DE2041610A1 - Thienobenzopyrans and thiopyranobenzopyrans, intermediates for their manufacture and processes for their manufacture - Google Patents

Description

ARTHUR D. IIITTLE, INO *, Cambridge, Mass./ZJSA

Thienobenzopyrane and thiopyrans "benzopyrans, intermediates for their preparation, and methods for their preparation

The invention relates to new chemical compounds as substituted Thienobenzopyrans and substituted thiopyranobenzopyrans designated type, intermediates for their production, the preparation of these compounds, as well as pharmaceutical compositions, which contain these.

In one of its aspects, the invention relates to a class of chemical compounds, including in particular those known as 7-alkyl- (and 7-cycloalkyl-lower-alkyl) - 9-hydroxy-4,4-di-lower-alkyl -T, 3-dihydro-4H-thieno- [3> 4 - c] [1 ) - benzopyrans, 7-alkyl- (and 7-cycloalkyl-lower-alkyl-) 9-hydroxy ~ 4,4-di- lower-alkyl-1,2-dihydro-4H-thieno [2, ^ - c lh ] benzopyrans and 8-alkyl- (and 8-cycloalkyl-lower-alkyl) -10-hydroxy-5,5-di-lower- alkyl-1,2,4,5-tetrahydro-thiopyrano [3,4-c3 [1J-benzopyrans are called, and certain ester and ither derivatives thereof ·

Compounds according to this aspect of the invention have their own uses inherent in having biological activity, as determined by pharmacology, the standard test methods for

109813/1964

therapeutic agents "and are intended to be therapeutic Medium "useful.

A main aim of the present invention is to provide it of new chemical compounds, new intermediates for their production and processes for producing the chemical • Compounds and their intermediates. Another goal of the Invention is to provide compositions which have central nervous system affecting properties. Other Objects and objects of the invention will be apparent from the description below.

The invention therefore relates to the various stages and the relationship of one or more such stages to each of the other stages and the compounds and compositions, which the properties, characteristics and the relationship of Have components as described by the following Compounds and compositions are illustrated.

Examples of the 7-alkyl- (and 7-cycloalkyl-lower-alkyl-) 9-hydroxy-A, 4-di-lower-alkyl-1,3-dihydro-4H-thienoO> 4-c] [1! Benzopyrans, 7-alkyl- (and 7-cycloalkyl-lower-alkyl-) 9-hydroxy-4,4-di-lower-alkyl-1,2-dihydric: ro-4H-thieno-Z2,3-c7 / i / benzopyrans and 8 -Alkyl- (and 8-cycloalkyl-lower-P-alkyl-) iO-hydroxy-5 _f 5-di-lower-alkyl-1,2,4,5-tetrahydro-thiopyrano [3 ^ -c] [1! Benzopyrans and preferred compounds among them are those of the formula

BATH ORIGINAL

109813 / 19B4

in the R. means a lower alkyl radical, Rp is an alkyl or cycloalkyl-lower alkyl radical and R ^ is a hydrogen atom or a lower alkyl, lower alkanoyl, garbamyl, üf-lower alkylcarbamyl, Έ , N-Di ~ lower-alkylcarbamyl or phosphonyl radical or a water-solubilizing substituent, such as, for example, Malkylaminoalkyl, a hemisuccinate or another such acid radical or a phosphate ester, m is the value 1 or 2, η is the value 0 or 1 and m + n is -2 or 3. If m is 1 and η is 1, the compounds are represented by the general formula

II

shown, while when m represents 2 and η represents O, the compounds by the general formula

OR,

III

and, if m is 2 and η is 1, the connections by the general formula

10 9 813/1954

IV

are shown, with meanings.

and R-, the Be given above

As used herein, the term "lower alkyl" means saturated to understand monovalent aliphatic radicals, including straight-chain and branched radicals, with 1 to 6 carbon atoms, for which, without making a restriction, methyl, ethyl, propyl, ibopropyl, butyl, sec-butyl, amyl, Hexyl and the like are examples.

The term "alkyl ¹¹ used here means saturated monovalent aliphatic radicals, including straight-chain and branched radicals, with 1 to 20 carbon atoms, for which, without hereby imposing a limitation, methyl, n-amyl, n-hexyl, 2-heptyl, n- Examples are heptyl, 3-methyl, 2-octyl, n-octyl, 2-nonyl, 2-tetradecyl, n-hexadecyl, 2-eicosanyl, and the like.

The term "cycloalkyl" used here includes cyclic saturated aliphatic radicals having 3 to 8 carbon atoms understand for which, without making a limitation, cyclopropyl, cyclobutyl, 2-methylcyclobutyl, cyclohexyl, 4-methylcyclohexyl, cyclooctyl, and the like are examples.

As used herein the term "lower alkanoyl" means saturated monovalent aliphatic radicals derived from a monocarboxylic acid, including straight or branched ones Radicals with 1 to 6 carbon atoms, for which, without

109813/1954

hereby to make a restriction, formyl, acetyl, propionyl, (jC-methylpropionyl, butyryl, hexanoyl and the like examples are.

Me ester and ether derivatives of the compounds of the formulas I and II, ie compounds for which R ^ a lower-alkyl, 'lower-alkanoyl-, carbaniyl-, N-lower-alkylcarbamyl ™, N ^ lf-di-lower alkyl carbamyl or phosphonyl radical or a water-solubilizing substituent are, by reaction of the corresponding compound, for which R, is a hydrogen atom, preferably in the presence of a basic catalyst, with a lower alkyl halide to form the compounds for which R * is a lower-alkyl radical, with a lower-alkanoic anhydride (or mixed anhydride) to form the compounds, for which R ^ is a lower-alkanoyl radical, with one molar equivalent of phosgene with subsequent reaction of the chloroformate obtained with ammonia, a lower-alkylamine or a di-lower alkylamine to form the compounds. ^ for which E ^ is an Oarb ^ amyl, H-lower-alkylcarbamyl or!, H-di-lower-alkylcarbamyl radical, with one molar equivalent of Phosphorox Chloride with subsequent reaction of the dichlorophosphinate obtained with aqueous sodium or potassium carbonate to form the compounds for which R ^ is in phosphonyl radical, or with an alkali alkylate to form an alkali derivative which, after treatment with a dialkylaminoalkyl halide, provides the dialkylaminoalkyl derivative Suitable solvents are benzene, toluene, xylene and the like, and suitable basic catalysts are alkali metal carbonates, bicarbonates or hydroxides, dimethylaniline, pyridine and the like »

The compounds of the formula I are made by reacting the corresponding 'OxoyerMndungen der.Formula

109813/1864

made with a lower alkyl magnesium halide as by the reaction

(CHr)) m / ητι N _n ,

<°%) η ^ Χ _{ΗιΗ £ χ (0H2}

₀ ^ k ₀ A ^ - ^E ₂ *

OH

is illustrated, where R. and R _? have the meanings given above and X represents a halogen atom. The reaction is carried out in an organic solvent which is inert under the reaction conditions. Suitable solvents are diethyl ether, dibutyl ether, tetrahydrofuran, anisole, pyridine and the like. It is preferred to use a solution of the 8-alkyl (or 8-cycloalkyl-lower alkyl) iO-hydroxy-5-oxo-1,2,4,5-tetrahydrothiopyrano [j5, ^ - c] [1 jbenzopyran in to add a mixture of dry benzene and dry ether to a solution of the Grignard reagent in ether.

The starting product that reacted with the Grignard reagent is can by reacting a compound of the formula

(CH ₉ ) n = 0

(CH ₂ ) m

JOO alkyl
109813/1954

in which m represents the value 1 or 2 and -η the value 0 or 1
"means and m + η the value 2 or 3" is prepared with a 5-alkylresorcinol (or an S-cycloalkyl-lower alkylresorcinol).

If the output rs- or intermediate product V of the formula

OH

VI

entopricht, this is made by reacting an alkyl 4-oxo-2,3,4,5-tetrahydrothiophene ~ 3-carboxylate of the formula VII with a 5-alkylresorcinol (or a 5-cyeloalkyl-lower-alkylresorcinol) of formula VIII produced. The response will be in attendance an acid catalyst, preferably HCl, dissolved in ethanol, carried out.

= 0 HO

COO alkyl

VII

OH

VIII

VI

wherein Rg has the meaning given above.

If the starting or intermediate product V of the formula

OH

IX 109813/195

BATH ORIGINAL

2Q41610

corresponds to, then dione is obtained by reacting an alkyl-3-oxc- 2,3, 4, 5-tGtra.bydrotl) .: i.ophon ~ 2-carboxylatö of the formula X with a Resorcinol dor Formula VIII manufactured »The reaction is under Carried out conditions which correspond to the preparation of the compound VI angev / o.'jdctoi), such as by the reaction

HO— ■

VIII

IX

is illustrated.

If the exit or. Intermediate V of the formula

XI

corresponds, this is done by reacting a 3-carboalkoxy-4-oxo-2,3,5,6-tetrahydro-4H-thiopyran of the formula XIl with a 5-alkylresorcinol of the formula VIII under the same hedinings, as used to prepare the compounds of formula VI, prepared as by the reaction

OH

^S O HO
COO alkyl

XII

0 '

VIII

XI

1 0981 3/1954

BATH ORIGINAL

is illustrated.

The 5-alkyl or S-cycloalkyl-lower alkyl compounds of the formula VIII used as starting materials or intermediates are expediently prepared by the generally customary methods which involve dehydration of a 3,5-di-lower alkoxyphenylalkyl (or -cycloalkyl-lower-alkyl) -carbinols, the reduction of the 3,5-di-lower-alkoxyphenylalkene obtained (or -di-lower-alkoxy-phenyl-cycloalkyl-lower-alkene) and cleavage of the ether group of the corresponding 5-alkyl means of hydrogen iodide to form (or 5-cycloalkyl-lower alkyl) comprise -resorcins. the carbinols used as starting materials are a turn by reacting a suitable Grignard Eeagens with a 3,5-di-low- alkoxybenzoic acid ester, amide or 3 ', 5'-di-lower-alkoxyalkanophenone (or 3', S'-di-lower-alkoxycycloalkyl-di-lower alkanophenone).

The alkyl-4-oxo-2,3,4,5-tetrahydrothiophene-3-carboxylates used as starting materials or intermediates of the formula VII and the alkyl 3-oxo-2,3,4,5-tetrahydrothiophene-2-carboxylates used as starting materials or intermediates of Formula X can be prepared by the method of Woodward and Eastman, J.Am.Chem.Soc. 63, 2229 (1946), and which are used as starting substances bzv /. Intermediates used 3-carboalkoxy-4-oxo-2,3,5,6- ^

Tetrahydro ~ 4H-thiopyrans can according to the method of G.M.Bennet " and L.V.D. Scorah, J. Chem. 8oc *, 194 (1927).

It was found that the compounds of the formula I have a depressant effect on the central nervous system, as has been demonstrated by the marked changes that can be seen in standard tests by intravenous administration in the mouse, including observations of the psychomotoric activity, the reactivity against stimuli and the _v ability normal niöht kondrfcionierte motor tasks to perform _P ψΛ ^ ₁ JFA - ^ rnTüoni This Afetifität iseist Üire Brauchbarkeii as

_ ₁₀ - 2Ü41610

The present invention also relates to the pharmaceutical compositions the at least one of the connections according to the invention contain.

The compounds can be ready for use by dissolving a salt form of the compounds in Wanner or in a physiologically acceptable one aqueous medium, such as a saline solution, Prepared under sterile conditions and in ampoules -for intramuscular Injection retained. Alternatively, they can be in a dosage unit form as tablets or capsules for oral use Administration either alone or together with 'suitable adjuvants, v / ie for example calcium carbonate, starch, lactones, Talc, magnesium st carate, agar-agar and the like v / earth. The compounds can also be used for oral administration in aqueous alcoholic, glycolic or oily solutions or in Ül-V / a s se r-Emulr. ions are prepared in the same way, manufactured as usual medical preparations.

The molecular structures of the compounds according to the invention were on the basis of the examination of their infrared, ultraviolet and NMR spectra and their conversion products the agreement between the calculated values and the values found in the elemental analyzes for typical examples is confirmed.

The following examples serve to further illustrate the invention.

example 1

1,2-0ihydro-9-hydroxy-7- (i, 2-dimethylheptyl) -

A. Meth y 1 -3-Q ₁ Xο ~ 2 _{m ?} '5_ _ι > _m A_ _f 5 ~ t etrahydrοthiοph en-2- carboxylate

The method of Wooäwaro, and Eastman / J. Am.Cheni.Soc »6 ^, 2229 (1946J7 was used to cyclize 100 g (0.55 mol) of methyl-3- (metlioxjrcarbonylmethylthio) -pro ρ ion. At , where 56 g

1 Oi 9 8 1 3; ί 3 S 4 "

BATH ORIGINAL

(65 7 °) Ilcl.hyl-3-οχο-ί ?,; 3,4,5-teti \ ahydrothiophene-2-carboxylate, DIo NMR analysis showed that the product is a mixture of isomers with oars Content of 80 ^c fo of the desired product

j - == 0
30OCH ₃
XIII
and 20 ¹ Jo Mefchyl ~ 4 ~ oxo-2,3 ··, A ₁ ~ 5-tetrahydrothiophene-3 ~ c ^% ar'boxylate

XIV
which could isoliej ^ tv / earth by fractional distillation, isb,

B. 1,2-Dihydro-9-hydroxy-7- (1,2-dimethylheptyl) -4-oxo-4H-2,3-c] f '\ ] benzopyran

A solution of 2.13 g (0.011 mol) of 5 ~ (1,2-Mmethylheptyl) resorcinol and 2.0 β (0.013 Hol) methyl 3-oxo-2,3,4,5-tetrahydrothiophene-2-carboxylate in 50 ml of absolute ethanol was cooled in a three-necked flask, which was equipped with a drying tube, in an ice-water bath and saturated with dry hydrogen chloride. Dao 5- (i, 2-Dimethylheptyl) -reooroin was according to the method of Adams, HacKenzie and Loev / e ^ J.Am.Chein.Soc. 7.0, 664-668 (1948J7. The reaction mixture was allowed to stand for three days at room temperature, during which time a thick yellow particulate substance formed. The hydrogen chloride was evaporated, the mixture was concentrated, and the solid substance was filtered off and washed with ethanol. The yield of crude benzopyrone obtained in this way was 2.6 g (59 ^° A)

is 205 ^° C.

109813/1954

BAD ORSGS ^ AL

Melting point from 190 to 205 ⁰ C.

Repeated crystallization from absolute ethanol produced an analytical sample from F = 209 to 212 ^° G of the compound of the formula

OH

CII,

CH,

-CIl CH

XV

obtain. 2 C ₂₀ H ₂₆ O ₃ S • C - 36 II = 7, 51 Analysis: calculated: 15th 7, 41 found: example - ■ 69, 69

S =

9.25 ^l / o $ 9.30>

1,2-dihydro-4,4-dimethyl-9-hydroxy-7- ("1,2-dimethyl-

heptyl) -41I-thieno- [2,3-c] [i-benzopyran

A solution of 1.5 g (0.0045 mol) dec. Benzopyrones by example 1 in 75 ml of benzene ether was added dropwise to a suspension of 10.4 g (0.084 mol) of methyl magnesium bromide in 50 ml Benzene added under nitrogen. The reaction mixture was Stirred at 4 ° C. overnight. Then it was cooled and the excess Grignard reagent was washed with saturated aqueous Ammonium chloride decomposes. The organic layer was separated, and the aqueous layer was extracted twice with benzene. The combined extracts were washed with aqueous sodium bicarbonate and washed with water and then dried over sodium sulfate. When the solvents evaporated, a darker one remained greasy residue that was sublimed back. After 40 hours Sublimation at 110 ° C / 0.03 mm, 680 mg of a deep purple-colored greasy substance were obtained. The connection can be used as a compound of the formula

10 9 8 13/19 5A

BATH ORIGINAL

CH

being represented.

XVI

Analysis: ^C 22 ^H 32 ° 2 ^S ''

calculated: C = 73.33 H = 8.91 S = 8.91 1 ° found: 73.10 9.16 8.75 1 <>

The greasy substance showed λ ^ ¹ 1 ^Άηο1 320 m / u (log ε 3.951).

IucLX. /

The infrared, ultraviolet and NMβ spectra confirmed this Pyran structure. The thin layer chromatography on silica gel with Ethyl acetate-IIexane (1: 4) showed one major spot (Ef = 0.54) and zv / ei traces of contamination (Kf = 0.20, 0.17).

The 1,2-dihydro-4,4-dimethyl-9-hydroxy-7- (1,2-dimethylheptyl) -411-thieno [ 2,2-c] [i-benzopyran produced can be mixed with potassium ethylate to form the potassium derivative of phenol be implemented, the corresponding compound of formula ■ on treatment with Dimethylaminoätiiylohlbrid in a suitable solvent, such as benzene

supplies.

XVII

10 9813/1954

BATH

-H-

According to procedures which are identical to those of Examples 1 and 2, the methyl-4-oxo-2, 3.4 _t 5-tetrahyclrothiophene-3-carboxylate irradiation can be reacted with the resorcinol to form a compound of the i'Orj

XVIII

to provide, which in turn can be reacted with the Grignard reagent to give the compound of the formula

CH _V

GH "

CH- C H

11

XIX

to obtain. This compound can be used to replace the hydrogen with a water-solubilizing substituent, such as the group -,"

be treated.

Example 3

10-Hydroxy-8- (i, 2-dimethylheptyl) -5-oxo-1,2,4,5-tetrahydro-thiopyrano [j5,4-c J [ijbensopyran

A solution of 6.4 g (0.027 mol) of 5- (1,2-dimethylheptyl) -rosoroin from Example 1 and 5.0 g (0.0266 mol) of ethyl-4-oxo-3,4,5,6-

10981 3/19 5 4

BATH ORIGINAL

• fcetrahydro-2H-thiopyri.u) ~ 3-carboxylate in 35 ml of absolute ethanol was chilled in an ice bath while οie with hydrogen chloride was saturated. The deep red solution obtained was tightly sealed and left to stand at room temperature for 120 hours. After one day a yellow crystalline material had developed. Sanded bottom of the Kolbon. The reaction mixture became mild warmed up on a steam bath for 113 minutes, cooled and poured onto a water-ice-mixture poured. The precipitated greasy material was extracted with several portions of chloroform. The chloroform solution was with aqueous potassium bicarbonate and with water washed and dried over sodium sulfate. When "evaporating the The solvent remained 7.5 g of a pale solid substance back · This material was several sharks with boiling petroleum ether triturated to remove unreacted ketoester. The residue was extracted from an iithylacetate-petroleum ether mixture recrystallized, where 6.5 g (68 ^) of the compound of the formula

OH

CH,

-CH-

XX

O,

from F = 153 to 155 0.

The HMR spectrum of this material was consistent with the assumed structure. From another manufacturing an analytical sample was obtained from F = 150 to 152 ⁰ C after two Uinkristallisationen from ethyl acetate-petroleum ether. This sample showed

Ethanol
Max

Analysis:

310nyu (log _£ 3,996).

calculated: C = 70.00 H = 7.78 found: 69.99 7.99

109813/195 A

S = $ 8.89> 8.83 i °

BATH ORIGINAL

Beispi a l 4

5,5-dimethyl-10-bydroxy-8- (1,2-dimethy] heptyl) -1, 2,4,5-

tctrahydro-thlopyrano i.3, ^ - c] ί '■■ Jbcvnzopyran

A Grignard RcMgons was produced in a previously flamed apparatus under a nitrogen atmosphere by introducing bromomethane into a 250 ml Drciha] oruiicllrolbon containing 2.03 g (0.0833 Hol) of magnesium in 50 ml of dry atom. Magnesium had completely reacted, 10 ml of ether were distilled off from the reaction mixture in order to remove the excess bromine than 2U. A solution of 3 β (0.00833 mol) dec "TIrJo] J ₁ VTOnS prepared above in 30 ml of dry benzene and 15 ral of dry zither was added dropwise to the Grignard solution within 45 minutes. Ι The reaction was heated for 5 days under cooling, cooled and slowly poured into a mixture of 75 parts of saturated ammonium chloride solution and 50 g of ice The combined extracts were washed with V / af3Sor, aqueous potassium bicarbonate solution and again with water, dried over lithium sulfate and then evaporated to give 3.5 g of a brown residue which was taken up in 150 ml of dry n-heptane The solution was brought to the boil and four drops of 48% hydrobromic acid were added. The boiling was continued for 40 minutes. The solution was left to stand overnight and then a small amount filtered off a precipitate. Evaporation of the filtrate 2.6 g (04 ^c / °) of the crude Thiopyrans were obtained. 1 g of this material, when cleaned in two 0.5 g batches by heating in a sublimation apparatus at 150 ° C./0.1 mm, gave 200 mg of a yellow viscous oil of the formula

OH

^XXI 3 BATH ORIGINAL

1 098 1 3/1 9RA

The NHR spectrum of this oil was consistent with the structure of the desired product XXI. Thin-layer chromatography (Ethyl acetate / hexane, 1: 9) showed one major spot (Rf = 0.80) and one minor spot (Rf - 0.74). -The ultraviolet spectrum

showed λ ^ ^an01 275 nyu (log ε 3.6). Analysis: G ₂₂ Hv ₂ O ₂ S

calculated: G = 73.33 II = 8.96 S = 8.91 i * found: 73.57 9.14 8.76 ^

In a manner corresponding to that described in Example 2, " can the thiopyranobenzopyran of the formula XXI with potassium ethylate and then with dimethyleminoalkyl chlorides to form a Group R ,, which has a water-solubilizing character, implemented.

It can be seen that the above and from the description ' apparent objectives have been effectively achieved and that certain changes have been made in the implementation of the above Methods and compositions can be carried out without departing from the scope of the invention.

^109813/1954 BADOR.ai _N AU

Claims (1)

in which R 1 denotes a n.iodrig-alkyl group, R 1 denotes an alkyl or cycloalkyl-lower alkyl group; represents, R-, a nuclear atom or a lower-alkyl-, lower-alkanoyl-, carbamyl-, IT-lower-alkylcarbamyl-, Ν, Ν-di-lower-alkylcarbamyl- or Phocphonylroi.it or a v / asr or soluble making substitutions bedoubet, m don represents the value 1 or 2 and η represents the word O or 1 and m -f η has the value 2 or 3. 2. Compounds of the formula R, • o (formula a: m = 1, ti = I) 3. I, 3-dihydro-4, 4-ei hnt) ethyl-y-hydthoxy-7- (i | 2 -dimothylhopbyl) · 4H-thiono \ 5.1 \ -q) [Iberizopyran (Formula b: R., = Mebhyl, FU = 1,2-i) imufchylhoptyi and Rv = Waöueroboff. 10 9 8 13/1954 BAD ORIGINAL 4 ♦ 1,3 ~ Dihydro ~ 4,4-dimethyl-9- (dimethylarainoethyl) -7- (1,2-dimethylheptyl0- ^ H-fchieno ^, 4 - ^ / T_ / banzapyran (Formula b: K1 = methyl, H2 = 1,2 ~ dimethylheptyl mid R ^ = Mmethylaininoäthyl) «· 5 * compounds of the formula (c) -η. (Formula a: rn = 2, η = O) 1,2 -3) Hydro-4 »4" "- dpI: ethyl-9-hydroxy-T- (1,2-diiuetliylheptyl) -4il-thieno [2,3-cJ [t jbenzopyran (formula c: T ^ = methyl, E2 = 1,2 ~ Mmethylheptyl and R7 = V / aooerstoff.1,2-Diliydr0-4,4-dinßthyl-9- (aimethylaminoethyl) -7- (1,2 ~ diynethylheptyl) -4H-thieno [2-, 3-c] [i] bcm; opyran (formula c: R1 = methyl, Rg = 1,2 ~ BiEiethylheptyl and IU = dirnethylaininoäthyl). 8. Compounds of the formula (Formula a: m = 2, η = 1) 9. 5,5-Dimethyl-10-hydroxy-8- (1,2-dimethyllieptyl) -1,2,4,5-tetrahydro-thiopyx'ano- [3> 4 -c] [1-benzopyran (formula d: R1 = methyl, R2 = 1,2-dimethylheptyl and R5 = V / water st off. 10. 5,5-Mmethyl-10- (dimethylaminoethyl) -8- (i, 2-dimethylheptyl) - 109813/1954 BAD ORIGiNAU 1 , 2, 4, 5 ~ tetrahydrn-thiopyra.no D, 4-c] [1 jbenzopyran (formula ύ: R. - methyl, R2 = 1,2-dimethylheptyl and R * = diine 11 j y II. Am: i: π ο ethyl). 11. Connections of the form] (CI12) m V- / J. L '7 (CH2) n 0- in dor Rp is an alkyl- ocU; r is cycloalkyl-lower-alkyl, R-, a V / asöerctoffatoin or a lower-alkyl-, lower-alkyl.] »Anoyl ~, carbamyl- , N-lower-alkylcarbamyl-, W, N-di ~ low ~ alkyiua.rlj; means imyl or phosphonyl radical, m represents the value 1 or 2 and η represents the value 0 or 1 and in + η the value 2 or 3 possesses, 12. Prebind in βon of the formula (Formula e: m = 1, η = 1) 13β Compounds of the formula (Formula e: m = 2, n = 0) 1098 13/1954 BAD ORIGINAL 14. Compounds of the formula (Formula e: m = 2, η = 1) 15. Process for the preparation of compounds of the formula (GH2) m OH (CH2) n in which Rp denotes an alkyl or cycloalkyl-lower alkyl radical, m represents the value 1 or 2, η represents the value 0 or 1 and m + η has the value 2 or 3, characterized in that a compound of the formula (CII2) m (OH «) n COOalkyl with a substituted resorcinol of the formula OH In dor R2 has the meaning given above owns, is implemented. 1,098 13/195 16. The method according to claim 15, characterized in that;.: Ία has the value 1 and η has the value 1. 17 · The method according to claim 15, characterized in that m represents the value 2 and η represents the value O. 18. The method according to claim 15, characterized in that m has the value 2 and η the value 1. 19. The method according to claim 15, characterized in that R _{2 is} a 1,2-dimethylheptyl radical. 1 098 1 3/1 9! U