl, toluoyl and like acyl groups are enumerated.
Preferable examples of sulfur-containing compounds are isobutyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, n-hexadecyl mercaptan, stearyl mercaptan, cyclohexyl mercaptan, thiophenol and like mercaptans; diisopropyl sulfide, di-n-octyl sulfide, di-n-dodecyl sulfide, di-n-hexadecyl sulfide, distearyl sulfide, diphenyl sulfide, dicyclohexyl sulfide, 2,2'-dipyridyl sulfide and like monosulfides; di-tert-butyl disulfide, di-n-octyl disulfide, di-n-dodecyl disulfide, di-n-hexadecyl disulfide, distearyl disulfide, diphenyl disulfide, dicyclohexyl disulfide, 2,2'-benzothiazolyl disulfide, diethyl tetrasulfide and like polysulfides; 2-mercaptobenzothiazole, tetrahydrothiophene, thiophene, 2-n-dodecyl-1,3,5-trithiane, 2-phenyl-1,3-dithian, 4-methylthiacyclohexane and like cyclic sulfur compounds; methyl cyclohexyl thioketone, 4,4'-bis(N,N-dimethylamino)thiobenzophenone, cyclohexanethion, 1-(n-heptadecyl)-2-thiourea, 1-isopropyl-3-(n-dodecyl)-2-thiourea, 1-(n-dodecanoyl)-2-thiourea, 1,3-dicyclohexyl-2-thiourea, 1-(p-tolyl)-3-(2-pyridyl)-2-thiourea, 1,1,3,3-tetra-n-propyl-2-thiourea, 1,4-diethyl-1,4-diphenyl-3-thiosemicarbazide, 1-isonicotinoyl-4-(n-octadecanoyl)-3-thiosemicarbazide, 1-(n-dodecanoyl)-4-(p-isoamyloxyphenyl)-3-thiosemicarbazide, 1-ethoxycarbonylmethyl-1-phenyl-4-ethyl-3-thiosemicarbazide, 1-(n-heptadecyl)-4-thiosemicarbazone, 1-(3-pyridyl)-5-ethyl-4-thiosemicarbazone, 1-pentamethylene-4-thiosemicarbazone, 1,5-diphenyl-3-thiocarbohydrazide, dithizone, 1,1,7,7-tetraphenyl-4-bisthiocarbohydrazone, 1,7-di-n-heptadecyl-4-bisthiocarbohydrazone, 1,7-dipentamethylene-4-bisthiocarbohydrazone, 5-ethyl-2-thiobiuret, 5-phenyl-1-(p-chlorophenyl)-2-thiobiuret, 5-(n-propyl)-2,4-dithiobiuret, N,N',N",N'"-hexamethylguanyl thiourea, 1-benzoyl-2-guanyl thiourea, thioacetanilide, thiobenzamide, thiobenzanilide, n-heptadecylthioamide, N-cyclohexylthiobenzamide, 2-benzothiazolylethyl thioanilide, thiophenylacetohydrazide, methylphenylthio-n-valerohydrazone, 2,4-dichlorophenylthiophenylacetohydrazone, N-(n-octyl)-N-aminoethyl dithiocarbamic acid, n-heptadecyl dithiocarbamic acid n-heptadecylammonium salt, 2-thiazolyldithiocarbamic acid triethylammonium salt, N-pentamethylene dithiocarbamic acid piperidinium salt, cyclohexyldithiocarbamic acid cyclohexylammonium salt, N,N-dimethyl S-(n-hexadecyl)dithiocarbamate, N,N-dimethyl S-(2-benzothiazolyl)dithiocarbamate, N-pentamethylene S-mercaptoethyl dithiocarbamate, N-diethyleneoxy S-hydroxyethyl dithiocarbamate, O-cyclohexylthioncarbamate, N-carboxymethyl O-(n-hexadecyl)thioncarbamate, N-pentamethylene O-(n-propyl)thioncarbamate, diethyl dithiocarbamyl sulfenamide, methylphenyl dithiocarbamyl sulfenamide, benzyl thionpropionate, methylthion cyclohexane carboxylate, isoamyl p-thiontoluate, dithiobenzoic acid, ethyl dithio-n-heptanoate, n-butyl dithiocyclohexanecarboxylate, carboxymethyldithio acid phenylacetate, n-dodecyl phenylthioncarbonate, tetramethylenethioncarbonate, diphenylthioncarbonate, di-n-octadecyl trithiocarbonate, di-n-dodecyl trithiocarbonate, di(4-chlorophenyl)trithiocarbonate, dicyclohexyl trithiocarbonate, S,O-(di-n-dodecyl)-xanthate, S-carboxydecamethylene O-(n-dodecyl)xanthate, S-(n-hexadecyl) O-cyclohexyl xanthate, S-lauroyl O-ethylxanthate, O-cyclohexylthion carbazate, 1-(n-dodecylidene) O-ethylthioncarbazate, 1-(n-dodecylidene) S-ethyldithiocarbazate, isobutyl isothiocyanate, n-octyl isothiocyanate, cyclohexyl isothiocyanate, p-(N,N-dimethylamino)phenyl isothiocyanate, 6-isothiocyanoquinoline, isothiocyanocapric acid methyl ester, ethylene diisothiocyanate, hexamethylene diisothiocyanate, methylenebis(N,N-dimethyldithiocarbamate), p-xylylenebis(N,N-dimethyldithiocarbamate), N,N-bis(N',N'-dimethylthiocarbamoylthioethyl)methylamine, bis(N,N-dimethylthiocarbamoylthioethyl)sulfide, p,p'-bis(dithiocarbamoyl)diphenyl sulfone, 1,4-phenylenebisisopropyl thiourea, dimethylene trithiourea, methylenebistetramethylene thiourea, bis(N-trimethylenethioacetamide), ethylenebisdithiocarbamic acid diammonium salt, diisopropyldithion oxalate, S,S'-diethyl O,O'-decamethylenebisxanthate, O,O'-dicyclohexyl S,S'-methylenebisxanthate, O,O'-di(n-octyl) S,S'-(p-xylylene)bisxanthate, cyclohexylxanthogene monosulfide, ethoxyethylxanthogene monosulfide, n-hexadecyl dixanthogene, benzyl dixanthogene, ethyl dixanthogene disulfide, O-ethylthiooxalamide, N,N'-dimorpholinodithiooxalic diamide, N,N-di(n-dodecyl)dithiooxalic diamide, N,N'-diphenyldithio(n-butyl)malonic diamide, N,N'-di-n-octyldithioadipic diamide, bis(piperidinothiocarbonyl)monosulfide, bis(morpholinothiocarbonyl)monosulfide, bis(hydrazinothiocarbonyl)monosulfide, bis(n-octylidenehydrazinothiocarbonyl)monosulfide, bis(di-n-butylthiocarbamoyl)disulfide, bis(piperidinothiocarbonyl)disulfide, bis(morpholinothiocarbonyl)disulfide, ethylene-1,2-bis[1,2-(dithiocarbamoyl)ethylene]disulfide, ethylene-1,2-bis(benzothiazolylthiocarbamoyl)disulfide, bis(dimethylthiocarbamoyl)tetrasulfide, bis(piperidinothiocarbonyl)hexasulfide, n-octadecyl thiocyanate, pentamethylene dithiocyanate, 2-chlorocyclohexyl thiocyanate, p-aminophenyl thiocyanate, 3-thiocyanopyridine, N-diethyleneoxy-2-benzothiazolyl sulfenamide, N-(n-heptadecyl)-n-octyl sulfenamide, N-tert-butyl-2-benzothiazolyl sulfenamide, N-cyclohexyl-2-benzothiazolyl sulfenamide, di-n-amyl thiosulfinate, tert-butylethyl thiosulfinate, thiostearic acid, thioterephthalic acid, cyclohexylthiol acetate, N,N-diethylaminoethylthiolphenylacetate, dicyclohexyldithiosebacate, 1,6-hexamethylenedithiol diacetate, S-phenacyl O-ethylthiolcarbonate, S,S'-dimethylenecarboxy O,O'-diethylbisthiolcarbonate, diphenyl dithiolcarbonate, N-(.zeta.-aminohexamethyl)thiocarbamic acid, N-phenylthiocarbamic acid, N-stearylthiocarbamic acid stearylammonium salt, N-isobutylthiocarbamic acid isobutylammonium salt, N-pentamethylene S-phenylthiol carbamate, N-cyclohexyl S-pentamethylenethiol carbamate, S,S'-pentamethylenebisthiol carbamate, n-hexylmercaptocapric acid, 2-thienylmercaptoacetic acid, n-octadecylmercaptosuccinic acid diethyl ester, 2-thienylmercaptoacetic acid n-dodecyl ester, methylmercaptopelargonic acid amide, n-octylmercaptobenzamide, S,S'-di(n-octadecyl)methyl thioacetal, S,S'-dibenzylcyclohexyl ketone thioacetal, ethylenebis(S,S'-di-n-octadecylmethyl)ketone thioacetal, tri-n-dodecyl trithioorthoformate, triphenyltrithioorthobenzoate, tetraisopropyl tetrathioorthocarbonate, tetracyclohexyl tetrathioorthocarbonate, di(.beta.-chloroethyl)sulfide, 1,10-decamethylenebischloroethyl sulfide, .gamma.-chloro-.gamma.'-(N,N-diethylamino)dipropyl sulfide, N-(n-octadecyl)iminomethylethyl sulfide, di(N-pentamethyleneaminoethyl)sulfide, n-butylmercaptoacetaldehyde, p-benzylmercaptobenzaldehyde, n-dodecylmercaptomethyl phenyl ketone, bis(n-heptylcarbonylmethyl)sulfide, n-octadecylmercaptopropionitrile, di(chloroacetyl)sulfide, dibenzoyl sulfide, ethylenebis(.beta.-cyanoethyl sulfide), 1,18-octadecamethylene bis(n-octadecyl sulfide), bis{2-[2-(2-chloroethylthio)ethylthio]ethyl}sulfide, poly(ethylenesulfide), poly(phenylenesulfide), .alpha.,.alpha.'-di-n-hexadecyldi(carboxymethyl)disulfide, di(.kappa.-carboxydecyl)disulfide, di(cyclohexyloxycarbonylethyl)disulfide, di(n-octadecyloxycarbonylethyl)disulfide, di(N-methyolanilinocarbonylmethyl)disulfide, di(.gamma.-carbamoylpropyl)disulfide, di(.zeta.-chlorohexyl)disulfide, di(2,4-dichlorophenyl)disulfide, di(N,N-dimethylaminohexamethyl)disulfide, di(m-aminophenyl)disulfide, di(.alpha.-formylisopropyl)disulfide, di(o-formylmethylthiophenyl)disulfide, di(methylcarbonylisobutyl)disulfide, di(2-methylcarbonyl-5-methoxyphenyl)disulfide, di(p-cyanophenyl)disulfide, .zeta.-cyano-.zeta.'-hydroxy dihexamethyl disulfide, dibenzoyl disulfide, di-3-nicotinoyl disulfide, poly(ethylformal disulfide), poly(ethylene disulfide), di(.gamma.-hydroxypropyl)disulfide, di(m-hydroxyphenyl)disulfide, di(.beta.-ethoxyethyl)disulfide, di(2-ethoxy-1-naphthyl)disulfide, di(carboxymethyl)trisulfide, di(o-carboxyphenyl)tetrasulfide, di(p-ethoxycarbonylphenyl)trisulfide, di(n-dodecyloxycarbonylmethyl)tetrasulfide, di(carbamoylmethyl)trisulfide, di(o-n-butylcarbamoylphenyl)tetrasulfide, di(.beta.-chloroethyl)tetrasulfide, di(.beta.-chloroethyl)pentasulfide, di(p-aminophenyl)trisulfide, di(ethylenediaminoethyl)tetrasulfide, di(.beta.-formylethyl)trisulfide, di(m-formylphenyl)trisulfide, di(acetylmethyl)trisulfide, di(3-acetyl-4-hydroxy-1-naphthyl)trisulfide, di(.beta.-cyanoethyl)trisulfide, di(p-cyanophenyl)trisulfide, dibenzoyl tetrasulfide, diacetyl tetrasulfide, poly(ethylene pentasulfide), poly(oxydiethylene tetrasulfide), di(.beta.-hydroxyethyl)trisulfide, di(2-hydroxy-1-naphthyl)trisulfide, di(n-dodecyloxyethyl)trisulfide, di(2-ethoxy-1-naphthyl)trisulfide, .alpha.-mercaptostearic acid, .kappa.-mercaptoundecylic acid, n-octadecyl mercaptoacetate, ethyl mercaptosuccinate, methyl p-mercaptobenzoate, .alpha.-mercaptopropionanilide, .epsilon.-mercaptocaproic acid amide, 2,3-dichloropropyl mercaptan, pentachlorothiophenol, .beta.-mercaptoethyl n-dodecylamine, N,N-di(.gamma.-mercaptoisobutyl)piperazine, .beta.-formylethyl mercaptan, .alpha.-phenyl-.beta.-formylethyl mercaptan, di(p-mercaptophenyl)ketone, mercaptomethyl n-hexyl ketone, .beta.-cyanoethyl mercaptan, p-cyanothiophenol, bis(ethylenedimercaptomethyl)methane, 2-n-heptylmercaptocyclohexanethiol, di(.beta.-mercaptoethyl)disulfide, p-hydroxy-p'-mercaptodiphenyl disulfide, di(2-mercapto-1-naphthyl)trisulfide, di(.beta.-mercaptoethyl)tetrasulfide, 1,6-hexamethylene dithiol, 1,18-octadecamethylene dithiol, 1,2-cyclohexane dithiol, 3,4-thiophene dithiol, etc.
Phosphorus-containing compounds employed in the invention are represented by the following formulae. ##STR5## Preferable examples of 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. In the above, examples of halogen are chlorine, bromine, etc. As the groups alkyl and aryl, the same are usable as those described in the nitrogen-containing compounds.
Examples of preferable phosphorus-containing compounds are tri-n-butylphosphine, tri-n-octylphosphine, tri-n-dodecylphosphine, n-octadecyldiphenylphosphine, triphenylphosphine, 1-mercaptoethyldiphenylphosphine, tricyclohexylphosphine, dicyclohexyl 4-chlorophenylphosphine, triisopropylphosphine sulfide, n-hexadecyldiphenylphosphine sulfide, triphenylphosphine oxide, tri-n-dodecylphosphine oxide, N,N-diethylhydrazinodiphenylphosphine oxide, 1-phenyl-1-phosphacyclohexane, n-octadecyl diphenyl phosphite, dicyclohexyl chloro phosphite, di-n-octyl phosphite, diphenyl cyclohexyl phosphite, triphenyl phosphite, tricyclohexyl phosphite, diiosopropyl chloro thiophosphite, tricyclohexyl thiophosphite, tri-n-dodecyl thiophosphite, triphenyl thiophosphite, tris(dimethylamino)phosphine, phosphorus tripiperidide, tris(di-n-butylamino)phosphine, phosphorus tri(N-methylanilide), diphenylphosphinic chloride, cyclohexylphenylphosphinothioic chloride, di-n-butylphosphinothioic acid, isopropyl n-hexyl phosphinic acid, dicyclohexylphosphinodithioic acid, methyl n-octyl n-hexyl phosphinate, O-methyl diisopropylphosphinothioate, phenyl diethylphosphinodithioate, methyl dicyclohexyl phosphinate, hexamethylene phosphoric triamide, phenyl phosphonus dichloride, cyclohexylphosphonic dichloride, S,S-diethyl phenylphosphonodithioate, diethyl-n-butylphosphonate, O,O-diethyl phenylphosphonothioate, O,S-diethyl phenylphosphonothioate, S-ethyl N,N-diethyl P-methyl phosphonamide thioate, O-ethyl phenyl phosphonodithioate, O-ethyl S-phenyl phenylphosphonodithioate, etc.
Useful oxygen-containing compounds of this invention are represented by the following formulae. ##STR6## Preferable examples of R.sup.22 and R.sup.23 are alkyl having 1 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, alicyclic of 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 hydrogen 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. In the above, as halogen, alkyl, aryl, alkyl in the groups alkoxyl, alkylamino, alkylamido and carboxyalkyl, aryl in the group aryloxy, the same are usable as those in the aforementioned nitrogen- or sulfur-containing compounds. Examples of oxyalicyclic and oxyheterocyclic ring are cyclohexyloxy, pyridyloxy, quinolyloxy, etc. In the invention are excluded ethers having boiling point of less than 70.degree. C.
Preferable examples of oxygen-containing compounds are 2,2'-dichlorodiethyl ether, di-n-butyl ether, di-n-octyl ether, di-n-octadecyl ether, diphenyl ether, naphthyl ethyl ether, dicyclohexyl ether, 4-pyridyl ethyl ether, p-dioxane, furan, tetrahydrofuran, 15-crown-5, dibenzo-18-crown-6, isobutyl alcohol, n-octyl alcohol, n-tetradecyl alcohol, n-octadecyl alcohol, m-cresol, 2,6-di-tert-butyl-4-methyl phenol, 2-(3-tolyoxy)-3-methyl phenol, 2,2'-methylenebis(4-methoxy-6-tert-butyl phenyl), 4,4'-thiobis(3-methyl-6-tert-butyl phenol), 4-hydroxypyridine, cyclohexyl alcohol, ethylene glycol, ethylene dithioglycol, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-dodecyl ether, propylene glycol diisopropionate, tripropylene glycol monostearate, ethylene glycol monophenyl ether, .beta.-cyclodextrin, 1,5-sorbitan monostearate, glycerin monopalmitate, bis(hydroxyethylthioethyl)ether, bis(mercaptoethylthioethyl)ether, bis(chloroethoxyethyl)ether, bis(aminoethylthioethyl)ether, ethylene dithioglycol hexamer, polyethylene glycol, polypropylene glycol, polyoxyethylene 1,5-sorbitan monostearate, polyoxyethylene glycerin monoplamitate, polyoxyethylene dodecyl ether, polyoxyethylene p-dodecylphenyl ether, polyoxyethylene laurylamine, polyoxyethylene laurylamide, etc.
In this invention, the above-mentioned nitrogen-, sulfur-, phosphorus- and oxygen-containing compounds are capable of forming charge-transfer complex with chlorine, chlorine radical or organic halogen compounds. These N, S, P and O-containing compounds are usable singly or at least two of them are usable, and are used in an amount of about 0.001 to 50 wt %, preferably about 0.01 to 30 wt % based on the starting phenoxytoluene derivative. With use of the above-mentioned range of the compound, the contemplated reaction proceeds effectively.
Examples of useful organic halogen compounds are represented by the formulae below. ##STR7## In the above, Hal means halogen atom such as chlorine, bromine, iodine, etc., 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.
Preferable examples of organic halogen compounds are carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, chloroform, bromoform, iodoform, methylene chloride, methylene bromide, dichloroethane, trichloroethane, tetrachloroethane, tetrachloroethylene, hexachlorocyclohexane, etc. Chlorinated paraffin is also included in organic halogen compound of the invention. More preferable organic halogen compound are carbon tetrachloride and carbon tetrabromide. These organic halogen compounds are usable singly or at least two of them are usable, and are used in an amount of usually 1 to 20 times, preferably 5 to 10 times the weight of the starting phenoxytoluene derivative.
Useful radical initiators of the invention are azo compounds or peroxides, and preferably are azobisisobutyronitrile, benzoyl peroxide, etc. The radical initiator is used in an amount of usually about 0.001 to 20 wt %, preferably about 0.01 to 15 wt % of the phenoxytoluene derivative. It is preferable to blow chlorine into the reaction system in an amount of about 0.5 to 10 mole %, preferably about 2 to 5 mole % of the phenoxytoluene derivative in a minute until the reaction is completed. The reaction is conducted at usually about 0.degree. to 150.degree. C., preferably at a temperature of reflux state of the reaction mixture.
The desired compound of the invention is easily purified by known methods such as concentration, extraction, distillation, recrystallization, column chromatography, etc.

The invention will be described below in greater detail with reference to the following examples.
EXAMPLE 1
Into a flask equipped with a thermometer, stirrer, gas-introducing pipe and reflux condenser are placed 95 g (0.52 mole) of m-phenoxytoluene, 10 g of azobisisobutyronitrile, 1 g of piperidine and 1,300 g of carbon tetrachloride. The mixture is heated with stirring at a temperature of 78.degree. to 82.degree. C. to bring the system in a mildly reflux state. To the flask are blown 0.023 mole/min. of chlorine and the mixture is reacted for one hour. After completion of the reaction, the mixture is cooled. The carbon tetrachloride is distilled off at a reduced pressure, giving a slightly yellow product. Analysis of the product by gas chromatography shows 1.2% (yield, same in hereinafter) of m-phenoxybenzyl chloride, 95.0% of m-phenoxybenzal chloride, 2.8% of m-phenoxyphenyl trichloromethane and 1.0% of nuclear-chlorinated compounds. For comparison, the same reaction is carried out with exception that piperidine is not added. The result shows 70.8% of m-phenoxytoluene, 28.2% of m-phenoxybenzyl chloride, 0% of m-phenoxybenzal chloride and 1.0% of nuclear-chlorinated compounds.
EXAMPLES 2 TO 17
Reactions are conducted in a similar manner as in Example 1 with use of typical phenoxytoluene derivatives in Table 1. The results are also shown in Table.
TABLE 1______________________________________Chlorination of phenoxytoluenes in the coexistenceof piperidine Reac.EX. Starting material time (yield,No. (g) (min.) Products %)______________________________________2 m-phenoxytoluene 30 m-phenoxytoluene (3.4) (95) m-phenoxybenzyl chloride (92.6) m-phenoxybenzal chloride (3.3) nucleus-substituted (0.7)3 p-phenoxytoluene 60 p-phenoxybenzyl (95) chloride (1.7) p-phenoxybenzal chloride (94.0) p-phenoxyphenyl trichloromethane (2.2) nucleus-substituted (2.1)4 3-phenoxy-6-chloro- 72 3-phenoxy-6-chloro- toluene benzyl chloride (7.5) (114) 3-phenoxy-6-chloro- benzal chloride (90.5) 3-phenoxy-6-chloro- phenyl trichloro- methane (1.0) nucleus-substituted (1.0)5 m,m'-dimethyldi- 120 m,m'-di(chloro- phenyl ether methyl)diphenyl (103) ether (2.2) m,m'-di(dichloro- methyl)diphenyl ether (90.6) m,m'-di(trichloro- methyl)diphenyl ether (4.7) nucleus-substituted (2.5)6 m-(m-chloromethyl- 72 m-(m-chloromethyl- phenoxy)toluene phenoxy)toluene (5.3) (121) m-(m-dichloro- methylphenoxy) benzyl chloride (90.3) m-(m-trichloro- methylphenoxy) benzal chloride (3.4) nucleus-substituted (1.0)7 m-(p-benzoylphen- 36 m-(p-benzoylphen- oxy)toluene oxy)toluene (4.3) (150) m-(p-benzoylphen- oxy)benzyl chloride (91.5) m-(p-benzoylphen- oxy)benzal chloride (3.2) nucleus-substituted (1.0)8 m-(p-benzoylphen- 72 m-(p-benzoylphen- oxy)toluene oxy)benzyl chloride (3.5) (150) m-(p-benzoylphen- oxy)benzal chloride (93.0) m-(p-benzoylphen- oxy)phenyl tri- chloromethane (2.3) nucleus-substituted (1.2)9 m-(p-cyanophenoxy) 72 m-(p-cyanophenoxy)- toluene benzyl chloride (1.9) (109) m-(p-cyanophenoxy)- benzal chloride (91.6) m-(p-cyanophenoxy)- phenyl trichloro- methane (4.8) nucleus-substituted (1.7)10 m-(p-nitrophenoxy) 84 m-(p-nitrophenoxy)- toluene benzyl chloride (6.8) (119) m-(p-nitrophenoxy)- benzal chloride (89.2) m-(p-nitrophenoxy)- phenyl trichloro- methane (3.3) nucleus-substituted (0.7)11 m-(p-phenylphen- 36 m-(p-phenylphen- oxy)toluene oxy)toluene (4.2) (135) m-(p-phenylphen- oxy)benzyl chloride (92.7) m-(p-phenylphen- oxy)benzal chloride (2.8) nucleus-substituted (0.3)12 m-(p-phenylphen- 72 m-(p-phenylphen- oxy)toluene oxy)benzyl chloride (3.1) (135) m-(p-phenylphen- oxy)benzal chloride (92.1) m-(p-phenylphen- oxy)phenyl trichloromethane (3.3) nucleus-substituted (1.5)13 m-(p-benzylphen- 72 m-(p-benzylphen- oxy)toluene oxy)benzyl chloride (1.2) (143) m-(p-benzylphen- oxy)benzal chloride (93.7) m-(p-benzylphen- oxy)phenyl trichloromethane (3.1) nucleus-substituted (2.0)14 m-(p-benzyloxy- 72 m-(p-benzyloxy- phenoxy)toluene phenoxy)benzyl (151) chloride (2.7) m-(p-benzyloxy- phenoxy)benzal chloride (91.6) m-(p-benzyloxy- phenoxy)phenyl trichloromethane (4.0) nucleus-substituted (1.7)15 p-(m-tolyloxy) 72 p-(m-chloromethyl- phenyl benzoate phenoxy)phenyl (158) benzoate (2.1) p-(m-dichloro- methylphenoxy)- phenyl benzoate (92.7) p-(m-trichloro- methylphenoxy)- phenyl benzoate (3.6) nucleus-substituted (1.6)16 m-(p-methoxyphen- 35 m-(p-methoxyphen- oxy)toluene oxy)toluene (3.2) (111) m-(p-methoxyphen- oxy)benzyl chloride (92.7) m-(p-methoxyphen- oxy)benzal chloride (3.1) nucleus-substituted (1.0)17 m-(p-methoxycar- 35 m-(p-methoxy- bonyl phenoxy)- carbonyl phenoxy)- toluene toluene (5.4) (126) m-(p-methoxy- carbonyl phenoxy)- benzyl chloride (90.3) m-(p-methoxy- carbonyl phenoxy)- benzal chloride (2.7) nucleus-substituted (1.6)______________________________________
EXAMPLE 18
Chlorination reactions are conducted in a similar manner as in Example 1 with use of m-phenoxytoluene and typical nitrogen- of sulfur-containing compounds listed in Table 2. The results are also given in Table.
TABLE 2______________________________________Effect of nitrogen-containing and sulfur-containingcompounds on the chlorination of m-phenoxytolueneNitrogen-containing Reac.or sulfur-containing time Products (Yield, %)No. compound (hr) (1) (2) (3) (4) (5)______________________________________1 Stearylamine 1 -- 1.4 92.6 2.9 3.12 Diethanolamine 1 -- 1.6 93.7 2.6 2.13 Cyclohexylamine 1 -- 4.1 92.8 1.2 1.94 N,Ndiethylaniline 0.5 3.3 92.6 3.2 -- 0.95 N,Ndiethylaniline 1 -- 1.0 95.3 1.9 1.86 Quinoline 1 -- 2.8 93.4 2.1 1.77 1,8-diazabicyclo(5,4,0)- 1 -- 1.6 95.7 2.0 0.7 7-undecene8 1,4-diazabicyclo(2,2,2) 1 -- 1.8 95.6 1.7 0.9 octane9 Morpholine 0.5 5.4 90.4 3.1 -- 1.110 Morpholine 1 -- 2.9 92.2 3.5 1.411 Di-n-dodecyl sulfide 0.5 4.8 93.1 1.3 -- 0.812 Di-n-dodecyl sulfide 1 -- 1.2 96.8 0.8 1.213 Diphenyl sulfide 1 -- 2.3 93.5 1.9 2.314 Dicyclohexyl sulfide 1 -- 1.9 93.9 3.2 1.015 2,2'-dipyridyl sulfide 1 -- 1.2 93.1 2.1 3.616 Di-tert-butyl disulfide 1 -- 9.1 87.9 2.2 0.817 Diphenyl disulfide 1 -- 5.1 90.6 2.4 1.918 Dicyclohexyl disulfide 0.5 4.0 90.1 5.4 -- 0.519 Dicyclohexyl disulfide 1 -- 3.1 94.7 1.3 0.920 2,2'-dibenzothiazolyl 1 -- 2.6 95.1 1.5 0.8 disulfide21 Diethyl tetrasulfide 1 -- 2.8 94.8 1.4 1.022 Tetrahydrothiophene 1 -- 4.7 91.2 2.1 2.023 Thiophene 0.5 4.5 90.8 3.4 -- 1.324 Thiophene 1 -- 3.6 92.7 1.9 1.825 2-phenyl-1,3-dithian 1 -- 2.7 93.4 2.7 1.226 n-octyl mercaptan 1.2 -- 4.0 92.8 2.3 0.927 Cyclohexyl mercaptan 0.6 5.1 90.2 3.6 -- 1.128 Cyclohexyl mercaptan 1 -- 2.9 91.8 3.6 1.729 Thiophenol 1 -- 4.8 90.3 2.9 2.030 2-mercaptobenzothiazole 1 -- 8.0 88.5 2.0 1.5______________________________________ ##STR8## ##STR9## ##STR10## ##STR11## ##STR12##
EXAMPLE 19
The procedure of Example 1 is followed with use of 95 g (0.52 mole) of m-phenoxytoluene, 10 g of azobisisobutyronitrile, 1 g of N-pentamethylenedithiocarbamic acid piperidinium salt and 1,300 g of carbon tetrachloride. The reaction time is 75 minutes. Analysis of the product by gas chromatography shows 0.9% of m-phenoxybenzyl chloride, 96.8% of m-phenoxybenzal chloride, 1.3% of m-phenoxyphenyl trichloromethane and 1.0% of nuclear-chlorinated compounds. For comparison, the same reaction is conducted, except that the above piperidium salt is not used. The result shows 41.0% of m-phenoxytoluene, 45.7% of m-phenoxybenzyl chloride, 12.1% of m-phenoxybenzal chloride and 1.2% of nuclear-chlorinated compounds.
EXAMPLE 20
Exactly the same procedure as in Example 19 is followed except that 1 g of N-diethyleneoxy-2-benzothiazolyl sulfenamide is used in place of 1 g of N-pentamethylenedithiocarbamic acid piperidinium salt. The result shows 2.1% of m-phenoxybenzyl chloride, 95.6% of m-phenoxybenzal chloride, 1.8% of m-phenoxyphenyl trichloromethane and 0.5% of nuclear-chlorinated products. The similar reaction without the above sulfenamide gives 41.0% of m-phenoxytoluene, 45.7% of m-phenoxybenzyl chloride, 12.1% of m-phenoxybenzal chloride and 1.2% of nuclear-chlorinated compounds.
EXAMPLES 21 TO 36
Table 3 shows the results of reactions which are conducted in a similar manner as in Example 19 with use of typical phenoxytoluene derivatives.
TABLE 3______________________________________Chlorination of phenoxytoluenes in the coexistence ofpiperidinium salt of N--pentamethylenedithiocarbamicacid Reac. Starting material time (yield,No. (g) (min.) Products %)______________________________________21 m-phenoxytoluene 35 m-phenoxytoluene (2.8) (95) m-phenoxybenzyl chloride (93.4) m-phenoxybenzal chloride (2.9) nucleus-substituted (0.9)22 p-phenoxytoluene 75 p-phenoxybenzyl (95) chloride (2.0) p-phenoxybenzal chloride (94.5) p-phenoxyphenyl trichloromethane (2.0) nucleus-substituted (1.5)23 3-phenoxy-6-chloro- 85 3-phenoxy-6-chloro- toluene benzyl chloride (5.6) (114) 3-phenoxy-6-chloro- benzal chloride (91.3) 3-phenoxy-6-chloro- phenyl trichloro- methane (2.1) nucleus-substituted (1.0)24 m,m'-dimethyldi- 150 m,m'-di(chloro- phenyl ether methyl)diphenyl (103) ether (2.5) m,m'-di(dichloro- methyl)diphenyl ether (89.8) m,m'-di(trichloro- methyl)diphenyl ether (4.8) nucleus-substituted (2.9)25 m-(m-chloromethyl- 85 m-(m-chloromethyl- phenoxy)toluene phenoxy)toluene (3.2) (121) m-(m-dichloro- methylphenoxy) benzyl chloride (91.0) m-(m-trichloro- methylphenoxy) benzal chloride (3.7) nucleus-substituted (2.1)26 m-(p-benzoylphen- 40 m-(p-benzoylphen- oxy)toluene oxy)toluene (3.9) (150) m-(p-benzoylphen- oxy)benzyl chloride (90.8) m-(p-benzoylphen- oxy)benzal chloride (4.2) nucleus-substituted (1.1)27 m-(p-benzoylphen- 80 m-(p-benzoylphen- oxy)toluene oxy)benzyl chloride (2.8) (150) m-(p-benzoylphen- oxy)benzal chloride (93.7) m-(p-benzoylphen- oxy)phenyl tri- chloromethane (2.0) nucleus-substituted (1.5)28 m-(p-cyanophenoxy) 85 m-(p-cyanophenoxy)- toluene benzyl chloride (1.2) (109) m-(p-cyanophenoxy)- benzal chloride (92.1) m-(p-cyanophenoxy)- phenyl trichloro- methane (4.3) nucleus-substituted (2.4)29 m-(p-nitrophenoxy) 85 m-(p-nitrophenoxy)- toluene benzyl chloride (5.9) (119) m-(p-nitrophenoxy)- benzal chloride (90.2) m-(p-nitrophenoxy)- phenyl trichloro- methane (2.4) nucleus-substituted (1.5)30 m-(p-phenylphen- 40 m-(p-phenylphen- oxy)toluene oxy)toluene (3.7) (135) m-(p-phenylphen- oxy)benzyl chloride (91.0) m-(p-phenylphen- oxy)benzal chloride (4.1) nucleus-substituted (1.2)31 m-(p-phenylphen- 80 m-(p-phenylphen- oxy)toluene oxy)benzyl chloride (3.9) (135) m-(p-phenylphen- oxy)benzal chloride (92.5) m-(p-phenylphen- oxy)phenyl trichloro- methane (2.0) nucleus-substituted (1.6)32 m-(p-benzylphen- 80 m-(p-benzylphen- oxy)toluene oxy)benzyl chloride (2.5) (143) m-(p-benzylphen- oxy)benzal chloride (93.6) m-(p-benzylphen- oxy)phenyl trichloro- methane (1.8) nucleus-substituted (2.1)33 m-(p-benzyloxy- 80 m-(p-benzyloxy- phenoxy)toluene phenoxy)benzyl (151) chloride (2.2) m-(p-benzyloxy- phenoxy)benzal chloride (93.3) m-(p-benzyloxy- phenoxy)phenyl trichloromethane (2.7) nucleus-substituted (1.8)34 p-(m-tolyloxy) 80 p-(m-chloromethyl- phenyl benzoate phenoxy)phenyl (158) benzoate (1.8) p-(m-dichloro- methylphenoxy)- phenyl benzoate (94.5) p-(m-trichloro- methylphenoxy)- phenyl benzoate (2.6) nucleus-substituted (1.1)35 m-(p-methoxyphen- 35 m-(p-methoxyphen- oxy)toluene oxy)toluene (3.9) (111) m-(p-methoxyphen- oxy)benzyl chloride (90.5) m-(p-methoxyphen- oxy)benzal chloride (3.5) nucleus-substituted (2.1)36 m-(p-methoxycar- 35 m-(p-methoxycarbon- bonyl phenoxy)- yl phenoxy)toluene (3.6) toluene m-(p-methoxycarbon- (126) yl phenoxy)benzyl chloride (89.5) m-(p-methoxycarbon- yl phenoxy)benzal chloride (4.4) nucleus-substituted (2.5)______________________________________
EXAMPLES 37 TO 52
Table 4 shows the results of reactions which are conducted in a similar manner as in Example 20 with use of typical phenoxytoluene derivatives.
TABLE 4______________________________________Chlorination of phenoxytoluenes in the coexistenceof N--diethyleneoxy-2-benzothiazolyl sulfenamide Reac.EX. Starting material time (yield,No. (g) (min.) Products %)______________________________________37 m-phenoxytoluene 37 m-phenoxytoluene (4.1) (95) m-phenoxybenzyl chloride (94.0) m-phenoxybenzal chloride (1.5) nucleus-substituted (0.4)38 p-phenoxytoluene 76 p-phenoxybenzyl (95) chloride (4.2) p-phenoxybenzal chloride (93.2) p-phenoxyphenyl trichloromethane (1.8) nucleus-substituted (0.8)39 3-phenoxy-6-chloro- 88 3-phenoxy-6-chloro- toluene benzyl chloride (4.7) (114) 3-phenoxy-6-chloro- benzal chloride (92.8) 3-phenoxy-6-chloro- phenyl trichloro- methane (1.8) nucleus-substituted (0.7)40 m,m'-dimethyldi- 150 m,m'-di(chloro- phenyl ether methyl)diphenyl (103) ether (7.2) m,m'-di(dichloro- methyl)diphenyl ether (88.7) m,m'-di(trichloro- methyl)diphenyl ether (3.0) nucleus-substituted (1.1)41 m-(m-chloromethyl- 86 m-(m-chloromethyl- phenoxy)toluene phenoxy)toluene (3.7) (121) m-(m-dichloro- methylphenoxy) benzyl chloride (92.4) m-(m-trichloro- methylphenoxy) benzal chloride (3.1) nucleus-substituted (0.8)42 m-(p-benzoylphen- 44 m-(p-benzoylphen- oxy)toluene oxy)toluene (5.7) (150) m-(p-benzoylphen- oxy)benzyl chloride (91.6) m-(p-benzoylphen- oxy)benzal chloride (2.2) nucleus-substituted (0.5)43 m-(p-benzoylphen- 80 m-(p-benzoylphen- oxy)toluene oxy)benzyl chloride (3.0) (150) m-(p-benzoylphen- oxy)benzal chloride (94.9) m-(p-benzoylphen- oxy)phenyl tri- chloromethane (1.3) nucleus-substituted (0.8)44 m-(p-cyanophenoxy) 87 m-(p-cyanophenoxy)- toluene benzyl chloride (4.3) (109) m-(p-cyanophenoxy)- benzal chloride (92.0) m-(p-cyanophenoxy)- phenyl trichloro- methane (2.5) nucleus-substituted (1.2)45 m-(p-nitrophenoxy) 90 m-(p-nitrophenoxy)- toluene benzyl chloride (8.5) (119) m-(p-nitrophenoxy)- benzal chloride (88.1) m-(p-nitrophenoxy)- phenyl trichloro- methane (2.0) nucleus-substituted (1.4)46 m-(p-phenylphen- 42 m-(p-phenylphen- oxy)toluene oxy)toluene (3.5) (135) m-(p-phenylphen- oxy)benzyl chloride (93.7) m-(p-phenylphen- oxy)benzal chloride (2.0) nucleus-substituted (0.8)47 m-(p-phenylphen- 84 m-(p-phenylphen- oxy)toluene oxy)benzyl chloride (1.1) (135) m-(p-phenylphen- oxy)benzal chloride (95.8) m-(p-phenylphen- oxy)phenyl trichloro- methane (2.0) nucleus-substituted (1.1)48 m-(p-benzylphen- 85 m-(p-benzylphen- oxy)toluene oxy)benzyl chloride (2.7) (143) m-(p-benzylphen- oxy)benzal chloride (94.9) m-(p-benzylphen- oxy)phenyl trichloro- methane (1.5) nucleus-substituted (0.9)49 m-(p-benzyloxy- 82 m-(p-benzyloxy- phenoxy)toluene phenoxy)benzyl (151) chloride (3.5) m-(p-benzyloxy- phenoxy)benzal chloride (94.0) m-(p-benzyloxy- phenoxy)phenyl trichloromethane (1.8) nucleus-substituted (0.7)50 p-(m-tolyloxy) 85 p-(m-chloromethyl- phenyl benzoate phenoxy)phenyl (158) benzoate (2.0) p-(m-dichloro- methylphenoxy)- phenyl benzoate (95.6) p-(m-trichloro- methylphenoxy)- phenyl benzoate (1.9) nucleus-substituted (0.5)51 m-(p-methoxyphen- 40 m-(p-methoxyphen- oxy)toluene oxy)toluene (3.6) (111) m-(p-methoxyphen- oxy)benzyl chloride (91.0) m-(p-methoxyphen- oxy)benzal chloride (4.1) nucleus-substituted (1.3)52 m-(p-methoxycar- 40 m-(p-methoxycarbon- bonyl phenoxy)- yl phenoxy)toluene (4.8) toluene m-(p-methoxycarbon- (126) yl phenoxy)benzyl chloride (90.4) m-(p-methoxycarbon- yl phenoxy)benzal chloride (3.2) nucleus-substituted (1.6)______________________________________
EXAMPLE 53
Table 5 shows the results of reactions which are conducted in a similar manner as in Example 19 with use of m-phenoxytoluene and typical sulfur-containing compounds.
TABLE 5__________________________________________________________________________Effect of sulfur-containing compounds on thechlorination of m-phenoxytoluene Reac.Sulfur-containing time Products (Yield, %)No. compound (min.) (1) (2) (3) (4) (5)__________________________________________________________________________1 Methyl cyclohexyl 70 -- 6.7 89.0 3.1 1.2 thioketone2 4,4'-Bis(N,Ndimethyl- 70 -- 3.5 90.8 3.9 1.8 amino)thiobenzophenone3 1-Isopropyl-3-(n-dodecyl)- 35 3.8 90.8 4.4 -- 1.0 2-thiourea4 1-Isopropyl-3-(n-dodecyl)- 75 -- 2.4 93.5 2.8 1.3 2-thiourea5 1-(p-Tolyl)-3-(2-pyridyl)- 75 -- 3.4 93.8 1.6 1.2 2-thiourea6 1,1,3,3-Tetra-n-propyl- 75 -- 3.9 91.7 3.4 1.0 2-thiourea7 1,4-Diethyl-1,4-diphenyl- 75 -- 4.1 92.1 2.7 1.1 3-thiosemicarbazide8 1-Isonicotinoyl-4-(n-octa- 75 -- 3.3 93.4 2.0 1.3 decanoyl)-3-thiosemi- carbazide9 1-(n-Heptadecyl)-4- 75 -- 3.8 92.2 3.1 0.9 thiosemicarbazone10 1-Pentamethylene-4- 35 3.9 90.3 4.6 -- 1.2 thiosemicarbazone11 1-Pentamethylene-4- 75 -- 2.4 93.7 2.4 1.5 thiosemicarbazone12 1,5-Diphenyl-3- 75 -- 3.1 92.9 2.1 1.9 thiocarbohydrazide13 Dithizone 75 -- 4.6 91.9 1.7 1.814 1,7-Di-n-heptadecyl-4- 75 -- 4.0 92.4 2.5 1.1 bisthiocarbohydrazone15 1,7-Dipentamethylene- 75 -- 2.6 93.5 2.9 1.0 4-bisthiocarbohydrazone16 5-Ethyl-2-thiobiuret 73 -- 4.0 90.4 3.5 2.117 5-(n-Propyl)-2,4- 75 -- 2.8 92.3 3.0 1.9 dithiobiuret18 N,N',N",N'"Hexamethylguanyl 70 -- 5.0 89.0 3.9 2.1 thiourea19 n-Heptadecylthioamide 75 -- 5.8 90.1 2.8 1.320 NCyclohexylthiobenzamide 75 -- 4.8 90.9 3.1 1.221 2-Benzothiazolylethyl 75 -- 5.0 91.7 2.2 1.1 thioanilide22 Thiophenylacetohydrazide 80 -- 5.1 88.7 2.9 3.323 2,4-Dichlorophenyl 75 -- 4.3 90.3 2.4 3.0 thiophenylacetohydrazone24 N(n-Octyl)-Naminoethyl 75 -- 4.1 93.4 1.3 1.2 dithiocarbamic acid25 2-Thiazolyldithiocarbamic 34 1.2 94.0 3.8 -- 1.0 acid triethylammonium salt26 2-Thiazolyldithiocarbamic 75 -- 1.3 95.6 2.0 1.1 acid triethylammonium salt27 Cyclohexyldithiocarbamic 74 -- 4.4 90.8 3.1 1.7 acid cyclohexylammonium salt28 N,NDimethyl S(n-hexa- 75 -- 3.3 91.8 2.9 2.0 decyl)dithiocarbamate29 N,NDimethyl S(2-benzo- 35 2.6 93.6 2.9 -- 0.9 thiazolyl)dithiocarbamate30 N,NDimethyl S(2-benzo- 75 -- 2.1 94.4 1.4 2.1 thiazolyl)dithiocarbamate31 NPentamethylene S 80 -- 5.1 92.7 1.0 1.2 mercaptoethyl dithio- carbamate32 NDiethyleneoxy Shy- 77 -- 5.7 91.8 1.2 1.3 droxyethyl dithiocarbamate33 NCarboxymethyl O(.eta.-hexa- 75 -- 7.1 90.0 1.8 1.1 decyl) thioncarbamate34 NPentamethylene O(n- 75 -- 6.6 89.1 3.1 1.2 propyl) thioncarbamate35 Diethyl dithiocarbamyl 78 -- 3.8 92.4 2.1 1.7 sulfenamide36 Benzyl thionpropionate 75 -- 4.1 88.7 4.1 3.137 Isoamyl p-thiontoluate 75 -- 6.1 87.9 3.8 2.238 Dithiobenzoic acid 85 -- 2.0 90.2 4.7 3.139 Ethyl dithio-n-heptanoate 76 -- 3.4 90.1 3.7 2.840 n-Buthyl dithiocyclo- 75 -- 3.5 90.0 4.0 2.5 hexanecarboxylate41 n-Dodecyl phenylthion- 75 -- 7.4 89.3 2.1 1.2 carbonate42 Tetramethylenethion- 75 -- 3.9 92.1 3.0 1.0 carbonate43 Di-n-octadecyl trithio- 78 -- 4.9 91.8 1.9 1.4 carbonate44 Di-n-dodecyl trithio- 76 -- 5.6 90.2 2.2 2.0 carbonate45 Dicyclohexyl trithio- 76 -- 5.4 90.7 2.0 1.9 carbonate46 S,O(di-n-dodecyl)- 75 -- 4.1 91.2 3.4 1.3 xanthate47 Scarboxydecamethylene 75 -- 5.3 90.9 2.8 1.0 O(n-dodecyl)xanthate48 S(n-hexadecyl) Ocyclo- 75 -- 5.4 90.3 3.1 1.2 hexyl xanthate49 1-(n-dodecylidene) 75 -- 5.0 91.9 1.9 1.2 Oethylthioncarbazate50 1-(n-dodecylidene) 75 -- 3.1 93.4 2.2 1.3 Sethyldithiocarbazate51 Cyclohexyl isothiocyanate 75 -- 6.3 88.1 3.9 1.752 p-(N,Ndimethylamino)- 76 -- 5.2 90.0 3.0 1.8 phenyl isothiocyanate53 6-Isothiocyanoquinoline 75 -- 3.9 90.8 3.2 2.154 Hexamethylene diiso- 35 5.1 88.9 5.0 -- 1.0 thiocyanate55 Hexamethylene diiso- 75 -- 6.4 89.0 3.5 1.1 thiocyanate56 Methylenebistetramethylene 75 -- 5.4 91.3 2.1 1.2 thiourea57 Bis(Ntrimethylenethio- 75 -- 4.1 90.8 3.1 2.0 acetamide)58 Ethylenebisdithiocarbamic 80 -- 1.7 96.0 1.2 1.1 acid diammonium salt59 O,O'dicyclohexyl S,S' 77 -- 4.3 92.4 2.3 1.0 methylenebisxanthate60 Cyclohexylxanthogene- 75 -- 3.8 92.9 2.1 1.2 monosulfide61 n-Hexadecyl dixanthogene 76 -- 2.7 93.4 2.8 1.162 Benzyl dixanthogene 75 -- 2.2 94.1 2.7 1.063 Ethyl dixanthogene 78 -- 1.5 95.6 1.8 1.1 disulfide64 N,N'dimorpholino 80 -- 2.6 90.9 4.1 2.4 dithiooxalic diamide65 Bis(piperidinothio- 75 -- 4.0 91.7 2.3 2.0 carbonyl) monosulfide66 Bis(morpholinothio- 75 -- 3.1 92.9 2.1 1.9 carbonyl) monosulfide67 Bis(piperidinothio- 75 -- 2.3 93.8 2.0 1.9 carbonyl) disulfide68 Bis(morpholinothio- 75 -- 2.1 94.1 2.0 1.8 carbonyl) disulfide69 Ethylene-1,2-bis[1,2- 78 -- 1.9 92.7 3.4 2.0 (dithiocarbamoyl)- ethylene] disulfide70 Bis(piperidinothio- 80 -- 1.2 94.8 1.9 2.1 carbonyl) hexasulfide71 Pentamethylene 75 -- 7.4 89.5 1.2 1.9 dithiocyanate72 3-Thiocyanopyridine 38 2.8 87.5 8.3 -- 1.473 3-Thiocyanopyridine 75 -- 5.7 90.2 1.3 2.874 N(n-Heptadecyl)-n-octyl 75 -- 3.4 93.5 2.4 0.7 sulfenamide75 Tert-Butylethyl 75 -- 5.0 90.2 2.3 2.5 thiosulfinate76 Thiostearic acid 80 -- 4.2 91.7 1.0 3.177 Dicyclohexyldithiol 75 -- 5.0 91.1 2.2 1.7 sebacate78 S,S'Dimethylenecarboxy 75 -- 11.3 86.4 1.1 1.2 O,O'diethylbisthiol carbonate79 Diisoamyldithiol 75 -- 7.2 89.5 1.7 1.6 carbonate80 N(.zeta.-Aminohexamethyl) 80 -- 4.3 91.8 1.1 2.8 thiocarbamic acid81 NStearylthiocarbamic 35 4.5 92.5 1.9 -- 1.1 acid stearylammonium salt82 NStearylthiocarbamic 75 -- 1.1 95.1 1.8 2.0 acid stearylammonium salt83 NPentamethylene Sphenyl 75 -- 1.8 94.5 1.9 1.8 thiol carbamate84 2-Thienylmercapto- 80 -- 4.7 90.3 2.6 2.4 acetic acid85 n-Octadecylmercapto- 75 -- 8.1 89.8 1.0 1.1 succinic acid diethyl ester86 Methylmercaptopelargonic 80 -- 2.6 92.7 1.9 2.8 acid amide87 S,S'Di(n-octadecyl)methyl 75 -- 10.9 85.4 1.6 2.1 thioacetal88 S,S'Dibenzylcyclohexyl 76 -- 8.5 88.4 1.9 1.2 ketone thioacetal89 Tri-n-dodecyl trithio- 75 -- 8.0 87.2 2.1 2.7 orthoformate90 Tetracyclohexyl tetra- 75 -- 6.5 89.0 2.4 2.1 thioorthocarbonate91 1,10-Decamethylenebis- 73 -- 5.2 91.2 1.0 2.6 chloroethyl sulfide92 Di(Npentamethyleneamino- 35 3.9 92.6 2.6 -- 0.9 ethyl) sulfide93 Di(Npentamethyleneamino- 75 -- 3.5 93.4 1.1 2.0 ethyl) sulfide94 p-Benzylmercapto- 75 -- 7.7 89.0 1.1 2.2 benzaldehyde95 n-Dodecylmercaptomethyl 75 -- 7.0 89.7 1.6 1.7 phenyl ketone96 n-Octadecylmercapto- 78 -- 9.7 86.3 2.2 1.8 propionitrile97 Dibenzoyl sulfide 75 -- 5.6 90.0 2.1 2.398 Bis{2-[2-(2-chloroethyl- 83 -- 3.8 93.4 1.7 1.1 thio)ethylthio]ethyl} sulfide99 Poly(ethylenesulfide) 75 -- 4.1 92.6 2.3 1.0 --Mn = 1,100100 Di(.kappa.-carboxydecyl)disulfide 76 -- 4.6 91.2 3.1 1.1101 Di(cyclohexyloxycarbonyl- 75 -- 4.9 91.7 2.1 1.3 ethyl)disulfide102 Di(Nmethylanilinocarbonyl- 35 4.1 90.3 4.5 -- 1.1 methyl)disulfide103 Di(Nmethylanilinocarbonyl- 75 -- 2.8 94.0 1.3 1.9 methyl)disulfide104 Di(2,4-dichlorophenyl) 75 -- 5.0 92.0 1.9 1.1 disulfide105 Di(N,Ndimethylamino- 80 -- 4.2 92.3 2.1 1.4 hexamethyl)disulfide106 Di(o-formylmethylthio- 78 -- 5.7 90.6 1.6 2.1 phenyl)disulfide107 Di(methylcarbonyl- 75 -- 6.5 90.3 2.0 1.2 isobutyl)disulfide108 .zeta.-Cyano-.zeta.'-hydroxy 78 -- 8.1 87.3 2.9 1.7 dihexamethyl disulfide109 Di-3-nicotinoyl disulfide 38 9.2 87.1 2.4 -- 1.3110 Di-3-nicotinoyl disulfide 78 -- 8.3 88.5 2.1 1.1111 Poly(ethylformal disulfide) 75 -- 4.5 92.1 1.3 2.1 --Mn = 2,400112 Poly(ethylene disulfide) 75 -- 3.1 93.8 1.1 2.0 --Mn = 500113 Di(.gamma.-hydroxypropyl) 76 -- 5.7 90.2 2.7 1.4 disulfide114 Di(2-ethoxy-1-naphthyl) 77 -- 4.5 90.7 2.2 2.6 disulfide115 Di(carboxymethyl) 78 -- 5.1 90.5 1.7 2.7 trisulfide116 Di(p-ethoxycarbonyl- 75 -- 5.4 91.5 1.8 1.3 phenyl)trisulfide117 Di(o-n-butylcarbamoyl- 78 -- 4.7 92.3 1.2 1.8 phenyl)tetrasulfide118 Di(.beta.-chloroethyl) 35 6.4 90.1 2.1 -- 1.4 pentasulfide119 Di(.beta.-chloroethyl) 75 -- 2.9 92.7 1.6 2.8 pentasulfide120 Di(ethylenediamino- 78 -- 5.5 90.3 1.9 2.3 ethyl)tetrasulfide121 Di(.beta.-formylethyl) 76 -- 6.6 89.8 1.7 1.9 trisulfide122 Di(acetylmethyl) 75 -- 7.7 88.1 2.2 2.0 trisulfide123 Di(.beta.-cyanoethyl) 75 -- 9.1 87.9 1.8 1.2 trisulfide124 Dibenzoyl tetrasulfide 36 6.5 88.2 3.4 -- 1.9125 Dibenzoyl tetrasulfide 75 -- 5.4 90.3 1.8 2.5126 Poly(ethyl ether tetra- 75 -- 2.6 93.4 1.1 2.9 sulfide) --Mn = 1,100127 Di(2-hydroxy-1-naphthyl) 80 -- 7.5 87.1 4.3 1.1 trisulfide128 Di(2-ethoxy-1-naphthyl) 75 -- 6.2 88.7 2.1 3.0 trisulfide129 .kappa.-Mercaptoundecylic acid 85 -- 4.8 91.2 1.7 2.3130 Mercaptosuccinic acid 84 -- 3.8 92.3 1.6 2.3 ethyl ester131 .epsilon.-Mercaptocaproic 90 -- 3.4 90.7 2.8 3.1 acid amide132 Pentachlorothiophenol 78 -- 3.9 90.8 2.8 2.5133 N,N'Di(.gamma.-mercaptoiso- 88 -- 2.7 93.4 1.1 2.8 butyl)piperazine134 .beta.-Formylethyl mercaptan 85 -- 4.1 90.9 2.6 2.4135 Di(p-mercaptophenyl) 90 -- 3.9 92.3 1.5 2.3 ketone136 .beta.-Cyanoethyl mercaptan 80 -- 3.2 89.8 3.4 3.6137 Bis(ethylenedimercapto- 90 -- 3.3 92.7 1.6 2.4 methyl) methane138 Di(.beta.-mercaptoethyl) 83 -- 3.5 91.4 2.4 2.7 disulfide139 Di(.beta.-mercaptoethyl) 85 -- 3.6 93.2 1.2 2.0 tetrasulfide140 1,6-Hexamethylene dithiol 85 -- 4.1 92.3 1.9 1.7__________________________________________________________________________ ##STR13## ##STR14## ##STR15## ##STR16## ##STR17##
EXAMPLE 54
The procedure of Example 1 is followed with use of 95 g (0.52 mole) of m-phenoxytoluene, 10 g of azobisisobutyronitrile, 1 g of triphenylphosphine and 1,300 g of carbon tetrachloride. The reaction time is 75 minutes. Analysis of the product by gas chromatography shows 4.9% of m-phenoxybenzyl chloride, 90.1% of m-phenoxybenzal chloride, 4.2% of m-phenoxyphenyl trichloromethane and 0.8% of nuclear-chlorinated compounds. For comparison, the same reaction is conducted, except that the above triphenylphosphine is not used. The result shows 41.0% of m-phenoxytoluene, 45.7% of m-phenoxbenzyl chloride, 12.1% of m-phenoxybenzal chloride and 1.2% of nuclear-chlorinated compounds.
EXAMPLES 55 TO 70
Chlorination reactions are carried out in a similar manner as in Example 54 with use of typical phenoxytoluene derivatives listed in Table 6. The results are also given in Table.
TABLE 6______________________________________Chlorination of phenoxytoluenes in the coexistenceof triphenylphosphine Reac. Starting material time (yield,No. (g) (min.) Products %)______________________________________55 m-phenoxytoluene 40 m-phenoxytoluene (4.4) (95) m-phenoxybenzyl chloride (90.3) m-phenoxybenzal chloride (4.8) nucleus-substituted (0.5)56 p-phenoxytoluene 80 p-phenoxybenzyl (95) chloride (4.2) p-phenoxybenzal chloride (91.5) p-phenoxyphenyl trichloromethane (3.4) nucleus-substituted (0.9)57 3-phenoxy-6-chloro- 90 3-phenoxy-6-chloro- toluene benzyl chloride (8.9) (114) 3-phenoxy-6-chloro- benzal chloride (87.6) 3-phenoxy-6-chloro- phenyl trichloro- methane (2.5) nucleus-substituted (1.0)58 m,m'-dimethyldi- 160 m,m'-di(chloro- phenyl ether methyl)diphenyl (103) ether (11.7) m,m'-di(dichloro- methyl)diphenyl ether (80.9) m,m'-di(trichloro- methyl)diphenyl ether (4.9) nucleus-substituted (2.5)59 m-(m-chloromethyl- 90 m-(m-chloromethyl- phenoxy)toluene phenoxy)toluene (12.6) (121) m-(m-dichloro- methylphenoxy) benzyl chloride (82.3) m-(m-trichloro- methylphenoxy) benzal chloride (3.1) nucleus-substituted (2.0)60 m-(p-benzoylphen- 40 m-(p-benzoylphen- oxy)toluene oxy)toluene (4.9) (150) m-(p-benzoylphen- oxy)benzyl chloride (90.6) m-(p-benzoylphen- oxy)benzal chloride (3.5) nucleus-substituted (1.0)61 m-(p-benzoylphen- 80 m-(p-benzoylphen- oxy)toluene oxy)benzyl chloride (2.8) (150) m-(p-benzoylphen- oxy)benzal chloride (92.7) m-(p-benzoylphen- oxy)phenyl tri- chloromethane (3.0) nucleus-substituted (1.5)62 m-(p-cyanophenoxy) 80 m-(p-cyanophenoxy)- toluene benzyl chloride (8.2) (109) m-(p-cyanophenoxy)- benzal chloride (85.6) m-(p-cyanophenoxy)- phenyl trichloro- methane (3.9) nucleus-substituted (2.3)63 m-(p-nitrophenoxy) 90 m-(p-nitrophenoxy)- toluene benzyl chloride (12.0) (119) m-(p-nitrophenoxy)- benzal chloride (80.5) m-(p-nitrophenoxy)- phenyl trichloro- methane (4.3) nucleus-substituted (3.2)64 m-(p-phenylphen- 40 m-(p-phenylphen- oxy)toluene oxy)toluene (3.2) (135) m-(p-phenylphen- oxy)benzyl chloride (93.5) m-(p-phenylphen- oxy)benzal chloride (2.1) nucleus-substituted (1.2)65 m-(p-phenylphen- 90 m-(p-phenylphen- oxy)toluene oxy)benzyl chloride (1.1) (135) m-(p-phenylphen- oxy)benzal chloride (93.0) m-(p-phenylphen- oxy)phenyl trichloro- methane (4.8) nucleus-substituted (1.1)66 m-(p-benzylphen- 90 m-(p-benzylphen- oxy)toluene oxy)benzyl chloride (4.9) (143) m-(p-benzylphen- oxy)benzal chloride (90.5) m-(p-benzylphen- oxy)phenyl trichloro- methane (3.8) nucleus-substituted (0.8)67 m-(p-benzyloxy- 90 m-(p-benzyloxy- phenoxy)toluene phenoxy)benzyl (151) chloride (5.5) m-(p-benzyloxy- phenoxy)benzal chloride (88.7) m-(p-benzyloxy- phenoxy)phenyl trichloromethane (4.3) nucleus-substituted (1.5)68 p-(m-tolyloxy) 80 p-(m-chloromethyl- phenyl benzoate phenoxy)phenyl (158) benzoate (2.7) p-(m-dichloro- methylphenoxy)- phenyl benzoate (90.9) p-(m-trichloro- methylphenoxy)- phenyl benzoate (4.5) nucleus-substituted (1.9)69 m-(p-methoxyphen- 40 m-(p-methoxyphen- oxy)toluene oxy)toluene (8.4) (111) m-(p-methoxyphen- oxy)benzyl chloride (87.1) m-(p-methoxyphen- oxy)benzal chloride (3.5) nucleus-substituted (1.0)70 m-(p-methoxycar- 40 m-(p-methoxycarbon- bonyl phenoxy)- yl phenoxy)toluene (6.9) toluene m-(p-methoxycarbon- (126) yl phenoxy)benzyl chloride (86.7) m-(p-methoxycarbon- yl phenoxy)benzal chloride (4.2) nucleus-substituted (2.2)______________________________________
EXAMPLE 71
Table 7 shows the results of reactions which are conducted in a similar manner as in Example 54 with use of m-phenoxytoluene and typical phosphorus- or oxygen-containing compounds.
TABLE 7__________________________________________________________________________Effect of phosphorus-containing and oxygen-containingcompounds on the chlorination of m-phenoxytoluenePhosphorus-containing Reac.or oxygen-containing time Products (Yield, %)No. compound (min.) (1) (2) (3) (4) (5)__________________________________________________________________________1 Tri-n-butylphosphine 40 9.3 89.1 1.1 -- 0.52 Tri-n-butylphosphine 75 -- 8.6 90.0 1.0 0.43 Tri-n-octylphosphine 80 -- 8.2 89.2 1.6 1.04 Tri-n-dodecylphosphine 80 -- 5.3 91.8 2.9 --5 n-Octadecyldiphenyl- 80 -- 5.5 92.4 1.2 0.9 phosphine6 Mercaptoethyldiphenyl 85 -- 4.7 89.8 3.3 2.2 phosphine7 Tricyclohexylphosphine 80 -- 5.9 90.7 2.4 1.08 Dicyclohexyl 4-chloro- 75 -- 7.5 91.0 1.5 -- phenylphosphine9 Triisopropylphosphine 80 -- 5.8 89.3 4.2 0.7 sulfide10 n-Hexadecyldiphenyl- 40 10.1 88.6 1.3 -- -- phosphine sulfide11 n-Hexadecyldiphenyl- 80 -- 4.5 90.8 3.2 1.5 phosphine sulfide12 Triphenylphosphine oxide 80 -- 7.8 87.5 3.5 1.213 Tri-n-dodecylphosphine 80 -- 4.8 92.6 2.6 -- oxide14 N,NDiethylhydrazino- 80 -- 7.7 90.3 1.5 0.5 diphenylphosphine oxide15 1-Phenyl-1-phosphacyclo- 80 -- 5.2 91.1 3.1 0.6 hexane16 n-Octadecyl diphenyl 80 -- 3.9 89.8 4.8 1.5 phosphite17 Dicyclohexyl chloro 80 -- 2.9 91.9 4.0 1.2 phosphite18 Di-n-octyl phosphite 40 11.3 78.5 10.2 -- --19 Di-n-octyl phosphite 80 -- 10.3 85.2 3.5 1.020 Diphenyl cyclohexyl 80 -- 8.8 89.1 2.1 -- phosphite21 Triphenyl phosphite 45 7.7 80.6 10.7 -- 1.022 Triphenyl phosphite 80 -- 5.0 91.7 3.3 --23 Tricyclohexyl phosphite 75 -- 8.1 85.3 4.5 2.124 Diisopropyl chloro 80 -- 12.5 83.9 2.1 1.5 thiophosphite25 Tricyclohexyl thiophosphite 80 -- 7.0 87.6 4.1 1.326 Tri-n-dodecyl thiophosphite 80 -- 6.4 90.9 2.7 --27 Triphenyl thiophosphite 45 15.3 80.5 4.2 -- --28 Triphenyl thiophosphite 80 -- 4.8 90.5 4.7 --29 Tris(dimethylamino)- 80 -- 7.4 87.6 1.9 3.1 phosphine30 Phosphorus tripiperidide 80 -- 8.1 89.9 2.0 --31 Tris(di-n-butylamino)- 80 -- 14.3 80.1 3.4 2.2 phosphine32 Phosphorus tri(Nmethyl- 80 -- 14.2 81.3 2.1 2.4 anilide)33 Diphenylphosphinic chloride 75 -- 12.3 82.2 4.1 1.434 Cyclohexylphenylphosphino- 80 -- 12.9 80.5 5.0 1.6 thioic chloride35 Di-n-butylphosphino- 80 -- 10.5 84.1 4.2 1.2 thioic acid36 Isopropyl n-hexyl 80 -- 7.7 85.3 4.8 2.2 phosphinic acid37 Dicyclohexylphosphino- 80 -- 13.4 78.8 4.8 3.0 dithioic acid38 Methyl n-octyl n-hexyl 40 15.7 78.5 5.8 -- -- phosphinate39 Methyl n-octyl n-hexyl 80 -- 11.4 84.5 3.1 1.0 phosphinate40 OMethyl diisopropyl- 80 -- 13.3 80.9 5.0 0.8 phosphinothioate41 Phenyl diethylphosphino- 80 -- 12.3 82.3 4.3 1.1 dithioate42 Methyl dicyclohexyl 75 -- 14.5 80.3 4.5 0.7 phosphinate43 Hexamethylene phosphoric 80 -- 16.3 77.5 4.1 2.1 triamide44 Phenyl phosphonus 75 -- 16.0 78.6 4.0 1.4 dichloride45 Cyclohexylphosphonic 75 -- 13.7 81.3 3.7 1.3 dichloride46 S,SDiethyl phenyl- 45 12.2 80.2 7.6 -- -- phosphonodithioate47 S,SDiethyl phenyl- 85 -- 8.9 88.1 3.0 -- phosphonodithioate48 Diethyl-n-butylphosphonate 80 -- 12.7 80.9 4.2 2.249 O,ODiethyl phenyl- 40 12.7 81.7 5.6 -- -- phosphonothioate50 O,ODiethyl phenyl- 80 -- 5.4 89.0 3.5 2.1 phosphonothioate51 O,SDiethyl phenyl- 80 -- 6.5 90.2 2.3 1.0 phosphonothioate52 SEthyl N,Ndiethyl 80 -- 6.4 87.6 4.5 1.5 Pmethyl phosphonoamide thioate53 OEthyl phenyl phosphono- 50 10.7 82.8 6.5 -- -- dithioate54 OEthyl phenyl phosphono- 90 -- 4.5 92.3 3.2 -- dithioate55 OEthyl Sphenyl phenyl- 80 -- 5.5 90.1 4.4 -- phosphonodithioate56 2,2'-Dichlorodiethyl ether 80 -- 19.5 77.0 3.5 --57 Di-n-butyl ether 85 -- 18.3 78.7 3.0 --58 Di-n-octyl ether 80 -- 15.5 80.3 3.1 1.159 Di-n-octadecyl ether 40 11.1 78.8 10.1 -- --60 Di-n-octadecyl ether 80 -- 6.6 87.2 4.7 1.561 Diphenyl ether 80 -- 12.8 80.5 4.7 2.062 Naphthyl ethyl ether 80 -- 8.3 85.3 3.6 2.863 Dicyclohexyl ether 80 -- 14.5 81.0 4.5 --64 4-Pyridyl ethyl ether 85 -- 11.7 83.4 3.0 1.965 p-Dioxane 80 -- 10.8 82.1 5.6 1.566 Furan 80 -- 7.2 89.8 2.0 1.067 Tetrahydrofuran 80 -- 5.3 90.2 4.5 --68 15-Crown-5 40 15.6 80.9 3.0 -- 0.569 15-Crown-5 80 -- 6.9 90.5 1.6 1.070 Dibenzo-18-Crown-6 40 16.2 80.0 2.6 -- 1.271 Dibenzo-18-Crown-6 80 -- 14.1 81.6 1.6 2.772 Isobutyl alcohol 80 -- 16.8 78.5 3.8 0.973 n-Octyl alcohol 80 -- 8.6 85.9 4.0 1.574 n-Tetradecyl alcohol 80 -- 10.9 83.6 3.4 2.175 n-Octadecyl alcohol 80 -- 14.5 80.8 3.5 1.276 m-Cresol 70 -- 16.8 75.8 3.2 4.277 2-(3-Tolyloxy)-3-methyl 70 -- 14.9 77.8 3.5 3.8 phenol78 2,6-Di-t-Butyl-4-methyl 70 -- 10.5 82.7 3.3 3.5 phenol79 2,2'-Methylenebis(4- 70 -- 9.1 83.3 3.6 4.0 methoxy-6-t-butyl phenol)80 4,4'-Thiobis(3-methyl-6- 75 -- 8.8 84.5 2.9 3.8 t-butyl phenol)81 4-Hydroxypyridine 40 10.7 82.5 5.8 -- 1.082 4-Hydroxypyridine 80 -- 7.4 85.9 3.1 3.683 Cyclohexyl alcohol 80 -- 12.6 83.1 3.1 1.284 Ethylene glycol 85 -- 12.3 83.1 3.7 0.985 Ethylene dithioglycol 85 -- 12.7 84.2 2.1 1.086 Ethylene glycol mono-n- 80 -- 16.1 79.3 3.6 1.0 butyl ether87 Diethylene glycol mono- 80 -- 12.7 80.9 4.9 1.5 n-dodecyl ether88 Propylene glycol 80 -- 13.0 83.1 2.8 1.1 diisopropionate89 Tripropylene glycol 80 -- 6.6 86.8 3.8 2.8 monostearate90 Ethylene glycol 80 -- 13.2 82.2 3.7 0.9 monophenyl ether91 .beta.-Cyclodextrin 45 11.8 85.7 2.5 -- --92 .beta.-Cyclodextrin 80 -- 5.2 89.2 4.1 1.593 1,5-Sorbitan monostearate 45 14.1 80.3 5.6 -- --94 1,5-Sorbitan monostearate 85 -- 12.1 83.5 3.5 0.995 Glycerin monopalmitate 85 -- 13.0 82.8 3.0 1.296 Bis(hydroxyethylthio- 40 12.0 80.7 6.3 -- 1.0 ethyl) ether97 Bis(hydroxyethylthio- 80 -- 10.6 85.9 2.8 0.7 ethyl) ether98 Bis(mercaptoethylthio- 85 -- 5.9 90.2 3.1 0.8 ethyl) ether99 Bis(chloroethoxyethyl) 80 -- 16.0 80.1 2.8 1.1 ether100 Bis(aminoethylthioethyl) 85 -- 9.7 85.5 3.8 1.0 ether101 Ethylene dithioglycol 85 -- 8.4 88.9 1.8 0.9 hexamer102 Polyethylene glycol 80 -- 9.4 86.5 2.6 1.5 --Mn = 1,000103 Polypropylene glycol 80 -- 10.1 85.0 3.7 1.2 --Mn = 3,000104 Polyoxyethylene 1,5-sorbi- 40 7.4 82.5 10.1 -- -- tan monostearate --Mn = 1,000105 Polyoxyethylene 1,5- 80 -- 10.8 84.6 2.5 2.1 sorbitan monostearate --Mn = 1,000106 Polyoxyethylene glycerin 80 -- 10.7 83.5 3.0 2.8 monopalmitate --Mn = 800107 Polyoxyethylene dodecyl 80 -- 14.3 80.8 3.1 1.8 ether --Mn = 800108 Polyoxyethylene p-dodecyl- 80 -- 14.7 81.7 2.3 1.3 phenyl ether --Mn = 700109 Polyoxyethylene lauryl- 80 -- 11.9 84.4 2.7 1.0 amine --Mn = 600110 Polyoxyethylene lauryl- 80 -- 15.8 80.3 3.0 0.9 amide --Mn = 600__________________________________________________________________________ ##STR18## ##STR19## ##STR20## ##STR21## ##STR22##

Number	Name	Date
2430822	Nevison	Nov 1947
2844635	Mayor	Jul 1958
3363013	Kyker	Jan 1968
4014940	Ume et al.	Mar 1977
4085147	Rosinger et al.	Apr 1978
4092369	Gelfand	May 1978
4108904	Brown et al.	Aug 1978
4146737	Sheldon et al.	Mar 1979

Number	Date	Country
2707232	Aug 1978	DEX
2010837	Jun 1979	GBX

Process for producing chlorinated phenoxytoluene derivatives

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