CS261142B1 - 4-(alkoxyalkoxy)phenylalkanoles with halogen in alkoxy group and their esters and method of their preparation - Google Patents

Description

The invention relates to 4- (alkoxyalkoxy) phenyl-alkanols with halogen in the alkoxy group and their esters as biologically active substances and to a process for their preparation.

The present invention provides 4- (alkoxyalkoxy) phenylalkanols with halogeno in the alkoxy group and esters of formula (I)

R OCH2CH2CH2 (CH3 O2)

?

CHRHxr (I) wherein symbol i

R @ ¹ denotes a straight or branched chain alkyl group having a maximum of 5 carbon atoms or a halo-straight chain or branched alkyl group having a maximum of 5 carbon atoms,

R ² represents hydrogen or alkyl with -alkylkarbonylskupinu straight or branched chain having up to 19 carbon atoms,

R ³ denotes a straight or branched chain alkyl having 1 to 3 carbon atoms.

The process for the preparation of 4 - (- alkoxyalkoxy, oxy, phenylalkanols with halogen in the alkoxy group and their esters) is characterized in that the keto compound of formula II

R ^OCH ^CHBrC ((II) wherein R ¹ , R ³ is as defined above) reacts with lithium aluminum hydride in an anhydrous diethyl ether environment to form a hydroxy compound (Formula I, R ² denotes hydrogen), which in turn can be reacted with a straight or branched chain alkyl acid of up to 19 carbon atoms in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide at a temperature of 10 to 20 ^and C, or by reaction with an organic acid chloride or anhydride in the presence of anhydrous pyridine at 20 to 60 ° C.

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

Example 1

A solution of 0.32 g (0.001 mol) of 4- (2-bromo-3-methoxy-1,1-dimethylpropoxy) -piropiophenone in 5 ml of anhydrous diethyl ether was added dropwise at 10 to 20 ° C with stirring and free of atmospheric humidity. a suspension of 40 mg of lithium aluminum hydride in 10 ml of anhydrous diethyl ether, the reaction mixture was then heated to reflux for 30 minutes, after cooling with ice water and diluting with diethyl ether, the unreacted ice hydride was decomposed with stirring, The separated ether layer was washed with saturated sodium chloride solution, dried over anhydrous MgSO 4, and evaporated under reduced pressure. column chromatography on silica gel with 8 h-wt% water (eluent petroleum ether-diethyl ether containing up to v / v diethyl ether) to give 0.29 g (88%) of chromatographically pure 1- (4- / 2-) bromo-1,1-dimethyl-3-methoxypropoxy / phenyl) -1-propanol.

IR analysis (CClI4, 5%):

618 (in OH),

834 (in -C-H in OCH 3),

612, 1 586, 1 51-5 (arom.),

463 (<J _as C-H3 in OCH3),

394, 1383, 1369 ($ _s CH3) cm ^-1 .

MS analysis:

-330/2 (M ⁺ ), (C 15 H 23 O 3 Br), 312/4 (C 15 H 21 O 2 Br),

301/3 (C 13 H 16 O 3 Br).

NMR analysis ( ¹³ C, 200 MHz):

10.15 (CH 3 CH 2), 22 .18 and 23.76 [(CH 3) 2 Cl 2,

31.76 (CH2),

49.90 (CHBr)

(OCH3)

69.80 (CH2OCH3)

75.55 (CHOH),

76.20 [C (CH3) 2]

114.70,

127.21,

137.33,

1-57.65 (arom. C).

1- (4- (2-Bromo-1,1-dimethyl-3-ethoxypropoxy) phenyl) -1-propanol was prepared in the same manner.

11

Example 2

0.36 g (0.0011 mol) of 1- (4- / 2-bromo-1,1-dimethyl-3-methoxypropoxy / phenyl) -1-proipanol, 0.17 g (0.001 mol) of decanoic acid, 22 g (0.0011 mol) of dicyclohexylcarbodiimide and 0.01 g (0.0001 mol) of 4-dimethylaminopyridine were stirred in 5 ml of anhydrous diethyl ether at 15-20 ° C for 2 hours. Then the reaction mixture was diluted with diethyl ether, filtered and the filtrate was washed successively with 5% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution, and the ether layer was dried over anhydrous magnesium sulfate and reduced in vacuo. The residue was then separated by column chromatography on silica gel with 8% by weight of void (eluent: petroleum ether containing up to 20% by volume of diethyl ether) to give 0.31 g (65% of 1- (4- / 2-) by volume. bromo-1,1-dimethyl-3-methoxypropoxy / phenyl) propyl decanoate;

IR analysis (CCU, 5%):

835 (v _with CH3 in OCH3),

737 (in C-O ester, j,

614, 1 588, 1 517 (in Arorn.),

393, 1383, 1369 _[<S (CH3) 2 gem.) Cm ^-1. MS analysis:

484/6 (M ⁺ ), (C 8 H 11 O 2 Br),

301/3 (C 13 H 18 O 3 Br).

¹³ C-NMR analysis (200 MHz):

22.17 and 23.77 [(CH 3) 2 C],

31.84 (CH 2 CH 3),

49.91 (CHBr).

58.82 (OCH3)

69.74 (CH2OCH3)

76.22 [G (CH3) 2]

76.75 (CHOCO)

114.127.96,133.40,

157.82 (Car.), 173.23 (OCO),

34.63 (OCOCH 2)

25.00 (OCOCH2CH2)

29.10 [OCO (CH 2) 2 CH 2],

29.23 [OCO _i (OH2) 3CH2]

29.23 [OCO ^! (CH 2) 4 CH 2],

29.16 [OCO (CH 2) 5 C'H 2],

29.39 [OCO (CH 2) 6 CH 2],

22.64 [OCO (CH 2) 7 CH 2],

14.09 [OCO (GH2) 8CH3].

Biological effects were monitored:

in termites, where it was found to affect soldiers and white soldiers, to influence the representation of castes and the resulting self-sufficiency and colony disappearance, as well as to detect overall development retardation, Dysdercus cingulatus, cotton pests, Tetranyqhus urticae spider, major economic pest, at the Varrca jacobsoni Oudemans rooted on the colony.

9.98 (CH3), Object of the invention

Claims (2)

1. 4- (alkoxyalkoxy) phenylalkanols with halogen in the alkoxy group and their esters of the general formula I R ¹ OCHXHBrC CHR ^ OR (I) where symbol R ¹ represents an alkyl group straight or branched having up to 5 carbon atoms or a haloalkyl group with a straight or branched chain having up to 5 carbon atoms, R ² is hydrogen or R₄ is alkyl straight or branched having up to 19 carbon atoms, R ³ denotes a straight or branched chain alkyl having 1 to 3 carbon atoms. 2. A process for the preparation of 4- (alkoxyalkoxy) phenyl-alkanols with halogen in the alkoxy group and their esters of formula (I) according to claim 1, characterized in that the keto compound of formula (II) COR ³ (n) wherein R ¹ , R ³ is as defined above, reacts with lithium aluminum hydride in an anhydrous diethyl ether environment to form a hydroxy compound of formula I wherein R ² is hydrogen, which optionally reacts with an organic acid with an alkyl straight or branched chain having a maximum of 19 carbon atoms in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide at 10 to 20 ° C, or with an organic acid chloride or anhydride in the presence of anhydrous pyridine at 20 to 60 ° C. Severography, n. Race 7, Most Price 2,40 Kčs