DE2252250A1 - PROCESS FOR THE PRODUCTION OF CATECHINE DERIVATIVES - Google Patents

Description

- & oda - AG 2? ζ? 2 5 0

Our reference: 0 “Z. 29 485 Sws / Wil

67ΟΟ Ludwigshafen, October 24, 1972 Process for the production of "catechol derivatives

The present invention relates to a valuable new method for the production of catechol derivatives.

It is known that pyrocatechol derivatives, in particular pyrocatechin ether, can be prepared by the following processes: Partial etherification of pyrocatechol (J. Chem. Soc. 1927, 1664; US Pat . No. 3,202,573),

Diazotization of o-aminophenyl-alkyl ethers (DAS 1 573 54j5) or dehydrogenation of the 1,2-cyclohexanedione Monoenoläthern by means of sulfur at reaction temperatures of 200 to 300 ⁰ C (DOS 1917602).

The process starting from pyrocatechol has the disadvantage of loss of pyrocatechol and alkylating agent through formation from bisether. The other two processes are partly technically complex, often multi-stage syntheses with the problems the air and wastewater pollution. In particular, the known fail Process if, due to reactive radicals R under the reaction conditions, follow-up reactions (ring closure or rearrangement reactions) occur.

It has been found that you can easily and with excellent Yields the valuable catechol ethers of the formula

0-R

In which R denotes an alkyl, alkenyl or alkynyl radical, which can be substituted by halogen, or denotes the aralkyl radical , if a pyrocatechol derivative of the formula is obtained

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in which R has the meanings given above and R is hydrogen

, 2

or lower alkyl (C 1 to C ^), B? ~ unsubstituted or halogen (Cl, Br, j), methoxy or ethoxy substituted lower alkyl (C ₁ to C ^) or benzyl, R ⁵ alkyl (C ₁ to C ^), Cycloalkyl (C ^, to C ₇ ), ß-chloroethyl, alkoxyalkyl (methoxyethyl, ethoxyethyl), alkenyl (to C>.), Alkynyl (to C,.), Acyl (acetyl) and

12th
furthermore R and R together with the carbon atom, whose substituents they are, and furthermore R and R ^ together with the carbon or oxygen atom, whose substituents they are, a five- or six-membered ring (cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl) , cleaves in acidic medium, e.g. B. by the action of aqueous acid or by exchange reaction with lower alcohols (C ₁ to C ₁ -) or phenols with acid catalysis.

The split is z. B. illustrated by the following equation:

H * / H ₀ O

- R ^ OH

- R R

CO

For example, the starting compounds are stirred in very dilute, e.g. B. 0.001 # (wt. #) Aqueous mineral acid, ζ. Β. H ₂ SO ^ _2, HCl, HNO ,, Η, ΡΟ ^, to the end of the cleavage, the reaction advantageously between 40 and 100 ⁰ C is performed. If appropriate, water-miscible organic solvents which increase the solubility of the starting compounds (for example alcohols, ketones, ethers) can also be added to the mixture in amounts of 0.1 to 90% (% by weight ).

The catechol monoethers of the formula thus produced

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OH OR

can be found in the following table:

R '· Kp; Pp .; n ^ -

Bp ₂₅ : 105 ⁰ C _{Bp 0n} : 100 ⁰ C

CH ^ H ₇ CUH, - H ₇ 2 5 -CH = CH ₂ η-O, i-C ^ -CH ₂

: 110 to 114 ° C

Kp _{0 2:} 66 ⁰ C

: 110 ⁰ C

C ¹ DD

S. ^k p _0.4 ^; 68 to 74 ° c

CH ₂ -CH = CCl-CH, n ^ ⁵ : 1.4875

CH ₂ -C = CC ^ ₁ ηψι 1.5295 Cl

CH ₂ -C = CCl ₂ n ^ ⁵ : 1.5027

-CH ₂ -C = CH Pp 49 to 5O ⁰ C

H Pp: 44 to 47 ° C

₂ H ₅ nj * ⁵ : 1.5360

-CHC ^v Pp: 52 to 53 ° C

The following examples illustrate the new process. example 1

o- (1-Butyn-3-yl-oxy) -pheno1

220 parts by weight of o- (l-methoxy-ethoxy) -phenyl- (1 · butyne-3 ^f -yleather are slowly converted into a refluxing and well

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stirred mixture of 2000 parts by weight of HgO, 500 parts by weight of ethanol and 2 parts by weight of H2SO2, cone, added dropwise. The mixture is then refluxed for a further 2 hours. It is allowed to cool and extracted J times with 150 parts by weight of chloroform each time. After drying over Na ₂ SO ^ the solvent is evaporated off. After standing for a short time, the remaining oil crystallizes. Yield 126 parts by weight. Mp 52 to 53 ° C. The substance proves to be uniform by thin-layer chromatography.

Example 2

ο-isopropoxyphenol

According to Example 1, 209 parts by weight of o- (l-methoxyethoxy) phenyl-i-propyl ether are hydrolyzed. Yield 149 parts by weight.
Kp _{0 2:} 66 ° C.

Example'5 Catechol mono- (1-butene - ^ - yl) ether

According to Example 1, 222 parts by weight of o- (1-methoxyethoxy) pheny1- (1'-buten-3 ^! -Yl) ether are hydrolyzed. Yield 152 parts by weight.
Kp _{0 4:} 68 to 74 ⁰ C.

. Example 4

Brenzkat echin-mono- (I-propin-3-yl) -ether

In accordance with Example 1, 206 parts by weight of o- (l-methoxy ethoxy) phenyl (l-propyn-3-yl) ether are hydrolyzed. Yield 140 parts by weight.
Fp: 49 to 50 ⁰ C.

Example 5 Pyrocatechol mono- (2-butyn-4-yl) ether

According to Example 1, 110 parts by weight of o- (l-methoxyethoxy) phenyl (2'-butyn-4'-yl) ether are used hydrolyzed. yield

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77 parts by weight.
Pp: 44 to 47 ° C. .

They are important intermediate products in the production of Plant protection active ingredients and pharmaceutical or veterinary Products,

The well-known production of the well-known crop protection agents takes place, for example, by reacting pyrocatechol ether with methyl isocyanate. For example, you get through implementation of o-isopropoxyphenol with methyl isocyanate the N-methylcarbamic acid-o-isopropoxyphenyl ester, which is a well-known insecticidal agent.

The catechol bisethers required as starting materials are obtained when pyrocatechol is substituted with a vinyl ether of the formula R OPr in which R is optionally substituted by lower alkyl. Vinyl group and Έ> Ρ denotes lower alkyl, cycloalkyl, ß-chloroethyl, alkoxyalkyl, lower alkenyl, lower alkynyl, acyl, or with a # -halogenoether of the formula

HaI-C-OR ⁵

in which Hal is Cl, Br or J and R ^ is hydrogen or

ρ
lower alkyl, R unsubstituted or substituted by halogen, methoxy or ethoxy lower alkyl, benzyl and Br lower alkyl, cycloalkyl, ß-chloroethyl ; Alkoxyalkyl, lower alkenyl, lower alkynyl, acyl mean, reacted in the presence of bases, any bisethers of the formula formed

■ R ¹ ι.

12 3
in. The R, R and R ^ have the meanings given above, reacts with pyrocatechol and the reaction product of the formula I.

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R.
0-C-OR

2
Around

1 2 5
in which R, R and R ^ have the meanings given above, with alkylating agents RX, such as alkyl sulfates, aryl sulfonic acid alkyl esters, or alkyl, alkenyl and alkynyl halides with branched or unbranched alkyl radicals which can be substituted by halogen (chlorine, bromine, iodine) , or with aralkyl halides (benzyl) in an alkaline medium according to the following equation:

RX

Base -HX "

1 2 ^
The radicals R, R, R ^ have the meanings given above, R denotes a branched or unbranched alkyl (C 1 to C 1) alkenyl or alkynyl radical, which can be substituted by halogen (chlorine, bromine, iodine) or an aralkyl radical (Benzyl). X denotes a halide (Cl, Br, I), an alkoxy, sulfonyl or arylsulfonyl radical.

The AlkyIierungsbedlngungen regarding temperature, pressure, solution agents and bases correspond to those of the known ether syntheses (cf. also Houben-Weyl, Methods of Organic Chemistry, volume 6/3, p. 83). To carry out the following implementation, for. B.

ONa

o-ch:

CH,

OCH.

3 H ₂ O

+ Cl-CH

o-ch:

o-ch:

'C = CH

-CH

-C = CH

" ^CH 3 • OCH,

- ^ NaCT
- 3 H ₂ O

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O =. ζ. 29

225225

the above Na salt is heated in the hydrate or in the dehydrated one Shape z. B. in acetonitrile or dimethylformamide with a slight excess of 1-butyn-3-yl chloride under reflux until the solution reacts neutrally. The etherification proceeds with good yield.

Other analogous catechol derivatives are, for example:

t ■ 0-C-OlP

OR *

Kp

CH

CH

CH,

CH

CH

-CH

PH ⁵

0.1: 82 to 85

0.1: 100 to IO3

0.1: 104 to 106

0.2: 60 to 66

0.2: 100

CH

CH,

H,

CH

CH

CH

CH

CH

CH

CH ₂ -CH = CH ₂

CH ₃ CH ₃ -CH ₂ -C = CH

CH ₂ -CH = CH-CH ₃

-CH

0.2: 100 to 111

0.3: 100 to 102 0.3: 85 to 91

0.2: IJO to 150

The following examples illustrate the preparation of the ethers.

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Example 6a

o- (l-Methoxy-ethoxy) -phenol-Na-Salt \ 3

200 parts by weight of 20% (% by weight) aqueous sodium hydroxide solution are added to 168 parts by weight of o- (1-methoxy-ethoxy) phenol in an Erlenmeyer flask under Np. It is shaken briefly and left to stand at room temperature for one hour. The crystalline paste is filtered off with suction and washed with a mixture of ether and 1-propanol (weight ratio 1: 1). The product is almost colorless. Yield 80 to 90 % of theory. M.p. 72 to 73 ° C. The water of crystallization can easily be removed ^{at 70 to 110 ° C. in a water jet pump vacuum.}
Analysis: C ₉ H ₁₇ NaOg (244)

Calc .: C 44.3 H 7.0 Na 9.4
Found: C 43.8 H 7.0 Na 9.0.

Example 6b

o- (1-methoxy-ethoxy) -phenyl- (1 '-but in-j? -yl) -ether 244 parts by weight of o- (1-methoxy-ethoxy) -phenol-Na-Salt · 3 or 190 g of dehydrated salt are suspended in 3OO parts by weight of dimethylformamide. The mixture is heated to the boil while stirring and 100 parts by weight of 1-butyn-3-yl chloride are then added dropwise. After about an hour, the stoichiometric amount of NaCl has separated out. The mixture is allowed to cool, the NaCl is filtered off with suction, concentrated, taken up in 1000 parts of benzene and washed thoroughly with 2 × 500 ml of 2 × aqueous NaOH. After drying over Na ₃ SO ^, the solvent is evaporated off and, after adding a spatula tip, succinic acid is distilled.

Yield 182 parts by weight. Kp _{0 2} : 100 to HO ⁰ C. Analysis: C ₁₅ H ₁₆ O, (220)

Calc .: C 70.9 H 7.3
Found: C 70.5 H 7.5.

Example 7

o- (l-methoxy-ethoxy) -phenyl-i-propyl-ether

According to Example 6, instead of 1-butyne

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3-yl chloride 150 parts by weight of i-propyl broraid. Bp. ₀₂ : 60 to 66 ⁰ C.

Example 8

o- (1-Methoxy-ethoxy) -phenyl- (l'-buten-3'-yl) -ether

In accordance with Example 6, 110 parts by weight of 1-buten-3-yl chloride are used instead of 1-butyn-3-yl chloride. Kp ₀ ,: 80 to 91 ⁰ C. "·
Analysis: C ₁₅ H ₁₈ O ₅ (222)

Calc .: C 70.3 H 8.1
Found: C 70.4 'H 8, J.

Example 9

ο - (1-A'thoxy-ethoxy) -phenyl- (I'-butyn-3'-yl) -ether

440 parts by weight of pyrocatechol are dissolved in 1500 parts of tetrahydrofuran. After adding 1 ml of HCl cone, 3O3 parts by weight of vinyl ethyl ether are added dropwise. Thereafter man.eine hour holds at 65 ⁰ C, allowed to cool and added 720 G.ewichtsteile J50 # cent (wt. ^) Technical NaOCH ^ / CH ^ OH-solution. 400 parts by weight of 1-butyn-3-yl chloride are then added and the mixture is refluxed until the reaction is neutral. Separated NaCl is filtered off and the piltrate is concentrated. The remaining oil is dissolved in 300 parts of benzene and washed five times with 1000 parts of 2N aqueous NaOH each time and then _{dried over Na 2} SO ^. After evaporation of the solvent, after adding 2 parts by weight of succinic acid, it is distilled. Kp _{2 0:} 100 to 111 ° C.
Analysis: C ₁₄ H ₁₈ O ₃ (234)

Calc .: C 71.8 H 7.7
Found: C 70.6 H 8.0.

Example 10

o- (l-methoxy-ethoxy) -phenyl-benzyl ether

According to Example 5, instead of l-butyn-3-yl

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chloride Ijj5 weight point benzyl chloride. The mixture is heated under reflux until neutralization.
Yield: 175 parts by weight, Kp _{Q g:} I30 to 15O ⁰ C.

The catechol is etherified, for example, by using catechol with preferably the amount necessary to etherify an OH group of the catechol or up to about 50 % excess or deficiency of vinyl ether of the formula

ROR ⁵

in which R is a vinyl group or a vinyl group substituted by lower alkyl (up to J5 carbon atoms) and Έ? Alkyl (C, to Cj,), cycloalkyl (C ₃ to C ₇ ), ß-chloroethyl, alkoxyalkyl (methoxyethyl, ethoxyethyl), alkenyl (to C ₁ ^), alkynyl (to C ^), acyl (acetyl) means, optionally with the addition of catalytically active substances, such as acidic substances such as mineral acids, acid salts, organic acids, α'-halogen ethers, organic and inorganic acid chlorides, and ion exchangers, including Lewis acids, e.g. B. AlCl ₃ , FeCl ₃ , BF _3, among others, in the temperature range from -5 to 120 ⁰ C, preferably at 40 to 50 ⁰ C and / or with the addition of solvents or diluents which are indifferent to the reactants (z. B. 5 to 80 Gew.jtf), such as ether (diethyl ether, tetrahydrofuran, dioxane), hydrocarbons (e.g., B. η-hexane, benzene, toluene, xylene), halogenated hydrocarbons (CH ₂ Cl _2, CHCl _3, CCl ^), is reacted.

Using the example of the implementation of catechol with vinyl methyl ether the reaction should be illustrated by the following equation:

S ^H 2 cat. + HC-O-CH, * -

The abovementioned compounds are preferably used as catalysts used.

Furthermore, the pyrocatechol ethers can be converted into-halogen ethers of the formula, preferably in equal molar amounts or with an excess or deficiency of up to about 50 %

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225225Qi

R ¹

Hal-C-0R ^: to

where Hal is Cl, Br, J and R is hydrogen or lower alkyl (C ₁ to C ^), R ^{2 is} unsubstituted or by halogen (Cl, Br, J), methoxy or ethoxy substituted lower alkyl (C ₁ to C-,) or benzyl, Έ? Alkyl (C ₁ to C ₂ ^), cycloalkyl (C, to C ₇ ), ß-chloroethyl, alkoxyalkyl (methoxyethyl, ethoxyethyl), alkenyl (to Ch), alkynyl (to Ci ₁ ), acyl (acetyl) and further

12th
R and R together with the carbon atom whose substituents they are, and also R and R- ^ together with the carbon atom or oxygen atom whose substituents they are, a five- or six-membered ring (cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl), with salts of pyrocatechol or with pyrocatechol in the presence of preferably equal molar organic or inorganic bases (e.g. alcoholates, alkali and alkaline earth hydroxides, suitable amines) or substances with an alkaline effect, such as alkali or alkaline earth carbonates.

The following equation should clarify the reaction:

+ Cl-C-OR ^ - »-

'2 - HCl

12 "3

The radicals R, R and Rr have the meanings given above. Is preferably carried out under dilution d ^ he reactants, for example, 5 to 80 wt.% Ether. (Diethyl ether, tetrahydrofuran) or hydrocarbons (n-hexane, benzene, toluene, xylene).

The vinyl ethers or-halogen ethers used for the reaction are known from the literature and can also be easily represented industrially (cf., for example, W. Reppe et al. Ann. 601 , 98 (1956)).

409818/1191 _{/ 12}

The above procedures arise depending on the one used Excess amounts of vinyl or -halogen ethers correspond to amounts of bisethers of the formula

,1

12 The remainders R, R and

II

have the meanings given above.

The abovementioned bisethers can preferably be obtained with quantitative yield by reacting pyrocatechol with at least the double molar amount of vinyl ethers.

The catalysts and reaction conditions with regard to temperature and solvents are analogous to those in the illustration of FIG Compounds of formula I.

Another method of making the compounds of
Formula I consists in converting the bisether of the formula II with pyrocatechol according to the following equation:
,1 ·

OH OH

Cat.

II

R ² ,

The radicals R ^x , R ¹ ″, Br, the catalysts and reaction conditions are the same as in the preparation of compounds of the formula I from the vinyl ethers.

The pyrocatechol derivatives of the formula I and II are obtained in the form of colorless oils which, after stabilization with organic or inorganic fec ^ «. ^ \ <* Y ^ ^ Wi ζ, are replaced by distillation.

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the can. The following tables provide an overview of the connections made:

Formula I:

Bp ⁰ C;

H
H H
H CH ₃ H
H CH ₃
CH ₃ CH ₃ H CH ₃ nC ₃ H ₇ H
H
H CH ₃
CH ₃
CH ₃ ! -C ₃ H ₇ H CH ₃ H COCH ₃ H
H .CH ₃
CH ₃ COC ₂ H ₅
-WXIq -OiI = LzXlQ H CH, -CH ₂ -ChCH

Kp ₀ ^: 89 to Kp ₀ 1:90 to Kp _{0 5} : 85 to 78 to 96 to 89 to: 94 to: 128 to

132 to

• I.5075 1.4905

Kp ₁ Kp ₁ Kp ₁

f:

CH

-CH

H,

H CH ₃ -CHg-CHg-OCH ₃ H CH ₃ -CHg-CHg-OCgH ₅ H CHgCl -CH ₃ H CH ₂ Cl -C ₂ H ₅ H CHgCl -CHg-CHgCl H CHgCl COCH,

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25. D '25.

D * 25th D ° 25. D °

1.5135 1.5146

1.4975 1.5012

/ 14

R ² _ 14 _ O. Z. 29,485 CH ₂ Br 2252250 R ¹ CH ₂ J R ^ Bp ° C; n ^ ⁵ H C ₂ H ₅ CH ₃ njp: 1.5340 H C ₂ H ₅ CH ₃ H C ₂ H ₅ CH ₃ Kp _{1 R} : 105 to 113 H CH ₂ -CH ₂ Cl C ₂ H ₅ Kp _{0 5} : 100 to IO3 H CH ₂ -CHCl-CH, CH ₂ -C = CH H CH ₂ -CHBr-CH, CH ₃ n ^ ³ : 1.5023 H CH ₂ -CHCl-C ₂ H ₅ CH ₃ H HC ₃ H ₇ CH, H 1-C ₃ H ₇ CH ₃ H CH = CH ₂ CH ₃ H C = CH CH ₃ H CH ₂ -C ^ CH CH ₃ H ^CH 2 ^ Q CH ₃ H CH, CH ₃ H CH ₃ CH ₃ CH ₃ CH ₂ Cl CH ₃ CH, CH ₂ Cl C ₂ H ₅ CH, CH ₂ Br CH ₃ rip ⁵ : 1.5024 CH, CH ₂ Br C ₂ H ₅ CH, C ₂ H ₅ CH ₃ CH, 11-C ₃ H ₇ C ₂ H ₅ CH, ! -C ₃ H ₇ - CH ₃ CH, ■ 5 ^C 2 ^H 5
O
C. CH ₃ CH, CH, C ₂ H CH ₃
CH ₃
CH ₃

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22522!

R ¹ R ² B? Bp ° C; _n 2

Bp: 115 to 118 0.5

'Formula II: _l

Xl

o-c-or ^

O-C-OR ^

RR R Kp. C

H H CH

, Kp ₀ ^: 105 to 109

H CH ₇ , CH ^ Kp _n ^: 99 to IO5

H CH _x C ₂ H ₅ Kp _0: 97 to 102

H CH, XC ₁₁ H _n , Kp _n ^: 124 to 128

Example 11a

o- (l-methoxy-ethoxy) -phenol

110 parts by weight of pyrocateein are suspended in 100 parts by weight of toluene. At +5 C ⁰ 64 Nominal-chtsteile -40 ° C are employed in a molding cold vinyl methyl ether and it is then added a drop of HCl cone. to. With stirring, heated to about +20 ⁰ C, the reaction starts whereupon the piston and increases an internal temperature of about 65 ⁰ C, possibly cooled from the outside with a little ice water. It is held at 65 ^° C. for half an hour and then 5 parts by weight of 2η NaOH are added. After cooling, it is dried using NapSOj,., The solvent is evaporated on a rotary evaporator and distilled in vacuo. Yield 155 parts by weight, bp _{0. 5:} 85 to 90 ⁰ C.
Analysis: C ₉ H ₁₃ O ₃ (I68)

Calc .: C 64.1 H 7.2.

Found: C'64.4 H 7.0

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Example lib

Pyrocatechol bis / ("l -methoxy) ethyl ether 7

If you carry out the same implementation as with lla, but with the twice the amount (128 parts by weight) of vinyl methyl ether, 122 parts by weight of a colorless oil are obtained.

^Bp _n c ^: 99 to 105 ° C.
0.5

Analysis: C ₁₂ ^H i8 ° 4 (226)

Calc .: C 63.7 H 8.0
Found: C 63.3 H 8.1.

Example lic

o- (l-methoxy-ethoxy) -pheno1

113 parts by weight of Br enzkatechin-bis - / ( "l-methoxy) -äthyläther7 and 55 parts by weight of pyrocatechol are added at 40 ⁰ C with 0.5 parts of SOCl ₂ and stirred for half an hour at this temperature then allowed to cool and add 2 ml. 25 # cent (wt.%) aqueous NaOH to Lb'sung, separated off, dried over Na ₂ SO ^ and the solvent evaporated. What remains are 168 parts of the above-mentioned compound of boiling _n, -J 85 to 90 C.

Example 12a

o- (l-ethoxy-ethoxy) -pheno1

220 parts by weight of pyrocatechol are suspended in 200 parts by weight of toluene. After adding 2 drops of HCl cone, 150 parts by weight of ethyl vinyl ether are added dropwise with stirring. By cooling with ice from the outside is ensured that the internal temperature does not exceed 65 ⁰ C. All of the catechol has dissolved at the end of the reaction. 5 parts by weight of 2 η NaOH are added, the mixture is allowed to cool, dried over Na ₂ SO 4 and distilled in vacuo after the solvent has been stripped off. Yield: nearly quantitative, Kp _1: 78 to 8l ° C. njp: 1.5032 Analysis: C ₁₀ H ₁ ^ O, (182)
Calc .: C 66.0 H 7.7
Found: C 66.3 H 7.9 ·

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Example 12b

Brenzkat echin-bis-ZCl-ethoxy) -äthyläther7 If one uses instead of 150 parts by weight of ethyl vinyl ether, 248 parts by weight of a colorless oil are obtained. Bp ₀ : 97 to 102 ° C. Analysis: C ₁₄ H ₂ ^ O ₄ (254) Calc .: C 66.2 H 8.6 Gei \: C 66.4 H 8.7,

Example 12c

o- (1-Ethoxy-ethoxy) -phenol 127 parts by weight of pyrocatechol bis (Cl-A'thoxy) ethyl ether7 and 55 parts by weight of pyrocatechol are reacted and worked up as in Example. Yield: 179 parts of the phenol compound.
Kp _1: 79 to 8O ⁰ C.

Example IjJ

ο - (Methoxy-methoxy) -pheno 110 parts by weight of pyrocatechol are dissolved in 400 parts by weight of benzene. At room temperature one drips at the same time. 101 parts by weight of triethylamine and 81 parts by weight of chloromethyl methyl ether are added so that the reaction medium has a weakly basic reaction. The mixture is then refluxed for a further hour. It is allowed to cool, the hydrochloride is filtered off with suction, washed with water, dried over Na ₂ SO ₄ , concentrated and distilled in vacuo. Yield: 120 Gewichtsteile.-Kp ₀ ^ _4: 89 ⁰ C, ηψι 1.5150. Analysis: GgH ₁₀ O ₃ (154) Calculated: C 62.5 H 6.5 'Found: C 62.0 H 6.5.

It is therefore possible to use the catechol monoether via the intermediate of formula III

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in which R, R, R ^ and R have the meanings given above, the reactions also being carried out as a "one-pot process" can be simple and up to total quantitative yield made from catechol.

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Claims (2)

- O ₀ Z ₀ 29 485 Claims . xProcess for the preparation of catechol ethers of the formula in which R denotes an alkyl, alkenyl or alkynyl radical, which may be substituted by halogen, or the aralkyl radical, characterized in that a pyrocatechol derivative of the formula 1 2 in which R is hydrogen or lower alkyl, R is unsubstituted or substituted by halogen, methoxy or ethoxy, lower alkyl, benzyl, Br lower alkyl, cycloalkyl, β-chloroethyl, alkoxyalkyl, lower alkenyl, lower alkynyl, acyl 1 2
and also R and R together with the G atom, whose substituents 1 "3 they are, and furthermore R and Br together with the carbon or oxygen atom, whose substituents they are, mean a five- or six-membered ring, and R has the meaning given above, cleaves in an acidic medium. 2. The method according to claim 1, characterized in that pyrocatechol with a vinyl ether of the formula R (3Fr, in which R is a vinyl group optionally substituted by lower alkyl and B? Has the meanings given in claim 1, or with a Λ-halogen ether the formula R ¹ HaI-C-OR ⁵ 'to · 12 "5 in which Hal means Cl, Br or J and R, R and Br have the meanings given in claim 1, reacts in the presence of bases, any bisethers of the formula that have formed 409818/1191 _{/ 20} - 20 - 0..Z. 29 485 1 2 "5
in which R, R and R ^ have the meanings given above, reacts with pyrocatechol and the reaction product of the formula 12 "5
in which R, R and R ^ have the meanings given above reacts with alkylating agents of the formula RX, in which R is an alkyl, alkenyl or alkynyl radical, which can be substituted by halogen, or an aralkyl radical and X is a halide, alkoxy, Means sulfonyl or arylsulfonyl radical, and the alkylation product cleaves in an acidic medium, Badische Anilin- & Soda-Fabrik AG ORIQfNAL INSPECTED 409818/1191