CS199376B1 - Insecticide based on compounds controlling insect development and method of preparing them - Google Patents

Description

The invention relates to an insecticidal composition based on substances regulating the development of insects and an ester bond in a molecule, to a process for its preparation and use.

At present, several thousands of synthetic and natural juvenoids are known, which are substances with a physiological effect analogous to insect juvenile hormone (JH). In practice, all of these substances were intended to be directly applied, whether in the form of sprays, dusts or aerosols. However, practical problems such as the volatility of the palliates, the biotic or abiotic conversion of some juvenoids into physiologically inactive ingredients can sometimes be envisaged. However, these can be overcome, for example, by the use of substances having properties of do o in practical applicability beneficial, releasing in the insect plant organism by the biotic or possibly biotic attack of the physiologically active ingredient (Sláma K., Romanuk M., J.Inseot Biochem. 1976)) · Examples of such phenomenonogenic substances are esters of acids with juveuidic alcohols ·

SUMMARY OF THE INVENTION The present invention relates to an insecticidal composition and based on insecticide controlling agents, characterized in that it contains as active ingredient juveuloid and juvenoldogenic compounds with an β ester bond in a molecule of the formula I *.

199 376

199 379

R ^X R ² (OR ³ ) O-eH ² - (OH ² ) a-CCR ⁴ Z ¹ ) -O (R ⁵ Z ² ) - (OH ² ) _b - (JHCR ⁶ ) -O - ^ - C 1 H (R ⁷ ) O0aR ⁸ where:

- the symbol a denotes an integer τ between 0 and 2

- the symbol b denotes 0 or 1

- R ¹ R ² represents methyl or ethyl

- the symbol R ³ tagged alkyl, straight or branched chain and a total of up to 6 carbon atoms, alkoxyalkyl with a straight or branched chain 8 a total of up to 6 carbon atoms, haloalkyl having straight or branched chain and up to 6 and knapsacks atoms, acyloxyalkyl straight or branched chain of up to 6 carbon atoms, (oycloalkyl) alkyl of up to 6 carbon atoms, aralkyl of up to 9 carbon atoms

R ⁴ , R ³ , R ⁸ also represent hydrogen, methyl or ethyl

- R ⁷ represents a straight or branched alkyl of up to 6 carbon atoms or a phenyl group

- the symbols z \ Z ² denote hydrogen or together form a double bond or, if s 2, Z 2 denotes an alkoxy group having a total number of not more than 6 carbon atoms

O

- the symbol R represents!

- a substituent sample of ³ - ₍ Z ⁾ wherein Z ³ , Z ⁴ is hydrogen or straight or branched alkyl of up to 5 carbon atoms, the symbol o denotes an integer ranging from 1 to 20

- substituent of formula:

Z ⁴ - (CH ₂ ) _d -CH = CH- (CH ₂ ) _e kds Z ⁴ is as defined above, the symbol d, e denotes an integer ranging from 0 to 10

- R ³ ¢ vzoroei 0¾) ^ laCH- where Z ³ is hydrogen or a group -COOZ ^7, the symbol Z ⁷ is hydrogen or straight or branched alkyl having a total of up to 4 carbon atoms, R ⁶ Z is hydrogen or methyl, symbol f is an integer ranging from 0 to 2

- substituent of formula »

From ⁴ - (GH) g where Z ⁴ is as defined above, the symbol Z ⁸ represents chlorine or bromine, or ³ sknpinu -COZ or a group Z or a group-Q-- JI- * ^AEB ° ^{slEUpÍBU "30Oz} ^» ^ sy dg

199 379 an integer ranging from 1 to 15, Z ⁹ denotes straight or branched alkyl of up to 6 carbon atoms, Ζ ^ θ denotes hydrogen or chlorine or bromine or -NOg or -ΟΘ0Ζ ⁷ , Z ¹ * Z ¹² denotes hydrogen or forms a double bond, h denotes 0 or 1, Z ⁷ denotes hydrogen or straight or branched alkyl having up to 4 carbon atoms;

A process for the preparation of compounds controlling the development of an ester-bonded insect in a molecule of formula I is to react a ketone of formula II »

R ² R ² (OR 4) O- ^; OH 2 - (CH ^{2) a} -OCB ^2f Z ¹⁾ -OCR ⁵ Z ² ) - (OH ² ) _b -CHCR ⁶ ) -O-4-OOR ⁷ (II) wherein R ¹ -R ⁷ , z ² , a, b, have the meaning given above with lithium aluminum hydride in an anhydrous medium of organic solvents inert to the reactants, for example in anhydrous diethyl ether, to give an alcohol of the general formula III '.

R ¹ R ² (OR ⁵ ) C-OH 2 - (CH 2) a -O (R ⁴ Z ¹ ) -0CR ⁵ Z ² ) - (OH 2) _b -0H (R ⁶ ) -0- ^ 5 ^ -0H ( 0H) R ⁷ (III)

Wherein R to R ', Z, Z, a, b, are as defined above,

Q which reacts further with compounds of the general formula ΙΥϊ R ° -CO-Y (IV)

S 8 where Y represents a hydroxyl group or chlorine or a -OOOR group and R represents *

ZVCH) _C Z ⁴ or Z ⁴ - (CH ₂ ) _d -CH ₂ OH -CH ₂ - or Z ⁵ - (CH 2 -C ⁶ CHZ ⁶ or Z - (CH) wherein the symbol o is an integer ranging from 1 to 20l by the symbols Z ^ Z ⁴ is hydrogen or straight or branched alkyl having up to 5 carbon atoms, R d and e are integers ranging from 0 to 10, the symbol Z ⁹ represents hydrogen nsbo group - COOZ ⁷ wherein Z ⁷ is hydrogen or straight or branched alkyl of up to 4 carbon atoms, Z is hydrogen or methyl, f is an integer ranging from 0 to 2, g is an integer ranging from 1 to 15f Z ⁸ is chlorine or bromine, or -COZ ⁹ or Z or (CH-OH) _h or -COOZ ⁷ , wherein Z ⁹ _Z 11 _Z 12 represents straight or branched alkyl of up to 6 carbon atoms, Z denotes hydrogen or "12 denotes hydrogen or chlorine or bromine or the group -NO ₂ or the group -COOZ ', the symbols Z, Z together form a double bond, the symbol h denotes 0 or 1 and Z ⁷ denotes hydrogen or 8 or branched alkyl having up to 4 carbon atoms, or Y and R together form a group

199 379 or

Z 2 -OH-OH-1-CO.

(gr ^ f where Z ¹³ , Z ¹⁴ denote hydrogen or together form a double bond, i, j denote O or

1, to the final product of formula I

In the following, the invention is explained in more detail by way of example without being limited thereto.

Example 1

- [4- (7-Ethoxy-3,7- (3-methyl-2-octynyloxy) phenyl] propan-1-ol

A solution of 250 mg of 4- (7'-Sthoxy-3,7-dimethyl-2-octenyloxy) propiophenone in 5 [mu] l of anhydrous diethyl ether was added dropwise at 10-20 [deg.] C. with stirring and inaccessible to 20 mg of LiAlH4 in 10 ml of anhydrous diethyl ether. The reaction mixture was then heated to reflux for 30 minutes. After cooling with ice and diluting with diethyl ether, stirring was quenched with unreacted hydride with ice water as well as precipitated aluminum hydroxide with 10-20% aqueous HgSO4. The separated ether layer was washed with saturated NaCl solution, dried over anhydrous MgSO 4 and evaporated under reduced pressure.

The obtained residue was then separated by silica gel column chromatography with 8% water (eluent: petroleum ether, containing up to 50% by volume of diethyl ether) to give 220 mg (88%) of chromatographically pure 1- [4- (7-ethoxy-3,7)]. -dimethyl-2-octenyloxy) phenyl] -propan-1-ol (mp 161-165 ° C / 13.3 P _a ). Elementary Analysis! for O ^ 11 ^ O ^ / 334) calculated!

% H, 75.47;% H, 10.28%.

Example 2

Lauric acid 1-pt- (7-ethoxy-3,7-aimethyl-2-octenyloxy) phenyl

To a solution of 334 mg of 1- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propan-1-ol in 5 ml of anhydrous dimethylformamide was added with stirring 79 mg of anhydrous pyridine and 218 mg of lauric acid chloride. (tt 194-195 ° 0 / 2kPa). The reaction mixture was then allowed to stand at room temperature overnight. After diluting the mixture and extracting with diethyl ether, the residue of the separated dried ethereal layer was further separated by column chromatography (silica gel with 8% by weight, eluent petroleum ether, containing up to 20% by volume of diethyl ether).

356 mg (62%) of lauric acid 1- [4- (7-ethoxy-3,7-dimethyl-2-thienyloxy) phenyl] propyl ester were obtained, n = 1.4830. Elementráni analýza! for Ο ^ Ηθ ^ Ο ^ (572) calculated!

% C, 77.58;% H, 11.26 found! 0 77.71%, 11.16% H. IR (5% solution in 0Cl ^) and 1237 (C = O ester.), 1364, 1381 (/ sCHj gem.) 1677 (^ 0 = 0), ⁰ 173flť ^{= 0} ester.).

Example 3

Using the same procedure as in Example 2, 1- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propyl oleic acid ester was prepared. n ^ ¹ and 1.4867,

199 379

3- (2-Furyl) propionic acid 1- (4- (7-ethoxy-3,7-dimethyl-2-octeayloxy) phenyl) propyl ester; ΐδ spectrum (6% ni solution in CGl ^):

1735 cm < -1 &gt; (V CaO ester) &lt; 1 &gt; P [(7- (1-chloro) ethyl] -3,7-dimethyl-2-octenyloxy) phenyl] propyl laurate, δδ spectrum (5% nl solution in 001) .Delta.: 1236 (Y 0 -O ester.), 1365, 1381 (.7OH OH), 1730.

1737 om ” ¹ )? O = O ester. 3-Ethoxycarbonylpropionic acid 1- [4 * (7'-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propyl ester. MS spectrum (70e ¥): 31 (021 ^H 33 ° 2? * 280 (0? H? O?)), Ϊ́35 (σ ₉ Η _1χ 0), ΙΙ (ΟθΗ).

Nuclear Magnetic Resonance Spectrum (60 MHz, ODO1j (TMS), δ f / ppm): 0.85 (t, 3H, 17 Hz), 1.13 (s, 3H), 1.13 (t, 3H, J = 7), 1, 22 / t / t.3H _, JB7/r17.71/e.3H/.2.56/s.4H/3.52/q.2H _, J preferred7/.4.08/q.2H _, J _and 7 /,4.50/a,2H,J=6.5/,5 required48/t,

H, 1 = 6.5 /, 5.60 ^, 8, ^ 5 /, 6.83.7.23 ^, ^, 1 ^^ = 9 /,

Benzoic acid 1- 4- (5,7-ethoxy-3,7-trimethyl-octyloxy) -phenyl-propyl ester! m / z = 1.5082

1- (4- (7-Methoxy-3,7-dimethyl-2-octenylose) phenyl) propyl pyruvate;

"22" _η P sl, 5072.lC septrum (5% solution in 001 ^ /: 1230 / 0-0 ester./.1686/ 0 = 0), 1728 cm vo = 0 ester · /,

4-chlorobenzoic acid 1- 4- (7-ethyl-3,7-dimethyl-2-octenyloxy) phenyl propyl ester MS spectrum (70 eV): 472 (H ⁺ ), 428 (30) M ⁺ -44 /, 362/0 ^^ 0 ^, 316/0 ^ 2 ^ 5 /, 290/2/0 ^^^ 010 ^ /, 261/3 / O ^ HjjQO ^ jy, 183/0 ₁₂ H ₂₅ 0 /, 156/8/0 ^ 010 ^, 139 (41/0 ^ 010), and 4- (7-ethoxy--3,7-dimethyl-2-octenyloxy) phenyl propyl 4-nitrobenzoate,

MS spectrum (TOeV): 483 (M ^& lt ^{; +} & gt ^; )

Example 4 Acetic acid 1- (4- (7-ethoxy-3,7-dlmethyl-2-octenyloxy) phenyl propyl ester)

A mixture of 480mg of 1- (4- (7-Bthoxy-3,7-dimethyl-2-octenyloxy) phenyl propan-1-ol, 140mg of anhydrous pyridine and 1g of acetic anhydride is allowed to stand at room temperature overnight. The residue of the dried ether layer was separated on a silica gel column with 8% by weight of water (eluent:

I® containing up to 50% by volume diethyl ether. Acetic acid 1- (4- (p-ethoxy-3,7-dimethyl-2-octenyl) phenyl) propyl ester was obtained (bp182-2.0 / 13.3 Pa / cm @ -1). Elemental Analysis Found: 73.04% c, 73.3% 0.9.23% Found: C, 73.04;

9.48% Η »

Acetic acid 1- 4- (7-benzyloxy-3,7-dimethyl-2-octenyloxy) phenyl propyl ester is obtained in the same manner,

1- 4- (7- (2H-methoxy) ethoxy-3,7-dimethyl-2-octenyl) phenyl acetic acid propyl ester,

199 378

Acetic acid 1- 4- (7- (2-acetyloxy) ethoxy-3,7-dimethyl-2-octenyloxy) phenylpropyl ester,

1- (4- (6-ethoxy-6-methyl-2-heptolyxy) phenyl) propyl acetate and 1-phenyl-1- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] methyl ester acetic.

All of the above compounds showed a CCl2 (5% solution) similar to the other cases

Y C-O ester. θ '/ 0 = 0 ester. Ý wavelengths 1230-1237 cm “ ¹ and 1728 to 1740 cm” ¹ .

Example 5

1- (4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl) propyl formate 1 mg of 1- (7-ethoxy-3,7-dimethyl-2-thenyloxy) phenyl] propane- of l-ol in 5 ml of acylation mixture (prepared by mixing 7 ', 5 ml of 90% HCOOH and 15 ml of acetic anhydride at -10 ° C, stirring for half an hour at 0 ° C, followed by heating at 50 ° C for a quarter hour and quenching below 0 The temperature is maintained at 0 DEG C. for 1 hour and then at room temperature for half an hour, after shaking between diethyl ether and saturated NaHCO3 solution, and the residue of the ether-dried layer is separated by silica gel column chromatography (eluent: PE containing up to 20%). of diethyl ether to give 0.65 g (60%) of 1- (4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl) propyl formate (179-180 ° C / 13.3 Pa).

Elemental analysis for C ₂₂ H ₂₁ N 2 O 3: 362 (calc.). % C, 72.88;% H, 9.45; found: 72,55%

C, 9.57% H. IR (5% solution in CC1 _4): 1728 cm ^-1 (yC = O ester./1671 cm ^"1) v 0 = 0 /,

1614, 1586, 1515 cm ¹ ) Varomatics).

Example 6

2-Methoxycarbonylbenzoic acid 1- [4- (3,7-diethoxy-3,7-dimethyloctyloxy) phenyl] propyl ester

A mixture of 380 mg of 1- (4- (3,7-diethoxy-3,7-dimethyloctyloxy) phenyl) propan-1-ol, 148 mg of phthalic anhydride and 87 mg of anhydrous pyridine was heated at 60 ° C for 7 hours and then left at at room temperature overnight. The reaction mixture was separated by column chromatography with 8% w / w silica gel. The isolated fraction with less than the starting alcohol of 150 mg was reacted with an ethereal CH ₂ N ₂ solution and was then purified again by passing through a silica gel column. Thereby obtaining 150 mg / 27% / £ l- 4- (3,7-dixethoxy-3,7-dimethyl octyloxy) phenyl ester 2-proplyesteru metohoxykarbonylbenzoové · Elemental analysis: for ^θ32 Η ^θ 46 ^7/542/70 calc. 81% C, 8.54% HjnalSzeno 70.82% C, 8.18% R. U.S. spectrum (70 eV): 314 / C ₁₈ H ₁₈ 0 ₅ /,

Example 7

Analogously to the procedure described in Example 6, 3-carboxypropionic acid 1- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propyl ester was prepared. iC spectrum (5% solution in 001 ^ /: 1236 / YC-0 ester./,1671/y0=0/,1740//θ% e ether./,1718? 0 = 0 dimeric acid), 26OO (y OH acid dimer), "

3,3-Dimethyl-4-carboxylic acid 1- [4- (7-ethoxy-3,7'-dimethyl-2-octenyloxy) phenyl] propyl ester. IR spectrum (5% CCl3 solution: 1720 (Yc = 0 acid dimer), 2605 cm @ ^-1 )

In acid OH dimer, and 1- (4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phepyl) propyl ester of acid 7

199 378 3-carboxy-2-propene (room temperature, 15). IR (5% in CCl3):

1727 (m / e) ester.).

The biological activity of the compounds prepared according to the invention was tested on the basis ^{of the} action of insect juvenile hormone. The substances were applied topically in 1 microliter of acetone at a dilution of 10 °, 1: 100 etc. to freshly stripped pupae of the beetles (Tenebrionidae family) and to freshly stripped larvae of the last instar bug (Pyrrhocoridae and Pentadomidae). metamorphosis. Some of the results obtained in Table 1 are expressed in standard units, which indicates the amount of the substance in micrograms per insect, which under the above experimental conditions gives rise to intermediate forms between pupae and adults (beetles) or between larvae and doepelo (bugs). .

Table 1

Examples of the activities of the compounds prepared according to the invention in insect individual ID? Q ns when topically applied to an insect of the family Pyrrhocoridae, Pentatomidae and Tenebrionidae

Dysdercus Graphosoma Tenebrio cingulatus italicum molitor

4-chlorobenzoic acid propyl ester 3 0.1 3,3-Dimethyl-4-carboxybutyric acid 10- (7-ethoxy-3, 6-dimethyl-2-diphenyloxy) phenyl Dichloroic acid 10- (3,7-diethoxy-3,7-dimethylocthoxy) phenyl] propyl ester 3-Carboxypropionic acid 10- (7-ethoxy-3,7-dimethyl-2-octyloxy) -phenyl] propyl ester 3 '1 1 0.1 3-Methoxycarbonylpropionic acid 10- (7-ethoxy-3,7-dimethyl-2-octyloxy) phenyl phenylpropyl ester 100 ALIGN! 0.008 Elaidic acid 10- (7-ethoxy-3,7-dimethyl-2-octyloxy) -phenyl-propyl ester 2-Methoxycarbonylbenzoic acid 1-O- (3,7-diethoxy-3,7-dimethyloctyl-phenyl) -propyl ester 10 10 Lauric acid 1-0- (7-ethoxy-3,7-dimethyl-2-octyloxy) phenyl 0.5 5 0.07 Trifluoric acid 1-O- (7-ethoxy-3,7-dimethyl-2-octyloxy) -phenyl propyl ester 5 8 0.4 Isobutyric acid 1-O- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl phenyl ester 4 1 0.08 Oic acid 1-O- (7-ethoxy-3,7-dimethyl-2-octenyloxy) -phenyl] propyl ester 0.7 10 0.04 10- (7- (2-chloro) ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propyl laurate 10 5 n-Propoxycarbonylpropionic acid 1-O- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl phenylpropyl ester 100 ALIGN! 0.08

β

199 379

N-heptyloxycarbonylpropionic acid 1- [4- (7-ethoxy-3,7-dimethyl-2-octyloxy) phenyl] propyl ester 10 0.08 (7-Ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propyl- ethoxycarbonylpropionic acid ester 10 0.1 1- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) -100 phenyl] 3,3-dimethyl-4-carboxylic acid propyl ester 100 ALIGN! 1 Θ-1 .- (t _e 7_ -methoxy-3,7-dimethyl-2-oktenyloxy) phenyl] pro- pivalic acid pyleeter 10 10 1 1-0- (3 * 7-diethoxy-3,7-dimethyloctyloxy) -phenyl] propyl- 2-methoxycarbonylbenzoic acid ester 10 10 3-Methyl-2-butenoic acid 1- (4- (7-ethoxy-3,7-dimethyl-2-octyloxy) -phenyl] -propyl ester 1- [4- (7-Ethoxy-3,7-dimethyl-yloxy) -phenyl] -propyl benzoic acid 1-phenyl-1- (4- (7-ethoxy-3,7-dimethyl-2-) -) octenyloxy) phenyl] methyl ester 1 acetic 1 100 ALIGN! 1- [4-7-Ethoxy-3,7-dimethyl-2-octyloxy) phenyl] propyl. arachic acid ester 1 10 0.05 1-O- (6-ethoxy-6-methyl-2-yloxy) phenyl] -propyl- acetic acid eater 1 1-O- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propyl linoleic ester 8 30 0.1 Acrylic acid 1 - 4- (7-benzyloxy-3,7-dimethyl-2-octeayloxy) phenyl] propyl ester 1- (1- (7-Ethoxy-3,7-dimethyl-2-octyloxy) -phenyl] - 0.5 Behenic acid pylester 5 100 ALIGN! 10 Acetic acid 1- (4- (7-cyclopropylmethoxy-3,7-dimethyl-2-octenyloxy) phenyl) propyl ester 1- [4- (7-ethoxy-3,7-dimethyl-2-octyloxy) -phenyl] prop 0.4 pollen of capric acid ester 1 20 May 0.1 1- [4- (7- (2-methoxy) ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propyl acetate 1 1- [4- (7-Ethoxy-3,7-dimethyl-2-octyloxy) -phenyl] -propyl- eater butyric acid 1 1 0.05 Acetic acid 1-0- (7- (2-ac ethyloxy) alkoxy-3,7-dimethyl-2-octyloxy) phenyl 10 1- N - (7-Ethoxy-3,7-dimethyl-2-octyloxy) -phenyl] -prop isovaleric acid ester 0.7 1 0.8 1-O- (7-ethoxy-3,7-dimethyl-2-octenyloxy) -phenyl] propyl- Valeric acid eater 0.2 2 0.5 1- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] propyl- heptanoic acid ester 10 10 0.1 Enanthic acid 1- (4- (7-ethoxy-3,7-dimethyl-2-oct-enyloxy) -phenyl] -propyl ester ' 5 5 0.06 1-O- (7-ethoxy-3,7-dimethyl-2-octyloxy) -phenyl] propyl- Caproic acid ester 10 10 0.4

Propionic acid 1- (4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl) propyl ester 5 7 199 378 0.8 Oleic acid 1-β- (7-ethoxy-3,7-dimethyl-2-octenyloxy) -phenyl propyl ester 5 10 0.1 Myristic acid 1- [4- (7-ethoxy-3,7-dimethyl-2-octyloxy) phenyl] propyl ester 1 10 0.1 Palmitic acid 1- (7-ethoxy-3,7-dimethyl-2-octyloxy) -phenyl] propyl ester Caprylic acid 1,4- (7-ethoxy-3,7-amino-2-octenyloxy) -phenyl propyl ester 1 0.5 10 0.06 0.5 1- | 4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) -phenyl] propyl stearic acid Acetic acid 1- (4- (7-alkoxy-3,7-dimethyl-2-octyloxy) phenyl) propyl ester 4 0.7 10 0.1 0.04 Acetic acid 1-iodo- (7-methoxy-3,7-dimethyl-2-oct-enyloxy) -phenyl] -propyl ester ⁴ 0.5 10 10 Reference substance: cis-10,11-epoxy-3,7, U-trimethyl-trans, trane-2,6-tridecadienic acid methyl ester 0,4 1 3

The object of the invention

Claims (2)

The object of the invention 1. An insecticidal composition based on insecticide regulating agents, characterized in that the active ingredient comprises juvenoid and juvenoidogenic compounds having an ester bond in a molecule of the formula I: R ¹ R ² / AB ³ / C-CH3 / CH2 / AC / R ⁴ Z ¹ / C / R ⁵ Z ² / - / CH2 / _b -CH / R ^6/0 • CH / R ^7/8 0C0R ( (I) in which: - the symbol a denotes an integer between 0 and 2 - the symbol b denotes 0 or 1 - h 1 R ² represents methyl or ethyl - the symbol r3 denotes: straight and branched chain alkyl having a total of no more than 6 carbon atoms, alkoxyalkyl and straight or branched chain having a total of no more than 6 carbon atoms, linear or branched straight chain alkyl of no more than 6 carbon atoms, straight or branched acyloxyalkyl of no more than 6 atoms carbon (cycloalkyl / alkyl of up to 6 carbon atoms, aralkyl of up to 9 carbon atoms) - symbols F ⁴ , R ⁹ , R ⁸ represent: hydrogen, methyl or ethyl - R ⁷ denotes straight or branched alkyl of up to 6 carbon atoms or phenyl 199 378 pins Τ 2 - the symbols Z, Z indicate: hydrogen or together form a double bond or in the case that a = 2, then Z ³ represents also alkoxyekupinu with a total of up to 6 carbon atoms Q - the symbol R represents: - substituent of formula: Z ³ - (H), where Z ³ , Z ⁴ is hydrogen or straight or branched alkyl of up to 5 carbon atoms, c is an integer ranging from 1 to 20 - substituent of formula: Z ⁴ - / CH ₂ / _and -CH = CH- / CH ₂ / _e wherein Z ⁴ is as defined above, d denotes an integer ranging from 0 to 10 - substituent of formula: 5 of ⁶ Z ⁵ - (CH ₂ ) _f - CH - where Z ^ denotes hydrogen or -COOZ ⁷ , Z ⁷ denotes hydrogen or straight or branched alkyl having a maximum of 4 carbon atoms, Z ® denotes hydrogen or methyl , f is an integer ranging from 0 to 2 - eubstituent of formula: * Z ⁴ - / CH / I ^e i ^& Kde O where the symbol z * is as defined above, the symbol Z denotes chlorine or bromine or the group -COZZ or the group Z ^3- ® - ⁿ ®b ° the group Jk - (CH-CH) - or the group -COOZ ⁷ , the symbol g denotes an integer ranging from 1 to 15, Z 'denotes straight or branched alkyl TO having a maximum of 6 carbon atoms, Z denotes hydrogen or chlorine or bromine or 7 TI 12 NO ₂ or -COOZ ', Z, Z denotes hydrogen or together form a double bond, h denotes 0 or 1, Z ⁷ denotes hydrogen or straight or branched alkyl having up to 4 carbon atoms. 2. A process for the preparation of the compounds according to claim 1, which comprises reacting a ketone of the formula II: R ¹ R ² / OR ³ / C-CH 2 - / CH 2 / a C / R ⁴ Z ¹ / -C / R ⁵ Z ² / - / CH 2 / _b -CH / R ⁶ / -O- CO-R ⁷ (II) wherein R ¹ to R ⁷ , Z ¹ , Z ² , a, b, are as defined above with lithium aluminum hydride in an anhydrous organic solvent inert to the reactants, e.g. to form an alcohol of formula III: 199 378 R ^L R ² / OR ³ / C-CH 2 - / CH 2 / a C / R ⁴ Z ¹ / -C / R ⁵ Z ² / - / CH 2 / _b -CH / R ⁶ / -O <^ Q ^> - CH (CH) -R ⁷ (III) wherein R 1 -R ⁷ , z 1, Z ² , a, b are as defined above, which reacts further with compounds of formula IV: R ⁸ -CO-Y (IV) wherein Y represents a hydroxyl group or chlorine or -COOR ⁸ and R ⁸ represents: Z ³ - (CH) or or Z ⁴ - (CH ₂ ) _and -CH = CH- (CH ₂ ) _e from ⁶ Z ⁵ - (CH ₂ ) _f -C = CH or Z ⁴ - / CH / _g wherein c is an integer ranging from 1 to 20; symbols Z ³ ? Z ⁴ denotes hydrogen or straight or branched alkyl of up to 5 carbon atoms, d, e denotes an integer from 0 to 10, Z ^ denotes hydrogen or -COOZ ⁷ , wherein Z ⁷ denotes hydrogen or straight or branched alkyl with a total of up to 4 carbon atoms, Z & denotes hydrogen or methyl, f denotes an integer ranging from 0 to 2, and 8 g denotes an integer ranging from 1 to 15; the symbol Z represents chlorine or bromine or the group / CH-CH3- or the group -CO2- or the group Z ¹⁰ 7 9 or the group -COOZ ', where Z ⁷ represents straight or branched alkyl and at most 6 carbon atoms, the symbol Ζ θ ^ is hydrogen or chlorine or bromine, 'or -COOZ -NOg or ⁷ symbols Z ^ Z ^ ² represents hydrogen or together form a double bond, the symbol h denotes 0 or 1 and the symbol Z ⁷ is hydrogen or straight or branched G alkyl β of up to 4 carbon atoms or Y and R together form _Z U _of 12 of ^13- oá ^ °° ^x o I 'or °° 0 where the symbols Z ^ ³ , Z ¹⁴ denote hydrogen or together form a double bond, the symbols i, j denote 0 or 1 ·