DE2256537A1 - NEW SULPHIDES - Google Patents

Description

• 4- -u -u ·· -ι -u ττ -P4- SUBMITTED I

with limited liability

Darmstadt 2 ^ 56537

New sulfides

The invention relates to new compounds of the general formula I,

, A-COOE ¹

worm

E H or optionally mono- or polysubstituted by Cl, Br or I alkyl, cycloalkyl, Aralkyl or aryl with up to 12 carbon atoms each,

E = 0, (H, OH) or (H, acyloxy with up to 4 carbon atoms) • κ

E H, OH or acyloxy with up to 4 carbon atoms,

E ^ optionally one or more times by F, Cl, Br, OH, acyloxy with up to 4 carbon atoms, phenyl or p-tolyl substituted, straight or branched Alkyl with up to 12 carbon atoms, and

A optionally one or more times by i ¹ , Cl,

Br, OH, acyloxy with up to 4 carbon atoms or phenyl-substituted, straight or branched alkylene with up to 8 carbon atoms

mean, and the bond marked by ** ' shows α- or ß-configuration,

and their physiologically harmless salts.

0-9 841/0980

It has been found that the compounds of the formula I "with good Tolerability in addition to a blood pressure lowering effect also have prostaglandin-like and anti-prostaglandin-like effects. The compounds of the formula I can therefore be used as medicaments and also as intermediates for the production of other medicaments be used.

The invention relates to compounds of the formula I in which

A, R

R and R have the meaning given above.

The invention also relates to the compounds of The following preferred formulas Ia to learn which correspond to the formula I and in which the radicals which are not specified in detail are have the meaning given for formula I, but in which:

Yes Ib. Ic. Id.

Ie. If. Ig.

Ii. Ij. Ik. II. In. In. Io. Ip.

R ¹ = H, R ² = O, R ³

R = H, R ⁼ O, R

R ¹ = H, R ² = 0, R ³

R ¹ = H, R ² = 0, R ³ n-heptyl

R ¹ = H, R ² = 0, R ³

R ¹ = H, R ² = 0, R ³

R ¹ = H, R ² = 0, R ³

R ¹ = H, R ² = 0, R ³ n-heptyl

R ⁼ H, R ⁼ 0, R

R ¹ = H, R ² = 0, R ³ =

R ¹ = H, R ² = 0, R ³ =, 1

= cc-OH, R ^ =

= a-OH, R ⁴ =

= α-ΟΗ, R ⁴ =

= α-ΟΗ, R ⁴ =

= β-OH, R ⁴ =

= β-OH, R ⁴ =

= β-OH, R ⁴ =

= β-OH, R ⁴ =

n-propyl n-heptyl

2-hydroxy-n-heptyl 2-hydroxy-2-methyl-

n-propyl n-heptyl

2-hydroxy-n-heptyl 2-hydroxy-2-methyl-

= a-0C0CH ,, ΈΓ = n-propyl

a-OCOCH ,,

a-OCOCH ,,

^l 3 '

^r 3

R ¹ = H, R * - = 0, R ^ = B-

1 R ¹ = H,

² = 0, R ³ 2

R ¹ = H, R ² = 0, R

R ¹ = H, R ² = (H, oc-

R ¹ = H, R ² = (H, a- ¹

Iq. R = H, R ^ = (H, a-

= B-OCOCH ₅ , = B-OCOCH ₃ , OH), R ³ = a OH), R ³ = a OH), R ³ = a

Έ7 = n-heptyl

R = 2-acetoxy-n-heptyl

R ⁴ = n-propyl

R ⁴ = n-heptyl

R ⁴ -OH -CH -OH

= 2-acetoxy-n-heptyl R ⁴ = n-propyl R ⁴ = n-heptyl R ⁴ = 2-hydroxy

n-heptyl

Ir. R ¹ = H, R ² = (H, a-OH), R ³ = a-OH, R ⁴ = 2-hydroxy-2-methyl-n-heptyl

Is.R ¹ = H, R ² = (H, a-It. R ¹ = H, R ² = (H, a-

OH), I -; - = ß-üH, R ^4. = N-propyl OH), R ³ = ß-OH, R ⁴ = n-heptyl

409841/0980

Iu. R ¹ = H, R ² = (H, .α-ΟΗ), R ³ = ß-OH, R ⁴ = 2-hydroxyn-heptyl

Iv. R ¹ = H, R ² = (H, α-ΟΗ), R ⁵ = β-OH, R ⁴ = 2-hydroxy-2-methyl-n-he.ptyl

Iw. R ¹ = H, R ² = (H, β-OH) ,. R ³ = α-ΟΗ, R ⁴ = n-propyl Ix. R ¹ = H, R ² = (H, β-OH), R ³ = α-ΟΗ, R ⁴ = n-heptyl

Iy. R ¹ = H, R ² = (H, β-OH-), R ³ = α-ΟΗ, R ⁴ = 2-hydroxyn-heptyl

Iz. R ¹ = H, R ² =. (H, ß-OH), R ³ = α-ΟΗ, R ⁴ = 2-hydroxy- 2-methyl-n-heptyl -

Iaa. R ¹ = H, R ² = (H, β-OH), R ³ = β-OH, R ⁴ = n-propyl IaI). · R ¹ = H, R ² = (H, β-OH), R ³ = β-OH, R ⁴ = n-heptyl

Iac. R ¹ = H, R ² = (H, β-OH), R ³ = β-OH, R ⁴ = 2-hydroxyn-heptyl

lad. R ¹ = H, R ² * (H, β-OH), R ³ = β-OH, R ⁴ = 2-hydroxy-2-methy1-n-heptyl

Iae. R ¹ = H, R ² = (H, O-OCOGH ₅ ), R ³ = CC-OCOCH ₅ , R ⁴ = n-propyl Iaf. R ¹ = H, R ² = (H, O-OGOCH ₃ ), R ³ = O-OGOOH ₃ , R ⁴ = n-heptyl

lay. R ¹ = H, R ² = (H, a-OGOOHj, R ³ = o-OGOCH ,, R ⁴ = 2-acetoxyn-heptyl -:> ■ ?.

Yeah R ^1. = H, R ² = (H, O-OGOCH ₃ ), R ³ = B-OCOCH ₅ , R ⁴ = n-propyl Iai. R ¹ = H, R ² = (H, .0-OCOCH ₅ ), R ³ = B-OGOCH ₃ , R ⁴ = n-heptyl

Iaj. R ¹ = H, R ² = (H, O-OCOCH ₇ ), R ³ = β-OCOCH-, R ⁴ = 2-acetoxyn-heptyl ^JD

Iak. R ¹ = "H ₁ R ² = (H, B-OCOGH ₅ ), R ^3. = A-OGOGH ^, R ⁴ = n-Propyl IaI. R ¹ = H, R ² = (H, B-OCOGH ₃ ), R ³ = O-OGOGH ₃ , R ⁴ = n-heptyl

lam. R ¹ = H, R ² - = (H, β-OCOCH ^), R ³ = α-OGOGH ,, R ⁴ = 2-acetoxyn-heptyl ^y ■ °

Ian. R ¹ = H, R ² = (H, B-OGOCH ₃ ), R ³ = B-OGOGH ₃ , R ⁴ = n-propyl Iao. R ¹ = H, R ² = (H, B-OGOCH ₃ ), R ³ = B-OGOGH ₃ , R ⁴ = n-heptyl

lap. R ¹ = H, R ² = '(H, 6-OCOCH ₃ ), R ³ = B-OGOCH ₃ , R ⁴ = 2-acetoxyn-heptyl

Iaq. R ¹ = R ³ = H, R ² = O, R ⁴ = n-propyl

Iar. R ¹ = R ³ = H, R ² = O, R ^4- = n-heptyl

read. R ¹ = R ³ = H, R ² = O, R ⁴ = 2-hydroxy-n-heptyl

Iat. R ¹ = R ³ = H, R ² = 0, · R ⁴ = 2-hydroxy-2-methy 1-n-heptyl

lukewarm. R ¹ = R ³ = H, R ² = O, R ⁴ = 2-acetoxy-n-heptyl

lav. R ¹ = R ³ = H, R ² = (H, α-ΟΗ), R ⁴ = n-propyl

law .. R ¹ = R ³ = H, R ² = (H, α-ΟΗ), R ⁴ = n-heptyl

lax. R ¹ = R ³ = H, R ² = (H, α-ΟΗ), R ⁴ = 2-hydroxy-ri-heptyl

lay. R ¹ = R ³ - H, R ² = (H, α-ΟΗ), R ⁴ = 2-hydroxy-2-methyln-heptyl

409841/0980

_ Λ -

Iba. Ibb. Ibc.

Ibd. Ibe. Ibf. Ibg. Ibh. Ibi. Ib j. Ibk. IbI. Ibm. Ibn. Ibo. Ibp.

Ibq. Ibr. lbs. Ibt.

Ibv. Ibw. Ibx.

Ibz. lea. live

Ice. led.

Rl TJ-2 TT T3 ^C - _ ^ TJ

—K = η, K - \ η,

R ¹ = R ³ = H, R ² = (H,

R = R - H, R = (H, 13

Rl Tl * S TT ΤΊ * -

ß-Oil), R ⁴

β-OH), R ⁴

β-OH), R ⁴

β-OH), R ⁴

CX-OCOCH ₃ ),

'= H, R = (H, n-heptyl

R ¹ = R ³ = H, R ² = (H,

R ¹ = R ³ = H, R ² = (H,

R ¹ = R ³ = H, R ² = (H,

R ¹ = R ³ = H, R ² = (H,

R ¹ = R ³ = H, R ² = (H,

R ¹ = R ³ = H, R ² = (H,

A = hexamethylene

A = hexamethylene, R = H

A = hexamethylene, R ¹ = R ³ = H

A = hexamethylene, R ¹ = R ³ = H,

A = hexamethylene, R ¹ = R ³ = H,

A = hexamethylene, R ¹ = R ³ = H, R

n-propyl
n-heptyl

2-hydroxy-n-heptyl 2-hydroxy ~ 2 ~ methyl-

ct-OCOCH-), R ⁴ = n-propyl

B-OCOCH ₅ ), B-OCOCH ₃ ), B-OCOCH ₇ ), R ^ = n-heptyl

R = 2-acetoxy-n-heptyl

R ⁴ = n-propyl

R ⁴ = n-heptyl

R ⁴ = 2-hydroxy-n-heptyl

A - hexamethylene, R η-he pty1

A = hexamethylene, R ¹ =

A = hexamethylene, R =

A = hexamethylene, R =

A = hexamethylene, R = n-heptyl

R ³ = H,

R ³ = H, Η, 'R ³ =

M, K =

H,

A = hexamethylene, R 2-me thy1-n-he pty1

H, R ^ =, 3 _

A = hexamethylene, R = H,

A = hexamethylene, R ¹ = H, R ³ =

A = hexamethylene, R η-he pty1

A = hexamethylene, R 2-methy1-n-hepty1

= H, R ³ =

A = hexamethylene, R ¹ = H,

H, R ^ = 3

A = hexamethylene, R =

A = hexamethylene, R = η-he pty1

A = hexamethylene, R '=

A = hexamethylene, R =

A = hexamethylene, R n-heptyl

= n-propyl

R " ¹ " = n-heptyl
'= 2-hydroxy-n-heptyl = 2-hydroxy-2-methyl-

R = 2-acetoxy-n-heptyl a-OH, R ⁴ = n-propyl = a-OH, R ⁴ = n-heptyl = a-OH, R ⁴ = 2-hydroxy-

a-OH, R ⁴ = 2-hydroxy-

β-OH, R ^ "= n-propyl, β-OH, R ⁴ = n-heptyl

B-OH, R

= 2-hydroxy-B-OH, R ⁴ = 2-hydroxy-

= Cx-OCOCH

H, R ^ = η, Κ =

H, R ^ Xl, K

H, R ³ -

₃ , η -

α-OCOCH ₃ , R ⁴ =

α-OCOCH ₃ , R ⁴ =

B-OCOCH ,, R ⁴ =

β-OCOCH ₃ , R ^

B-OCOC ¹ H ^, R ⁴

n-propyl n-heptyl 2-acetoxy-

n-propyl = n-heptyl - 2-Acctox "-

403841/0980

Icf. A = hexamethylene, R ¹ = R ³ = H, R ² = O

leg. A = hexamethylene, R ¹ = R ⁵ - H, R ² = (H, a-OH)

I. A = hexamethylene, R ¹ = R ³ = H, R ² = (H, B-OH)

Ici. A = hexamethylene, R ¹ = R ³ = H, R ² = (H, OC-OCOCH ₇ )

Ic j. A = hexamethylene, R ¹ = R ⁵ = H, R ² = (H, B-OCOCH ₅ )

k A = hexamethylene R ¹ = CH R ² = 0 R ³ = H

Ick. A.

IcI. A = hexamethylene, R ¹ , = ₂₅

Icm. A = hexamethylene, R ¹ = C ₂ H ₅ , R ² = (H, B-OH), R ⁵ = H.

Hexamethylene, R ¹ = C ₂ H ₅ , R ² = 0, R ³ = H hexamethylene, R ¹ , = C ₂ H ₅ , R ² = (H, oc-OH), R ⁵ = H

The compounds of the formula I and thus also the compounds of the formulas Ia-Icm contain at least two asymmetric ones

2 3

C atoms in the five-membered ring. If R is not equal to 0 or R is not equal to H, then

a third carbon atom in the ring is asymmetrical; if R is not equal to 0 and R is not equal to H, there are four asymmetry zones in the ring. If A or R is substituted or branched alkylene or alkyl, further centers of asymmetry can occur in the two side chains.

The compounds of the formula I and thus also the compounds of the formulas Ia-Icm can therefore be used in a large number of stereoisomeric Forms occur and are usually present as mixtures of racemates.

The invention also relates to optically active compounds of the formula I, preferably of the formulas Ia to Icm, and their racemates. The optically active stereoisomers of the formulas Icn - Icx, their optical antipodes and ' their racemates:

E ²
S. A-COOR ¹
β
Λ E ² A-COOR ¹
( R ² .A-COOR ¹
Λ
\ \ 4 ϊ 'SR ⁴ *
• Icn Ic ο Ic Ό

A OS 841/0980 "

A-COOR

'S-R

A-COOR

SR ^f

^R A-COOR ¹

S-R *

Icq

Icr

Ics

R.

A-COOR ¹

OR

worm

15th
RH or acyl with up to

C atoms means

lev

OR

15th

U S-R '

A-COOR

OR

, · A-COOR

R-

Icw

lex

Those compounds are particularly preferred which have the steric relationships shown in the formulas Icn-Icx and in which the substituents R to R m A have the meaning given in the formulas Ia-lern.

409841 / U980

The invention also relates to a method for. Establishing the connections of the. general formula I, characterized in that a compound of the general formula II,
, 2

wherein

I) -CH = CA-COOR ¹ or -CHX-CH-A-COOR ¹ , and

X Cl, Br, J, alkylsulfonyloxy with up to to 4 carbon atoms or arylsulfonyloxy

TT

with up to 10 carbon atoms "mean, and

1 2 3

R, R, R and A are those given above

Have meanings with a compound of the general formula III,

wherein

WSR ⁴

¥ H or an equivalent of an alkali or Alkaline earth metal atom means'

¹¹¹ «na

R ^ "has the meaning given above, converts,
or that a compound of the general formula IV,

wherein

R is a radical which can be converted into a -COOR group in one or more stages means and

R to R and A are those given above

Have meanings

treated with a thermolytic or solvolyzing agent,

A09 8A1 / 0980

or that a compound of the general formula V,

wherein

R ⁶ R ² , (H, X) or (X, Y) R 7 3

.A-COOR ¹ ο er, un

Y Cl, Br, I, alkylsulfonyloxy with up to 4 carbon atoms or arylsulfonyloxy with up to 10 carbon atoms

mean and

V RR ₁ A and X those given above

Have meaning
and in which at least one residue X resp.

Y is included,

with a solvolyzing agent,

or that a compound of the general formula VI,

wherein

-COOR ¹ R ⁸ = 0 or (H, R ⁵ ), and

9 4

R R or optionally one or more times by F, Cl, Br, OH, acyl oxy with up to 4 carbon atoms, phenyl or p-tolyl substituted, straight or branched one Oxoalkyl with up to 12 carbon atoms

mean, and

1 2
R, R and A have the meaning given above

have and

which contains at least one carbonyl group, reacts with a reducing agent,
or that a compound of the general formula VII,

wherein

-COOR ¹ R to R, A and W have the meaning given above,

VII - 9 -

with a compound of the general formula YIII,

BR
VIII

worm "■ η 10

H or optionally one or more times through F, Cl, Br, OH, acyloxy straight or branched chain substituted by up to 4 carbon atoms or phenyl Alkyl with up to 10 carbon atoms, and

111? 1 "! - 1 ^

11

R ^{! 1} R

XR ¹¹ R ¹² C-CR ¹³ R ¹ * -

mean, and

¹¹ , R ¹² , R ¹⁵ and R ¹ * are identical or different and are H or optionally straight or branched alkyl substituted one or more times by F, Cl, Br, OH, acyloxy with up to 4 carbon atoms or phenyl up to 10 C-

Mean atoms, where the sum of

10 aliphatic carbon atoms in B and R

must not be greater than 12 and has the meaning given above,

implements,

or that one in a. Compound which otherwise corresponds to formula I, but in which hydroxyl and / or keto groups are present and / or the carboxyl group is present in a functionally modified form, the groups by treatment with solvolyzing or hydrogenolyzing agents in freedom puts,

and / or that one obtained compound of the formula I by treatment with esterifying or solvolysing agents in another triple bond of the formula I is transferred,

40 9 841/0980

- 10 -

and / or that a compound of the formula I is cleaved into its racemates and / or optical antipodes,

and / or that a compound of the formula I by treatment with a base in one of its physiological transferred harmless salts, or sets free from one of their salts by treatment with an acid.

In the above formulas, R preferably denotes, in addition to hydrogen, an alkyl radical having up to 12 carbon atoms, which can also be substituted one or more times by Cl, Br or I. Above all, it is unsubstituted Alkyl with in particular up to 6 carbon atoms, e.g. around methyl, ethyl, n-propyl, η-butyl, n-pentyl, n-hexyl, isopropyl, Isobutyl, sec-butyl, tert-butyl, isopentyl, pent-2-yl, pent-3-yl, tert-pentyl, neopentyl, hex ~ 2-yl, Hex-3-yl or isohexyl groups, but for example also around n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl radicals, as well as haloalkyl radicals such as 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-dibromoethyl, 2,2-diiodoethyl, 2,2,2-trichloroethyl, 2,2,2-tribromoethyl or 2,2,2-triiodoethyl groups.

Examples of cycloalkyl groups with up to 12 carbon atoms including, which also include alkyl-substituted cycloalkyl radicals are cyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl-, 2,3-diethylcyclopropyl-, 2-butylcyclopropyl-, Cyclobutyl, 2-methylcyclobutyl, 3-propylcyclobutyl, 2,3,4-triethylcyclobutyl, cyclopentyl, 2,2-dimethylcyclopentyl, 3-pentylcyclopentyl, 3-tert-butylcyclopentyl, Cyclohexyl, 4-tert-butylcyclohexyl, 3-isopropylcyclohexyl, 2,2-dimethylcyclohexyl, cyeloheptyl, Cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl groups.

40984 1 / Ü980

Examples of Aralky! Gruppeη with "up to 12 G-atoms including, are benzyl, phenethyl, 1-phenylethyl, 2-phenylpropyl, 4-phenylbutyl, 3-phenylbutyl, 2 - ('i-Iaphthylethyl) - and 1- (2 ~ naphthy! Methyl) groups.

If R is aryl with up to "12 carbon atoms", then unsubstituted hydrocarbon radicals such as phenyl, 1-l-taphthyl or 2-eaphthyl is preferred, it can also preferably be Alley be substituted by halogen and / or alkyl with up to 4 carbon atoms, "for example p-Chi or phenyl, m-chlorophenyl, o-chlorophenyl, 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, p-tolyl-, m-tolyl-, o-tolyl-, p-ethylphenyl-, p-tert-butylphenyl-, 2,5-dimethylphenyl-, 4-chloro-2 "methylphenyl- and 2,4-dichloro-3-methyIpheny! Groups.

In addition to = 0, E also means (H, OH) or (H, acyloxy with up to 4 carbon atoms), where the OH or the acyloxy group α- or

2
can be ß-constant. If E is acyloxy, the acid radicals are derived, preferably from carboxylic acids, in particular aliphatic carboxylic acid radicals ah. They are therefore preferably pormyloxy, acetoxy, propionyloxy or butyryloxy groups. The acid radicals can, however, also come from sulfonic acids or inorganic ones, for example The acyloxy group in this pail is therefore, for example, a methylsulfonyloxy, ethylsulfonyloxy, 2-hydroxyethylsulfonyloxy, HOSO ₂ P or (H0) ₂ P (0) -0 group.

In addition to H or OH, E is also an acyloxy group with up to 4 carbon atoms. The OH "or the acyloxy group can be in the α or β position

Be 2. The acyloxy groups mentioned above come in particular in embossing. If E (H, acyloxy with up to 4 carbon atoms) and E (Acyloxy with up to 4 carbon atoms) "mean the acyloxy groups preferably the same.

E "denotes an optionally substituted one or more times by P, Cl ₅ Br. OH, acyloxy with up to 4 carbon atoms, phenyl or p-tolyl,

AÜ9H4 1 / Uyaü - 12 -

straight or branched alkyl with up to 12 carbon atoms. Preferred alkyl radicals are methyl, ethyl, propyl, Butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, 2,2-dimethylpropyl, 3,3-dimethylbutyl, 4,4-methylpentyl, 5,5-dimethylhexyl, 6,6-dimethylheptyl, 7,7-dimethyloctyl, 8,8-dimethylnonyl, 9,9-J-dimethyldecyl; but also isopropyl, Isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, 2-butyl, 2-pentyl, 2-hexyl, 2-heptyl, 2-octyl, 1,3-dimethylbutyl, 1,2,3-trimethylbutyl, 1,3,5-trimethylhexyl, 1,3,5-trimethylheptyl, 2-ethylheptyl, 2-propylheptyl, 2,6,6-trimethylheptyl, 2-ethyl-6,6-dimethylheptyl, 2-propyl-6,6-dimethylheptyl, 2,7,7-trimethyloctyl, 2-ethyl 1-7,7-dimethyl octyl or 2,8,8-trimethylnonyl; 3,3-dimethylpentyl are particularly preferred, 3,3-dimethylhexyl, 3,3-dimethylheptyl, 3,3-dimethyloctyl, 3,3-dimethylnonyl, 2,3,3-trimethylpentyl, 2,3,3-trimethylhexyl, 2,3,3-trimethylheptyl, 2,3,3-trimethyloctyl and 2,3,3-trimethylnony1.

Particularly preferred are also alkyl groups which are substituted in the 2-position by OH or acyloxy with up to 4 carbon atoms, such as 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxypentyl, 2-hydroxyhexyl, 2-hydroxyheptyl, 2-hydroxyoctyl, 2-hydroxy-6-methylheptyl, 2-hydroxy-6,6-dimethylheptyl, 2-hydroxy-2-methylheptyl, 2-hydroxy-2,6-dimethylheptyl, 2-hydroxy-2,6,6-trimethylheptyl, 2- Hydroxy-7,7-dimethyloctyl, 2-hydroxy-2,7,7-trimethyloctyl, 2-formyloxypropyl, 2-formyloxyheptyl, 2-formyloxy-2-methylheptyl, 2-formyloxy-r6,6-dimethylheptyl, 2-formyloxy 2,6,6-trimethylheptyl, 2-formyloxy-7,7-dimethyloctyl, 2-formyloxy-2,7,7-trimethyloctyl, 2-acetoxyheptyl, 2-acetoxy-6,6-dimethylheptyl, 2-acetoxy-7, 7-dimethyloctyl, 2-hydroxysulfonyloxyheptyl, 2-hydroxysulfonyloxy-6,6-dimethylheptyl, 2-hydroxysulfonyloxy-7,7-dimethyloctyl _/ 2-hydroxynonyl, 2-hydroxy-2-methylnony1, 2-hydroxy-3,3-dimethylnonyl, 2-hydroxy-8,8-dimethylnonyl, 2-hydroxy-2,3,3-trimethylnony1, 2-hydroxy-2,8,8-trimethylnonyl, 2-hydroxy-2,3, 3,8,8-pentamethylnonyl, sov / Ip, sov; eit not yet mentioned here, the alkyl groups listed above which are substituted in the 2-position by OH.

- 13 AOytU 1 / U980

R ^ can also be substituted one or more times by F., Cl or Br alkyl with "up to 12 carbon atoms, for example a 2-fluoroethyl ~, 2-fluorobutyl, 3-5 ¹ IuOrbutyl-, 4-FlUOrbutyl- , 5-fluoropentyl, 4-fluoro-4-methylpentyl, 3-fluoroisoheptyl, 8-fluorooctyl, 3,4-difluorobutyl, 4,4-difluoropentyl, 5,5-difluoropentyl, 5,5,5 -Trifluorpentyl-, 6,6-Oifluorohexyl-, 6,6,6-Trifluorohexyl-, 7,7-Difluorheptyl-, 7,7,7-Trifluorheptyl-, 8,8, S-Trifluoroocty1-, 2-Chlorheptyl-, 7,7-dichloroheptyl, 2-chlorooctyl, 8,8-dichloroctyl, 2-bromoheptyl, 7,7-dibromoheptyl, 2-bromooctyl or 8,8-dibromooctyl When R 1 is an alkyl group substituted by phenyl is, as it is mainly to omega-phenyl-alkyl groups such as 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6 ~ phenylhexyl, 7-or 8-Phenylheptyl- Phenyloctylgruppen. R ⁴ can also be a alkyl radical substituted by p-tolyl, preferably an omega-p-tolylalkyl radical, such as 2-p-tolylethyl, 3-p-tolylpropyl or 4-p-tolylbutyl.

Of course, R can also be an alkyl radical with up to 12 carbon atoms, which has several different substituents wearing. Preferred examples of such radicals R are: 2-hydroxy-7,7,7-trifluoroheptyl-, 2-hydroxy-8,8,8-trifluorooctyl-, 2-hydroxy-7-phenylheptyl-, 2-hydroxy-2-methyl-7-phenylheptyl-, 2-formyloxy-7-phenylheptyl-, 2-acetoxy-7,7,7-trifluoroheptyl-, 2-acetoxy-8,8,8-trifluorooctyl groups, 2-hydroxy-2-p-tolylethyl, 2-hydroxy-3-p-tolylpropyl, 2-hydroxy-4-p-tolylbutyl, 2-hydroxy-2-methyl-4-p-tolylbutyl, 2-hydroxy-3,3 ~ dimethyl-4-p-tolylbutyl, 2-hydroxy-9,9,9-trifluorononyl, 2-Hydroxy-2-methyl-9,9,9-trifluorononyl, 2-hydroxy-3,3-dimethy1-9,9,9-trifluorononyl.

- 14 409841/0980

A is preferably a tm-substituted alkylene with up to 8 carbon atoms, such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene radicals and their isomeric branched-chain forms. If A is a substituted alkylene with "up to 8 carbon atoms," it is preferably haloalkylene groups, in particular fluoroalkylene groups such as -CH ₂ CHF-, -CH -CH ₂ CH ₂ CH ₂ CF ₂ -, -CH ₂ CH (CH ₅ ) CH ₂ CHF-, -

CH ₂ Ch ₂ -, - (ch ₂ ) ₅ cf ₂ -

or - (CH ₂ ) .CHFCHF-. However, A can also be a hydroxyalkylene or acyloxyalkylene, for example -CH (OH) - (CH ₂ ) (-, -CH ₂ CH (OH) (CH ₂ ) ₄ -, -CH (OCOCH ₅ ) - (CH ₂ ) ₅ -, -CH ₂ CH (OCOCH ₅ ) - (CH ₂ ) ^ -,

-CH (OSO ₅ H) - (CH ₂ ) ₅ - or -CH (6sO ₅ H) - (CH ₂ ) ₂ -CP ₂ - (CH ₂ ) ₂ -; a phenylalkylene such as 2-phenylpropylene- (1,2), 2-phenylhexylene- (1,6) or 3-phenylhexylene- (1,6); Chloroalkylene such as -CH ₂ CHCl-, -CH ₂ CHClCH ₂ -, - (CH ₂ ) ₅ CCl ₂ -, - (CH ₂ J ₅ -CCl ₂ - (CH ₂ ) ₂ ~; or bromoalkylene such as - (CH ₂ J ₅ -CHBr-, - (CHg) ₅ CBr ₂ - or - (CH ₂ J ₅ -CBr ₃ -

(CH ₂ ) ₂ - be.

13 means either one, possibly one or more than one straight or branched omega-hydroxycarbonyl-2-alkenylene- (1,2) -, substituted by P, Cl, Br, OH, acyloxy with up to 4 carbon atoms or phenyl, omega-alkoxy-carbonyl-1-alkenylene- (1,2) -, omega-cycloalkoxycarbonyl-i-alkenylene- (1,2) -, omega-aralkoxycarbonyl-1-alkenylene (1,2) or omega-aryloxycarbonyl-1-alkenylene (1,2) radical; or one optionally one or more times by F, Cl, Br, OH, acyloxy with up to straight or branched omega-hydroxycarbonyl-1-halo-alkylene- (1,2) -, substituted to 4 carbon atoms or phenyl, omega-alkoxycarbonyl-1-halo-alkylene- (1,2) -, omega-cycloalkoxycarbonyl-1-halo-alkylene- (1,2) -, omega-aralkoxycarbonyl 1-halogen-i-alkylene- (1,2) - or omega-aryloxycarbony1-1-halogen-1-alkylene radical, and the corresponding 1-alkylsulfonyloxy or 1-arylsulfonyloxy groups. For example, there are the following Leftovers in question:

409841 / U930 " ¹⁵ ~

7-Hydroxyearbonyl-1-heptenylen- (1,2) -, 8-hydroxycarbonyl-1-octenylene- (1,2) -, 9-hydroxycarbonyl-1-nonenylene - (. 1,2) -, 7-ethoxycarbonyl-1-heptenylene- (1,2) -, 8-ethoxycarbonyl-1-octenylene- (1,2) -, 9-Äthoxycarbony1-1-nonenylen- (1,2) -, 1 -Chlor-S-Hydroxycarbonyl-ootylen- (1,2) -, 1-bromo-8-hydroxycarbonyl-octylene- (1,2) -, 1-iodo-8-hydroxycarbonyl-octylene- (1,2) -, 1-chloro-8-yneth oxycarbonyl-octylene- (1,2) -, 1 -Bromo-8-methoxycarbonyl-oe tylen- (1,2) -, i-iodo-8-methoxycarbonyl-octylene- (1,2) -, 1-methylsulfonyloxy-8-ethoxycarbonyl-octylene- (1,2) -, 1 -ethylsulfonyloxy-8-ethoxycar "bonyl ~ oc tylen- (1,2) -, 1 -p-Tolylsulfonyloxy-S-ethoxycarbonyl-oetylen- (1, 2) -, 1- (4-bromophenyl) -sulfonyloxy-S-ethoxycarbonyl-octylene-i1,2) -, 1-a-naphthylsulfonyloxy-8-ethoxycarbonyl-octylene- (1,2) -,

In addition to Cl, Br or I, X is also alkylsulfonyloxy with up to to 4 carbon atoms, preferably methylsulfonyloxy or ethylsulfonyloxy, but also 2-hydroxyethylsulfonyloxy or butylsulfonyloxy; or arylsulfonyloxy with up to 10 carbon atoms, such as p-tolyl-bulfonyloxy, p-bromophenylsulfonyloxy, 1-naphthylsulfonyloxy or 2 -Ifa, phthylsulfonyloxy.

In addition to H, ¥ denotes an equivalent of an alkali metal or alkaline earth metal allatoms, preferably Na, K or 1/2 Ca.

E "is a one- or multistage convertible into a COOE group, preferably thermolysable or solvolyzable, in particular a functionally modified carboxyl group, preferably a halocarbonyl group such as -COCl or -COBr; a nitrogen-containing, functionally modified carboxyl group, in particular -CON ₅ , -CONE ¹⁶ E ¹⁷ , -CC = SiH) OE ¹⁶ , -C (= NH) NH ₂ , -CONHNH ₂ , -CONHOH, -C ^ N, -C (= NH) C1, -C (= NH) Br; one sulfur-containing, functionally modified carboxyl group, in particular '-COSE ¹⁶ , -CSOE ¹⁶ , -CSSE ¹⁶ , -CSNE ¹⁶ E ¹⁷ : or one only oxygen

409841 / .Ü98Ü ~ ¹⁶

Functionally modified carboxyl group containing, in particular -C (OR ¹⁶ ). ,, -COOCOR ¹⁶ or -COOR ¹⁶ . R ¹⁶ and R ^{1 l} are identical or different and denote next II is an organic radical, such as alkyl groups, preferably straight-chain, with in particular up to 4 carbon atoms; by Cl, Br, J, OH, alkoxy with up to 4 carbon atoms, acyloxy with up to 4 carbon atoms, phenyl or naphthyl substituted alkyl with up to 4 carbon atoms, cycloalkyl with up to 6 carbon atoms, optionally one or more times by Cl, Br, NOp, OH, alkoxy with up to 4 carbon atoms, acyloxy with up to 4 carbon atoms, substituted aryl with up to M carbon atoms; together also polymethylene with up to 6 carbon atoms, preferably unsubstituted polymethylene with up to 6 carbon atoms such as - (CHp), -, - (CHp) ₁ - or - (CH ₂ ) ^ -; or together also a polymethylene interrupted by 0, N or S atoms with preferably up to 6 C atoms, such as - (CHg) ₂ -O-CH ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, - (CHg) ₂ -NH-CH ₂ -, - (CHg) ₂ -NH- (CHg) ₂ -, - ₃ - (CHg) ₂ -S-CH ₂ -, - (CHg) ₂ -S- (CHg) ₂ - or - (CHg) ₃ -S-CH ₂ -.

In addition to Cl, Br or J, Y can also be alkylsulfonyloxy with up to 4 carbon atoms or arylsulfonyloxy with up to 10 carbon atoms mean. For this purpose, the radicals indicated above under X are preferably imprinted.

Q λ

If R is not equal to R, it is preferably optionally substituted 2-oxoalkyl groups, in particular to optionally substituted 2-oxohexyl, 2-oxoheptyl, 2-oxooctyl or 2-oxononyl groups, such as 3,3-dimethyl-2-oxoheptyl, 6,6-dimethyl-2-oxoheptyl-, 3,3,6,6-tetramethyl-2 ~ oxoheptyl-, 7,7,7-trifluoro-2-oxoheptyl-, 7,7,7-trifluoro-3,3-dimethyl-2-oxoheptyl-, 3,3-dimethyl-2-oxononyl, 9,9-dimethyl 2-oxononyl-, 3,3,9,9-tetramethyl-2-oxononyl-, 9,9,9-trifluoro-2-oxononyl-, 9,9,9-trifluoro-3,3-dimethyl-2-oxononyl radicals, but e.g. also 2-0xo-3-phenylpropyl-, 2-oxo-3-p ~ tolylpropyl-, 2-0xo-4-p-phenylbutyl, 2-0xo-4-p-toly / butyl or 2-oxo-5-phenylpentyl rusts.

40b84i / U980 -17-

In addition to H, R is a branched or preferably straight alkyl with Ms having 10 carbon atoms, for example a methyl, ethyl, n-propyl, η-butyl, n-pentyl, n-hexyl or n-heptyl group, but it can also be, for example, isopropyl-lsobutyl, sec-butyl, tert-butyl, isopentyl, pent-2-yl, pent-3-yl, tert-pentyl, neopentyl , Hex-2-yl, hex-3-yl, isohexyl, 4,4-dimethylpentyl, 1,3-dimethylpentyl, 1,4,4-trimethylpentyl, isoheptyl, 5,5- Act dimethylhexyl or 1,5,5-trimethylhexyl group; straight or branched alkyl with up to 10 carbon atoms, for example mono-, di- or trifluoroalkyl, preferably 5- ITu.orpentyl, 4,5-difluoropentyl, 5,5-difluoropentyl, 5,5,5-trifluoropentyl, 6-fluorohexyl, 6,6-difluorohexyl, 6,6,6-trifluorohexyl; 5-chloropentyl, 5,5-dichloropentyl, 5,5,5-trichloropentyl, 6-chlorohexyl, 6,6-diehlorhexyl, 6,6,6-trichlorohexyl; 5 ~ bromopentyl, 5,5-dibromopentyl, 5,5,5-tribromopentyl, 6-bromelexyl, 6,6-dibromohexyl, 6,6,6-tribromohexyl; 3-hydroxypentyl, 4-hydroxypentyl, 3-hydroxyhexyl, 4-hydroxyhexyl, 5-hydroxyhexyl; 4-acetoxypentyl, 4-acetoxyhexyl, 5-acetoxyhexyl, 4-Butyryloxj ^r pentyl, 4-Butyryloxyhexyl, 5-Butyryloxyhexyl; 4-phenylbutyl, 5-phenylpentyl or 6-phenylhexyl.

B denotes an ethylenyl radical which is one, two or three times by optionally substituted one or more times by P, Cl, Br, OH, acyloxy with up to 4 carbon atoms or phenyl, straight or branched alkyl can be substituted. It should be noted that the number of C atoms that make up the acyclic Form a chain in the compound of formula YIII, at most 12 may be. B is therefore preferably an Alkyläthylenyü.rest, e.g. a 1-methyl-, 2-methyl-, 1-ethyl-, 1-ethyl-2-methyl-, · 2-Ethyl-1-me thy1-, 1,2-Di äthy1-, 1,1-Dime thy1-, 1,2-Dime thy1-, 1,1,2-trimethyl, 1-ethyl-2,2-dimethyl, or 1-propyl, and especially when R = H also 1-butyl, 1-pentyl, 1-hexyl, 1- (4,4-dimethylpentyl) -, 1- (5,5-dimethylhexyl) -, .2-methyl- (4,4-dimethylpentyl) - or 2-methyl- (5,5-dimethylhexyl) -äthylenylrest; a haloalkylethylene radical, e.g. a 1- (5-

- 18 40984 1 / Ü980

Fluoropentyl) -, 1 - (5, 5-Dif Iuorpen.ty 1) -, 1 - (4, 5-Dif luorpenty 1) -, 1- ( 5, 5,5-Trifluorpontyl) -, 1 - (6 , 6,6-trifluorohexyl) -, 1- (5-chloropentyl) -, 1- (5,5,5-trichloropentyl-, 1- (6,6,6-trichlorohexyl) -, 1 - (5 »5 _f 5-tribromopentyl) or 1- (6,6,6-tribromohexyl) -ethylene radical; a hydroxyalkylethyleneyl radical, e.g. 1- (4-hydroxypentyl) ~, 1- (4-hydroxyhexyl) -, 1- (5-hydroxyhexyl) ~ äthylenylrest; an acyloxyalkyläthylenylrest, e.g. 1- (4-formyloxypentyl) -, 1- (4-acetoxypentyl) -, 1- (4-butyryloxypentyl) -, 1- (4-formyloxyhexyl) -, 1- (4-acetoxyhexyl) -, 1- (4-Butyryloxyhexyl) -, 1- (5-Formyloxyhexyl) -, 1- (5-Acetoxyhexyl) -, 1- (5-Butyrylox3 ^r hexyl) -äthylenylgruppe; or a Phenylalkyläthylenylrest, preferably an omega-Phenylalkyläthylenylrest , e.g. a 1- (4-Phenylb * utyl) -, 1- (5-Phenylpentyl) -, 1- (6-Phenylhexyl) -äthylenylrest; but also e.g. a 1- (4-Phenylpentyl) -, 1- (3 -Phenylpentyl) -, 1- (5-Phenylhexyl) - or 1- (4-Phenylhexyl) -äthylenylrest.

But B can also mean a 2-chlorine, 2-bromine, 2-iodine, 2-alkylsulfonyloxy or 2-arylsulfonyloxyäthylres.t, which one, two, three or four times through optionally one or more times F, Cl, Br, OH, acyloxy with up to 4 carbon atoms or phenyl-substituted straight or branched alliyl can be substituted. It should be noted that the number of carbon atoms which form the acyclic chain in the compound of formula VIII must not exceed 12. B is therefore preferably also a 2-halo-1-alkyl-ethyl radical, for example a 2-chloro-1-methyl-, 2-chloro-2-methyl-, 2-chloro-2,2-dimethyl, 2-chloro 1,2-dimethyl-, 2-chloro-1,1,2,2-tetramethy1-, 2-chloro-i-ethyl-, 2-chloro-2-methyl-1-ethyl- or 2-chloro-1, 2-dimethyl-1-ethyl, and especially when R ¹⁰ = H, also 2-chloro-1-butyl, 2-chloro-i-pentyl, 2-chloro-1-hexyl, 2-chloro 2-methyl-1-pentyl-, 2-chloro-1- (4,4-dimethylpentyl) -, 2-chloro-1- (5,5-dimethylhexyl) -, 2-chloro-2-methyl- (4, 4-dimethylpentyl) - or 2-chloro-2-methyl- (5,5-dimethylhexyl) -ethyl radical, or a corresponding 2-bromo or 2-iodo-1-alkylethyl radical; a 2-alkylsulfonyloxy-1-alkyl-ethyl radical, e.g. a 2-methylsulfonyloxy-1-ethyl-, 2-methylsulfonyloxy-

- 19 -403841 / Ua «ü

1-pentyl or 2-methylsulfonyloxy-1-hexyl - ethyl radical; or a 2 ~ arylsulfonyloxy-1-alkyl-ethyl radical, e.g. a 2-p-tolylsulfonyloxy ~ 1 ~ pentyl ~, 2-p ~ TolylBulfonyloxy - 1 ~ hexyl ~ or 2 ~ p-Tolyl ~ sulfonyloxy- * 1, 2, 2-trimethyl-1-pentylethyl radical.

B is also optionally substituted in the 2-position Oxiranyl (2) group, preferably an oxiranyl (2) or 2-methyl-oxiranyl (2) radical.

The radicals E ¹¹ , R ¹² , R ¹⁵ and R ¹ ^ are identical or different and "in addition to H denotes straight or branched branches which are substituted one or more times by Έ, Cl, Br, OH, acyloxy with up to 4 carbon atoms or phenyl Alkyl with up to 10 carbon atoms, preferably one
or ethyl.

v / eise one of the radicals indicated for R, in particular methyl

In the case of keto groups, which are present in functionally modified form, are the usual groups, preferably -C (OH) (OR ¹⁶ ) -, -C (OR ¹⁶ ) ₂ -, -C (OCOR ¹⁶ ) ₂ ~, - C (= K ^T OH) -, -CC = NNH ₂ ) -, -OC = NH) -, -C (= NR ¹⁶ ) -, = C (-OR ¹⁶ ) -, ^ 0 ( ^{16 6}

₂ ,
or = C (-NR ¹⁶ R ¹⁷ )

Hydroxy groups which are present in a functionally modified form are preferably OH-G groups esterified with, for example, a saturated or unsaturated aliphatic, cycloaliphatic or aromatic, substituted or unsubstituted carboxylic acid or sulfonic acid or also an inorganic acid. Preferred carboxylic acids are fatty acids with 1 to 18, preferably 1 to 6, carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isocaproic acid, enanthic acid, caprylic acid, pe! Argonic acid, capric acid, lauric acid, myristic acid, Palm! tinsäure, stearic acid, further crotonic acid, oleic acid, cyclohexanecarboxylic acid, Cyclohexylessig- and propionic acid, benzoic acid, phenylacetic _r and propionic acid, dicarboxylic acids such as oxalic, halon, succinic, maleic, glutaric, Dimethy1-

40Β84Ί / Ü98U

glutaric, adipic, pimeline, aoetondicarbon, phthalic, tetrahydrophthalic, Wood hydrophthalic or diglycolic acid, hydroxycarboxylic acids such as glycolic acid, halogenated fatty acids such as chloroacetic acid, Dichloroacetic acid, triehloroacetic acid or trifluoroacetic acid.

Preferred sulfonic acid esters are those derived from Alkylsulfonic acids with 1 to 6 carbon atoms are, e.g. Methane or Ethanesulfonic acid, and aryl sulfonic acids with 6 to 10 carbon atoms. e.g. benzene, p-toluene, 1- and 2-naphthalenesulfonic acid. Bevoi ~~ Added inorganic acids are sulfuric acid and phosphoric acid ..

JPunktionell modified OH may further represent an etherified OH group, for example aralkoxy preferably having from 7 to 19 carbon atoms, such as benzyloxy, p-methylbenzyloxy, 1- and 2-Pl.> Enyl-ethoxy, Oiphenylmethoxy, Triphen3 ^r lmethoxy or 1- or p-naphthylmethoxy; Alkoxy with preferably up to 6 carbon atoms, in particular tert-butoxy; Tetrahydropyranyloxy; or trialkylsilyloxy, preferably trimethylsilyloxy.

The compounds of the formula II are therefore substituted cyclopentanones, 2-cyclopentenones, cyclopentanols or 2 ~ cyclopentenols; preferably around 3-halocyclopentanone, 3-alkylsulfonyloxycyclopentanone or 3-arylaulfonyloxycyclopentanone, especially around 3-chloro-2-omega - oar · boxyalkyl-, 3-bromo-2-omega ~ carboxyalkyl-, 3-iodo-2-omega-carboxyalkyl-, 3 ~ methylsulfonyloxy-2-omega-carboxyalkyl-, 3 ~ p-tolylsulfonyloxy-2-omega-carboxyalkyl-, 3-bromo-4α-hydroxy-2-omega-carboxyalkyl-, 3-bromo-4β-hydroxy-2-omega-carboxyalkyl-cyclopentanones; around 2-carboxyalkyl- or 2-carbalkoxyalkyl ~ 2-cyclopentanones, in particular 2-omega-carboxyalkyl-, 2-omega-carbalkoxyalkyl-, ^ -Hydroxy-P-oniega-carboxyalkyl-, 4a-hydroxy-2-omega-carbalkoxyalkyl-, 4oc-acyloxy-2-omega-carboxyalkyl-, 4a ~ acyloxy-2-omega-carbalkoxyalkyl-, 4β-Hydroxy-2-omega-carboxyallryl-, 4β-hydroxy-2-omega-carbalkoxyalkyl-, 4β-acyloxy-2-orüega ™ carboxyalkyl-, 4ß-acyloxy-2-omega-carbalkoxyalk3'-l-2-

409841/0980

cyclopentenone; around 3-halocyclopentanols, 3-alkylsulfonyloxycyclopentanols or 3-arylsulfonyloxycyclopentanols, in particular around 3-chloro-2-omega ~ carboxyalkyl-, 3 ~ bromo-2-oniega-carboxyalkyl-, ^ -Iodine - ^ - omega-carboxyalkyl-, 3-methylsulfonyloxy-2-omega-carboxyalkyl-, 3-p-tolylsulfonyloxy-2-omega-carboxyalkyl, 3-bromo-4-hydroxy-2-omega-carboxyalkyl, 3-iodo-4-hydroxy-2-omega-carboxyalkyl-cyclopentanols; around 2-carboxyalkyl- or 2-carbalkoxyalkyl-2-cyelopentenols, especially uin 2-0megac arb oxy alkyl-, 2-omega-carbalkoxyalkyl-, 4cc-hydroxy-2-omegacarboxyalkyl-, 4o: -Hydroxy-2-omega-carbalkoxyalkyl-, -4a; -Acyloxy-2-omega-carboxylalkyl-, 4a-acyloxy-2-omega-carbalkoxy-alkyl-, 4ß-hydroxy-2-omega-carboxyalkyl-, 4ß-hydroxy-carbalkoxyalkyl-, 4β-acyloxy-2-omega-carboxyalkyl-, 4β-acyloxy-2-omega-carbalkoxyalkyl-2-pentenols.

The compounds of the formula III are optionally substituted thiols or alkali metal or alkaline earth metal thiolates, preferably n-alkyl or 2-hydroxyn-alkyl thiols, or their alkali salts, in particular to optionally substituted n-propyl, n-hexyl, n-heptyl ~, n-octyl-, 2-hydroxy-n-hexyl-, 2-hydroxy-n-heptyl-, 2-hydroxy- ' n-octylthiols or the corresponding sodium thiolates.

The compounds of the formula IV are optionally substituted functional acid derivatives of omega (2-alkylthio-5-oxo-cyclopentyl), omega (2-alkylthio-3-acyloxy-5-oxo-cyclopentyl) or omega - (2-alkylthio-3,5-diacyloxycyelopentyl) alkanoic acids, preferably omega (2-alkylthio-5-oxo-cyclopentyl) -, omega ^ -alkylthio ^ -acyloxy-S-oxo-cyclopentyl) - or omega (2-alkylthio-3,5-diacyloxycyclopentyl) alkanoic acid halides, or omega- (2-alkylthio-5-oxo-cyclopentyl) -, omega- (2-alkyl- thio-3-acyloxy-5-oxo-cyclopentyl) - or 0mega- (2-alkylthio-3,5-diacyloxycyclopentyl) -alkyl acid nitriles, in particular omega- (2-alkylthio-5-oxo-cyclopentyl) -, 0mega- (2-alkylthio-3-acyloxy-5-oxo-cyclopent3 ^r l) -, omega- (2-alkylthio-3,5-diacyloxycyclopentyl) -heptanoic acid chlorides, omega- (2-alky1-

AO9841 / 0980

thio-5-oxo-cyclopentyl) -, omega- (2-alkylthio-3 ~ acyloxy-5-oxocyclopentyl) -, 2 ~ alkylthio-3,5-diacyloxycyclopentyl) -heptanoic acid broroids or omega (2-alkylthio-5-oxo-cyclopentyl) -, Omega (2-alkylthio-3-acyloxy-5-oxo-cyclopentyl), omega (2-alkylthio-3,5-diacyloxycyclopentyl) -heptane-ethenitrile; to omega- (2-alkyithio-S-oxo-cyclopentyl) -, omega- (2-alkylthio-3-acyloxy-5-oxo-cyclopentyl) -, Omega (2-alkylthio-3,5-diacyloxycyclopentyl) alkanoic acid ester, preferably around 0mega- (2-alkylthio-5-oxo-cyclopentyl) -, Omega (2-alkylthio-3-acyloxy- ^ -oxo-cyclopentyl) -, omega (2-alkyltMo-3,5-diacyloxycyclopentyl) -alkanoic acid alkyl ester, especially omega- (2-alkyI-thio - ^ - oxo-cyclopentyl) -, Omega (2-alkylthio-3-acyloxy-5-o: cyclopentyl) -, 0mega- (2-alkylthio-3j 5-diacyloxycyclopentyl) -heptanoic acid tert-butyl ester or omega- (2-alkylthio-5-oxocyclopentyl) -, Omega- (2-alkylthio-3-acyloxy-5-oxo-cyclopentyl) -, Benzyl omega (2-alkylthi0-3,5-diacyloxycyclopentyl) heptanoate.

The compounds of the formula V are, for example, optionally substituted 1-alkylsulfonyloxy-, 1-arylsulfonyloxy-, 1,4-dialkylsulfonyloxy-, 1,4-diarylsulfonyloxy-, 1-halogen-, 1,4-dihalogen-2- Comega-carboxyalkyl) -3-alkylthiocyclopentanes; 1-halo, 1-alkylsulfonyloxy-, 1-arylsulforiyloxy-2- (omega-carboxyalky1) -3-alkylthio-4-hydroxycyclopentanes; 4-halo, 4-alkylsulfonyloxy, 4-arylsulfonyloxy-2- (omega-carboxyalkyl) -3-alkylthio-cyclopentane oils; or 4-halogen-, 4-alkylsulfonyloxy- or 4-arylsulfonyloxy-2- (omega-carboxyalkyl) -3-alkylthio-cyclopentanones; preferably the corresponding bromine, iodine, methylsulfonyloxy or p-tolylsulfonyloxy derivatives; in particular about 4-bromo-2- (7-carboxyhexyl) -3-alkylthio-cyclopentanones and 4-bromo-2- (7-carboxyhexyl) ~ 3- (2-hydroxyalkylthio) pentanones.

-23-

The compounds of the formula YI are preferably to optionally substituted 2- (0mega ~ carboxyalkyl) -3-alkylthio-cyclopentanones, 2- (0mega-carboxyalkyl) -3 ~ all ^ lthiohydroxy-cyclopentanone, 2- (omega-carboxyalkyl) -3-alkylthio ~ 1,4-cyclopentanedione or 2-all ^ lthio-3- (omega-earboxyalkyl) -4-hydroxy-cyclopentanone, in particular 2- (6-carboxylhexyl) 3-thio-cyclopentanones, 2- (6-carboxylhexyl) -3-thio-4-hydroxycyclopentanones , 2- (6-carboxyhexyl) 3-thio ~ 1,4-cyclopentanedione, 2-alkylthio-3 ~ (6 ~ carboxyhexyl) ~ 4-hydroxy-cyclopentanone, 2- (6-carboxyhexyl) -5- (2-hydroxyallcylthio-cyclopentanone, 2- (6-Carboxyhexyl) -3- (2-hydroxyalkyIthio) -4-hydroxy-cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxyalkylthio) -1,4-cyelopentanedione or 2- (2-hydroxyalkylthio-3- (6-carboxyhexyl) ~ 4 ~

hydroxy-cyclopentanones, in particular, they are also optionally substituted 2- (omega-carboxyalkyl) -3- (2-oxoaUcylthio) -cyclopentanones, -cyclopentadione (1,4) »-cyclopentanols, -cyclopentanediols-ii, 4), -4-hydroxycyclopentanone or -4-oxo-cyclopentanols, such as 2- (0mega-carboxyhexyl) -3- (2-oxo-allcythio) -, 2- (omega-carboxyhexyl) -3- (2-oxo-3-methylai : kyrthio) - or 2- (0mega-carboxyhexyl) -3- (2-0X0-3,3-dimethylal! kyIthio) -cyclopentanone, -cyclopentanedione (1,4), -cyclopentanole, -cyclopentanediol (1,4) , - ^ - hydroxycyclopentanone or -4-oxo-cyclopentanole.

The compounds of the formula VII are substituted cyclopenty! Thiols or alkali metal or alkaline earth metal cyclopentylthiolate; it is preferably 3-0xo-2- (omegacarboxyalkyl) -cyclopentylth.iole, 3-0xo-5-hydroxy-2- (omega-carboxyalkyl) -cyclopentylth.iole, 3-hydroxy-2- (omega-carboxy, alkyl) -cyclopentylthiols, 3,5-dihydroxy-2- (omega-carboxyalkyl) -cyclopentylthiols, especially 3-oxo-2- (6-carboxyhexyl) -cyclopentylthiols, 3-oxo-5-hydroxy-2- (6-carboxyhexyl) -cyclopentylthiols, 3-hydroxy-2- (6-carboxyhexyl) cyclopentyl thiols or 3,5-dihydroxy-2- (6-carboxyhexyl) -cyclopenty! thiols.

A09841 / 0980 -24-

The compounds of the formula VIII are optionally substituted alkenes, alkyl halides, alkylsulfonyl-oxyalkanes or arylsulfonyloxyalkanes, preferably 1-alkenes, chloroalkanes, bromoalkanes, methylsulfonyloxyalkanes or p-tolylsulfonyloxyalkanes, each with a chain length of up to 12 carbon atoms, in particular 1 -Heptens, 1-octenes, 1-nonenes, 8-pheny1-1-octenes, 8-fluoro-i-octenes, 8,8-difluoro-1-octanes, 7,7, 7-T _r if luor-1- heptene or 8,8,8-trifluoro-1-octenes; 1-chloroheptane, 1-bromoheptane, 1-p-tolylsulfonyloxyheptane, 1-chloro-7,7,7-trifluoroheptane, 1-chloro-7-phenylheptane, 1-ChIor-6,6 -dime thy lhe pt an e, 1-bromo-7 »7,7-trifluoroheptane, 1-bromo-7-phenylheptane, 1-bromo-6,6-dimethylheptane, 1-p-tolylsulfonyloxy-7,7,7-trifluoroheptane, 1-p- Tolylsulfonyloxy-7-phenylheptane or 1-p-tolylsulfonyloxy-6,6-dimethylheptane.

In the case of the compounds which otherwise correspond to formula I, in which existing hydroxyl and / or keto groups and / or the carboxyl group are present in a functionally modified form, it is, for example, optionally substituted 1,1-dialkoxy, 1,1,4-trialkoxy, 1,1-alkylenedioxy, 1, i-alkylenedioxy-4-alkoxy-; 1-alkyloxy, 1,4-dialkoxy, 1-aralkoxy, 1,4-aralkoxy, 1-tetrahydropyranyloxy, 1,4-bis-tetrahydropyranyloxy-,

1-trialkylsilyloxy-, 1,4-bis-trialkylsilyloxy ~ 2- (omegacarbalkoxyalkyl) -3-alkylthio-cyclopentanes; preferably to optionally substituted 1,1-diethoxy-2 - (omegacarbethoxyalkyl) -3-alkylthio-cyclopentane & , 1,1,4-triethoxy, 1,1-ethylenedioxy or 1,1-ethylenedioxy-4-ethoxy-2- (omegacarbathoxyalkyl) -3-alkylmercapto-cyclopentane; 1-tert-butoxy-2- (omega) ~ tert-carbutoxyalkyl) -3-alkylthio-cyclopentane, 1,4-di-tert-butoxy-, 1-benzyloxy-, 1,4-M ~ benzyloxy-, 1-tetrahydropyramyloxy-, 1,4-bis-tetrahydropyranyloxy-, 1-trimethyl-bilyloxy-, 1,4-bis-trimethylsilyloxy-, 1,1-diethoxy-i, 1-diethoxy-4-tert.-butoxy, 1,1,4-triethoxy, 1, i-diethoxy-4-benzyloxy, 1, i-ethylenedioxy-4-tert.-butoxy-, 1, i-ethylenedioxy-4-benzyloxy-, 1,1-ethylenedioxy or 1,1-ethylenedioxy-4-ethoxy-2- (omega-tert-carbbutoxyalkyl) -3-alkylthio-cyclopentanes; or to

4GyiU1 / Uy8ü -25-

1 - "ter" t. -Butoxy-, 1, 4 ~ I> i-tert. -butoxy-, 1 -benzyloxy-, 1,4-dibenzyloxy-, 1-tetrahydropyranyloxy-, 1,4-bis-tetrahydro ~ pyranyloxy-, 1-trimethylsilyloxy-, 1,4-bis-triraethylsilyloxy-, 1, 1-diethoxy, 1, 1,4-triethoxy, 1,1-ethylenedioxy, 1, T-ethylenedioxy-4-ethoxy, 1, 1-diethoxy-4-tert.-butoxy-, 1,1-diethoxy-4-benzyloxy-, 1, .i-ethylenedioxy-4-tert-butoxy- or 1,1-ethylenedioxy-4-benzyloxy-2- (omega-carbbenzyloxyalkyl) -3-alkylthiomercaptans; in particular to optionally substituted 1-tert-butoxy, 1,4-di ~ tert-butoxy, 1-benzyloxy, 1,4-dibenzyloxy, 1-tetrahydropyranyloxy, 1,4-bis-tetrahydropyranyloxy, 1-trimethylsilyloxy-, 1,4-bis-trimethylsilyloxy-, 1,1-diethoxy, 1,1,4-triethoxy, 1,1-ethylenedioxy, 1,1-ethylenedioxy-4-ethoxy, 1,1-diethoxy-4-tert.-butoxy-, 1,1-diethoxy-4-l3enzyloxy-, 1, i-ethylenedioxy-4-tert.-butoxy- or 1,1-Ethylenedioxy-4-benzyloxy-2- (6-tert-carbbutoxyhexyl) -3-heptylthio-cyclopentane, 1-tert-butoxy-, 1,4-di-tert-butoxy-, 1-benzyloxy-, 1,4-dibenzyloxy-, 1-tetraliydropyra-nyloxy-, 1,4-bis-tetrahydropyranyloxy-, 1-trimethylsilyloxy-, 1,4-bistrimethylsilyloxy-, 1,1-diethoxy, 1,1,4-triethoxy, 1,1-ethylenedioxy, 1, i-ethylenedioxy-4-ethoxy, 1,1-diethoxy-4-tert.-butoxy, 1,1-diethoxy-4-benzyloxy-, 1,1-ethylenedioxy-4-tert. -butoxy- or 1,1-ethylenedioxy-4-t> enzyloxy ~ 2- (6-tert. c arbbut oxyhe xyl) -3- (2-hydroxy-2-me thy1-he ρty1thiο) -cycIopentane, 1-tert-butoxy, 1,4-di-tert-butoxy, 1-benzyloxy, 1,4-dibenzyloxy, 1-tetrahydropyranyloxy-, 1,4-bis-tetrahydropyranyloxy-, 1-trimethylsilyloxy-, 1,4-bis-trimethylsilyloxy-, 1,1-diethoxy, 1,1,4-triethoxy, 1,1-ethylenedioxy, 1,1-ethylenedioxy-4-ethoxy, 1,1-diethoxy-4-tert.-butoxy-, 1,1-diethoxy-4-benzyloxy-, 1,1-ethylenedioxy-4-tert-butoxy- or 1, i-ethylenedioxy ^ -benzyloxy ^ - (6-tert-carbbutoxyhexyl) -3-. (2-hydroxyl-2-methyl-3-p-tolyl-propylthio) -eyelopentane, 1-tert. · Butoxy, 1,4-di-tert-butoxy, 1-benzyloxy, 1, 4-dibenzyloxy, 1-tetrahydropyranyloxy, 1,4-bis-tetrahydropyranyloxy, 1-trimethylsilyloxy, 1,4-bis-trimethylsilyloxy-, 1,1-diethoxy-, 1,1,4-triethoxy, 1,1-ethylenedioxy, 1,1-ethylenedioxy.

0 9841/0980

4-ethoxy-, 1,1-diethoxy-4-tert-butoxy-, 1,1-diethoxy-4-benzyloxy-, 1, i-ethylenedioxy-4-tert-butoxy- or 1,1-ethylenedioxy-4-benzyloxy-2- (6-tert-carbbutoxyhexyl) -3- (2-hydroxy-2,6,6-trimethyl- heptylthio ^ cyclopentane, 1-tert-butoxy, 1,4-di-tert-butoxy, 1-benzyloxy, 1,4-dibenzyloxy, 1-tetrahydropyranyloxy, 1 ^ -Bis-tetrahydropyranyloxy-, 1-trimethylsilyloxy-, 1,4-bis-trimethylsilyloxy, 1,1-diethoxy, 1,1,4-triethoxy, 1,1-ethylenedioxy, 1, i-ethylenedioxy-4-ethoxy, 1,1-dlethoxy-4-tert.-butoxy, 1,1-diethoxy-4-benzyloxy-, 1,1-ethylenedioxy-4-tert-butoxy- or 1, i-ethylenedioxy-4-benzyloxy-2- (6-tert-carbbutoxyhexyl) -3- (2-hydroxy-2-methyl-7,7,7-trifluoroheptylthio) -cyclopentane; or optionally substituted 1-tert-butoxy, 1,4-di-tert-butoxy, 1-benzyloxy, 1,4-dibenzyloxy, 1-tetrahydropyranyloxy, 1,4-bis-tetrahydropyranyloxy, 1-trimethylsilyloxy-, 1,4-bis-trimethylsilyloxy-, 1,1-D.iäthoxy-, 1,1,4-triethoxy-, 1,1-ethylenedioxy, 1,1-ethylenedioxy-4-ethoxy, 1, i-diethoxy-4-tert.-butoxy-, 1,1-diethoxy-4-benzyloxy-, 1, i-ethylenedioxy-4-tert. -butoxy- or 1,1-ethylenedioxy-4-benzyloxy-2- (6-carbbenzoxyhexyl) -3-heptylthio-cyclopentane, 1-tert-butoxy, 1,4-di-tert-butoxy, 1-benzyloxy, 1,4-dibenzyloxy, 1-tetrahydropyranyloxy, 1,4-bis-tetrahydropyranyloxy, 1-trimethylsilyloxy, 1,4-bistrimethylsilyloxy, 1,1-dlethoxy, 1,1,4-triethoxy, 1,1-ethylenedioxy, 1,1-ethylenedioxy-4-ethoxy, 1,1-diethoxy-4-tert.-butoxy, 1,1-diethoxy-4-benzyloxy-, 1,1-ethylenedioxy-4-tert-butoxy- or 1,1-ethylenedioxy-4-benzyloxy-2- (6-carbbenzoxyhexyl) -3- (2-hydroxy-2-methyl-heptylthio) -cyclopentane, 1-tert-butoxy, 1,4-di-tert-butoxy, 1-benzyloxy, 1,4-dibenzyloxy, 1-tetrahydropyranyloxy-, 1,4-bis-tetrahydropyranyloxy-, 1-trimethylsilyloxy, 1,4-bis-trimethylsilyloxy, 1,1-diethoxy, 1,1,4-triethoxy, 1,1-ethylenedioxy, 1,1-ethylenedioxy-4-ethoxy, 1,1-diethoxy-4-tert.-butoxy-, 1,1-diethoxy-4-benzyloxy-, 1, i-ethylenedioxy-4-tert-butoxy- or 1,1-ethylenedioxy-4-benzyloxy-2- (6-carbbenzoxyhexyl) -3- (2-hydroxy-2-methyl-7-phenyl-heptylthio) - cyclopentane,

409841/0980

1-tert-butoxy, 1,4-di-tert-butoxy, 1-benzyloxy, 1,4-dibenzyloxy, I-tetrahydropyranyloxy-, 1,4 ~ bis-tetrahyd.ropyranyloxy-, 1-tri-ethylsilyloxy-, 1,4-bis-trimethylsilyloxy-, 1,1-diethoxy, 1,1,4 ~ triethoxy, 1,1-ethylenedioxy, 1,1-ethylenedioxy-4-ethoxy, 1,1-diethoxy.-4-tert.-butoxy-, 1,1-diethoxy-4-benzyloxy-, 1,1-ethylenedioxy-4 ~ tert. ~ Butoxy- or 1,1-ethylenedioxy-4-benzyloxy ~ 2- (6-carbbenzoxyhexyl) -3- (2-hydroxy-2, 6,6-tri-ethyl-heptylthio) -cyclopentane.

The compounds of the formula II are known or can be prepared from known compounds by processes known per se will.

For example, the diethylacetal can be prepared from 2-brora-2-cyclopentenone in a manner known per se by reacting with ethanol, which, after treatment with lithium in ether, is reacted with / JCH ^ O ^ P / pCuJ and the organic copper compound obtained, for example, with omega -tert.-Butoxycarbonylalkyliodiden to react. This reaction sequence is preferably carried out between -50 and + 5 °, in particular between -30 ° and -10 ° and under an inert gas atmosphere, for example under argon. But it is also possible, for example, cyclopentanone ^ -carboxylic acid ethyl ester in a manner known per se with omega-alkoxycarbonyl or omega-cyanoalkyl bromides or iodides in the presence of alkali metal alcoholates, for example NaOOPHc »to react the reaction product in an inert solvent, preferably a hydrogen chloride such as CGI . to brominate with Brp and then with H ₂ SO. to treat. The compounds of the formula II are formed according to a reaction mechanism that has not yet been clarified.

The compounds of the formula III are known or can be used according to known methods, such as those in HOUBEN-WEYL, Methods of Organic Chemistry, Volume IX, pages 3 ff., Stuttgart, 1955. It is preferable to use compounds which otherwise correspond to formula III,

409841 / Oböü

special Br, and sets it with an alkyl metal hydrogen sulfide, preferably KIIS or NaHS to. The reaction is mostly carried out using a solvent, preferably a Alcohol such as methanol, ethanol or isopropanol, if appropriate also in the presence of water or an aprotic dipolar Solvents such as acetone, dimethylformamide, dimethyl sulfoxide, Tetramethylurea, hexamethylphosphoric acid triamide, tetrahydrothiophene-S, S-dioxide, Ethylene carbonate or propylene carbonate or mixtures of such solvents. If the reaction mixture is worked up under acidic conditions, so receives; one usually the free thiols of the formula III, which by reacting with bases, preferably alkali metal or alkaline earth metal hydroxides, in particular NaOH or KOH, can be converted into the thiolates of the formula III.

If the compounds of the formula III are 2-hydroxyalkanethiols, these are preferably prepared from the corresponding 1,2-epoxyalkanes and H _? S prepared in the presence of a basic catalyst.

The compounds of the formula IV can be prepared from compounds which otherwise correspond to the formula II, but which are an

1 5

Contain a radical R in place of the COOR group. Such compounds can be prepared similarly to the compounds of the formula II: Nitrites of the formula IV (Ir = CN) are obtained, for example, by a method known per se from ethyl 2-oxocyclopentylcarboxylate by reacting with omega-iodine-alkyl nitriles, preferably in a solvent, in the presence a base, reaction of the reaction product with Br _? , Treat with H ₀ SO. and addition of a compound of formula III. Esters of the formula IV (R ⁵ = COOR) are obtained, for example, by a method known per se from ethyl 2-oxocyclopentylcarbonate by reacting with omega-iodine-alkanecarboxylic acid ester, preferably in a solvent, in the presence of a base, reacting the reaction product with Br ^, treating with H _? SO. and addition of a compound of formula III. Amides of the formula IV (R ⁵ = CONR ¹⁶ R ¹⁷ ) are also obtained, for example, according to

4Oy tu ι / üaeu -29-

known method from 2-Oxocyclopentylcarbonsäureäthy! ester by reaction with omega-iodine-alkanecarboric acid amides, preferably in one. Solvent, in the presence of a base, reacting the reaction product with Br ^, treating with HpSO, and • Addition of a compound of the formula III.

Acids of the formula I (R =. H) can be prepared in the presence or absence of an inert solvent by treatment with inorganic acid halides, eg. B. SOCl ₂ or SOBr ₂ ? can be converted into the corresponding acid halides IV (R = e.g. GOGl or COBr). Hydrochlorides of the imino ethers (IV, R ⁵ = CC = OJH) OR ¹⁶ ) can be obtained from the nitriles (IV ₅ R ⁵ = CN) with alcohols R-OH in "ether" in the presence of HCl.

It is also possible to treat the acids of the formula I (R = H) or their functional derivatives, preferably their halides and esters (IV, R ⁵ = COCl, COBr or esterified COOH group) by treatment with amidating agents, e.g. . B. with ammonia or amines of the formulas R ¹⁶ -NH ₂ , (R ¹⁶ ) ₂ NH or R ¹⁶ R ¹⁷ M (or with hydroxylamine) to convert into the corresponding amides (or hydroxamic acids). Possible amines are, for example:

Monoalky! Amines, e.g. B. methylamine, ethylamine, n-propylamine, Isopropylamine, n-butylamine, isobutylamine; Dialkylamines, ζ-. B. dimethylamine, methylethylamine, diethylamine, di-npropylamine, Diisopropylamine, di-n-butylamine, diisobutylamine; also aryl and aralkylamines, e.g. aniline, benzylamine; Hydroxyalkylamines, e.g., ethanolamine, diethanolamine; further heterocyclic amines such as pyrrolidine, piperidine, morpholine, "thiomorpholine, piperazine, N-alkylpiperazines, e.g. N-methyl- or N-ethylpiperazine; N-Hydroxyalky! Piperazine, ζ. Β. N-2-hydroxyethyl piperazine. In the manufacture of the amides is the addition of an inert solvent, e.g. B. an alcohol such as methanol or ethanol or a chlorinated one Hydrocarbon such as CHCl-, as well as the application of pressure (up to about 200 at) possible, but not required. the

A09841 / Ü980 -30-

Reaction temperatures are between about -20 and + 150 °, preferably between 0 and 100 °. A variant of amidation consists in that you get the acid I (R = H) first with a chlorinated acid ester ClGOOR in the presence of a base such as triethylamine into the mixed anhydride of the formula IV (R = COOCOR) and this then further with the amine implements.

Furthermore, amides of the formula IV (R = CONH ₀ ) can, if desired, be dehydrated to the nitriles (IV, R = CN), ζ. B. with deliydrating agents such as P _o 0 (-} POCl. ,, ρ-toluenesulfochloride / pyridine, at temperatures between about 0 and 200 °, preferably 20 and 100 °. Heating carboxylic acids I (R = H) with lower alkanoic anhydrides leads to the Acid anhydrides IV (R ⁵ = -CO-O-CO-R ¹⁶ ).

In the processes described above, products can be obtained in which the radical R is already partially COOH was solvolyzed. The mixtures prepared in this way can be used directly for the preparation of the compounds of the formula I. will.

Compounds of the formula VI (R ² = 0; R ⁹ =? -Oxoalkyl) are obtained, for example, from compounds of the formula II (R = 0, R = H, D = -CH = OA-COOR ¹ ) by reacting with a 2- Oxo-alkylthiol. The reaction conditions for the reaction can be found, for example, in the literature; in particular, those given below are suitable.

Compounds of the formula VII are obtained according to known ' Methods, for example from 2- (omega-carboxyalkyl) -2-cyclopentenones by addition of HpS.

The compounds of the formula VIII are known and can be prepared by methods known per se.

- 31 409841 / UÖ80

A compound which otherwise corresponds to the formula I, wherein but existing hydroxyl and / or .. keto groups and / or the carboxyl group are present in a functionally modified form, j = "can also be produced in a manner known per se.

Compounds in which E is a functionally modified oxo group are, for example, in the following Eeaktions-

result: A compound of the formula II (E = 0, D = -CH = (JA-COOE ¹ ) is reacted with a 2-hydroxyalkylthiol of the formula III (W = H), the ketone obtained is analogous to the method described in the literature, for example by Treatment with a trimethyl orthoformate converted into the dimethyl ketal, converted into the corresponding, substituted 2-ketoalkyl-cyelopentyl sulfide by oxidation with, for example, dimethyl sulfoxide, and from this the 2-hydroxy-2-methylalkyl-cyclopentyl sulfide produced with methyl magnesium bromide.

Functional carbonyl derivatives of compounds of the formula I are obtained in known? Way, for example from the cyclopentanones of the formula I by reaction with a corresponding-N-containing carbonyl reagent, for example a hydroxylamine such as HpHOH or O-alkyl-hydroxylamines; e, inem hydrazine, such as H ₂ MiH ₂ , N-methylhydrazine, Ν, Ν-dimethylhydrazine, phenylhydrazine, 4-nitrophenylhydrazine or 2,4-dinitrophenylhydrazine; Semicarbazide; or a primary amine, preferably an aliphatic, alicyclic or aromatic primary amine, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, cyclonexylamine, aniline, p-toluidine, α-naphthylamine or β-uaphthylamine. These reactions take place with elimination of water, generally using an inert solvent, preferably lower alcohols with up to 4 carbon atoms, such as methanol or ethanol, and in the presence of an acidic or basic catalyst, preferably an inorganic or organic acid, such as HCl, H _? 30. or acetic acid; or an alkali hydroxide, such as NaOH or KOH, or a basic salt, such as K ₂ CO ^, or Na acetate. The reaction temperatures are mostly

-32-

between room temperature and 120, preferably at the boiling point of the reaction mixture.

The N-containing Carbpnylderivate the compounds of formula I are from these compounds either for isolation from the Reaction mixtures or prepared for cleaning, since they are in general crystallize better than that - as a rule oily - compounds of formula I themselves; but you can also use them for the preparation of other compounds of the formula I. For example, 2- (omega-tert-carbutoxyalkyl) ~ 3- (2-hydroxyalkylthio) -cyclopentanones after conversion into the corresponding phenylhydrazones by known methods 2- (omega-tert-carbbutoxyalkyl) -3- (2-oxoalkylthio) -cyclopentanone-phenyl-hydrazones be oxidized. These compounds are then obtained by reaction with alkyl Grignard compounds the corresponding 3- (2-alkyl-2-hydroxyalkylthio) ~ cyclopentanone derivatives, which in turn are converted into Can be converted into compounds of the formula I in a known manner.

The reaction of a compound of the formula II (D = -CH = CA-COOR ¹ ) with a compound of the formula III is generally carried out in the presence of a basic catalyst and using a suitable solvent, preferably an alcohol such as methanol or ethanol; you can z. B. but also use a hydrocarbon such as benzene or toluene; H ₂ O or liquid ammonia are also suitable. It is also possible to work without a solvent.

Suitable basic catalysts are preferably metal hydroxides, in particular alkali metal or alkaline earth metal hydroxides such as NaOH, KOH or Ca (OH) n; Alkali metal alcoholates, such as NaOCH ₅ , NaOC ₂ II ₅ or KO-tert.-CH _g ; basic salts, preferably carbonates or acetates such as KpCO ^ or NaOCOCH ₇ ; Ammonia; Amines such as trimethylamine, triethylamine, isopropylamine, tert-butylarain or ethylenediamine; alicyclic amines such as cyclohexylamine, dicycloxylanjine or dimethylaniline;

or heterocyclic amines such as piperidine, pyrrolidine, pyridine, quinoline, diazabicyclo [2, 2, 2] octane or diazabicyclo [3 »4.0] monene; or quaternary ammonium hydroxides "such as tetramethylammonium hydroxide or benzyltrimethylammonium hydroxide.

The presence of such a basic catalyst is "special favorable if a compound of the formula III with ¥ - H is used. If you have a compound of the formula III 'W = one equivalent of an alkali or alkaline earth metal atom), is used, the reaction mixture usually reacts basic and the addition of a basic catalyst is not necessary. You can of course also choose a suitable one Use basic catalyst as solvent (especially liquid ammonia). You work between -40 ° and 120 °, preferably between room temperature and the boiling point of the reaction mixture; the response times are, depending according to the reaction conditions, between 3 hours and 7 days.

In the same way, compounds of the formula VII (W = H) can be reacted ^{with compounds of the formula VIII (B = R 11} R ¹² C = OR ^{15 -).}

The reaction of a compound of the formula II (D = -CHX-CH-A-OOOR ¹ ) with a compound of the formula III (W = one equivalent of an alkali or alkaline earth atom) takes place in a manner known per se and described in detail in the literature. Preference is given to working in an inert solvent, in particular one of the abovementioned ones. The reaction temperatures are preferably between 0 ° and 120 °, in particular between room temperature and the boiling point of the reaction mixture; the reaction times are between 3 hours and 7 days, depending on the reaction conditions.

In the same way, compounds of the formula. VII (W = one equivalent of an alkali or alkaline earth metal atom) ^{are reacted with compounds "of the formula VIII (B = XR 11} R ¹² C-CR ¹⁵ R ¹⁴ -).

40 9.84 Ί / U98Q - 34 -

Compounds of the formula IV in which the radical R ^{5 is} a functionally modified carboxyl group can be solvolyzed or thermolyzed, in particular hydrolyzed, to give the compounds of the general formula I by methods described in the literature. The hydrolysis is carried out in an acidic or optionally alkaline medium at temperatures between -20 and 300, preferably at the boiling point of the selected solvent. Suitable acidic catalysts are, for example, inorganic acids, such as hydrochloric, sulfuric, phosphoric or hydrobromic acid; The basic catalysts used are advantageously metal hydroxides or basic salts, such as sodium, potassium or calcium hydroxide, sodium or potassium carbonate. The preferred solvent is water; lower alcohols such as ethanol, methanol; Ethers such as dioxane, tetrahydrofuran; Amides such as dimethylformamide; Nitriles such as acetonitrile; Sulfones such as tetramethylene sulfone; or their mixtures, especially the water-containing mixtures.

But you can use the acid derivatives z. B. also in ether or benzene with the addition of strong bases such as potassium carbonate or without solvents by fusing with alkalis such as KOH and / or NaOH or alkaline earths to form compounds of the formula I saponify.

Another embodiment of the invention is the saponification of corresponding thioamides of the formula IV (Ir = CSNR R), z. B. the appropriately substituted Thiomorpholides, piperidides, pyrrolidides, dimethylamides or diethylamides.

In particular, however, the compounds of the formula I are also obtained by solvolysis of nitriles of the formula IV (R = CN). This solvolysis can be carried out and leads as hydrolysis in a manner known per se in aqueous media

-35-

then to the acids of the formula I, or analogously in the literature ■ methods described with the exclusion of water and in Presence of an alcohol run and then results Esters of the formula I. The reaction is carried out in the presence of an acidic or "basic catalyst".

The conversion of the nitriles (IV; R ^ = CE) into the esters

(I; R not equal to H) takes place z. B. in the presence of an acid catalyst, preferably a hydrogen halide such as HCl, but e.g. B. also BP with intermediate formation of a Imino ethers (IV; R = C [= NH] -OR), which in turn with "for example aqueous alcohol to I (I; R not equal to H) is converted.

The hydrolysis of the nitriles (IV; R = CN) to the acids (I; R = H) is preferably carried out in the presence of an acidic catalyst, in particular sulfuric acid or hydrochloric acid. The reaction takes place between -10 ° and 100. Preferably the reaction mixture is initially left in for "up to 6 days" Stand at room temperature and then cook for up to 6 hours.

If you use a basic catalyst, is it preferable to use an alkali metal or alkaline earth metal hydroxide such as NaOH, KOH or Ba (OH) _? or a basic salt such as KpCO-z or Na ₂ CO ₅ . in question. One works in HgO or H ₂ O / alcohol mixtures at elevated temperature, preferably at the boiling point of the reaction mixture, optionally also in an autoclave at elevated pressure.

- 36 / U98U

tr

The solvolysis of amides of the formula IV (R = CONR ^ R ■>) takes place under the reaction conditions specified for the nitriles.

Esters of the formula I can also be saponified in this way or, if appropriate be transesterified.

The acids of the formula I are also obtained by dry heating of, in particular, tertiary alkyl esters of the formula IV (R ⁵ = COO-tert-alkyl) to temperatures between 50 and 350 °. The thermolysis can also be carried out in inert solvents, such as benzene, water, dimethylformamide, ethylene glycol, glycerol, dimethyl sulfoxide, cyclohexanol, preferably with the addition of catalytic amounts of acids, such as p-toluenesulfonic acid.

According to the invention, the compounds of the formula I are obtained from the compounds of the formula V by reaction with solvolyzing, preferably hydrolyzing, agents. It is particularly favorable in aqueous media in the presence of basic catalysts, preferably alkali metal or alkaline earth metal hydroxides, such as KOH, NaOH or Ba (OH) _? or in the presence of basic salts such as K _? CO, or Na ^ CO ^ to work. The reaction temperatures are between room temperature and 140 °, preferably at the boiling point, of the reaction mixture. The hydrolysis can expediently also be carried out in the presence of a further solvent, for example an aprotic dipolar solvent such as acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide or tetramethylurea; but you can also in the presence of a protic solvent, preferably one

- 37 -409841/0980

Alcohol with in particular "up to 4 carbon atoms such as methanol, Ethanol, isopropyl alcohol or 2-butanol work.

The compounds of the formula V (R = / H, X7> X = Cl, Br or J, E ⁷ = H; or R ⁷ = Y, Y = Cl, Br or J, R ⁶ = 0; or R) are obtained ⁶ = / H, X7 and R ⁷ = Y, X = Cl, Br or J and Y = Cl, Br or J, the corresponding 1-acylöxy-, 4-ACyIoXy-I-OXo- or 1,4-diacyloxy- 2- (omega-carboxyalkyl) -3-alkylthiocyclopentanes by reaction with a metal acylate, preferably a silver acylate, in an inert solvent in which the metal acylate should have "considerable solubility," for example acetone or dimethylformamide. The reaction temperatures are between 10 and 140 ° , preferably between 40 ° and the boiling point of the reaction mixture. The reaction times are between 3 and 72 hours.

It should be noted that such a solvolysis is usually associated with an inversion at the substituted carbon atom Reaction on the same carbon atom "is usually in β-position and vice versa. According to the process just described, 4-acyloxy- or 4-hydroxy-2- (omega-carboxyalkyl) -3-alkylthio-cyclopentanones can also be used Formula I (R = 0) can be prepared, in particular from compounds of the formula V with R ⁶ = / !, Υ ?, X = Cl, Br or J and Y = Cl, Br or J.

The compounds of the formula VI are converted into the compounds of the formula I (R ² = [H, OH], R ³ = H or R ² = [H, OH] and R ⁵ = OH)) by treatment with a reducing agent. Only those come. Reducing agents in question, which leave the carboxyl group or carbalkoxyl group unchanged, so preferably complex metal hydrides, in particular NaBH.,

AO 984 1/09 8.0

optionally in the presence of AlCl ^ or LiBr, or LiBH .. It is expedient to work in the presence of an inert solvent, for example in a lower alcohol; an ether such as tetrahydrofuran or ethylene glycol dimethyl ether. The reaction is advantageously brought to an end by boiling the reaction mixture. The decomposition of the metal complexes formed can be carried out in the usual way, e.g. B. with an aqueous ammonium chloride solution. But you can also work with chemically activated hydrogen under suitable reaction conditions. For example, a selective reduction of the carbonyl group is possible by stirring with zinc dust in 50 % acetic acid at 0; Aluminum alcoholates, such as aluminum isopropoxide (according to the Meerwein-Ponndorf method, for example in benzene or toluene at temperatures between about 20 and about 110) are also suitable reducing agents.

Compounds which otherwise correspond to the formula I, in which

ρ
but R is a functionalized, in particular ketalized, oxo group, are preferably ketals, in particular ethylene ketals, hemiketals, thioketals, hemithioketals; but also oximes, hydrazones, semicarbazones or Schiff bases. These functional derivatives of the compounds of the formula I can be hydrolyzed to the compounds of the general formula I by methods described in the literature. The hydrolysis is carried out in an acidic or optionally alkaline medium at temperatures between -20 and 300, preferably at the boiling point of the reaction mixture. Suitable acidic catalysts are, for example, hydrochloric, sulfuric, phosphoric or hydrobromic acid, or organic acids such as oxalic acid, tartaric acid, p-toluenesulphonic acid; the basic catalysts used are advantageously sodium, potassium or calcium hydroxide, sodium or potassium carbonate. The preferred solvent is water; lower alcohols such as ethanol, methanol; Ethers such as dioxane, tetrahydrofuran; Amides such as dimethylformamide; Nitriles such as acetonitrile; Sulfones such as tetramethylene sulfone; or their mixtures, especially the water-containing mixtures.

409841/0980

- 39 -

Schiff bases can be prepared by briefly heating them with dilute acids, e.g. B. the above mineral acids or oxalic acid, optionally with the addition of solvents such as ethanol or acetic acid, are cleaved. The ketones can also be set free by hydrolysis of their condensation products with compounds of the acid amide type, such as carboxamides, sulfonic acid amides, urethanes, urea derivatives, by treatment with acids.

Ketones of the formula I (R = 0) can also be prepared by hydrolysis of hydrazones of the formula

N-EHR ¹

A-COOR

S-R '

or azines of the formula

A-COOR

can be obtained. 'In general, the split will be this Derivatives are preferably made by acid hydrolysis. A dilute solution of · oxalic acid or Phthalic acid can be used. Aqueous mineral acids are also suitable for the cleavage, in which case the compounds to be cleaved are used by adding ethanol, tetrahydrofuran, acetic acid or dioxane in solution. You can also do hydrazones cleavage by connecting them to other Carbony! compounds, e.g. B. p-nitrobenzaldehyde, 2,4-dinitr © benzaldehyde or pyruvine

A09Ö41 / Ü980

acid, treated; in the resulting equilibrium mixture the ketone is released while the corresponding, usually forms less soluble derivative of the added carbonyl compound. One proceeds appropriately so that the hydrazone and the carbonyl compound in aqueous suspension or in alcoholic-aqueous solution under Heated to reflux. If the ketones are in the form of their Girard derivatives T or P, they can be cleaved with Hydrochloric acid or sulfuric acid at temperatures from 0 to the boiling point of the solvent used, e.g. B. water, if necessary in a mixture with methanol or ethanol, set free; the ketone formed is with a suitable organic solvents, e.g. B. CHCl. ,, from the aqueous Phase extracted.

Oximes of the formula

l-COOR ¹

SR ⁴

can also be oxidized by treatment with nitrous acid or amyl nitrite or FeCl, in the presence of acids columns.

Ketones of the formula I (R = 0) can also be obtained by cleavage of enol ethers of the formulas

OR ¹⁶

Ά-COOR ¹ ^ "^ A-COOR ¹

SR ⁴

wherein

R means an organic radical

40ÖÖ41 / U98Q

can be obtained. The enol ethers are z. B, with diluted Mineral acids, such as HCl or HpSO ,, can be cleaved. The split can also be carried out with acetic acid or NaHCO. at For sensitive enol ethers, heating in water to 100 under increased pressure is sufficient. The split can also be with Hydroxylamine hydrochloride, or semioarbazide hydrochloride be where "when you get the ketones in the form of oximes or Semicarbazone isolated.

Ither, which otherwise correspond to formula I, in which the

2 3
The remainder of R and R have the following meaning,

R ² = [H, OR ¹⁸ J, R ³ = H; R ² = [H ₅ OR ¹⁸ J, R ³ = OR ¹⁸ ;

R ² = [E ₅ OR ¹⁸ J, R ³ = OH; or R ² = 0, R ³ = OR ¹⁸ can according to the ether cleavage methods known from the literature in

Alcohols of the formula I (R ² = [H, OHj and / or R ³ = OH; or

2 "5

R = O and R = OH) are converted. For example you can the ethers split through treatment with hydrogen bromide or hydrogen iodide in aqueous or acetic acid solution Heating with Lewis acids such as AlCl or boron trihalides or by fusing with pyridine or aniline hydrohalides hot about 200.

Esters of the formula I (R = alkyl, cycloalkyl, aralkyl or aryl, each with up to 12 carbon atoms, optionally substituted _{one or more times by Cl 5} Br or I) can be prepared from other compounds of the formula I by methods described in the literature . So you can, for example, an acid of the formula I (R = H) with the alcohol in question in the presence of an inorganic or organic acid, such as HCl ₅ HBr, HJ ₅ H ₂ SO ,, H ₅ PO ,, Trif ^ Luoroacetic acid, a sulfonic acid such as Benzenesulfonic acid or p-toluenesulfonic acid, or an acidic ion exchanger, optionally in the presence of an inert solvent, such as. B. benzene, toluene or xylene, at temperatures between about 0 and preferably boiling point. The alcohol is preferably used in excess. Preferred

409841/09 80 - 42 -

Alcohols are those of the formula

wherein

19th
R optionally one or more times

R OH by Cl, Br or J substituted

tes alkyl, cycloalkyl, aralkyl or aryl, each with up to 12 carbon atoms

means.

In particular, these are unbranched primary alcohols with up to 12 carbon atoms, such as methanol, ethanol, propane oil, Butanol, hexanol, octanol, decanol or dodecanol; but it can also be, for example, isopropyl alcohol, sea-butyl alcohol, tert-butyl alcohol, 2,2,2-trichloroethanol, 2-iodoethanol, benzyl alcohol or triphenylmethylcarbinol.

You can also work in the presence of water-binding agents, e.g. anhydrous heavy metal sulfates or Molecular sieves. The water of reaction can also be removed azeotropically, advantageously using hydrocarbons (e.g. benzene or toluene) or chlorinated hydrocarbons (e.g. chloroform or 1,2-dichloroethane). Runs in mild conditions the esterification, if the water of reaction is chemically added by the addition of carbodiimides (e.g. Ν, Ν'-dicyclohexylcarbodiimide) binds, using inert solvents such as ether, dioxane, 1,2-dimethoxyethane, benzene, CHpClp or CHCl, and Can add bases such as pyridine. The methyl esters (or ethyl or benzyl esters) can also be converted by the free acids with diazomethane (or diazoethane or phenyldiazomethane) in an inert solvent such as ether, benzene or methanol. Esters are obtained of the formula I (R not equal to H) also through addition of the carboxylic acids (I, R = H) to olefins (e.g. isobutylene, Cyclohexene), preferably in the presence of catalysts

40yfcU1 / 0980 - 43 -

(e.g. ZnClp, BF ₅ , H ₂ SO ₄ , arysulfonic acids, pyrophosphoric acid, boric acid, oxalic acid) at temperatures between about 0 and about 200 °, pressures between 1 and 300 at and in inert solvents such as ether, tetrahydrofuran, dioxane, Methylene chloride, benzene, toluene or xylene.

Furthermore, esters of the formula I (R = not equal to H) can be prepared by reacting metal salts of the carboxylic acids of the formula I (R - H), preferably the alkali metal, lead or silver salts, with alkyl halides, e.g. B. those of the formulas R ¹⁷ Gl, optionally in an inert solvent,

z. B. ether, benzene, DMF or petroleum ether, or with alkyl

19 chlorosulfites, e.g. B. those of the formula R-OSOCl and after-

IQ

subsequent thermolysis of the adducts obtained. A radical R that can be esterified into a Compound of the formula I was introduced is only to be regarded as a special case of a radical R.

You can also use acid halides, anhydrides or nitriles of the formula IY (R ⁵ = COCl, COBr, COOAc or CN) by reaction with an alcohol, -ζ. B. an alcohol of the formula ¹ R'rOH, optionally in the presence of an acidic catalyst or a base such as NaOH, EOH, Na _? CO _v KpCO ,, or pyridine, in esters of the formula. Convert I (R not equal to H). An excess of the alcohol in question is preferably used and temperatures between 0 ° and the boiling point are used. Alcohols of the formula I (R ² = / H, OH /, R ⁵ = H; R ² = / 1.0H /, R ⁵ = OH; R ² = 0, R ⁵ = OH) or their alkali metal alcoholates can be mixed with the halides or anhydrides of the acids to be esterified are reacted with or without the addition of acid-binding agents such as sodium or potassium hydroxide, sodium or potassium carbonate or pyridine. Inert organic solvents such as ether, THF or benzene can be used as solvents. The excess halides or anhydrides can also be used as solvents. In a preferred procedure, the alcohol of the formula I (R ² = / E ₁ CKfJ, R ⁵ = H; R ² = / !, ^{.OH ?, R 5} = OH; R ² = 0, R ⁵ = OH) is added in pyridine solution together with the halide or anhydride of the acid to be esterified.

- 44 409841/0980

ρ _

It is also possible to esterify alcohols of the formula I (R = / !! R ³ = H; R ² = / !, OH /, R ⁵ = OH; R ² = 0, R ⁵ = OH) with ketenes. It is preferred to work in inert solvents such as ether, benzene or toluene and with the addition of acidic catalysts such as sulfuric acid or p-toluenesulfonic acid.

Furthermore, you can esters of the formula I (R = not equal to H) by transesterification of other esters, which otherwise correspond to the formula I

116
speak, but in which R = R, with an excess of the alcohol in question or by reacting the carboxylic acids I (R = H) with any other esters of the alcohol in question, which are preferably used in excess. Esters of the formula I can be obtained analogously by transesterification of alcohols of the formula I (R = / H, OH7, R ³ = H; R ² = / H, OH /, R ⁵ = OH; R ² = 0, R ³ = OH ) with an excess of a lower alkyl ester or by transesterification of other esters which otherwise correspond to formula I in

2 3
but where R and R have the following meanings: R ² = / ΪΓ, esterified OH /, R ³ = H; R ² = / H, esterified OH /. R ³ = OH; R = / H, esterified OH ?, R = esterified OH; R ² = / !, OH ?, R ³ = esterified OH; or R ² = 0, R ³ = esterified OH, with an excess of the carboxylic acid to be esterified. The transesterification methods described in the literature are used, in particular in the presence of basic or acidic catalysts, for example sodium ethylate or sulfuric acid, at temperatures between about 0 ° and the boiling point. The operation is preferably carried out in such a way that, after equilibrium has been established, a reactant is removed from the equilibrium by distillation.

409841 / 098Q

Esters of the formula I (R not equal to H) can also be obtained by using compounds of the formula IY in which R is a thioester, imino ether, oximino ether, hydrazone ether, thioamide, amidine, amidoxime or amidhydrazone grouping with Water or dilute aqueous bases or acids, e.g. B. ammonia, NaOH, KOH, Ea ₂ CO ₃ , K ₂ CO ₃ , HCl, H ₂ SO., Solvolyzed with addition of the alcohol in question and elimination of hydrogen sulfide, ammonia, amines, hydrazine derivatives or hydroxylamine. While z. B. most Iminoätherhydrοchloride in aqueous solution immediately decompose into the esters and ammonium chlorides at room temperature, the solvolysis of other derivatives takes place, z. B. the amidoximes or thioamides, only at higher temperatures up to 100 °.

As already explained, the compounds of the formula I have -; generally several centers of asymmetry, but always at least two. They are therefore mostly a mixture of different obtained stereoisomeric forms, 'd. H. as racemates or in the P ^ egel as mixtures of racemates. Since different racemates are diastereomeric to one another, they can be due to their different physical properties can be isolated from their mixtures and obtained in pure form, for example by recrystallization from suitable solvents (In particular, instead of the compounds themselves, derivatives which crystallize well can be used) Separation by distillation, but especially with the aid of chromatographic methods, both by adsorption chromatography or distribution chromatographic methods as well as mixed forms come into question.

- 46 -

409841 / 0-980

The racemates can be known in a number of ways Methods as given in the literature can be separated into their optical antipodes. The method chemical separation is preferred. Then from the racemic mixture by reaction with a optically active auxiliary formed diastereomers. So you can optionally an optically active base with the carboxyl group a compound of the formula I (R = H). For example, one can use diastereomeric salts of the compounds of Formula I with optically active amines, such as quinine, quinchonidine, brucine, cinchonine, hydroxyhydrindamine, morphine, 1-phenylethylamine, 1-naphthylethylamine, phenyloxynaphthylmethylamine, Quinidine, strychnine, basic amino acids such as lysine, arginine or the amino acid esters. In a similar way ester diastereomers can be established by esterification of compounds of the formula I (R = H) with optically active alcohols such as borneol, menthol, octanol-2. The difference The solubility of the resulting diastereomeric salts or esters allows the selective crystallization of one form and the regeneration of the respective optically active compounds from the mixture.

The hydroxy acids and hydroxy esters of the formula I (R = [H, OH], R ⁵ = H; R ² = [H, OH], R ⁵ = OH; R ² = 0, R ⁵ = OH) can also be esterified with an optically active acid such as (+) - and (-) - tartaric acid, dibenzoyl - (+) - and (-) - tartaric acid, diacetyl - (+) - and - (-) - tartaric acid, camphoric acid, ß-camphor

- 47 AQ 98 A 1 / U980

sulfonic acid, (+) - and (-) - mandelic acid, (+) - and (-) - apple acid, (+) - and (-) - 2-pheny! butyric acid, (+) - dinitrodiphenic acid or (+) - and (-) - lactic acid can be converted into suitable diastereomeric esters, which differ due to their different Let solubility separate. The optically active connections of the iOrmel I are then each through Saponification of the pure diastereomer obtained. But you can also start with phthalic or succinic anhydride represent the acidic phthalic acid esters or succinic acid esters and the dibasic acids obtained in this way or their monoesters with one of the optically active bases indicated above into the diastereomeric salts and from these the win pure enantiomers. From the ketosaurs and the Ketoesters of formula I (E = 0) can be converted with optically active ketone reagents, such as. B. -Menthy! Hydrazine or menthyl semicarbazide, the "corresponding diastereomeric hydrazones" or Semicarbazones are represented from which the pure enantiomers can also be obtained. The separation of the racemates "or Racemate-Gemisehe with the help of chromatographic methods. Either optically active support materials, such as e.g. B. Tartaric acid, starch, cane sugar, cellulose or acetylated cellulose and optically inactive and / or optically active mobile solvents use for separation into the pure enantiomers or an optically inactive carrier material, such as. B. Egg gel or aluminum oxide in combination with an optically active mobile phase. The optical antipodes can also be biochemical separated using selective enzymatic reactions. So you can the racemic acids of the formula I (R = H) to an Oxiäase or "if necessary expose decarboxylase, which by oxidation or Decarb-

- 43 409841 / Ü980

- 43 -

oxylation destroys one form while the other form remains unchanged remain. It is also possible to use a Hydrolasc in the case of a functional acid derivative of the racemic one Mixture for preferentially forming an optically active form. So you can esters or amides of the acids of the formula I (R = H) expose to the action of a hydrolase, which selectively saponifies one enantiomer and the other unchanged leaves.

Furthermore, it is of course possible to obtain optically active compounds by the methods described by starting materials are used that are already optically active.

Are the compounds by reacting a compound of the formula II (D = -CH = C-A-COOR) with a compound of the formula III (W - H) produced, the radicals -A-COOR and -S-R ^ are usually trans, i.e. H. when the alkylthio group is ß-position, so is the omega-carboxy or carbalkoxyalkyl group α-constant and vice versa.

If now a compound of the formula I or a precursor with certain steric relationships at one or more C atoms in a compound of the formula I or another compound of the formula I with the formation of a new one Asymmetry center converted, it can be achieved by a suitable reaction procedure that this carbon atom predominantly a specific, preferably the desired configuration having.

_ 49 _

The alkylthio group occurs "for example" with the addition of a compound of the formula III (¥ = · H) to a compound of the formula IV (D = -CH = CA-COOR ¹ ; B? - a-acyloxy with "up to 4 C- Atoms) preferably in the ß-position. The corresponding 4ß-hydroxy-2- (omega-carboxyalkyl) -3ß-alkylthiocyclopentanone is obtained, for example, from 4 <x-bromo-2- (omega-carboxyalkyl) -2-cyclopentene by addition a compound of the formula IV (W = H) and subsequent hydrolysis with inversion of configuration in the 4-position.

Compounds of the formula I (R = H) can by reaction be converted with a base into one of their physiologically harmless metal or ammonium salts. As salts come in particular the sodium, potassium, magnesium, Calcium and ammonium salts into consideration, also substituted ammonium salts, such as. B. the dimethyl and dietary ammonium, Monoethanol, diethanolammonium and iriethanolammonium, cyclohexylammonium, Dicyclohexylammonium and dibenzylethylenediammonium salts.

Conversely, compounds of the formula I can be obtained from their metal and ammonium salts by treatment with acids, in particular Mineral acids such as hydrochloric or sulfuric acid, set free will.

The new compounds can be used as a drug in a mixture with solid, liquid and / or semi-liquid excipients used in human or veterinary medicine. The carrier substances used are organic or inorganic Substances in question that are for parenteral, enteral or

- 50 / U98Ü

topical application are suitable and which do not react with the new compounds, such as, for example Water, vegetable oils, benzyl alcohol, polyethylene glycols, gelatine, lactose, starch, magnesium stearate, talc, petrolatum, Cholesterol. Solutions, preferably oily or aqueous solutions, are used in particular for parenteral administration Suspensions, emulsions or implants. Tablets, coated tablets, syrups and juices are suitable for enteral application or suppositories, for topical application ointments, creams or powders. The specified preparations can optionally sterilized or with auxiliaries such as lubricants, preservatives, stabilizers or wetting agents, emulsifiers, Salts to influence the osmotic pressure, buffer substances, Coloring, flavoring and / or flavoring substances and / or other active ingredients, such as vitamins, are added.

The substances are preferably administered in a dosage of 0.1 to 2,000 mg per dosage unit.

The IR spectra given below were obtained with Perkin Bucket 6 recorded as a film, and the NMR spectra with Varian HA 100 or A 60 in CDCl, against tetramethylsilane as internal Standard measured.

example 1

A mixture of 6 g of 2- (6-carboxyhexyl) -2-cyclopentenone, 10 ml of propylthiol and 7.2 ml of piperidine is allowed to stand for 5 days at room temperature, diluted with 150 ml of ether, and the ether phase is first washed with a mixture of 60 ml Ice water and 6 ml of concentrated HCl and then with saturated aqueous NaCl solution, dried over Na ^ SO., The solvent is distilled off and, after chromatographic purification of the residue (silica gel / CH ^ OH: CHCl ₅ = 1: 9) 2- ( 6-carboxyhexyl) -3-propylthiocyclopentanone as an oil, R ~ = 0.3 f silica gel / chloroform: methanol = 95: 5);

- 51 4Uyö41 / U98Ü

Analysis found: 62.9-1 ° C, 9.15 $ H, 11.19-1 ° S; Analysis found: 61.5-1 ° C, -9.4-1 ° H, 10.95 ° S;

IR spectrum: bands at 1 695, 1 730, 2 860 and 2 940 cm ^-1 ,

—1 ■ —1

wide band between 3 000 cm and 3 400 cm

Nuclear Magnetic Resonance Spectrum: Signals at 0.86 ppm, 3.0 ppm and 9.75 ppm.

Analogously one obtains from

Me th anthi ο1, ethanthine oil,
Prbpan-2-thiol, butanthi oil,
2-methylpropanethiol, 2-methylpropane-2-thiol, pentanethiol, 3-methylbutanthiol, hexanthiol,
4-methylpentanethiol, heptanethiol, 5-methylhexanethiol, octanethiol, 6-methylheptanethiol, non-anthi oil,
7-methyloctanethiol, 5,5-dimethylhexanethiol, 6,6-dimethylheptanethiol, 7,7-dimethyloctanethiol, 8,8-dimethylnonartanethiol, 2-methylhexanethiol, 2-methylheptanthi oil, 2-methylocanthiol , 2-MethylnonarLthiol, 3,3-Dimethylhexanethiol, 3,3-Dimethylheptanthiol,

- 52 -

3,3-dimethyl octanethiol, 3,3-dimethylnonanthiol, 2,3,3-trimethylhexaethiol, 2,3,3-trimethyl ptanthiol, 2,3,3-trimethyl octane thiol, 2,3,3-Trime thy lnon; anthiol, 2,5,5-trimethylhexanethiol, 2,6,6-trimethylheptanethiol, 2,7,7-trimethyl octanethiol, 2,8,8-trimethylnonanethiol, 3,3,5,5-tetramethylhexanethiol, 3,3,6,6-tetramethylheptanethiol, 3,3,7,7-tetramethyloctanethiol, 3,3,8,8-tetramethylnonanethiol, 2,3,3,5,5-Pen tame thy lhexar.thiol, 2,3,3,6,6-Pentamethylheptanethiol, 2,3,3,7,7-pentamethyloc tanethiol, 2,3,3,8,8-pentymethylnonanethiol, 6,6,6-trifluorohexanethiol, 7,7,7-trifluoroheptanethiol, 8,8,8-trifluorooctanethiol, 9,9,9-trifluorononanethiol, 2-methyl-6,6,6-trifluorohexanethiol, 2-methyl-7,7,7-trifluoroheptanethiol, 2-Methy1-8,8,8-trifluorooctanethiol, 2-methyl-9,9,9-trifluoronone anthiol, 3,3-dimethyl-6,6,6-trifluorohexanethiol, 3,3-dimethyl-7> 7,7-trifluoroheptaiithiol 3,3-dimethyl-8,8,8-trifluorooctanethiol, 3,3-dimethyl-9,9,9-trifluorononanethiol, 2,3,3-trimethyl-6,6,6-trifluorohexanethiol, 2,3,3-trimethyl-7,7,7-trifluoroheptanethiol, 2,3,3-trimethy1-8,8,8-trifluorooctanethiol, 2,3,3-trimethyl 1-9,9,9-trifluorononanethiol, 2-phenylethane thiol, 3-phenyl propane thiol, 4-phenylbutanthio oil,

-53 -

5-phenylpentanthiol,

6 - Ph'e ny lhe xanthi ο 1,

7-Pheny Ine ptanethiol,

2-methyl-2-phenylathethiol, 2-methyl-3-phenylpropane thiol, 2-methyl-4-phenylbutane thiol, 2-methyl-5-phe nj lpeiit anthiol, 2-methyl-6-phenylhexane thiol, 2-methy1 -7-phenylheptanethiol, 3,3-dimethyl-3-phenylpropanthiol, 3,3-dimethy 1-4-ph.enyXb-utanthiol, 3,3-dimethyl-5-ph.enylpentanethiol, 3, 3-dimethyl-1-6-phenylhexanethiol, 3,3-dimethyl-7-pnenylheptanthiol, 2,3,3-trimethyl-3-pnenylpropanthiol, 2,3,3-trimethyl 1-4-plienynDU. t anthiol, 2,3,3-trimethy1-5-phenylpentanethiol, 2,3,3-trimethy1-6-phenylhexanethiol, 2,3,3-trimethy1-7-phenylheptanethiol, 2 -hydroxy ethethiol,

2-Hydr oxyprο ρ anthiol, 2-Hydroxybut anthiol,

2 -Hydr oxyis otrat anthi ol,

2-Hydroxypent anthiol, 2-Hydroxy is ο pent ahthi ol, 2-Hydroxyhexaitthiol,
2-Hydroxyisohex anthiol, 2-Hydroxyheptanthiol, 2-Hydroxyis oheptanthiol,

2-Hydroxyoctarthiol, -

2-Hydroxyisοoct anthiol, 2-hydroxynonanethiol,

2-hydroxyis ononanthi ol, 2-hydroxy-5,5-dimethanhexylthiol, 2-hydroxy-6,6-dimethylheptanethiol, 2-hydroxy-7,7-dimethylootanethiol,

- 54 A09Ö41 / U980

2-Hydroxy-8,8-dimethyl thiol, 2-Hydroxy-2-methylhexanethiol, 2-Hydroxy-2-methylheptanethiol, 2-Hydroxy-2-methyloctanethiol, 2-Hydroxy-2-methylnonanethiol, 2- Hydroxy-3,3-dimethylhexanethiol, 2-hydroxy-3-, 3-dimethylphenethiol, 2-hydroxy-3,3-dimethyloctanethiol, 2-hydroxy-3,3-dimethylnonanethiol, 2-hydroxy-2,3 , 3-trimethylhexanethiol, 2-hydroxy-2, 3, 3-trimethylheptanethiol, 2-hydroxy-2,3,3-trimethyloctanethiol, 2-hydroxy-2,3,3-trimethylnonanethiol, 2-hydroxy-2, 5 , 5 trimethylhexanethiol, 2-hydroxy-2,6,6-trimethylheptanethiol, 2-hydroxy-2,7,7-trimethyl octanethiol, 2-hydroxy-2,8,8-trimethylnonanethiol, 2-hydroxy-3,3,5 , 5-rtetramethylhexane thiol, 2-hydroxy-3,3,6,6-tetramethylheptanethiol, 2-hydroxy-3,3,7,7-tetramethyloctanethiol, 2-hydroxy-3,3,8,8-tetramethylnonanethiol , 2-hydroxy-2,3,3,5,5-pentamethylhexanethiol, 2-hydroxy-2,3,3,6,6-pentamethylheptanethiol, 2-hydroxy-2,3,3,7,7-pentamethylocanthiol, 2-hydroxy-2,3,3,8,8-pentamethylnonanethiol, 2-hydroxy-6,6,6-trifluorohexanethiol, 2-hydroxy-7,7,7 trifluoroheptanethiol, 2-hydroxy-8,8,8-trifluorooctanethiol, 2-hydroxy-9,9,9-trifluorononanethiol, 2-hydroxy-2-methyl-6,6,6-trifluorohexar: thiol, 2-hydroxy-2 -methy1-7,7,7-trifluoroheptanethiol, 2-hydroxy-2-methyl-8,8,8-trifluorooctanethiol, 2-hydroxy-2-methy1-9,9,9-trifluorononanethiol, 2-hydroxy-3,3 -dimethyl-6,6,6-trifluorohexanethiol, 2-hydroxy-3,3-dimethy1-7,7,7-trifluoroheptanethiol, 2-hydroxy-3,3-dimethyl-8,8, R-trifluorooctanethiol, 2- Hydroxy-3,3-dimethyl-9,9,9-trifluorononanethiol,

-, 55 409841 / Ü98Ü

" ⁵⁵ " 225653?

2-hydroxy-2,3,3-trimethyl-6,6,6-trifluorohexanethiol, 2-hydroxy-2,3,3-trimethyl 1-7,7,7-trifluoroheptanethiol, 2-hydroxy-2,3,3 trim thy 1-8,8, 8-trifluoro octane thiol, 2-hydroxy-2,3,3-trimethy1-9,9,9-trifluorononanethiol, 2-hydroxy-2-phenylethanethiol,
2-hydroxy-3-phenylpropane thiol,
2-hydroxy-4-phenylbutane thiol ,.
2-hydroxy-5-phenylpentanethiol,
2-hydroxy-6-phenylhexane thiol,
2-Hydroxy-7-phenylheptane thiol,
2-Hydroxy-2-methyl-2-phenylethiol, 2-Hydroxy-2-methyl-3-phenylpropane thiol, 2-Hydroxy-2-methy 1-4-phenylbutanthiol, 2-Hydroxy-2-me thy 1-5-phenylpentanethiol, 2-hydroxy-2-methyl-6-phenylhexanethiol, 2-hydroxy-2-methyl-7-phenylheptanethiol,. 2-Hydroxy-3,3-dimethyl ~ 3-phenylpropane thiol, 2-Hydroxy-3,3-dime thy 1-4-phenyl-butane thiol, 2-Hydroxy-3,3-dime thy 1-5-phenylpent rethiol, 2- Hydroxy-3,3-dimethyl-6-phenylhexahthiol, 2-hydroxy-3,3-dimethyl-7-phenylheptanethiol, 2-hydroxy-2,3,3-trimethy1-3-phenylpropanethiol, 2-hydroxy-2,3, 3-trimethyl 1-4-phenylbutanethiol, 2-hydroxy-2,3,3-trimethyl 1-5-phenylpentanethiol, 2-hydroxy-2,3,3-trimethy1-6-phenylhexanethiol, 2-hydroxy-2,3,3 -trimethyl-7 ~ phenylheptanethiol,

by reacting with 2- (6-carboxyhexyl) -2-cyclopentenone:

2 ~ (6-carboxyhexyl) -3-methylthio-cyclopentanone, 2- (6— carl3oxyhexyl) -3-ethylthio-cyclopentanone, 2- (6-carboxyhexyl) -3-propylthio-cyclopentanone, 2- (6-Carl) oxyhexyl) -3-isopropylthio-cyclopentanone, 2- (6-carboxyhexyl) -3-btitylthio-cyclopentanone, 2- (6-CarlDOxyhexyl) -3-isobutylthio ~ cyclopentanone, 2- (6-carboxyhexyl) -3-tert-butylthio-cyclopentanone,

40 98A1 / 098Ü

2- (6-Carboxyhexyl) -3-pentylthio-cyclopentanone, 2- (6-carboxyhexyl) -3-isopentylthio-cyclopentanone, 2- ('6-carboxyhexyl) -3-hexylthio-cyclopentanone, 2- (6-CaT ¹ OOXyhexyl ) -3-isohexylthio-cyclopentanone, 2- (6-carboxyhexyl) -3-heptylthio-cyelopentanone, 2- (6-carboxyhexyl) -3-isoheptylthio-cyclopentanone, 2- (6-carboxyhexyl) -3- octylthio-cyclopentanone, 2- (6-cart) oxyhexyl) -3-is ο oc tylthio-cyclopentanone, 2- (6-car "boxyhexyl) -3-nonylthio-cyclopentanone, 2- (6-carboxyhexyl) -3 -isononylthio-cyclopentanone, 2- (6-carboxyhexyl) -3- (5,5-dimethylhexylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (6,6-dimethylheptylthio) -cyclopentanone, 2- (6- Carboxyhexyl) -3- (7,7-dimethylthioj-cyclopentanone, 2- (6-carboxyhexyl) -3- (8,8-dimethylnonylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2 -methylhexylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-methylheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-methyloctylthio) -cyclopentanone, 2- (6-carboxyhexy1) - 3- (2-methylnonylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (3,3-dimethyl 1hexylthio) cyclopentanone, 2- (6-carboxyhexyl) -3- (3,3-dimethylheptylthio) cyclopentanone, 2- (6-carboxyhexyl) -3- (3,3-dimethyloctylthio) cyclopentanone, 2- (6- Carboxyhexyl) -3- (3,3-dimethyinonylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,3,3-trimethylhexylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2, 3,3-trimethylheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,3,3-trimethyloctylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,3,3-trimethylnonylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,5 »5-trimethylhexylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,6,6-trimethylheptylthio) -cyclopentanone, 2- ( 6-carboxyhexyl) -3- (2,7,7-trimethyloctylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,8,8-trimethylnonylthio) -cyclopentanone, 2- (6-carboxyhexy1) -3 - (3,3,5,5-tetramethylhexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3,6,6-tetramethylheptylthio) ~

cyclopentanone,

2- (6-carboxyhexyl) -3-0,3,7,7-tetramethyloctylthio) -eyelopentanone, 2- (6-carboxyhexyl) -3- (3,3,8,8-tetramethylnonylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3,5,5-pentamethylhexylthio) -

cyclopentanone,

- 57 409841/0980

2- (6-carboxyhexyl) -3 ~ (2,3,3,6,6-pentamethylheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3,7,7-pentamethyloctylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3,8,8-pentamethylnonylthio) -

cyclopentanone,

2- (6-Carboxyhexyl) -3- (6,6., 6-trifluorohexy ItM o) -cyclopentanone,

2- (6-carboxyhexyl) -3- (7,7,7-trifluoroheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (8,8,8-trifluorooctylthio) -cyclopentanone, 2- (ö-Cax ^ boxyhexyl) -3- (9,9,9-trif Iu ornony lthio) -cycl opentanon, 2- (6-Car "boxyhexyl) -3- (2-methyl ~ 6, 6, 6-trifluorohexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-methyl-7,7,7-trifluoroheptylthio) -

'cyclopentanone,

2- (6-carboxyhexyl) -3- (2-methyl-8,8,8-trifluoroetylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-methy1-9,9,9-trifluoronylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3-dimethy1-6,6,6-trifluorohexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3-dimethy1-7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3-dimethyl-8,8,8-trifluorooctylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3-dimethy1-9,9,9-trifluoronylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-6,6, β-trifluorohexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-7,7,7-trilfuorheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethy1-8,8,8-trifluoroctylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethy1-9,9,9-trifluorononylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-phenylethylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (3-phenylpropylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (4-phenylbutylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (5-phenylpentylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (6-phenylhexylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (7-phenylheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-methy1-2-phenylethylthio) -cyclopentanone,

409841/0980 -58.

2- (6-carboxyhexyl) - 3- (2-methyl-3-phenylpropylthio) -

cyclopentane,

2- (6-Carboxyliexyl) -3-C2-methyl-4-plienylb'utylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-niethyl-5-phenylpentylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-methy1-6-phenylhexylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-methyl-7-phenylheptylthio) -

cyclopentanone,

2- (6 ~ carboxyhexyl) -3- (3,3-dimethyl-3-phenylpropylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3 ~ dimethyl-4-phenylbutylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3-dimethyl-5 ~ phenylpentylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3-dimethyl-6-phenylhexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3-dimethyl-7-phenylheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-3-phenylpropylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-4-phenylbutylthi ο) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-5-phenylpentylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-6-phenylhexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethy1-7-phenylheptylthio) -

cyclopentanone,

2- (ö-Carboxj'-hexyl) -3- (2-hydroxyethylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxypropylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxybutylthio) -cyclopentanone, 2- (6-Carboxyhexyl) -3- (2-hydroxyisobutylthio) -cyclopent anon,

2- (6-carboxyhexyl) -3- (2-hydroxypentylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxyisopentylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxyhexylthio) -cyclopentanone, 2- (6-Oarboxyhexyl) -3- (2-hydroxyisohexylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxyheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxyisoheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxyoctylthio) cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxyis ο oc tylthiο) -cyclopentanone,

- 59 -409841/0980

2- (6-Carboxyhe: ^ l) -3 ~ (2-nydroxynonylthio) -cyclopentanone, 2- (6-Carboxyhexyl) ~ 3- (2-hydroxyisononylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxy-5, -5-dimethylhexylthio) -

cyclopentanone,

2- (β-carboxyhexyl) -3- (2-hydroxy-6,6-dimethylheptylthio) -

cyclopentanone,

2- (6 ~ carboxyhexyl) -3 ~ (2 ~ hydroxy-7,7-dimethyloctylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-8,8-dimethylnonylthio) -

cyclopentanone,

2- (6-Carboxyhexyl) - '3-' ^ -hydroxy ^ -methylhexylthioO-cyclo-

pentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methyIneptylthiο) -cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methyloctylthio) -cyclopenta, non, 2- (6-carboxyhexyl) -3- (2-hydroxy-2-methylnonylthio) cyclopentahone.

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethylhexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyloctylthio) -

cyclopentanone,

2- (6-0arboxyhexyl) -3- (2-hydroxy-3,3-dimethylnonylthio) -cyclopentanone,

2- (6-0arboxyhexyl) -3- (2-hydroxy-2,3,3-tro.me thy lhexy lthio) -

. cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethylheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyloctylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethylnonylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,5,5-trimethylhexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) ~ 3- (2-hydroxy-2,6,6-trimethylheptylthio) -

cycloijentano.n,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,7,7-trimethyloetylthio) -

cyclopentanone,

2- (6-Oarboxyhexyl) -3- (2-hydroxy-2,8,8-trimethylnonylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3,5,5-tetramethylhexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3,6, β-tetramethylheptylthio) -

cyclopentanone,

4098 A 1/0980

2- (6-carboxyhexyl) ~ 3- (2-hydroxy-3,3,7,7-tetramethyloctylthio) -

eyelopentanon,

2- (6 ~ carboxyhexyl) -3- (2-hydroxy-3,3,8,8-tetramethylnonylthio) -

cyclopentanone,

2- (6-carboxybexyl) -3- (2-hydroxy ~ 2,3,3,5,5-pentamethylhexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3,6,6-pentamethylheptyl-

thio) -eyelopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3,7,7-pentamethyloctylthio ; -eye lopentanon,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3,8,8-pentamethylnonyl-

thio) -eyelopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-6,6,6-trifluorohexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-8,8,8-trifluorooctylthi ο) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-9,9,9-trifluorononylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methyl-6,6,6-trifluorohexylthio) -eye lopentanon,

2- (6-carboxyhexyl) ~ 3- (2-hydroxy-2-methyl-7,7,7-trifluoroheptyl-

thio) -eyelopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methy1-8,8,8-trifluorooctyl-

thio) -eyelopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methyl-9,9,9-trifluorononylthio) -eye lopentanon,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-6,6,6-trifluorohexylthio; -cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7,7,7-trifluoro-

heptylthio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-8,8,8-trifluoro-

octylthio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethy1-9 »9,9-trifluoro-

nonylthio-cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-6,6,6-trifluorohexylthio) -eye lopentanon,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-7,7,7-trifluoro-

heptylthio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl 1-8,8,8-trifluoroc ty lthio) -eye lopentanon,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-9,9,9-tr3fluor-

nonylLhiο j-eyelopentanon,

- 61 AO ⁽ JB I * 1 / O 9 Ö O

2- (6-Carboxyhexyl) -3- (2-liydroxy-2-plienylätliylthIo) -cyclo-

pentanone,

2- (6-Carboxyhexyl) -3- (2 ~ hydroxy-3 ~ phenylprbpylthio ^ cyclopentanone,

2- (6-carton oxyhexyl) -3 ~ (2-hydroxy-4 ~ phenylbutylthio) ~ eyclo ~

pentanone,

2- (6-Carboxyhexyl) ~ 3- (2-hydroxy-5 ~ phenylpentylthio ^ cyclopentanone,

2 ~ (6-Carboxyhexyl) -3 - ^ - hydroxy-ö-phenylhexylthio) -cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-7-phenylheptylthio ^ cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methyl-2-phenylethylthio)

cyclopentanone,

2- (6-Carboxyhexyl) -3- ^ -hydroxy ^ -methyl ^ -phenylpropylthio) -

cyclopentanone,

2- (6-Carboxyhexyl) -3- (2-hydr oxy ~ 2-methyl-4-plienylbutylthio) -

cyclopentaiiori,.

2- (6-carboxyllexyl) -3- (2-hydroxy-2-methyl-5-phenylpentyltMo) -

c yc Io pe η tan on,

2- (6-Carboxyhexyl) -3- (2-hydroxy-2-meth.yl-6-phenylliexylt] iio) -

cycloperitanone,

2- (6-Carb oxyliexyl) -3- (2-hydr oxy-2-me thy l-7 ~ phenylhepty lthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-3-phenylpropyl-

thio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3, 3-dimethyl-4- ^b phenylbutyl-

thio) -eyelopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-5-phenylpentylthio)

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethy1-6-phenylhexylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7-phenylheptyl-

thio) -eyelopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2, 3, 3-trimethyl-3-phenylproρyl- ..;

thiο) -eyeIopentanon,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-4-phenylbutyl-

thio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-5 ~ phenylpentyl-

thio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-6-phenylhexyl-

thio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydro>: y-2, 3, 3-trimethyl-7-phenylhepty 1-

thio) -eyelopentanone.

A0S8A1 / 0980

Example 2

It is added to a mixture of 3.1 g of 2- (6-carboxyhexyl) -2-cyclopentenone and 1.5 g of 2-hydroxyheptanethiol, dissolved in 30 ml of dry ethanol, 5 g of dry triethylamine, boiled for 8 hours, the reaction mixture is in a mixture of 150 ml of ice water and 10 ml of concentrated HCl, extracted with 200 ml of ether, the organic phase is washed with saturated aqueous NaCl solution, dried over NapSO ,, the solvent evaporates and after chromatographic purification of the residue obtained (KieseIge1 / CH ₃ OH: CHCl ₅ = 1: 9) 2- (6-carboxyhexyl) -3- (2-hydroxyheptylthio) cyclopentanone as an oil;

R _f = 0.2 (silica gel / chloroform: methanol = 95: 5);

"Calculated analysis: 63.65 $ C, 9.56 $ H, 8.94 % S; found analysis: 62.7 $ C, 9.5 $ H, 8.3 % S;

IR spectrum: bands at 1,700, 1,730, 2,880 and 2,950 cm " ¹ ,

-1 -1

wide band between 3,000 cm and 3,500 cm

Nuclear Magnetic Resonance Spectrum: Signals at 0.9 ppm, 3.1 ppm, 3.75 ppm and 6.8 ppm.

Analogously one obtains from

Heptanethiol,

Nonanethiol,

2-methylheptanethiol,

2-methylnonanethiol,

3,3-Dimethylhepta ^ .thiol,

3,3-dimethylnonanethiol,

- 63 40 ^ 841/0980

- .63 -

6,6-dimethylheptanethiol, 8,8-dimethylnonanthiol, 2,3,3-trimethy! Heptane thiol, · ■ 2,3,3-trimethylnonanethiol, 2,6,6-trim thylheρΐanthiο1, 2,8,8-trimethylnonanethiol, 3,3,6,6-tetramethylheptane thiol, 3,3,8,8-tetramethylnonanethiol, 2,3,3,6,6-Pentamethy lhe'pt an thiol, 2,3,3,8,8-pentamethylinonanethiol, 7,7,7-trifluoroheptanethiol, 9,9,9-trifluorononanethiol, 2-methyl-7,7,7-trifluoroheptanethiol, 2-methyl-9,9,9-trifluorononanethiol, 3,3-Dimethyl7,7,7-trifluoroheptanethiol, 3,3-Dimethy1-9,9 * 9-trifluorononanethiol, 2,3,3-trimethyl-7,7,7trifluoroheptanethiol, 2,3,3-trimethyl-9,9,9-trifluorononanethiol, 3-phenylpropane thiol,

5-phenylpent anthiol,

2-methyl-3-phenylpropane thiol, 2-methy1-5-phenyl pentane thiol, 3,3-diethyl-3-phenylprop.anthiol, 3,3-Dimethyl-5-pheny Ipent anthiol, 2,3,3-Trimethy1-3-phe nyIprο ρ anthi ο1, 2,3,3-Trime thy 1-5-pheny Ipent anthiol, 2-Hydroxyheptanethiol, 2-Hydr oxynon anthi ol,

2-hydroxy-2-methylhe pt anthiol, 2-Hydroxy-2-methylnoranthiol, 2-hydroxy-3,3-dimethylhept anthiol, 2-hydroxy-3,3-dimethylnon anthiol, 2-hydroxy-6,6-dimethylhept anthiol, 2-Hydroxy-8,8-dimethylnon anthiol, 2-hydroxy-2,3,3-trimethylhept anthiol, 2-hydroxy-2,3,3-trimethylnon anthiol, 2-hydroxy-2,6,6-trimethylhe pt anthiol,

A0 ^r d841 / Ü980

2-hydroxy-2,8,8-trimethylnonanethiol, 2-hydroxy-3,3,6,6-tetrame thy lheptanethiol, 2-hydroxy-3,3,8,8-tetramethylnonanethiol, 2-hydroxy ~ 2,3, 3,6,6-pentamethylheptanethiol, 2-hydroxy-2,3,3,8,8-pentamethylnonanethiol, 2-hydroxy-7,7,7-trifluoroanthiol, 2-hydroxy-9,9,9-trifluoronanethiol, 2 -Hydroxy-2-methyl-7,7,7-trifluoroheptanethiol, 2-hydroxy-2-methy1-9,9,9-trifluorononanethiol, 2-hydroxy-3,3-dimethyl-7,7,7-trifluoroheptanethiol, 2 -Hydroxy-3,3-dimethyl-9,9,9-trifluorononanethiol, 2-hydroxy-2,3,3-trimethyl-7,7,7-trifluorohept an thiol, 2-HydroDcy-2,3,3-trimethyl ~ 9,9,9-trifluoronanethiol, 2-hydroxy-3-phenylpropanthiol,
2-Hydr oxy-5-phe ny lpent anthi oil,
2-hydroxy-2-methyl-3-phenylpropantethiol, 2-hydroxy-2-methyl-5-phenylpentanethiol, 2-hydroxy-3,3-dimethy1-3-phenylpropanethiol, 2-hydroxy-3,3-dimethyl- 5-phenylpentane thiol, 2-hydroxy-2,3,3-trimethyl-3-phenylpropane thiol, 2-hydroxy-2,3,3-trimethyl-5-phenylpentane thiol,

by reacting with 2- (6-carbethoxyhexyl) -2-cyclopentenone,

2- (6-carbethoxyhexyl) -3-heptylthio-cyclopentanone, 2- (6-carbethoxyhexyl) -3-nonylthio-cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (2-methylheptylthio) -cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (2-methylnonylthio) cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (3,3-dimethylheptylthio) -cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (3,3-dimethylnonylthio) cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (6,6-dimethylheptylthio) -cyclopentanone, 2- (6-carbethoxyhexyl) -3- (8,8-dimethylnonylthio) cyclopentanone, 2- (6-carbethoxyhexyl) -3- (2,3,3-trimethylheptylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2,3,3-trimethylnonylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2,6,6-trimethylheptylthio ) -

cyclopentanone,

A0Ü8A1 / 0980 -65-

2- (6-carbethoxyhexyl) -3- (2,8,8-trimethylnonylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (3,3,6,6-tetramethylheptylthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (3,3 ', 8,8-tetrame thy lnony lthio) r-

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2,3,3,6,6 _T pentamethylhe ptylthio) -

■ cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2,3,3,8,8-pentainethylnony lthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (7,7,7 -trifluoroheptylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (9,9,9-trifluorononylthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-methy1-7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-0arbethoxyhexyl) -3- (2-methyl-9,9,9-trifluorononylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (3,3-dimethyl-7,7,7-trifluorohe ptylthio ) -cyclopentan on,

2- (6-carbethoxyhexyl) -3- (3,3-dimethy1-9,9,9-trifluoronony1-

thio) cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2,3,3-trimethy1-7,7,7-trifluoroheptylthio) -cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2,3,3-trimethyl-9,9,9-trifluoronony1-

thio) cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (3-phenylpropylthio) -cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (5-phenylpentylthio ^ -cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (2-methy1-3-phenylpropylthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-methy1-5-phenylpentylthio) -

cyclopentan on,

2- (6-carbethoxyhexyl) -3- (3,3-dimethy1-3-phenylpropylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (3,3-dimethyl-5-phenylpentylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2,3,3-trimethy1-3-phenylpropylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2,3,3-trimethyl-5-phenylpentylthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxyheptylthio) -cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (2-hydroxynonylthio) -cyclopentanone, 2- (6-carbethoxyhexyl) -3- (2-hydroxy-2-methylheptylthio) -

cyclopentanone,

40 9 84 1/09 80 - 66 -

2- (6-Carbethoxyhexyl) -3- (2-hydr oxy-2-methylnonylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethylnonylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-6,6-dimethylheptylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-8,8-dimethylnonylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trimethylheptylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trimethylnonylthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2,6,6-trimethylhe ptylthio) - ·

eyelopentanon,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2,8,8-trimethylnonylthi ο) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3,6,6-tetramethylheptyl-

thiο; -eyelopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3,8,8-tetramethylnonylthio) -eye lopentanon,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2, 3, 3, 6, -6-pentamethylheptyi-

thio; -cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,3,3,8,8-pentamethylnonylthio) -eye lopentanon,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-7,7,7-trifluoroheptylthiο) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-9,9,9-trifluorononylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2-methyl-7,7,7-trifluoro-

heptylthio) -eyelopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2-methyl-9,9,9-trifluorononylthio) -cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7,7,7-trifluoroheptylthi ο) -eyelopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethyl-9,9,9-trifluorononylthio) -eye lopentanon,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trimethy1-7,7,7-tri-

fluoroheptylthio) cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trinethyl-9v9,9-tri-

fluornonylthi ο) -eyelopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-3-phenylpropylthio) -eyelopentanone,

409841/0980

2- (6-Carbethoxyhexyl) -3- (2 ~ hydroxy-5-phenylpentylthio) -

cyclopentanone,

2 ~ (6-Car ■ ethoxyhexyl) -3- (2-] aydroχy- ~ 2-methyl-3-pl·lenylpropyltilio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-liyaroxy-2-methyl-5-plienylpenty ItMo) -

cyclopentanone,

2- (6-Oarbathoxyhexyl) -3- (2 ~ hydroxy ~ 3, 3 ~ dimethyl-3 ~ phenylpropyl-

tnioj-cyclopentanone,

2- (6-Carbethoxyhexyl) -3 ~ (2-hydroxy-3,3-dimethyl-5-phenyipentyl-

thi o) -eyelopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy ~ 2, 3, 3 ~ trietnyl ~ 3-phenyl-

propylthiο) -eyelopentanone,

2- (6-Carbethoxyhexyl) -3- (2 ~ hydroxy-2, 3, 3 ~ trimethyl-5-phenyl-

pentylthio) cyclopentanone.

Example 3

3.2 g of 2- (6-carbethoxyliexyl) -2-cyclopentenone, dissolved in 20 ml of dry ethanol to a solution of sodium heptanethiolate (Can be produced by dissolving 0.24 g of sodium in 30 ml dry ethanol and addition of 1.3 g of heptylthiol), stir under nitrogen for 24 hours at 40 °, dilute the reaction mixture with 150 ml of ice water and 10 ml of concentrated HCl, extracted with CHpCIp, washed with saturated aqueous NaCl solution, dries over NapSO ,, the solvent is distilled off and after chromatographic purification of the residue, 2- (6-carbethoxyhexyl) -3-heptylthio-cyclopentanone is obtained;

R _f = 0.7 (silica gel / chloroform);

Analysis calculated: C 68.07 fo, 10.33 $ H, 8.65% S; Analysis found: 67.8 % H, 10.4% H, 8.6% S;

IR spectrum: bands at 1,730, 2,870 and 2,950 cm ""¹;

409841/09

- 60 -

HMK-SpO / iLrtiiif .: signals l) oi 0.9 ppm αυπα 3.0 yjpr.u Signal Kv.'ir.chon 3.95 ppm and 4.3 pp: n (quartott)

Analogously one obtains from

Sodium p ~ tolyl methanethiolate, Sodium 2-p-tolyl ethanethiolate, Sodium 3-ρ-1οIylprοpanthiοlat, Sodium-4-p-toylbut anth i ο la t, Sodium ~ 5-p - to lylpent anthiolate, sodium 2-hydroxy-2-p-tolylethanthiolate, Sodium 2-hydroxy-3-p-tolylpropanthiolate, Sodium 2-hydroxy-4-p-tolylbutanethiolate, Sodium 2-hydroxy-5-p-tolylpentanthlolati Sodium 2-methy1-2-p-tolyl ethanethiolate, Sodium - ^ - methyl - ^ - p-tolylpropane thiolate, Sodium-2-me thy 1-4-p-to Iy lbut anthiolä / t,.

Sodium-2-methy 1-5-ρ-to Iy lpent anthiolat, Natr ium-2 -hy dr oxy-2-me thy 1-2- ρ-to Iy lath airth i ola t, Sodium 2-hydroxy-2-methy1-3-p-toylpropanthiolate, Sodium 2-hydroxy-2-methy1-4-ρ-toylbut anthiolate, Sodium 2-hydroxy-2-methy1-5-p-tolylpentanthiolate, Sodium 2-hydroxy-3,3-dimethyl 1-3-p-tolylpropanthiolate, Sodium 2-hydroxy-3,3-dimethy1-4-p-toylbutanthiolate, Sodium 2-hydroxy-3,3-dimethyl-5-p-tolylpentanthiolate, Sodium 2-hydroxy-2,3,3-trimethyl-3-p-tolylprop. anthiolate, Sodium 2-hydroxy-2,3,3-trimethy1-4-p-toylbutanthiolate, Sodium 2-hydroxy-2,3,3-trimethyl 1-5-p-tolylpentanthiolate,

by reacting with 2- (6-carbethoxyheptyl) -2-cyclopentanone,

2- (6-Carbethoxyhexyl) -3-p-tolylmethylthio-cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (2-p-tolyläthylthiο) -cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (3-p-tolyIpropylthio) -cyclopentanone, 2- (6-Carbethoxyhexyl) -3- (4-p-tolyIbutylthio) -cyclopentanone,

_ 69 4 Ü y b Λ 1 / U980

2- (6-Carbethoxyhexyl) -3- (5-p-tolylpenty ItMo) -cyclopentanone, 2- (6 ~ CarlDäthoxyhexyl) -3- (2-hydroxy-2 - p-tolyläthyltliio) -

cyclopentanone,

2- (6 - carbethoxyhexyl) -3-- (2-hydroxy ~ 3-p-tolylpropylthio) -

cyclopentanone,

2- (6 ~ carbethoxyhexyl) -3- (2-hydroxy ~ 4 ~ p-tolylbutylthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-5-p ~ tolylpentylthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-methy 1-2- p-tolyläthy ItMo) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-methyl-3-p-toylpropyltMo) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-methyl-4-p-tolylbutylthio) -

cyclopentanone,

2- (6-Garbäthoxyhexyl) -3- (2-methyl-5-p-tolylpentylthio) -

cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2-methy1-2-p-tolyläthy1-

thlo) -cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2-methyl-3-p-tolylpropyl-

thiο ) -cyclopentanone,

2- (6-Carbethoxyhexyl) -3 ~ (2-hydroxy-2-methyl-4-p-tolylbut.yl-

thlo; -cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2-methyl-5-p-tolylpentyl-

thio; cyclopentanone /

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethyl-3-p-tolyl-

propylthio) cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethyl-4-p-toly1-

butylthio; cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy ~ 3,3-dimethyl-5-p-toIyI-

pentylthio) cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trimethy1-3-p-

tolylpropylthio) cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-4-p-

tolylbutylthio) - cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trimethy1-5-p-

tolylpentylthio) cyclopentanone.

Α0984Ί / 0980

Example 4

Analogously to Example 1, one obtains from

2- (4-carbethoxybutyl) -2-cyelopentenone, 2- (5-carbethoxypentyl) -2-cyclopentanone, 2- (7-Carbethoxyhe ptyl) -2-cycl opentenone, 2- (8-carbethoxyoctyl) -2-cyclopentenone,

by reacting with heptanethiol:

2- (4-carbethoxybutyl) -3-heptylthio-cyclopentanone, 2- (5-carbethoxypentyl) -3-heptylthio-cyclopentahone, 2- (7-carbethoxyheptyl) -3-heptyithio-cyclopentanone, 2- (8 ^ -Carbäthoxyoctyl) -3-heptylthio-cyclopentanone,

by reacting with nonanethiol:

2- (4-Carbethoxybutyl) -3-nony ItM σ-eycl opentan on, 2- (5-carbethoxypentyl) -3-nonylthio-cyclopentanone, 2- (7-carbethoxyheptyl) -3-nonylthio-cyclopentanone, 2- (8-carbethoxyoctyl) -3-nonylthio-cyclopentanone,

by reacting with 2-hydroxyheptanethiol:

2- (4-carbethoxybutyl-3- (2-hydroxyheptylthio) cyclopentanone, 2- (5-Carbethoxypentyl) -3- (2-hydroxyheptylthio) -cyclopentanone, 2- (7-Carbäthoxyhe ptyl) -3- (2-hydroxyhe ptylthi ο) -cyclopentan on, 2- (8-Carbäthoxyoc tyl) -3- (2-hydroxyhe ptylthio) -cyclopentan on,

by reacting with 2-hydroxynonanethiol:

2- (4-Carbethoxybutyl) -3- (2-hydroxynonylthio) -cyclopentanone, 2- (5-Carbethoxypentyl) -3- (2-hydroxynonylthio) -cyclopentanone, 2- (7-Carbethoxyheptyl) -3- (2-hydroxynonylthiο) -cyclopentanone, 2- (8-Carbethoxyoctyl) -3- (2-hydroxynonylthio) -cyclopentanone,

409841/0980 -71-

by reaction with 2-hydroxy-3,37dime't] iyllieptan. "tliiol:

2- (4-Carbethoxyhutyl) -3- (2-rliydroxy-3, 3 ~ dimethylheptyltliio) -

cyclopentanone,

2- (5-carbethoxypentyl) -3- (2 ~ hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,

2- (7-carbethoxyheptyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,

2- (8-carbethoxyoctyl) -3- (2-hydroxy-3, 3-dimethylheptylthio) -

cyclopentanone,

by reaction with 2-hydroxy-3,3-dimethylnonylthiol:

2- (4-carbethoxyl3utyl) -3- (2-hydroxy-3,3-dimethylnonylthio) -

eyelopentanon,

2- (5-carb ethoxypentyl) -3- (2-hydroxy-3,3-dimethylnonylthi ο) -

cyclopentanone,

2- (7-Carbethoxyheptyl) -3- (2-hydroxy-3,3-dimethylnonylthio) -

cyclopentanone,

2- (8-carbethoxyoctyl) -3- (2-hydroxy-3,3-dimethylnonylthio) -

cyclopentanone.

Example 5

A mixture of 6 g of 2- (6-carbethoxyhexyl) -2-cyclopentenone, Stand 10 ml propanethiol and 7.2 ml piperidine for 5 days at room temperature, dilute with 150 ml. Ether, wash the Ether phase first with a mixture of 60 ml of ice water and 6 ml of concentrated HCl and then with saturated aqueous KaOT solution, dried over Na2SO., The solvent is distilled and after chromatographic purification of the residue (silica gel / chloroform), 2- (6-carbethoxyhexyl) -3-propylthio-cyclopentanone is obtained as oil;

409841/0980

R _f = 0.7 (silica gel / chloroform);

Analysis found: 64.93 % C, 9.61 % H, 10.2 $ S; Analysis found: 65.6 56c, 9.7 $ H, 9.8 $ S;

IR spectrum: bands at 1,730, 2,870 and 2,950 cm ""¹;

Nuclear Magnetic Resonance Spectrum: Signals at 1.0 ppm, 3.0 ppm and 4.0-4.22 ppm (Quartet).

Example 6

3.2 g of 2- (6-cyanohexyl) -3-heptylthio-cyclopentanone (obtainable from the potassium salt of ethyl 2-oxocyclopentanecarboxylate) are boiled and 6-cyanohexyl bromide, treating the 1- (6-cyanohexyl) -2-oxo-cyclopentanecarboxylic acid ethyl ester obtained with Bromine and then with sulfuric acid and addition of heptylthiol to the obtained 2- (6-cyanhexyl) -2-cyclopentenone) 3 hours in a mixture of 30 ml of water and 20 ml of concentrated sulfuric acid, pour into 100 ml after cooling Ice water, extracted twice with 40 ml of CHoCIp each time, washes the organic phase with water, dried over NapSO-, distilled the solvent is removed and, after purification by chromatography of the residue (silica gel / chloroform), 2- (6-carboxyhexyl) -3-heptylthi is obtained o-cyclopentanone;

R _f = 0.3 (silica gel / chloroform: methanol = 95: 5);

Calculated Analysis: $ 66.62 C, $ 10.01 ^ H, $ 9.36 S; Analysis found: 65.5 1 ° C, 9.71 % H, 9.8% S;

IR spectrum: bands at 1,700, 1,730, 2,860 and 2,940 cm " ¹ ,

—1 —1

wide bands between 3,000 cm and 3,400 cm;

Nuclear Magnetic Resonance Spectrum: Signals at 0.86 ppm, 3.0 ppm and 9.75 ppm.

40984 1 / U980

Example 7

3.4 g of 2- (6-carboxamidohexyl) -3-heptylthio-cyclopentanone (obtainable from the potassium salt of ethyl 2-oxocyclopentanecarboxylate and 6-carboxamidohexyl bromide / obtainable from 7-bromoheptanoic acid and thionyl chloride and reacting the resulting 7-bromoheptanoic acid chloride with aqueous ammonia chloride are boiled /, Treating the 1- (6-carboxamidohexyl) -2 ~ oxo-cyelopentanearboxylic acid ethyl ester with bromine and then with HgSO, and adding heptylthiol to the 2- (6-carboxamidohexyl) -2-cyclopentanone) obtained for 1 hour with a mixture 30 ml of 2η aqueous NaOH and 10 ml of ethanol, after cooling, poured into 50 ml of aqueous 2N HCl, extracted twice with 30 ml of CH ₂ Cl ₂ each time, the organic phase was washed with water, dried over Na ₂ SO., The solvent was distilled off and after purification of the residue by chromatography (silica gel / chloroform), 2- (6-carboxyhexyl) -3-heptylthio-cyclopentanone;

R ₁ P = 0.3 (silica gel / chloroform! Methanol = 95: 5);

Analysis calculated: 66.62 i> C, 10.01 ° ß> H, 9.36 $ S; Analysis found: 65.5 $ C, 9.71% H, 9.8 $ S;

IR spectrum: bands at 1,700, 1,730, 2,860 and 2,940 cm " ¹ ,

-1 ~ 1

wide band between 3 000 cm and 3 400 cm

NMJ? Spectrum: signals at 0.86 ppm, 3.0 ppm and 9.75 ppm.

0-ÖÖ4 1 / UU 80

Example 8

5.1 g of 1,1-dibromo-2- (6-carbethoxyhexyl) -3-heptylthiocyclic pentane are stirred (obtainable from 2- (6-carboxyhexyl) -3-heptylthio-cyclopentanone by reacting with PBr, - and ethanolysis of the obtained 2- (6-bromocarbonylhexyl) -3-heptylthio-1,1 dibrorapentans) 4 hours in 100 ml of a mixture of 1 g KOH, 50 ml HpO and 50 ml dioxane, pour into 100 ml after cooling 2N aqueous HGl, extracted twice with 50 ml CHpCIp each time, washes the organic phase with water, dries over NapSO., the solvent is distilled off and after chromatographic purification of the residue (silica gel / chloroform) 2- (6-carboxyhexyl) -3-heptylthio-cyclopentanone;

R _f = 0.3 (silica gel / chloroform / methanol = 95: 5);

calculated analysis: 66.62 t G ₁ 10.01 # .H, 9.36 # S; Analysis found: 65.5 1 * C, 9.71 1Ό H, '9, B # S;

IR spectra: bands at 1,700, 1,730, 2,860 and 2 940 cn "' ¹ ,

- 1 - 1

wide band between 3 000 cm and 3 400 cm

NMR spectrum: signals at 0.86 ppm, 3.0 ppm and 9.75 ppm.

- 75 -

Example 9

5.0 g of 1 oc-p-toluenesulfonyloxy - 2- (6-carboxyhexyl) -3-heptylthiocyclopentane are boiled (obtainable from 2- (6-carboxyhexyl) -3-heptylthiocyclopentanol- (ia) and p-toluenesulfonic acid chloride) 2 hours in 60 ml of 2N aqueous NaOH, after cooling poured into 100 ml of 2N aqueous HOl, extracted twice with 50 ml each time CHgClg, wash the organic phase with water, dry over NäpSO., The solvent is distilled off and obtained after chromatographic Purification of the residue (silica gel / chloroform) 2- (6-carboxyhexyl) -3-heptylthlo-cyclopethanol- (1β).

R _f = 0.5 (silica gel / chloroform. Methanol = 95: 5);

Calculated analysis: 66th, 62 % C, 10.01 ^σ / ό H, 9.36 fo S; Analysis found: 65.5 $> C, -9.71% H, "9 * 8 # S- ₅ .

IR spectrum: bands at 1,700, 1,730, 2,860 and 2,940 era " ¹ , * 1-1

wide band between 3,000 cm "and 3,400 cm.

liMR spectrum: signals at 0.86 ppm, 3.0 ppm and 9.75 p

-76 -

409841 / Ü9

- • 76 ~

Example 10

Add 2.0 g of lisTiR, °, after cooling, poured into 100 rcl of saturated aqueous NaCl solution, extracted three times with 30 ml each time;: r, v; ash the organic phase with Va.st? he, dries over 1-Ta.pSO ^, do f.! if the solvent abolishes, after chromatographic purification the Küokstandeo is obtained. (KieKelgol / Chloroforra) 2- (6 ~ carboxyhexyl) -3-lieptylcyclop9ntanol.

Analogously one obtains from

2- (6-carboxyhexyl) -3-nonylthi o-cycIopentanone, 2- (6-carboxyhexyl) -3- (2-methylheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-methylinonylthio) -cyclopentanone, 2- (6-Carboxyhexyl) -3- (3 * 3-dimethylhe ptylthio) -cyclopentan on, 2- (6-carboxyhexyl) -3- (3,3-dimethyInonylthio) -cyclopentanone, 2- (6-Carboxyhexyl) -3- (6,6-dimethylheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (8,8-dimethylnonylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,3 »3-trimethylheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,3,3-trimethyinonylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,6,6-trimethylheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2,8,8-trimethyinonylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (3,3,6,6-tetramethylheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3,8,8-tetramethyinonylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3,6,6-pentamethylheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3,8,8-pentamethyInonylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (7f7,7-trifluoroheptylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (9,9 »9-trifluorononylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-methy1-7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-methyl-9,9,9-trifluorononylthio) -

cyclopentanone,

- 77 -

409841 / U980

BATHROOM ORIGINAL.

2- (6-Carboxyhexyl) -3 ~ (3,3-dimethyl-7,7,7-trifluoroheptylthio) ~

cyclopentanone,

2- (6-carboxyhexyl) -3- (3,3-dimethyl ~ 9,9,9-trifluorononylthio) -

cyclopentanone,

2- (6 ~ carboxyhexyl) -3- (2,3, 3-trimethyl-7,7,7-trifluorheptylthio) - ·

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-9,9,9-trifluorononylthio) -

cyclopentanone, -

2- (6-carboxyhexyl) -3 - '(3-plienylpropyltliio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (5-phenylpentylthio) -cyclopentanone, 2- (6-Carboxyhexyl) -3- (2-methyl-3 ~ phenylpropylthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-methyl-5-phenylpentylthio ^ -cyclopentanone, 2- (6-carboxyhexyl) -3- (3,3-dimethyl-3 ~ phenylpropylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (3 j3-dimethy1-5-phenylpentylthio) -

• cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-3-phenylpropylthio) r-

cyclopentanone,

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-5-phenylpentylthio) -

cyclopentanone,

2- (6 ~ Cart oxy hGxyl) ~ 3- (2-hydroxyheptylthio) -cycl opent-aiipn ",

2 --- (6-Carboxy ^ hexyl) -3- (2-hydroxyl; y-2-ynethylheptylthio) - ~

cyclopentanone, '■

2- "(6-Car1) oxyho xjrl) - 3- (2-hydroxy-2-ri3" thyj.nonylt} iio) -cyclopenta ?!

2- (6-Carbo7iy-oexyl) -3 ~ (2-hydroxy-3,3 ~ di-ioethylheptylthio) -

"cyelopantanori,

2- (6- carboxyhexyl) -3- (2-ir / droxy-3, 3 ~ direethy lnony 3.thio) ~

cyclppejitanon, .. ·

2 ~ (6-carboxyhexyl) -5 - (? ~ Hydro>: y ~ 6, 5-aiiriethyl] ieptylthip) "

cyclopentanone,

2- (G-Carboxyhexy-1) ~ 3- ■ (2-hycLr oxy-8,8-dime thy lnony lthio) -,.

cyclopentanone ,, ■

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethylheptylthio) - '

cyclpperitanon ,. ·

2- (6 --Ca ₁ IbOXy hexyl) ~ 3- (2-hydr oxy-2,3, 3 ~ triraethylncnyl thio) -

cycl open tan or),

2 - (6 - Carboxy} ie xyl) -3- (2-hy or oxy - 2,6,6 - tr Ικθ thy lhe pt y 1 thi ο) -

cyclopcircaaon,

n,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3,6,6-tetramethylheptyl

thio) cyclopentanone,

AÖ98A1 / Ü980 - 78 -

- 7β -

2 ~ (6-Carboxyhexyl) -3- (2-hydroxy-3,3,8,8 ~ tetramethylnonyl ~

thio) --cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3,6,6-pentamethyl-

heptylthiο) -cyclopentanone,

2- C 6-carboxyhexyl) -3- (2-hydr oxy-2,3,3,8,8-pentamethyl-

nonylthio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-9, 9, 9- ^ trif luornonylthio) -

cyclopentanone,

.2- (6-Carboxyhexyl) -3- (2-hydr oxy-2-methy 1-7, 7, 7-trifluorheptylthio ) -cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methyl ~ 9,9,9-trifluoro-

nonylthio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7,7,7-trifluoroheptylthio ) -eyelopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl) -9,9,9-trifluoro-

nonylthiο) -eyelopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-7, 1, 7-tri fluoro

heptylthio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-9,9,9-trifluoro

nonylthio) cyclopentanone,

ylpiy> py lth Io) c ye 1 ο pe η t a n on,

2 - ( G- Carljoxy hexyl ) - 3 - (2 - -hy dr oxy - 5 pho ny 1 pen ty 1 th i ο)

cyclopentan on,

2- (6-Carbo: iyh3>: yl) -3- (2 - hyclr oxy-2-ικϊ tliy 1-5-phe ny lpenty 1 thi ο)

cyclopentanone,

2- (6-Carbozyhö>: yl) -3- (2 - hyö.roxy-3,3-d.linotiiyl ~ 3- phony lpropy 1 -

thiVlt

2- (6-Carbo>: yho: iyl) -3- (2 ~ hydr oxy-3,3 ~ d.i t.-is thy 1--5- pbeny lpe · ■ t.y 1-

thio; -cyclopentanone,

2- (6-Carbcc-: yh «: ryl) -3- (2 ~ hydroxy ~ 2, 3, 3 - t? - i ns thy 1-3-phony 1-

propylthio) -cyclop2ntanone,

(D: iyhoxyl) 3 (2hyaroxy2,3.3trir ^ thylS) pheiiyl ^ 'pentyltliio) -cyolops; itano? I _r .

2- (6-Carbethoxyhexyl) -3-he ptylthio-cyol cyiritan on, 2- (6-Carbethoxyhexyl) -3-nonylthio-cyclopentanone , 2- (6-Carbethoxyhexyl) -3- (2-methylheptylthio) -cyclopentanone, 2 - (6-Carbethoxynexyl) -3- (2-methylnonylthio ^ cyclopentanone, 2- (6-carbethoxyhexyl) -3- (3,3-dimethylheptylthio) cyclopentanone

409841/0980

- 79 -

- ₇₉ - ' ^: 22SB537

2 -'- (G-Garbäthojtyliexyl) -3- (3,3 - dlmethy niionyl-i ^ ii ο) -cybiopentanone,

? .- (6 ~ Co, rbäthöxyhaxyl) ~ 3 ~ (8,8 - dimo thylnony lthio) -cyclopentanone, 2- (6-Garbäthoxyhexyl) ^ 3- (2,3,3 ™ triine-fchylhe ptyl-bhib) -

cyclopentanone,

2 «(6 ~ Carbäthöxyhexyi) -3- (2 ', 3,3-trimethylhönyithib) -

c y c 1 o'peiit an on,

2- (6-Carbätha! Cyxiexyi) -3- (2,6,6-trimethylheptylthio) -

'cyclopentanone,

2- (6 - Car "Oäthoxyhexyi) -3- (2; · 8, S-trirce thylhony lthio) -

cyclopentanone, ....-_ "..".

2- ~ (6-carbethoxyhexyl) -5 ~ (3,3,6,6-tetramethylheptylthio) -

cyclopentanone,

■ 2 ~ ('6 "Carbethoxyhex3 ^r l) -3 ~ (3 ■> 3.8; 8th tr ame thylnony Ithib) -

cyclopentanone,

2 - (6-Gybethoxyhexyl) -3- (2,3, 3, 6j 6-pentamethylheptylthio) -. . _: cyciopentanone,

2- ~ (6-carbethoxyhexyl) -3- ^; (2 j 3, 3,8 ,, 8-pehtame thylnony lthio) - ■■ - ■■ "" cyclopentanone, "-

2- (6-carbethoxyhexyl) -3- (7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- ( b-Carbethoxyhexyl) -3- (9,9,9 -trif 3.uornony lthio) ~

, - cyclopentanone, ■

2 »(6-carbethoxyhexyl) ~ 3- (2-methyl-7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-Carbätfloxyhexyl) -3- (2-methy1-9 »9,9-trifluorononylthio) -

cyclopentanone,

2- (6-Oarbäthoxyhex5 ^r -l) -3- (3,3- dime thy 1 ^ -7,7,7-trif luoriieptyl-

thib) -cyclopontanone,

2- (6-Carbethoxyhexyl) -3- (3,3-dimethy1-9,9,9-trifluorononyl-

thio) -cyclope-ntanone,

2- (6 ~ Carbethoxyhexy-1) -3- (2,3.3-trime thy 1-7,7,7 -trif luor heptyl-r

thio) cyclopentanone,. '

2- (5-0arbethoxyhexyl) -3- (2,3,3-trimethy1-9,9,9-trifluorononyl-

thiο) -eyclopentanone,

2- (6-Carbethoxyhaxyl) ~ 3- (3-phenylpropylthio) -cyclopentanone, 2 ™ (6 "CLirbätlioxyhexyl) ~ 3 ~ (5-phenylpentylthio) -cyclopGntanone, 2- (6-Carbethoxyhexyl) ~ 3 ^: - (2- methyl-3-phenylpropylthio) -

cyclopentanone,

2-- (6-Carbethoxyhexyl) ~ 3- (2 ~ iDethyl-5-phsnylpentylthio) -

cyclppontanone,

2- (G - Garb thoxyhe χyl) -3- (3 >> -dime thy 1-3- phe ny 1 per py lthIo) -

cyclopentanone,

- 80 - 409841/0980

2- (6-carbethoxyhexyl) -3 - (3,3-dimethyl-5-phenylpentylthio) -

cyclopentanone,

2- (6-0arbethoxyhexyl) -3- (2,3,3-trimethyl-3-phenylpropylthio) -

cyclopentanone,

2- (6-Carbethox3'hexyl) -3- (2,3,3-trimethyl-5-phenylpentylthio) -

cyclopentanone,

2- (e ~ Ci ': rValhozjhQxyl) -3- (2-hytb: oxyhc; ptylthioV-eyelopenti-.non, 2- (6- Caruäthoxyhozyl) - 3- (2 "hydroxyηoriy 1thJ.ο) -eye! Opontanon ,

cyclopontanone,

?. ~ (6 ~ Carbethoxyhc> :. yl) - 3- (2-hydro> :. y-2-mGi: .hyl: iOiiyl-tiiio) -

cycl ορό η tan on,

2 - (6-CarbethoxyhGxyl) -3- (2-hydroxy-3 / i-di; ne ^J cljylhi; ptylthio) -

eyclopent an on,

2 - (G-- Ca rb ö. Lh oxy he xy 1) - 3 - (2 -hy βτ oxy -?, 3 —el i ir.c thy In οι iy 1 lh χ ο)

cyclopentanone,

2 - (6 - Carb ät / i oxy he xj ^ l) - 3- (2 -hy or ozy -6,6 -d j. Αια thy Xhs pt y 11) ι χ ο) -

cyclopentanone,

2- (ε-Carbäth oxyhexyi) -3- (2-hydr oxy - O, O - d: ur.ethy Inony lchio) -

cycl opontanon,

2 ~ (S-carbethoxyhaxyl) -3- (2-hydroxy-2,3,3-trircethylheptylthio) ■

cyclopantanone,

2 - (6-Carbätlioxyhexyl) -3- (2-hyih: oxy - 2,3,3-tri.ticthylno-nyj.th ::. O) · -

cyclopentanone,

(yy

cyclopontanone,

2- (6-Carbätiioxyhoxyl) -3- (2-'lTydx: oxy-2, 8, B-trircctbylrionyl-lhAC)

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3,6,6-tetramethylheptyl-

thio) -eyelopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3,3,8-tetramethylnonyl-

thio) cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,3,3,6,6-pentamethyl-

heptylthio) -eyelopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2,3,3,8, B-peηtamehtyI-

nonylthioj-cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2 ~ hydroxy-7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-9,9,9-trifluorononylthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2-methyl-7,7,7-trifluoro-

heptylthio) -cyolopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2-methy1-9,9,9-trifluorononylthio ) -cyc "l ο pe η tan on,

40aöA1 / ua80

2- (6 - Carbäthoxylieay I) -3-- (2-hydroxy _T 3, 3-dimö thy 1-7,7,7-trifliior-

. .Iiex »'tyltliio) -" cyclopGntanon-, "

2- (6 ~ Carbethoxyhexyl) -3- (2 ~ hydroxy ~ 3, 3-aiiaGthy 1-9,9,9-trif ruor-

nonylthio) cyclopentanone,

2- (6-Carbätlioxyhoxyl) -3- (2-hydroxy ~ 2, 3,3-trimsthy 1-7,7,7-

trl fliiorheptyltM ο) -cy el opontan on,

2- (6-carbethoxyliexyl) -3- (2-hydroxy-2,3,3,3-tri-ethyl-9,9,9,9-

t2? ii'luornonylthio) -cyclopentanone,

2 - (ö-Carbätiioxyliexyl) -3-- (2-hydr oxy-3-pnen3''lpro py lthio) -

cyclopentanoM,. · ·

2- (6 ~ carbethoxyhexyl) -3- (2-hy d.r.oxy ~ 5-plie nylpenty lthio) -

cyclopentanone,

2- (6-Car "ethoxyhexyl) -3- (2-hydroxy-2-methyl-3-plienylpropylthio)

cyclopentanone,

2- (o-Carbathoxyhexyl) -3- (2-hydr oxy-2-methy 1-5-phenyipenty lthio) -

cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethyl ~ 3-phenylpropyl-

thio / cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy ~ 3,3-dimethy1-5-phenylpentyl-

thioj-cyclopentanone,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trimethy1-3-phenyl-

propylthio) cyclopentanone,

2- (6-carbethoxyhexyl) -3- (2-hydroxy ~ 2,3,3-trimy1-5-pheny1-

. 'pentylthiο) -cyclopentanone,

2- (6-Garbodecyloxyhexyl) -3-heptylthiocyclopentanone, 2- (6-Garbodecyloxyhexyl) -3-nonylthioeyclopentanone,.

2- (6-Carbodecyloxyhexyl) -3- (2-methylheptylthio) -cyclopentanone, 2- (6-Carbodecyloxyhexyl) ~ 3- (2-methylnonylthio) -cyclopentanone, 2- (e-Carbodecyloxyhexyl) -3- (3,3-dimethylhe ptylthio) -cyclopentanone, 2- (6-Carbodecyloxyhexyl) -3- (3,3-dimethylnonylthio) -cyclopentanone, 2- (6-Carbodecyloxyhexyl) -3- (6,6-dimethylheptylthio) -cyclopentanone, 2- (6-Carbode cyloxyhexyl) -3- (8,8-dime thy Inonylthi ο) -cycl opentanon, 2- (β-CarbodecyiDxyhexyl) -3- (2,3,3-trimethylheptylthio) -

cyclopentanone, - '"

2- (6-Carbode cyloxyhexyl) -3- (2,3,3-trimethylnonyitthio) - ■

cyclopentanone,

2- (6-CarbodecylDxyhexyl) -3- (2,6, β-trimethylheptylthio) -

cyclopentate ion,.

- 32 - 409841 / Ü980

2- (6-Carbodecylttxyhercyl) - '') - { 2,8,8,8 ~ triwe thyinonylthio) -

cyclopentanone,

2 ~ (6-Carbodecyloxyhexyl) - 3- (3,3, 6, 6-tetrazothylheptylthio) -

cyelopentanon,

2- (6-Carbode cyloxyhexyl) -3- (3,3,8, β-te trarae thy lnony lthi ο) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2,3,3,6,6-pentamothyllioptylthio) »

cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2,3,3,0,8-pentamethylnonylthiο) -

cyclopentanone,

2- (6-Carbodecylo.xyhexyl) - 3- (7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (9,9,9-trifluorononylthio) -

. Cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-ir.ethyl-7,7,7-trifluoroheptylthio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-methyl-9,9,9-trifluorononylthio) ~

cyclopentanone,

2- (6-Carbodecylo.xyhexyl) -3- (3,3-diDiethyl-7,7,7-trifluoroheptyl-

thio) cyclopentanone,

2- (6-Carbode cyloxyhexyl) -3- (3,3 -diine thy 1-9,9,9 ~ trifluorom''''l-

thio) cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2,3,3-trimethyl-7,7,7-trifluoroheptyl-

thio) cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2,3,3-trimethyl - 9,9,9-trif luornony 1 · -

thio) -cyclopenta ^ on,

2- (6-Carbodecyloxyhexyl) -3- (3-pheriylpropylthio) -cyc] .opentanone,

oxyhoxyl) ~ 3- (5-phenylpentylthio) -cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-methyl-3 ~ phenylpropylthio) ~

cyclopentan on,

2- (6-Carbodeeyloxyhexyl) -3- (2-methyl-5-phenylpentylthio) -

cyclopentan on,

2- (6-Carbodecyloxynexyl) -3- (3,3-dimethyl-3-phenylpropylthio) "

cyclopentanone,

2- (6-Garbodecyloxyhexyl) -3- (3,3-dimethyl-5 ~ phenylpentylthio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2,3,3-trircethyl-3 ~ phenylpropylthio) -

cyclopentanone,

2- (6-Carbodecylo3: y hexyl) -3- (2,3,3-trircethyl-5-phenylpenty-thio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxyheptylthio) -cyclopentancn, 2- (6-Carbodecyloxyhexyl) -3- (2-hydroxynonylthio) -cyclopentanone, 2- (6-Carbodecylo: cyh3xyl) -3- (l'-hydro: cy-2-: r.o LhyIhe ptylthio) -

cyclopentanone,

- 83 -A0984i / uy80.

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy ~ 2-methylnonylthio) -

cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,

2 - (6- Carbode cyloxyhe xyl) -3- (2-hy dr oxy-3,. 3 -dime thy lnony lthl ο) -

cyclopentanone,

2- (6-Carbodeeyloxyhexyl) -3 ~ (-2-hydroxy-6,6-diine thy lhe pty lthio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyi) -3- (2 ~ hydroxy-8,8-dime thy lnony lthio) -

■ cyclopentanone,

2- (6-Carbode cyloxyhexyl) -3- (2 -hy dr oxy ~ 2,3,3 -trime thy lhe ptyIthlo). ■ cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydr oxy-2,3,3-trime thy lnony lthio) ~

. . . cyclopentanone,

2- (ö-Carbodecyloxyhexyl) -3- (2-hydroxy-2,6,6-trimethylhepbylthio) -

cyclopentanone, '

2- (6-carl3odecyloxyhexyl) -3- (2-hydroxy ~ 2,8,8 ~ trim thy lnony lthio) -

cyclopentanone,

2- (6-Car "bodecyloxyhexyl) -3- (2" hydroxy-3,3,6,6 - tetramethylheptyl ~

thioj-cyclopentanone,

2- ( G- carbodecyloxyhexyl) -3- (2 ~ hydroxy-3,3,8,8-tetramethylnonyl-

thioj-cyclopentanone,

2- (6-Cartiode cyloxyhexyl) -3- (2 ~ hydr oxy-2,3,3,6,6-pentamethyl-

heptylthio) cyclopentanone,

2- (6-Cart »odeeyloxyhexyl) -3- (2-hydr oxy-2,3,3,8,8-pent ame thy 1-

nonylthi o) -cyclopentanone,

2- (6-Carbodeeyloxyhexyl) -3 ~ (2-hydroxy-7,7,7-trifluoroheptylthio> -

- cyclopentanone,

2- (6-Carl) ode cyloxyhe xyl) -3- (2-hydroxy-9,9, 9-trif Iu ornony lthio) -

cyclopentanone,

2- (6-cart) odecyloxyhexyl) -3- (2-hydr oxy-2-methy 1-7,7,7-trifluoro-

heptylthio) cyclopentanone,

2- (6-CarDodecyloxyhexyl) - ⁱ 3- (2 ~ hydroxy-2 ~ methyl-9r9> 9-trifluoro-

nonylthio) cyclopentanone,

2- (6-Carhodecyloxyhexr> 'l) -3- (2-hydroxy-3,3-dimethyl-7,7,7-trifluoroheptylthio ^ cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3,3-dimethy1-9,9,9-trifluoro-

nonylthio) cyclopentanone,

2- (6-cart) odeeyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-7,7,7-

trifluorheptyIthio) -cyclopentanone,

2- (6-Carhodecyloxyhexyl) -3- (2-hydroxy ~ 2,3,3-trimethyl-9,9,9-

trifluoronylthio) cyclopentanone,

2- (6-Car "bodecyl3xyhexyl) --3- (2-h: / dr oxy-3-phe-nylpropy lthio) -

cyclopentanone,

- 84 4ÜÜÖ41 / U9 8Ü

2- (6-Carbodecyloryhrj χτΊ.) -3- ('r? - hy dr oxy ■ - 5 ~ phe nylpentylthio) -

cyclopentane »!,

2- (6-Carbodecyloxyhexyl) ~ 3 ~ (2-hydruxy-2-methyl-3-phenylpropylthio) -

cyclopentanone,

2- (6-Carbodecylozyhoxyl) -3- (2-hydro: <: y - 2 "methyl-5-plienylpontylthio) -

cyclopentanone,

2- (6-Carbodecyloxylie: <: yl) "3- (2-hydroxy-3,3-dimethyl-3-plienylpropyl ~ -

thio; -cyclopentanone,

2- (6-Carbodecylcyhexyl) ~ 3- (2-hydroxy-3,3-dimethyl-5-phenylpentyl--

tliio; -cyclopentanone,

2- (6-Carbodecyloxyhex; yl) -3 ~ (2 - hydroxy-2, 3, 3-trimethyl-3-phenyl-

prox> y ltlii ο) -cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy ~ 2,3,3-trimethyl ~ 5 ~ phcny1-

. - pentylthio) cyclopentanone.

by reacting with NaBH .:

2- (6-carboxyhexyl) -3-heptylthio-cyclopentanol, • 2- (6-carboxyhexyl) - ^ - nonylthio-cyclopentanol, 2- (6-Carboxyhexyl) -3- (2 ~ methylheptylthio) -cyclopentanol 2- (6-Carboxyhexyl) -3- (2-methylncnylthio) -cycloporjtanol.

2- (6-CaTbOXj ^ hO xyl) -3- (3,3-dime thy lhe ptylthio) -cyclopentane oil, 2- (6-carboxyhexyl) -3 ~ (3,3-dimetliylnony lthio) -cycloijentanol, 2 - (6-Carboxyhexyl) -3- (6,6-dimethylheptylthio) -cyclopentanο1, 2- (6-carboxyhexyl) -3- (8,8-dimethylnonylthio) -cyclopentanol, 2- (6-carboxyhexyl) - 3- (2,3,3-trime thylheptyltliio) -oyclopentan · oil, 2- (6-carboxyhexyl) ~ 3- (2,3, 3 ~ trlmethylnonylthio) -cyclopüntanol, 2- (6-carboxyhexyl) -3- ( 2,6,6-trimethylheptylthio) -cyclopen can ο1,2- (6-carboxyhexyl) -3- (2,8,8-trimethylheptylthio) -cyclopentane; 1, 2- (6-carboxyhexyl) ~ 3 ~ (3,3, 6,6- -te tr ame thy lhe ptyl thi ο) -

cyclopentane ^,

2- (6-carboxyhexyl) -3- (3,3, 8,8-tetrair; ethylnonylthio) ~

cyolopentano.l,

2- (6-carboxyhexyl) -3- (2,3,3,6,6-pentönis thylhspt y lthio) -

cyclopentano: l,

2- (6-Carboxyhexyl) -3 ™ (2,3,3,8,8-pe nt am-j thy Inony lthio) ~

cyclο pe ntan oil,

2- (6-Carboxyhexyl) -3- (7,7,7-tri flu or he ptylthio) -cyclopsirban oil, 2- (6-Carboxyhexyl) -3- (9,9,9-trifluorononylthio) -cyclopenta !! el, 2- (6-Carboxyhexyl) -3- (2-methy] -7,7,7 ~ t:, - if luorhe ptylthio) - ·

eye] .upr. ntan oil,

2- (6-Carboxyhexyl) -> - · (2-me thy J -9,9, 9-trJ f luornonylthi.o) -

cyclopenta «oil,

$ 5

2 ~ (6 »carboxyhexyl) - 3 ~ (3/3-dime thy 1-7 , 1 , 7-trifluorhepty ItMo) -

cyclopentanol,

2- (6-Carboxy} iexyl) "3 ~ (3,3-diraetliyl ~ 9.9, 9" tri «uornonyltl-j.io) -

cyolopentanol,

2- (6-carboxyhexyl) -3-- (2,3, 3-trimethyl ~ 7,7, 7-tz-ifluorhepty lthi ο) -

cyelopentanol,

cyelopentan ol.,

2- (β-carboxyhexyl) -3- (3-pheny1prοpylthiο) cyclopentanol _i 2- (6-carboxyhexyl) -3- (5-phenyIpentylthio) -cyelopentanol, 2- (6-carboxyhexyl) -3- (2 -methyl-3-pheiiylpropylthiO) -eyelopentaTio ^ ... 2- (6-carboxyhe> ^ rl) -3- (2 ~ methyl ~ 5-pheny Ipentylthio J-cyclopentanol, 2- (6-carboxyhexyl) -3 - (3,3, -dimetliyl-3-phenyipropylthio) -

cyclopentanol,

2- (6-Carboxyhexyl) --- 5 ~ (3,3-dimeth3'-l ~ 5-phenylpent3'-lthio) ~

cyclopentanol,

2- (6-Carboxyhexyl) »3- (2 ■ -, 3,3-trimethyl-3-phenylpropylthio) -

eyclopentaiiol,; - .. ·. "-".

2- (6-carboxyhexyl) -3- (2,3,3-trimethyl-5-phenyIpentylthio) -

cyelopentandi,

2- (6-carboxyhexyl) -3- (2-hydroxyheptylthio) -cyelopentanol, 2- (6-carboxyhexyl) -3- (2-hydroxynonylthio) -cyclopentanol, 2- (6-carboxyhexyl) -3- (2-hydroxy-2-methylheptylthio) -

cyclopentanol, -

2- (6 ~ carboxy hexyl) ~ 3- (2-hydroxy-2-methylene thy lthio ^ eyclopentaiiol; 2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyelopentanoi,

2- (6-Carboxyhexyl) -3- (2-hydroxy-3,3-dimethylnonylthio) ~

cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-6,6-dimethylhe ptylthio) -

cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-8,8-dimethylnonylthio) -

cyclopentanol ·,. ". ' .

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-triiethylheptylthio) - /

cyclOpentanol,

2- (6-Carboxyhexyl) -3- (2-hydroxy ~ 2, '3, 3-trimethylnonylthio) ~

cyclopentanol,

2- (6-carboxyhexyl) -3- (2 ~ hydroxy-2,6,6-trimethylheptylthio) -

cyclopentanol,

2 ~ (6-Carboxyhexyl) ~ 3- (2-hydr oxy-2,8, G-triniethylnonjathio) - '

cyciopentanol,

2 "(6-carboxyhexyl)» 3- (2-hydro: i: y-3, 3, 6, o-tetrar ^ t> iylhc-ptirlfhio '> -

"cyclopentanol,. ·

A0Ü8A1 / UB80 ~ ⁸⁶ - ·

2- (6-carboxyhexyl) -3- (2-hydr oxy-3,3,8,8-tetramethylnonyl-

thio) cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3,6,6-pentamethylheptyl-

thio) cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3,8,8-pentamethylnonyl-

thio) cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-7,7,7-trifluoroheptylthio) -

cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydr oxy-9, 9, 9-tr if luononylthio) -

eyelopentanol,

2- (6-Carb oxyhexyl) -3- (2-hydroxy-2-methy1-7,7,7-trifluorohepty1-

thio) cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methyl-9,9,9-trifluorononyl-

thio) -eyelopentanol,

2- (6-Carboxyhexyl) -3- (2-hydroxy-3, 3-d imethyl-7, .7,7-tr if luor-

heptylthiο) -eyelopentanol ,

2- (6-cart) oxyhexyl) -3- (2-hydroxy-3,3-dimethyl-9,9,9-trifluoro-

nonylthio) -eyelopentanol,

2- (6-cart) oxyhexyl) -3- (2-hydroxy-2, 3, 3-trimethyl-7,7,7-trifluorhe ptylthio) -eye lopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-9,9,9-trifluoro-

nonylthio) cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-3-phenylpropylthiο) -eyelopentanol,

2- (6-Carboxyhexyl) -3- (2-hydroxy-5 ~ phenylpentylthio) -cyclo-

pentanol,

2- (6-Car "boxyhexyl) -3- (2-hydroxy-2-methyl-3-phenylpropylthio) ~

cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-2-methyl-5-phenylpentylthio) -

cyelopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-3-phenylpropyl-

thio) cyclopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy - 3, 3- ⁱ -dimethyl-5-phenylpentyl-

thio) -eyelopentanol,

2- (6 ~ carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-3-phenylpropyl-

thio) -eyelopentanol,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-5-phenylpentyl-

thio) -eyelopentanol,

2- (6-Carbethoxyhexyl) -3-heptylthio-cyclopentanol, 2- (6-carbethoxyhexyl) -3-nonylthio-cyclopentanol, 2- (6-carbethoxyhexyl) -3- (2-methylheptylthio) ~ cyclopentanol, 2- (6 -Carbäthoxyhexyl) -3- (2-methylnonylthio) -cyelopentanol,

/ uyso

2- (β-Carbethoxyhexyl) -3- (3,3 -dime thy llie ptylthi ο) -cyclopentane) !, 2- (6-Carbethoxyhexyl) -3- (3,3-dimethylnonylthio) -cyclopentanol, 2- (6 -Carbäthoxyhexyl) -3 -. (6,6-dimet} lyllieptyltMo O-cyclopentanol, 2- (6-Carbäthoxyhexyl) -3- (8,8 ~ dimethyInonylthio) -cyclopentanol, 2- (6-Carbäthoxyhexyl) -3- (2. % 3-trimethylheptylthio) cyclopentanol, 2- (6-carbethoxyhexyl) -3- (2,3, 3-trimethylnonylthio) cyclopentanol, 2- (6-carbethoxyhexyl) -3- (2,6 , 6-trimethylheptylthio) -

cyclopentanone,

2 ~ (6 - Carbethoxyhexyl) ~ 3- (2, ö, 8-trimethyInonylthio) -

cyclopentanol,

2 ~ (6 - Carbethoxyhexy 1) -3- (3,3,6 »6 - tetraiGe thylhe pty lthio) -. ■

cyclo |) entanol,

2- (ö-CarlDäthoxyhexyl) -3- (3,3,8,8 -tetraine thy Inony lthio) -

cyclopentanol,

2 - »(6-Carbethoxyhexyl) -3- (2,3 ^ 3,6, 6-pf? Ntam.ethy lhe pty lthio.) -

cyclopentanol,

2- (6-Carbäthoxyhe xyl) -3- (2, -3,3,8,8-pentamethy Inony lthio) -

cyclopentanol, -

2- (6 ~ carbethoxyhexyl) -3- (7,7,7 -tri'fluorhe pty lthio) -

cyclopents / aol,

2 ~ (e-Carhathoxyhexyl) -3- (9 ₅ 9 , 9-trifluorononylthio) -

^,. cyclopentanoli, ■. ■■. '.

2- (6-Car "ethoxyhexyl) -3 - (2-riiethy 1-7,7, 7-trifluorheptylthio) - ■

cyclopentanol,

2- (6-Carbethoxyhexyl) -3 ~ (2 ~ methy1-9,9,9-trifluorononylthio) -

cyclopentane !,

2- (6 ~ Carbethoxyhexyl) -3- (3,3-dimethyl-7,7,7-trifluorheptyl-

thio) cyclopentanol.,

2- (6-Gart) ethoxyhexyl) -3- (3,3 ~ dimethyl-9,9,9-trifluorononyl-

thio) -cyclopenta.nol,

2- (ö-Garhäthoxyhexyl) -3- (2,3,3-trime thy1-7,7,7-trifluoroheptyl-

thio) cyclopentanol,

2 ~ (6-Carbethoxyhexyl) -3- (2,3,3-trimethyl-9,9,9-trifluorononyl- ■ ' - ■ thioj-cyclopentanol., ·

2- (6-Carl) ethoxyhexyl) -3- (3-phenylpropylthio) -cyclopentanol, 2- (6-Carbethoxyhexyl) -3- (5-phenylpentylthio) -cyclopentanol, 2- (6-Carbethoxyhexyl) -3- (2 ™ me thy 1-3 ~ 'Dhenyl pro py lthio) -

cyclopentanol,

2- (6-Garbäthoxyhexyl) ~ 3- (2-methyl-5 ~ phenylpentylthio) -

cycl opentanol,

2- (6-Carbethoxyhex2rl) ~ 3 ~ (3 , 3-dimethyl-3-pheny lpro py.lthio) -

■ .. cyclopentanol.,

_ 88 _

. 4 u a- ö 4 τ / u y 8 ü

2 ~ - (6 ~ Carl) ethoxyliiixyl) ~ 3 - (3,3-d imo thy l-5-p'n.onylj: s3ntylt ¹ aio) ~

cyclopsntanol,

2- (6 ~ carbethoxyhexyl) -3 ~ (2, 3,3-trimethyl ~ 3 ~ ptonylpropyXthio) -

c y c 1 ο pe η t a ti ol,

2 - (6 - Carbethoxyhexyl) -3- (2,3,3 ~ trime thy l-5-pbß ny lperi ty 1 thi ο) -

cyclopentanol,

2- (6 - Carbethoxyhexyl) -3- (2 -hydroxyheptylthio) -eye 1 ope nt an ol, 2_ (6-Carbäthcxyhexyl) ~ 3- (2-hydroxynonylthio) -cyclopentanol, 2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2 ~ nyj thy lhepty lthio) -

cyclopentanol.,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2-methylncnylthio) -

cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) ~

eyclopentariol,

2- (G-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethylnonylthio) -

cyclopentanol,

2- (6-Carbethoxyhex3'-l) -3- (2-hydroxy-6,6-diinethylheptylthio) -

cyclopentanol,

2- (6--0arbäthoxyhexyi) -3- (2-hydr oxy-8,8- -dime thy lnony lthi ο) -

cyclopentanol,

2- (6-Oarbäthoxyhexyl) -3- (2-hydroxy-2,3,3-trimethylheptylthio) -

cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,3,3-trimythy lnony lthio) -

. - cyclopentanol,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2,6,6-trimethylheρtylthio) -

cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2,0,8-trimethylnonylthio) -

cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3,6,6-tetramethylhepty1-

thio) cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3,8,8-tetramethylnonyl-

thio; -cyclopentanol,

2- (6-Carbethoxyhexyl) ~ 3- (2-hydroxy-2,3,3,6,6-pentaryßthy 1-

heptylthio) cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-2, 3, 3,8,8-pentaniothyl-

nony lthio; - cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-7,7,7-trifluorohoptylthio) -

cyciopentanol,

2- (6-0arbätho>: yheryl) -3- (2 - hyaroxy-9,9,9, 9-trifluorononylth I.o) -

cyclopentancl,

2- (6-Carbethoxyhexyl) -3- (2-hydr oxy-2 ~ TOeth_yl-7,7,7-trifluorine -

heptylthi ο) -cyclopentanol,

2- (6-C ^ / «: ethoxyhexyl) ~ 3 - (2 - hydro: cy ~ 2 - methyl - 9,9,9 - trixluoro-

nonylth-io) -cyclopentanol,

~ 89 -

2- (6-carl3ethoxyhexyl) -3- (2-] hydroxy-3, 3-dimethyl-7, 7,7-trl-

fluorneptylthio) -eyclopentanol,.

2- (6-Carbätnoxynexyl) -3- (2-nydr oxy-3,3-dimethyl-9,9,9-trifluor-

nonyrth ± o) -cyclopentanol, ^

2- (6-Carbethoxyhexyl) -3- (2-hydrooxy-2,3,3-trimethyl-7,7,7-tri-

fluorneptylthio ^ cyclopentanols

2 ~ (6-Carbätlioxyliexyl) -3- (2-hydroxy-2,3,3-trimet] riyl-9 * 9,9-tri-

f luornonyltliio) -eyclopentanol,

2- (6-Gar "bätlioxyliexyl) -3 - '(2-liydroxy-3-plienylpropyltliip) -cyclo-

pentanol,

2- (6-Car ^^ ät] loxyllexyl) -3- (2-llydroxy-5-p ¹ ώenylpentyltllio) -eyclo ~ -

pentanol,

2- (6-Carbätlioxyliexyl) -3- (2-liydr oxy-2-rae thyl-3-plienylpr opylthi c) -

'cyclopentanol,

2- (6-Carbätlioxyliexyl) -3- (2-liydroxy-2-metliyl-5 - plie.nylpej: ityl-

■ tMo) -cyclopen-ta, nol,.

2- (S-Carldätlioxyliexylo - ^ - (2-h.ydroxy-3,3-dimethyl-3-plieTiylpropyl

tMo) -cyclopentanone.,

Z- (6-Carbethoxyliexyl) -3- (2-hydroxy-3,3-dimethyl-5-phenylpenty7i ~

tliloj-cyclopentaiiol,

2- (S-Oarbathoxyhexyl) -3- (2-hydroxy-2, 3,3-trimothyl-3-piienyl-

propylthio) -eyelopentanol,

2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2,3,3-ti-imethyl-5-phenyl-

pentylthio) ~ cyclopentanol,

2- (6-car "bodecyloxyliexyl) -3-neptylthiocyclopentanol, 2- (6-carbodecyloxyliexyl) -3-nonyltniocyclopentanol, 2-C6-carbodecyloxyhexyl) -3- (2-methylheptylthio) -cyclopentanol, 2- (6-Carbodecyloxyhexyl) -3r (2-metbylnonylthJo) ~ cyclopentanol, 2- (6-Carbodecyloxynexyl) -3- (3,3-dimethylheptyltMo) -cyclo-

pentanol,

2- (6-Carbodecyloxyhexyl) -3- (3, 3-dimet] 'iylnonyltti.io) -eyelopentanol,

2- (6-Carbodeeyloxyhexyl) -3- (6,6-diinethylheptylthio) -cyclo-

'pentanol,

2- (6-Carbodecyloxyliexyl) -3- (8,8-dimethylnonyltMo) -cyclo-

pentanol,. .

2- (6-Carbodeeyloxyhexyl) -3- (2,3,3-trimethylbeptyltliio) -cyclo-

pentanol,

Z- (6-earbodecyloxyhexyl) -3- (2, -3,3-trimethylnonyltb.io) -cyelo-

pentanol,

2 - (6-CarbOdecyloxyhexyl) -v - (?., 6, o-trimethyllieptyltliioX-cyclopentanol,

409841 / Ü98Ü

2- (ö-Carbodecyloxyhexyl) -3- (2,8,8-trimethylnonylthio) -

cyclopentanols

2- (6-Carbodecyloxyhexyl) -3 ~ (3,3,6,6-tetramethylheptylthio) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) ~ 3- (3,3,8,8-tetramethylnonylthio) -

cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (2,3,3,6,6-pentamethylheptylthiq) -

cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (2-3,3,8,8-pentamethylnonylthio) -

cyclopentanol ,,

2- (6-carbodecyloxyhexyl) -3- (7,7,7-trifluoroheptylthio) -cyclo-

pentanol,

2- (6-carbodecyloxyhexyl) -3- (9,9,9-trifluorononylthio) -cyclo-

pentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-methy1-7,7,7-trifluoroheptylthio) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-methyl-9,9, 9-trifluorononylthio) -

cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (3,3-dimethy1-7,7,7-trifluoroheptylthio ) -eyelopentanol,

2- (6-carbodecyloxyhexyl) -3- (3,3-diraethy1-9,9,9-trifluorononylthio ) -eye lopentanol,

2- (6-carbodecyloxyhexyl) -3- (2,3,3-trimethyl 1-7,7,7-trifluoroheptylthio ) -cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (2,3,3-trimethyl-9,9,9-trifluorononylthio ) -cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (3-phenylpropylthio) -eyelopentanol, 2- (6-Carbodecyloxyhexyl) -3- (5-phenylpentylthi ο) -eyelopentanol, 2- (6-Carbodecyloxyhexyl) -3- (2-me thy l ^ -pher ^ lpropyl thio) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-methyl-5-phenylpentylthio) -

cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (3,3-dimethyl-3-phenylpropylthio) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (3,3-dimethy1-5-phenylpentylthio) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2,3,3-trimethy1-3-phenylpropylthio) -

cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (2,3,3-trimethyl-5-phenylpentylthio) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxyheptylthio) -eyelopentanol, 2- (6-Carbodecyloxyhexyl) -3- (2-hydroxynonylthio) -cyclopentanol, 2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2-methylheptylthio) -

cyclopentanol,

409841/0980

2- (6-Carbodeeyloxyhexyl) -3- (2 ~ hydroxy ~ 2-methylnonylthio) -

eyeIopentanol,

2- (6 ~ carl3odecyloxyhexyl) -3- (2-hydroxy-3,3-dimet] iyllieptyltliio) -

cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3> 3-dimethylnonylthio) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) ~ 3- (2-hydroxy-6, 6-dime thy lhepty ItMo) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-8,8-dime thy Inony ItMo) -

cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethyllieptyltlilo) -

cyclopentane-].,

2- (6-Carbodeeyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethylnonyltMo) -

cyclopentanol,

2- (δ-Carbodecyloxyhexyl) -3- (2-hydroxy-2,6,6-trimethylheptylt'b5.c) ~

- eyclopentanoi, ■

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2,8,8-trimethylnonylthio) -

cyclopentanol,

2- (β-Carbodecyloxyhexyl) -3 -. (2-hydroxy-3,3,6,6-tetramethylheptyl-

thioj-cyclpentanol,

2- (6-carbadecyloxyhexyl) -3- (2-hydroxy-3-3,8,8-tetramethylnonyl-

thio) cyclopentanol,

2- (6-CarT3Odecyloxyhexyl) -3 ~ (2-hydroxy-2,3,3,6,6,6 ~ pentamethyl-

heptylthio) cyclopentanol, ■

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-2,3,3,8,8-pentamethylnonyltMo) -eye Io pentano 1,

2- (6 ~ carbodecyloxyhexyl) -3- (2-hydroxy-7,7,7-trifluoroheptylthio) -

cyelopentanol,

2- (6-Carbodecyloxyhexyl) -3 ~ (2-hydroxy-9,9> 9-trifluorononylthio) -

eyclopentanoi, '

2- (6-Carbodecyloxyhexyl) -3 ~ (2-hydroxy-2-methyl-7,7,7-trifluoro-

heptylthiο) -cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-2-methyl-9,9,9-trifluorononylthio> -cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7,7,7-tri- '

fluoroheptylthio) cyclopentanol,

2- (6-Carbodeeyloxyhexyl) -3- (2-hydroxy-3,3-dimethy1-9,9,9-tri-

fl-uornonylthio) -cyclopentanol,

2- (6-Carbodecyioxyhexyl) -3- (2-hydroxy-2,3,3-trimethy1-7,7,7-

trifluoroheptylthio) -cyelopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-2, 3, 3-trimethyl-9,9,9-.

trifluorononylthio) cyclopentanol,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-3-phenylpropylthio) -

cyclopentanol,

A OS 84 1/09 80

2- (ö-Carbodecyloxyhexyl) -3- (2-hydroxy ~ 5-phenylpentylthio) -

cyclopentanols

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-2-methyl-3 ~ phenylpropyl-

thiο) -eyelopentanol,

2- (6-Carbodeeyloxyhexyl) -3- (2-hydroxy-2-methyl-5-phenylpentyl-

thioj-cyelopentanol,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3,3-dimethyl-3-phenyl-

propylthio) cyclopentanol,

2- (6-Carbodecyloxyhexyl) ~ 3- (2-hydroxy-3,3-dimethyl-5-phenyl-

pentylthiο) -eyelopentano1,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl ~ 3-phenyl-

propyltliio) cyclopentanol,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-5-phenyl-

pentylthiο) -eyelopentano1.

Example 11

A mixture of 3.6 g of 2- (6-carboxyhexyl) -3- (2-oxoheptylthio) -cyclopentanol (obtainable from 2- (6-carboxyhexyl) -2-cyclopentenone by reaction with 2,2-ethylenedioxyheptanethiol, reduction of the 2- (6-carboxyhexyl) -3- (2,2-ethylenedioxyheptylthio) -cyclopentanone obtained with NaBH. and acidic saponification of the ketal), 0.8 g of hydrazine, 1 g of potassium tert-butoxide and 30 ml of dimethyl sulfoxide 1 Hour at room temperature, poured into 80 ml of 2N aqueous HCl, saturated with NaCl, extracted three times with 30 ml of CH ₂ Clp each time, the organic phase was washed with water, dried over Na ₂ SO., The solvent was distilled off and obtained after chromatographic purification of the Residue (silica gel / chloroform) 2- (6-carboxyhexyl) -3-heptylthio-cyclopentanol.

Example 12

3.6 g of 2- (6-carboxyhexyl) -3- (2-oxo-heptylthio) -cyclopentanone are stirred (obtainable from 2- (6-carboxyhexyl) -2-cyclopentenone by adding 2,2-ethylenedioxyheptanethiol and acid Saponification of the ketal) with 4.0 g NaBH. 2 hours at 25 ° in 60 ml

A09841 / U9S0

Ethanol, after cooling, pour "in" 15Q ml saturated aqueous NaCl solution, extracted three times with 40 Ether, the organic phase washes with water, tiOclaiet via NapSO., the solvent distills ah and receives after chromatographic purification of the residue -

(Silica gel / chloroform) 2- (6-GarTDoxyhexyl) -3- (2-hydroxyheptylthio) -cyclopentanol.

Example 13.

A mixture of 2.7 g of 7- (2-thio-5-oxo-cyclopentyL) -heptanoic acid ethyl ester is heated (Can be prepared from 2- (6-Carhoxyhe3cyl) -2-cyclopentenone by esterifying with ethanol in the presence of HCl and addition of HpS in the presence of piperidine), 0.9 g 1-heptene and 0.02 g dihenzoyl peroxide closed for 24 hours Tube in nitrobenzene to 130 °, extracted the reaction mixture after cooling with ether, the ether phase washes with it 20 $ aqueous ITaOH and water, dry over MgSO., the solvent is distilled off and, after purification by chromatography, the residue is obtained 2- (6-carbethoxyhexyl) -3-heptylthio-cyclopentanone;

R _f = 0.7 (silica gel / chloroform);

Calculated analysis: 68.07 ° /> C, 10.33 % H, 8.65 % S; Analysis found: 67.8 % C, 10.4 ^ H, 8.6 ^ S;

IR spectrum: bands at 1,730, 2,870 and 2,950 cm "¹;

Nuclear Magnetic Resonance Spectrum: Signals at 0.9 ppm, 3.0 ppm and '-_- "'. Between 3.95 ppm and 4.3 'ppm (quartet) -.

- 94 409 8A1 / 0980

Example 14

A mixture of 2- (6-carbethoxyhexyl) -3-oxocyelo ~ pentyllithium thiolate (prepared by adding dropwise 2.7 g of 2- (6-carbethoxy ₎ hexyl) -3-oxo-cyclopentanethiol, dissolved in 20 ml of dry tetrahydrofuran, is boiled a solution of 0.65 g of butyllithium in 20 ml of dry tetrahydrofuran), 1.1 g of 1,2-epoxyheptane in 50 ml of dry tetrahydrofuran for 72 hours under nitrogen, after cooling poured into 100 ml of 0.1 η aqueous HCl, extracted twice with 40 ml CHpCIo, the organic phase is washed with water, dried over Na SO _n., the solvent is distilled off to give after chromatographic purification of the residue (silica gel / chloroform) of 2- (6 ~ carbo-xyhexyl) -3- (2 -hydroxyheptylthio) -cyclopentanone;

R _f = 0.2 (silica gel / chloroform / methanol = 95: 5);

calculated analysis: $ 63.65> C, $ 9.56 H, $ 8.94>S; Analysis found: 62.7 $ C, 9.5 $ H, 8.3 ^ S;

IR spectrum: bands at 1,700, 1,730, 2,880 and 2,950 cm " ¹ , broad band between 3,000 and 3,500 cm;

Nuclear Magnetic Resonance Spectrum: Signals at 0.9 ppm, 3.1 ppm, 3.75 ppm and 6.8 ppm

- 95 -

409841/0980

Example 15

A mixture of 2- (6-car-bethoxyhexyl) -3- oxocyclopentyllithiximtlii is stirred ola t (can be prepared by adding 2.7 g of 2- (6-Oar "bethoxyhexyl) ~ 3-oxo - cyclopentanethiol, dissolved in

20 ml of dry tetrahydrofuran to a solution of 0.6 g of butyllithium in 20 ml of dry tetrahydrofuran), 2.3 g of heptyl iodide and 50 ml of dry tetrahydrofuran 8 hours "under nitrogen, poured after cooling into 100 ml of ice water, extracted twice with each 40 ml of CB ₂ CIp, the organic phase is washed with water, dried over Ma ₂ SO., The solvent is distilled off and, after chromatographic purification of the residue (silica gel / chloroform), 2- (6-carboxyhexyl) -3-heptylthio-cyclopentanone is obtained. ~

R _f = 0.7 (silica gel / chloroform);

/ calculated analysis: 64.93 $> C, 9.61 f H, 10.2 Ü Sr analysis found; 65.6 5 ^ C, 9.7 -foil, 9.8 1 ° 3;

IR spectrum: bands at 1,730, 2,870 and 2,950 cm "¹;

KMR spectrum: signals at 1.0 ppm / 3.0 ppm and 4? 0 - 4.22 ρρ "> {quartet).

4 0 3 8 A 1 / o 9 8 0

Example 16

A mixture of 2- (6-Carbätboxyhex3 '"" j) -3-oscocyclopentyllithium thiolate (prepared by adding dropwise 2.7 g of 2- (6-Carbethoxyhexyl) ~ 3 ~ oxo ~ cyclopentanethiol, dissolved in 20 ml of dry tetrahydrofuran is stirred a solution of 0.65 g of butyllithium in 20 ml of dry tetrahydrofuran), 2.7 g of 1-p-TοIuο! sulfonyloxyheptane and 50 ml of dry tetrahydrofuran at 0 ° for 6 hours under nitrogen, poured into 100 ml of ice water after cooling, extracted twice with 40 ml of ether each, wash the organic phase with water and dry over NapSO . , the solvent is distilled off and, after purification by chromatography of the residue (silica gel / chloroform), 2- (6-carboxyhexyl) -3-heptylthio-cyclopentanone is obtained;

R _f = 0.3 (silica gel / chloroform / methanol = 95: 5);

Analysis calculated: 66.62 $ C, 10.01 fo H, 9.36% S: Analysis found: C 65.5 $ 5, 9.71% H ,. 9.3 % S;

IR spectrum: bands at 1,700, 1,730, 2,860 and 2,940 cm " ¹ .

- 1 - 1

broad band between 3 000 cm and 3 400 cm <

Nuclear Magnetic Resonance Spectrum: Signals at 0.86 ppra, 3.0 ppm and 9.75 ppm.

- 97 -

409841 / U980

Example 17

3.9 g of 2- (6-carbethoxyhexyl) -3-lieptylthlö-cyclopentanone oxime (obtainable by reacting 2- (6-carbethoxyhexyl) -I-heptylthio-cyclopentanone with hydroxylamine) are boiled for 3 hours in a mixture of 50 ml of 2 η aqueous KOH and 50 ml of ethanol, after cooling, poured into 70 ml of 2 η sulfuric acid, saturated with UaCl, extracted three times with CH ₂ Clp, the organic phase was washed with water, dried over Ua ₂ SO-, the solvent was distilled off and retained after chromatographic purification of the residue (silica gel / chloroform) 2- (6-carboxyhexyl) -3-heptylthio-cyclopentanone;

R _f = 0.3 (silica gel / chloroforincmethanol = 95: 5);

Analysis calculated: 66.62 i »C, 10.01 foil, 9.36% S; Analysis found: C 65.5 ^, 9.71 fo H, 9.8% S;

IR spectrum: bands at 1,700, 1,730, 2,860 and 2,940 cm " ¹ ,

—1 —1

wide band between 3 000 cm and 3 400 cm

HMR spectrum: signals at 0.86 ppm, 3.0 ppm and 9.75 ppm.

409 841/09 80

Example 18

3.8 g of 2- (6-hydrazinocarbonylhexyl) -3-hep'tylthiocyclopentanone hydrazone (obtainable by reacting 2- (6-carbethoxyhexyl) -3-heptylthio-cycloperitanone with hydrazine) are boiled for 3 hours in a mixture of 50 ml of 2 η aqueous KOH and 50 ml of ethanol, after cooling, poured into 70 ml of 2N sulfuric acid, saturated with NaCl, extracted three times with CHpCl ₂ , the organic phase was washed with water, dried over NapSO., the solvent was distilled off and obtained after chromatographic purification of the Residue (silica gel / chloroform) 2- (6-carboxy hexyl) -3-heptylthio-cyclopentanone;

R _f = 0.3 (kieselge-1 / chloroform / ethanol - 95: 5);

Calculated Analysis: 66.62 # C, 10.01 # H, 9.36 % S; Analysis found: 65.5 % C, 9.71 ° /> II, 9.8% S;

IR spectra: bands at 1,700, 1,730, 2,860 and 2 940 era * " ¹ , broad bands between 3,000 cm" and 3,400 cm ".

NK-Spolrtrvua: signals at 0.86 ppm, 3.0 pp ^ n and 9.75 ppm.

- 99 -

409841/0980

Example 19

4.7 g of 1,1-ethylenedioxy-2- (6-tert-butoxycarbonylhexyl) -3- (2-hydroxy-2-methyl-heptylthio) -cyclopentane (prepared from 2- (6-carboxyhexyl) -2 are stirred) -cyclopentenone, addition of 2-hydroxyheptanethiol, subsequent ketalization with ethylene glycol, and oxidation with CrO ~ in ether, addition to isobutylene and conversion of the 1, T-ethylenedioxy-2- (6-tert-butoxycarbonylhexyl) -3- (2 -oxoheptylthio) cyclopentane with methylmagnesium bromide) 2 hours at room temperature in 60 ml of 2N aqueous HOl, extracted after cooling three times with CHpCl ₂ , the organic phase was washed with water, dried over Na ₂ SO /, the solvent was distilled off and obtained after chromatographic Purification of the residue (silica gel / chloroform) 2- (6-carboxyhexyl) -3- (2-hydroxy-2-methy1-heptyl) -cyclopentanone;

R _f = 0.25 (KieseIgel / ChIorοform: Methanöl = 95: 5);

Calculated analysis: 64.48 </ o C, 9.74 i ° H, 8.61 % S; Analysis found: 65.6 % C, 10.7% H, 7.9% S;

IR spectrum: bands at 1705, 1740, 2850, 2920 and 3400 cm "" ¹ , broad band between 3,000 cm and 3,300 cm ";

HMR spectrum: signals at 0.9 ppm, 2.75 ppm, 3.0 ppm and 6.4 ppm ..

- TOO

409841 / 098Q

Example 20

4.6 g of 1-tetrahydropyranyl- (2) -oxy-2- (6-carbethoxycarlionylhexyl) -3-heptylthio-cyclopentane (which can be prepared from 2- (6-carbethoxycarbonylhexyl) -3-heptylthio-cyclopentanone by reduction with NaBH) are stirred. and reaction of the 2 ~ (6-carb ~ ethoxycarbonylhexyl) -3-heptylthio-cyclopentanol obtained with dihydropyran) for 6 hours in 30 ml of 50% CH ₅ COOH at 25 °, extracted twice with CHpCl ₂ , the organic phase was washed with water, dries over NapSO., the solvent is distilled off and, after chromatographic purification of the residue (silica gel / chloroform), 2- (6-0arboxyhexyl) -3-heptylthiocyclopentanol is obtained.

Example 21

4.0 g of 2- (6-tert-butoxycarbonylhexyl) -3-heptylthiocyclopentanone are boiled (obtainable by introducing isobutylene into a dry ethereal solution of 2- (6-carboxyhexyl) -3-heptylthio-cyclopentanone in the presence of BF,) 5 hours in dry p-xylene, the solvent is distilled off and after chromatographic purification of the residue (silica gel / chloroform), 2- (6-carboxyhexyl) -3-heptylthiocyclopentanone is obtained;

R _f = 0.3 (silica gel / chloroform: methane oil = 95: 5);

Calculated analysis: 66.62 ^c / o C, 10.01 i> H, 9.36 <£ S; Analysis found: 65.5 1 ° 0, 9.71 # H, 9.8 % S;

IR spectrum: bands at 1,700, 1,730, 2,860 and 2,940 cif ¹ ,

- 1 - 1

wide band between 3 000 cm and 3 400 cm

NMR spectrum: signals at 0, ^ - 5 ppm, 3.0 ppn and 9? 75 TP ' ¹ -

- 101 409841/0980

Example 22

4.7 g of 2- (6-carbethoxyhexyl) -3- (2-tetrahydropyranyl-oxyheptylthio) -cyclopentanone are boiled (obtainable from 2- (6-carbon ethoxyhexyl) ~ 2-cyclopentenone and 2-tetrahydropyranyloxyheptylthiol / can be prepared from 2-hydroxyheptyl bromide and dihydropyran and subsequent reaction with NaHS / 2 hours under nitrogen with 40 ml of aqueous 1 ή HCl, extracted twice with washes the organic phase with water, dries over ^ the solvent is distilled off and obtained after chromatographic Purification of the residue (silica gel / chloroform) 2- (6 ~ carboxyhexyl) -3 ~ (2-hydroxyheptyl) cyclopentanone;

R _f = 0.2 (silica gel / chloroform / methanol: 95: 5);

Analysis calculated: 63.65 f ° C, 9.56 # .H, 8.94 9 ^ 'S, Analysis found: 62.7% C, 9.5% H, 8.3 1 <> S; . ■ __ ■

IR spectrum: bands at 1,700, 1,730, 2,880 and 2,950 cm " ¹ , broad band between 3,000 and 3,500 cm;

NMR spectrum:

Signals at 0.9 ppm, 3.1 ppm, 3.75 ppm and 6.8 ppm.

- Π2 -

984 1/09 80

Example 23

It is added to a solution of 3.4 g of 2- (6-carboxy he xyl) -3-heptylthio-cyclopentanone in 25 ml of dry ethanol at room temperature 70 ml of a 0.2N diazoethane solution in Ether, pour the reaction mixture into 100 ml of ice water containing 5 ml of concentrated HCl, stir, separate the The organic phase is extracted, the aqueous phase is extracted three times with 30 ml of chloroform each time, and the combined organic phase is washed Phases with water, dried over NapSO ,, the distilled The solvent is removed and, after purification by chromatography of the residue (silica gel / chloroform), 2- (6-carbethoxyhexyl) -3-heptylthio-cyclopentanone is obtained; -

R _f = 0.7 (silica gel / chloroform);

Calculated Analysis: $ 68.07> C, $ 10.33 H, $ 8.65 S; Analysis found: 67.8 $> C, 10.4 $ H, 8.6 # S;

IR spectrum: bands at 1,730, 2,870 and 2,950 cm "¹;

RMR spectrum: signals at 0.9 ppm, 3.0 ppm and between 3.95 ppm and 4.3 ppm (quartet).

- 103 409841 / 098Q

Analogously one obtains from

2- (6-carboxyhexyl) -3-heptylthio: -cyelopentanone, 2- (6-carboxyhexyl) -3-nylthio-cycropentanone, "

2- (6-carboxyliexyl) -3- (2-methyl iheptylthio) -cyclopentanone, 2- (6-Carboxyhexyl) ^ 3- (2 ~ hydröxyheptylthio) -cyclopentanone, 2- (6 - Carbooxyhexyl) ~ 3- (2-hydr oxynonyithio) -cyclopentanone, 2- (6-Carboxyxyl) -3- (2 ~ hydroxy ~ 2-methyIheptylthio) -

cyclopentanone,

2- (6-Oarboxyhexyl) -3- (2-hydr oxy-2-HB thy InonyIthio) -cyclopentanone, 2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone, '

2- (6-Carboxyhexyl) -3- (2-hydroxy-3> 3-dimethyInonyIthio) -

eyeIopentanon,

2- (6-Car "boxyhexyl) -3- (2-hydroxy-6,6-dimethylheptylthio) -

^{.cyclopentanon;}

2- (6-carboxyhexyl) -.3- (2-hydr oxy-8,8-dime thy Inony Ithio) -

cyclopentanone, -

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethylheptylthio) -

cyclOpentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-2,3,3-trimethylnonyIthio) -

cyclopentanone,

2- (6-Carboxyhexyl) -3- (2 ~ hydroxy-2,6,6-trimethylheptyIthio) -

cyclopentanone, '

2- (6-carboxyhexyl) -3- (2-hydr oxy-2,8,8-trimethyynonylthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3,6, β-tetramethylheptylthio) -

cyclopentanone,

2- (6-Carboxyhexyl j -3- (2-hydr oxy-3,3,8,8-te tr äice thyInony 1-

thio; -cyclopentanone,

2- (6-carboxyliexyl) -3- (2-hydr oxy-2,3,3,6,6-pent ame thy 1-

Hei) tylthio) -cyclopentanone,

2- (6-Carboxyh.exyl) -3- (2-hydroxy-2, 3, 3,8,8-pentaiBthyl-

nonylthio; ~ cyclopentanone, -

2- (6-Carb03cyhe2cyl) -3- (2-hydroxy-7,7,7-trifluoroheptyIthio) -

cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydroxy-9,9,9-trifluorononylthio) -

cyclopentanone,:

2- (6 ~ Carbo: -cyliexyl) -3 - (2 -hydr oxy-2-me thy 1-7,7,7 -trif Iu or -

heptylthio) -cyclopentanOn,

nonylthloj-cyclopentanone,

- 104 403841 / ÜS8Q ^:

2- (6-carboxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7,7,7-trifluoro-

heptylthiο) -cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydro3cy-3,3-dime thy 1-9,9,9-trifluor-

nonylthioj-cyclopentanone,

2- (6-carboxyhexyl) ~ 3- (2-hydroxy-2,3,3 ~ tri me thy 1-7,7,7-

trifluoroheptylthio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2 - hydroxy-2,3,3 - tr! Methyl-9,9,9-

trifluoronylthio) -cyelopentanone, *, *

2- (6-carboxyhaxyl) -3- (2-hydroxy-3-phenylpropylthio) -

cyclopentanone,

2- (6-Carboxylic xyl) -3- (2 ~ hydroxy-5-pheny lpenty lthio) '-

cyclopentanone,

2- (6-Carbo: xyhexyl) -3- (2-hydroxy-2-methyl-3-phenylpropylthio) -

cyclopentanone,

2- (6-Carboxyhexyl) -3- (2-hydr oxy-2-methy 1-5-phenylpenty lthio) .-

cyclopentanone,

2 - (6- carboxyhexyl) -3 - (2-hydroxy-3,3 -dime thy 1-3- phe ny lpro py 1-

thio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydr oxy-3,3 -dime thy 1-5-phe ny lpentyl-

thio) cyclopentanone,

2- (6-carboxyhexyl) -3- (2-hydr oxy-2,3,3-trimethy 1-3-phenyl-

propy lthio) -cyclopentanone,

2- (6-carboxyhexyl) ~ 3- (2-hydroxy-2,3,3-trimethy 1-5-phenyl- - 'pentylthioj-cyclopentanone,

by reacting with diazobutane:

2- (6-carbobutoxyhexyl) -3-heptylthio-cyclopentanone, 2- (6-carbobutoxyhexyl) -3-nonylthio-cyclopentanone, 2- (6-Carbobutoxyhexyl) -3- (2-methylheptylthio) -cyclopentanone, 2- (6-Carbobutoxyhexyl) -3- (2-hydroxyheptylthio) -cyclopentanone, 2- (6-Carbobutoxyhexyl) -3- (2-hydroxynonylthio) -cyclopentanone, 2- (6-carbobutoxyhexyl) -3- (2-hydroxy-2-methylheptylthio) -

cyclopentanone,

2- (6-Carbobutoxyhexyl) -3- (2-hydr oxy-2-methy lnony lthio) -

c ycl ope ntan on,

2 - (6-Carb obutoxyhe xyl) -3- (2 -hy dr oxy-3,3 -dime thy lhe pty lth i ο) -

cyclopentanone,

2- (6-Carbobutoxyhexyl) -3- (2-hydr oxy-3,3-dime thy lnony lthio) -

cyclopentanone,

2- (6-carbobutoxyhexyl) -3- (2-hydroxy-6,6-dimethylheptylthio) -

cyclopentanone,

- 105 -409841/0980

2- (6-Carbobirt oxyhexyl) -3- (2-hydr oxy-8, 8-dimethylnonylthio) -

cyclopentanone,

2- (6-Carbobut oxyhexyl) -3- (2-hydroxy-2,3,3-trimythy Ine ptylthio) -.

cyclopentanone,

2- (6-carbobut oxyhexyl) -3- (2-hydroxy-2,3,3-trimethylnonylthio) -

cyclopentanone,

2- (6-Carb ohut oxyhexyl) -3 - (2-hydr oxy-2, 6, 6-trime thy lhe pty lthi ο) -

.cyclopentanone, - (6-Carbobut oxyhexyl) -3- (2-hydr oxy ~ 2,8,8-trime thy lnonylthio) -

cyclopentanone,

2- (6-Garbobutoxyhexyl) -3- (2-hydroxy-3,3,6, δ-tetramethylheptylthio ; -cyclopentanone,

2- (6-Carbobut oxyhexyl) -3- (2-hydroxy ~ 3,3,8,8 ~ tetramethylnonylthio; -cycl open an on,, .._

2- (6-carbobut oxyhexyl) -3- (2-hydroxy-2,3,3,6,6-pentamethy.l-

heptylthi ο) -cyclopentanone,

2- (β-carbobut oxyhexyl) -3- (2-hydroxy-2,3,3,8,8-pentamethyl-

nonylthio; cyclopentanone,

2- (6-0arbobut oxyhexyl) -3- (2-hydroxy-7,7,7-trif luoroheptylthio) -

cyclopentanone,

2- (6-carbobut oxyhexyl) -3- (2-hydroxy-9,9,9-trifl-aornonylthio) -

cyclopentanone,

2- (6-Carbobut oxyhexyl) -3- (2-hydr oxy-2-methyl-7,7,7-trifluoro-

heptylthio ^ -cyclopentanone,

2- (β-carbobut oxyhexyl) -3- (2-hydroxy-2-ine thy 1-9,9,9-trif liior- ^-

nohylthi'o) -cyclopentanone,

2- (6-carbobut oxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7,7,7-trifluoro-

heptylthio) cyclopentanone,

2- (6-Garbobut oxyhexyl) -3- (2-hydroxy-3,3-dimethy1-9,9,9-trifluoro-

nonylthiοj-eyelopentanon,

2- (6-carbobut oxyhexyl) -3- (2-hydroxy-2,3,3-trimethy1-7,7,7-

trifluoroheptylthio) cyclopentanone,

2- (6-carbobut oxyhexyl ) -3- (2-hydroxy-2,3,3-trimethyl-9,9,9-

trifluorononylthio) cyclopentanone,

2- (6-carbobut oxyhexyl) -3- (2-hydroxy-3-phenylpropylthio) -

cyclopentanone,

2- (6-carbobutoxyhexyl) -3- (2-hydroxy-5-phenylpentylthio) -

cyclopentanone,

2- (6-Carbobut oxyhexyl) -3- (2-hydroxy-2-ynethyl-3-phenylpropylthio) .-

cyclopentanone,

2- (6-carbobut oxyhexyl) -3- (2-bydroxy-2-methy1-5-phenylpentylthio) -

cyclopentanone,

2- (6-carbobutoxyhexyl) -3- (2-hydroxy-3 ₅ 3-diffiethyl-3-phenylpropyl-

thio; -cyclopentanone,

Ä09841 / 0980

2 ~ (6 ~ carbobutoxyhexyl) ~ 3 ~ (2-hydroxy-3,3-dircethyl "5 ~ pnenylpentyl-

thio; -cyclopentanone,

2- (6-Carbobutoxyhexyl) -3 ~ (2-hydroxy-2, 3, 3-trimethyl-3-phenyl-

propylthio) cyclopentanone,

2- (6-Carbobutoxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-5-phenyl)

pentylthio) cyclopentanone,

by reacting with 1-diazohexane:

2- (6-Carbohexyloxyhexyl) -3-heptylthio-cyclopentanone, 2- (6-Carbohexyloxyhexyl) -3-nonylthio-cyclopentanone, 2- (6-Carbohexyloxyhexyl) -3- (2-methylheptylthio) -eyclopentanone, 2- (6-Carbohexybxyhexyl) -3- (2-hydroxyhe ptylthio) -cyclopentan on, 2- (6-Carbohexy] oxyhexyl) -3- (2-hydroxynonylthio) -eyclopentanone, 2- (6-Carbohexyloxyhe: r5rl) -3- (2-hydroxy-2-methylheptylthio) -

cyclopentanone,

2- (6-Carbohexyloxyhexyi) -3- (2-hydr oxy-2-methy lnonylthio) -

cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-3,3-dimethylnonyl-aiio) -

cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-6,6-dimethylheptylthio) -

cyclopentanone,

2- (6-Carbohexyloxyhexyi) -3- (2-hydroxy-8,8-dimethylnonylthio) -

cyclopentanone _r

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethylheptylthio) -

cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethylnonylthio) -

cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-2,6,6-trimethylheptylthio) ■

cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-2,8,8-trimethylnonylthio) -

cyclopentanone,

2- (6-carbohexyloxyhexyl) -3- (2-hydroxy-3,3,6,6-tetramethylheptylthio; -cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-3,3,8,8- · te trans thy lnony 1-

thio; -cyclopentanone, ....

2- (6-carbohexyloxyhexyl) -3- (2-hydroxy-2,3,3,6,6-pentamethyl-

heptylthio) cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-2,3,3,8,8-pcntairethyl-

nonylthiο) -cyclopentanone,

- 107 -

409841/0980

2- (6-Carbohexyloxyhexyl) -3 ™ (2-hydroxy ~ 7,7,7-trifluorheptylthio) -

cyclopentanone, ■

2- (6-Carbohexyloxyhexyl) - 3- (2-hydr αχ3 ^Γ -9,9, 9-trifluorononylthio) -

cyclopentanone,

2 - (6 - Garb one xy loxyhexy 1) -3 - (2 -hy dr oxy ~ 2-me thy 1-7,7,7-trifIu or -

heptylthio) cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (.2 ~ hydroxy-2 ~ ine thyl-9,9,9 -trifluoro-

nonylthio ^ cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7,7,7-trifluoro-

heptylthio) cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-3,3-aimethyl-9,9,9-trifluoro-

nonylthio; cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydoxy ~ 2,3,3 ~ trimethyl-7,7,7-

trif Iu or heptylthio) -cyclopentanone,

2- (6-Oarbohexyloxyhexyl) -3 - ^^ (2-hydroxy-2,3,3-trimethyl-9,9,9-

trifluorononylthio) -cyolopentanone,

2- (6-Garbohexyloxyhexyl) -3- (2-hydroxy-3-phenylpropylthio) -

cyclopentanone,

2- (6-Carbohexy] bxyhexyl) -3- (2-hydr oxy-5-phenylpenty lthip) -

cyclopentanone,. ■ ■ '

2- (6-CarbohexyODxyhexyl) -3- (2-hydroxy-2-methyl-3-phenylpropylthio) -

cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydroxy-2-methy 1-5-phenylpentylthIo) -

cyclopentanone,

2- (6-CarbohexylPxyhexyl) -3- (2-hydroxy-3,3 -dime thy 1-3- pheny lpropyl-

thiο ) -cyclopentanone,

2- (6-Carbohexyloxyhexyl) -3- (2-hydr oxy ~ 3,3-dime thy 1-5- pheny Ipentyl-

• thio; cyclopentanone ^ ■

2- (6-Carbohexyloxyhexyl) -3- (2-hydr oxy-2,3,3-trimethy 1-3-phenyl-

propylthio) cyclopentanone,

2- (6-Garbohexyloxyhexyl) -3- (2-hydroxy ~ 2,3,3-trimethyl-5-phenyl-

pentylthio) -cyclopentan.on. ".

by reacting with 1-diazodecane:

2- (6-Carbodecyloxyhexy.l) -3-heptylthio-cyclopentanone _i 2- (6-Garbodeeyloxyhexyl) -3-nonylthio-cyclopentanone ■

2- (6-Carbodecyloxyhexyl) -3- (2-methylheptylthio) -cyclopentanone, 2- (6-Carbodecyloxyhexyl) -3- (2-hydroxyheptylthio) -cyclopentanonej 2- (6-Carbodecyloxyhexyl) -3- (2-hydroxynonylthio) -cyclopentanone, 2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-2-methyIheptylthio) -

cyclopentanone,

Α098ΑΪ / 0980

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2-methylnonylthio) -

cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-3,3-climetliylnonyltMo) -

cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-6,6-dimethylheptylthio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2 ~ hydroxy-8,8-dimethylnonylthi ο) -

cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethylheptyl-

thiο; -eyelopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethylnonylthio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-2,6,6-trimethylheptylthi ο) -

cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2,8,8-trimethylnonylthio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-3f 3 _f 6,6-tetramethylheptylthio) -cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3,3,8,8-tetramethylnonyl-

thio) -eyelopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2,3 »3,6,6-pentamethyl-

heptylthio) cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2,3,3,8,8-pentamethyl-

nonylthiο; -eyelopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-7,7,? - trifluoroheptylthio) -

cyclopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-9,9 »9-trifluorionylthio) -

cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-2-methyl-7,7,7-trifluoro-

heptylthio) -eyelopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-2-methyl-9,9,9-trlfltior-

nonylthiο; -eyelopentanone,

2- (6-Carbodecyloxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7 * 7,7-tri-

fluoroheptylthio) -eyelopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3,3-dimethyl-9,9,9-tri-

fluornonylthio) -eyelopentanone,

2- (6-Garbodecyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-7,7,7- '

trifluoroheptylthio) cyclopentanone,

2- (6-Carbodeeyloxyhexyl) -3- (2-hydroxy-2,3,3 ~ trimethyl-9,9. »9-

trifluorononylthio) cyclopentanone,

2- (6-carbodecyloxyhexyl) -3- (2-hydroxy-3-phenylpropylthio) -

cyclopentanone,

4ÜÜ841 / 0980

2- (6-Carbodecyloxyh.exyl) -3- (2-h.ydro3qr-5-phenylpentyithio) -

cyclopentanone,

2- (6 ~ carbodecyloxyliexyl) -3- (2-hydroxy-2-methyl-5-p] ienylpropyl-

thio) -cyclopentanone,

2- (G-Carbodecyloxyhexyl) -3- (2 ~ hydroxy-2-methyl-5-phenylpentyl-

thioj-eyelopentanon,

2- (6-Carbode cyloxyhexyl) -3- (2-liydr oxy-3,3-dimethyl-3-phenyl-

. propylthiO) -eyelopentanone, ■

2- (6-Garbodecyloxyhexyl) -3- (2-hydroxy-3, ^ -dimetiiyl-S-phenyl-

■ pentylthio) cyclopentanone,

2- (6-Carbodeeyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-3.-phenyl-

propylthio) cyclopentanone,

2- (6-carbodecyloxyliexyl) -3- (2-hydroxy-2,3,3-trimethyl-5-phenyl >> ³

pentylthio) cyclopentanone;

by reaction with t-diazododecane:.

2- (6-carbododecyloxyhexyl) -3-heptylthio-cyciopentanone, 2- (6-carbododecyloxyhexyl) -3-nonylthio-cyelopentanone, 2- (6-carbododecyloxyhexyl) -3- (2-methylheptylthio) -cyclopentanone, 2- (6-Carbododecyloxyhexyl) -3- (2-hydroxyheptylthio) -cyclopentanone, 2- (G-Carbododecyloxyhexyl ') -3- (2-hydroxynonylthio) -cyclopentanone, 2- (6-, carbododecyloxyhexyl) -3- (2-hydroxy-2-methylheptylthio) -

cyclopentanone, ■

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-2-methylnonylthio) -

eyelopentanon,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-3,3-dimethylnonylthio) -

cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-6,6-dimethylhe.ptylthio) -

cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-8,8-dimethylnonylthio) -

• cyclopentanone,

2- (6-Carbododecyloxyhexyl) -2 ~ (2-hydroxy-2,3,3-trimethylheptyl-

thiο) -eyelopentanone,:

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethylnonyl-

thio; -cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-2,6,6-trimethylheptyl-

thioj-eyelopentanon,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-2,8,8-trimethylnonyl-

thiο) -eyelopentanone,

AO9841 / Ü9 80

2 ~ (6-Carbododeeyloxyhexyl) -3- (2-hydroxy-3, 3,6, 6-tetrainethylheptyl-

thio) cyclopentanone,

2- (6-Carbododecyloxyhexyl) -3- (2 ~ hydroxy-3,3,8, £ i-tetrainethylnonyl "

thiο J-cyclopentanone, ...

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-2,3,3,6, ö-pentamethyl-

heptylthio) cyclopentanone,

2- (ö-Carbododecyloxyhexyl) -3-C2-hydroxy-2,3,3,8,8-pentamethy 1-

nonylthiο) -cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-7,7,7-trifluoroheptylthio) -

cyclopentanone,

■ 2 - (. 6-Carbododecyloxyhexyl) -3- (2-hydroxy-9,9,9-trifluorononylthio) -

cyclopentanone,

2- (6-carbododecyloxyhexyl) -3-C2-hydroxy-2-methy1-7.7 _t 7-trlfluoro-

heptylthio) cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-2-methyl-9,9,9-trifluoro-

nonylthio) cyclopentanone,;

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-3,3-dimethyl-7,7,7-trifluoro-

heptylthio) cyclopentanone,

2- (6-Carbododecyloxyhexyl) -3- (2-hydroxy-3,3-dimethy1-9,9,9-trifluoro ~

^ y

O)

nonylthio) cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-7,7,7-

trifluoroheptylthio) cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- {2-hydroxy-2,3,3-trimethyl-9,9,9-

trifluoronylthio) cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-3-phenylpropylthio) -

cyclopentanone,

2- (6-σarbododecyl · xyhaxyl) -3- (2 ^ hydroxy-5-phenylpentylthio) -

cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydroxy-2-methyl-3-phenylpropylthio) -

cyclopentanone,

2- (6-Carbododecyloxyhexyl) ~ 3- (2-hydr oxy-2-methy 1-5-phenylpen ty lthio) -

cyclopentanone,

2 -. (6-Carbododecyloxyhexyl) -3- (2-hydroxy-3,3-dimethyl-3-phenylpropyl-

thio; -cyclopentanone,

2- (6-carbododecyloxyhexyl) -3- (2-hydr oxy-3,3-dime thy 1-5-pheny lpentyl-

thio; -cyclopentanone,

2- (6-Carbododecyloxyhexyl) -3- (2-hydr oxy-2,3,3-trinfö thy 1-3-phenyl-

propylthiο) -cyclopentanone,

2- (6-Carbododecyl oxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-5-phenyJL-

pentylthio) cyclopentanone,

- 111 409841/0980

by reacting with pheny! .diazomethane:

2- (6-carbobenzyloxyhexyl) ~ 3-heptyithio-cyclopentanone, 2- (6-carbobenzyloxyhexyl) -3-nonylthio-cyclopentanone, 2- (6-Carbobenzyloxyhexyl) -3- (2 ~ methylheptylthio.) - cyclopentanone, 2- (6-Carbobenzyloxyhexyl) -3- (2 ~ hjrdroxyheptylthio) -cyolopentanone, 2- (e-Carbobenzyloxyhexyl) -3- (2-hydroxynonylthio) -cyclopentanone, 2- (6 ~ carbobenzyloxyh3xyl) -3- (2-hydroxy-2-methylheptylthio) -

cyclopentanone,

2- (6-carbobenzyloxyhexyl) -3- (2-hydroxy-2-me, thy Inony lthio) -;

cyclopentanone, \

2- (6-carbobenzyloxyhexyl) -3 ~ (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanone,;

2- (6-Carbobenzyloxyliexyl) -3- (2-hydroxy ~ 3,3 -dime thy In ony lthio) - · ■

cyclopentanone, ■ ■ ■;.

2- (6-carbobenzyloxyhexyl) -3- (2-hydroxy-6,6-dimethylheptylthio) -

cyclopentanone,

2- (6-Carbobenzyloxyhexyi ) -3-> (2-hydroxy-8,8-dime thy Inony lthio) -

cyclopentanone,.

2- (6- Carbobenzyloxyhexyl) -3- (2-hy dr oxy-2,3,3 -tr ime thy Ihe pty lthio) -

cyclopentanone,

2- (6-Carböbenzyloxyhexyl) -3- (2-hydr oxy-2,3,3-tri me thy Inony lthio) -

cyclopentanone,;

2- (6-Carbobenzyloxyhexyl) -3- (2-hydr oxy-2, 6, 6-trime thy Ihe pty lthio) ~,

cyclopentanone, i

2- (6-Carbobenzyloxyhexyi) -3- (2-hydroxy-2,8,8-trime thy Inony lthio) -

. cyclopentanone, '■

2- (6-carbobenzyloxyhexyl) -3- (2-hydroxy-3, 3,6, 6-tetramethylheptyl-

thioj-cyclopentanone,

2- (6-Garbobenzyloxyhexyl)> - 3- (2-hydroxy-3 »3,8,8-tetrame thy Inony i ~

thio; -cyclopentanone, ■

2- (6-carbobenzyloxyhexyl) -3- (2 ^ -hydroxy-2,3,3,6,6-pentamethyl-

heptylthio) cyclopentanone,

2- (6-Carbobenzyloxyhexyl) -3- (2-hydr oxy-2,3,3,8,8-pent ame thy 1-

nony lthio; -cyclopentanone,

2- (6- Carb abovezyloxyhexyl) -3- ¹ (2-hydr oxy-7,7,7-trif Iu or he pty lthio) -

cyclopentanone,

2- (6-Carbobenzyloxyhexyl) -3 ~ (2-hydr oxy-9,9 , 9-tri fluornony lthio) -

cyclopentanone,

2- (6-carbobenzyloxyhexyl) -3- (2-hydr oxy-2-methy 1-7,7,7-trifluoro-

heptylthio) cyclopentanone,

40984170980

2- (6 - carbobenzyloxyhexyl) ~ 3- (2-hydroxy-2-ynethyl ~ 9,9,9-trifluoro-

nonylthio) cyclopentanone,

2- (6-CarbobenzyliKyliexyl) -3- (2 ~ hydroxy-3,3-dimethyl-7,7,7-trifluoro-

heptylthiο) -cyclopentanone _t

2- (6-Carbobenzyloxyhexyl) -3- (2-hydroxy-3,3-dimethyl-9,9,9-triflnor ~

nonylthio ) cyclopentanone,

2- (6-carbobenzyloxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-7,7,7-

trifluoroheptylthio) cyclopentanone,

2- (6-carbobenzyl-oxyhexyl) -3- (2-hydroxy-2 _f 3,3-trimethyl-9,9,9 ~

trifluorononylthio) cyclopentanone,

2- (6-carbobenzyloxyhexyl) -3- (2-hydroxy-3-phenylpropyltliio) - '

cyclopentanone,

2- (6-Carbobenzy] Dxyhexyl) ~ 3- (2-hydroxy-5-phenylpentylthio) -

cyclopentanone,

2- (6-Carbobenzyloxyhexyl) -3- (2-hydroxy ~ 2-metb.yl-3-phenylpropyltliio) -

cyclopentanone,

2- (6-Carbobenzy loxyhexyl) -3- (2-hydroxy-2-n3eth.y 1-5-phenylpentylth.io) -

cyclopentanone,

2- (6-CarbobenzyODxyhexyl) -3- (2-hydroxy-3,3-dimethyl-3 ~ phenylpropyl ~

thiο; -eye1opentanon,

2- (6-Carbobenzy loxyhexyl) -3- (2-hydroxy-3,3-dimethy 1-5-plie nylpentyl-

thio; -cyclopentanone,

2- (6-Carbobenzy] oxyhexyl) -3 ~ (2-hydroxy-2,3,3-trimethyl ~ 3-phenyl ~

propylthio) cyclopentanone,

2- (6-Carbobenzy] oxyhexyl) -3- (2-hydroxy-2,3,3-trimethyl-5-pneny 1-

pentylthio) cyclopentanone.

- 113 -A09841 / U98Q

Example 24

It is added dropwise - with stirring "to a solution at room temperature of 3.9 g of 2- (6-carbethoxyhexyl) -3- (2-hydroxyheptylthio) cyclopentanone in 20 ml of benzene 10 ml of a solution of 0.8 g of acetyl chloride in 20 ml of benzene, give 10 ml after 10 minutes a 0.5 η aqueous NaOH solution, then the drops add the remaining 10 ml of the benzene acetyl chloride solution., and after a further 20 minutes gives again 10 ml of a 0.5 η aqueous NaOH solution, stir for another 30 minutes, separates the organic phase, washes it with HwO, dried over MgSO., the solvent is distilled off and obtained after chromatographic purification (Silica gel / chloroform) 2- (6-carbethoxy- * hexyl) -3- (2-acetoxyheptylthio ^ cyclopentanone.

Example 25

To a solution of 3.9 g of 2- (6-carbethoxyhexyl) -3- (2-hydroxyheptylthio) -eyclopentanone in 30 ml of pyridine, 2.0 g of acetic anhydride, dissolved in 20 ml of pyridine, is stirred at -25 ° 14 Hours, the reaction mixture is poured into 100 ml of water, saturated with ITaCl, extracted three times with 40 ml of ether each time, the organic phase is washed with water, dried over ". Na ₂ SO., The solvent is distilled off and obtained after chromatographic purification of the Residue (Eieselgel / Chloroform) 2- (6-Carbethoxyhexyl) -3- (2-acetbxyheptylthio) - cyclopentanone.

- 114 -

40a841 / ü9B0

Example 26

Example 25 is obtained from

2- (6-Carbethoxyhexyl) -3-heptylthi o-cyclopentanol, 2- (6-Carbethoxyhexyl) -3-nonylthio-cyclopentanol, 2- (6-Carbethoxyhexyl) -3- (2-methylheptylthio) -cyclopentanol, 2- (6-Carbethoxyhexyl) -3- (2-methylnonylthio) cyclopentanol, 2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2-methyIheptylthio) -

cyclopentanol,

2- (6-Carbethoxyhexyl) -3- (2-hydr oxy-2-methylnonylthio) -

cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethylheptylthio) -

cyclopentanol,

2- (6-carbethoxyhexyl) -3- (2-hydroxy-3,3-dimethylnonylthio) -

cyclopentanol,

by reacting with acetic anhydride in pyridine:

2- (6-carbethoxyhexyl) -3-heptylthio-cyclopentylacetate, 2- (6-carbethoxyhexyl) -3-nonylthio-cycloperitylacetate, 2- (6-Carbethoxyhexyl) -3- (2-methyIheptylthio) -cyclopentyl acetate, 2- (6-Carbethoxyhexyl) -3- (2-methylnonylthio ^ cyclopentylacetat, 2- (6-Carbethoxyhexyl) -3- (2-acetoxy-2-methylheptylthio) -

cyclopentyl acetate,

2- (6-Carbethoxyhexyl) -3- (2-acetocy-2-methylnonylthio) -

cyclopentyl acetate,

2- (6-Carbethoxyhexyl) -3- (2-acetoxy-3,3-dimethylheptylthio) -

cyclopentyl acetate,

2- (6-Carbethoxyhexyl) -3- (2-acetoxy-3,3-dimethylnonylthio) -

cyclopentyl acetate.

- 115 4 0 y 8 4 1 / Ü980

Example 27

4.3 g of 2- (6-CarT3ethoxyh.exyl) -3- (2-acetoxyheptyltnio) cyclopentanone are stirred at room temperature for 2 hours in 30 ml of a 1% solution of EOH in a dioxane-water mixture (1: 1), poured into 60 ml of 2N aqueous HCl with cooling, extracted three times with 30 ml of CHpCl ₂ each time, the organic phase was washed with water, dried over Na ₂ SO ^, the solvent was distilled off and, after chromatographic purification of the residue, obtained C silica gel / Chloroform) 2- (2-carboxyhexyl) -3- (2-hydroxyheptylthio) cyclopentanone;

R _f = 0.2 (silica gel / chloroform: methanol = 95: 5);

Calculated Analysis: $ 63.65 C, $ 9.56 H, 8.94 ° S; Analysis found: 62.7 ° C, 9.5-1 ° H, -8.3 % S;

IR spectrum: bands at 1,700, 1,750, 2,880 and 2,950 cm, • broad band between 3,000 and 3,500 em;

HMR spectrum; Signals at 0.9 ppm, 3.1 ppm, 3.75 ppm and 6.8 ppm.

Example 29. . ·

0.24 g of sodium is dissolved in 20 ml of dry ethanol, and a solution of 3.4 g of 2- (6-carboxyhexyl) -2-heptylthio-cyclopentanone is added dropwise in 20 ml of dry ethanol, diluted with 60 ml of dry ether and filtered the precipitated sodium salt des 2- (6-carboxyhexyl) -2-heptylthio-cyclopentanone from.

- 116 40984 1/0980

Example 30

10 ml of 1N aqueous HCl are added to a solution of 3.7 g of the sodium salt of 2- (6-carboxyhexyl) -2-heptylthio ~ cyclopentanone in a mixture of 30 ml of water and 30 ml of ethanol, the reaction mixture is saturated with NaCl and extracted three times with 20 ml of benzene, the organic phase is washed with water, dried over Na ₀ SO., distilled

£ 4 removes the solvent and, after purifying the residue by chromatography (silica gel / chloroform), gives 2- (6-carboxyhexyl) -3-heptylthio-cyelopentanone;

R _f = 0.3 (silica gel / chloroform: methanol = 95: 5);

Calculated Analysis: $ 66.62 C, 10.01 % H, $ 9.36>S; Analysis found: 65.5 f> C, 9.71 % H, 9.8 % S;

IR spectrum: bands at 1,700, 1730, 2,860 and 2,940 cm " ¹ , broad bands between 3,000 cm and 3,400 cm.

Nuclear Magnetic Resonance Spectrum: Signals at 0.86 ppm, 3.0 ppm and 9.75 ppm.

/ Ü980

In the following examples A and B, the preparation of some of the starting materials used according to the invention is described described:

Example A.

20 g of a 20 follow sodium hydride dispersion in laraffin oil are washed three times with 30 ml of dry n-pentane, the solvent is removed, 33 g of trimethylsulfoxonium iodide are added, 100 ml of dimethyl sulfoxide are then added dropwise, and the mixture is stirred at room temperature for 20 minutes until the evolution of gas has ceased , add dropwise a solution of 14.2 g of 2-heptanone in 15 ml of dimethyl sulfoxide, stir for a further 2 hours, add 500 ml of water while cooling with ice, extract three times 250 ml of ether, wash the combined ether extracts with water, dry with sodium sulfate, distilled the solvent is removed and, after fractionation of the residue, 2-methyl-2-pentyloxirane is obtained as a colorless liquid; Kp = 55 ° (20 mm Hg).

Hydrogen sulfide is passed into 150 ml of methanol while cooling with ice until the increase in weight is 3.2 g Solution of 370 mg of diethylamine in 11 ml of methanol and then 4.8 g of 2-methyl-2-pentyloxirane in 18 ml of methanol to passes hydrogen sulfide gas into the for another 15 minutes Solution, leave to stand for 12 hours at room temperature, the solvent is distilled off, the residue is dissolved in 50 ml of petroleum ether (Ep = 50 - 70 °), washed with water, dries with sodium sulfate, the solvent is distilled off and the residue obtained is 2-hydroxy-2-methyl-heptanethiol as a colorless liquid;

-113 -

Q.

calculated analysis: 59.2 % C ,. 11.18 % H, 19.76 1 ° S, analysis found: 60.1 <f ₀ 0, 11.6 % H, 20.2 # S;

IR spectrum: bands at 920, 1 HO, 1 380, 1 465,

2,570 and 3 45O cm "¹;

Nuclear Magnetic Resonance Spectrum: Signals at 0.96 ppm, 1.26 ppm, 2.27 ppm and 2.67 ppm.

Other 2-hydroxy-2-methyl-R sulfides can also be used analogously of the formula II prepared from the corresponding ketones be, especially those mentioned in Examples 1 and 2 ^.

Example B.

500 g of 2-oxocyclopentanecarboxylate potassium salt are added to a boiling solution of 55Og of ethyl 7-bromoenanthate in 6 liters of toluene while stirring, the mixture is boiled, and after 1 hour another 250 g of 2-oxocyclopentanecarboxylate, potassium salt, are cooked for a further 24 hours, filtered after Cooling down, the solvent is distilled off, the residue is diluted with 3 liters of ether, washed with water, dried over Na _? S0., The solvent is distilled off and, after fractionation of the residue, 2-carbethoxy-2- (6-carbethoxyhexyl) cyclopentanone is obtained as a colorless oil, b.p. 165 ° (0.3 mm Hg).

_{48 g of Br 2} , dissolved in 500 ml of CHCl, are added dropwise to a solution of 100 g of 2-carbethoxy-2- (6-carbethoxyhexyl) cyclopentanone in 1 1 of OHCl ₅ with stirring over the course of 2 hours at 20.degree from, the residue takes in a mixture of 4 l of ethanol, 1 kg of HpSO. (Density = 1.84) and 100 ml of HpO, boiled for 18 hours under Np », after cooling, poured onto 10 kg of ice, extracted three times with 5 liters of ether each time, dried the combined ether extracts over Na ₂ SO, and the solvent was distilled off and after purification of the residue by chromatography (silica gel / petroleum ether: ether ~ 1: 1), 2- (6-CarbJithoxyhexyl) -2-cyclopentenone is obtained.

/ U98Q _ 119 -

Claims (10)

A-COOR S-R ' Process for the preparation of a compound of the general Formula I, R R, or optionally one or polysubstituted by Cl, Br or J Alkyl, cycloalkyl, Aralkyl or aryl with up to 12 carbon atoms each, R ² = 0, (H, OH) or (H, acyloxy with up to 4 carbon atoms), j RH, OH or acyloxy with up to 4 carbon atoms, R ^ "optionally one or more times through-1, Cl, Br, OH, acyloxy with up to 40 atoms, phenyl or tolyl substituted, straight or branched one Alkyl with up to 12 carbon atoms, and A optionally one or more times substituted by F, Cl, Br, OH, acyloxy with up to 4 carbon atoms or phenyl, straight or branched alkylene with up to 8 carbon atoms mean, ; and the bond indicated by / ^ v shows α- or ß-configuration, as well as their physiologically harmless salts, 409841 / U980 120 - 2. Compounds of the general formulas la - Iz and their physiologically harmless salts. 3. Optically active compounds of the general formulas Iza - Izd. 4 x 2- (6-carboxyhexyl) -3-propylthiocyclopentanone. 5. 2- (6-carboxyhexyl) -3-heptylthiocyclopentanone. 6. 2 ~ (6-Carbethoxyl) -3-propylthiccycl-pentanone. 7. 2- (6-Carbethoxyhexyl) ~ 3-heptylthiocyclopentanone, 8. 2- (6-carboxyhexyl) -3-nonylthiocyelopentanone, 9. 2- (6-Carbethoxyhexyl) -3-nonylthiocyclopentanone. 10. 2- (6-Carboxyhexyl) -3- (2-hydroxyheptylthio) cyclopentanone. 11. 2- (6-Carbethoxyhexyl) -3- (2-hydroxyheptylthio) -cyclopentanorx> 12. 2- (6-Carboxyhexyl) -3- (2-hydroxy-2-methylheptylthio) - cyclopentanone. 13. 2- (6-Carboxyhexyl) -3- (2-hydroxy-2-methylnonylthio) - cyclopentanone. 14. 2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2-methylheptylthio) - · cyclopentanone. 15. 2- (6-Carbethoxyhexyl) -3- (2-hydroxy-2-methylnonylthio) - cyclopentanone. 16. A process for the preparation of a compound of the general formula I, characterized in that a verb: inchir _{A (} -; of the general formula II, - 121 4 0 9 8 A 1 / U 9 8 0 2 where ■ ■ . D -CH-OA-COOR ¹ or -GHX-OH-A-COOR ¹ , 'D'. and - X Gl, Br, J, alkylsulfonyloxy with R ^ "up to 4 carbon atoms or arylsul- fonyloxy with TdIs to 10 carbon atoms II ■■ '■: .-' · ■ "mean, and ·,." .-. , R _f R _f R and A have the meaning given above; ' with a compound of the general formula III, where ■ ^: W-S-R ¥ H or an equivalent of one Alkali or alkaline earth metal atom III. . means, and R ^ has the meaning given above
. Has, · . implements, '■ · ■■■■ "■ -. ■. or that one'a compound of the general formula IV, wherein R ^ one or more stages into one -COOR -group means transferable radical and R to R and A are those given above Have meaning treated with a thermolytic or solvolyzing agent, or that τη -ιη a Vc-rb-i nflurj ^ - di ^j r ailgftrneinen I ¹ or me IV, A098A17Ü980 worm R ² or (H , X), E ⁶ E ³ or Y, and E ⁷ Y Cl, Br, J, alkylsulfonyloJty with up to 4 carbon atoms or arylsulfonyloxy with up to 10 C- Atoms mean and V 14. R - R, A and X have the meaning given above, and in which at least one radical X or Y is contained, with a solvolyzing agent, or that a compound of the general formula VI, wherein R ⁸ = 0 or (H, R ⁵ ), and 9 4
RR or straight or branched oxoalkyl with up to 12 carbon atoms which is substituted one or more times by F, Cl, Br, OH, acyloxy with up to 4 carbon atoms, phenyl or p-tolyl mean, and ^VI 12th R, R and A have the meaning given above , and which contains at least one carbonyl group, implemented with a reducing agent, 40üb41 / U98U - 123 - or that a compound of the general formula YIX, ^A ~ ^{COOr1 :} where - _: ■ R to_ R, A and W are those given above ■ · have meaning, with a compound of the general formula VIII, , .... in which. ........ ... R; "... .H or possibly a or several times by F, Cl. Br, OH ₁ BR ¹⁰ acyloxy with up to 4 G atoms or phenyl substituted; straight or branched alkyl VIII ■ -.... _: . ■ with up to 10 C breaths, and XR ¹¹ R ¹² C-CR ¹³ R ¹⁴ -bedexiten, and R ¹¹ , R ¹² , R ¹⁵ and R ^{14 are the} same or ■ "■ -"'- ■ _ ■ are unequal, and H or optionally one or more times by F, Cl, Br, OH, acyloxy with up to 4 C- Atoms or phenyl .. ■ substituted, straight or branched alkyl with up to 10 carbon atoms mean, where the sum of the aliphatic carbon atoms in B 10
• and R must not be greater than 12 may, and X has the meaning given above, / UB8Ü. -. ¹ 24 implements, or that in a compound which is otherwise of the formula 1 corresponds, but in which existing hydroxyl and / or keto group η and / or the carboxyl group in functionally altered. * Form present, these groups by treatment with solvolyzing or hydrogenolyzing agents in freedom puts, and / or that one obtained compound of formula I by Treatment with esterifying or solvolyzing agents converted into another compound of formula I, and / or that a compound of the formula I is converted into its racemate and / or optical antipodes, and / or that a compound of the formula I by treating converted with a base into one of its physiologically harmless salts, or by treatment with an acid from a sets their salts free. 409841