DE1618946A1 - New organic compounds and processes for making new organic compounds - Google Patents

Description

PATENT LAWYERS

dr. W. Schalk dipl-ing. P. Wirth · dipl.-ing.G. Then ε ν berg

DR.V. SCHMIED-KOWARZIK ■ DR. P. WEI NHOLD · DR. D. GUDEL

6 FRANKFURT AM MAIN

GR. ESCHENHEIMER STBASSE 39

ZOECOIT CORPORATION 975 California Avenue PaIo Alto, California / USA.

New organic ver >> in fertilizers and processes for the production of new organic compounds

SK

Ga.se PA 264/5

/ 6 Gocip.

The present invention relates to new chemical processes for the production of new organic compounds and for the new organic compounds produced in this way.

The present invention particularly relates to methods for the production of new long-chain hydrocarbon solids, acids and alcohols (and esters and ethers of the same), -amides, halides, amines and phosphonates used in the Basic hydrocarbon chain containing 12-17 carbon atoms, and to certain unsaturated and substituted or otherwise molecularly modified derivatives of these, which can be represented by e fol ^ '.- riöe i'ormel (A):

Ϋ f -

Et '' -C - GH - (GH,) - Ό - GH - (GH) - C - CH - R

ζ ¹¹ ζ ¹ ζ ⁷ ζ ⁶

BAD ORIGINAL 209824/1184

I I! I I I

ζ ¹¹ ζ ¹ ζ ⁷ ζ ⁶ ζ ³ ζ ²

In the oxy formula.

ά stands for one of the groups -COR '', -CH ₂ OR ⁰ , -CJM ¹ R ⁸ , -CH ₂ X,

-CH ₂ NR ⁷ K ⁰ and -CH ₂ PO (OR ⁹ ) ₂ , where

R represents ./hydrogen or alkyl;

R ^{0 represents} hydrogen, alkyl or aoyl; ^r 7 ΡΪ

R 'and R each represent hydrogen, alkyl, hydroxyalkyl, alkyloxyalkyl, phenyl or, together with the nitrogen atom to which they are attached, represent pyrrolidino, iviorpholirio, piperidino, piperazino or 4- ^ft alkylpiprazino; R stands for AIk ^ l or Phcnjl; and

.X. is r'-ir "rom, chlorine or fluorine;

12 ^ 4
R, R, k and R each represent an itlky group with 1-6 carbon atoms;

Z stands for liquid or hydroxy; ¹ J stands for hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine

or, together with Z, for a carbon-carbon double bond between C-2,3, or one of the groups ^ U, J ^ CH ₂ ^ CCl ₂ and> CP ₂ ;
Z represents hydrogen, hydroxy, bromine, chlorine or fluorine;

Z stands for hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine

6th
or, together with Z, for a carbon-carbon

Double bond between C-6.7 or one of the groups ^ O, ^ CH ₂ , J>and> ÜF ₂ J

Z represents hydrogen, hydroxy, bromine, chlorine or fluorine;

11
Z stands for hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine or, together with Z, for a carbon-carbon double bond between C-1-0, 11 or one of the groups ^ · 0, / CH3, C

/ CH "

^and ' ^GF 2'> 209824/1 184

BATH ORIGINAL

and the acid addition salts of acids and amines.

The present invention is further directed to new compounds of formula (A) above, in which each of the radicals · R

(II ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X), R ¹ , R ² , R ³ , R ⁴ _? Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰

11
and Z has the above meaning, which, however, are still characterized by the following independent conditions:

1) Z ² is hydrogen when Z ^{3 is} hydrogen; Z

7 '1Ω

represents hydrogen when Z 'represents hydrogen; and Z represents hydrogen when Z represents hydrogen;

209 824/118
BATH ORIGINAL

η 7 8
2) With the proviso that R denotes -CNR'R

2 3

a) when Z is hydrogen, Z for hydrogen, a

Hydroxy or (lower) alkoxy group;

b) when Z and Z together form a carbon-carbon double bond, Z and Z 'together form a carbon-carbon double bond, R, R and R ^{3 are} methyl and R ⁴ (lower)

11
Denotes alkyl, Z denotes hydroxy, (lower) alkoxy, bromine, chlorine, fluorine or together with Z denotes one of the groups

>! H ₂ ,> CC1 ₂ or ₂

c) if Z and Z together form a carbon-carbon dop

6 7

pel bond, Z and Z together are a carbon-carbon double bond, R ¹ , R ^{2 are} methyl, R ⁵ (lower) alkyl and R ^ methyl, Z is hydroxy, (lower) alkoxy, bromine, chlorine * fluorine or together with Z for one of the groups

or> CF ₂ ; '

d) when R ¹ , R ² and R ^{3 are} methyl, R ⁴ "4-methylpentyl, Z ³ , ζ / and

11 7 'Ω

Z denotes hydrogen, at least one radical R 'or R

not for hydrogen; ■

e) when R ¹ , R ^{2 are} methyl, R ^{3 are} 4-methylpentyl, R ^{4 are} methyl, Z ³ , Z ⁷

11

and Z is hydrogen, at least one of the radicals R '

or R is not hydrogen; and

f) Z ² for hydrogen or hydroxy and Z ³ for hydrogen,

Hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or together

with Z for a carbon-carbon double bond between C-2,3, or for one of the groups ^ .0 or

209824/1 184

5) Provided that R -CH ₂ OR "means, is

a) if R, R, R and

each methyl, Z together with Z

7 6

a carbon-carbon double bond and Z 'and Z together form a carbon-carbon double bond

11 '

ten, Z for hydroxy, (low) alkoxy, bromine, chlorine, F.luor,

or together with Z or ^.

for one of the groups

: CH _O ,

2 '^ ^CC1 2

"1 9 ^ ¹ ! A 7

b) when R, R, R and R are each methyl, Z together with

J- ^ O mean, Z ⁵ for hydrogen, hydroxy, (low)

"" Alkoxy, bromine, chlorine, fluorine or together with Z for e ^ ne of the groups ü> 0, "^ CH ₂ , ^ CCl ₂ or

c) when R, R, R and R ^ methyl, Z 'and Z together are one Carbon-carbon double bond and Z and Z together represent a carbon-carbon double bond, Z stands for hydrogen, (lower) alkpxy, fluorine or together with Z for one of the groups J ^ O,

or
if

d) / R ¹ ,

and R ⁵ each methyl, R ^ (lower) alkyl, Z ■ water, 11

substance and Z denote hydrogen, Z ^D for (low) AIk-

oxy, bromine, chlorine, fluorine, or together with Z for one} of the groups HO, --CH ₂ , ^ CCl ₂ or

e) when R ¹ , R ² and R ⁴ "are each methyl, R ⁵ (lower) alkyl, | Z ^

11 "5 '

and Z is hydrogen, Z is (lower) alkoxy, bromine,

, 2

2
Chlorine, fluorine, or together with Z for one of the groups t> 0, ^ CH ₂ , i> CCl ₂ or ^

and Z together with Z respectively

2 09824/1184

f) when R ¹ , R ^{2 and R 5 are} each methyl, R ^{4 is} 4-methylpentyl, Z ⁷ and Z together form a carbon-carbon double bond

1110
and Z and Z together denote a carbon-carbon double bond, Z denotes hydrogen, hydroxy, (lower

p rig) alkoxy, bromine, chlorine, fluorine, or together with Z for one of the groups! ^ CH ₂ , ^ CCl ₂ or> CF ₂ ;

g) when R, R ² and R ^{4 are} each methyl, R ^{3 is} 4-methylpentyl,; z 'and Z together form a carbon-carbon double bond

1110 ^!

and Z and Z together form a carbon -carbon-dop-

_v denotes a bond, Z stands for hydrogen, hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or together with Z I stands _{for one of the groups> CH 2 , -HXl 2} or]> CF ₂ ;

h) when R ¹ , R ² and R ^{3 are} each methyl, R ⁴ (lower) alkyl ,! Z ⁵

2 '

and Z together is a carbon-carbon double bond

7 6

and Z 'and Z together form a carbon-carbon Ddppel-

11
bond, Z for hydroxy, (lower) alkoxy, bromine,

Chlorine, fluorine, or together with Z for one of the groups 2 ^ 0, ^ CH ₂ , ^ rCCl ₂ or> CF ₂ ; !

i) when R ¹ , R ² and R ^{4 are} each methyl, R ³ (lower) alkyl, Z ³

2
mid Z together form a carbon-carbon double bond

7 6

and Z 'and Z together form a carbon-carbon double bond mean, Z stands for hydroxy, (lower) alkoxy, bromine,

10
Chlorine, fluorine, or together with Z for one of the groups

or> -CF ₂ s

j) when R ¹ , R ² and R ^{3 are} each methyl, R ⁴ (lower) alkyl,

3 2

Z together with Z a carbon-carbon double pole

209824/1184

16189 ^ 6.

i 1110

bond and Z. and Z together form a carbon-carbon

7 '

substance double bond mean, Z 'for hydroxy, (low)

g I

Alkoxy, bromine, chlorine, fluorine, or together with Z for one of the groups ^ C-, ^ H ₂ ,> CC1 ₂ or> € F ₂ ; and J

k) when R ¹ , R ² and R ⁴ ″ are each methyl, R ⁵ (lower) alkyl,! Z ⁵

9 '

together with Z a carbon-carbon double bond

11 10 '

and Z together with Z together a carbon-carbon * -

7 '

fabric double bond mean, Z 'for hydroxy, (low)

Alkoxy, bromine, chlorine, fluorine, or together with Z for one

ί of the groups ^ 0, ^ CH ₂ , - ^ CCl ₂ or) CF ₂ ; j

_0 - ι

ti ς Ι

4) Under the gate exposure that R means -C-OR ^, ί stands

a) if R, R, R ^ and B7 are each methyl, 1 * and Z together

7 6 a carbon-carbon double bond, Z 'and Z to-

11 together a carbon-carbon double bond and JZ and Z together ^ X) mean, R " ³ for (lower) alkyl! With 2 to 6 carbon atoms;

b) when R ¹ and R ⁴ ″ are each methyl, R ² and R ^{5 are} each ethyl, Z ⁵

and Z together form a carbon-carbon double bond,

7 6
Z 'and Z together form a carbon -carbon double bond-

1110 ζ '

dung and Z and Z together denote jzO , R for hydrogen or (lower ^ alkyl with 2 to 6 carbon atoms;

c) when R ¹ and R ^{5 are} each methyl, R ² and R ^{4 are} each ethyl, Z ⁵

2 '

and Z together form a carbon-carbon double bond, 7 6 '

Z and Z together form a carbon-carbon double bond and Z and Z together mean Z ^ O, R- for water-

209824/118 4

1618346

substance or (lower) alkyl having 2 to 6 carbon atoms;

d) when R ¹ , R ² and R ^{5 are} each methyl, R ⁴ ethyl, 7? and Z ² "to-

7 ^! together a carbon-carbon double bond, Z 'and Z ⁶ together a carbon-carbon double bond and Z ¹¹ and Z ¹⁰ together> · 0, R ^ for hydrogen or

(lower) alkyl of 2 to 6 carbon atoms; !

e) when R ¹ , R ² and R ⁴ each add methyl, R ⁵ ethyl, Z ⁵ and Z ² to-

7 together a carbon-carbon double bond, Z 'and

Z together are a carbon-carbon double bond and * -Z and Z together are Ü ^ O, Rr is hydrogen or lower) alkyl with 2 to 6 carbon atoms;

f) if R, R ² , R · ⁵ and R ^{4 are} methyl, 7? and Z together one

7 6

Carbon-carbon double bond, Z and Z together

^ O and Z and Z together are ^ O, R ^p for (lower) alkyl having 2 to 6 carbon atoms; I.

g) when R, R, R- ^ and R ^ methyl, Z ^ and Z together are one

Carbon-carbon double bond m Z 'and Z ^ XO and

11 10
Z and Z together form a carbon-carbon double.

bond, R ^ for lower alkyl with 2 to 6 carbon atoms;

h) if R ¹ , R ² , R ⁵ and R ^{4 are} methyl, Z ⁷ and Z ⁶ together form a carbon-carbon double bond and Z ¹¹ and Z ¹⁰ |

together mean a carbon-carbon double bond, Z ⁵ for (lower) alkoxy, chlorine, bromine, fluorine or together with Z ² for the group Z ^

209824/1 184

i) when R-, R ² , R ^3. and R ^{4 are} methyl, Z ^{7 is} hydrogen and Z ¹¹

and Z together form a carbon-carbon double bond

tion mean, 7r for hydrogen, (lower) alkoxy, bromine

"2 *" ■ "■!" Chlorine, fluorine, or together with Z for one of the groups

^ O or ^ CH ₂ ;

j) when R ¹ , R ² , R ³ and R ^ each denote methyl, Z ⁷ denotes hydrogen and Z ^{denotes hydrogen, Z 3} denotes (lower) alkoxy, bromine, chlorine, fluorine, or together with Z one of the groups * ■ or - CH ₂ J '

khwhen R η-butyl, R ² , R ³ and R ^ are each methyl, Z 'and

each mean hydrogen, Z for hydrogen, (low)

2 'alkoxy, bromine, chlorine, fluorine, or together with Z for one

Carbon-carbon double bond or one of the gimpps "I.

¹ ^ O or 2 ^ CH ₂ ;

1) when R ¹ , R ² and R ^{3 are} each methyl, R ⁴ 4-methylpentyl, " ¹¹

7 6
Hydrogen and Z 'and Z together form a carbon-carbon

■ 2

substance double bond mean, Z * for hydrogen, (low)

Alkoxy, or together with Z for one of the groups

or

m) when R ¹ , R ² and R ^ are each methyl, R ^{5 is} 4-methylpentyl,

7 6
Hydrogen and Z ' and Z together form a carbon-carbon

) I.

substance double bond mean, Z ^ for hydrogen, (low)

₂
Alkoxy, or together with Z one of the groups ^ O ode

-CH ₂ ;

1 ·· ¹ ^ ρ!

η) if R ethyl, Ir and Z together form a carbon-carbon

7 6 ■

_# fabric double bond, Z 'and Z together form a carbon

209824/1184

_ 16189416

M> j

1110

Carbon double bond and Z and Z together are one

A carbon-carbon double bond denotes one of the radicals R ² , R ³ or R ⁴ for (lower) alkyl having 2 to ¹ carbon atoms;

o) when R is methyl, R (lower) alkyl, Z and Z together are one

7 6 'carbon-carbon double bond, Z' and Z together a carbon-carbon double bond and Z and Z

together mean a carbon-carbon double bond

th, one of the radicals R or R ² for (lower) alkyl having 2 to 6 carbon atoms; I.

p) if R ³ (lower) alkyl, R ⁴ methyl, Ί? and Z ² together

■ 7 mean a carbon-carbon double bond, Z and Z together is a carbon-carbon double bond

11 10
and Z and Z together form a carbon-carbon

1 P ■

Double bond mean one of the radicals R or R füif

j (lower) alkyl of 2 to 6 carbon atoms; j

q) when R ⁵ (lower) alkyl, R ⁴ methyl, 7? and Z ² together one

7 fi "■ ^:

Carbon-carbon double bond, Z 'and Z together

11 ^; a carbon-carbon double bond and Z water

1 ρ i ■

mean one of the radicals R or R for (low)

Alkyl of 2 to 6 carbon atoms; !

r) when R ^{5 is} methyl, R ^ (lower) alkyl, Z ⁵ and Z ² together form a hydrocarbon-hydrocarbon double bond, Z 'and Z together form a carbon-carbon double bond and

11 1 ρ

Z denotes hydrogen, one of the radicals R or R for

, (lower) alkyl of 2 to 6 carbon atoms;

209824/1184

- l g -

. ■ μ-;

s) when R ¹ , R ² and ^1, R ^{3 are} methyl, R ^ 4-methylpentyl, Z ³ and Z; ²

together a carbon-carbon double bond and Z 'denote hydrogen, Z for hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or together with Z for one of the! Groups JiO,.> CH ₂ , ^ ^CC1 2 P ^ er

t) when R ¹ , R ² and R ^{4 are} each methyl, R ^{3 is} 4-methylpentyl, | Z ³ and Z together form a carbon-carbon double bond

7 11

and Z 'are hydrogen, Z is hydroxy (low)

* λ -i

Alkoxy, bromine, chlorine, fluorine, or together with Z for j

2 »i

"■ one of the groups ^ 0, -XH ₉ , ^ CCl ₉ or XJF

u) when R ^{3 is} methyl, R ^{4 is} 4-methylpentyl, Z ³ , Z ⁷ and Z ¹¹ . respectively

1 2 i ¥ hydrogen, one of the radicals R or R is (lower) alkyl having 2 to 6 carbon atoms; v) when R ^{3 is} 4-methylpentyl, R ^ is methyl, Z ³ and Z are each hydrogen, one of the radicals R or R is (lower) alkyl with 2 to 6 carbon atoms \ • ζ η

w) if Z ^ and Z together form a carbon-carbon double bond, R ^ (lower) alkyl, Z and Z each water

7 11
substance and Z and Z each mean chlorine, one of the

Radicals R ¹ , R ² , R ³ or R ^{4 represent} (lower) alkyl having 2 to carbon atoms; and ■!

i Ο "Z ■

x) Z for hydrogen or hydroxy and Z ^ "for hydrogen, Hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or with

ο
Z together for a carbon-carbon double bond

between C-2,3 or one of the groups 2 ^ 0 or 20982A / 1184

V R ■

5) With the proviso that R is -CH ₂ NR 'R, stands

a) when R, R ² and R ^{5 are} each methyl, R ^ (lower) alkyl and Z ^ and Z are each hydrogen, 7? for (low),

Alkoxy, bromine, chlorine, fluorine or together with Z for one of the groups ^ O,> CH ₂ ,> CC1 ₂ or

1 P A *? 7th

b) when R, R and R ^ are each methyl, R - ^ (lower) alkyl, Z '

11 ¹ ^

and Z are each hydrogen, Z is (lower) alkoxy,

Bromine, chlorine, fluorine or together with Z for one of the groups

^ 0, ^ CH ₂ , ^ .CCl ₂ or> CF ₂ ; · J

c Γ when R ¹ , R ² and R ^{5 are} each methyl, R ⁴ (lower) alkyl, Z ⁵ * together with Z is a carbon-carbon double bond

11 '

mean, Z. for hydroxy, (lower) alkoxy, bromine, chlorine, fluorine

or together with Z one of the groups - == - 0, ^ or -CF ₂ ;

d) if R ¹ , R ² and R ^{4 are} each methyl, R ³ (lower) alkyl, T? -

2 I.

together with Z a carbon-carbon double bond and Z 'together with Z a carbon-carbon double bond

* -j alkoxy,

.bond mean, Z for hydroxy, (low) / bromine,

Chlorine, fluorine or together with Z for one of the groups> 0, "^ = CH ₂ , - ^ CCl ₂ or> CF ₂ ;

e) if R ^1,. R ² and R ^{5 are} each methyl, R ⁴ (lower) alkyl, Z ⁵

2
and Z together is a carbon-carbon double bond

10 11!

and Z and Z together represent a carbon-carbon double bond, Z ⁷ for hydroxy, (lower) alkoxy, bromine, j chlorine fluorine or together with Z for one of the groups ^ tO,

5 ^ CHo, "CC1" or -CF ₉ ; and ;

together with Z a carbon-carbon double bond

^Z 209824 / 11-8 4!

f) when R ¹ , R ^{2 and R 4 are} each methyl, R ³ (lower) alkyl, Ί?

ο !

and Z together is a carbon-carbon double bond

11 1Ω!

and Z and Z together represent a carbon-carbon double bond, Z ¹ for hydroxy, (lower) alkoxy, bromine, chlorine,

Fluorine or together with Z for one of the groups ^ 0,: CC1 ₉ or ^

6) Provided that R is -CH ₂ X, a) when R ¹ , R ² and R ^{5 are} each methyl, R ⁴ (lower) alkyl, 'Zj'

11 ¹⁵ S '

Hydrogen and Z denote hydrogen, Z ^D denotes (low ¹ ) AIk-

o I oxy, bromine, chlorine, fluorine or together with Z for one of the groups ^ 0, ^ CH ₂ , ~ ^ CQ, 1 ^ or ^ CF ₂ ; b) 'when R ¹ , R ² and R ^{4 are} each methyl, R ⁵ (lower) alkyl, Z

Z each mean hydrogen, 7? for (lower) alkoxy,

2
Chlorine, fluorine or together with Z for one of the groups

or

and bromine, 0,

c) when R, R and R * are each methyl, R ⁴ (lower) alkyl, Z

2
and Z together is a carbon-carbon double bond

7 6 '- ■ I

and Z 'and Z together form a carbon-carbon double? -.

11

bond, Z for hydroxy, (lower) alkoxy, bromine,

10 ■

Chlorine, fluorine or together with Z for one of the groups '' ^ CHr ,, ^ CCl ₂ or -

d) when R ¹ , R ² and R ^{4 are} each methyl, R ³ (lower) alkyl, Z ³

and Z together is a carbon-carbon double bond

7 6!

and Z 'and Z together form a carbon-carbon double

1 1

education mean, Z for hydroxy, (lower) alkoxy, bromine, "

209 824 / t184

Chlorine, fluorine or, together with Z, one of the groups ^ tG, ι > CC1 ₂ or ^ CF ₂ ; ■:]

e) when R ¹ , R ² and R ^{5 are} each methyl, R ⁴ (lower) alkyl, and Z together form a carbon-carbon double bond

1 1 10:

and Z and Z together form a carbon-carbon double

bond, Z 'for hydroxy, (lower) alkoxy, bromine, j Chlorine, fluorine or together with Z for one of the groups ^ O,

: CC1 _O or ^ = CF ₀ ; and J

f) when R ¹ , R ² and R ^{4 are} each methyl, R ³ (lower) alkyl, Z ³

2!

together with Z a carbon-carbon double bond

11 10 *

and Z together with Z is a carbon-carbon double bond mean, Z 'for hydroxy, (lower) alkoxy, bromine, chlorine,

6 - I.

Fluorine or together with Z for one of the groups ^> 0 _t

j or> CF ₂ .

209824/1184

In the above definitions, the term "(lower) alkyl means straight or branched chain ¹¹ aliphatic ^ hydrocarbons having 1-6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl including the various isomeric forms thereof. The (low) · Alkoxy groups are straight-chain derivatives of identical length. The term "(lower) hydroxyalkyl" refers to a (lower) alkyl group as defined above which is substituted with one or two hydroxy groups. Typical (lower) alkoxyalkyl groups include methoxymethyl, 2-methoxyethyl, 4- - & thoxybutyl etc. The acyloxy groups herein are derived from the corresponding hydrocarbon carboxylic acids having 1-12 carbon atoms and have a straight, branched, cyclic or cyclic-aliphatic chain structure, saturated, unsaturated or aromatic and optionally by groups such as hydroxy, alkoxy with up to 5 carbon atoms, acyloxy groups with up to 6 carbon atoms atoms, nitro, amino, halogen groups, etc. can be substituted. Typical esters include formate, acetate, propionate, enanthate, benzoate, trimethyl acetate, tert-butyl acetate, phenoxyacetate, cyclopentyl piopionate, aminoacetate, S-chloropropionate, adamantoate, etc.

The entire chemical conversion according to the present invention The following equation can generally be used to describe the various levels:

20 98 2 U 118A

Ϋ R ²

R ⁴ -G ΠΗ- (ΠΤΤ ₂ ) ₂ - C ΠΐΤ- ₂ ^

(i-h)

■ ζ 2 1

R ³ RR

R ⁴ -C -CH- (CH ₂ ) ₂ -C-GH- (CH ₂ ) ₂ -C -CH-R

ζ ¹¹ ζ ¹⁰ z ⁷ z ⁶ z ⁵ z ²

(A)

In the above formulas have R (Ε '*, R, R ⁷ , R ⁸ , R ⁹ and Χ), R, R, R ⁵ , R ⁴ , Z ² , Z ^, Z, Z ⁷ , Z ¹⁰ and Z ^{11 has} the above meaning. The dashed line between each pair of carbon atoms of the basic chain in formula (ih) means that either a carbon-carbon single bond or a carbon-carbon double bond can be present independently of one another.

According to the above transformation and the inventive ^ emassen new The method is the ketone via certain, arbitrarily carried out, preferred conditions described in more detail below in the Corresponding hydrocarbon esters, acids, alcohols (their esters and ethers), amides, halides, amines and phosphonates reversed. The molecule is in any order and up formed into various substituted and / or unsaturated derivatives to the required and desired extent.

According to the above conversion and according to the preferred ones according to the invention Conditions is the starting ketone (i-h) with a Garbalkoxymethylphosphonat, preferably a diethyl or dimethyl carbalkoxymethylphosphonate, in the presence of an alkali metal hydride, e.g. Sodium hydride to form the corresponding ester der i'Ormel (A; treated, in which R for the Ji-uf: u> -oVR ", in the

209 824/1184 BAD ORIGINAL

R is alkyl.

The ester thus produced is made under mildly basic conditions hydrolyzed to the corresponding acid of formula (I), in which

Il c c;

R stands for the group -GOR, in which R is hydrogen, or it can be reduced, e.g., with lithium aluminum hydride, etc., to the corresponding alcohol of formula (A) in which R stands for the group -GHp-OR, in which R is hydrogen ". The subsequent usual esterification and etherification gives the corresponding esters and ethers of these alcohols, so that R denotes acyl "or alkyl.

The esters prepared in the manner described above also serve as precursors in the preparation of the hydrocarbon amides according to the invention. Sin customary process for their preparation is carried out by treating the ester with a selected amine salt ^ prepared by treating the selected amine, for example such as ammonia or a di- or monosubstituted amine (so that R and / or R have a meaning other than hydrogen) with a Alkali metal alkyl reagent, preferably butyllithium, in an organic solvent such as hexane, for example in Journ.Am.Chem.üoc. §O _t 2850 (1958) described V / eisey, preferably in ether (or a similar, inert, organic solvent) and at room temperature, as a result of which the corresponding amide of the formula (A) is obtained immediately thereafter, in which

0 7 8

K stands for the group n _Mr , 7-r, 8, where R and R are the above

—U DJ K xl

Have meaning.

BATH
209 8 24/11: 8 A.

The starting ketone (ih) can also be treated with vinylinagnesium bromide in an inert, non-aqueous, organic solvent to form the 1-en-1-ol, and so on _; : The formed £ rol is then rr. with a fho ^ phortrihalide, such as, for example, 3.

Phosphorus trichloric ¹ and phosphorus trichloride, in "hasic solution, as it is created by pyridine, l'riathy larain, etc., converted to the corresponding halide of the .Formula (A), in which H stands for the group -CHp-X, where X is prom or chlorine.

The 1-fluoro compounds are made by treatment of the 1-bromo derivative thus obtained with aluminum fluoride or silver fluoride in an inert organic solvent.

The 1-chloro compounds thus obtained are used to prepare the corresponding amines of the formula (A) used, in which R

7 ^a

for the group -CH-, NR R stands by adding a selected Amine, e.g. ammonia or a di- or monosubstituted

7 ft *

ten amine (where R and / or R have a different meaning than water / 3toff /) treated.

The disubstituted phosphonates thereof are prepared by treating the 1-halides, preferably the bromides, with a trialkyl phosphite or triphenyl phosphite in an inert, organic solvent, preferably at temperatures above about "TOO ⁰ C".

Although for the preparation of the compounds according to the invention preferred methods have been described, certain other methods can also be used.

209824/118 BAD ORIGINAL

For example, the above-mentioned starting ketone can also be used with a dialkyl cyanomethylphosphonate to the corresponding hydrocarbon-2,6,10-triene-1-cyanide (llitrile) to be treated * This compound can then be converted into the acid, ester and amide in a known manner being transformed. The amines can also be converted into the Stoire or the acid halide by known conversion of the corresponding ester of the same, the acid halide, in particular the chloride, being preferred. The acid halide will then treated with a selected amine in a non-aqueous, inert solvent, usually at or around room temperature and gives the amide. The amines can be prepared from the amides by conventional reduction, and the chlorides can be used as Precursors for the ethers and amides are used. How later also mentioned, can for the preparation of the compounds according to the invention other known or obvious methods can also be used.

The molecule of the esters, acids, alcohols (and their esters and ethers) so produced amides, halides, amines and phosphonates with a hydrocarbon backbone eventually came over preferred conditions and reaction sequences further developed

p -ZC

>> between are converted (see formula (A), groups Z , Z, Z, Z ⁷ , Z ¹⁰ and Z ¹¹ ).

for a compound «η with an oC, ß-unsaturated carbonyl system, ie the esters, oururs and amides, the addition of a fused!« • ethylene (cyclopropyl) group can be carried out selectively at C-2,3 by using the unrosc ■ tti _e -th compound with dimethyl sulfoxonium-

209824/1184 BATH ORIGINAL "

-J ₀ -

methylide base (prepared according to Journ.Am.Chem.Soc. J37_, 1353 (1965) converts it into dimethyl sulfoxide. The addition is annelated Methylene group at C-6.7 and C-10.11 for these compounds or at C-2,3, C-6,7 and / or C-10,11 for compounds which are not Oi, ß-unsaturated Containing carbonyl system, i.e. the alcohols, amines, halides and phosphonates, takes place after the corresponding reaction unsaturated bonds with methylene iodide and a zinc / copper pair according to Journ.Am.Chem.Soc. 8_1_, 4256 (1959) ·

A preferred method for the selective preparation of the 2,3-methyleneamines takes place through selective formation of the 2,3-methylenamides in the manner described above and subsequent reduction thereof, e.g. with lithium aluminum hydride etc., to the corresponding 2,3-methylenamines.

In a similar way, the formation of the epoxide takes place selectively at C-2,3 of the ß, ß-unsaturated carbony compounds by reaction with hydrogen peroxide in an aqueous alkali medium such as is usually created by sodium hydroxide. The addition of the Oxido-ßruppe at C-6.7 and C-10.11 of the oC, ß-unsaturated carbonyl compounds or at C-2,3, C-6,7 and / or C-10,11 for compounds without the oC, ß-unsaturated carbonyl system takes place with m-Chloroperbenzoic acid, preferably in methylene chloride or Chloroform solution.

The fused difluoromethylene group at C-6.7 and C-10.11 of the o (, ß-unsaturated carbony! Compounds is added by adding the starting monoene or diene with trimethyltrifluoromethyltin in the presence of sodium iodide in a benzene / mono ^ lym solution

209824/1184

BATH ORIGINAL

at reflux within a few hours, reacts * By varying the MoI ratio a of the "two reactants and the Reaction temperature and time, the reaction with respect to dea one or the other llonoadducts and dea bia adducts are favored The G-2,3 position is not attacked - auasar under more severe conditions.

For compounds without the 0C, ß-unsaturated carbonyl system the fused bifluoroethylene group at 0-2.5, G-6.7 and / or G-10.11 added according to the method described above, with a Inheritance of the molar ratio a of the reaction components and the Reaction time, and temperature the addition of one or the other Determine monoadduct, bisadduct or trisadduct.

The following applies to the addition of the fused dichloromethylene group that narrowed for the difluoroethylene addition. The dichloroethylene group is introduced into the corresponding monoene, diene or triene with phenyldichlorobroeaethylmercury in benzene Reflux for 1-5 hours. Again the relative varies Yield dea; one or the other monoadduct tea, bieadduktea and Triedduktes (for compounds without oC $ ö -unsaturated carbonyl • ystem) with the amount of Queokeilberrea ^ ena and the applied Reaction conditions. Usually supplies about, an "olaree Equivalent or about a more the monoadducts the biadducts are favored by using τοπ two or more equivalents and the tried duct is favored by using 5 or more equivalents.

BATH ORIGINAL
2Q9824 / 1TS4

a *

The hydrogenation of one or more double bonds into the corresponding saturated (carbon-carbon single bond) Bonding (Z -Z »hydrogen, Z» z '»hydrogen, Z» Z »hydrogen) is expediently carried out in Benaol over a 5-% palladium catalyst on carbon, with halogen atoms being reformed or introduced later if necessary, as described later.

The hydroxyl, (low) ilkoiy, bromine, chlorine and fluorine groups at one or more positions of the basic chain according to the above Definitions relating to formula (A) are introduced through various methods.

In the C-2,3 position, the monohydroxy substituent on C-3 (Z »hydrogen, Z» hydroxy) introduced by first being selective forms the 2,3-oxido derivative in the manner described above and then the ring by treating old a mole or less Lithium aluminum hydride under mild conditions, e.g. at temperatures from 0 C to about 30 C for a few minutes, 8.B. approximately ■ »5-30 minutes, opens.

In the taurus and acid series of the compound, the above gives Ring opening of the corresponding · 1,3-diol and 2,3-0xido-1-pl | therefore, in this series are the 3-monohydroxy compounds produced via a Reforaatsky reaction carried out on a K * tonauegang »v * r connection (v§-l. S * B. d $« U3-P »tentachrift 3 031 481),

BAD ORIGINAL 209824/1184

114

The bis-2,3-dihydroxy connections are made by treatment of the 2,5-oxido derivative with 0.1- "to Ο, ΟΟΙΗ-perchloric acid in aqueous solution at room temperature for about 16 hours. The Z-hydroxy-J- (lower) alkoxy compounds are produced by similar catalytic treatment of epoxy with perchloric acid in the presence of an alkanol. The 2-hydroxy-3-halogen compounds are produced by treating the 2,3-epoxide with bromine ^, chlorine or hydrogen fluoride, where "at the ^ -Halo & engruppe is the halogen of the acid used.

The C-6.7 and 0-10.11 positions are also formed in a similar manner. The monosubstituted derivatives at each of these positions (Z and / or Z ° »hydrogen, Z 'and / or Z = other than ffassez ^- substance) are prepared by treating the mono- or diene with aqueous formic acid or aqueous sulfur

7 11

acid to form the monohyaroxy compounds (Ζ and / or Z ■ * ■ hydroxy). The monohalogen compound at each position (Z 'and /

11 3

or Z »halogen and Z for compounds without o ^ ß-unsaturated Carbonyl system) is produced by similar treatment of the unsaturated "bond with bromine, chlorine or hydrogen fluoride, the halogen substituent being that of the acid used is. .-V-

Is used in this reaction in the 6,10-diene or 2,6,10-Irien-Heihe uses a halogenated hydrocarbon solvent with a low dielectric constant, such as carbon tetrachloride, so the mono-11-halogen adducts are favored. By use another solvent, e.g. an ether such as diethyl ether, orK-for a hydrocarbons, e.g. "Penzene" is

209 824/1184 BAD ORIGINAL

and each of the 0-2.5, C-6.7 and C-10.11-2) double bonds is halogenated to some extent, depending on the reaction conditions. So the 3-halogen, 7-halogen,

I 11-halogen-, 3,7-dinalogen-, 3,11-bihalogen-, 7,11-dihalogen- and 3j | 7 »11-trihalogen adducts, with the C-2,3-position not reactive in the c (, ß-unsaturated carbonyl compounds is.

The bishydroxy derivatives at each position (Z = Z «hydroxy and / or Z « Z «hydroxy) are prepared from the corresponding precursor epoxide (introduced in the manner described above) with an aqueous acid in the manner indicated above. * The use of a dry alkanol solvent results in the corresponding 6 (10) -hydroxy-7 (ii) -alkoxy compounds. The procedures given above apply analogously to Ruch for the introduction of the 6 {10) -hydroxy-6 (11) «halogen-substituted substituents»

Be the preparation of the 6 (1O) -Brtm- and 6- (iO) -Chlor-7 (11) -hydroxyverbindungen becomes the unsaturated starting compound alt the corresponding amount of if-bromo- or H-chlorosuceinimide in an aqueous organic solvent such as dioxane. The corresponding 7 (1i) -alkoxy compounds are more similar Way prepared in the presence of a dry alkanol solvent. The use of hydrogen fluoride with the appropriate Without the starting oxido compounds, some of the 6 (10) -fluoro-7 (11) -hydroxy derivatives are obtained. Treatment of the same with an acidified alkanol solution provides the corresponding (low) Alkoxy compounds. Treatment of the 6 (10) -halo-7 (11) -hydroxy compounds with a diazo (low) alkane in Bortrii'luo-

209824/118 A BAD ORIGINAL

rid "at about O C. yields the corresponding 6 (1O) -halo-7 (11) -alkoxy derivatives.

The bi-halogen compounds at each of the C-6, 7 and G-10, 11 positions (Z -Z = halogen and / or Z = Z = halogen) are formed by treating the corresponding olefin with bromine, chlorine or fluorine in one chlorinated hydrocarbon solvents such as chloroform and. Methylene chloride. The starting olefin can be a monoene, diene or triene. The C-2, ^ position is not attacked by this reaction in compounds with the Of> ß-unsaturated carbonyl system.

The etherification of free hydroxyl groups takes place in a known manner Way, jo can e.g. use the corresponding hydroxyl groups Sodium hydride and then and with an alkyl halide, such as Ethylhromide, to form the desired (lower) arkoxy group ■ be traded. For the corresponding tetrahydropyran-2-yl and tetrahydrofuran-2-yl ether become 2-halo-tetrahydropyran and 2-halo-tetrahydrofuran are used. Acylation too is done in a known manner, e.g., by using an acid anhydride in the presence of an acid catalyst such as p-toluenesulfonic acid, or with an acid chloride in the presence a base such as pyridine and triethylamine.

In the above-described elaborations of the invention Connections make the relative sensitivities of the different Groups in relation to certain reaction conditions a certain sequence of the reaction stages necessary. Inventor therefore methylenation usually occurs originally on the trien. As mentioned, this can be done selectively.

'209 824/1184 BAD ORIGINAL

The remaining unsaturation is usually called next stage epoxidized. This is especially true for epoxidations at the C-2,3 position, for which it is expedient to have no halo substituent is present on the ürundkette. As the for the addition of hydrogen halides necessary acidic conditions, however, cleave the epoxy, it is preferred to use the oxide after such To initiate reactions if the epoxy is not necessary for the introduction of the hydroxy (alkoxy) -halogen-bis-substituent, etc. is.

Except for the above conditions for the oxo group will be the fused halomethylene groups are preferably introduced after the fused methylene and oxido groups are present as these responses are contractual with these groups.

After all of the work described has been completed, the hydrogenation of any remaining, unsubstituted double bond take place. When a tertiary halogen atom is introduced, the halogenation is expedient on the desired olefin isolated after the hydrogenation.

There are certain exceptions to the above general and preferred reaction sequences; by slight modification of the Reactions corresponding to the purpose desired in the desired preparation of the particular compounds according to the invention however, difficulties are overcome. These modifications, as a whole, are obvious to those skilled in the art from the manufacturing process specified here.

BAD ORIGINAL 209824/1184

set

The above-described overall preferred sequence for the preparation of the compounds according to the invention can of course be subject to modifications which are obvious and / or which emerge from the present application. These modifications are also the subject of the application. For example, * the starting ketone of the formula (ih) can originally be worked out in any way along the basic chain / cf. Z, Z, Z, Z, Z and / or Z in formula (A) _- /, and then the corresponding ester,! Acid, alcohol, amide, halide, amine and phosphonate is produced one of the final derivatives, for example, be carried out the ester, and diese.Verbindung can then converted to the corresponding other final derivative, for example, be converted to the alcohol "a such obvious modification is also true in the preparation of various other iodine ^ represented by formula (a \ J _t such as the acid formed to the alcohol, the amide formed sum amine, etc.

The presence of at least one and optionally two or free double bonds and the oxido, methylene and diholmethylene groupings in the compounds according to the invention enables the presence of geometrical *: iomers * in the configuration of these compounds; These feoinere occur with respect to the double bond of the oxy-methylene and alkali-methylene groups which connect the C-2,3, C-6.7 and C-10H carbon atoms. The isomers of the monoene series are cis and trans; in the diene series they are eis, cisj eis, trans j trans, eis and trans, trans \ and in the trien series

209 82A / 1184

there are 8 isomers; each isomer of each series is included in the present invention. Generally speaking, create the inventive method all forms and / or mixtures thereof and each isomer can be separated from the leaction mixture, from which they are made by customary processes due to their different physical properties and such as chromatography, including thin layer chromatography and gas / liquid chromatography.

The separation of these various geometric isomers can be carried out at any convenient point in the entire process take place. An advantageous and in particular synthetically evaluable point for the separation of isomers by chromatography etc. 'results at the end of each stage of the basic chain synthesis, as will be described in more detail below} or after each selective, forming addition reaction, such as the selective addition of the methylene group at C-2,3

The starting ketones (i-h) are known or can be according to known ones Process are produced. A suitable method for their production can be shown as follows »

209824/1 184

16189

.3 Ii "4

3
* -C = CH-

(Ia) JZJ ₃ P = CH-

(I-c)

H ⁺ / H ₂ O

R ⁴ - <

.1 (Id)

(I-e)

-C = CH- (CH ₂ ) ₂ -C = CH-

(I-f)

RR ⁴ -C = CH- (CH ₂ J ₂ -C = CH-

^ v

(I-g)

: - (CH ₂ ) ₂ -C • = ⁱ = ^aÄ CH- (CH ₂ ) ₂ - (

209824/1184

₁ 2
In the above. In the scheme, R, R, R and R have the meanings given above, the dashed line in formula (ih) shows the independent presence of either a double or a single bond; and the symbol φ stands for the phenyl group.

In the above reaction scheme (i-a ^ I-h) the selected

Dialkyl ketone (i-s.) In equal molar amounts, and preferably an excess of the Wittig reagent derivative of the form! (i-b) in an organic reaction medium, e.g. as is the case with dimethyl sulfoxide is created at reflux temperature to form the corresponding substituted Wittig reaction adduct of Formula (i-c) implemented.

In the above procedure, Wittig's reagent (i-b) is used by usual Process prepared (cf., for example, Advances in Organic Chemistry, Vol. I, pages 83-102; Quarterly Review, Vol. 16-17, pages 406-410; and Journ.Org.Chem. Z8, 1128 (1963) from the 4-jithylene ketal of a 1-halo-4-alkanone after treating it with triphenylphosphine, the phosphonium halide obtained being subjected to the action of butyl or phenyllithium.

The 4-ethylene ketal of i-halo-4-alkanone is obtained by subjecting the 4-keto compound with ethylene glycol in benzene in the presence of an arylsulfonic acid to a customary catalysis. The 1-halo-4-alkanol, in particular the 1-bromo derivative , can be prepared by known processes (cf., for example, German patent specification 801 276, Chem. Abstr. 4 ^, 2972h, Arch. Pharm. 295 , 896 (1960) Chem. Abstr. j £, 5470g). These processes are carried out under Treatment of butyrolactone with the desired

209824/1184

Alkyl alkanoate to form the corresponding o-acylbutyrolactone adduct. The treatment of the latter adduct with alkali metal halide, in particular sodium bromide, in aqueous sulfuric acid then gives the corresponding 1-bromo-4-alkanone. Thus, after treatment with ethyl acetate ^ -Acetylbutyroladone, which in turn is converted into 1-bromo-4-pentanone.

The hydrolysis of the Wittig reaction adduct (l-c) with aqueous Acid provided the free ketone (i-d)

By repeating the yifittig reaction just described the so formed ketone (i-d) with the Wittig-Seagens (l-e) (produced as already described), the corresponding ethylene ketal diene adduct (i-f) is obtained, which in turn with aqueous Acid hydrolyzed to the tetraalkyl-substituted bienone (l-g) is »which is also represented by the formula (i-h), among other things.

Subsequently, any hydrogenation carried out by a known or described process yields the corresponding monoene or saturated derivatives, which are represented, inter alia, by formula (l ~ ⁿ ).

bowerden according to the novel process according to the above general formula (a) together with their definitions of the attached groups and conditions, the new hydrocarbon esters, acids, alcohols, amides, halides, amines and phosphonates with 12-17 carbon atoms in of the hydrocarbon base chain, each of the positions G-3, 7, 11 containing an alkyl group (R, & , IT, K *) and t-omit the G-11 carbon atom is disubstituted. Farther

209824/1184 BAD ORIGINAL

each of the hydrocarbon base chain positions C-2 _{,; 5 r} 6,7 »10,11 can be worked out differently (Ζ, Ζ, Ζ, Ζ, .Ζ, Ζ); they are ', independently of one another, unsubstituted (Z group =, hydrogen) or substituted (Z groups have a different meaning than hydrogen) with various groups, including hydroxyl groups, (lower) alkoxy groups, bromine, chlorine and fluorine groups. According to the conditions mentioned, each pair of carbon atoms G-2,3, C-6,7 and C-10,11 can be linked by a single bond, a double bond or a fused group such as an oxido, methylene, dichloromethylene and Difluoromethyl group. Where the basic chain is formed by the addition of two or more halogen atoms, they are preferably identical.

The new compounds shown in this way can be further broken down by individual subclasses of compounds according to the following Formulas (A-1, A-2, A-3, A-4, A-5, A-6 and A-7) are given in which for the different groups (R to R, Z, Z, Z, Z, Z, Z and X) the above definitions and conditions apply.

1) In the ester series (formula A-1) contains the "alkyl" group of the ester moiety 1-6 carbon atoms.

R ⁴ - C - GH - (CH ₂ J ₂ -C-CH- (CH ₂ ) ₂ - C - GH - COalkyl Z ¹¹ Z ¹⁰ Z ⁷ Z ⁶ Z ³ Z ²

(A-1)

209824/1184

BATH ORIGINAL

2) From the S & oire-fieihe (Formula A-2) are the acidic Addition salts of the same included.

^ R ² R ¹ 0

R ⁴ - C - CH- (CH _{2) 2} - C - CH - (CH _{2) 2} -C-CH COH

z ¹¹ z ¹⁰ z ⁷ z ⁶ z ⁵ z ²

(A-2)

3) The compounds of the formula A-3 include the alcohols per se (R = i hydrogen), the ulsters of the same (R = acyl) and the zither of the same (R = ■ alkyl).

f f Ϊ

R ⁴ -C -.CH- (CH ₉ ) ρ -C-CH- (CH ₉ ) _9-0 -CH-CH ₉ OR ⁶

Il ^ά I I -ti ^

₇ 11 ₇ 10 ₇ 7 ₇ 6 ₇ 3 ₇ 2

(A-5)

4) The amides of Formula A-4 include those in which the amide

7 f \

group is unsubstituted (R -R »hydrogen), monosubstituted

7 B
is (one of the groups R and R is hydrogen) or is disubstituted (r '* R ^ meaning other than hydrogen).

^ R ² R ¹ 0

⁷ R ⁸

R ⁴ - C - CH - (CH ₉ ) ₉ -G-CH- (CH _p ) ₉ -G-CH- CHR ⁷ R

If ^ ^ t I I I

z ¹¹ z ¹⁰ z ⁷ z ⁶ z ³ z ²

(A-4)

^) The formula A-5 includes the hydrocarbon bromides, chlorides and fluorides.

, 3 2 1

Ii R R

R ⁴ - C - CH - (Cd.). -C-CH- (CH ₉ ) _? -C-CH- UH ₉ X

Il ^ ^ I I I I

₇ 11 10 7 6 3 μ

UU Ü U UU

(A-5)

209824/1184

6) The amines of formula A-6 include, as in the case of the amides,

7 Q

the primary amines (R = R «hydrogen), the secondary amines (one of the groups R and R is hydrogen) and the tertiary Amines (R = R = other meaning than hydrogen). Also included are the acid addition salts

Ϋ R ² R ¹

r4 _ £ _ _CH _ (gh) -C-CH- (CH ₉ ) ρ -C-CH- CH ₉ IIR ⁷ R ⁸

Il ^ά ^ II ^ ^ II ^

ζ ¹¹ z ¹⁰ z ⁷ ζ ⁶ z ³ z ²

(A-6)

7) The phosphonates of the formula A-7 can be the dialkyl phosphonates

(R eilkyl) be, in eichen, the alkyl group 1-6 carbon atoms

q contains, or the diphenylphosphonates (R = phenyl).

Ϋ R ² R ¹

R ⁴ - C - CH - (CH ")" -C-CH- (CH ₉ ) ₉ - C-CH- CH P0 (üR ⁹ ) ₉

Il ^ ^ II. * ■ * 1 i ^ *

z ¹¹ z ¹⁰ z ⁷ z ⁶ z ³ z ²

(A-7)

Typical new compounds of the above formula prepared according to the invention are those with the 3> 7 »11-1- ' ^r iniethj'ldodecane, 3,7111-trimethyltridecane and 3,11-dimethyl-7-ethyltridecane-round chain and the various Dehydro and substituted derivatives thereof. Further typical compounds are the 10,11-0xido-2,6-dienes, 6,7; 10,11-bisoxido-2-enes, 6,7-dichloro-10,11-oxido-2-enes, 7,11 -Dichlor-IO-hydroxy-Z-ene, 7,11-dichloro-2-ene, 11-hydroxy-2,6-dienes, 11- (lower ;-) alkoxy-2,5-dienes, 11-chloro- 2,6-dienes, 10,11-dichloro-2,6-dienes, 6,7; 10,11-letraohlor-2-enes, 10-hydroxy-11-chloro-2,6-dienes and the various

209824/1184 BAD ORIGINAL

6.7-10.11 and 6.7; 10, TI-methylene, -chloromethylene and -Difluoromethylene compounds, especially those of each series, which have the G-round chain specified above as typical.

As mentioned above, the acid addition salts are also the new Acids and amines according to the invention. These salts are produced by known methods. Typical salts include the potassium, sodium, calcium, aluminum salts etc. of the duur and the hydrochloride, citrate, tartrate, acetate, sulfate, Pamoate and similar salts of amines. In the above iteactions, which are characterized by acidic "conditions, the amines obtained as a product are used as their acid addition salts isolated. I) Ie neutralization of the reaction mixture The extraction of the product avoids this formation of salt.

The hydroxyl groups can also be esterified in the usual way etherified, and the esters and ethers thus obtained fall also under the present invention.

Also included are the various compounds formed as intermediate products in the formation of the halides, ie the hydrocarbon - !, 6,1O-trien-3-ols and the 6,7- and / or 10,11 -dihydro- or the 6, ¹ J, 10,11 -substituted derivatives thereof. These compounds can also be formed in the G-1,2-position in a manner analogous to the other positions in the molecule, the C-1 ^ double bond can be hydrogenated to form a saturated bond or to the corresponding 1,2- Dibroni-, 1,2-j) chloro- and 1,2-difluorocompounds halogenated errOr ,. The ΰ-1, ^ - l-uopel ^ indixng can aucli jur Bilßunr; one

2098-24 / 1 184

BAD ORIGJNAU

terminal "in" compound dehydrated (a triple bond between the 1- and 2-carbon atoms) or e.g. to Addition of an oxido, methylene, dichloromethylene or difluoromethyl group can be treated via the double bond.

The new hydrocarbon esters produced according to the invention, -acids, -alcohols (and their esters and i.ther), -amides, -halides, -amines and -phosphonates are arthropod growth and maturation inhibitors. They can grow or mature of members of phylum Arthropoda, especially insects, in the passage from one metamorphic stage to the next control metamorphic level. In the case of insects that move from the embryo stage to the larval stage and from there to the pupa stage and continue to switch to the adult stage, inherently

e.g.
the contact with an effective amount of a compound according to the invention in one of the first three stages causes the entry into the next stage of development, with the insect either repeating the passage through the current stage or dying. Furthermore, these compounds with insecticides show ovicidal properties and are therefore suitable for controlling them. The compounds according to the invention are extremely potent and can therefore be used in extremely small amounts, for example from 10 ~ to 10 g; they can be administered in an advantageous manner over large areas in the amounts suitable for the estimated insect population. Usually the substances are liquids and can be used in conjunction with liquid or solid carriers for the purposes described herein.

209824/1184 BAD ORIGINAL

-η-

Typical insects against which the compounds according to the invention are effective include mealworms, house flies, mosquitoes, cockroaches, moths, "cotton boll beetles", "cornborers" (Pyrausta unbilabis).

Without wishing to be bound by any theoretical explanation, the effectiveness of these derivatives appears to be based on their ability decrease the effectiveness of certain so-called "juvenile hormone" substances (See e.g. IS Patent 2,981,655 and Proe.Nat.Acad.Sei. yyy ^, 57 & (1966) * due to the high effectiveness of the compounds according to the invention As mentioned, they are used in extremely low concentrations in order to achieve them reproducible and predictable levels of effectiveness can be used.

The following examples illustrate the present invention, without limiting them. Although in any of the reaction stages the different isomeric forms may not be indicated * the carbon-carbon double bonds independently have the Gis or trans configuration, or isomeric mixtures can actually be used they used frequently.

Unless otherwise stated, examples are taken from the following all nuclear magnetic resonance (NMR) data from analyzes * in a "Varian HÄ-100" proton resonance spectrograph in perdeuterated Chloroform using tetraethylsilane as » Reference connection. These measurement methods are hereby referred to of the following KMH data of the individual compounds included in the present application.

209824/1184

BAD ORfGJNAL.

example 1 Part A

20 g of triphenylphosphine were added to a solution of 20.9 g of the ethylene ketal of 1-bromo-4-pentanone (prepared by treating i-bromo-4-pentanone with ethylene glycol in benzene in the presence of p-toluenesulphonic acid) in 100 ecm of benzene . The mixture was refluxed for 2 hours and then filtered. The ao collected solid material was washed with benzene added "in vacuo and dried to 6.49 E butyllithium in 50 com DimethylauXoxyd. This mixture was stirred, an orange solution was obtained, then 3.8 g of methyl ethyl ketone was added. This mixture was stirred for about θ hours at about 25 ° C., poured into water and this mixture was extracted with ether. The ethereal extracts were concentrated and the residue thus obtained was added to a 0.1N solution of hydrochloric acid in aqueous acetone and stirred for about 15 hours. Then the mixture was poured into ice water and extracted with ethyl acetate. After washing these extracts with water and drying over sodium sulfate, the mixture was evaporated to give a mixture of the cis and trans isomers of 6-methyl-5-octen-2-one, which was separated into the individual isomers by gas / liquid chromatography .
part B

The ethylene ketal of 4-ketopentylidenephosphorane was produced vegetable part k after reaction of the ethylene ketal of 1-bromo-4-pentanone with triphenylphoephine. 5 »5 g of trans-b-methyl - ^ - octen - ^ - one were added to the mixture containing the ttitti ^ reagent

209824/1184

BAD ORIGINAt

(the ketone obtained in Part A) was added and the obtained Mixture held, worked up and hydrolyzed as in Part A; thus became a mixture of the trans, trans and cis, trans isomers of 6,10-dimethyldodeca-5,9- * dien-2-one obtained by Gas / liquid chromatography into the individual isomers was separated.

By repeating the above procedure using instead of trans-6-methyl-5-octen-2-one cis -o-methyl-S-octen-1-one became a mixture of the cis, cis and trans, cis isomers obtained from 6,10-dimethyldodeca-5, f-dien-2-one, which was separated as above.

In the above process, a mixture of the isomers of 6-methyl-5-octen-2-one can also be used as starting material, where a mixture of the four isomers is obtained, which is defined by Gae / Liquid chromatography can be separated into the four individual isomers.

Example 2

A suspension of 0.5 g of 5 - $> igeni palladium-on-charcoal catalyst in 50 ecm benzene was hydrogenated for 30 minutes. A solution the end. 2 g 6,10_Dimethyldodeca-5, ^ - dien-2-one in 100 ecm benzene was added and hydrogenated with stirring until the theoretical amount of hydrogen had been absorbed. Then the Catalyst filtered off and the solution evaporated} were so 6,1O-dimethyldodec-S-en-S-one, 6,10-bimethyldodec-9-en-2-one and 6,10-dimethyldodecan ~ 2-one obtained by gas / liquid chromatography separated and cleaned.

209824/1184 BAD ORIGINAL

Following the above procedure, the various isomers des 6,10-dimethyldodeca-5,9-dien-2-one or mixtures thereof are hydrogenated.

Example 5

By repeating process A in Example 1 using the ketones listed under I instead of methyl ethyl ketone and using the resulting ketones in the procedure of Part B of Example 1, the corresponding products were made under II (including all possible isomers) obtained, each of which can be hydrogenated in Example 2.

I II

Acetone 6,10-dinothylundeca-5,9-dien-2-one

Diethyl ketone 6-methyl-10-ethyldodeca-5,9-diene

2-on

Methyl isopropyl acetone 6,10,11-trimethyldodeca-5,9-dien-2-one ethylnn-propyl ketone 6-methyl-10-ethyltrideca-5,9-dien-2-one Methyl tert-butyl ketone 6,10,11,11-tetramethyldodeca-5,9-dien-2-one

By repeating example 1, whereby (in part A) e.g. 1-bromo-4-alkanones of column III instead of 1-bromo-4-pentanone were used, the corresponding products listed under IV (including all possible isomers) obtained, which can be hydrogenated according to Example 2.

Ill IV

1-Bromo-4-hexanone 6-ethyl-10-methyldodeca- ₅ , 9-dien-2-one 1-Bromo-4-heptanone 6- (n-propyl) -10-methyldodeca-5,9-diene-2 -one 1-bromo-5-methyl-4-hexanone 6- (isopropyl) -10-methyldodeca-5,9-diene-

2-on

1-Bromo-5,5-dimethyl-6- (tert-butyl) -10-methyldodeca-5,9-4-hexanone dien-2-on

2 0 9 8 2 4/1184 BAD ORIGINAL.

1618940

By using the 1-bromo-4-alkanones listed in column JII in repeating the procedure of paragraph 1 of this Example was obtained: 6-Ethyl-10-methylundeca-5,9-dien-2-one, 6- (n-propyl) -10-methylundeca-5,9-dien-2-one, 6- (isopropyl) -10-methylundeca-5 »9-aien-2-one, 6- (tert-butyl) -1Ü-methylundeca-5,9-dien-2-one, 6,1O-I) iäthyldodeca-5j9-dien-2-one, 6- (n-propyl -) -10-ethyldodeca-5 »9-dien-2-one etc. These compounds can be hydrogenated as in Example 2.

The procedure of Example 1 was repeated, except that (in part B) instead of 1-bromo-4-pentanone those listed in column III 1-Bromo-4-alkanones were used. So were the following products obtained: Tjii-Dimethyltrideoa-ojiO-dien-S-one, 8,12-Dimethyltetradeca-7,11-diene-4-ση, 2,7,11-trimethyltrideca-6,10-diene-3-όη and 2,2,7 »11-tetramethyltrideca-6, IO-dien-5-one. These Compounds can be hydrogenated as in Example 2.

By repeating the procedure of this example mentioned in the first paragraph, using the 1-bromo-4-alkanones listed in column III instead of 1-broa-4-pentanone in part B of example 1, the following was obtained: 7 »11-dim ^e thyldodeca-6,1O-dien-3-one, 8,11-dimethyltrideca-7,11-dien-4-one, 2,7,11-trimethyldodeca-6,10-dien-3-one, 2.2 , 7,11-tetramethyldodeca-6,10-dien-3-one, 7-methyl-11-ethyltriaeca-6,10-dien-3-one, a-methyl-12-ethyltetradeca-7,1l- dien-4-one, 2,7-dimethyl-i1-äthyltrideca-6,1O-dien-3-one etc., Ήβ can be hydrogenated as in Example 2 *

209824/1184
BATH ORIGINAL

The procedure of the second paragraph of this example using the 1-bromo-4-alkanones listed in Column III in place of 1-bromo-4-pentanone in Part B of Example 1 provided :. 7-A.thyl-i i-methyltrideca-OjiO-dien- ^ - one, 8-üth.y 1-12-methyltetrade ca-6,11-dien-4-one, 2,11-dimethyl-7-ethyltrideca -6,10-dien-3-one _t 2,2,11 -Trimethyl ^ -athyltritf.eca-o, 10-dien-3-one, 7- (n-propyl) -11 -methyltrideca ^ jiO-diene- ^ -one, 8- (n-propyl) -12-methyltetradeca-7,11-dien-4-one, etc., which can be hydrogenated as in Example 2.

In repeating the procedures of this example using other ketones than those listed in column I, such as methyl-n-propyl ketone, methyl-n-butyl ketone, methyl isohutyl ketone, Ülethyl-n-butyl ketone, ethyl isopropyl ketone, methyl-n-amyl ketone, Ethyl-n-butyl ketone, 3-ethyl-2-pentanone, diisopropyl ketone, diethyl-hexyl ketone, 5-ethyl-3-heptanone, 4-deeanone, di-n-amyl ketone, Di-n-hexyl ketone, etc., and 1-bromo-4-alkanones other than them in column III are listed, such as i-bromo-4-octanone, 1-bromo-4-

φ,

nonanone, 1-bromo-o-methyiTkeptanon, etc., the present Example and Example 1 corresponding products are produced. These can be hydrogenated according to Example 2. Of course these processes provide the various isomers or mixtures thereof of the product compounds.

For the sake of simplicity in the procedures of the following examples each compound mentioned includes all isomers or isomeric mixtures, without these being specified in detail will. That is, the following examples show methods that are applicable to starting materials and products that each Include isomers or isomeric mixtures.

209824/1184 BADORiGlNAL

Example 4

A mixture of 11.2 g of dietary carathoxymethyl phosphonate in 1 cm of diglyme was treated with 2.4 g of sodium hydride. This mixture was stirred until the evolution of gas ceased, then 7> 5 g of 6,10-dimethylundeca-5 »9-oil were added. 2-one was slowly added with stirring, keeping the temperature below 30 C. The mixture was stirred for about 15 minutes, then diluted with water and extracted with ether. The ethereal extracts were washed well with water, dried over sodium sulfate and removed to remove The solvent was evaporated to give ithyl 3,7, ii-trimethyldodeca-2,6,10-trienoate ^ NMB .: 1.23 ppm (-OCH ₂ CH ₅ ); 1.57 ppm (7-CH ₅ + H-CH ₅ ); 1.64 ppm. (11-CH ₅ ); 2.11 ppm, doublet, J * 1.4 c / s, (3-CH ₅ ) I 4.08 ppm (-OCII ₂ CH ₅ ); 5.03 ppm (6-H + 10-H); 5.61 ppm (2-B) J, which was separated by gas / liquid chromatography.

Ethyl 3,7 »11-trimethyltrideca-2,6,10-trienoate and ethyl 3,11-dimethyl-7-fa.thyltrideca-2,6,10-trienoate from 6, TO-dimethyldodeca-5,9-dien-2-one or 6-ethyl-10-methyldodeca-5,9-dien-2-one manufactured.

By repeating the above procedure using Diiithylcarbomethoxymethylphosphonate became methyl 3,7 »11 -'trimethyl dodeca-Zjö.iO-trienoate, η = 1.4824, methyl 3,7,11-trimethyltrideca-2,6,10-trienoate and methyl 3,11-dimethyl-7-ethyl trideca-2,6,10-trienoate manufactured. The use of other dialkylcarbalkoxymethylphosphonates, e.g. diethyl n-propoxycarbonylmethylphosphonate, Dietary tert -butoxycarbonylmethylphosphonate etc., yields corresponding alkyl esters thereof.

20982A / 1184

BATH ORIGINAL

Geraass Rieses example can also use the corresponding esters of the other starting compounds prepared in "Example 1" to 3 getting produced.

Example 5

At O C., anhydrous hydrogen chloride was converted into 100 ecm carbon tetrachloride initiated until a saturated solution is obtained. 1 g of ethyl 3,7,1i-trimethyldodeca-2,6,10-trienoate was obtained added and the resulting mixture then hot for 4 days Left to stand at 0 C. The mixture was then evaporated under reduced pressure to an oil which was determined by column chromatography has been cleaned; this became ethyl 3,7> 11-trimethyl-11-chlorododeca-2,6-dienoate obtain.

Methyl 3>7-> 11 -trimethyl-11-chlorododeca-2,6-dienoate / NMR: 1.60 ppm (2x11-CH, + 7-CB,) was also prepared from the corresponding starting compounds; 1.70 ppm (-CH ₅ -CH ₀ -); 2.15, doublet, (3-CH,) i 3 _f bb ppm (-OCH,); 5.10 ppm (6-H)} 5.70 ppm

, as well as ethyl 3 »7» 11-trimethyl-11-chlorotrideca-2,6-dienoate, Ethyl 3t11-dimethyl-7-ethyl-11-chlorotrideca-2,6-dienoate, ethyl 3,7 »11-trimethyl-1i-chlorotrideca-2,6-dienoate and methyl 1-3,11-dimethy1-7-ethy1-11-chlorotrideca-2,6-dienoate.

The corresponding hydro-derivatives of the above compound, viz ethyl 3,7,11-trimethyl-11-chlorododec-2-enoate, ethyl 3,7,11-trimethyl-11-chlorododec-t) -enoate and ethyl 3> 7 »11 -trimethyl-11-chlorododecanoate were by hydrogenation of the triene prior to the chlorination according to paragraph 1 of Example 2, separation of the desired hydrogenated, at least the C-10,11 double bond containing compound and chlorination -itjrpolben in o ^ on

209824/118 4
BATH ORIGINAL

> Veise manufactured. Also the 11-hydroxy compound (see Example 7 below) was hydrogenated and the desired saturated compound isolated and, for example, with phosphorus oxytriochloride dehydrated in pyridine, where the 0-10 double layer obtained is called then how oheri was chlorinated.

"Example 6

^ ■ ei O'C. anhydrous hydrogen chloride was introduced into 100 ecm die-thylafcher, a saturated solution was obtained. For 3s 1 g of ethyl->, 11-dimethyl-Y-ath / ltrideca-Z, ό, 10-trienoate was added and the mixture obtained was then allowed to stand at 0 ° C. for 4 days.; Elas3en. Τνα .ηη the mixture under reduced pressure, an oil-au evaporated which was purified by silica chromatography urde ^;. was thus iibhyl-5,11-dime thyl-7, 11 receive dichloro-7-athyltridec-2-enoate.

By repeating the above procedure with methyl 3 »11-dimethyl-7-ethyltrideca-2, β, 10-trienoate, methyl 3,11-dimethyl-7,11-dichloro-7-ethyltridec-2-enoate was prepared. Furthermore, methyl 3,7 »11-trimethyl ~ 7» 11 -dichl.ordodec-2-enoate was prepared / NMR: 1.54 ppm (7-CH,); 1.59 ppm (2x11-OH ₃ ) J 1.71 ppm (-GH ₂ -OH ₂ -); 2.17 ppm (5-ÜH. + 4-CH ^) ι 3 ", & 9 ppm (-OCH ₃ ); 5.70 ppm (2-H) y; the corresponding ethyl ester was also obtained.

Following the same procedure, and a ^ gy separates the corresponding 7-monochloro compounds, such as , -. thy 1-3, 11-dimethyl-7-ghloro-7-iithyltrideoa-2,10-dienoate and the "tit.abrechende iiethyleater of the same.

209824/1184 BAD ORIGINAL '

■ Pei the Harstellung the corresponding hydrogenated derivatives of With chlorine compounds, it is "preferred over chlorination." au hydrogenate, vfohei the desired, isolated, unsaturated The product is subjected to such a chlorination.

Example 7

3 g of ethyl 3,7> 11 -fcrimethyldodeea-2,6,10-trienoat., Urden to a mixture of 30 ecm SQ-falger formic acid, 20 ecm water and 150 mg sodium formate added, the mixture obtained was stirred for 10 hours and then divided between water and ethyl acetate. The .athylace tat phase was washed approximately neutral with iVaseer, dried over sodium sulfate and evaporated under reduced pressure; thus ^ thyl-3,7j11-trimethyl-11 -hydroxydodeca-2,6-dienoate was obtained / NMR: 1.20 ppm (2x11-ÜH,) j 1, ^ 7 ppm triplet, J => 7 c / s, (-OCHpCH ^); 2.15 ppm »doublet, J» 1.2 c / s, (3-CH,) i 4 »14 ppm quartet, J = 7 c / s, (-UGH ₂ CH ₅ ); ^, 09 ppm (6-H) j 5.65 ppm (2-H) 7 and ethyl 3,7,11-trimethy1-7,11-dihydroxydodec-2-enoate _r n ^ ⁵ - 1.4762, Ι .Ά. _ητιηΊ »7610, / IiMR: 1.16 ppm

J) UXlL / It

(7-CH,) | - 1.21 ppm (11-CH ₅ ) J 1.26 ppm triplet, J «7 c / s,

j 1.43 ppm (-CH ₂ CH ₂ -); 1.71 ppm (2x0g), 2.13 ppm, 1.2 c / a, (3-CH,) j 4.13 ppm quartet, J = 7 c / s, gH,); 5.65 ppm (2-Hl / separated by chromatography.

In the same way, methyl 3.7-11-trimyl-H-hydroxyciodeca-2,6-dienoate / NMRi 1.20 ppm (2xT1-CH,) j 1.60 ppm (7-CH ₅ ); 1.86 ppm doublet, J-1.5 c / s, (3-CH, from 2-trana)} 2.16 ppm (3-CH, from 2-cis); 3.67 ppm (-üOH,) j 5.1 ppm (6-H); 5.66 ppm (2-H) _ / and the corresponding 7,11-dihydroxy compound obtained. iius the

209824/1184

BAD ORIGINAL ^

1518946

corresponding starting compounds were also the methyl and r.thyl ester of 3,7,11 -'Jrimethyl-i 1 -hydroxytrideea-2,6-dlenoate and 3,11-I »icEthyl-7- & thyltrideca-2,6-dienoate and the corresponding 7j 11-Dinydroxyver "prevent the same produced.

The 11-monohydroxy compounds can also be prepared as follows will:

6 g .-. Thy 1-3,7 »11 -trimethyldodeca-2,6,10-trienoate were dissolved in 250 ecm of dioxane and 150 cam of water, the solution was cooled to 10 ° C. and added dropwise with stirring with 4 S N- Bromosuccinimide treated. The mixture was stirred for 15 hours at about 25 ° C., then diluted with water, treated with sodium bisulfite and extracted with /.ther. The iitheric extracts were washed with water, dried over sodium sulfate and evaporated to an oil which was chromatographed on silica, eluting with 1% methanol in chloroform; so were obtained: Ethyl-3 '7> 11-trimethyl-10-bromo-11-hydroxydodeca-2,6-dienoate, ethyl-3,7 "11-t ^r imethyl-6 ~ bromo-7-hydroxydo.deca- 2,10-dienoate, and ethyl 5,7,11-trimethyl-6,10-dibromo-7,11-dihydroxyd.odec-2-enoate.

The use of a (low) alkanol solvent instead of the above materials dioxane and water provided the corresponding 7 (ii) - (HLieärig) -alkoxy compounds,, vie -methoxy-, -athoxy-, -propoxy, etc. The material mentioned can also be used for the production of the corresponding methyl ester derivatives as well as the Methyl and ethyl ester derivatives of 3,7,11-irimethyl-10-bromo-11-hydroxytridee <a.-2,6-dienoate and 3,11 -Dimethyl-7- ^ thyl - 10-T? romo-

20 9 824/1

BATH

11-hydroxytrideca-2,6-dienoate (and the 6-bromo-7-hydroxy-2,10-diene and 6, IO-Dibronio-7,11-dihydroxy-2-ene) can be used. Using N-chlorosuccinimide, the corresponding Ohlorhydrine made.

A solution of 2.8 g of ethyl 3>7> 11 -trimethyl-IO-bromo-i1-hydroxydodeca-2,6-dienoate in 50 ecm of ethanol was treated with a suspension of 5 »5 S for 2 hours at 20 ° C Baney nickel stirred in 5 ecm ethanol. The mixture was then filtered through celite-diatomaceous earth and the filtrate evaporated; in this way ethyl 3 »7> 11-trimethyl-11-hydroxydodeca-2,6-dienoate was obtained which was identical to the material prepared above and which can be purified by chromatography on silica and eluting with 1% methanol in chloroform.

The i? -Bromo-7-hydroxyderivate were also used to achieve the treated corresponding 7-hydroxy compounds.

Example 8

A suspension of 0.5 g ^ followers. Palladium on carbon catalyst in 50 com benzene was hydrogenated for 50 minutes. A solution of 2 g of ethyl 3 _f 7> 1 -1-trimethyl-i1-hydroxy-dodeca-2,6-dienoate in 100 ecm of benzene was then added and hydrogenated with stirring until the theoretical amount of hydrogen had been absorbed. The catalyst was then filtered off and the solution evaporated j so a mixture of ethyl 3,7 »11-trimethyl-11 hydroxydodee-2-enoate, ^ KMRj 0.85 ppm doublet, J = 6 c / e, (7- CH,); 1.19 ppm (2x11-CH,) 5 1.24 ppm triplet, J = 7 c / s, (-

209824 / 118A
BATH ORIGINAL

1.84 ppm doublet, J * 1.5 c / s (3-CH ₃ of 2-cis); 2.115 ppm, doublet, J = 1.2 c / s, (3-CH, from 2-trans); 4.10 ppm, quartet, - J = 7 c / s ,. (-OCH ₂ CH); 5.61 ppm (2-H) methyl-3,7,1i-trimethyl-11-hydroxydodec-6-enoate and ethyl 3,7,1i-trimethyl-11-hydroxydodecanoate obtained by gas / liquid chromatography separated and cleaned.

The use of the corresponding methyl ester gave methyl 3,7,11-trimethyl-11-hydroxydodec-2-enoate, Hethyl-3 »7» 11-trimethyl-11-hydroxydodec-6-enoate, ^ NAQl: 0.92 ppm, Doublet, J = 6 c / s, (3-CH ₃ ); 1.19 ppm (2XH-CH ₅ ); 1.57 ppm (7-GH ₃ ); 3.63 ppm '(-OCH ₃ ); 5.08 ppm (6-H ^ ⁷ and methyl-3,7, H-trimethyl-11-hydroxydodecanoate.

Example 9

1 chemical equivalent of diazouthane was added to 5 g of ethyl 3,7,11-trimethyl-11-hydroxydodeca-2,6-dienamide in 100 ecm of anhydrous ether. Then 1 drop of boron trifluoride was added and the reaction mixture was left to stand at 0 ° C. for 1 hour and then kept at room temperature for a further 2 hours. The mixture was then washed with water, evaporated and chromatographed; thus ethyl-3 »7» 11-i ^; riniethyl 11-athoxydodeca-2,6-dienoate obtained, / NMR »1.13 ppm (2x11-CH,) j 1.14 ppm, triplet, J-7 c / s, (11-OCH ₂ CH ₃ ); 1.26 ppm, triplet, J = 7 c / s, '(-COOCH ₂ CH ₃ ); 1.59 ppm (7-GH ₃ ); 2.145 ppm (3-GH ₃ ); 3.335 ppm »quartet, (11-0CH ₂ CH,); 4.125 ppm, quartet, J-7 c / s, (-CuOGH ₂ CH ₃ ); 5.07 ppm (6-H); 5.64 ppm (2-

209824/1184

BATH ORIGINAL

By using other diazoalkanes, such as diazomethane, the corresponding alkoxy derivatives were prepared, ie the 11-methoxy compounds.

Other ethers were prepared as follows: 1 g of ethyl 3,7> 11-trimethyl-ii-hydroxydodeca ^ jo-dienoate in 10 ecm diglyme was added within 20 minutes to a slurry of 1 g sodium hydride in 10 ecm diglyme. 0.9 g of 2-chlorotetrahydropyran was then added dropwise over the course of 10 minutes. This mixture was stirred at about 25 ° C. for 30 minutes and then poured into ice water. The organic phase was separated off and extracted with ether. These extracts were washed with water, dried over sodium sulfate and evaporated} so ethyl 3,7 »H-trimethyl-11- (tetrahydropyran-2 ¹ -yloxy) -dodeca-2,6-dienoate was obtained.

By using 2-chlorotetrahydrofuran in the above procedure It became ethyl 3,7> 11-trimethyl-1! - (tetrahydrofuran 2 »-yloxy) -trideca-2,6-dienoate manufactured.

A mixture of 1 g Xthyl-3,7 "11-t ^r i ^me thyl-11-hydroxydodeca-2,6-dienoate, 1 g of p-Toluolsulfonaäuremonohydrat, 50 cc and 25 cc Kssigsäure acetic anhydride for 24 hours at room temperature and allowed to stand then poured into water and stirred. This mixture was then extracted with methylene chloride and the extracts dried and evaporated. The Rüekatand was then dissolved in 250 cc of methanol, ^5-c c ^m konz.Salzsaure containing dissolved. After 1 hour of heating to return

209824/1184

- • κ

BATH ORIGINAL

The mixture was fluxed with an aqueous 10-colored solution neutralized from potassium bicarbonate and evaporated. The residue was extracted with methylene chloride and the methylene chloride extract washed neutral with water, dried and evaporated; so became ethyl-5,7, ii-trimethyl-11-acetoxydodeca-2,6-dienamide obtained which was recrystallized from acetone / ether.

The use of other acid anhydrides provided the corresponding ones Ester.

The above procedure can also be used with others prepared above 11-hydroxy compounds are carried out.

The analogous treatment of the 7> 11-dihydroxy compounds prepared above provided the corresponding bisethers and bisesters, e.g. methyl (and ethyl) -3,7,11-trimethyl-7,11-diethoxydodec-2-enoate, Methyl- '(and ethyl) -3,7,11-trimethyl 1-7,11-diethoxytridec-2-enoate and methyl (and ethyl) -3,11-dimethyl-7,11 -diethoxy ^ -äthyltridee ^ -enoate.

Example 10

To a mixture of 2 g of ethyl ^^. H-trimethyldodeca-Z ^, 10-trienoate in 150 ecm of methylene chloride was at OC. slow 1.0 molar equivalent of m-chloroperbenzoic acid in 100 ecm of methylene chloride admitted. The resulting mixture was then 15 minutes at 0 ° C. left to stand and washed with 2- ^ aqueous sodium sulfite solution, .with 5% aqueous sodium bicarbonate solution and Washed with water, dried over sodium sulfate and closed

2-0 ^ 824/1184

BATH ORIGINAL

an oil evaporated, which is a mixture of the 1ü, 11-Oxitfo-, b, 7-Oxido- and 6,7; 10,11-Bisoxidoderivat des ^ thyl-i, 7,11-trimethyldodeca-2,6,10- contained trienoats. This mixture was then purified by chromatography on silica and separated into the individual epoxides, yielding ethyl 3,7,11-trimethyl-10,11-oxidodoc? Eca-2,6-dienoate, / KMR: 1.28; 1.30 ppm (2x11-CH 4) j 1.27 ppm triplet, J = 7 o / s, (-OCH ₂ CH ₅ ); "2.69 ppm triplet, J = 6.25 c / s, (IO-H); 4.15 p quartet, J = 7 c / s, (-OCH ₂ CH ₃ ); 5.18 ppm (6- H); 5.68 ppm (2-H) /; ethyl-3, _7,11-trimethyl-6 _f T-oxidododeca-ZjiO-dienoate and ethyl

25 3,7,11-trimethyl-6,7} 1O, 11-bitoxidododec-2-enoate, η ^y »1.4712,

^{I <R} / CHCl ₃ = 7823 ,, / NMR: 1.26 ppm (3XCH ₃ -CO-); 1.26 ppm triplet, J = 7 c / s, (-OCH ₂ CH ₃ ); 2.16 ppm doublet, J = 1.6 c / s, (3-CHv) j 5.67 ppm (2-H); 4.11 ppm, quartet, J = 7 c / s (-OCH ₂ CH

The corresponding oxido derivatives of Ethyl (and methyl) -3,7,11-trimethyltrideca-2,6,10-trienoate and Ethyl (and methyl) -3,1T-dimethyl-7-ethyltrideca-2,6,10-trienoate, e.g., ethyl 1-3,7,11-trimethyl-6,7,10,11-bisoxidotririec-2-enoate and ethyl-3,11-dimethyl-7-ether, vl-6,7; 10,11 -bisoXidotridec-2-enoate, manufactured.

In a mixture of 2 gx, ethyl-5,7 ""l-'fc ^r i ⁿ i ^e ethyl 10,11-oxidododeca-2,6-dienoate in 150 ecm of ether, 1 hour at OC became a slow one Hydrogen chloride stream introduced. The mixture was then ^{left to stand at 0} ° C. for 18 hours, washed with 5% aqueous sodium bicarbonate solution, dried over sodium sulfate and evaporated to an oil which was a mixture of ⁺ ) 1.65 ppm (7-CH ₅ ); 2.16 ppm doublet, J-1.7 c / a,

209824/1184

BATH ORIGINAL

J.thyl-J ^ jii-trimethyl-IO-hydroxy-ii-chlorododeca ^ jS-dienoate, / SIM: 1.55, 1> 58 ppm (2x11-CH,) i 1.63 ppm (7-GH,) ; 2.1-6 ppm, doublet, J-1.6 a / a, (5-CH ^), x 5.2 ppm (6-H); 5.68 ppm (2-H) 7, and ethyl-IjTjH-trifnethyl-IG-chloro-1-hydroxydodeca-2 »6-aienoate, / ϊΤΜΚ: 1.23 μm (2XiI-CH ₅ ); 1.28 ppm, triplet, J = * 7 o / a, (-UuII ₂ GH), 1.63 ppm (7-CH ₅ )} 2.05 ppm (11-OH) 5 2.16 ppm, doublet, J = »1.6 e / s, (3-CH-,); 5.2 ppm multiplet, (6-H); 3.6 ppm (Zd) I contained, which was purified by dux-ch chromatography on silica ^ ure and separated.

The corresponding chlorohydrins of ^ ethyl 3,7,11-trimethyltrideca-2,6-dienoate,> ethyl 3,11-dimethyl-7-ethyltx'ideca-2,6-dienoate and the corresponding methyl esters thereof prepared. ; / eitex * were the corresponding 7,11 -J) ichloin-10-hydraxy- and 7 »IO-dichloro-11 -hydroxyderivate of the above compounds and obtained in the manner described separated.

In an analogous manner, the o, 7-oxido derivatives of the same were used in the 6-hydroxy-7-chloro, 7-ChIOrO-O ^ yUrOXy- and o-Hydroxy-7,11-dichloro compounds formed »

Hydrogenation of the unsaturated oxido derivatives thus prepared!? Emass Example 2 yielded the corresponding compounds saturated in one or more red positions of the round chain. So, 2.B. Ethyl 3,11 -diinethyl-7-kthyl-IO, 11 -oxidotrideca-2,6-dienoate after hydrogenation xithy 1-3,11-dimethyl-7-ethyl-10-1 Ιο ^ idotride c-2-anoate , 1. fchyl-3,11-dimethyl-7-'- ^| ethyl 10,11 -oxidotridec-b-enuate and. ü.thyl-3,1 i-dimethyl-7-u.thyl-iU, 11-oxidetrT-decunt / it

209 8 24/1184

BATH ORIGINAL

- one replaced the hydrogen chloride in each case in the oxy process by hydrogen bromide and hydrogen fluoride, the corresponding jithyl-3.7 j 11 -trimeth ^ l-iu-hydroxy-i 1- "hromododeca-2,6-dienoate, £ thy1-3,7 »11-trimeth.y l-IÜ- ^ roiiio-i1-hydros dodeca-2,0-dienoat-, üthyl - ^, 7,11-trimethyl-10-h / droxy-i1-fluorododeca 2,6-dienoate and i = ethyl-317> 11 -trimethyl-10-fluoro-11 -h ;, droxydodeca-2,6-dienoatverhindunöen obtain. Acetylation ^ eEiass for example, Example 9 below provided ethyl-3,7,1i-fcrimethyl-10 acetoxy-11-fluorododeca-2,6-dienoate.

Example 11

10 ei ¹ ethyl-3, 7 "11-triniethyl-1E, 11-o: vidododeoa-2,6-r ^l ienoat were added to 100 cc of a 0 _r 01li - '/ cs ^ membered Perchlorsc urelosung added and the solution obtained. Left to stand for 25 hours> the cerebral temperature. The mixture was then washed with an aqueous sodium thiicarbonate solution, dried over sodium sulfate and evaporated to give ethyl 3,711-trimethyl-10,11-dihydroxydodeca-6,10-dienoate.

By repeating the process using a 0.0111 solution of perchloric acid in a (low) alkanol solvent instead of the aqueous perchloric acid solution, the corresponding 10-hydroxy-11- (lower) alkoxy derivative was prepared, i.e. ... thyl-3, 7,11 -trimethyl-10-hydroxy-11 -athoxydodeoa-ü, u-dienoate. Mass spectrum 326 / k + J , ^ NMRi 1.12 ppm (2χ11-0Η,); 1.62 ppm (7-CH); 1.15 PPm »triplet, ■■ (11 -üüH ^ CH ^); T, ^r c \ ppm, 'Lriplet, (-COOCH ₂ CHj; 2.1.5 ppm, doublet, J-1.5 o / s, (3-CH ₃ ) I 2.53 (10-0H), 3, 42 ppm Quartet, J-6.5. (11-0CH ₂ CH ^)} 4, H ppm, 4uartet, J = b, 5 c / s, (-COuCH ₂ CH ₅ ) j 5.2 ppm (7- H); ^ 5 ^ 8 ppm

20982A / 1184 BAD ORIGINAL

(2-H) / *, νίβηη ethanol was used as the solvent. the Use of !! ethanol, propanol, etc. yielded the corresponding -11-methoxy-, 1I-propoxy compounds, etc.

In this way, ethyl-3,7,11-trimethyl-1O-hydroxy-1 was also prepared 1 - .. thüxy trideca-2,6-dienoate, ^ thyl-3,11 -dimethy 1-7-cithyl-IO-fxydiOxy-H-ci-thoxytrideca-Z ^ -dienoate and the corresponding methyl esters thereof.

Hydrogenation of these compounds in the manner described above gave the corresponding saturated compounds, e.g. ethyl (and methyl) -3, 7i-1 i-trimethyl-IO-hydroxy-H- ^ thoxydonec-2-enoate and iithyl (and methyl) -3,11-dimethyl-7-ethyl-10-hydroxy-11 -u.thoxytridec-2-enoate.

Example 12 .

.-: thyl-3 rl) 11 -trimethyl-10,11 -oxidododeca-2,6-dienoate was prepared according to "Example TO" and then as in the following Example 17 to "form ethyl-3-, 7,11-trimethyl -6 _f 7-dichloro-10,11-oxidodod.ec-2-enoate ". According to this process, the corresponding 6,7-dichloro-10,11-oxide derivatives were obtained from compounds without the OC, ß-unsaturated carbonyl system The final reaction mixture is separated by chromatography from the corresponding Z ^ jöiY-tetrachloro-IO, 11-oxido compound which is present.

A.thyl-3.7 »1 i-trime.thyl-6,7-dichloro-10.1 were obtained in a similar manner i-oxidotridec-2-enoate and ethyl-3,, 11-dimethyl-6,7-dichloro-7-ethyl-iO, 1i-oxidotridec-2-enoate as well as the corresponding ffiethyl esters thereof.

20 98 24 / 118Λ

BATH ORIGINAL

Example 13

A suspension of 0.5 g of a 5% Palladiura-on-charcoal catalyst in 50 ^{cc of} benzene was hydrogenated for 30 minutes. A solution of 2 g of methyl-3,7,11-trimethyl-7, 11- dihydroxy-dodec-2-enoate in 100 ecm benzene was added and the mixture was hydrogenated with stirring until the theoretical amount of hydrogen had been absorbed. The catalyst was then filtered off and the solution was evaporated; thus methyl 3, 7> 11-trimethyl-7, 11-dihydroxydodecanoate obtained / & MR: 0.93 ppm doublet, J = 6 c / s, (3-GH ₅ ); 1.15 ppm (7-CH,); 1.20 ppm (2x11-CH,); 1 , 57 ppm (2xOH) _7; which was separated and purified by gas / liquid chromatography.

Ethyl esters of the above compound (, * der; as well as the methyl and ethyl esters of the others prepared in Example 7 7 »H-Uihydroxyverhindungen hydrogenated.

Example I4

A solution of 1.2 g of ethyl 3 »7» 11-trimethyl-dodeca-2,6,10-trienoate in 5 ecm of dimethylsulphoxide was converted into a solution of equivalent of dimethylsulphoxonium methylide in dimethylsulphoxide (prepared according to the ancestor in Journ.Am. Ühem. Soc. 87 1 1353 (1965)) added. The mixture was stirred under nitrogen and at room temperature for about 20 hours and then at 50 ° C. for about 7 hours. Then there were 50 ecu. tfusaer was added and the mixture obtained was extracted 4 times with 50 ecm of ethyl acetate each time. The combined extracts were washed with water and with saturated aqueous sodium chloride solution, dried and evaporated; so wux'de ethyl-2, i ^ meth ^ ien - ^^^ - | 1 -trimethyldodüca-6,10-dienoate obtained by chromatography on

209824/1184 BAD ORIGINAL

Silicic acid has been cleaned.

In a sensual way, thyl-2,3-methyl-3,7 »11-trimethyltrideca-t), 10-rlienoate and Ilthy 1-2,3-methylene-3, ii-aimethyl-7- ^ ethyl trideca-6,10-dienoate and the ifethyl esters of the above compounds. These compounds were then prepared and as in Example 5 to 12 ^ ergaber flows corresponding methyl and j methyl ester of 2,3-iiiethylenverbindungen, inter alia Ιΐ-chloro, 7, 11-dichloro-10,11-oxido, 6 , 7, '10, 11- "BiSOXXdO-, 7, MM-hydroxy- (alkoxy) and / or 10-hydroxy (acyloxy) -11-hydroxy (alkoxy) substituents and the various hydrogenated derivatives thereof.

Example 15

1.2 molar equivalents of methyl trifluoromethyltin and 1.2 molar ... (Equivalent sodium iodide in 10 ecm of ionoglyme was added. The mixture was heated to reflux for 2 hours, then cooled, washed with water and evaporated to give an acid which, after purification, was separated by liquid chromatography, ethyl-3,7,11- trimethyl-6,7-difluoromethylendodeca-2,10-dienoate, Ithy1-3, 7,11- brimethyl difluorüraethylendodeca-10,11-2,6-dienoate and ethyl-3,7,11-trimethyl-

erga "b.

By '.Viederholung the above traversed using ■ ifh ra "> luren equivalent'I'rimethyltrifluoromethylzinn and sodium JO (Ud a predominant amount of 6,7} ΙΌ, ΙΙ-Bisdifluoromethylen-Adduktea ivurdie get.. ■

4 ^ 2/11

BATH ORIGINAL

The Iul'luoromethylenadduct von Ethyl-5,7,11-triraethyltrideca-2, u, 10-trienoate and ^ thyl -;>, 11-

and the corresponding ethyl esters of the o ^ i ^ en compounds, for example ^ .thyl - ^, 11-dimethyl-6,7 j 10,11 -bis-difluoroine 'thylen-J-Ltiiy ltririec-2-enoat obtained. These Vei can _'t bonds -; enäss example 5 ^ is 1 j> be further trained. The 2,3-Iviethlen adducts produced in Example 14 can also be treated according to the present invention, whereby the corresponding 2, ^ - de ethylene-b, 7 (1 ^ »11) -difluoromethylene, eg A thy1 -2, ^ - methylen -), 11-rlimethyl-6, 7, '1 vJ, 11 -> ^ isdif luoromethylene-7-cithyltridecanoate.

Example 1b

In a mixture of 2 _e -iith / 1-5.7>11-trimethyl-6.7; iU, 11-V> i £ 3-uxidododec-2-enoate in 150 ecm it was heated for an hour (J. a slow stream of hydrogen chloride was stirred in. The liquor was then left to stand at 0 ° for 18 hours, then cat one

Washed aqueous IiatriurahicarVionatlösung, dried over sodium sulfate and evaporated to a oil, which is a:,; Ischung the chlorohydrins including ethyl-3 »711-trimethyl b, 10-dihydroxy-7,11-dichloropdodec-2- enoate, which was purified and separated by silica auratography.

This ancestor is also applicable to ethyl 3i7t "'1-trimethyl-6,7 {10,11-bisoxidotridec-2-enoate and i-thyl -; $, 11-dimethyl- (i, 7} lOjH-hiaoxidotridec-S-enoate and the corresponding methyl eeter of the same.

209824/1184

BATH ORIGINAL

Example .17

Gaseous chlorine was introduced into 200 ecm carbon tetrachloride, ("Hei ΰ C.) ^x ± p a ü, JjM solution was obtained» There were i? Ö * j th ^ lp, 7,11-trirje thylaodeca-2,6, 1E-trienoate added and the mixture stirred and 24 hours hei 0 C. allowed to stand. Then it was evaporated to give an oil which was a üischung from ι, thyl-3,7,11-trimethy1-6,7-dichlorododeca-2 , 10-dienoate, ethyl-3,7 »11-trimothyl-iU, 1i-dichlorododeca-2,6-dienoate and? Ethyl-3,7 * 1i-trimethyl-6,7» 10 »ii-tetrachlorododec-2- enoate, which was purified and separated by gas / liquid chromatography; it can also be purified and separated, if necessary, by two successive distillations using a spinning hand iraction column.

Example 18

In the procedure of Example 17, when chlorine was replaced by "bromine, in this way a mixture of the corresponding Tiromierte compounds was obtained, predominantly & thyl-3,7,11-trimethyl-6,75iO, 11-tetra> iromododec-2-enoate, which was separated by chromatography.

The use of a mixed halogen reagent, such as chlorine; 3? Luor Example 17 provided the corresponding mixed dihalogen compounds.

In Lhnlicher, the corresponding 6,7-Di 10 "were IrOm- ^1, -11-Di hrom- and 6,7j10,11-Tetrabromoderivate the main action indungen ^ £ thyl-3,7,11-trimethyl-trideca-2 , ö, 10-trienoate and ethyl 5,11-dimethy1-7-b trideca-2,6,10-trienoate.

20 98 24/1184 BADORIGJNAU

Example 19

To a mixture of 5 g of i-ethyl-3 »7» 11 -trimethyldodeca-2, 6,10-

o trienoate in 100 ecm fluorotrichloromethane was at about -78 C.

anhydrous fluorine added. Bach stirred the for about 16 hours The reaction mixture at this temperature was obtained Mixture evaporated and chromatographed on silica and gave a mixture of the 6,7} 10,11 and 6,7,10,11-fluorinated ones Compounds predominantly ethyl 3> 7i1i-trimethyl-6,7,10,11 tetrafluorododec-2-enoate.

Similarly, the corresponding fluorinated derivatives of ethyl - ^ / fjH-trimethyltrideca-Z.o-trienoate and ethyl-3,11 -dimethyl ^ -äthyltrideca ^, 6,10-trienoate produced.

Example 20

Anhydrous hydrogen chloride was added to diethyl ether in 100 ecm 0 G. initiated until a saturated solution was obtained. Then 1 g of ethyl-J ^ fii-trimethyl-H-hydroxy-dodeca- ^ iodienoat added and the mixture obtained then 4 lay at 0 C. ditched. Then it was evaporated to an oil under reduced pressure by chromatography on silica purified to give ithyl 3,7,11-trimethyl-7-chloro-11-hydroxydodec-2-enoate.

B ice ρ i e 1 21

Ethyl 5,7,11-trimethyl-10-hydroiy-11-chlorododeca-2,6-dienoate and ithyl 3,7,11-trimethyl-10-chloro-11-hydroxy-dodeca-2,6-dienoate were treated according to Example 10 and gave ethyl 3,7,11-trimethyl-6,7-oxido-10-hydroxy-11-chlorododec-2-enoate

209824/1184

BATH ORIGINAL

or ^ ethyl 3,7,11-trimethyl-6,7-oxido-1O-chloro-11-hydroxydodeo-2-enoate. ■

The corresponding! Derivatives of ethyl 5,7,11-trimethyl-trideca-2,6,1O-trienoate and ethyl-5,7,11-dimethyl-7-ethyltrideca-2,6,1O-trienoate as well as the methyl esters of the above compounds. These can be found in the above i7seise to be further trained.

Example '22

To a solution of 7 g of ethyl 3,7i11- "brimethyldodeca-2,6,10-trienoate in 350 ecm of dioxane were stirred with 20 ecm of 4K aqueous liatrium hydroxide and 20 ecm 30- ^ igea hydrogen peroxide added,

ο
the temperature was kept at about 0 g. The solution was left to stand until the reaction was complete (thin layer chromatography) and poured into ice water. The mixture was evaporated with water, dried and delivered jtthyl-3,7,11-trimethyl-2,3-oxidododeca-6 _r 10-dienoate, which was purified by chromatography.

Similarly, the 2,3-oxido derivatives of ethyl 3,7,11-trimethyltrideca-2 _r 6,1O-trienoate and ethyl 3,11-dimethyl-7-ethyltrideca-2,6,10-trienoate and the corresponding methyl esters of the above compounds prepared. The hydrogenation in the manner described above gave the corresponding saturated compounds.

209824/1184

BATH ORIGINAL

Example 23

As an example using the Reformatsky reaction has been made 6,10-dimethylundeca-5, £ -dien-2-one in 3 »7> 1i-trimethyl-3-hydroxydodeca-6,10-dienoate ester converted to 3 j7> 11-trimethyl-3-hydroxydodeca-6,10-dienoic acid was hydrolyzed.

Za a solution of 24 g of 3>7> 11-l ^l rimethyldodeca-2,6 '(0-trienoic acid in 100 cc of benzene 2.44 g of sodium hydride were added and the mixture stirred at 25 C. until the evolution of hydrogen ceased, and then cooled to "J C. Then 14.5 g of oxalyl chloride in 25 ecm benzene were slowly added with stirring and the mixture was left to stand for 6 hours at 25 C. After this time, 20 ecm ethanol were added and the mixture obtained was further 14 Hours at 25 ° C. This mixture was washed 3 times with 200 ecm of water each time, dried and evaporated in vacuo and yielded ethyl 3,7,11-trimethyl-dodeca-2,6,10-trienoate.

The use of other alcohols in the above process, e.g. Methanol, propanol, isopropanol, Heianol, octanol etc. instead of ethanol provided the corresponding alkyl esters.

The above procedure is suitable for making the other 3-hydroxy acids and esters thereof.

Example 24

10 g -i.thyl-3I7> 11- "fc ^r iniethyl-2,3-oxidododeca-6,10-dienoate was added to 100 cc of a 0.01N wuS8rigen PerchlorsäurelQsung added. The solution was for 24 hours at room temperature, allowed to stand, washed with aqueous sodium bicarbonate solution, dried over sodium sulfate and evaporated to an oil, which through

209824/11

BATHROOM ORIGl

1613946 -ü-

Chromatography on silica, ethyl 3,7,11-trimethyl-2,3-dihydroxydodeca-6,1O-dienoate revealed.

Repeating the above procedure using a 0f1M ~ solution of perchloric acid in a low, monovalent Alcohol, e.g. methanol, ethanol, propanol, etc., instead of the aqueous perchloric acid solution yielded the corresponding 2-hydroxy-3-alkoxy derivatives., e.g. ethyl 3.7> 1i 1 -trimethyl-2-hydroxy-3-athoxydodeca-6,10-dienoate.

Example 25

A mixture of J methylene iodide and 3 g of zinc-copper couple in 15 oom anhydrous zither was heated under nitrogen for 3 hours under reflux. The mixture was then cooled and 2 g of ethyl 3,7,11-trimethyldodeca-2,6,10-trienoate were added. This mixture was left to stand for 2 hours at room temperature, poured into 200 ecm 2-foigea aqueous sodium carbonate and extracted twice with 100 ecm ether each time. The extracts were dried over sodium sulphate and evaporated under reduced pressure. The oily residue was kept at 0.01 mm Hg to remove unreacted methylene iodide and then purified by gas / liquid chromatography} so were ethyl 3,7,11-trimethyl-6,7-methylenedodeca-2,10-dienoate , ithyl-3,7,11-trimethyl-10,11-methylendodeca-2,6-dienoate and ethyl-3,7-trimethyl-11 6,7j10 1 | 11-bismethylendodec-2-enoate obtained.

Using the 2,3-methylene compounds from Example 14 the starting material in the above process was ethyl-3,7> 11-trimethyl-2,3 j 6,7-bismethylendodec-10-enoate, ethyl 3,7,11 -triraethyl-2,3} 10.11 -bismethylene-dodec-6-enoate, ethyl-} ·, 7.11 -tri-

JLQ9824 / 1184

BATHROOM ORiGINAL

methyl 2,3j6,7; 10,11-trianethylene dodecanoate, etc. were obtained.

Example 26

To a solution of 10 g of ijthyl-3,7> 11-trimethyl-dodeca-2,6,10-trienoate In 50 ecm of benzene, 1.2 molar equivalents of phenyl-dichlorobromomethyl-mercury became added. The mixture was refluxed for 4 hours, cooled and evaporated to an oil, which has been purified and separated by silica chromatography; so were ethyl 3,7ι11 -trimethyl-b ^ -dichloromethylendodeca-2,10-dienoate, Ethyl 3,7,11-trimethyl-10,11-dichloromethylendodeca-2,6-dienoate and ^ ethyl-3,7,11-trimethyl-6> 7l ^ .. 10,11-bisdichloromethylene dodec-2-enoate.

By repeating the above procedure using 2.5 molar equivalents of phenyldichlorobromomethylqueekilver predominantly the 6,7} 10,1i-bis-dichloromethylene compound obtain.

Example 27

In a solution of 5 g of ethyl 3,7 »11-trimethyl-10,11-oxidododecanoate (obtained by hydrogenation of the corresponding 10,11-0xido-2,6-dieneB to 5 fo Pd / C) in 100 ecm carbon tetrachloride slowly introduced hydrogen fluoride with stirring at ^{0 ° C.} When about one chemical equivalent was added, the mixture was left to stand for 6 hours, washed with water and evaporated to an oil which was chromatographed on silica} so were ethyl 3,7,11-trimethyl-IO-hydroxy-i1-fluorododecanoate and Ethyl 3.7 »11-trimethyl-IO-fluoro-i1-hydroxydodecanoate was obtained.

209824/1184 BAD ORIGINAL

To 5 S ^ ethyl jJjii-trimethyl-IO-hydroxy-ii-100 in fluoxotridecanoat Gem. Anhydrous ether is a chemical equivalent of diazoethane was added. 1 drop of boron trifluoride was then added and the reaction mixture was left to stand for 1 hour "at 0 ° C. and then kept at room temperature for a further 2 hours". Then the Ήβ mixture was washed with water, evaporated and chromatographed and gave * ethyl 3,7,11-trimethyl-10-ethoxy-11-fluororodecanoate.

Using other diazoalkanes, such as diazomethane, the corresponding alkoxy derivatives have been prepared, e.g. 1O-methoxy compounds.

Example 28

A mixture of 1 g _JJ .thyl-3,7 "11-trimethyldodeca-2, $ _i trienoate 10, 60 cc of methanol, 0.1 g of sodium carbonate and 6 cc .Vaaser was heated to reflux for 2 hours. Then the mixture was cooled, diluted with water and extracted with ether. The essential extracts were washed with water, dried over sodium sulfate and evaporated to remove the solvent. The residue was subjected to a fractional vacuum distillation and gave 3 »7» 11-Trimethyldode.ea-2,6,10-triensLure.

■ Kirch repetition of the mild, basic hydrolysis process of this Example with others, prepared according to Example 4 to 27 Kiters were made to use the appropriate acids. Also the According to Example 4 produced, non-formed ester can be hydrolyzed to form the corresponding acids

209824/1184 BATH

the acids can then be used in any order and "Chemically trained to the necessary and desired level as described above for the "esters".

Example 29

1 molar equivalent of potassium bicarbonate was added with stirring to a solution of 2 g of 3>7> 1 i-trimethyl-H-chlorotrideca-2,6-dienoic acid in 50 ecm of benzene. The mixture was stirred, the his Kohlendioxyc ¹ were to release ceased, then was evaporated; in this way, KaIiUm-JjYfI1-trimethyl-1-chlorotrideca-2,6-dienoate was obtained, which can optionally be purified by silica chromatography.

Will be the other acids described here from the examples above Subjected to the procedure of the present example, the corresponding acidic potassium salts are obtained.

By using sodium bicarbonate, etc. in the process of

In the present example, the corresponding acid sodium t

received salts, etc.

Acid salts can also be prepared by mixing a solution of the acid with an alcoholic solution of an alkali or Alkaline earth alkoxide titrated, e.g. «a solution of 2 g 3,7,11-trimethyl-11-hydroxy-trideca-2,6-dienoic acid in 50 ecm Section. Methanol becomes a 0, IN-methanolic solution of Sodium methoxide was added until neutral. The solvent it is evaporated off under reduced pressure and sodium 3,7,11-trimethyl-i1-hydroxy-trideca-2,6-dienoate is obtained can be purified by silica chromatography.

209 824/1184.

BATH ORIGINAL

"Example 30

2 g of ethyl 3,7,11-trimethyldodeca-2,6,10-trienoate in 50 ecm anhydrous ether were added within 30 minutes while stirring to a suspension of 1 molar equivalent of lithium aluminum hydride in 50 ecm anhydrous ether up to -20 C. under nitrogen added. The mixture was stirred for 15 hours at -20 C. and then carefully with about 10 ecm of ethyl acetate and then 4 molar Equivalent glacial acetic acid and about 4 cm «barrels treated. then the mixture was filtered and the solid so collected was good washed with ether. The ether solution was over sodium sulfate dried and evaporated to give 3 »7» 11-triniethyldodeca-2,6,10-trien-1-ol.

By repeating this reduction process with others, Esters prepared according to Examples 4 to 27 were the corresponding Alcohols produced. The non-formed esters produced in Example 4 can also be hydrolyzed as above be, whereby one obtains the corresponding alcohols} the latter then indulge in any order and up to necessary, desired and chemically possible degree as above for esters and acids described are further elaborated. For example, the following typical alcohols were produced:

209824/1184 BAD ORIGINAL

10,11-Oxiclo-3,7,11-trimethyldO (ieca-2,6-dien-1-olj 3,7 »11-trimethyldodeca-2, b-diene-1,11-diol; 3,7,1.1 -Trimethyl-10,11-oxidododec-2-en-1-ol; 3,7,11-trimethyl-10,11-oxidotridec-2-en-i-ol; 3,7,11-trimethyl-10,11 -oxidotrideca-2,6-dien-1-ol; 3,11-dimethyl-7-athy1-10,11 -oxidotridec-2-en-i-ol; 3,11 -dimethyl-7- θyl- 10,11 -oxidotrideca-2, b-dien-1-olj 3,7,11-trimeth-1-6,7 | 10,11-bisoxidodec-2-en-1-ol; 3,7,11-trimethyl -6,7j10,11-thiisoxidotridec-2-en-1-ol} 3,11-dimethyl-7-ethyl-6, 7j 10,11 -bisoxidotridec-2-en-i -ol; 11-ethoxy-3 , 7,11-trimethyldodec-2-en-1, 10-diolj 11 -jVth.oxy-3,7 »11 -trimethyldodeca-2,6-diene-1, 10-diol j 11-lthoxy-3,7, 11-trimethyltrideca-2-en-1,10-diol 11-} Äthöxy-3,7,11-trimethyltrideca-2,6-diene-1,10-diol \ 11-i, .thoxy-3,11-dimethyl -7-Ethyltridec-2-ene-1,10-diol {11-ethoxy * -3,7,11 -trimethyltridec-2-ene-1,10-diol | 11-ethoxy-3,11-dimethyl-7 -athyltrideoa-2,6-diene-1,10-diol5 3,7,11-trimethyl-6,7-oxidododeca-2,10-dien-1-ol | 3,7,11-trimethyl-6,7- oxidotrideoa-2,1O-dien-1-olj 3 , 11-dimethyl-7-ethyl-6,7-oxidotrideca-2,1O-dien-1-ol, etc.

Example 31

A mixture of one g of 3,7,11-trimethyldodeca-2,6,10-trien-1-ol, 4 ecm of pyridine and 2 ecm of acetic anhydride was left to stand for 15 hours at room temperature, then poured into water, untouched. The mixture was with methylene

209824/1184

BATH ORIGINAL

chloride extracted and the organic extracts dried and evaporated} so was 1-acetoxy-3, 7> 11-trimethyldodeca-2,6,10-triene obtain.

By repeating this procedure with other C-1 alcohols, as they are prepared e.g. in Example 30, as starting materials, For example, the following compounds were obtained: i-acetoxy ^^ H-trimethyltrideca- ^ jö, 10-triene; 1-acetoxy-3,11-dimethyl ^ -äthyltrideca ^, 6,10-triene; 1-acetoxy-3,7-diethyl-11-methyltrideca-2,6,10-trienj 1-acetoxy-3,11-dimethyl-T-ethyldodeca-Z, 6,1O-trienj 1-acetoxy-7,11-dimethyl-3-ethyltrideca-2,6,10-triene { . 1-acetoxy-7,11-dimethyl ^ -äthyldodeca-Z, 6,10-triene and the corresponding 1O, 11-0xido-2-en-, 10,11-oxido-2,6-diene, 6,7110,11-bisoxido- and 6,7-oxido derivatives thereof, etc.

By using other carboxylic anhydrides in the above process instead of the acetic anhydride, e.g. propionic anhydride, n-Butyric anhydride, n-Oaproic anhydride, etc., the corresponding 1-acylates were obtained, e.g. 1-propionate, 1-butyrate, etc.

Example 32

28 g of 3,7,11-trimethyldodeca-2,6,10-trien-1-ol became a Suspension of 3.0 g of sodium hydride in 110 ecm of benzene was added. This mixture was stirred until hydrogen evolution

209Ö24 / 118 4

BATH ORIGINAL

stopped, then 47 g of ethyl iodide were added with stirring. The mixture was refluxed for 2 hours, then washed with water and yielded after evaporation of the solvent in a vacuum 1 -Ä.thoxy-3>, 7> 11 -trimethyldodeca ^ jo ^ O-trien, the was purified by chromatography.

By using other alkyl halides, e.g. methyl iodide, Propyl bromide etc. instead of ethyl iodide became the corresponding Methyl ether, propyl ether, etc. obtained.

The following procedure can also be used To 5 g of 3,7,11-trimethyldodeca-2, o, 10-t.rien-1-ol in 100 ecm 1 chemical equivalent of diazoethane was added to anhydrous ether. Then 1 drop of boron trifluoride was added and the Reaction mixture for 1 hour at 0 ° C. and then for a further 2 hours left to stand at room temperature. Then the mixture was washed with water, evaporated and chromatographed and provided 1-ethoxy-3,7,11-trimethyldodeca-2 »6,10-triene.

By using other diazoalkanes, e.g. diazomethane, the corresponding alfcoxy derivatives, e.g. the 1-ethoxy compounds manufactured.

By repeating the procedure of this example using the other C-1 alcohols prepared in Example 30 instead of the 3,7 »1i-trimethyldodeoa-2,6,10-trien-1-ol made the following ethers:

209824/1184 " BAD ORIGINAL

Bp 0.18 now 120 ° C; n ^ ⁴ = 1.4738 / NMR: 1.58 ppm (7-CH ₅ HH-trans); 1.66 ppm (11-cie + 5-GH, from 2-trans) j 1.75 ppm (5-CB, from 2-cis); 2.29 ppm (-2.90 douhlet, j-6.5 c / s, (-CHpOGH ₅ ); 5.08 ppm (6-H + 10-H); 5.53 ppm, triplet, J = 6 , 5 c / s, · (2-E) 7, 1-methoxy-Iu, 11-oxido-3,7,11 -trimethyldodeca-2,6-diene;

• ^v D

1-kethoxy-11-hydroxy-3,7,11-trimethyl-dodeca-2,6-diene, 1.22 ppm (2 χ H-CH ₅ ); 1.62 ppm (7-CH ₅ ); 2.08, '214 ppm (3-CI of 2-trans and 2-cis) 5 3.34 ppm (-OCH,); 3.97 ppm, doublet J = 6.4 c / s, (-CH ₂ OCH ₅ ) j. 5125 ppm multiplet, (2-Η + 6-Η ^.

/ The following were also produced:

1-ethoxy-3,7 »11-trimethyl-10, H-oxirloci.odec-2-en; 1-ethoxy-3,7,11-trimethyl-10,1.1-oxide orodeca-2, ü-diene j 1-methoxy-3,7,11-triraethyl-10,11-oxidododec-2-en; 1-methoxy-3,7 »11-trimethyl-10,11-oxidododeca-2,6-diene; 1-ethoxy-3,7,11-trimethyl-10,11-oxidotridec-2-en} 1-ethoxy-3,7 »11-trimethyl-10,11-oxidotrideca-2,6-diene5 1 -methoxy-3 , 7,11-trimethyl-10,11-oxidotridec-2-en; 1-methoxy-3-, 7,11-trimethyl-10,11-oxidotrideca-2,6-diene; 1-ethoxy-3,11-dimethyl-7-ethyl-10,11-oxidotridec-2-enj 1-ethoxy-3 j 11-dimethyl-7-ethyl-10,11-oxidotrideca-2,6-dienj 1- Kethoxy-3,11-dimethyl-7-fathyl-i0,11-oxidotridec-2-en5 1 - Xthoxy-3,7,11 -trimethyl-6,7j 10,11 -Μ8οχίαΌαβο-2-βη | 1-methoxy-3,7,11-trimethyl-6,7; 10.11 ->) isoxidodec-2-en; 1-methoxy-3 »11-dimethyl-7-ethyl-i0,11-oxidotrideoa-2,6-diene

20982A / 1184

BATH ORIGINAL

1-ethoxy-3,7 »11-trimethyl-6,71 10,11 - ■ bisoxidotriäec-2-enj 1 -Methoxy-3, 7,11 -trimethyl-6,7 (10,11 -'biBoxidotridec-2-en. { 1-Ethoxy-3,11-dimethyl-J-ethyl-ö, 7} 10,11 -hisoXido tridec-2-en f 1-methoxy-3,11-dimethyl-7-ethyl-6,7; 10,11 -bisoxidotridec ^ -enf 1,11 -Diethoxy-3,7 »1 1-trimethyl-1O-hydroxydodec-2-enj 1,11 -I) iathoxy-3 ·, 7 j 11 -trimethyl-10-hydroxydodeca-2,6-dienj 1-methoxy-3,7,11-trimethyl-10-hydroxy-i1-uthoxy-dodec-2-enj 1-methoxy-3,7,11-trimethyl-10-hydroxy-11-ethoxy-dodeca-2,6-diene j 1,11-dietoxy-3 »7» 11 -1 trimethyl-10-hydroxytrideca-2,6-diene; 1,11-ethoxy-3,7 »11-trimethyl-10-hydroxytridec-2-enj 1-methoxy-3,7,11-trimethyl-1O-hydroxy-11-athoxytridec-2-en} 1-methoxy-3,7,11-trimethyl-1O-hydroxy-11-athoxytrideca-2,6-diene} 1,11-diethoxy-3,11 -dimethyl ^ -äthyl-IO-hydroxytridec ^ -eii; 1,11-Dietoxy-3,11-dimethyl-7-ethyl-10-hydroxytrideca-2,6-diene | 1 -Methoxy-3,11 -dime thy 1-7 -äthyl-IO-hydroxy-H-ethoxy-tridec-2-en j 1-Methoxy-3,11-dimethyl-7-ethyl-1O-hydroxy-11-ethoxytrideca-2,6-diene | 1-ethoxy-3,7,11-trimethyl-6,7-oxidododeca-2,10-dienj 1-methoxy-3.7.11-trimethyl-6,7-oxidododeca-2,10-diene ( 1-Ethoxy-3,7,11 -triine thyl-6,7-oxidotrideca-2,1 Ü-dienj 1-methoxy-3,7,11-trimethyl-6,7-oxidotrideca-2,10-dienj 1-ethoxy-3,11-dimethyl-7-ethyl-6,7-oxidotrideca-2,10-dienj 1-methoxy-3,1.1-dimethyl-7-ethy1-6,7-oxidotrideca-2,10-diene, etc.

209824/1184 BAD ORIGINAL

Example 33

'Δη. a solution of 2 g of ethyl 7,11-diehloro-3 »7» 1 1-trimethyldodec-2-enoate in 50 ecm of anhydrous ether was added at 0 ° C. with stirring, 0.36 B lithium aluminum hydride. For 1 hour 2.4 com acetic acid were added, the mixture was washed with ice water, the ether phase was dried and evaporated; 7,11-lichloro-3t7f 11 - trimethyldodec - 2-en-1-ol was thus obtained.

The C-1 alcohol thus prepared was converted into the corresponding -Acyla te, e.g. the acetate, converted.

The C-1 alcohol thus produced is also in the corresponding Ether, e.g. ethyl ether, convertible in the manner described above.

8 24/1184
BADORLGiNAL

Example 54

To a solution of 2,5 ^ 3,7,11-trimethyläodeca-2,6,10-trien-1-ol in 100 ecm methylene chloride / nirde at OG. 1 molar equivalent of m-chloroperbenzoic acid in 50 ecm of methylene chloride was added, after which the solution was washed with aqueous sodium sulfate, aqueous potassium bicarbonate and water, and then dried and evaporated to give an oil which, according to silica-based chromatography, 2,3-oxido-3, 7 »11-trimethyldodeca-6,10-dien-1-ol yielded.

3 6tf> i game 35

Example 10 was prepared using 3 »7i11-T3" iniethyldodeca-2,6,10-trien-1-ol repeated, mainly the 10,11-oxido, 6,7-oxido and some 6,7j10,11-bisoxido derivatives of the same were obtained.

By repeating this procedure using 2.5 molar equivalents, m-chloroperbenzoic acid became predominant the 6,7; 10,11-bisoxido and some 6,7-oxido and 10,11-oxido derivatives obtain.

The use of 4> 2 molar equivalents of m-chloroperbenzoic acid gave 2.3 | 6.7 | 10,11-trisoxido-3,7,11-trimethyldodecane-1-oil.

The corresponding oxido adducts of 3,7,11-trimethylirideca-2,6,10-trien-1-ol and 3 _f 11-I) imethyl-7-ethyltrideca-2,6,10-triene were prepared in a similar manner. i-ol manufactured.

Example 36

The 1,11-diethoxy compounds were prepared by conversion the corresponding 11-ethoxy ester into the C-1 alcohols and then Treatment of these compounds according to Example 9>

209824/1184

BATH ORIGINAL

Example 3? -. . - -

10 lithium aluminum hydride was added to a solution of 10 g of ethyl 2,3-oxido-3,7 »11-trimethyldodecä-6,10-dienoate in 150 ecm of ether; Then the solution was heated to reflux for 6 hours, whereupon 25 com ethyl acetate and 2 ecm (drums were carefully added. Then a saturated sodium sulfate solution was added with stirring until the precipitation had just ended; the mixture was filtered and the filtrate evaporated to give 3,7,11-trimethyldodeca-6 _i 10-diene-1,3-diol, which can be purified and separated by chromatography on silica.

Following the above procedure, 3 »7> 11-triynes ± hyltrideca-6.j 10-diene-1,3-diol and 3 | Ί 1-dimethyl-7-ethyltrideca-6, / 10 ~ diene-1,3-dio.l prepared from the corresponding 2,3-oxido compounds ·. . . -

Example 36 · ■. ·: -

The repetition of Example 25 using the C-r.1 alcohols as output connections. predominantly the 2,3-methylene adducts. , \ ■ *

Example 26 was made using the C-1 alcohols as starting compounds repeated so were some of the 2,3-dichloromethylene adducts including the bis-adducts. By using 5 molar equivalents of the mercury reagent and a 5-hour a The 2,3; 6V7} lOJII-TrisdlflUOfomethylene adduct was heated to reflux of the C-1 alcohol used as the starting compound manufactured.

In an analogous manner, by repeating the procedure of Example 15 the difluoromethylene adducts (which additionally contained the difluoromethylene group in the C-2,3 position) from the

209824/1184
BATH ORIGINAL

C-1 alcohols produced.

Example 59

At -10 ° C., chlorine was slowly passed into carbon tetrachloride, which contained 2 g of 5,7,1i-trimethyldodeca-2,6,10-trien-1-ol, until no more chlorine was consumed. The solution was evaporated under reduced pressure at 0 ^{° C. and gave 2} »3j6.7; 10,11-hexachlpro-5,7,11-trimethyldodecane-1-oil.

The tetrachloride derivatives can be introduced in a similar manner a smaller amount of chlorine can be produced. The oily reaction product contains a mixture of tetrachloro and dichloro derivatives, which are separated by column chromatography.

Example 40

A, 15- ^ solution of butyllithium in hexane (420 cc), a solution of 49 E dry Di & methylamine was added in 530 cc of anhydrous ether at -10 C. with stirring. Then the mixture was stirred for 1 hour at 20 C. to create a 1 molar solution of diethylaminolithium,

Aneohliessend an aliquot was added to 12.5 g added (50 cc) of the · ο solution prepared methyl 3,7f11-trimethyl-2,6-trienoate _f 10 in 50 cc of ether and the mixture stirred for 4 hours at room temperature. Then eie was treated with an aqueous 0.1N-ß, "l""äurelösung and water \ washed neutral, dried over sodium sulfate and evaporated to dryness eo was Ν, Ν-Ditithyl-3" 7 "11-triiaethyldodeca-2,6, 10-trienamide with a

Kp - i _m J90 ° C. | nj ⁵ - 1.4905, obtained, vj j ι mm χί

209824/1184

BATH ORIGINAL

In this way the following were also prepared: N, lf-diethyl-3> 7 »11 trimethyl-trideca-ZjojiO-trienamide and ir, H" -diethyl-3 »11-dimethyl-7-ethyltrideca-2,6,1O- trienamicl trimethyl-trideca-2,6,10-trienoate from ivlethyl-3.7> 11 and methyl-3, 1 1-diynes thyl-7-a.thyltrideca-2,6, 1 0-trienoate.

The repetition of the oxy process using ammonia, 3) imethylamine and liorpholine gave 3,7> 11-irini ^e thyldodeca-2,6,10-trienamide, H, Nl) imethyl-3,7,1 i-triynethyldQdeca- 2 , 6,10-trienamide hzvf. NjH-Mörpholino ^ S »7» 11 -trimethyldodeoa-2,6,10-trienamide. The use of other amines, for example methylamine, ethylamine, diphenylamine, di- (2-hydroxyethyl) amine, pyrrolidine, etc., gave the corresponding li-substituted amides thereof. .

The corresponding amides were prepared by repeating the amide preparation procedure of this example using the other esters prepared according to Example 4 bis. The undeveloped esters, according to the example, can also preferably be treated as above for the corresponding amides, whereupon the amides at other points of the molecule in any order and up to the necessary, desired and chemically feasible degree as obety for Ister and acids described, allow for further training. For example, the following typical amides were made!

- 209824/1184 BAD ORIGINAL

N, N-diethyl-3,7 »11- * ^r iniethyl-11-hydroxy-odeca-2,6-dienamide N, N-diutyl-3,7,11-trimethyl-IO-bromo-11-hydroxy-odeca-2 , 6-dienamide N, N-diethyl-3,7,11-trimethyl-7,11-dichloroaodec-2-enamide N, N-dimethyl-3,7,11-trimethyl-7,11 -dichlorododec-2 -enainid N, N-morpholino-3,7,11-trimethyl-7,11-dichlorododec-2-enamide N, N-diethyl-3,7,11-trimethyl-7 _T 1i-dichlorotridec-2-enamide N, N-Diine thyl-3,7,11 -trimethyl-7,11 -dichlorotridec-2-enamiä N, N-Morpholino-3j7 »11-trimethyl-7,11-dichlorotridec-2-enamid N, N-diethyl- 3,11-dimethyl-7-ethyl-7,11-dichlorotridec-2-enamia N, N-dimethyl-3,11-dimethyl-7-ethyl-7,11-dichlorotridec-2-enainide K, N-morpholino -3,11-dimethyl-7-methyl-7,11-diehlorotridec-2-enan ^ id N, N-diethyl-317 »11-trimethyl-1i-chlorododec-S-enamide N, M-diethyl-3,7 , 11-trimethyl-11-chlordodeca-2,6-dienamide N, II-dimethyl-3 »7» 11 -trime thyl-11 -chlorodoäec-2-enaiiiid Ν, Ιί-dimethyl-3 »7,11- trimethyl-11-chlorododeca-2,6-dienamide N, H-morpholino-3 »7» 11-trimethyl-11-chlorododec-2-enamide N, W-morpholino-3, 7> 11-trimethyl-11-chloroäodeca-2,6-dienamide N, N-diethyl-3,7,11-fcrimethyl-11-ohlorotrideo-2-enamide N, lί-difathyl-3t7 _> 11-tΓimβthyl-11- ohlorotrideca-2,6-diβnamid N, N-dimethyl-3,7,11-trimethyl-11-chlorotriaec-2-enamid N, N-dimethyl-3,7,11-trimethyl-1t-chlorotrideoa-2,6- dienamide N, N-morpholino-3,7,11-trimethyl-11-chlorotrideo-2-enamide, N, N-morpholino-3,7 »11-trimethyl-11-chlorotrideca-2,6-dienamide N, IT- Diethyl 3,11-dimethyl-7-ethyl-11-chlorotridec-2-enamide N, N-diethyl-3,11-dimethyl-7-ethyl-11-chlorotrideca-2,6-dienamide

20982A / 118 4_

BATH ORIGINAL

N, If-dimethyl-3, 11-aimetbyl-7-ttthyl-i 1 -chlorotridec-2-enaiEid

H, IT-Morpholino-3, II-dimethyl-ethyl-II-chlorotridec-enamide II, H-Morpholino- ^ jii-aimethyl ^ -ethyl-ii-chlorotrideca ^, 6-dienamide

N, N-diethyl-3,7,11-trimethyl-10,11-oxide-pdodeca-2,6-dienamide. Ii, N-Dimethyl-3,7,11 - tri'methyl-10 _r 11 -oxido d ode c-2-enamid li _> N-Dimethyl-3,7 _i 11-trimethyl-10, H-oxidododeGa-2, 6-öienamid Ii, N ^ Morpholino-3,7 * 11 -trime thy 1-10,11 -oxidoclode, c-2-en.amid K ^ lI-Morpholino-3,7 j 11 -trimethyl-10,11 - oxidodoaeca-2,6-dienamide 11, N-diethyl-3,7,11-triethyl-10 ,,. 11-oxidotridec-2-enamide N, N-picthy 1-3,7,11-tri-diethyl-10,11 -oxidotrideca-2,6-dienamide K, li-l) imethyl-3,7,11 -trimethyl-10,11 -oxidotridec-2-eiiamid H, IT-dimethyl-3,7., 11 -trime tbyl-10 , 11 -oxidotrideca ^, 6-dienamide H, N-morpholino-3,7,11-triπlethyl-10 _f 11-oxidptriäec-2-enamid N, U-morpholino-3,7,11-trimethyl-10,11- oxidotrideca-2,6-dienamide N, K-Diktiiyl-3,11 -djLmethyl ^ -äthyl-i 0,11 -oxidotridec-2-enamid ΪI, Iί-diethyl-3, i1-dimethyl-7-ethyl-10 _ί 11-oxidotrideqa '■ 2,6-dienamide K, ir-dimethyl-3,11-dimethyl-7 ~ iitiiyl-10,11-oxidotridec-2-enamide N, If-I) imethyl-3,11 -dimethyl- 7-ethyl-10,11 -oxidotrideca-2,6-dienamide H, ii-morpholine b-3,11 -dimethyl-7-ethyl-IO, 11 -oxidotriftec-2-enamide Ii iϊr -lίorpholino-3 ₎ 11-dimethyl-7- £ ithyl-10,11-oxidot £ ideoa-2,6-dienamide Ν, N-diethy1-3,7,11-trimethy1-61,7f10,11-bisoxidodofleö- S-enamid N, li-Diinethyl-5,7,11 -trimethyl-6,7 j 10 _# 11 -bieoxidododec-g-enamid K (H-Morpholino-3,7,11 _r trimethyl-6,7 j 10 , 11 - "biBOxidododec-2-enamid Ii, If-Biethyl-3,7,11-tximethy 1-6,7} 10,11-hisoxidotridec-2-enamid

209824/1184

I «, N-Aiorpholino-3,7» 11-trimethyl-6.7 $ 10.1i-MsüxirOtridee-2-enamid H, li-2) iu.t] iyl-3,11-dimethyl-7-ethyl-o.7; 10,11 -bisoxidotridec ^ -enamid

amide

I, N-Morpholino-3,11-dimethyl-7-kthyl-6,7; 10,11-'biEOxidotridec-

2-enamide

li, N-diethyl-3,7,11-trimethyl-7,11-ethoxydodec-2-enamide N, H-dimethyl-3,7,11-trimethyl-7,11-diathoxydodec-2-enamide N, l> - morpholino-3> 7> 11-trimethyl-7,11-diathoxydodec-2-enamide N, li! -Diä, thyl-3 »7» 11 -trimethyl-7,11 -dictthoxytridec-2-enamide N, III-Dimethyl-3,7,11 -trimethyl-7,11 -diathoxytridec-2-enamide ii, N-Morpholino-3> 7 »11-trimethyl-7,1 i-diethoxytridec-2-enamide N, ü-diethy1-3,11-dimethyl-7-ethyl-7,11-diethoxytridec-2-enamide N, ii-dimethyl-3 »11-dimethyl-7-ethyl-7,11-di & thoxytridec-2-enamide li, rf-Morpholino-3,11-dimethyl-7-ethyl-7,11-diethoxytridec-2-enamide N, lj-diethyl-3,7,1 i-trimethyl-IO-hydroxy-H-athoxydodec-2-enamide N, fJ-Diethyl-3,7,11-trimethyl-10-hydroxy-11-ethoxydodeca-2,6-dienamide li, H-dimethyl-3 »7j11-trimethyl-10-hydroxy-11-ethoxydodec-2-enamide II, N-dimethyl-3,7,11-trimethyl-1O-hydroxy-ii-athoxydodeca-2,6-

flienamid

N, N-morpholino-3,7 » 11-trimethyl-10-hydroxy-11-ethoxydodec-2-enamide K, K-morpholino-3,7 » 11-trimethyl-10-hydroxy-11-ethoxydodeca-2 , 6-

dienamide

N, W-diethyl-3,7,11-trimethyl-10-hydroxy-11- & thoxytrideo-2-enamide K, N-ethyl-3,7,11-trimethyl-10-hydroxy-H-ethoxytrideca-2,6-dienamide

209824/1184

, if-Diaiethyl-3,7 »11 -trime thyl-iü-hyö.roxy-1 i-a.thoxytridec-2-enaiaid

dienaaid N, II-Liorpholino-5, J, 11 -trimethyl-10-hydroxy-11 -athoxytridec-2-enamide II, xT-Mürpholino-3 »7> 11 -trimethyl-10-hydroxy-11 -o.thoxytrideca -2.6-

Oienamide

K, Ii-Di & th / l-3,11-dimeth / l-7-ethyl-10-hydroxy-11-ethoxytrideG-2-

enamid

K, ii-Biathyl-3,11 -dimethyl-7-ethyl-i O-hydroxy-11 -athoxytrideca-2,6-

dienamide

K, N-Dimethyl-3,11-dimeth.yl-7-kth.yl-1 O-hydroxy-11 -ethoxytridec-2-

enamid

lί, iί-dimethyl-5,11-di! Ilethyl-7-ethyl-10-hydroxy-11-ethoxytriae-2,6-

dienamide

N, Ji-Morpholino-3,11-dimethyl-7-ethyl-1O-hydroxy-11-ethoxytridec-

2-enamide

N,? F-Morpholino-3 »11-dimethyl-7-ethyl-10-hydroxy-11-ethoxytrideca-

2, b-dienamide

Ii, Ii-diethyl-2,3-methylene-5, 1 »11 -trimethyldodeca-b ₁ 10-dienamide H t ^ -" Whore thyl-2 , 3-methylene-3 »7 * 11 -trime thyldodeca-6,10-dienamide rl, S-lIorpholino-2,3-methylene-3 »7 * 11 -trime thyldodeca-6,10-dienamide N, N-diet1-2,3-methylene-3,7» 11-trimethyltrideca-6,1O-dienamide • iI, iJ-Dimethyl-2,3-methylene-3 _l 7 »11-trimethyltrideca-6,1O-dienamide N, ii-Hörpholino-2,3-methylene-3» 7 , 11-trimethyltrideea-6,10-dienamide N, ii -]>iethyl-2,3-methylene-3> 1 i-dimethyl-7-ethyltriae-o, 10-dienamide «, ί (-dimethyl-2,3 -methylene-3,11-diethyl-7-ethyltrideca-6,1O-dienamide X ^, S-jttOrpholino-2,3-methylene-3 »11-dimethyl-7-ethyl trideca-6,10-

dienamide

209824/1184

Bathroom original

N, ir-I) iathyl-2,3-methylen-o, /, · 1 J, 11 -Ms- (difluoroue th "len) -3, 7,11-

trimeth / lciodecanamide

N, II-dimethyl-2,3-meth / len-6,7; 10,11-Ms-i _% dii'luoromethyIen) -

3, 7 11 i-trimethyldor'ecananiid

U , ii-Hiürpholino-2,3-methylene-6,7} 10,1 1-Ms- (difLuoroirie thylen) -

3.7 »11-trimethyldodecanamide

Ii, iI-diithyl-2,3-methylene-6,7; 10.11 -his- (c? Ifluoromethylene) -

3.7> 11-trimethyltridecanamide

N, Ii-Dimethyl-2, 3-methy len-6, 7 j 10,11-Mc- (UIfIuOx ^ r-Ie tny len) -

3.7 j 11-trimethyltridecanaaid

N, N-Morpholino-2,3-niethylen-6, 7 j 10,11 -Ms- (difluoromethylene) -

3.7 »11 -trimethyltridecanamide

ii, N-diethyl-2,3-methylene-6,7; 10,11-Ms- (difluoromethylene) -3,11-

dimethy1-7-fc.thyltridecanamide

l ϊ, K-dimethyl-2,3-methylene-6,7; 10,11-bi3- (difluoroΓomethylene) -3,11-

methyl-7-ethyltridecanamide

N, N-morpholino-2,3-ethylene-6,7; 10,11-Ms- (difluoromethylene) -3,11-

dimethyl 1-7 ethyl tridecanamide

N, N-diethyl-6,7} 10,11-Ms- (difluoromethylene) -3,7,11-trimethyl-

dodec-2-enamide

N, N-dimethyl-6,7} 10,11-M s- (difluoromethylene) -3 »7,11 -trimethyl-

dodec-2-enamide

N, Ii-Mo rpholino-6,7; 10.11 -his- (difluoromethylene) -3.7, 11 - trimethyl-

dodec-2-enamide

II, N-diethyl-o.7; 10.11 -Ms- (difluoromethylene) -3.7.11 -trimethyl-

tridee-2-enamid

K, N-dimethyl-6,7; 10,11-bis- (difluoromethylene) -3,7 »11-t-riniethyl-

tridtc-2-enamide

NjK-morpholino-b //; 10,11-Ms- (difluorome thylen) - 3,7, 11-trin: e thyi-

tridec-2-enamiö

209824/1184,

BATH ORIGINAL

h, Ii-di-ethyl-6,7; 10,11-TiIs- (OIf luromethylene) -3,11-dime thy1-7-

ethyltridec-2-enamiö

K, N-bimethyl-6 _f 7j 10,11- ■ his- (difluoromethylene) -3,11-dimethyl-7-

ethyltridec-2-enamide

1 », N-Morjjholino-6,7; 10,11-bis- (diiluoromethylene) -3,11-dimethy1-7-

ethyltridec-2-enamide.

The amides can also be prepared by the following procedure
will.

Example 41

A suspension of 2.3 g (0.1 mol) of sodium hydride in 50 ecm of benzene was added to a solution of 23.6 g (0.1 mol) of 3.7 I-rime-thylflodeca- 2,6,10-trienoic acid and 100% benzene were added. The lViischung was stirred for 4 hours ₉ cooled to 0 G., and then were slowly
19/0 g (0.15 mol) of oxalyl chloride were added within one hour. The mixture was left to stand for 3 hours. To the mixture containing 3} 7 »11-ΐΓί-methyldodeca-2,6,10-trienyl chloride, 21.0 g (0.3 mol) of diethylamine were added and the resulting mixture was left to stand for 2 hours at room temperature under reduced pressure to dry evaporated, the residue taken up in benzene, washed neutral with aqueous ^ -foiger sodium bicarbonate solution and water, dried over sodium sulfate and evaporated to dryness} so H, lT-diethyl-3f7 »1i-trimethyldodeca-2,6,10-trienamide was obtained.

Example 42

According to Example 22, lί, N-di £ l-ethyl-2,3-oxido-3,7,11-trimethyldodeca-6,10-dienamide was obtained from N, W-diethyl-3,7,11-trimethyldodeca-2,0,10-trienamide manufactured.

209824/1184

BADORfGiNAL

To a solution of 10 g of E, N-diethyl-2,3-oxido-3,7> 11-trimethyldodeca-6,10-dienamide in 150 ecm .i.ther became 1 molar equivalent Lithium aluminum hydride added, '' ie mixture obtained 30 Left to stand for minutes at 0 ° C., and then 5 ecm of ethyl acetate and then carefully added 2 ecm of water. Then sodium sulfate was added, the mixture was filtered and the Evaporated filtrate; so became N, N-di> .thyl-3-hydroxy-3,7 »11-trimethyldodeca-6,10-dienamide obtain.

Similarly, N, N -diamethyl-3-hydroxy-3i7> ^ 1-trimethyltrideca-6,10-dienamide and li, N-diethyl-3-hydroxy-3,11-dimethyl-7-ethyltrideca-6,10-dienamide manufactured. Likewise, the corresponding 3-hydroxy derivatives of the others were according to the invention Hydrocarbon amides produced. Similarly, were the 6,7-oxido, 10,11-oxido and b ^ ilOjH- ^ isoxido compounds formed into the corresponding monohydroxy compounds.

Example 43

After treatment of N, lf-diethyl-2,3-oxido-3,7 »11-trimethyldodeca-6,10-dienamide According to paragraph 3 of Example 10, N, N-I) iathyl-2-hydroxy-3-chloro-3,7 »H-trimethyldodeoa-6,10-dienamide, N, W-diethyl-2-hydroxy-3,7-dichloro-3,7 > 1i-trimethyldodec-10-enamide and N, N-diethyl-2-hydroxy-3,7,11-trichloro-3,7,11-tri-ethyldodecanamide prepared, and then by silica gel chromatography separated and cleaned.

By using hydrogen bromide and hydrogen fluoride in the above procedure, the corresponding N, N-diethyl-2-hydroxy-3-bromo-3,7, ii-trimethyldodeca-6, 10-dienamide, H, N-diethyl-2-

209824/1184

BATH ORIGINAL

1818946

hyflroxy-3-fluoro-3,7,11 -trimethylene! eca-o, 1O-dienaaiitf, fl, f; -I) iäthyl-2-hj.-droxy-3 j 7 - <3ibro'mo - 3 , 7 "11 - trimethyldodec-1-O-enamide, H, M-3) ifcthyl-2-hjdroxy-3,7-öifluoro-3,7-11 _J-10-enamide trimethyldodeG" N, lf-Diathyl-2-hydroxy ~ 3,7> 11-tribromo-3, Y, 11-trimethyldodecanainide and S, iI-difcthyl-2-hydroxy- ^, 7 »11-trifluoro-3> 7» f-1-trimethyldodecanamide.

From the starting compounds K, li-DiL.thyl-2, 3-oxido-J, 7s 11-trimethyltrideca-6,1O-dienamide and H, IT-Mathyl-2,3-oxido-3,11-dimethyl-7- ci-thyltrideca-6,1O-dienainid were in a similar dieise the corresponding 2-HyOrOXy-J-ChIOrO-, 2-hydroxy-3-hromo-, 2-hydroxy-3-fluoro-, 2-ßydroxy-3 »7- dichloro-, 2-fiydroxy-3 »7-di'hromo-, 2-hydroxy-3,7-difluoro-, 2-hydroxy-3,7,11-trichloro- _r 2-hydroxy-3,7,11- tribromo and 2-hydroxy-3,7,11-trifluoroderivate.

Example 44

A solution of 21 g (0.1 mol) of 6,1O-dimethylündeca-5,9-dien-2-one (prepared according to Example 1 and 3) and 100 ecm of dry diethyl ether slowly became a suspension of 13 »1 g (0 , 1 mol) vinyl magnesium bromide in dry diethyl ether was added. The addition took place at -20 ° C. After the addition had ended, the reaction mixture was allowed to come to room temperature and then refluxed for one hour. The mixture was added to an ice-cold aqueous ammonium chloride solution and extracted with methylene chloride. The combined extracts were dried over sodium sulfate and evaporated under reduced pressure and gave 3,7,11-'i ¹ rime thy ldodeca-1,6, IO-trien-3-ol.

P9B24 /

BATH ORIGINAL

According to one of the above procedures, using b, 10-l) I-fflethyld.odsca-5,9-dien-2-one and ö- ^ ethyl-IO-metlvl-dodeca- ^ y 2-one as starting materials 3 »7> 11-trimethyltrideca-i, b, 10-trien-5-ol and 3j 11-dimethyl-7-ethyltrideca-i, 6,10-trien-3-ol.

Also the various other vegetables, ice cream 1 "to 3 produced Ketones can be used as links in the process of the present example can be used to prepare the corresponding 1-en-3-ols.

Example 45

15.7 g of phosphorus trichloride were carefully added to a mixture of 23.7 S 3i7.11-T ^r i.nie'fchyldod.eca-1,6,10-trien-3-ol _and 200 ecm pyridine at -15 ° C , added with stirring. After the addition had ended, the mixture was stirred for a further 4 hours at -15 G., 100 g of ice and 200 ecm of diethyl ether were added. The sustainer bene mixture was washed with water until neutral, dried over sodium sulfate and evaporated to dryness so} 1-Chloro-3,7,11-trimethyldoäeca-2,6,10-triene with a Kp _Q "120 C. n ^ »1.4908, received.

Likewise, i-chloro-3,7,1i-trimethyltrideca-2,6,10-triene became and 1-chlorine-3, T1-dimethyl-7-ethyltrideca-2, b, 10-triene from 3> 7 »11-i ^ i'nethyltriäeca-1,6,10-trien-3-ol or 3> 11-dirnethyl-7-ethyl-trideoa-1,6,10-trien-3-ol manufactured.

Repeat the above procedure using Phosphorus tribromide instead of phosphorus trichioride provided the corresponding compounds 1-bromo-3,7 »11-trimethyldofleoa-

20982471184

BATH ORIGINAL

2,6,10-triene, 1-bromo-3 ₅ 7? 1i-trimethyltrideca-2,6,10-triene and 1-bromo-3,11-dimethyl-7-ethyl-trideca-2,6,10-triene ,

Example 46

A mixture of 20 g of i-bromo-3,7,1i-trimethyldodeca-2,6,10-triene (prepared according to Example 45), 10 ecm of acetonitrile and 1ΰ g of potassium fluoride was heated to 125.degree. heated. The mixture was then cooled, 200 ecm of dietary ether was added, and the mixture was washed with barrels until the wash water was free of fluoride and bromide ions. The washed mixture was then dried over magnesium sulphate and evaporated to dryness; 1-fluoro -3 ₉ 7,1i-trimethyldodeca-2,6,10-triene was thus obtained.

Similarly, 1-fluoro-3,7,1i-trimethyltrideca-2,6,10-triene and i-iTuoro-3,11-dimethyl-7-ethyltrideca-2 _II 6,1O-triene from 1-bromo- 3.7 »1i-trimethyltrideca-2,6,10-triene and 1-bromo-3,11-dimethyl-7-ethyltrideca-2,6,10-triene. The use of silver fluoride in place of potassium fluoride in the above procedure gave similar results.

The repetition of the manufacturing process for 1-halides according to Example 45 and 46 with others prepared according to Example 43 1-en-3-ols as starting materials (those from the other, ketones prepared according to Example 1 to 3) gave the corresponding 1-halides. The 1-halides thus produced were then in other parts of the molecule in any order and up to the necessary, desired and chemically feasible degree in the above for the esters, acids, Formed alcohols and amides as described.

209824/1184

■ '"- ^

BATH ORIGINAL

Example ^ X

13.7 g of phosphorus trichloride were slowly added "at -15 ° C. under dry" conditions to a mixture of 23.6 g of 5,7,11-trimethyl-3-hydroxydoaeea-1,6,10-triene and 100 ecm of pyridine, When the addition was complete, the mixture was stirred for a further 2 hours at -15 G and then allowed to come to room temperature. Then 20 g of diethylamine were added to the 1-chloro-3,7 »11-trimethyldodeca-2,6,10 -triene-containing reaction mixture was added and the mixture obtained was left to stand for 2 hours, then ecm Kethylene chloride was added, washed neutral with fesser, dried over sodium sulfate and evaporated to dryness in vacuo, whereupon N, lJ-diethyl-3.7 »11 -trimethyld ode ca-2,6,10-trienylamine, b.p. _{Q 1} , -130 ° Cj η = 1.4775, was obtained.

Similarly, IT, N-diethyl-3,7,11-trimethyltrideca-2,6,10-trienylamine and H, S-diethyl-3,11-dimethyl-7-ethyltrideea-2,6,10-trienylamine from 1-chloro-3,7,11-trimethyltrideca-2,6,10-triene "or 1-chloro-3,11-dimethyl-7-ethyltrideca-2,6,10-triene.

By repeating the above procedure using ammonia, diethylamine and morpholine, 3,7,11-triethyldodeca-2,6,10-trienylamine, H, N-diethyl-3,7,11-trimethyldodeca-2,6, 10-trienylamine and IΓ, lί-morpholino-3,7 »11-trimethyldodβca-2.6 _t 10-trienylamine produced. The use of other amines, e.g. methylamine, ithylamine, diphenylamine, fii- (2-hydroxyltrithyl) * aein, piperazine, etc., gave the corresponding H-substituted amines.

209824/1184

BATH ORIGINAL

Repetition of the oxigenic amine production process with other 1-chloro compounds (prepared according to Example 45 ff) the corresponding amines were obtained as starting compounds. Those produced according to Example 45, not trained Chlorides can also preferably be treated as above to obtain the corresponding amines, whereupon the amines to others Place the molecule in any order and up to the necessary desired and chemically feasible measure as described above for the esters, acids, alcohols, amides and halides can be trained. The amines can also be prepared from the amides (preferably those already formed according to Example 40 Amides) can be prepared by the following general procedure «

To a solution of 3% H, N ~ Biäthyl 5,7,1-trimethyl-2-t> -3-öxidododeca _{6-t-äienamid} 10 in 60 cc of tetrahydrofuran was added a solution of 1.2 g of lithium aluminum hydride in. 25 ecm tetrahydrofuran was added and the mixture was refluxed for 5 hours. Then ithylacetat and then 250 ecm of water was carefully added, whereupon the product was extracted old ether and the extracts were washed with water, dried and evaporated under reduced pressure. In this way N, ii-diethyl-5 »7> 11-trimethyl-5-hydroxy-dodeca-6,10-dienylamine, which can optionally be purified by column chromatography, was obtained.

In a similarly quiet manner, e.g. lI, U-I) iathyl-5,7,11-trimethyl-i 1-hydroxydodeca-2,6-dienylamine, ^ TOlRi 1.02 ppm, triplet, J = * 7 c / s, j 1.19 P pm (2x11-0 ^); 1.57 ppm (7-Cn ^)} 1.62 ppm

fJH ^ from 2-trans)} 1.70 ppm (3-ÜÜ, from 2-cis) j 2, i> 0 ppm quartet,

20982A / 1184 BAD OMQINAL

J-7 o / s, (2XiTCH ₂ UH ₃ ); 3.04 ppm, doublet, J = 6 c / s, (1-GH ₂ ~); 5.10 ppm, multiplet, (6-H); 5.25 ppm, multiplet, (2-E) J, K, NI »iathyl-

3.7 » ¹ 1- ' ^fc rimethyldodeca-6,10-dienylamine, bp . 150 ° Cj η =

UjI ium D

1.4695) N, N-diethyl-3,11-diethyl-7-and-ethyl-H-hydroxy-trideca-2,6-dienylamine and IT, N ~ Diivthyl-3,1i-dimethyl-7- ^ ethyl-H-hydroxytrideca-6,10-dienylamine obtain.

Example 48

A mixture of 29.2 g of i-bromo-3,7 »1i-triraethyldodeca-2,6,10-triene, 300 ecm xylene and 100% tritithyl phosphite became 1 otund heated to reflux under a nitrogen atmosphere, the cooled mixture became neutral with 1N-3 hydrochloric acid and then with fesser washed, dried over sodium sulfate and under vacuum for Evaporated to dryness} this gave diethyl 3,7,11-trimethyl-dodeca-2,6,10-trienylphosphonate, since it was isolated by column chromatography.

T> iä ± hyir3.7 _f TI-trimethyltrideca-2,6,10-trienylphosphonate and diethyl-3,11-dimethyl-7-ethyltrideca-2,6,10-trienylphosphonate were obtained from 1-bromo-3, 7,11-trimethyltrideca-2,6,10-triene tzw. i-Bromo-3,11-dimethyl-7-ethyltrideca-2,6,10-triene was obtained.

By repeating the above procedure using Dimethylphoephit, Dipropylphoaphit and diphenyl phosphite were Dimethyl-3,7 '1i-trimethyl-2,6,10-trienylphosphonat, dipropyl-3,7 1 11-trime thyldodeca-2,6,10-trienylphosphonat and diphenyl 3,7 »11-trimethyldodeca-2, ο, 10-trienylphosphonate. Use of other trialkyl phosphites provided the corresponding dialkyl phosphonates.

BATH ORIGINAL

209 824/1184 ■ "

By. -Repeat the above phosphonate preparation process below
Using other 1-bromine compounds, prepared according to Example 45 ff, as starting materials, the corresponding phosphonates were used
manufactured. The non-formed bromides prepared in accordance with Example 45 can also preferably be used to achieve the corresponding
Phosphonates are treated as above, whereupon aie phosphonates at other locations on the molecule in any order and to the necessary, desired and chemically feasible degree as described above for the esters, acids, alcohols, amides, halides and amines
v / be trained. For example, the following typical phosphonates were made}

Diethyl 3,7,11-trimethyl-10,11-oxidododeca-2,6-dienylphosphonate
Diethyl-5,7 _r 11-trimethyl-10-bromo-11-hydroxydodeca-2,6-dienylphosphonat

Diethyl 2 _> 5i 6.7} 10,11-trisoxido-3,7,11-trimethyldodeca-2,6-dienylphosphonate

Diethyl 3,7,11-trichloro-3,7,11-trimethyldodeca-2,6-dienylphosphonate

Those given in Examples 34, 35, 38 and 39 above for alcohols Reactions are equally applicable to those according to the invention Halides, amines and phosphonates to produce the corresponding Halides, amines and phosphonates, which include the various oxido, fused methylene, fused dichlorine thylen-, fused Difluoromethylene and Hexahalogengruppierungen contain, where "for compounds that contain a Οζβ-unsaturated Carbonylaystem, no addition is provided at the G-2,3 position of these compounds is.

209824/1184

BATH ORIGINAL

I6189A6

Example 49

20 g of benzene were added to a solution of 20.9 g of the x.thylenketalß of 1-bromohexan-4-one (prepared by treating 1-bromo-4-hexanone with ethylene glycol in benzene in the presence of p-ioluenesulphonic acid) in 100 ecm of benzene Triphenylphosphine was added, the mixture heated to reflux for 2 hours and then filtered. The solid material thus collected was washed with benzene, dried under reduced pressure and added to 6.49 g of butyllithium in 50 ecm of dimethyl sulfoxide. The solution was stirred to obtain an orange solution, whereupon 1.8 g of ethyl methyl ketone were added. This mixture was stirred for about 8 hours at about 25 ° C., poured into water and the mixture was extracted with ether. The ethereal extracts were concentrated and the residue thus obtained was added to an O, 1N solution of maltic acid in aqueous acetone and about The mixture was then poured into ice water and extracted with ethyl acetate. After washing the extracts with water and drying over sodium sulfate, they were evaporated and a mixture of the cis and trans isomers of 7-lletb.ylnon-6 was introduced -en- ~ j> -one, which was separated into the individual isomers by preparative grass / liquid chromatography.

20 g of triphenylphosphine were added to a solution of 20.9 g of the ethylene ketale of 1-bromopentan-4-one in 100 ecm of benzene, this mixture was refluxed for 2 hours and then filtered. The solid material thus collected was washed with benzene, dried under reduced pressure and added to 6.49 g of butyllithium in 50 ecm of dimethyl sulfoxide. This mixture was "up to the achievement."

209824/1184

BATH ORIGINAL

an orange "solution, whereupon 5.5 g of the cis-7-2fethylnon-6-en-; 5-one (prepared in the above paragraph) were added. This mixture was stirred at about 25 g for about 8 hours, in water The ethereal extracts were concentrated and the residue thus obtained was added to a Q, Hf solution of hydrochloric acid in aqueous acetone and stirred for about 15 hours. _f-2-one 10-methyldodeca-5i9-dien .After bottles these extracts with water and *. drying over! sodium sulfate were evaporated to give a mixture of trans, cis and ciSjCis isomers of 6-ethyl ~ by preparative Gas / liquid chromatography was separated into the individual isomers.

By repeating the above procedure using trans-7-methylnon-6-en-5-one in place of cia-7-methylnon- $ - en-3-one a mixture of the cis, trans and trans, trans isomers was obtained from o-JLthyl-IO-methyldodeca ^ jiJ-dien ^ -on, described in above she was separated. .

In the above process, instead of the trans or cis isomer of 7-methylnon-6-en-3-one ⁸ Js starting material, a mixture of the isomers obtained in paragraph 1 can be used, whereby a mixture of the four isomers is obtained, which then can be separated into the four isomers by preparative (ias / liquid chromatography).

A mixture of 11.2 g of diethylcarbethoxymethylphoaphonate in 100 ecm "diglyoi was treated with 2.4 g of sodium hydride. This mixture was stirred until evolution ceased, then

_209824 / 1184

BATH ORIGINAL

slowly with stirring 7 »5 S trans, cis-o-ethyl-1O-methyldodeca-5,9-dien-2-one added, the temperature being kept below 30 ° C. vmrde. The mixture was stirred for about 15 minutes, diluted with water and extracted with i-ether. The ethereal extracts were washed well with water, dried over sodium sulfate and evaporated to remove the solvent; This gave a mixture of the trans, trans, cis and cis, trans, cis isomers of ethyl-3,11-rÜmethyl-7- £ i.th, yltrideca-2,6,10-trienoate, which was produced by preparative gas / Liquid chromatography was separated.

■ The above procedure was repeated 5 times, the first time ciSjCis-ö-Äthyl-IO-methyldodeca - ^,; ^, 2-one as starting material; the second time trans, trans-6- / ethyl-10-methyldodeca-5,9-dien-2-one and the third time eis, trans-o-Ethyl-IO-methyldodeca ^^ - dien-2-one was used; so you got the ice, ice, trans- and ice, ice, cis-j die trans, trans, trans- and trans, trans, cis-; or the cis, trans, trans and cis, trans, cis isomers of ethyl-3,11-diinethyl-7-ethyltrideca-2,6,1ü-triehoate. The isomers were separated by preparative gas / liquid chromatography.

1.0 molar equivalent of m-chloroperbenzoic acid in 100 ecm of methylene chloride was slowly added to a mixture of 2 g of tranSjtrans ^ is-ethyl ^ fH-diEiethyl-7-ethyltrideea-2,6,10-trienoate in 150 ecm of methylene chloride at 0 G. The mixture obtained was then left to stand for 15 minutes at 0 ° C. and then washed with 2% aqueous sodium sulfite solution, with 5 aqueous sodium bicarbonate solution and with water, dried over sodium sulfate and evaporated to an oil, which is a mixture

209824/1184

BATH ORiGINAL.

the 10.11-üxido-, the b, 7-0xido- and the 6.7? 10,11- "bis oxido compounds of trans, trans, ois-ethyl-3 , 11-dimethyl-7-ethyltrideca-2,6,10-trienoate. This mixture was then purified and separated into the individual epoxides by chromatography on silica , whereby trans, cis-iithyl-3,11-dimethyl-7-ethyl-10,11-oxidotrideca-2,6,10-trienoate was obtained.

Me above mentioned epoxy processes can also be done with different other isomeric starting compounds are carried out, whereby one ζ.3. trans, trans, trans-ethyl-3,11-dimethyl-7-ethy1-10,11-oxidotrideca-2,6-dienoate, cis, trans, cis-ithyl-3,11-dimethyl-7- & -thyl-10,11-oxicO-trideca-2,6-oleoate etc. receives.

example ^ O

A mixture of 1 mg of trans, trans, "trans-Αthyl-3, 1 -1-dimethyl-7-ethyl-10,11-oxidotrideca-2, b-r'ienoate and trans, trans, cis-ethyl-5, 11 -dime thy 1-7-ethj-1-10,11-oxidotrideca-2,6-dienoate was chromatographed in a glass column 6 m long and 3 mm internal diameter filled with 100/120 mesh neutral brick which was filled with plated 5- ^ sodium Diäthylenglykolsuccinat v ^ ar. the flow rate of nitrogen used as' irägcrgas was 40 cai / min and the separation was performed using a Ternpöi-iVarprogrammes, f "as" ^ ei 1> 0 ^u C. began and continued at 2 C./min. It was started with the introduction and continued for 10 minutes. The separation was completed at 170 G. Two fractions were thus collected, one of which was trans, trans, trans-ethyl-5,11- dimethyl-7-ethyl-1O, i1-oxidotrideca-2, b-dienoate and

209824/1184 BATH

the other trans, trans, cis- ^ thyl-3, H-dimethyl-7-octthyl-IO, 11 oxidotrideca-2,6-dienoate contained. The two fractions were identified by a combination of the IR spectral, mass spectral and nuclear mass spectral data and by common uzonolysis.

Similarly, the others made in Example 1 were made Isomers separated and identified, such as cis, trans, trans-Jithyl-3,11-dimethyl-7-ethyl-1O, 11-oxidotrideca-2,6-dienoate and cis, trans, cis-Ethy1-3,11-dimethyl-7-ethyl-IO, 11-oxidotrideca-2,6-dienoate.

209824/1184 BAD ORIGINAL

Claims (1)

H- Claims 1, - Process for the production of new connections, characterized in that that one can connect the formula: R ³ . f Y R ⁴ - C - GH - (CH ₀ ). - C - GH - (CHJ ₉ - C \ z ¹¹¹ z ¹⁰ 'z ⁷ ' z ^6t in which R to R each represent an alkyl group with 1-6 carbon 61 7
material atoms stands; Z and Z each represent hydrogen or together - represent a carbon-carbon double bond; 10 '11'
Z and Z each represent hydrogen or - together - represent a carbon-carbon double bond; in any order and up to the necessary and desired level A) a carbalkoxymethylphosphonate to the corresponding hydrocarbon -2,6,1O-trienoate alkyl ester or the 6,7- and / or 10,11-dehydro derivative treated of the same and 1) the hydrocarbon enoate alkyl ester to the corresponding Kohlwasaeratoff-2,6,10-trienoic acid or the 6,7- and / or 10,11-dihydro derivatives thereof hydrolyzed and / or 2) the hydrocarbon enoate alkyl ester to the corresponding hydrocarbon 2,6, iQ-triene - '{- ol or the 6,7- and / or 10,11-dihydro derivatives thereof reduced and / or 5) the hydrocarbon enoate alkyl ester with an alkali metal amine salt to give the corresponding hydrocarbon-2, _l 6,10-trienamide or the. 6,7- and / or 10,11-dihydro derivatives thereof treated) or with B) Vinyl magnesium bromide to the corresponding hydrocarbon 1,6,10-trien-3-ol or the 6,7- and / or 10,11-dihydro derivatives thereof treated and the enol thus provided with a phosphorus tri 209824 / 1184- B ^A Documents {Art.? ^ l paragraph; » rir. l Sau adetÄndeturUeeei.v.4 »iHv. -ar - halide to the corresponding hydrocarbon ^, 6,10-triene-1-halide or the 6,7- and / or 10,11-dihydro derivatives thereof treated and 1) the hydrocarbon-en-1-halide with an amine to the corresponding Hydrocarbon-2,6,10-triene-amine ofler the 6,7- and / or 10,11-Dihy'droderiva th same traded and / or 2) the carbon-en-1 halide with a tri-substituted one Phosphite to the corresponding hydrocarbon 2,6,10-triene-1-phosphonate or the 6,7- and / or 10,11-dihydro derivatives thereof treated and then in any order and up to the necessary and desired degree any of the connections thus made treated by » 1) Introduction of the oxido group in the C-2,3-, C-6,7- and / or C-10.11 position 2) Introduction of the methylene group on the C-2,3, C-6,7 and / or C-10.11 position j 3) Introduction of the difluoromethylene group in the C-2,3-> C-6.7 and / or C-10.11 position 4) Introduction of the bichloromethylene group in the G-2,3-, C-6,7- and / or G-10,11 position 5) Hydrojcylation in the C-2-, C-3, C-6, C-7- »C-10- and / or C-11 position 6) etherification of any hydroxy group 7) Esterification of any hydroxy group 8) Halogenation in the C-3, C-6, C-7, C-10 and / or C-1Ιο division BAD ORIGINAL 209824/1184 1618949 9) Hydrogenation in the C-2,3, C-6,7 and / or C-10,11 positions and or 10) Formation of acid addition salts of acids and amines to form a compound of the following form Ϋ H ² ■ E ¹ R ⁴ - C - CH - (CH ₀ ), -C - GH - (CH ₉ ) _o - C - CH --R I f ^ ^ t I ^ ^ I "I z ¹¹ z ¹⁰ z ⁷ z ⁶ z ⁵ z ² ; - 0 0 in which R represents one of the groups -COR ⁵ , -CHgOR, -CHR'R ⁸ , -CH ₂ X, -CH ₂ KR ⁷ R ⁸ or -CH ₂ PO (OR ⁹ ) ₂ , where R is hydrogen or alkyl ", b
R is hydrogen, alkyl or acyl, 7 ft R 'and R each represent hydrogen, alkyl, hydroxyalkyl, alkyloxyalkyl, Phenyl or - together with the nitrogen atom to which it is attached are bound - for pyrrolidino, morpholino, piperidino, pipeiazino or 4-alkylpxperazino, R denotes alkyl or phenyl and
Jt represents "bromine, chlorine or fluorine; R, R, R and R each represent an alkyl group with 1-6 carbon atoms,
Z represents hydrogen or hydroxy, Ί? for hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine or - together with Z - stands for a carbon-carbon double bond between C-2,3 or one of the groups ^ O, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ , Z denotes hydrogen, hydroxy, bromine, chlorine or fluorine, 7th
Z 'represents hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine or - together with Z - for a carbon-carbon double bond 209824/1184 r- BAD ORIGINAL between C-6.7 or one of the groups , O, / CH ₂ , / GCl ₂ ^and / ^CF 2, Z denotes hydrogen, hydroxy, bromine, chlorine or fluorine, Z denotes hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine or - together with Z - a carbon-carbon double bond between C-10, 11 or one of the groups ^ O, Means ^ CH ₂ , ^ CCl ₂ and ^ ₂ , provided that 1) if Ί? Is hydrogen, Z means hydrogen, 7 6 2) if Z 'is hydrogen, Z is hydrogen, 3) if Z ^{11 is} hydrogen, Z ^{10 is} hydrogen, 4) if R is group 0 - C - 0R ^P 3 2 means, then Z together with Z is a carbon-carbon double bond between C-2,3 or one of the groups ^ ¹ O or / CH ₂ J and 5) if R is group O "7 8
- CNR ^f R - χ 2 \ means, then Z together with Z is a carbon-carbon double bond between C-2,3 or one of the groups ^ 0 or
and the acid addition salts of the acids and amines. 2.- Method according to claim 1, characterized in that R to R ⁴ each represent methyl or ethyl. 3.- method naoh claim 1, daduroh gekennze is worth the fact that R for ti 5 c the group -COR ^ , in which R ^ denotes Wasieretoff or alkyl , R to R ^ each represent iithyl or methyl, 209824/1184,
BATH ORIGINAL 2 3 Z and Z have the above meaning, Z stands for hydrogen or chlorine, 7th Z is hydrogen, chlorine or - together with Z - is a carbon-carbon double bond between C-6.7 or one of the groups ^ 0, ^ CH ₂ and ^ CF ₂ , Z is hydrogen, hydroxy or chlorine and 11 Z denotes hydroxy, alkoxy, chlorine or - together with Z - one of the groups ^ 0, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ . 4 · - Process according to claim 3, characterized in that B. stands for methyl or ethyl, R ¹ and R each stand for methyl and 2 4 R and R each represent methyl or ethyl. 5 · - The method according to claim 1, characterized in that R for ⁰ the group ■ η _ητ > 5, in which R denotes jithyl, R and R- * each represent methyl, R and R each represent ethyl, 2 3 Z and Z geeeiB »aifff for ⁱ - * ifewir =: i« iUe »8toff-Kohl.e £ istoffhJ3 double bond between C-2,3, £ t 7 Z and Z together represent a carbon-carbon double bond between C-6.7 and Z and Z together represent the group ^ O. 6, - The method according to claim 1, characterized in that R stands for the group -CH ₂ OR, where R is hydrogen or alkyl, 14 R to R each represent ethyl or methyl, 2 3 Z and Z each have the above meaning, Z stands for hydrogen or chlorine, 7th Z for hydrogen, chlorine or - together with Z - for one 2-09824 / 11 BAD ORIGINAL I · 1 t ι I ■ ι Carbon-carbon double bond between C-6.7 or one of the groups ^ 0, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ , 10
Z denotes hydrogen, hydroxy or chlorine, and Z denotes hydroxy, alkoxy, chlorine or - together with Z - denotes one of the groups ^ 0, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ . 7 · - Method according to claim 6, characterized in that R stands for methyl or ethyl, R and R each represent methyl, and 2 4
R and R each represent methyl or ethyl. 8.- The method according to claim 1, characterized in that 0 7 θ R for the group ] ϋ, τ. _ττ >7τ> ^θ , in which R 'and R each represent -OJMn It Hydrogen, alkyl or - together with the nitrogen atom to which they are bound - stand for pyrrolidino or morpholino, 14th
R to R each represent ethyl or methyl, 2 5
Z and Z have the above meaning Z represents hydrogen or chlorine, Z for hydrogen, chlorine or - together with Z for a carbon-carbon double bond between C-6.7 or one of the groups ^ O, v ^CH 2 'x ^CC1 2 ^and s ^Gi> 2 ^ateht »Z for hydrogen, hydroxy or Is chlorine, and Z is hydroxy, alkoxy, chlorine or - together with Z - is one of the groups ^ 0, ^ CH ₂ , ^ CCl ₂ and ^ ¹ CF ₂ . 9 · - The method according to claim 8, characterized in that R and R each represent methyl and R and R each represent methyl or ethyl. 10.- The method according to claim 1, characterized in that R is the group -CH ₂ X eteht, where X is bromine, chlorine or fluorine, 209824/1184 BATH ORIGINAL 1,189,6 1 4 R "to. R each represent ethyl or methyl, 2 ■ 3 Z and Z have the above meaning Z represents hydrogen or chlorine, 7 6 ■ Z 'represents hydrogen-chlorine or - together with Z represents a carbon-carbon double bond between 0 * 6.7 or one of the groups ^ O, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ , Z is hydrogen, hydroxy or chlorine means, and Z for hydroxy, alkoxy, chlorine or - together with Z - for one of the groups ^ iO, ^ ⁰² ? ' ^ ⁰⁰¹ P ^etc. 11.- The method according to claim 1, characterized in that 7 ft 7 ft R represents the group -CH ₃ NR'R, in which R 'and R each represent hydrogen or alkyl or - together with the nitrogen atom to which Bie are bonded - represent pyrrolidino or morpholino, R to R ^ each represent ethyl or methyl , 2 3
Z and Z have the above meaning Z denotes hydrogen or chlorine, Z stands for hydrogen, chlorine or - together with Z - for a carbon-carbon double bond between C-6.7 or one of the groups ^> O, ^ CCl ₂ , ^ CH ₂ and ^ CF ₂ ^Btelrt »Z hydrogen, hydroxy or Means chlorine, and Z stands for hydroxy, alkoxy, chlorine or - together with Z - for one of the groups> 0, ^ CH ₂ , ^ CCl ₂ and / 01g. Stands. 12. Process according to Claim 1, characterized in that R stands for the group -CH ₂ P0 (OR ⁷ ) ₂ , where R ^{7 is} alkyl or phenyl, 2Q182A / 1184 SAD ORIGINAL -m- R to R each stand for ethyl or methyl, ' 2 3
Z and Z have the above meaning Z denotes hydrogen or chlorine, Z 'represents hydrogen, chlorine or - together with Z - represents a carbon-carbon double bond between C-6.7 or one of the groups ^ O, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ , Z is hydrogen, hydroxy or Chlorine means, and 11 10 Z represents hydroxy, alkoxy, chlorine or - together with Z - represents one of the groups ^ 0, ^ CH ₂ , ^ CCl ₂ and / CP ₂ . 13 - compounds of the general formula: f R ² R ¹ . R ⁴ - O - CH - (CH ₉ ) _p - C - CH - (CHp) ρ -C-CH-R I I ^ I I It z ¹¹ z ¹⁰ z ⁷ z ⁶ z ⁵ z ² 0 0 ·· S 6 "78 in which R stands for one of the groups -COR, -CH ₂ OR, -CWR ¹ R, -CH ₂ X, -CH ₂ NR ⁷ R ⁸ and -CH ₂ PO (OR ⁹ ) ₂ , in which B. is hydrogen or alkyl,
R denotes hydrogen, alkyl or acyl, R 'and R each denote hydrogen, alkyl, hydroxyalkyl, alkyloxyalkyl, phenyl or - together with the nitrogen atom to which they are attached, pyrrolidino, morpholino, piperidino, piperazino or 4-alkylpiperazino,
R ^{9 represents} alkyl or phenyl, and
X is bromine, chlorine or fluorine,
R to R each represent an alkyl group with 1-6 carbon atoms, 2
Z is hydrogen or hydroxy, Ί? Hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine or - in common- sam with Z - a carbon-carbon-iicjjjnulbinduiv <3viiichen 209824/118 4
BATH ORIGINAL C-2,3 or one of the groups ^ 0, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ "means, Z means hydrogen, hydroxy, bromine, chlorine or fluorine", 7th
Z represents hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine or - together with Z - represents a carbon-carbon double bond between C-10,10 or one of the groups ^ O, ^ CH ₂ , ^ CCl ₂ and ^ CFg , Z denotes hydrogen, hydroxy, bromine, chlorine or fluorine, Z denotes hydrogen, hydroxy, alkoxy, bromine, chlorine, fluorine or - together with Z - a carbon-carbon double bond between C-6.7 or one of the groups ^ 0, ^ GH ₂ , - ^ ¹ CCl ₂ and ^ CF ^, and the acid addition salts of acids and amines; with the following, independent conditions that 1) Z does not represent hydrogen when Z represents hydroxy} 2 · 3 Z is hydrogen when Z is hydrogen} 7 6 Z does not represent hydrogen when Z is hydroxy, bromine, chlorine or Fluorine means} 6 7 Z is hydrogen when Z is hydrogen} Z does not represent hydrogen when Z represents hydroxy, bromine, chlorine or fluorine and Z is hydrogen when Z is hydrogen} BATH ORIGINAL
209824/1184 it 7 a 2) Under d, the prerequisite that R means -CNR'R is a) when Z is hydrogen, Z is hydrogen, a Hydroxy or (lower) alkoxy group; b) if Z and Z ^ together form a carbon-carbon double 6 7 ^! bond, Z and Z together form a carbon-carbon double bond, R, R and R- ⁵ methyl and R ⁴ (lower) | 11 ^! Alkyl, Z for hydroxy, (lower) alkoxy, bromine, 10 chlorine, fluorine or together with Z for one of the groups ₂ , > CC1 ₂ or ₂ | ρ * 5! c) if Z and Z together form a carbon-carbon dop 6 7 ■ I pelbindung, Z and Z together represent a carbon-carbon double bond, R ^1, R ² is methyl, R ⁵ is (lower) alkyl and R ₁ ⁴ 11 l Mean methyl, Z stands for hydroxy, (lower) alkoxy, bromine, Chlorine, fluorine or together with Z for one of the groups or XJF ₂ ; d) when R ¹ , R ² and R ^{3 are} methyl, R ^{4 is} 4-methylpentyl, Z ³ , Z ⁷ and 11 7 ' Z denotes hydrogen, at least one radical R 'or R not for hydrogen; ; e) when R ¹ , R ^{2 are} methyl, R ^{3 are} 4-methylpentyl, R ^{4 are} methyl, Z ³ , Z ⁷ 11 '7 and Z is hydrogen, at least one of the radicals R ' 8 ^! or R is not hydrogen; and i f) Z ² for hydrogen or hydroxy and Z ³ for hydrogen, Hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or together with Z for a carbon-carbon double bond between C-2,3, or for one of the groups ^ .0 or 209824/118 Λ
BATH ORIGINAL /O* 3) Provided that R is -CH ₂ OR, is a) when R, R, R and R are each methyl, Z together with; a carbon-carbon double bond and Z 'and j together means a carbon-carbon double bond 11 ■ ten, Z for hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, 10
or together with Z for one of the groups or ^ ¹ CF ₂ ; b) when R, R ·, R and R- are each methyl, Z together with; Z S ^ Q mean, Z for hydrogen, hydroxy, (low) 2 ^; Alkoxy, bromine, chlorine, fluorine or together with Z for one of the groups "^ X), " ^ CH ₂ , ^> CC1 ₂ or c) when R ₁ R, R and R ^ methyl, Z 'and Z together are one 11 1Π Carbon-carbon double bond and Z and Z together mean a carbon-carbon double bond, Ίι for hydrogen, (low) alkoxy, fluorine or together with Z for one of the groups ^ 0, or if- _? ,
d) / R ', R ^ and R ^ are each methyl, R ⁴ (lower) alkyl, Ζ' is hydrogen and Z ^{11 is} hydrogen, 7? for (lower) alkoxy, bromine, chlorine, fluorine, or together with Z ² for one groups or e) when R, R and R ^{4- are} each methyl, R ^ (lower) alkyl, and Z ^{11 is} hydrogen, Z ^{3 is} (lower) alkoxy, Chlorine, fluorine, or together with Z for one of the groups "! ^ 0, ^ CH ₂ , 2> CC1 ₂ or ■ χ- ίι 10 and Z together with Z respectively 209824/1184 f) when R ¹ , R ² and. R ³ each methyl, R ⁴ 4-methylpentyl, Z ⁷ and 3 together a carbon-carbon double bond and Z ¹¹ and Z together a carbon-carbon-carbon ■ 2 ' Mean double bond, Ίτ for hydrogen, hydroxy, ( ^! Low- 2 'rig) alkoxy, bromine, chlorine, fluorine, or together with Z for one of the groups> CH ₉ ,> CC1 _P or g) when R ¹ , R ² and R ^{4 are} each methyl, R ³ 4-methylpentyl, ¹ Z ⁷ c. ! and Z together is a carbon-carbon double bond 11 1Ω ' and Z and Z together represent a carbon-carbon double bond, Z ³ for hydrogen, hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or together with Z for one of the groups> CH ₂ , ^ -CCl ₂ or i ^ CFgj h) when R, R ² and R ^{3 are} each methyl, R ⁴ (lower) alkyl, and Z together is a carbon-carbon double bond 7 6 ι and Z 'and Z together form a carbon-carbon Dqppel- 11
bond, Z for hydroxy, (lower) alkoxy, bromine, 10 chlorine, fluorine, or together with Z for one of the groups CC1 ₂ or> CF ₂ ; i) when R ¹ , R ² and R ^{4 are} each methyl, R ³ (lower) alkyl, and Z together is a carbon-carbon double bond 7 6
and Z 'and Z together form a carbon-carbon double 11
bond, Z for hydroxy, (lower) alkoxy, bromine, Chlorine, fluorine, or together with Z for one of the groups ^ O,> CH ₂ ,> CC1 ₂ or> CF ₂ J when R ¹ , R ² and R ^{3 are} each methyl, R ⁴ (lower) alkyl, 3 2 '■! Z ^ together with Z a Kohl ens toff -Kohl ens toff-DoppeJIf 209824/1184 1110
bond and Z .and Z together mean a carbon-carbon double bond, Z for hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or together with Z for one of the groups ^ P, ^ CH ₂ , 3CC1 ₂ or> CF ₂ ; and k) when R ¹ , R ² and R ^{4 are} each methyl, R ⁵ (lower) alkyl, ' 7? ρ
together with Z a carbon-carbon double bond and Z together with Z together a carbon-carbon 7 ⁽ Substance double bond mean, Z 'for hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or together with Z for one of the groups 1 ^ 0, - ₂ 0! 4) With the proviso that R means -C-OR ^, stands 12 3 4. 3 2 a) if R, R, R ^ and R ^ "each methyl, Z ^ and Z together a carbon-carbon double bond, Z 'and Z to- 11 together a carbon-carbon double bond and Z ■ and Z together ^> 0 mean, R ^ for (lower) alkyl with 2 to 6 carbon atoms; ; b) when R ¹ and R ^{4 are} each methyl, R ² and R ^{5 are} each ethyl, Z ⁵ and Z together form a carbon-carbon double bond, 7 6 Z 'and Z together form a' carbon-carbon double bond 1110 - ^ 5 tion and Z and Z together mean J> 0, R "^ for hydrogen or (lower ^ alkyl of 2 to 6 carbon atoms; c) when R and R ^{5 are} each methyl ,. R and R ^ each ethyl, Z ^ 2 ' and Z together form a carbon-carbon double bond, 7 6 Z and Z together form a carbon-carbon double bond and Z and Z together mean Z ^ O, R ^ for water BATH ORIGINAL 209824/1184 substance or (lower) alkyl having 2 to 6 carbon atoms; d) if R, R and R ^ are each methyl, R ^ ethyl, 7r and Z j to- 7 together a carbon-carbon double bond, Z 'and Z together form a carbon-carbon double bond 1110 ζ Z and Z together are 2> -0, R ^ is hydrogen (lower) alkyl having 2 to 6 carbon atoms; e) when R ¹ , R ² and R ^ "are each methyl, R ^ ethyl, 7? and Z and or to- 7 'together a carbon-carbon double bond, Z and Z together form a carbon-carbon double bond Z and Z together mean ^ rO, R ^ for hydrogen or Lower) alkyl of 2 to 6 carbon atoms; f) when R, R, R ^-3 and R ^ "are methyl, Z ^ and Z together are one 7 6 Carbon-carbon double bond, Z 'and Z together and ^ iO and Z and Z together mean Ξ> 0, B? for (n ^ .edrig) alkyl of 2 to 6 carbon atoms; g) if R, R, R and R ^ methyl, Z u | ^ d Z together represent a carbon-carbon double bondm Z 'and Z ^ O and Z and Z together represent a carbon-carbon double bond, R ⁵ for lower alkyl of 2 to 6 carbon atoms; Λ η μ rf / * h) when R, R, R and R are methyl, Z and Z together are a carbon-carbon double bond and Z ¹¹ and Z ¹⁰ 'together are a carbon-carbon double bond, Z ^ for (lower) alkoxy, chlorine, bromine, Fluorine or together with Z ² for the group Z BAD ORIGINAL 209824/1184 i) when R ¹ , R ² , R ³ and R ^{4 are} methyl, Z ^{7 are} hydrogen and Z ¹¹ and Z ¹⁰ together are a carbon-carbon double bond, Ί? for hydrogen, (lower) alkoxy, bromine 2
Chlorine, fluorine, or together with Z for one of the group ^ O or> CH _O ; j) when R ¹ , R ² , R ⁵ and R ^{4 are} each methyl, Z ^{7 is} hydrogen, and Z ^{11 is} hydrogen, Tr for (lower) alkoxy, bromine, ρ
Chlorine, fluorine or, together with Z, one of the groups or - k) if R ¹ η-butyl, R ² , B? and -R ^ each denotes methyl, Z 'and each denotes hydrogen, Z ⁵ denotes hydrogen, (low) 2 alkoxy, bromine, chlorine, fluorine, or together with Z for one Carbon-carbon double bond or one of the groups ^ -0 or c - 1) when R, R and R ^ are each methyl, R ^ "4-methylpentyl, 7 6
Hydrogen and Z 'and Z together mean a carbon-carbon double bond, Z ^ for hydrogen, (low) Alkoxy, or together with Z for one of the groups J ^ or m) when R ¹ , R ² and R ⁴ "are each methyl, R ^{5 is} 4-methylpentyl," ¹¹ 7 6
Hydrogen and Z 'and Z together mean a carbon-carbon double bond, Ί? for hydrogen, (low) Alkoxy, or together with Z one of the groups ^ O odejr 1 'ζ · ο
η) if R is ethyl, Ί / and Z together are a carbon-carbon 7 (\ . carbon double bond, Z 'and Z together a carbon 209824/1184 11 10 carbon double bond and Z and Z together denote a carbon-carbon double bond, one of the radicals R ² , R ⁵ or R ^{4 stands} for (lower) alkyl with 2 b ^ s 6 carbon atoms; o) if R ^ methyl, • Ζ ρ (lower) alkyl, Tr and Z together are one 7 6 Carbon-carbon double bond, Z 'and Z together 11 I is a carbon-carbon double bond and Z. and Z together a carbon-carbon double bond means 1 2
th, one of the radicals R or R for (lower) alkyl ijait 2 to 6 carbon atoms; p) when R (lower) alkyl, R ^ methyl, Z and Z together denote a carbon-carbon double bond, and Z together represent a carbon-carbon double bond and Z and Z ° together form a carbon-carbon 1 2 double bond, one of the radicals R or R for (lower) alkyl of 2 to 6 carbon atoms; q) when R ⁵ (lower) alkyl, R ^ methyl, 7? and Z ² together one 7 6 Carbon-carbon double bond, Z 'and Z together 11 a carbon-carbon double bond and Z! is hydrogen, one of the radicals R or R ^{2 is} (lower) alkyl having 2 to 6 carbon atoms; r) if B? Methyl, R ⁴ (lower) alkyl, 7? and Z ² together one I ₇ hydrocarbon-hydrocarbon double bond, Z 'and Z together have a carbon-carbon double bond and 11 ι ρ Z denotes hydrogen, one of the radicals R or RT for (lower) alkyl of 2 to 6 carbon atoms; 209824/1184 s) when R ¹ , R ² and ¹ R ³ methyl, R ⁴ 4-methylpentyl, Ί? and Z together represent a carbon-carbon double bond and Z ^ hydrogen, Z ¹¹ for hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or together with Z for one of the pen ^ O,> CH ₂ ,> CC1 ₂ or ; t) when R ¹ , R ² and R ^{4 are} each methyl, R ^{5 is} 4-methylpentyl, and Z together is a carbon-carbon double bond 7 11 and Z is hydrogen, Z is hydroxy (low) 10 Alkoxy, bromine, chlorine, fluorine, or together with Z for one of the groups JiO, -XIH ₂ , ^ CCl ₂ or XF ₂ ; u) when R ^{3 is} methyl, R ^{4 is} 4-methylpentyl, Z ³ , Z ⁷ and Z ^11, respectively 12! Denotes hydrogen, one of the radicals R or R denotes (lower) alkyl having 2 to 6 carbon atoms; v) when R ^{3 is} 4-methylpentyl, R ^{4 is} methyl, Z ³ and Z ^{11 are} each hydrogen, one of the radicals R or R is (! lower) alkyl having 2 to 6 carbon atoms; • ζ ο w) if Z and Z together form a carbon-carbon double bond, R (lower) alkyl, Z and Z each water 7 11 substance and Z 'and Z each mean chlorine, one of the Radicals R ¹ , R ² , R ³ or R ^{4 represent} (lower) alkyl having 2 to carbon atoms; and 2 ^ 5 x) Z for hydrogen or hydroxy and Z ^ for hydrogen, Hydroxy, (lower) alkoxy, bromine, chlorine, fluorine, or m: .t 2
Z together for a carbon-carbon double bond between C-2,3 or one of the groups ^ O or Ί 209824/1184 7 8 ' 5) Provided that R is -CH ₂ NR'R, a) when R, R and R ^ are each methyl, R ^ (lower) alkyl and Z 'and Z each represent hydrogen, Z ^ for (low) j 2 l alkoxy, bromine, chlorine, fluorine or together with Z for one of the Groups ^ rO,> CH ₂ , ^ CCl ₂ or b) when R ¹ , R ² and R ^ each denote methyl, R ⁵ (lower) alkyl, Z ⁷ and Z each denote hydrogen, 7? for (lower) alkoxy, Bromine, chlorine, fluorine or together with Z for one of the groups ^ O, or> CF ₂ ; c) when R ¹ , R ² and R ^{5 are} each methyl, R ^ (lower) alkyl, Z ⁵ 6 i together with Z a carbon-carbon double bond mean, Z for hydroxy, (lower) alkoxy, bromine, chlorine, fluorine or together with Z one of the groups -sO, ^ CH ₉ , -CCl ₉ f Cm C. or -CF ₂ ; d) when R, R and R ^ are each methyl, R ^ (lower) alkyl, Z 2
together with Z a carbon-carbon double bond 7 6 I. and Z together with Z a carbon-carbon double -J ₁ alkoxy, bond, Z for hydroxy, (low) / bromine, 10
Chlorine, fluorine or together with Z for one of the groups> 0, "^ = CH ₂ , ^ CCl ₂ or e) if R, R and B? each methyl, R ^ (lower) alkyl, Zr and Z together denote a carbon-carbon double bond and Z and Z together denote a carbon-carbon double bond, Z 'denotes hydroxyl, (lower) alkoxy, bromine, chlorine, fluorine or, together with Z, denotes one of the groups 5 ^ CH ₉ , ^ CCl ₀ or ~ CF ₀ ; and
■ κ- ο together with Z a carbon-carbon double binary and Z ⁷ 2 0 9 8 2 4/1184 f) when R ¹ , R ² and R ^ are each methyl, R ⁵ (lower) alkyl, and Z together a carbon-carbon double bond and Z ¹¹ and ^{-Z 10} together a carbon-carbon Dojpel bond, Z ⁷ for hydroxy, (lower) alkoxy, bromine, chlorine, fluorine or together with Z for one of the groups ^ 0, : CC1 ₂ or 2 ' 6) With the proviso that R is -CH ₂ X, stands a) when R ¹ , R ² and R ^{5 are} each methyl, R ⁴ (lower) alkyl, ζ 'is hydrogen and Z is hydrogen, Ί? for (low) AIk- 2 oxy, bromine, chlorine, fluorine or together with Z for a dej: Groups ^ iO, "U ^ -CH ₂ ," ^ CCl ₂ or and bromine, 0, b) when R ¹ , R ² and R ⁴ "are each methyl, R ⁵ (lower) alkyl, 2 Z are each hydrogen, Z ^{3 is} (lower) alkoxy, 2
Chlorine, fluorine or together with Z for one of the groups ΙΞ or CC C c) if R, R and R- ^ are each methyl, R λ lower) alkyl, 2
and Z together form a carbon-carbon double bond 7 6 and Z 'and Z together form a carbon-carbon double bond mean, Z stands for hydroxy, (lower) alkoxy, bromine, 1 0 chlorine, fluorine or together with Z for one of the groups' "" "" ** CH "***" CCl or ^^ CF * d) when R ¹ , R ² and R ^{4 are} each methyl, R ⁵ (lower) alkyl, Z ³ 2 "■ i and Z together is a carbon-carbon double bond 7 ft ' and Z 'and Z together are a carbon-carbon double bond, Z ¹¹ for hydroxy, (lower) alkoxy, bromine, 4/1184 10 chlorine, fluorine or together with Z one of the groups JiO, > CC1 ₂ or 2w
e) when R ¹ , R ² and R ^{5 are} each methyl, R ⁴ (lower) alkyl, and Z together form a carbon-carbon double bond and Z and Z together denote a carbon-carbon double bond, Z denotes hydroxy, (lower) alkoxy, bromine Chlorine, fluorine or together with Z for one of the groups! ^ - 0, or IiCFr ,; and f) when R ¹ , R ² and R ^{4 are} each methyl, R ⁵ (lower) alkyl, | Z ⁵ 2 ' together with Z a carbon-carbon double bond 11 10 ' and Z together with Z a carbon-carbon double 7 i bond mean, Z 'for hydroxy, (low) alkoxy, bromine,' chlorine, Fluorine or together with Z for one of the groups ^ -0, or> CF ₂ . 209824/1 1 - 99 * - 14 · - Compounds according to claim 13, characterized in that R to R each represent methyl or ethyl. 15 · - Connections according to claim 15, characterized in that ⁰ 5 ■ R stands for the group! Ίητ> 5, in which R is hydrogen or alkyl —Ουκ means, R to R each represent iithyl or methyl, 2 3
Z and Z have the meaning given, Z is hydrogen or chlorine, τ f> Z represents hydrogen, chlorine or - together with Z - represents a carbon-carbon double bond between C-6.7 or one of the groups>0,> CH ₂ , ^ CCl ₂ and ^ CP ₂ , Z is hydrogen, hydroxy or chlorine and Z is hydroxy, alkoxy, chlorine or - together with Z - is one of the groups> 0, ^ CH ₂ , ^ CCl ₂ and ^ CP ₂ . 16.- Compounds according to claim 15 »characterized in that R <stands for methyl or ethyl, R and R each represent methyl, and R and R ^ each represent methyl or ethyl. 17.- Compound according to claim 13 »characterized in that 5 ·· R stands for the group "5, where R ^ is ethyl, - uUxt * R and R each represent methyl, R and R each stand for ethyl, Z and Z- * together for a carbon-carbon double bond 209824/1184 are between C-2,3, f \ 7 Z and Z together for a carbon-carbon double bond are between C-6.7, and Z and Z together represent the group ^ O. 18.- Compounds according to claim 13 »characterized in that R is the group -CH ₂ OR, in which R is hydrogen or alkyl, R to R ^ each represent ethyl or methyl, 2 5
Z and Z have the meaning given, Z stands for hydrogen or chlorine, 7 6 Z represents hydrogen, chlorine or - together with Z - represents a carbon-carbon double bond between C-6.7 or one of the groups ^ O, ^ CH ₂ , ^ CCl ₂ and ^ CFg, Z denotes hydrogen, hydroxy or chlorine , and Z represents hydroxy, alkoxy, chlorine or - together with Z - represents one of the groups ^ O, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ . 19 · - Compounds according to claim 18, characterized in that R ^{6 stands} for methyl or ethyl, R and R each represent methyl, and R and R each represent methyl or ethyl. 209824/1184 m- 20.- Compounds according to claim 13, characterized in that "° 7 8 R represents the group "} !, _ΤΏ 7 _Ώ 8, in which R 'and R each represent hydrogen or alkyl or - together with the nitrogen atom to which they are attached - represent pyrrolidino or morpholino, R to R each represent ethyl or methyl, 2 5
Z and Z have the meaning given, Z is hydrogen or chlorine, 7 6 Z 'represents hydrogen, chlorine - or together with Z - represents a carbon-carbon double bond between 0-6.7 or one of the groups> 0, ^ CH ₂ , ^ CCl ₂ and> CF ₂ , Z is hydrogen, hydroxy or Chlorine means, and 11 10 Z, for hydroxy, alkoxy ,. Chlorine or - together with Z -for one of the groups> 0 ^ CH _2, CCl ^ ₂ and> CF _g ^stehti 21. Compounds according to Anspruoh 20, characterized in _t that R ¹ and R ⁵ each are methyl, and R and R are methyl or ethyl respectively. 22. Compounds according to claim 13 »characterized in that R represents the group -CHgX in which X is bromine, chlorine or fluorine means, 1-4- ~ R to R 'each represent ethyl or methyl, 2 3 Z and Z have the meaning given, Z is hydrogen or chlorine, 7 7 Z represents hydrogen, chlorine or - together with Z - represents a carbon-carbon double bond between C-6.7 or one of the groups ^ O, J> CH ₂ , ^ CCl ₂ and ^ CF ₂ , 209824 / 1-184 16189Λ6 Z denotes hydrogen, hydroxyl or chlorine ", and Z denotes hydroxyl, alkoxy, chlorine or - together with Z - denotes one of the groups ^ O, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ . 23.- Compounds according to claim 13 »characterized in that rl Q 7 ft R represents the group -CH ₂ NR R, in which R 'and R each represent hydrogen or alkyl or - together with the nitrogen atom to which they are attached - represent pyrrolidino or morpholino, 1 A R to R each represent ethyl or methyl _r 2 3 Z and Z have the meaning given, Z denotes hydrogen or chlorine, 7 6 Z represents hydrogen, chlorine or - together with Z - represents a carbon-carbon double bond between C-6.7 or one of the groups £ o, ^ CH ₂ , ^ CCl ₂ and ^ CF ₂ , Z is hydrogen, hydroxy or chlorine and Z is hydroxy, alkoxy, chlorine or - together with Z _ is one of the groups ^ O, ^ CH ₂ , ^ ¹ CCl ₂ and ^ CF ₂ . 24.- Compounds according to claim 13, characterized in that R represents the group -CH ₂ PO (OR ^) ₂ , in which R ^ is alkyl or phenyl, 14 -
R to R each represent ethyl or methyl, 23
Z and Z have the meaning given, Z is hydrogen or chlorine, 20982 A / TT8 7 fi Z represents hydrogen, chlorine or - together with Z - represents a carbon-carbon double bond between C-6.7 or one of the groups> 0, ^ CHg,> CC1 ₂ and> CF ₂ , j 10 "■ Z denotes hydrogen, hydroxy or chlorine, and ^: Z denotes hydroxyl, alkoxy, chlorine or - together with Z - denotes one of the groups ^ .O, ^ CH ₂ > CC1 ₂ and> CF ₂ . 25. - "Compounds according to claim 13, characterized in that Q 5
R stands for the group -C-OFr. 26. - Compounds according to claim 25, characterized c "3 2
that Fr ethyl and Z ^ and Z together mean a carbon-carbon double bond. 27 * - compound according to claim 26, characterized in that R, R, R ^ and R ^ each methyl and Z together with Z and 11 1Π Z together with Z each mean ^ O. 28. - A compound according to claim 26, characterized in that 1 P "5 A. 7 ίΐ R, R, R- ^ and R ^ "are each methyl, Z together with Z one Carbon-carbon double bond and Z together with Z mean. 29. - A compound according to claim 26, characterized in that R ¹ and R ^{5 are} each methyl, R ⁴ "and R ⁴ " are each ethyl, Z ⁶ and 11 10 each represent hydrogen and Z together with Z ^ O. 209824/1184 Ί 618946 30. - Compound according to claim 26, characterized in that R ¹ and R ^{5 are} each methyl, R ² and R ^{4 are} each ethyl and Z ⁶ , Z ⁷ , Z and Z are hydrogen. 31. - Compound according to claim 26, characterized in that: that R, R, R and R ⁴ each represent methyl and Z 'together with Z and Z together with Z each mean CH ₂ . 32. - Compounds according to claim 25, characterized in that 2 · I R stands for the ethyl group. 33. - Connections according to claim. 13, marked thereby, P ₇₈
R stands for the group -CNR'R °. 34. Compounds according to claim 33, characterized in that 3 2 '' Z and Z together for a carbon-carbon double bond stand dung. 35. - Compound according to claim 34, characterized in that R ¹ , R ² , R ³ and R ^{4 are} each methyl, R ⁷ and R ^{5 are} each ethyl, and Z together is a carbon-carbon double bond and Z and Z together are the group ^ CH ₉ mean. 36. - Compound according to claim 34, characterized in that R ¹ and R ^{5 are} each methyl, R ² , R ⁴ , R ⁷ and R ^{8 are} each ethyl, 7 6
Z 'and Z together form a carbon-carbon double bond 1110 \ ^ and'Z and Z together represent the group> CH ₂ . 209824/1184 -443- »618946 37. - Compound according to claim 34, characterized in that R ¹ , R ² , R ⁵ and R ⁴ "are each methyl, R ⁷ and R ^{8 are} each ethyl, Z ⁷ and Z are a carbon-carbon double bond and Z and Z together ^ iO mean. 38. - Compound according to claim 34, characterized in that R ¹ and R ^{5 are} each methyl, R ² , R ⁴ ", R ⁷ and R ^{8 are} each ethyl, j and Z together is a carbon-carbon double bond 1110 »^
and Z and 'Z together represent ¹ ^ O. 39. - Connection according to claim 34, characterized in that idaß R ¹ , R ² , R ⁵ and R ⁴ "are each methyl, R ⁷ and R ^{8 are} each ethyl and 7 6 11 "10" "v. Z 'together with Z and Z together with Z each - ^ O be interpret. 40. Compounds according to claim 13, characterized in that R stands for (lower) alkyl with ₍ t 2 to 6 carbon atoms; eht. 41. Compounds of the following structural formula ₃ CH ₂ CH ₅ 0 CH ₅ -CH ₂ -C - CH-CH ₂ -CH ₂ -C = CH-CH ₂ -CH ₂ -C = CH-CO-CH ₂ -Ch ₅ 0 including the isomeric forms, in particular the trans trans, cis, trans, trans, trans and the cis, trans, cis isomers. 209824 / 118A 42. - Means of combating or controlling arthropods, in particular insects, consisting of or containing a compound according to claims 13 to 41. 43. Compounds of the same formula as in claim 1 |, where the radicals R - R ⁹ , X, Z ² - Z ^{11 have} the same meaning as in claim 13, as well as the addition salts with acids and amines; with the following independent conditions that • χ ρ 1) Ίι does not represent hydrogen when Z is hydroxy; ρ -x Z is hydrogen when Z ^ is hydrogen; 7 6 Z 'is not hydrogen when Z is hydroxy, bromine, chlorine or fluorine; Z stands for hydrogen if Z 'represents hydrogen; Z does not represent hydrogen when Z represents hydroxy, bromine, chlorine or fluorine; and Z is hydrogen when Z is hydrogen; 2) R and R * each for an alkyl group with 2-5 carbon atoms when Z, Z, Z, Z, Z and Z each represent hydrogen; 3) Z ¹⁰ and Z ¹¹ each do not represent hydrogen and Z ¹⁰ and Z together do not represent a carbon-carbon p * Double bond when Z and 1 together represent a carbon-carbon double bond and Z and 7 "6 7 Z 'each mean hydrogen or s and Z' together represent a carbon-carbon double bond; 0 0 4) if R stands for one of the groups .Q ₀ R ^ or -CNR ^ R ^{8 s} * ^elrfc » pe - Z and Z- * together for a group other than } CCl ₂ and > CF "stand; and 7? not for bromine, chlorine or fluorine 2
when Z is hydrogen; 5) when R stands for the group -qOR ^ or -CH ₂ OR, a) Z not for hydrogen or hydroxy and z 'not for Hydrogen, hydroxy, alkoxy, bromine, chlorine or fluorine 209824/1184 2 "*>
stand, where Z and Z ^J together have the above meaning, with the exception of the condition mentioned under 4); and b) if Z and Z ^ together represent the group SO, 1Ω 11 ¹ ^ Z and Z each do not represent hydrogen and at least one pair of Z and Z 'or Z and Z, respectively together have a meaning other than a carbon-carbon double bond or the group ^> 0; and C-) if Z and Z together represent the group ^ O , 6 7
Z and Z together represent a group other than ^>0; and . d) if Z and Z together for the group > 0 stand and R * is methyl and R has the above meaning, 2 λ "" 6 7 at least one pair of Z and Ί » or Z and Z together has a meaning other than a carbon-carbon double bond; and (\ 7 e) if Z and Z 'together for group J> Stand 0, 2 ^ 5 10 11 at least one pair of Z and Z ^ or Z and Z together has a meaning other than a carbon-carbon double bond; and O ₇ 11 6) if R stands for the group _g _OR 5 and Z and Z individually each stand for bromine, chlorine or fluorine and Z and Z ⁵ together form a carbon-carbon double bond interpret, the radicals R and R each stand for one Alkyl group with 2-6 carbon atoms. 0982A / 118A