JPS6366817B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides highly selective chlorination of chlorinated phenoxytoluenes represented by phenoxybenzyl chlorides or phenoxybenzal chlorides by selectively chlorinating the methyl side chains of phenoxytoluenes. The present invention relates to a method for manufacturing the same. The chlorides obtained here are easily converted into phenoxybenzyl alcohols and phenoxybenzaldehydes, respectively, by hydrolysis, and among these, m-phenoxybenzyl alcohol and m-phenoxybenzaldehyde are
It is an important intermediate raw material for agricultural chemicals (insecticides). Although various methods for synthesizing phenoxybenzyl alcohols or phenoxybenzaldehydes have been reported, the best method that can be implemented industrially has not yet been established. Regarding the methyl side chain chlorination method of phenoxytoluenes, which is considered to be one type of industrially advantageous synthesis method, the following patents have already been filed in the past. 1 Japanese Patent Publication No. 51-45573, West German Patent No. 2402457; A method is disclosed in which m-phenoxytoluene is directly chlorinated using halogenated phosphorus in a high temperature range of 220° C. or higher. This method is industrially disadvantageous since it involves reaction operations at high temperatures and consumes a large amount of energy. Moreover, this method has been shown to produce large amounts of nuclear chlorides when the reaction temperature is lower than 220°C. 2 JP-A-53-40732, US Patent Application No. 726017; Chlorination of m-phenoxytoluene is carried out in carbon tetrachloride using sulfuryl chloride or chlorine and bromine as halogenating agents. However, it has been shown to use a radical initiator for reactions using sulfuryl chloride, and a powerful incandescent light source for reactions using chlorine and bromine.
It has been shown that this method suppresses nuclear chlorination and causes side chain chlorination. 3 JP-A-53-46929, British Patent Application No. 41526/1976; A method for side chain chlorination of m-phenoxytoluene in carbon tetrachloride in the presence of a radical initiator using sulfuryl chloride as a halogenating agent was demonstrated. ing. 4 JP-A-53-103433, West German patent application number P27072328; m-phenoxytoluenes in carbon tetrachloride,
A side chain chlorination method using UV light and chlorine or bromine as the halogenating agent has been demonstrated. 5 JP-A-53-112824, French Patent Application No. 77-06941;
- Side chain chlorination methods using chloracetamide, N-bromoacetamide, N-chlorsuccinimide, N-bromsuccinimide, chlorine or bromine are shown. However, sulfuryl chloride, N
- Reactions using chloracetamide, N-bromoacetamide, N-chlorsuccinimide, N-bromsuccinimide or bromine, as well as methods using light, have economical disadvantages and There are many problems that need to be solved, such as non-uniformity. On the other hand, the method using chlorine and a radical reaction initiator is easy to operate and economically advantageous;
Examples 1, 2, and 3 of 103433 and JP-A-53-112824
The yield of m-phenoxybenzyl chloride and m-phenoxybenzyl chloride shown in Example 4) is at most 60 to 70% even under optimal conditions.
The selectivity is not high, at only a few percent, and this value is still not industrially satisfactory. In view of this situation, the present inventors have conducted extensive research and found that one type or mixture of sulfur-containing compounds that can form a charge transfer complex with chlorine, chlorine radicals, or organic halogen compounds in the presence of a radical reaction initiator. We discovered that when phenoxytoluenes were chlorinated with chlorine in the presence of chlorine, the methyl side chains were chlorinated with high selectivity. What is noteworthy is that by selecting the reaction conditions in the present invention, phenoxybenzyl chlorides or phenoxybenzyl chlorides can be converted into a known carbon tetrachloride-chlorine-free radical initiator system (including light). It has been found that the compound can be synthesized in a significantly higher yield and with higher selectivity. This is a completely new method that cannot be found in conventionally known techniques, and is an economical invention that can be easily implemented industrially. It is generally known that in the chlorination of aromatic compounds, nuclear substitution by electrophilic reactions and side chain substitution by radical reactions proceed competitively. This also occurs in the chlorination of phenoxytoluenes; for example, it has been shown in Japanese Patent Publication No. 45573/1987 that a large amount of nuclear substitution occurs at the same time as side chain substitution. On the other hand, although it has been shown that ring substitution can be suppressed by using a radical initiator or light in carbon tetrachloride, as mentioned above, m-phenoxybenzyl chloride or m-phenoxybenzyl chloride The yield of sibenzal chloride was not completely satisfactory. Further, as the chlorination of the methyl side chain progresses, phenoxyphenyltrichloromethanes are generated from phenoxybenzal chlorides. Therefore, in order to produce phenoxybenzal chlorides in high yield and with high selectivity, it is necessary to suppress not only nuclear chlorination but also the formation of trichlorides. It has not been reported in any known literature. Therefore, the present inventors investigated various conditions under which the methyl side chain chlorination of phenoxytoluenes proceeds with high selectivity, and the nuclear chlorination and the formation of phenoxyphenyl trichloromethanes are suppressed. , arrived at the present invention. That is, the features of the present invention are:
By coexisting in the reaction system a sulfur-containing compound that can form a charge transfer complex with chlorine, chlorine radicals, or organic halogen compounds, the chlorination of the methyl side chain of phenoxytoluenes by chlorine can proceed more selectively. At the same time, this method also suppresses the production of phenoxyphenyltrichloromethanes. As a result of quantifying the products obtained from this reaction system using gas chromatography and NMR, the present inventors found that phenoxybenzyl chlorides or phenoxybenzyl chlorides can be obtained almost quantitatively. Furthermore, at this time, we succeeded in reducing the amount of by-products of phenoxyphenyl trichloromethanes to 5% or less. The amount of carbon tetrachloride used in the present invention is equivalent to 20% by weight based on the weight of phenoxytoluenes.
The amount ranges from 5 to 10 times, preferably from 5 to 10 times. The sulfur-containing compound used in the present invention is a compound represented by the general formula () [X-(S-) _i -] _j -(Y-Z-) _k X () [wherein X is the same or different R ³ ,
CN, ^NR4R5 , C(O) ^R4 , S(O) ^R4 , ^C (O)
OR ⁴ , C(O)NR ⁴ R ⁵ , C(O)SR ⁴ , R ⁶ C(O)
OR ⁴ , R ⁶ C(O)NR ⁴ R ⁵ , R ⁶ SR ⁴ , R ⁶ NR ⁴ R ⁵ ,
R ⁶ C(O)R ⁴ and HNR ⁴ R ⁴ R ⁵ (R ³ , R ⁴ and R ⁵ are
Represents hydrogen or an alkyl group, an aryl group, an alicyclic ring, and a heterocyclic ring, each with or without a substituent; when k is 0, R ³ is an alkyl group, an aryl group, and an alicyclic ring, each having a substituent. . ), and R ⁶ is an alkylene group or aryl group having 1 to 12 carbon atoms with or without a substituent, and Y is R ⁶ , R ⁶ C(O)
R ⁶ , C(O) R ⁶ C(O) and C(O), Z is atomic sulfur and NR ⁴ , and i
represents 1 to 8, j represents 1 to 50, k represents 0 to 50, and when i is 2 or more, X represents R ⁶ OR ⁴ and
R ⁶ OR ⁶ OR ⁶ ] For example, thiocyanates, sulfenamides, thiosulfinates, thiol acids, thiol esters, thiol carbonates, dithiol carbonates, thiocarbamic acids, thiocarbamates, thiol carbamates Esters, sulfide acids, sulfide esters, sulfide amides, mercaptals,
Mercaptols, trithioorthoesters,
Tetrathioorthoesters, halogenosulfides, aminosulfides, aldehyde sulfides, ketosulfides, cyanosulfides,
Acyl sulfides, sulfide multimers, disulfide acids, disulfide esters, disulfide amides, halogen disulfides, amino disulfides, aldehyde disulfides, keto disulfides, cyanodisulfides, acyl disulfides polysulfides, disulfide polymers, hydroxy disulfides, alkoxy disulfides, polysulfide acids, polysulfide acid esters, polysulfide amides, halogenopolysulfides, aminopolysulfides, aldehyde polysulfides, Keto polysulfides, cyanopolysulfides, acyl polysulfides, polysulfide polymers, hydroxy polysulfides, alkoxy polysulfides, mercapto acids, mercapto acid esters,
Representative examples include mercapto acid amides, halogenomercaptans, aminomercaptans, aldehyde mercaptans, ketomercaptans, cyanomercaptans, sulfide mercaptans, disulfide mercaptans, polysulfide mercaptans, and dimercaptans. one type or mixture of sulfur-containing compounds such as n-octadecylthiocyanate, pentamethylene dithiocyanate, 2-chlorocyclohexylthiocyanate, p-aminophenylthiocyanate, 3-thiocyanopyridine, N-diethylene Oxy-2-
Benzothiazolylsulfenamide, N-(n-
heptadecyl)-n-octylsulfenamide,
N-tert-butyl-2-benzothiazolylsulfenamide, N-cyclohexyl-2-benzothiazolylsulfenamide, di-n-amylthiosulfinate, tert-butylethanethiosulfinate, thiostearic acid , thioterephthalic acid, cyclohexylthiol acetate, N,N-diethylaminoethylthiol phenylacetate, dicyclohexyldithiol sebacate,
1,6-Hexamethylenedithiol diacetate, S-phenacyl O-ethylthiol carbonate, S,S'-dimethylenecarboxy O,O'-diethylbisthiol carbonate, diisoamyldithiol carbonate, diphenyldithiol carbonate, N- (ζ-aminohexamethyl)
Thiocarbamic acid, N-phenylthiocarbamic acid, N-stearylthiocarbamic acid stearyl ammonium salt, N-isobutylthiocarbamic acid isobutylammonium salt, N-pentamethylene S-phenylthiol carbamate, N-cyclohexyl S-penta Methylenethiol 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-octylmercaptobenzoic acid amide, S,S'-di(n-
octadecyl) methylthioacetal, S,S'-
Diethyl ethyl mercaptoethyl thioacetal, S,S'-dibenzylcyclohexylketone thioacetal, ethylene bis(S,S'-di-n-
Octadecyl methyl ketone thioacetal, tri-n-dodecyl trithio orthoformate, triphenyl trithio orthobenzoate, tetraisopropyl tetrathio orthocarbonate, tetracyclohexyl tetrathio orthocarbonate, di(β-chloroethyl) sulfide, 1,10
-decamethylene bischloroethyl sulfide, γ
-chloro-γ'-(N,N-diethiamino)dipropylsulfide, N-(n-octadecyl)iminomethylethylsulfide, di(N-pentamethyleneaminoethyl)sulfide, n-butylmercaptoacetaldehyde, p -Benzylmercaptobenzaldehyde, n-dodecylmercaptomethyl phenyl ketone, bis(n-heptylcarbonylmethyl) sulfide, n-octadecylmercaptopropionitrile, di(chloroacetyl)
Sulfide, dibenzoyl sulfide, ethylene bis(β-cyanoethyl sulfide), 1,18-
Octadecamethylene bis(n-octadecyl sulfide), bis(ethylene dimercaptochloroethylethyl) sulfide, poly(ethylene sulfide), poly(phenylene sulfide), α, α′-
Di-n-hexadecyl di(carboxymethyl) disulfide, di(κ-carboxydecyl) disulfide, di(cyclohexyloxycarbonylethyl) disulfide, di(n-octadecyloxycarbonylethyl) disulfide, di(N-methylanilinocarbonylmethyl) disulfide,
di(γ-carbamoylpropyl) disulfide,
Di(ζ-chlorohexyl) disulfide, (2,
4-dichlorophenyl) disulfide, di(N,
N-dimethylaminohexamethyl) disulfide, di(m-aminophenyl) disulfide, di(α-formylisopropyl) disulfide, di(o-formylmethylthiophenyl) disulfide, di(methylcarbonylisobutyl) disulfide, di(2-methyl carbonyl-5-methoxyphenyl) disulfide, di(p-cyanophenyl) disulfide, ζ-cyano-ζ'-hydroxydihexamethyl disulfide, dibenzoyl disulfide, di-3-nicotinoyl disulfide,
Poly(ethyl formal disulfide), poly(ethylene disulfide), di(γ-hydroxypropyl) disulfide, di(m-hydroxyphenyl) disulfide, di(β-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-(on
-butylcarbamoylphenyl)tetrasulfide, di(β-chloroethyl)tetrasulfide,
Di(β-chloroethyl)pentasulfide, di(p-aminophenyl)trisulfide, di(ethylenediaminoethyl)tetrasulfide, di(β-formylethyl)trisulfide, di(m
-Formylphenyl) trisulfide, di(acetylmethyl) trisulfide, di(3-acetyl-4-hydroxy-1-naphthyl) trisulfide, di(β-cyanoethyl) trisulfide, di(p-cyanophenyl) trisulfide, dibenzoyltetrasulfide , diacetyl tetrasulfide, poly(ethylene pentasulfide), poly(ethyl ether tetrasulfide), di(β
-hydroxyethyl) trisulfide, di(2-
hydroxy-1-naphthyl) trisulfide, di(n-dodecyloxyethyl) trisulfide,
Di(2-ethoxy-1-naphthyl) trisulfide, α-mercaptostearic acid, κ-mercaptoundecyl acid, mercaptoacetic acid n-octadecyl ester, mercaptosuccinic acid ethyl ester, p-mercaptobenzoic acid methyl ester, α
-Mercaptopropionic acid anilide, ε-mercaptocaproic acid amide, 2,3-dichloropropyl mercaptan, pentachlorobenzenethiol, β-mercaptoethyl, n-dodecylamine, N,N'-di(γ-mercaptoisobutyl)
piperazine, β-formylethyl mercaptan,
α-phenyl-β-formylethyl mercaptan, di(p-mercaptophenyl) ketone, mercaptomethyl n-hexyl ketone, β-cyanoethyl mercaptan, p-cyanobenzenethiol, bis(ethylene dimercaptomethyl)methane, 2-n -heptylmercaptocyclohexanethiol, di(β-mercaptoethyl) disulfide, p-hydroxy-p′-mercaptodiphenyl disulfide, di(2-mercapto-1-naphthyl) trisulfide, di(β-mercaptoethyl) tetrasulfide, 1,6-hexamethylene dithiol, 1,18-octadecamethylene dithiol, 1,2-cyclohexane dithiol, 3,
It is one kind or a mixture of sulfur-containing compounds represented by 4-thiophenedithiol and the like. These sulfur-containing compounds are
0.001-50% by weight, preferably 0.01-30% by weight are used. If the amount added is 50% by weight or more, the desired reaction may hardly proceed, or
If it is less than 0.001% by weight, almost no effect will be seen. The radical reaction initiator used is an azo compound or peroxide, preferably azobisisobutyronitrile or benzoyl peroxide, and the amount used is 0.001 to 20% by weight based on the phenoxytoluenes. , preferably 0.01-15% by weight
It is. In addition, the amount of chlorine used in the reaction is 0.5 to 10 mol%, preferably 2 to 10 mol% of the phenoxytoluene per minute.
It is blown into the reaction system in a range of 5 mol % until the reaction is fully completed. On the other hand, the reaction temperature is 0 to 150℃
, preferably at a temperature at which the reaction system gently refluxes. The present invention will be explained in more detail with reference to Examples below. Example 1 m as phenoxytoluenes in a flask equipped with a thermometer, a stirrer, a gas inlet tube, and a reflux condenser tube.
- 95 g (0.52 mol) of phenoxytoluene, azobisisobutyronitrile as radical initiator
10 g, 1 g of N-diethyleneoxy-2-benzothiazolylsulfenamide as a sulfur-containing compound,
Add 1300 g of carbon tetrachloride as an organic halogen compound, raise the internal temperature of the flask to a range of 78 to 82°C,
Gently reflux the system. This was reacted for 75 minutes while blowing 0.023 mol of chlorine per minute into the flask from the gas inlet tube. After the reaction was completed, the flask was cooled, and carbon tetrachloride was distilled off under reduced pressure to obtain a pale yellow product. As a result of gas chromatographic analysis of this product, the yield was 2.1% m-phenoxybenzyl chloride, 95.6% phenoxybenzyl chloride, 1.8% m-phenoxyphenyl trichloromethane, and 0.5% nuclear substitute. It was hot. As a comparative example, when N-diethyleneoxy-2-benzothiazolylsulfenamide is not added, the yield of the reaction product obtained under the same conditions is 41.0% m-phenoxytoluene, m-phenoxybenzyl chloride
45.7%, m-phenoxybenzal chloride 12.1
%, nuclear substitutes 1.2%. Examples 2 to 15 Table 1 shows the yields of reaction products obtained when typical phenoxytoluenes were used in place of m-phenoxytoluene in the same manner as in Example 1. Examples 16-85 Collection of reaction products obtained when m-phenoxytoluene is used as the phenoxytoluene and a typical sulfur-containing compound is added to the reaction system in the same manner as in Example 1. The rates are shown in Table 2.

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Claims (1)

[Claims] 1. Compound represented by general formula () [In the formula, R ¹ and R ² may be the same or different and each represents hydrogen, halogen, alkyl group, halogenoalkyl group, acyl group, cyano group, nitro group, aryl group, aralkyl group, alkoxyl group, alkoxy Representing a carbonyl group] The side chain methyl group of (a) General formula () [X-(S-) _i -] _j -(Y-Z-) _k -X(
) [In the formula, X may be the same or different and R ³ ,
CN, ^NR4R5 , C(O) ^R4 , S(O) ^R4 , ^C (O)
OR ⁴ , C(O)NR ⁴ R ⁵ , C(O)SR ⁴ , R ⁶ C(O)
OR ⁴ , R ⁶ C(O)NR ⁴ R ⁵ , R ⁶ SR ⁴ , R ⁶ NR ⁴ R ⁵ ,
R ⁶ C(O)R ⁴ and HNR ⁴ R ⁴ R ⁵ (R ³ , R ⁴ and R ⁵
represents hydrogen or an alkyl group, an aryl group, an alicyclic ring, and a heterocyclic ring, each with or without a substituent; when k is 0, R ³ represents an alkyl group, an aryl group, and an alicyclic ring, each having a substituent. It is. ), and R ⁶ is an alkylene group or an aryl group having 1 to 12 carbon atoms with or without a substituent, and further Y
represents R ⁶ , R ⁶ C(O)R ⁶ , C(O)R ⁶ C(O) and C(O), Z is atomic sulfur and NR ⁴ , and i is 1 ~8,j is 1~
50, k represents 0 to 50, and when i is 2 or more, X includes R ⁶ OR ⁴ and R ⁶ OR ⁶ OR ⁶ ], and General formula () or () characterized by selective chlorination with chlorine in the presence of (b) carbon tetrachloride and (c) a radical reaction ^initiator . R ² has the same content as above.] A method for highly selectively producing chlorinated phenoxytoluenes. 2 The compound () is o-phenoxytoluene, m-phenoxytoluene, p-phenoxytoluene, 3-phenoxy-6-chlorotoluene,
m, m'-dimethyl diphenyl ether, m-(m
-chloromethylphenoxy)toluene, m-(p
-benzoylphenoxy)toluene, m-(p-
cyanophenoxy)toluene, m-(p-nitrophenoxy)toluene, m-(p-phenylphenoxy)toluene, m-(p-benzylphenoxy)toluene, m-(p-benzyloxyphenoxy)toluene or p-(m-tolyloxy)phenylbenzoate, the method according to claim 1. 3 The sulfur-containing compounds are thiocyanates, sulfenamides, thiosulfinates, thiol acids, thiol esters, thiol carbonates, dithiol carbonates, thiocarbamic acids, thiocarbamates, thiol carbamate esters, sulfide acids, Sulfuric acid esters, sulfuric acid amides, mercaptals, mercaptols, trithioorthoesters, tetrathioorthoesters, halogenosulfides, aminosulfides, aldehyde sulfides, ketosulfides, cyanosulfides, acylsulfides sulfide polymers, disulfide acids, disulfide esters, disulfide amides, halogen disulfides, amino disulfides, aldehyde disulfides, keto disulfides, cyano disulfides, acyl disulfides disulfide polymers, hydroxy disulfides, alkoxy disulfides, polysulfide acids, polysulfide acid esters, polysulfide amides, halogenopolysulfides, aminopolysulfides, aldehyde polysulfides, keto Polysulfides, cyanopolysulfides, acyl polysulfides, polysulfide polymers, hydroxy polysulfides, alkoxy polysulfides, mercapto acids, mercapto esters, mercapto amides, halogenomercaptans, Claims 1 or 2 are aminomercaptans, aldehyde mercaptans, ketomercaptans, cyanomercaptans, sulfide mercaptans, disulfide mercaptans, polysulfide mercaptans, or dimercaptans. The method described in. 4. The method according to any one of claims 1 to 3, wherein the radical reaction initiator is selected from an azo compound and a peroxide. 5. The method according to any one of claims 1 to 4, wherein the radical reaction initiator is azobisisobutyronitrile or benzoyl peroxide. 6. The method according to any one of claims 1 to 5, wherein the reaction is carried out at a temperature in the range of 0 to 150°C.