DE2554790A1 - TETRA-SUBSTITUTED ORGANIC TIN COMPOUNDS - Google Patents

Description

The invention relates to tetrasubstituted organotin compounds which are used to combat Insects and "pests" and are applicable as herbicides. Many of these are tetra-substituted organotin Connections are new connections.

In the prior art, some are tetrasubstituted Organotin compounds known. For example, in British patent specification 966 813 (Ziegler) a. Procedure for Preparation of tetrasubstituted organic sense compounds which are useful as high polymers, described, however there is no indication that these compounds can be used in the control of insects and other pests or as herbicides and fungicides could be useful.

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It is also known other substituted organotin
To use compounds as pesticides, acaricides, bactericides, fungicides and herbicides or as protective coatings.

for example, U.S. Patent 3,642 (Ramsden) bistrialkyl tin compounds of the formula

(KKSnH ¹ Sn (R)

described ,, where R is an alkyl group and R ^{r is} a hydrocarbon radical having at least eight carbon atoms. These compounds have a systemic pesticidal action, in particular against Lepidoptera insect larvae, for example the
Bama wool moth caterpillar. · ·

Another example is US Pat
formula

R.
| 2

describes

where R ₁ * R ₂ , E ₅ and R ^ alkyl radicals with 1 to 12 carbon atoms and an aromatic hydrocarbon radical can be, where appropriate, one of the R substituents is an alkyl radical, which is limited by a lower aliphatic thioic acid group, which by the presence

60) 9827/1022

is characterized by a thiocarboxyl function. These compounds are stated to be useful as herbicides are. ;

Another example is U.S. Patent 3,591,614 (Bublitz), in the compounds of the formula

--Sn-R

are described, in which R is a 2-cyanoethyl, 2-carooxyethyl, or 2-carb (lower) alkoxyethyl group. It is stated that these substituted ethyl derivatives of tricyclohexylamine. Can be used as acaricides for combating mites and ticks are.

In another U.S. Patent 3,641,037 (Bublitz) are compounds of the formula

-Sn-R

described, wherein R.2-Fury1, 2-pyridyl, 3 ~ pyridyl, 1-indenyl or 2- (2-pyridyl) ethyl, these compounds being applicable as pesticides, in particular for combating mites and ticks.

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Another example is the German patent specification 2 231 814 (Peterson)., In .which compounds of the formula

(R) ₃ SnCH ₂ -X

are described, where X is alkyl or ary! sulfonyl, alkyl or Is arylthio or dialkylamino and R. is alkyl of 1 to 14 carbon atoms .is. It is described that these compounds in Protective coatings against bacteria, fungi, termites and barnacles can be used.

In. U.S. Patent 3,725,446 describes some similar compounds (RS-CHp-Sn-R ') where R is alkyl of 1 to 14 carbon atoms, aryl or substituted aryl and R ^{1 is} alkyl of 1 to 14 carbon atoms. These compounds are said to have herbicidal activity before germination and after germination

The German patent 2 106 04o (US Pat. No. 3,784,580 to Peterson) also describes compounds of the formula (R) ^ SnCHp-X, in which X is alkylsulphonyl, -arylsulphonyl or dialkylsulphamoyl, the compounds - & 1b being pesticides and acaricides are usable. ·.

The. described in the two German patents Connections, -üie-discussed immediately before, 'under-. differ from the compounds of the invention in that ·· ■ - ·

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the "X" side part with the tin atom through a single Methylenediradikai instead of a diradical with at least two carbon atoms is connected.

In the reference: Peterson, "Preparation and Reactions of Some Sulfur-Substituted Tetraorganotin. Compounds ", J. Organometal. Chem. _2j5, 215-223 (197D, it says on page 218:

"It has been found that i_ (Phenylsulfonyl) methyl] tributyltin! (IV)] is unreactive towards carbon dioxide and oxygen at room temperature, while exposure of a thin layer of (IV) to air causes about 50 % decomposition to phenylmethylsulfone and tributyltin oxide within four days. These findings, when considered in context, are consistent with the hydrolysis responsible for the air sensitivity of (IV). "

In U.S. Patent 3,794,670 (Peterson) a Process for preparing (organosulfonylmethyl) triorganotin compounds described, wherein one triorgan.tin amine and reacting an organosulfonylmethyl compound.

In the reference: Ayvey et al., J. Organometal. Chem. 25, 105-109 (1972), in which the preparation of 3 ~ (trialkylstannyl) propylaryl sulfides, R ^ SnCH ₂ CH ₂ CH ₂ SR 'is described, is not a possible application for these compounds

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listed.

■ In US Pat. No. 3,031,483, compounds the structure '

-Sn - Q

described in which IL, Rp and FU the same or different can be and alkyl groups with 1 to 12 carbon atoms, Denote phenyl groups or pialogenphenyl groups, and Q one of a number of groups including OSCgHjiCHL (ρ) represents. These compounds have fungicidal and bactericidal properties Properties on.

The new organotin compounds of the invention are tetrasubstituted tin compounds with the general

Formula:

R ¹

(I) (CH ₃ ) ₃ Sn (CH ₂ ) _n -CH-X.

where:.

R ^{1 is} hydrogen, hydroxyl, methyl or ethoxy; X has one of the following meanings:

(a) -SO ₂ R ₁ , where R ^{1 is} hydrogen, and where R _{1 is} a straight-chain or branched alkyl having 1 to 18 carbon

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atoms, cyclohexyl, benzyl, phenyl or phenyl, which is substituted with one or more groups, which can be the same or different and which are linear or branched alkyl with 1 to 20 carbon atoms, a cycloaliphatic radical with 4 to 6 carbon atoms, straight-chain or branched alkenyl with 2 to 20 carbon atoms, alkoxy with 1 to 8 carbon atoms, alkylthio with 1 to 8 carbon atoms, halogen, nitro, acetyl, acetamido, carboxy, alkoxycarbonyl, carbamoyl, cyano, hydroxy, trifluoromethyl, benzyl, naphthyl or norbornyl; Naphthyl, biphenylyl, piperidinoethyl methiodide, -R ₅ Sn (CH,). ,, where R _{p is} polymethylene of 2 to 11 carbon atoms, or -R _{11 is} SO ₂ Kj-Sn (CH,), where. R ^ is ethylene and R ₁ - is as defined above Rp;

(b) -OR ₇ , where R 'is hydrogen, and where R "is a straight-chain or branched alkyl with 8 to Ib carbon atoms, aryl, alkoxyaryl, alkaryl, haloaryl, N, N-dialkylarainoalkyl, or -RgSn (CH,), where Rn is alkylene with 2 to 11 carbon atoms, a cycloaliphatic radical with 4 to 6 carbon atoms, "or tetrahydro-l, l-dioxy-3-thienyl;

(c) -SR ^ q, where R? Is hydrogen and wherein R _{10 is} a straight-chain or branched alkyl having 1 to 16 carbons. Atoms of substance, phenyl, chlorophenyl, t-butylphenyl or -R ₂ Sn (CH,), is; .

(d) -COR ^, where R ^{1 is} hydrogen, and where R ₁₁

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-NHR ₁₂ , where R ₁₂ - is straight-chain or branched alkyl having 1 to 12 carbon atoms or aryl; -NKCH ₂ OH; -NHNK ₂ ; -NHCH ₂ NHCOR ₂ Sn (CH); or -OR ₁ , where R _{1 is} straight-chain or branched alkyl having 8 to 15 carbon atoms; - (CH ₂ ) OH, where m is an integer from 2 to ^; - (CH ₂ ) N (R ₁ Jj) ₂ , where p "is an integer from 2 to 4 and R ₁ J is a straight or branched chain alkyl having" 1 to 5 carbon atoms; - (CH ₂ ) OCQR ₂ Sn (CH,) ,, wherein q is as defined above ρ; or - (CHp) N (CH,), J.

<- S yy

is where s is as defined above ρ;

(e) -NHCONH ₂ ', where R ^{1 is} hydrogen; ". (f) -NHCSNH ₂ , where R ^{1 is} hydrogen; '

(g) 1-immazolyl, where R ^{1 is} hydrogen;

(h) N-2-i-oxopyrrolidinyl, where R ^{1 is} hydrogen;

(i) -OCOR ₁₇ where R 'is hydrogen and where R _{17 is} -NHR ₁ O where R ₁ Q is straight or branched chain alkyl of 1 to 5 carbon atoms; 2-furyl; or -0 (CH ₀ ), Sn (CH,),

^ w J ¹ J

is where t is 2 to 11;

(j) -PO- (OR ₂₀ ) p, where R ¹ 'is hydrogen or ethoxy, and where RpQ is straight-chain or branched alkyl having 1 to 5 carbon atoms; '-' (k) - tetrahydro - !, l ^ dioxo-2-thenyl, where R ^{1 is} hydroxyl;

(1) -Si (ORJ ₁ ), - _% wherein R ^{1 is} hydrogen, and wherein Rp _{1 is} straight or branched alkyl having 1 to 5 carbon atoms; "■.."'' .. ^: '■ ·

"-CH ₂ Sn (CH ^) - Cj where R 'is methyl;

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where R ^{f is} hydrogen j

(b) 2-pyridyl; (ρ) 4-pyridyl;

(q) 2-alkyl-5 - "* pyridyl; and η is an integer of Ibis 10 is. .

The term "aryl" as used in this specification and is used in the claims also includes phenyl and substituted phenyl, e.g. phenyl which is substituted with a halogen (s) or alkyl group (s) with 1 to 4 carbon atoms substituted

tl

is tuated. X can also be "SRpo, where Rpg is a straight chain or branched alkyl with 1 to 18 carbon atoms, cyclohexyl, Is benzyl, phenyl, t-butylphenyl or chlorophenyl.

Palls X is -SOpR ^, a preferred group of compounds is that in which R. is straight-chain or branched alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, bicyclo {2.2. l] heptyl, benzyl, phenyl, alkoxyphenyl with 1 to 3 carbon atoms in the alkoxy group, halophenyl, piperidinoäthy lmethjodid, -R ₂ Sn (CH-,) ,, where Rp is polymethylene with 2 to 11 carbon atoms, or · R ₁ , SOpR ₁ -Sn (CH,) -, where R 1 is ethylene and R ₁ - is as defined _{above R 2.}

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These and other organotin compounds of the invention have been found to have a wide variety of Exhibit activities. For example, they have been found to be useful as insecticides, acaricides and herbicides.

The compounds exhibiting these and derived usabilities are tetra-substituted tin compounds with the general formula

. (II) '. (CH ₃ ) ₃ Sn (CH ₂ ) ^ GH-X i

wherein R ^{1 is} hydrogen, hydroxyl, alkoxyl or a straight-chain or branched alkyl group having 1 to 5 carbon atoms; -.

X has one of the following meanings:

Ca) '- SOpR. where R 'is hydrogen and where R is straight-chain or branched alkyl with 1 to 18 carbon atoms, Cyclohexyl, benzyl, phenyl or phenyl which is substituted with one or more groups which are the same or can be different and which linear or branched alkyl having 1 to 20 carbon atoms, a cycloaliphatic Remainder with 4 to 6 carbon atoms, straight-chain or branched Alkenyl with 2 to 20 carbon atoms, alkoxy with 1 to 8 carbon atoms, halogen, nitro, acetyl ,. Acetamido, Carboxy, alkoxycarbonyl, carbamoyl, cyano, hydroxy, trifluoromethyl, Can be benzyl, naphthyl or norbonyl; Naphthyl,

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Biphenylyl, piperidinoethyl methiodide, -R ₃ Sn (CH ₃ J ₃ , where R _{2 is} polymethylene having 2 to 11 carbon atoms, or -R _{4 is} SO ₂ RcSn (CH ₃ J ₃ , where R _{4 is} ethylene and R ^ as R above _{3 is} defined;

(b) -OR ₇ , in which Rn is a straight-chain or branched alkyl having 1 to 20 carbon atoms, haloalkyl, aryl, haloaryl, alkaryl, alkoxyaryl, epoxyalkylene, in which the alkylene group has 2 to 4 carbon atoms, N, N-dialkylaminoalkyl, tetrahydro-1 , l-dioxo-3-thienyl, or -R ₈ Sn (CH ₃ J ₃ , where Rq is alkylene with 2 to 11 carbon atoms, a cycloaliphatic radical with 4 to 6 carbon atoms or aryl

(c) ~ SR, _O , where R ^{1 is} hydrogen and where R, _{Q is} a straight-chain or branched alkyl having 1 to 18 carbon atoms, cyclohexyl, benzyl, phenyl or phenyl which is substituted by one or more groups which - · the same or can be different and which are linear or branched alkyl with 1 to 20 carbon atoms, a cycloaliphatic radical with 4 to 6 carbon atoms, straight

6 0 9827/1 022 · ■

chain or branched alkenyl with 2 to 20 carbon atoms, alkoxy with 1 to 8 carbon atoms. atoms / alkylthio with 1 to 8 carbon atoms / halogen, nitro ,, acetyl, acetamido, carboxy, alkoxycarbonyl, carbamoyl ,, cyano., hydroxy, trifluoromethyl, benzyl, naphthyl or norbonyl; Naphthy 1, biphenylyl, piperidinoethyl methiodide, -R ₂ Sn (CH ₃ ). ,, where R- is polymethylene of 2 to 11 carbon atoms, or -R _{4 is} SO ₃ R ₅ Sn (CH ₃ ) ₃ , where R _{4 is} ethylene and R _{5 is defined} as R ₃ above;

(d) -COR ₁₁ ZWOrIn R ₁₁ -NH ₃ , -NHNH ₃ , -NHCH ₂ OH, where R _{13 is} straight-chain or branched alkyl having 1 to 12 carbon atoms or aryl; -NHCH ₂ NHCOR ₂ Sn (CH ₃ ) or -ORh 71st, where R ,, is straight-chain or branched

Alkyl with 1 to 15 carbon atoms, - (CI ^^ OH, wherein m is an integer from 2 to 4, "

) N (R ₁₄ V ₂ ,

where ρ is an integer from 2 to 4 and R _{14 is} a straight-chain or branched alkyl having 1 to 5 carbon atoms, - (CH-) OCOR ₉ Sn (CH-,). ,, where q is defined as ρ above

- Θ θ is nated, or - (CH-) N (CH ₃ ) ₃ J, where s is as above

ρ is defined;

(e) -NHCONH ₂ ;

(g) 2-pyridyl; _. .. _: /.-. (h) 4-pyridyl;

(i). 2-alkyl-5-pyridyl ;. . _ ■ _. . ,

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(j) 9-carbazolyl;

(k) 1-imidazolyl;

(1) N-2-oxopyrrolidinyl;

(m) -OCOR ₁₇ , wherein R ₁₇ -NHR ₁ Q, wherein R ₁ Q is straight or branched alkyl having 1 to 5 carbon atoms or aryl; 2-furyl; or -0 (CH ₃ ) _t Sn (CH ₃ ) ₃ , where t is an integer from 2 to 11;

(n) -PO (OR ₂₀ ) 2 / wherein R _{30 is} straight or branched chain alkyl of 1 to 5 carbon atoms;

(o) tetrahydro-1,1-dioxo-2-thenyl;

(p) -Si (OR ₂₁ ) ₃ , wherein R _{21 is} straight or branched chain alkyl of 1 to 5 carbon atoms;

-C-CH ₂ Sn (CH ₃ ) ₃ ;

(r) Cyanoj
(s) GH; ■

and η is an integer from 1 to 10.

The insecticidal, acaricidal and herbicidal activities of the compounds of the invention have been found to originate from the trimethyltin portion of the molecule / ie (CH ₃ J ₃ Sn-. The level and nature of the activity

6 0 9 8 2 7/1 0 2

of these compounds is further influenced by the

R ¹ that part of the molecule that has the _ _(ru * '"" residue,

Ιν-Π— / CHA

contains; these include, for example, phytotoxicity for useful plants, herbicidal active; 'cä ^; For harmful plants, uptake and distribution in plants, retention in the soil, oral and / or dermal toxicity to mammals, control of physical properties such as volatility and solubility, hydrolytic and / or oxidative stability, sensitivity to ultraviolet sunlight, ease of entry into the food chain , Degradation by microorganisms and / or higher life forms, and convenient preparation and usable rate of use.

In general, the compounds according to the invention according to the one-step reaction method used by R.Sommer and H.G. Kuivila in J. Org. Chem. 3 ^, 802

(1968) was obtained. This method comprises reacting a compound containing an olefinic side chain with trimethyltin hydride according to the following scheme; .

■ "R ^1. R" ■ '■ R ¹ R "

¹ Il

(A) (CH ₃ J ₃ SnH + H ₂ C = C- (CH) _m -X>

wherein X is as defined above, R ^{1 can be} hydrogen, a straight-chain or branched alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and R "can be hydrogen, hydroxyl, or an alkyl group having 1 to 5 carbon atoms and m is an integer from 0 to 9.

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This synthesis uses the substituted olefinic compounds and an equivalent amount of the organotin hydride in a conventional glass reaction vessel under an inert atmosphere in the presence of a suitable one Solvent, where desired or when necessary, and used with adequate agitation. The reaction mixture is irradiated by a mercury vapor lamp, until no more organotin hydride is present, which can be determined by analysis of the. Infrared spectrum while observing the absence the additional Sn-H absorption is determined. The time required for this will depend on the particular The substituted olefinic compound used will vary, but will generally be from about 4 to 48 times Hours, but it can if η is 3 or greater / up to 232 hours. The reaction mixture will normally held at a temperature of about 0 ° to 50 ° C. In cases where the reactants are heterogeneous and / or if the starting material is a solid, ether solvents can be used such as diethyl ether and tetrahydrofuran, aromatic Solvents, such as benzene and toluene, esters and nitriles, such as ethyl acetate and acetonitrile> Alcohols such as methanol and ethanol, amides such as dimethylformamide, and the like are used, to facilitate mixing of the reactants.

An MpI of an unsaturated sulfon that passes through Addition of one mole of the organotin hydride m, iIb one. Mole of one Sulphone, with a proportion of two unsaturated (-C = C -) groups,

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for example, divinyl sulfone is formed, may also according to the above (A) with reagents, ^T - ^r fiarcaptanen ie, amines, alcohols and phenols are reacted. The following equations, in which the starting sulfone is divinyl sulfone, as in Example 3 below, illustrate this aspect

the invention:

HH - H

I I I

(B) (CHj ₃ SnH + H ₂ C = C-SO ₂ -C = CH ₀ - / (CH) "SnCH" CH SO C = CH ₂

JI

where Z (CH ₃ ) ₃ Sn ~, (R ₂₄ ) ₃ Si-, ( ^Κ 25 ^ 2 ^Ν ~ ' ^R 26 ^S ~ ^{Ocler can be a R} 27 ° ~ group; R-., R ₂₅ ' ^R ₂ p ^{and R} 27 may be ^a straight or branched alkyl group having 1 to 5 carbon atoms or an aryl group.

Using the same general method described for obtaining the organotin compound from (A) can be two equivalents of organotin hvdrids can be reacted to form an adduct containing two organotin side chains according to the following equation

form:

R ¹ R "R" R ¹ ti ι ι

(D) 2 (CHJ SnH +

R ¹ R "R" R ¹

wherein R ¹ , R "and m are as defined above, w can

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a sulfonyldiradical (-S0-) as in compounds 1 and 2 in Table I below, a 1,2-ethylenedisulfonyldiradical (-SO ₂ -CH ₂ -CH ₂ -SO ₂ -), as in compound 17 in Table I below, an oxydiradical (-0 -), as in compounds 25 and 26 in Table I below, a thiodiradical (-S-), as in compound 36 in Table I below, _a N, N'-methylenebis-

Il Il

carbamoyldiradical (-C-NHCH ₂ NHC-), as in compound 41 in Table I below, a 1,2-.J \ thylenedioxydicarbonyldiradical (-CO-CH ₂ CH ₂ -OC-), as in compound 45 in Table I below , a carbonyldioxydiradi-

cal (-0-Ö-0), as in connection 52 in the table below I, a phenylenediradical,

as in compound 60 in Table I below and a 2,4,8,10-Tetraoxaspiro | 5.5J undec-3, 9-ylenediradical with the structure:

as in compound 63 in Table I below. The preparative method is the same as the one that for Scheme (A) above, except that two equivalents of the organotin hydride are required, when the other reactant contains two olefinic side chains.

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- If desired, the organotin compound can be purified using standard distillation, column chromatography or recrystallization.

On the other hand, the inventive compounds by the process of British patent specification 966 813 (Karl Ziegler) using the usual free radical formers, such as azobisisobutyronitrile, azotriphenylmethane and the like.

In this way, a wide variety of substituted olefinic compounds can be used to make to prepare the connections according to the invention. Examples such compounds are listed below and divided into groups according to their main function. Additionally the connection numbers are also displayed in which certain connectionsTi from the list were used, where the number for the compounds according to the invention is representative. These connections are even more complete in marked below in Table I.

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Sulf one Y ⁶ JL *? Indun ^ No.

Divinyl sulfone; 1,2,16 2554790

Methyl vinyl sulfone; 3

Ethyl vinyl sulfone; . 4 n-propyl vinyl sulfone;

Isopropyl vinyl sulfone; 5

n-eutyl vinyl sulfone;

sec-butyl vinyl sulfone; 6th

tert-butyl vinyl sulfone; η-pentyl vinyl sulfone;

Isopentyl vinyl sulfone;

sec-pentyl vinyl sulfone;

tert-pentyl vinyl sulfone; 7th

n-hexyl vinyl sulfone;

Cyclohexyl vinylsulfon; 11

4-methylcyclohexyl vinyl sulfone; Methallyl vinyl sulfone;

n-octyl vinyl sulfone; 8th

tert-octyl vinyl sulfone;

Benzyl vinyl sulfone; 12th

4-chlorobenzyl vinyl sulfone; Phenyl vinyl sulfone; . 13th

p-tolyl vinyl sulfone; 6 6

o-ethylphenyl vinyl sulfone; p-ethylphenyl vinyl sulfone; 67 p-n-propylphenyl vinyl sulfone; p-i-propylphenyl vinyl sulfone; 68 p-n-butylphenyl vinyl sulfone; p-butylphenylvinylsulfine; p-t_-butylphenylvinylsulfone; 14th

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-ZO--

p-1- butylphenyl vinyl sulfone;

p-n-amylphenyl vinyl sulfone; 69

p-t-arylphenyl vinyl sulfone; 70

pn-hexylphenyl vinyl sulfone;
pn-heptylphenyl vinyl sulfone;

p-n-octylphenyl vinyl sulfone; 71

pt-octylphenyl vinyl sulfone;
p-nonylphenyl vinyl sulfone;
p-decylphenyl vinyl sulfone;

p-dodecylphenyl vinyl sulfone; 72

p-n-dodecylphenyl vinyl sulfone; 73

p-tridecylphenyl vinyl sulfone; 74

p-cyclopentylphenyl vinyl sulfone; 79

p-cyclohexylphenyl vinyl sulfone; 80

p-bicyclo £ 2.2. Ϊ] -hept-2-ylphenylvinylsulfone * 81 3, 4-dimethylphenylvinylsulfone;
2,4-diraethylphenyl vinyl sulfone; 75

2,5-dimethylphenyl vinyl sulfone; 76

2,4-diethylphenyl vinyl sulfone; 77

2,5-diethylphenylvinylsulfon, -2, 4-diisopropylphenylvinylsulfon;
2,5-diisopropylphenyl vinyl sulfone; 78 2,5-di-t-butylphenyl vinyl sulfone;
2,5-dicyclohexylphenyl vinyl sulfone;
2,4,6-trimethylphenyl vinyl sulfone;
2,4,6-triethylphenyl vinyl sulfone;
2, 4_, 6-triisopropylphenyl vinyl sulfone;
2,3,5,6-tetramethylphenyl vinyl sulfone;
2,3,4,5,6-pentamethylphenyl vinyl sulfone;

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p-allyl phenyl vinyl sulfone; p-propenylphenyl vinyl sulfone; p-crotylphenyl vinyl sulfone; p-methallylphenyl vinyl sulfone; p-4-pentenylphenyl vinyl sulfone; p-3-methylcrotylphenyl vinyl sulfone; p-oleylphenyl vinyl sulfone; p-methoxyphenyl vinyl sulfone; p-ethoxyphenyl vinyl sulfone; p-butoxyphenyl vinyl sulfone; p-octoxyphenyl vinyl sulfone; 2,4-dimethoxyphenyl vinyl sulfone; 2,5-dimethoxyphenyl vinyl sulfone; 3,4-diraethoxyphenyl vinyl sulfone; p-methylthiophenyl vinyl sulfone; p-butylthiophenyl vinyl sulfone; p-octylthiophenyl vinyl sulfone; 5-chloro-2-methoxyphenyl vinyl sulfone; 2-chloro-4-methoxyphenyl vinyl sulfone; 3-chloro-4-yne ethoxyphenyl vinyl sulfone; 5-bromo-2-methoxyphenyl vinyl sulfone; 2-bromo-4-methoxyphenyl vinyl sulfone; 3-bromo-4-methoxyphenyl vinyl sulfone; 3-acetamido-4-methoxyphenyl vinyl sulfone; 5-acetamido-2-methoxyphenyl vinyl sulfone; 5-nitro-2-methoxyphenyl vinyl sulfone; 2-nitro-4-methoxyphenyl vinyl sulfone; 3-nitro-4-methoxyphenyl vinyl sulfone; 2-methy1-4-methoxyphenyl vinyl sulfone;

2-methyl-5-methoxyphenyl vinyl sulfone; 6 0 9 8 2 7/1022

■ i-methyl-S-chlorophenyl vinyl sulfone;

2-methyl-5-bromophenyl vinyl sulfone; ^ ^υ

p-fluorophenyl vinyl sulfone; 84

p-broinphenyl vinyl sulfone; 83

p-chlorophenyl vinyl sulfone; 15th

2,5-dichlorophenyl vinyl sulfone; * "

3,4-dichlorophenyl vinyl sulfone; 85

2,4,5-trichlorophenyl vinyl sulfone; Trifluoromethylphenylvinylsulfone; 4-chloro-3-nitrophenyl vinyl sulfone; 3-nitrophenyl vinyl sulfone;

2-nitrophenyl vinyl sulfone;

3, S-dichloro-Z-hydroxyphenyl vinyl sulfone; p-acetamidophenyl vinyl sulfone; p-carboxyphenyl vinyl sulfone;

p-alkoxycarbonylphenyl vinyl sulfone; p-carbamoylphenyl vinyl sulfone; p-cyanophenyl vinyl sulfone;

p-acetylphenyl vinyl sulfone;

2-naphthyl vinyl sulfone; 86

4-biphenyl vinyl sulfone;

n-dodecyl vinyl sulfone; 9

n-octadecyl vinyl sulfone; 10

1,2-ethylene bis (vinyl sulfone); 17th

1-ethyl-1,2-ethylene bis (vinyl sulfone); 1,4-tetramethylene bis (vinyl sulfone); 1,6-hexamefchylenebis (vinyl sulfone); 1,8-octamethylene bis (vinyl sulfone); 2,2-propylidene bis (vinyl sulfone); 1 / 1'-methylenebismethylvinylsulfone;

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2- (trimethylstannyl) ethyl vinyl sulfone; Methyl 3-butenyl sulfone; Ethyl 4-pentenyl sulfone; n-propy1-5-hexenyl sulfone; Isopropyl 6-heptenyl sulfone; n-butyl-7-octenyl sulfone; sec-butyl-8-nonenyl sulfone; tert-buty1-9-decenyl sulfone; n-pentyl-10-undecenyl sulfone; Isopentyl-3-butenyl sulfone; sec-pentyl-4-pentenyl sulfone; tert-Penty1-5-hexenylsulfone; n-hexyl-6-heptenyl sulfone; Cyclohexyl-7-octenyl sulfone; 4-methylcyclohexyl-B-nonenyl sulfone; Methallyl-9-decenyl sulfone; n-octyl-10-undecenyl sulfone; tert-octyl-3-butenyl sulfone; Benzyl-4-pentenyl sulfone; 4-chlorobenzyl-5-hexenyl sulfone; 6-hexenylphenyl sulfone; 3-butenyl-p-tolyl sulfone; 3-buteny1-p-t-butylphenylsulfone; 4-pentenyl-p-ethylphenyl sulfone; 5-hexenyl-p-tolylphenyl sulfone; 6-heptenyl-p-n-propylphenylsulfone; 7-octenenyl-p-i-propylphenyl sulfone; 8-nonenyl-p-n-butylphenyl sulfone; 9-decenyl-p-s-butylphenylsulfone; iO-undecenyl-p-tolylsulfone;

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4-pentenyl-p-i-butylphenylsulfon; 5-lexenyl-pn-amylphenylsulfone; 6-heptenyl-t-amylphenyl sulfone; 7-octenyl-pn-hexylphenylsulfone; 8-nonenyl-pn-heptylphenylsulfone; 9-decenyl-p-octylphenyl sulfone; 10-undecenyl-t-octylphenylsulfone; 3-butenyl-p-nonylphenyl sulfone; 4-pentenyl-p-decylphenyl sulfone; 5-hexenyl-pn-dodecylphenylsulfone; 6-heptenyl-p-dodecylphenylsulfone; 7-octenyl-p-tridecylphenylsulfone; 8-nonenyl-p-cyclopentylphenylsulfone; 9-decenyl-p-cyclohexylphenylsulfone; 10-undecenylbicyclo [_2.2.1] hept-2-ylphenylsulfone; 3-butenyl-3,4-diraethylphenyl sulfone; 4-pentenyl-2,4-dimethylphenyl sulfone; 5-hexenyl-2,5-dimethylphenylsulfone; 6-heptenylr2,4-diethylphenylsulfone; 7-octenyl-2,5-diethylphenyl sulfone; 8-nonenyl-2,4-diisopropylphenyl sulfone; 9-decenyl-2,5-diisopropylphenyl sulfone; 10-undecenyl-2,5-di-t-butylphenyl sulfone; 3-butenyldicyclohexylphenylsulfone; 4-pentenyl-2,4,6-trimethylphenyl sulfone; 5-hexenyl-2,4, 6-triäthylphenylsulfon; 6-heptenyl-2,4,6-triisopropylphenyl sulfone; 7-octenyl-2,3,5,6-tetramethylphenyl sulfone; 8-nonenyl-2,3,4,5,6-pentamethylphenylsulfone; 9-decenyl-p-methoxyphenyl sulfone;

609827/10 ^ 2

- 2S-

10-undecenyl-p-ethoxyphenyl sulfone; 9 ξ R Λ 7 Q Π

3-butenyl-p-butoxyphenyl sulfone; 4-pentenyl-p-octoxyphenyl sulfone; 5-hexenyl-2,4-dimethoxyphenyl sulfone; 6-heptenyl-2,5-dimethoxyphenyl sulfone; 7-octenyl-3,4-dimethoxyphenyl sulfone; 8-nonenyl-p-methylthiophenyl sulfone; 9-decenyl-p-butylthiophenyl sulfone; 10-undecenyl-p-oetylthiophenyl sulfone; 3-butenyl-5-chloro-2-methoxyphenyl sulfone; 4-pentene 1-2-chloro-4-ynethoxypheny lsulfon; 5-hexenyl-3-chloro-4-methoxyphenyl sulfone; 6-heptenyl-5-bromo-2-methoxyphenylsulfone; 7-octenyl-2-bromo-4-methoxyphenyl sulfone; 8-nonenyl-3-bromo-4-methoxyphenyl sulfone; 9-decenyl-3-aceta ₁ iiido-4-inethoxyphenylsulfon; 10-Undeceny1-5-acetamido-2-methoxyphenylsulfone; 3-butenyl-2-nitro-4-methoxyphenylsulfone; 4-pentenyl-3-nitro-4-methoxyphenyl sulfone; 5-hexeny1-2-methy1-4-methoxyphenylsulfone; 6-hepteny1-2-methy1-5-methoxyphenylsulfone; 7-octenyl-2-methyl-5-chlorophenyl sulfone; 8-nonenyl-2-methyl-5-bromophenyl sulfone; 9-decenyl-p-fluorophenyl sulfone; 10-undecenyl-p-bromophenyl sulfone; 3-butenyl-p-chlorophenyl sulfone; 4-pentenyl-2,5-dichlorophenyl sulfone; 5-hexenyl-3,4-dichlorophenyl sulfone; 6-heptenyl-2,4,5-trichlorophenyl sulfone; 7-octenyl trifluoromethylphenyl sulfone;

6 0 9 8 2 7 / I Ü 2 2

8-nonenyl-4-chloro-3-nitrophenyl sulfone; 9-decenyl-3-nitrophenyl sulfone;
10-undecenyl-2-nitrophenyl sulfone;
3-butenyl-3,5- <3ichlor-2-hydroxyphenyl sulfone;
4-pentenyl-p-acetamidophenyl sulfone;
5-hexenyl-p-carboxyphenyl sulfone;
6-heptenyl alkoxycarbonylphenyl sulfone;
7-octenyl-carbamoylphenylsulfone;
8-nonenyl cyanophenyl sulfone;
Si-decenyl-p-acetylphenylsulfone;
10-undecenyl-2-naphthylsulfone;
3-butenyl-4-biphenylyl sulfone;
4-pentenyl-n-dodecyl sulfone;
5-hexenyl-n-octadecyl sulfone.

2. Ether

Divinyl ether; . 2 5

Ethyl vinyl ether; 18th

n-propyl vinyl ether;
Isopropyl vinyl ether;

. n- butyl vinyl ether Ί 19

Isobutyl vinyl ether? 20th

n-pentyl vinyl ether;
n-hexyl vinyl ether;
Cyclohexyl vinyl ether;
n-octyl vinyl ether;

Isooctyl vinyl ether; 21

n-decyl vinyl ether; ■ 22

n-dodecyl vinyl ether; 23

Hexadecyl vinyl ether; 3 3

B 0 9 8 2 7/1 ü 2 2

Benzyl vinyl ether; 2 O O 4/9 U

2,2,2-trifluoroethyl vinyl ether; 31

Phenyl vinyl ether;

p-chlorophenyl vinyl ether;

o-tolyl vinyl ether;

p-methoxyphenyl vinyl ether;

2,6,8-trimethyl-4-nonyl vinyl ether; 65

N, N-dimethylaminoethyl vinyl ether; 32

Diallyl ether; 26th

Allyl glycidyl ether; 24

Allyl phenyl ethers; ■ 27

Allyl p-tert-butylphenyl ether; 28

Allyl p-methoxyphenyl ether; 29

Allyl p-chlorophenyl ether; 30th

Allyl (tetrahydro-l, l-dioxo-3-thienyl) ether; 34 1,4-divinyloxybutane;

3-vinyl-7-oxabicyclo \ _A. 1. OJheptane;

3,9-diviny1-2,4,8,10-tetraoxaspiro \ 5.5jundecene; 6 3-butenyl vinyl ether;

Di (3-butenyl ether;

4-pentenyl ethyl ether;

5-IIexenyl-n-propylene ether;

6-heptenyl isopropyl ether;

7-octenyl-n-butyl ether;

8-nonenyl isobutyl ether;

9-decenyl-n-pentyl ether;

10-undecenyl-n-hexyl ether;

3-butenylcyclohexyl ether;

4-pentenyl-n-octyl ether;

5-hexenyl isooctyl ether;

609827/1022

- Z8 -

6-heptenyl-n-ndnyl ether; 7-octenyl-n-decyl ether; 8-nonenyl-n-dodecyl ether; 9-decenyl hexadecyl ether ;.

10-undecenyl benzyl ether; 3-butenyl-2,2,2-trifluoroethyl ether; '4-pentenylphenyl ether; 5-hexenyl-p-chlorophenyl ether; 6-heptenyl-o-tolyl ether; 7-octenyl-p-methoxy ether; 8-nonenyl-2,6,8-trimethyl-4-nonyl ether; 9-decenyl-N, N-dimethylaminoethyl ether; 3-butene-nyl-N, N-dimethylaminoethyl ether; 3-bis-iitenyl allyl ether; ■ · 4-eeutyl glycidyl ether; 5-hexenylphenyl ether; 6-neptenyl-p-methylphenyl ether; 7-octenyl-p-t-butylphenyl ether; 8-nonenyl-p-methoxyphenyl ether; 9-decenyl-p ~ chlorophenyl ether; 1O-undecenyl-p-bromophenyl ether; 3-butenyl-p-trifluoromethylphenyl ether; 4-penteny1-p-methoxyphenyl ether; 5-hexenyl (tetrahydro-1,1-dioxo-3-thienyl) ether.

3. Thioether

Diallylsulfide; ■ allyl methyl sulfide; · Allyl ethyl sulfide;

Allyl n-propyl sulfide; 6 0 9 8 2 7/1022

- J \ Q -

Allylisopropylsulfide; Allyl n-butyl sulfide; Allyl isobutyl sulfide; Ally1-n-pentyl sulfide; Allyl n-hexyl sulfide; Allyl cyclohexyl sulfide; Allyl n-octyl sulfide; Allyl isooctyl sulfide; Allyl decyl sulfide; Allyl hexadecyl sulfide; Allyl benzyl sulfide;

/ vllylphenylsulfide; 3

AlIy1-p-chlorophenyl sulfide; Methyl vinyl sulfide; Ethyl vinyl sulfide; n-propyl vinyl sulfide; n-butyl vinyl sulfide; n-hexyl vinyl sulfide; Cyclohexyl vinyl sulfide; n-octyl vinyl sulfide; Ilexadecy! Vinyl sulfide; Allyl vinyl sulfide; Benzyl vinyl sulfide; Phenyl vinyl sulfide; p-tert-butylphenyl vinyl sulfide; o-tolyl vinyl sulfide; p-chlorophenyl vinyl sulfide; 3-butenylraethyl sulfide; 4-pentenyl sulfide; 5-hexenyl-n-propyl sulfide; Ö0982 7 ⁷ 1Ü2?

6-heptenyl isonropyl sulfide; 7-octenyl-n-butyl sulfide; 3-nonenyl isobutyl sulfide; 9-decenyl-n-pentyl sulfide; Ig-undecenyl-n-hexyl sulfide; 3- · 3utenylcyclohexyl sulfide; 4-pentenyl-n-octyl sulfide; 5-hexenyl isooctyl sulphide; 6-IIeptenyldecylsulfide; 7-octenylhexadecyl sulfide; 8-nonenylbene sulfide; 9-decenyl phenyl sulfide; 10-unecenyl-p-chlorophore.yl sulfide; 3-butenylbenzyl sulfide; 4-pentenyl-p-tert-butylphenyl sulfide; 5-hexenyl-o-tolyl sulfide; 6-Hepteny.l-p-bronphenylsulfid; Di (3-butenyl) sulfide.

4. Esters

Divinyl carbonate; Diallyl carbonate;

609827/1022

Dimethallyl carbonate;

Allyl-N-methylcarbanuit; 54

Allyl N-ethyl carbamate; Allyl-N-propylene carfoarnate; Allyl-IJ-n-butyl carbamate; .Allyl-K-n-cctyiccirbaraat; Ally I-il-uodecy lcarbaraat; Ally 1-IJ-phenyl carbainate;

Allyl 2-furoate; 53 '

Methyl aerylate;

Λ "thy! Acryl at; 42, 43

n-propyl acrylate; Isopropyl acrylate; n-butyl acrylate; n-pentyl acrylate; n-hexyl acrylate; Cyclohexyl acrylate; n-octyl acrylate; n-decyl acrylate;

n-dodecyl acrylate; 44

n-octadecyl acrylate; Benzyl acrylate; Plienyl acrylate; p-chlorophenyl acrylate j

1/2 ethylene diacrylate; 45

• 1,4-tetrainethylene diacrylate; 1, S-hexamethyl iidiacrylate; 1, e-octalethylenedlacrylate; 1, 10-decamethylene diacrylate; 1,12-dodecamethylenediacrylate; Methyl methacrylate;

809827/1022

Ethyl methacrylate;

Isopropyl methacrylate;

n-butyl methacrylate; ·

Hexyl methacrylate; Cyclohexyl methacrylate; n-octyl methacrylate;

n-decyl methacrylate; . ·

n-dodecyl methacrylate; 2-hydroxyethyl methacrylate; Benzyl methacrylate; Allyl methacrylate; Phenyl methacrylate; p-chlorophenyl methacrylate; tert-butylapiinoethyl methacrylate; N-N-dimethylaminoethyl methacrylate; 1,2-xethylene dimethacrylate; 1,4-tetramethylene dimethacrylate; 1,6-hexainethylene diraethacrylate; 3-butenyl vinyl carbonate; 4-pentenyl allyl carbonate; 5-hexenyl methallyl carbonate; 6-heptenyl-N-methylcarbainate; 7-octenyl-N-ethyl carbamate; 3-Nonenyl-N-propylcarbaip.at; 9-decenyl N-n-butyl carbamate; 10-undecenyl-N-n-octyl carbamate; 3-butenyl-N-dodecylcarbaraate; 4-pentenyl-N-phenylcarbamate; 5-hexenyl 1-2 furoate;

6098 2 7/1022

- 33 Hethyl 1-6-hentenoate;

Ethyl 7-octenoate; n-propy 1-8-noneiioate; Isopropyl 9-decenoate; n-eutyl-10-undecenoate? n-pentyl 3-butenoate; n-i-exyl-4-pentenoate; Cyclohexyl 5-hexenoate; n-octyl 6-heptenoate; n-decyl 7-octenoate; n-dodecyl-8-nonenoate; n-octadecyl Q-decenoate; Benzyl 10-undecenoate; Phenyl 3-butenoate; p-chlorophenyl 4-pentenoate; 1,2-ethylenedi (4-pentenoate); ' 1,4-tetramethylenedi (5-hexenoate); 1,6-hexamethylenedi (6-heptenoate); 1,8-octamethylene di (7-octenoate); 1,10-decamethylene diol (8-nonenoate); 1,12-dodecamethylenedi (9-deceneoate); Methyl 1-methyldi (10-undecenoate); Ethyl 1-methyl-3-butenoate; Propyl 1-methyl-4-pentenoate; Isonropyl 1-methyl-5-hexenoate; n-butyl-1-methyl-6-heptenoate; Hexyl 1-ir.ethyl-7-octenoate; Cyclohexyl 1-methyl-8-nonenoate; n-octyl-1-methyl-9-decenoate; n-decyl 1-methyl-10-undecenoate;

609827/1 over 22

n-dodecvl-1-ethyl-3-butenoate; “Y c C LH O Π

2-hydroxyethyl-1-methyl-4-pentenoate, · Benzyl-1-methyl-5-hexenoate; Allyl-1-methvl-6-hentenoate; Phenyl 1-methyl-7-octenoate; p-chlorophenyl-1-ethyl-S-nonenoate; tert-butylaminoethyl-1-methyl-9-decer.oate; NjN-dimethylaminoethyl-1-methyl-10-undecenoate; 1,2-ethylenedi (1-ethyl-3-butenoate); . 1,4 - ^ - tetramethylenedi (1-methyl-4-nentenoate); 1,6-hexamethylene (1-methyl-5-hexenoate).

5. amides

Acrylamide; - ■ -

N-Mathvlacrylamid; .

M-hydroxymethyl acrylamide; N-ethyl acrylamide; N-isopropyl acrylamide; Nn-butyl acrylamide; N-tert-butyl acrylamide; Nn-octylacrylamide; N-dodecylacrylamide; N, N ¹ -riethylenebisacrylamide; N-phenylacrylamide; N, N ¹ -tetramethylene bisacrylamide; ■ Ν, Ν ¹ -hexamethylene bisacrylamide; N-alkyl acrylamide; Methacrylamide;

N-riethy! Methacrylamide; K-ethyl methacrylamide;

609827/1022

- 35 -
N-isonropy! Methacrylamide; .

. 2 b b 4 / y υ

N-n-butyl methacrylamide; N-hexadecyl methacrylamide; N-tert-butyl methacrylamide; IJ-octadecyl methacrylamide; N-phenyl methacrylamide; Ν, ΙΙ-dimethyl methacrylate; N, N-diethyl methacrylamide; N ^ 7-di-n-butyl methacrylate; N, ϊ,-di-n-octy! Methacrylamide; N-methyl-3-butenetnide; H-hydroxy-4-pentenamide;

N-ethyl-5-hexenamide; · ■

N-isopropyl-6-heptenamide; Nn-butyl-7-octenamide; N-tert-butyl-8-nonenaiaid; Nn-octyl-9-decenamide; N-dodecyl-10-undecenainide; N-phenyl-3-butenamide; Ν, Ν ^1- methylenebis (4-nentenainide); N-pheny1-5-hexenamid; Ν, Ν ¹ -TetraiTiethylenbis (6-her> tena! Tiid); Ν, Ν'-hexamethylene bis (7-octenamide); N-allyl-8-nonenamide; l-methyl-9-decenarrdd; N-methyl-1-methyl-10-undecenamide; ■ N-iithyl-1-methyl-3-butenainide; NI sopropyl-1-methyl-4-pentenamide; Nn-butyl-1-methyl-5-hexenamide; N-hexadecyl-l-methyl-S-heptenair.id;

609827/10

". tI-tert-Ilutyl-1-ethyl-7-oct'iPF.mid;." 2 5 5 "i 7 3

N-Octadecvl-l-mothyl-S-nonennniclj - '·. N-phenyl-1-inethvl-9-decenamj δ · N-Phenyl-l-methyl-lO-undecerami.cl; 'N-phenyl-1-niethvl-3-butenanide;
N, H-dimethyltl-ethyl-4-pentenaiTiide; NjH-diethyl-1-methyl-S-hexenair.id; N, N-di-n-butyl-1-methyl-6-heptenamide; ■ N, N-di-n-octyl-1-methy1 -7 -nc tenanid.

6th Phosphon ate '..

Diethyl vinyl phosphonate; '51

Dj.-n-butylvinylphosohonate; '-

Di-n-hexylvin-vlbhosnhonat;

Dicyclohexyl vinyl phosphonate; - "

Di-n-octylvinylnhosohonate;

Di-dodecyl vinyl phosphonate; '■

Di-hexadecyl vinyl nhosnhonate; ".. - -

Dibenzyl vinyl phosphate;

Dinhenyl vinyl phosphonate; '

Diethyl 1-ethoxyvinylphosphonate. 64

7. Pyridines

2-vinylnyridine; 55

3-vinyl pyridine;

4-vinyl pyridine; 57

2-methyl-5-vinyl pyridine; 56

5-methyl-2-vinylpyridine ;.

6-methyl-2-vinyl pyridine; 6-butyl-2-vinylnyridine; 2,6-dimethyl-4-vinyl pvridine; _Λ

609827/1022

2-allyl pyridine; .

3-allyl pvridine;
4-allyl pvridine;
2- (3-butene-vinyl) pvridine; 3- (3-bufcenyl) pyridine; 4- (3-butenyl) nyridine; 3- (4-pentenyl) pvridine; 4- (5-hexenyl) pvridine; 2-methyl-5 (3-butenyl) pvridine; 2-methyl-5 (7-heOtenyl) pvridine; 2-methyl-5 (9-nonenyl) pvridine; 5-Nlethvl-2 (4-pentenvl) pvridine; 5-methyl-2 (-C-hexenyl) pvridine; 5-Me- ^t: hyl-2 (8-octenvl) nyridin; 5-Hethvl-2 (10-decenyl) pyridine; "6-methyl-2- (3-butenyl) pvridine; 6-butyl-2 ~ (4-pentenvl) pyridine; 2,6-diinethyl-2- (3-butenyl) pyridine; 2/6-diinethyl-2- (5-hexenvl) pyridine; 4-t -butenevl-2- (6-hentenevl) pyridine;

8. Other nitrogen heterocycles

N-vinyl imidazole; 50

N-vinyl-2-methyl-imidazole; N-vinyl-2-phenyl-imidazole; N-vinyl-4,5-diinethvl-imidazole; N-vinyl-4/5-dinhenyl-iinidazole;

N-Vinvl-carbazole; 4B -

N-vinyl-2-pyrrolidinone; 4 9

609827/1022

N- (S-hexenyU-iinidazole; N- (6-heptenvl) -2-methvl-imidazole; N- (7-octenyl) -2-phenyl-irr, .idazole; 1-Ϊ- (3-nonenyl) -4, 5-diinethyl - imidazole; N- (9-decenyl) -4, 5-diphenyl-inida7.ol? N- (10-undecenyD-carbazole; N- (3-butenvl) -2-pvrrolidinone; N- (5-texenyl) -2-nyrrolidinone; • N- (7-octenyl) -P.-r-vrrolidinone.

9. Urea

Universal urea; .4P.

Μ-Λ1 IvI-IT'-nhenvlurstof f; TI-Allvl-N'-benzovlurea;

N-Allvl-N ¹ -butyl urea; ;

N-allvl-N'-methylurea; K-allvl-N * -n-octylurea; N, H'-diallyl urea; W-Al IyI-Ti ¹ , N'-cli ^ thvlurea; N-1-M aliy ^1, 11 '-dibatylharnstof f; N-Allvl-N ¹ , W-diphenyl urea; N- (3-butenyl) urea; N- (4-T ^J o _n tenvl) -TT '--nh ^ nylharnnto ^:

N- (5-IIexenyl) -71 '-benzoylharnstof f; N- (6-heptenyl) -N * -butylurea *; N- (7-octenyl) -TI ¹ -methanolurea; N- (8-honenyl) -N ¹ -n-octy-urea; N, N ^r ~ D ± (9-decenvl) urea; N- (10-unoecenyl) -N ', TT'-dinietvivlurea;

609827/1022

N- (3-butenyl) -N '_;N'-dibutylurea; N- (4-pentenyl) -N ', N'-diphenylurea;

10. Thioureas

Ally! Thiourea; . 47

N-allyl-N * -benzoylthiourea 7 N-allyl-N'-butylthiourea ' N-allyl-N'-methylthiourea; N-allyl-N ¹ -n-octy! Thiourea; N-allyl-N'-pheny! Thiourea; N ₇ N'-dially! Thiourea; N-allyl-N'νN'-dimethylthiourea; N-allyl-N ¹ , N ¹ -dibutv! Thiourea; N-allyl-N ', N'-diphenylthiourea; N- {3-butenyl) thiourea; N- (4-pentenyl) -II ¹ -benzoylthiourea N-ί 5-nexenyl) -N'-buty! Thiourea; N- (6-heptenyl) -N'-methylthiourea; N- (7-octenyl) -N'-n-octy! Thiourea; N- (8-nonenyl) -N'-pheny! Thiourea; N, N · -Di C9-decenyl) thiourea; N- (1O-undecenyl) -N ', N'-dimethylthiourea; N- (3-butenyl) -H ', N'-dibutylthiourea; N- (4-pentenyl) -N ^f , N'-dipheny! Thiourea;

11. Silanes

Vinyl trimethoxysilane; Vinyltriethoxysilane; Vinyltributoxysilane;

Vinyl trihexy loxysilane; 609827/1022

Vinyl tricyclohexyloxysilane;

Viny-.ltrioctoxvra lan;

V.inyltrinher.oxysilnri; / You A / cJ U

"Vinyltr.tbenzvloxvs.ilan;." "". '

Divinyldimethylsil an; . '

Allvltrimethoxvsilane; . ''

Allyltricithoxysilnr;

Allyltributoxysil ar .;

Allyltricyclohexyl oxysilane; ■ "" "·

Allyl triphenoxysilane; (3-Bucenyl) trimethox ^ 'si lan;

(4-pentenvl) trintlioxysilane; -

(5-hexenyl) tri-butoxysilane; '' ... "■ · ■

{6-IIeptenyl) trihexyloxysilane; .

(7-Oct.GTiyl) tricyclohexylnxypilane; . . '■ "..

(8-nonenyl) trioctoxysilane;

(D-decenyl) triphenoxysilar .; · ^;

(1Q-undecenyl) tribenzvloxysilane; (3-butenyl) tribenzyloxysilane; (4-pentenyl) triphenoxysilane;

(5-hexenyl) trioctoxysilane; ■ · "-

(6-heptenvl) tricyclohexyloxysilane; (7-octenyl) trihexvloxysilane; "

12. Alcohols ■. '■

Allyl alcohol; * 2 ""

Methallyl alcohol;

3-butene-1-oi;

2-i'ethyl-2-propen-1-ol; 4-penten-1-ol;

4-pentene-2-ol;

608827/1022

2-methyl-3-buten-1-ol; 3-methyl-3-buten-l ~ ol; 2-methyl-4-penten-2-ol; 4-methyl-1-r> duck-3-ol; 1,5-hexadien-3-ol; 9-decen-1-ol; ■ 10-undecen-l-ol;

l- <tetrahydro-l, l-dioxo-2-thifinvl) -3-huten-2-ol; 58 5-hexen-1-ol; 6-IIepten-1-ol; 7-octen-1-ol; S-nonen-1-ol.

Acrylonitrile; Methacrylonitrile; Allyl cyanide; 3-butenenitrile; 4-pentenenitrile; 5-hexenenitrile; 6-heptenonitrile; 7-octenenitrile; 8-nonenenitrile; 9-decenenitrile; 10-undecenenitrile.

14. Benzene derivatives o-vinylbenzene; m-vinylbenzene; p-divinylbenzene;

609827/1022

- Ί2 -

"m-Diisoproneny! benzene;. 6O 9 π π η η g η p-diisopropenylbenzene; allyl (3,4-Fiethylenctioxy) benzene; 2-chlorostyrene; 3-chlorostyrene;

4-chlorostyrene; '

4-methylstyrene;
o-methylstyrene;
4-methoxystyrene;
4-ethoxystyrene;
2,5-dimethoxystyrene; 2,5-dichlorostyrene; (3-butenyl) benzene; (4-Pentenvl) benzene • p-Di (5-hexenyl) benzene; m-Dl (6-henhenyl) benzene ;. p-di (6-heptenyl) benzene; 7-octenyl- (3,4-methyleneclioxy) benzene; 2-chloro (7-octenyl) benzene; 3-bron- (8-nonenyl) benzene; 4-chloro (9-decenyl) benzene; 4-methyl- (10-undecenyl) benzene; 2-methyl- (3-butenyl) benzene; 4-methoxy (4-pentenyl) benzene; 4-thoxy (5-hexenyl) benzene; 2,5-dimethoxy- (G-heptenyl) benzene; 2,5-dichloro (7-octenyl) benzene; 2-trifluoromethyl- (8-nonenyl) benzene; 2,5-dibromo (9-decenyl) benzene.

609827/1022

Triraethyl tin hydride with the following formula is used in used in this invention: (CH,), Sn-H. This organosine hydride is prepared by known methods as described in the following references:

K. Hayashi, J, Iyoda and I. Shiihara, J.

Organometal. Chem., 10, 31 (1967) .. Kuivila, HG, Advan. Organometal. Chem., I,

H7 (1964).
WP Neumann, Angew. Chem., Internat. Edit ,, 2, 165 (1963).

The use of the compounds according to the invention as insecticides and herbicides can be practiced in a variety of ways. For practical uses, the compounds of the invention alone or in suitable carriers such as water, alcohols, ketones, phenols, toluene or xylenes can be used dissolved or suspended. Optionally, one or more surfactants and / or inert Diluents can be added to the formulation for ease of handling. The approaches can be in the form of Dusts, granules, wettable powders, pastes, emulsifiable concentrates, aerosols, water solution concentrates or one water-soluble solid can be used.

For example, the compounds according to the invention can be used as dusts when they are mixed with powdered solid carrier materials

609827/10 2 2

mixed or absorbed on it, such as the various mineral silicates, for example mica, TaIk ₅ pyrophillite vvrl clays, or used as liquids or sprays if they are added to a liquid carrier material; · ..- .., -: as in solution in a suitable solvent, for example acetone, benzene or kerosene, or when they are dispersed in a suitable non-dissolving medium, for example water. In crop protection (the term includes parts of plants) the chemicals of the invention are preferably used as aqueous emulsions containing a surface-active dispersant which can be an anionic, nonionic or cationic surface-active agent. Such surfactants are known and detailed examples are described in U.S. Patent No. 2,57,724, columns 3 and 4. The chemicals of the invention can be mixed with such surfactant dispersants, with or without an organic solvent, as concentrates for subsequent water addition to produce aqueous suspensions of the chemical of the desired concentration. The chemicals according to the invention can be mixed with powdered solid carrier materials, for example mineral silicates together with a surface-active dispersant, so that a wettable powder is obtained which can then be applied directly to the point which is to be protected. Or they can be mixed with water to form a suspension of the chemicals (or a powdered solid carrier material) in the water for use in

6 0 9 8 2 7/1022

be shaken in such a form. The chemicals of the invention can be applied in the place where they are intended to protect through the a'.rosolrnethod.e. The solutions for the ac-. treatment can be prepared by dissolving the CheniiKali directly in the aerosol carrier material, which is liquid under pressure, but which is ^{a gas at normal temperature (for example 20 0} C) and atmospheric pressure. Or the aerosol solution can be prepared by first dissolving the chemical in a less volatile solvent and then mixing such a solution with the highly volatile liquid aerosol carrier material. The chemicals can be used in admixture with carrier materials which are themselves active, for example other insecticides, acaricides, fungicides or bactericides.

These approaches will contain amounts of the compounds that are effective for the particular regulatory method. These amounts can vary widely; typically they range from 0.1 to 95 % of the active ingredient. The spray dilutions can contain a few parts per million to strong concentrates obtained by ultra low volume techniques. The concentration per unit area, with the plants being the treated area, can vary from 0.012 to 11.2 kg per hectare.

In general, the compounds are applied immediately. To control aphids for example Sprays the compounds directly on the aphids

609827/1022

the plants they feed on, or both. applied. The sprays on the aphid-infested plants be applied, bags effectively, even if a direct one; !-Ion'; · does not occur, for example where the aphids adhere to the inner surface of a curled leaf or in a protected leaf sheath, for example a grain plant. Another effective control method includes that. Application of the compounds to the soil or another medium in which insect-infested plants live. The connections act systemically on the insects after the compound is absorbed by the plants. Harmful insects and derived pests, e.g. mites, infest a wide variety of plants, including both ornamental and arable plants such as chrysanthemums, azaleas, cotton, cereals, wheat, Apples and tobacco, and damage them by pulling vital juices out of plants, secreting toxins, and often disease transfer. The compounds of the invention can prevent such damage. The application methods and the selection and Concentrations of these compounds will of course depend on such conditions as area, climate, prevailing Diseases etc. vary. A person skilled in the art can choose the right approach through simple experimentation.

The following examples show how to use the above described method for the preparation of the invention Organotin compounds and their usability as insecticides and heroicides:

60982 7/102 2

example 1

An 80-ml, 2-neck Pyrex glass Schlenk reaction tube equipped with a magnetic stirrer was thoroughly purged with nitrogen and kept in an air-free condition. The tube was then charged with a mixture of 16.5 g (100 mmoles) of trimethyltin hydride and 5.9 g (50 mmoles) of divinyl sulfone, plugged and then irradiated with the aid of a 100 watt mercury vapor lamp for 4 hours. The reaction mixture was kept at 20 ^° C. and stirred with a magnetic stirrer. The recrystallization of the solid product from petroleum ether gave 15 g of 2,2'-sulfonylbisäthyltrimethyIstannan, m.p. 78.5 ° to 80.5 ° C, compound 1 of Table I. The presence of both the sulfonyl and the trimethyltin group was through strong infrared absorption bands at 1300 cm,

- 1 - 1 - 1 - 1

1240 cm, 1140 cm, 1105 cm and 765 cm were indicated using a KBr pellet. Nuclear magnetic resonance spectroscopy (NMR) showed the following: the protons in the alpha position to the sulfonyl part appeared as a complex multiplet with the center at 302 Hz (4 protons), the protons in the ^ eta position ^{to the} sulfonyl part appeared as a complex multiplet with the center at 114 .5 Hz (4 protons), the protons of the trimethyltin group appeared as a singlet at 14.5 Hz accompanied by a!, Satellite band on both sides (9 protons).

Analysis: Calculated on C ₁ ^ H _n -O-SSn (percent): '. '. . . · * ■ "^ - <b * .--

C, 26.9; H, 5.87; S, 7.17; Sn, 53.0. Found: C, 26.9; ^H; 6.16; S, 6.89; Sn, 52.6.

609827/10 2J:. . -

. Baispiel "-2 ': ■ - ■ _■; .-.

This example illustrates the use of a solvent in the reaction described in Example 1 is. ".

Using the equipment and method of Example 1, 46 g (279 mmoles) of trimethyltin hydride, 16.5 g (139 mmoles) of divinyl sulfone and 30 ml of benzene were placed in the Glas-Schlenk reaction tube. The tube was irradiated for 18 hours with stirring at 20 ° C. under a nitrogen blanket. After filtration and evaporation of the solvent, the crude product was recrystallized from petroleum ether to give 48.5 g of 2,2'-SuIfonylbisäthyltrimethylstannan, F. ■ 78.3 ° to 79.3 ⁰ C, compound 2 of Table I, is obtained. The analysis was the same as in Example 1 above .. Compounds Ib, 46 and 53 shown in Table I below were prepared using the equipment of Example 1 and the following special process conditions.

Example 3

A mixture of 4 , A ml (5 g, 42.4 mmol) of divinyl sulfone, 5 ml (42.4 mmol) of trimeth, yl tin hydride and 5 ml of toluene were irradiated for 18 hours. Filtration and evaporation of the solvent gave a liquid residue. 5 ml of piperidine were added to the crude product with stirring and cooling. After stirring for 2 hours at room temperature, the excess piperidine was removed under reduced pressure

609827X102: 2 ;; ,. ■; · ■

removed, 9.2 g of an oil remaining. To a solution of 5.2 g of this oil in 50 ml of benzene was added 1.25 ml of methyl iodide. After stirring for 3 days at room temperature 2.3 g of a solid was collected by filtration. Purification of the solid by precipitation from an acetone solution with ethyl ether gave 2- (2-piperidinoethylsulfonyl) -äthyltrimethylstannan-meth, odid, F. 122 ° to 124 ° C, compound 16 of Table I. The presence from both the sulfonyl and trimethyltin moieties was determined by the infrared absorption bands at 1305 cm, 1260 cm ~ and 1120 cm and at 770 cm using a KBr pellet are indicated.

Analysis: Calculated for C ₁₃ H ₃₀ JNO ₃ SSn (percent):

C, 30.61; H, 5.93; N, 2.75. Found: C, 30.08; H, 5.87; N, 2.83.

Example 4

A mixture of 8 g (30 mmol) of 2- (ethoxycarbonyl) ethyltrimethylstannane (Compound 47), 5 ml of 95% hydrazine (150 mmol) in 10 ml of ethanol was taken for 2 hours Refluxed. The volatiles were removed under reduced pressure. The distillation of the crude product yielded 5.26 g of 2- (hydrazinocarbonyl) ethyltrimethylstannane, b.p. 92 ° -98 ° C. (0.07 mm), compound 4 2 of Table I. The infrared spectrum of the distillate showed the following characteristic absorptions: 3300 cm (N-H), 1660 cm and

60982 7/102 2

153Q cm " ¹ CCN =) and 760 cm ^-1 (-Sn (CH ₃ J ₃ ). A gas chromatogram of the sample showed a single peak on a 1.83 m 3.2 mm commercially available column containing 10 % The NMR spectrum showed the following proton absorptions: a broad singlet at 752 Hz (1 proton), attributed to NH, a singlet at 388 Hz (2 protons), to the

NH »attributed to a triplet with the center at 235 Hz ² 0

It

(2 protons), assigned to the -C-CH-, a triplet with the center at 98 Hz (2 protons), assigned to the CH ₃ -Sn, and a singlet with the center at 6 Hz (9 protons), the Sn ( Attributed to CH-) _3.

Analysis: Calculated on C, -H,, -N ^ OSn (percent):

C, 28.72; H, 6.43; N, 11.17. Found: C, 28.08; H, 6.44; N, 10.53.

Example 5 '

An 80 ml two-necked Pyrex glass Schlenk reaction tube with a Teflon-coated magnetic stir bar was thoroughly mixed with Purged with nitrogen and kept in an air-free condition. The tube was filled with 10.7 g (42.5 mmol) of 3-butenyl-4-t-butylphenyl sulfone and 7.0 g (42.5 mmoles) of trimethyltin hydride charged, plugged in, and in a water bath at 20 ° C used. The tube was irradiated for 70 hours by a 100 watt mercury vapor lamp placed in a large test tube and placed in the same bath 5 to 10 cm from the reaction tube. Recrystallization of the solid

609827/1022

Product from petroleum ether gave 3.6 g of 4- (4-t-butylphenylsulfonyDbutyltrimethylstannane, 80 to 8l, 8 ° C. The presence of both the sulfonyl and the the trimethyltin part was also strengthened by strong.

—1 "~ 1

Infrared absorption bands at 1300 cm, 1282 cm,

1147 era " ¹ (-SO ₂ -) and 780 cm ^-1 [(CH ₃ J ₃ Sn-] displayed using a KBr pellet. Nuclear magnetic resonance spectroscopy (NMR) showed the following:

• The aromatic protons appeared as two multiplets with one center each at 777 and 753 Hz (with two protons each); the protons in the alpha position to the sulfonyl part appeared as a complex multiplet with the center at 307 Hz (2 protons); the methylene protons published in beta and gamma position to the Sülfony! group as a complex multiplet with the center at 162 Hz (4 protons); the methyl protons of the t-butyl group er. appeared as a singlet at 134 Hz (9 protons); the methylene protons appeared adjacent to the tin atom as a complex part with, the center at 73 Hz (2 protons) - '; the protons of the trimethyltin group appeared at: the same chemical shift as Tetramethylsilane (the internal standard) at approximately 1 Hz.

• Analysis: Calculated on. C.-H, _O ~ S.Sn (percent): .-.- "- ■ ..:; ·, ■ ■: -. · C, 48.94; H, 7, <25; S, 7.68;, Sn, 28.45. Found: C, 49.06? H ^ 7.33; S, 8, .19; Sn, 27.60.

6 0 9 8 2 7/1022

Example 6

The procedure described in Example 5 was used; with the exception that 10/1 g (^ 2.5 mmol) 5-hexenyl-p-tolylsulfone and 14.0 g (85 mmol) trimethyltin hydride were the reactants. The reaction mixture was irradiated for 232 hours. The excess trimethyltin hydride was allowed to evaporate from the reaction mixture under a stream of nitrogen. The unreacted 5-hexenyl-p-tolylsulfone was removed from the reaction mixture at 1 × 10 mm Hg, with 3.25 g of crude product remaining . Column chromatography of the distillation residue over silica gel, using toluene and 1% acetone in toluene as the eluent, gave an oil, 6- (p-tolylsulfonyl) hexyltrimethylstannane. The presence of both the sulfonyl and trimethyltin moieties was indicated by the strong infrared absorption bands at 1315 cm, 1300 cm, 1285 cm and 1140 cm (-SO ₂ -) and 760 cm-1 (CH ₃ ) ₃ Sn-J. The NMR showed the following:

The aromatic protons appeared as two multiplets with one center each at 775 and 732 Hz (2 protons each); the protons in the alpha position to the sulfonyl group appeared as a complex multiplet with the center at 303 Hz (2 protons); the methyl protons of the tolyl group appeared as a singlet at 243 Hz (3 protons); the methylene paws in beta to epsilon position to Sulphonyl group appeared as a broadened complex

609827/1022

Multiplet by the center at 147 Hz (8 protons); the protons of the 'methylene group, those with the tin atom are connected ^ s chicle η as a triplet with the center at 74 Hz (2 protons); the protons of the trimethyltin group appeared as a singlet at -2 Hz, the is accompanied by a satellite band on both sides (9 protons).

Analysis: Calculated for C ₁₆ H ₂₈ O-SSn (percent):

C, 47.67; H, 7.00. Found: C, 47.52; H, 1 , 07.

Ex iel 7

The procedure described in Example 5 was used except that 13.1 g (42.5 mmoles) of 10-undecenyl p-tolylsulfone and 14.0 g (85 mmoles) of trimethyltin hydride were the reactants. The reaction mixture was irradiated for 189 hours. The excess trimethyltin hydride was allowed to evaporate from the reaction mixture under a stream of nitrogen. The remaining oil weighed 15.5 g. One half of the crude product was chromatographed on a column containing silica gel using toluene and 2% acetone in toluene as the eluent. The product, II- (p_-tolylsulfonyl) undecyltrimethy-stannane, was obtained as an oil. The presence of both the sulfonyl and trimethyltin groups was indicated by the strong infrared absorption bands at 1315 cm ~, 1300 cm, 1285 cm ',

60982 7/1022

- 1 - 1 ■

1140 cm (-S0-) and 760 cm (CH-J., Sn- displayed.

The NMR showed the following:

The aromatic protons appeared as two multiplets, each with a center at 771 and 728 Hz (2 protons each); the protons in the alpha position to the suIfonyi part consisted of a multiplet with the center at 300 Hz (2 protons); the methyl protons of the tolyl group appeared as a singlet at 240 Hz (3 protons); the methylene groups - (CH-) _g - appeared as a broadened multiplet with peak maximums at 161 and 119 Hz (18 protons); the methylene protons in the alnha position to the tin atom appeared as a triplet with the center at 76 Hz (2 protons); the protons of the trimethyltin group appeared as a singlet at 0 Hz, which is accompanied by a satellite band on either side (9 protons).

Analysis: Calculated for C ₂₁ H ₃₃ O ₃ SSn (percent):

C, 53.29; H, 8 ₇ O9; Found: C, 53.81; H, 8.09.

Example 8

Using the procedures and apparatus described above and detailed in Examples 1 and 2, additional organotin compounds of the invention have been prepared and these are together with the products of Examples 1 to 7 below

6 0 9827/1022

Table I where the term "high vacuum" means a pressure of at least 0.1 mm Hg. Table I also shows those examples where a solvent was used and / or the compound was purified, as well as the melting point or boiling point at a given pressure in mm of mercury. All compounds are referred to as stannans because they can be viewed as substitution products of "stannane", ie SnII ^ ₉ .

The compounds identified by the numbers 1-17 _s 21-23 ₃ 25-3 ¹ I, .36, 39-42, 44-47, 49-56, 58-6Ο and 63-92 are believed to be new and are not suggested by the prior art. The other compounds are either anticipated in publications, or they are close to the compounds of the prior art, or they are obvious variants thereof. The state of the art referred to in the two preceding sentences consists of:

J. Appl. Chem. £, 106-113 (1959); :

Approx. 68, II90 H (1968) ,.

Ayrey et al., Supra;

Ziegler, British Patent 966,813; '

Bublitz, U.S. Patent 3,591,614; Bublitz, U.S. Patent 3,614,037;

B09827 / 1022

German patent specification 1 153 J. Appl. Chenu £ "Γ / 6 · (1959); J, Appl ν Ciiem, 7., 356 (1957); Diss. Abstr-. £ 2, -73 (1561);

as well as the state of the art on the above in the. Description has been referred to.

609827/1022

No.

I. 2

S *

ro ₆

7th
8th
9

Table I.

Organotin compounds of the formula (CH ₃ ) ₃ Sn (CH ₂ ) _n stannane compound -R ^{1 n} X

Reaction solvent

R ¹

-CH-X

Cleaning method

2,2 -Sulfonylbisäthyltrimethyl-

2,2'-sulfonyibis methyl

trimethyl

Trimethyl-2- (methylsulfonyDäthyl-

2- (ethylsulfonyl) ethyltrimethyl-

Trimethyl-2- (_i-propylsulfonyl) ethyl "

2- (s-Eutylsulfonyl) -äthyltrimethyl-

Trimethyl-2- (t-pentylsulfonyl) ethyl

Trimethyl-2- (n-octylsulfonyl) ethyl "

2- (n-Dodecylsulfonyl) -äthyltrimethyl-

H H H H H H H H H

SO ₃ CH ₃

^S0 2 ^C 2 ^H 5

SO ₂ -IC H ₇

no

toluene

no

-SO ₂ CH (CH ₃ ) CH ₂ CH ₃ none

-SO C (CIU) ₂ CH CH, none

no

- OVJp -ii ~ oi plL-i c

toluene

Uinkrist.

tmkrist-

Recryst.

distillation

distillation

distillation

distillation

High vacuum

High vacuum

F. or Kp; ⁰ C (mm Hg)

78.5-80.5 '

78 _; 3-79 ^ 3

51-53

98-108 (Oil-. · 2)

90-98 (0.01)

96-99 (0.06)

97-102 (0.07-0.09)

oil

oil

Table I (continued)

No. Organotin compounds of the formula .η χ. · (CH ₃ J ₃ Sn (CII ₂ ) _n R ¹ '
-CH-X F. or ) cn
CJt 10 Stannane compound R ' ι- - _S 0 ₂ -nC ₁₈ H ₃₇ Reaction
solvent Cleaning
method Bp. ⁰ C
(mm Hg) -j
CD
CD 11 Trimethyl-2- (n-octa- ^
decylsulfonyl) ethyl- I. -so ₂ - (s) toluene Recryst. 55-55.5 co 12th 2- (Cyclohexylsulfonyl) - H
ethyltrimethyl 1 -SO ₂ CH ₂ - (O) no distillation 140-50
■ (, O7 -, - X5) 0982 ^13th 2- (Benzylsulfonyl) - H
ethyltrimethyl " ι -SO ₂ - (O) Aceto
nitrile High vacuum oil —J. 14th Trimethyl-2- (phenyl-H
sulfonyl) ethyl 1 -S0 ₂ - <2> -C (CH ₃ ) ₃ no High vacuum oil O
ro 15th 2- (p_ -t-Butylphenylsul- H
fonyl) ethyltrimethyl ~ 1 -SO ₂ - (O) -Cl toluene Recryst. 118-20 16 2- (p-chlorophenylsul- jj
sonyl) ethyltrimethyl- ¹ CH ^ no Recryst. 57-60 17th 2- (2-piperidinoethylsul- _H
fonyl) ethyltrimethyl,
methiodide -SO ₀ (CH ₅ J ₉ SO ^ (CH no Ther-
washing 122-24 18th 2,2 '- (ethylenedisulfonyl) - "
-bisäthyltrimethyl- 1 -OC ₂ H ₅ ^y vinyl acetate
₂ ) ₂ Sn (CH ₃ ) ₃ Recryst. 14], 5
(Decompose. 2- ^A thoxyäthyltrimethvl-
H no distillation 80-82
(50)

Table I (continued)

, Organotin compounds of the formula (CH ₃ ) ₃ Sn (CH ₂ ) _n ~ CH-X

No'. Stannany connection R- H H η 1 . X Reaction
solvent Cleaning
method F. or
Bp. ⁰ C
(mm Hg) 2554790 19th 2 * -n-butoxyethyltrimethyl- H H 1 ' no distillation 86-91
(15) 20th 2 ⁱ -l-butoxyethyltrimethyl-
■, "■ ■ ' Trimethyl-2 ^ -_ i-octoxyethyl-H H 1 -00H _2CiI (CH ₃ ) _s no distillation 95-98
- (30) O
to
CO 21 2-decoxyethyl trimethyl H 1 -0-1-C ₈ H ₁₇ no distillation 58-62
(0.05) ro
* ■ *
* 'fr 22nd 2-dodecoxyethyltrimethyl- H 1 - ⁰⁰ 10 ^H 21 ' no distillation 68-71
(0.03) O
ro 23 3- (2,3-epoxypropoxy) -
piropyltrimethyl- H 2 no distillation 113-17
(, 07) 24 2,2 * -Oxybisäthyltri-
methyl- 1 A.
-OCH ₂ CHCI-I ₂ no distillation 100-2
(4.5) 25th 3,3'-oxybispropyltri-
methyl- 2 -OCH CII Sn (CH) ^ no distillation 55-58
(0.1) 26th Trimethyl-3-phenoxy-
propyl 2 -OCa ₂ CH ₂ CH ₂ Sn (CH \ no
3 ^; 3 distillation 74-5
, (0.07) 27 no distillation 66-70
(0.025)

Table I (continued)

R ¹

Organotin compounds of the formula (CH ₃ ) ₃ Sn (CH ₂ ) _n ~ CH-X

F. or ⁰

No'. Stannan connection R ¹ H η Χ Reaction
solvent Cleaning
method Kp- C
(mm Hg) 03) 28 3- (p_-t-butylphenoxy) -
propyltrimethyl II no distillation 98-100
(0.08) 29 Trimethyl-3- (p _-: methoxy-
phenoxy) propyl H 2 ■ -0- (O) -OOH ₃ no distillation 98-100
(0.1) cn
O
CO 30th 3- (£> -chlorophenoxy) pro-
pyltrimethyl- H 2 -0- (O) -Cl no distillation 84-88
(0.07) KJl
cn 3 2 7 / 31 2- (2,2,2-trifluoroetho-
xy) ethyltrimethyl - H 1 -OCII ₂ CF ₃ ' no distillation 81-86
(50) CQ
O rc 32 2- (N, N-dimethylamino-
ethoxy) ethyltrimethyl- H 1 -OCH ₂ C ₁₁₂ H (OH ₃ ) _n none distillation 43-43.5
(0.07-0, ro 33 2- (hexadecoxy) ethyl
trimethyl H ¹ - ^OC 16 ^H 33 no High vacuum oil 34 3- (tetrahydro-1,1-
dioxo-3-thienyloxy) pro-
pyltrimethyl- H
H no High vacuum oil 3 pp
36 Trimethyl-3-phenylthio-
propyl
3, 3'-thiobispropyltri-
methyl- 2 -S- (O) no
_cw % none distillation
distillation 82.5-7
(0.06)
94-98
(0.06)

Table I (continued)

R ¹ ι

Organotin compounds of the formula (CH ₃ ) ₃ Sn (CH ₂ ) _n ~ CH ~ X

No stannan connection

R '

η Χ

Reaction solvent

Cleaning
method

F. or Kp. ⁰ C (mm Hg)

37 38 σ; O 39 CO OO 40

° 41

42

43

44

2- (£ -chlorophenylthio) -H äthyltrimethyl-

2-carbamoylethyltri- H methyl-

2- (N-t-butylcarbamoyl) - II ethyltrimethyl-

2- (N-hydroxymethylcar- H bamoyl) ethyltrimethyl-

N, N'-methylenebis (2- _H χ

carbamoyl ether brain

ethyl)

2- (hydrazinocarbonyl) - H äthyltrimethyl-

2- (Kthoxycarbonyl) ethyl H trimethyl-

2- (dodecoxycarbonyl) -. H äthyltrimethyl -

-C-NH

q -

-6-EHC (CH

II H

-C-IiKCH ₂ OII

"2

-COOC ₂ IL-

no distillation 90-92
(0.07) to
cn
cn Tetra
hydrofuran Recryst. 69-70.2 cc.
G Tetra
hydrofuran Recryst. 74-75.5 Tetra
hydrofuran Recryst. 79-84 Aceto
^) 0 nitrile Recryst. 128-8.5 Ethanol distillation 92-98
(0.07) no distillation 85-6
(10) no distillation 116-17
(0.003)

Table I (continued)

No'. Organotin compounds of the formula (CH ₃ ) ₃ Sn (CH ₂ ) Stannan connection R ' η Reaction
X ■ solvent R ¹
_n -CH-X Bp. ⁰ C
(mm Hg) D. 45 2,2 '- (ethylene dioxide
carbonyl) bisethyltri-
methyl ¹ H 1 -COO (CH ₂ J ₂ ¹ OOC none
(CH ₂ ) ₂ Sn (CH ₃ ) ₃ Cleaning
method 122-30
(0.07-0, 46
47 Trimethyl-3-ureido-
propyl
Trimethyl-3-thioureido-
propyl " H
H d
2 ² tetra
hydrofuran
"""^ * ² tetra
^ -. hydrofuran distillation 79.5-82
124.5-
125.5 6098 48 2- (N-carbazolyl) ethyl
trimethyl H 1 \ ^ - \ _iT / \ / ^ toluene
I j ■ Uncrist.
Recryst. 93.5-
95.5 ro 49 Trimethyl-2- (2-oxopyrro-
lidinyl) ethyl H 1 *. U, - _} none
l / Recryst. 69-80
(0.03) ro
to 50 2- (N-imidazolyl) ethyltri-
methyl- H 1 distillation 85-6
(0.1) 51 2- (0,0-diethylphosphono) -
Methyltrimethyl-. H 1 _r none
1 distillation 49.5-51
(0.02) CJl 52 3,3 '- (carbonyldioxy) -
bispropyltrimethyl- H 2 \ _rJ <none distillation 104-103
(0.05) 790 no
-OCOO (CI ^) ₀ Sn (CH) distillation

Table I (continued)

R '

Organotin compounds of the formula (CH ₃ ) ^ Sn (CH ₂ ) -CH-X

No. Stannan connection

Reaction solvent

Cleaning method

F. or Kp. ⁰ C (mm Hg)

53 54 6 0 9 8 2 7, 55
56 ^ v
O
N. ' 57
58 59 60

3- (2-furoyloxy) propyl-H trimethylr

3- (N-methylcarbamoyloxy) H propyltrimethyl-

2- (2-pyridyl) äthyltri- H methyl-

2- <2-methyl-5-pyridyl) - H äthyltrimethyl-

2- (4-Pyridy1) ethyltri- H methyl-

4- (Tetrahydro-1,1-dioxo-OH 2-thienyl) -3-hydroxybutyltrimethyl-

-OGO-

2- (triethoxysilyl) ethyl trimethyl "

2,2 * -m-phenylenebispropyltrimethyl-

1 1 1 2

1 1

0> -CH

i; 3

Or

no
no
no
no
no
no

no
no

'3

distillation
distillation
distillation
distillation
distillation
Recryst.

92-95 (0.1)

78-81 (0.15)

56
(0.1)

72-7 (0.05)

63-66 (0.15)

99-103.5

Distillation 56-7

(0.09)

Distillation 110-11

(0.1) TSS

Table I (continued)

R '

Organotin compounds of Γογγ: «1 (CH ₃ ) ₃ Sn (CH ₂ ) -CH-X

No stannan connection

Reaction solution smitt el

Cleaning method

F. or Kp; ⁰ C in Hg)

61

62

<D 63 co

64

65

66

2-cyanoethyl trimethyl

3- (hydroxypropyl) trimethyl-

2, 2 '- Γ2, 4, 8 _r 10-tetraoxaspiro [5. 5] undec-3, 9-yleii] -bisäthyltrimethyl-

2-XthGxy-2 (0,0-diethyl- ' phosphono) methyltrimethyl-

2- (2,6,8 ~ trimethyl-4-nonoxy) ethyltrimethyl-

2- (p_-Tolylsulfonyl) ethyltrimethyl ".

-CN -OH

((H

-OC-H

no

no

HC (CH ₂ ) ₂ Sn (CH ₃ ) ^k ₃ ^one

no

no

JH CK (CHjCH CH (CHJ

distillation 87-9
(10) I. distillation 37-8
(0.1) ÖS distillation 144
(0.0025) I. distillation 79
(0.45-0.05) distillation 67-71
(0.003) Recryst. 55.5-58

drofuran

cn

■ -J CD CD

Table I (continued)

R ¹

Organotin compounds of the formula (CH ₃ ) ₃ Sn (CH ₂ ) _n ~ CH-X

No stannan connection

R ¹

Reaction solvent

Cleaning method

F. or Kp. ⁰ C (mm Hg)

O
IO
OO

67

68

69

70

71
72

73

2- (p-Ethylphenylsulfonyl) -H ethyl trimethyl

2- (p-Isopropylphenyl-H sulfonyl) ethyltrimethyl-

2- (£ -n-pentylphenylsulfonyl) äthyltrimethyl-

2- Γρ_- (1,1-dimethylpro- H pyl) phenylsulfonyljäthyltrimethyl-

2- (p_-Octvlphenylsulfonyl) ethyltrimethyl-

2- (n-dodecylphenylsul- H fonyl) ethyltrimethyl-

2 - (^ - n-Dodecylphenylsul- H ι fonyl) ethyltrimethyl-

-so

CCHoCII
hu '-

Tetrahydrofuran

Tetrahydrofuran

toluene

toluene

, _Tn , ^ _{r% l} Tetrahy- ""2'7 ^ '3 drofuran

25th

branched

Tetrahydrofuran

Cu toluene

Recryst.

Uncrist.

High vacuum

Recryst.

High vacuum

High vacuum

Recryst.

52-56.5

53-57.5

oil

72-74

oil

oil

33-34

Table I (continued)

R ¹

Organotin compounds of the formula (CH ₃ ) ₃ Sn (CH ₂ ) _n ~ CH-X

No stannan connection

R ¹

Reaction solvent

Cleaning method

F. or Kp. ⁰ C (mm Hg)

74 75

76

77

2- (p-n-Tridecylphenylsul- K fonylfäthyltrimethyl-

2- (2,4-dimethylphenyl sul- H fonyl) ethyltrimethyl

2- (2,5-dimethylphenylsulfonyl) ethyltrimethyl

2- (2,4-diethylphenylsulfonyl) ethyltrimethyl-

■ "■ .j

: h ch

toluene

Tetrahydrofuran

Recryst.

Tetrahy high vacuum drofuran

Tetrahy high vacuum drofuran

High vacuum

43.3-44.8

oil

2- (2,5-diisopropylphenyl- η sulfonyl) ethyltrimethyl-

2- {£ -Cyclopentylphenyl- H sulfonyl) äthyltrimethyl · -

-CH (CFU
CH (CK ₃ J ₂

Tetrahydrofuran

High vacuum

Tetrahy recryst. drofuran

oil

94-95

cn cn

CO O

Table I (continued)

R ¹

Organotin compounds of the formula (CH ₃ ) 3Sn (CH ₂ ) _n ~ CH-X

No stannan connection

Reaction solvent

Cleaning
method

F. or Kp. ⁰ C (mm Hg)

80 2- (p_-Cyclohexylphenyl-
sulfonyl) ethyltrimethyl- H 1 C) 81 2- (p_-bicyclo [2.2.lJ hept-
2-ylphenylsulfonyl) -
ethyl trimethyl H 1 0 9 8 2 7/1 82
83 2- (p_-methoxyphenyl-
sulfonyl) ethyltrimethyl-
2- (p-bromophenylsulfonyl)
ethyl trimethyl H
H 1
1 to
to 84 2- (pj-fluorophenylsul- _%
fonyl) ethyltrimethyl- H 1 85 2- (3,4-dichlorophenyl-
sulfonyl) ethyltrimethyl H 1 86 2- (2-Naphthylsulfonvl) -
ethyl trimethyl H 1

(X

Tetra
hydrofuran Recryst. 116-118 Tetra
hydrofuran Recryst. 106-110 Tetra ■
hydrofuran Recryst. 35.5-39 Tetra
hydrofuran Recryst. . 84.5-SG, 5 Tetra
hydrofuran Recryst. 65-66.5 toluene Recryst. 102.2-
103.5 Tetra
hydrofuran Recryst. 88.5-90.7 2554790

Table I (continued)

No.

Organotin compounds of the formula (CH ₃ ) ₃ Sn (CH ₂ ) -CH-X

Stannan connection

Reaction solvent

Cleaning method

F. or bp ° C (mm Hg)

O CD OO

87

88

89

4-ÜE-d, 1-DimethyläthyD- H phenylsulfonylbutyltrimethyl-

6- (p_-Tolylsulfonyl) -hexyltrimethyl-

ll- (p_-Tolylsulfonyl) -undecyltrimethyl-

10

- (0> -C (CH ₃ ) ₃ none

no

-SO ₂ - ( _χ 0) -CH ₃

-SO ₂ - < 0> -CH ₃ none

Recryst. 80-81,

Column chromatography

Column chromatography

Compounds 90-92, and similar compounds in which η = 2 or more and X -SO ₂ R., -OR ^ or -SR ₁ QiSt, can be prepared by an alternative method than those shown above, where the starting materials:

(a) (CH-J-Sn (CH,) -CH-Z, where Z is chlorine, bromine or

• J -J £ * XX

Iodine is, and

(b) AIkSO ₂ R ₁ , AIkOR ₇ or AIkSR ₁₀ , where Alk is sodium, potassium or lithium, are.

Suitable starting materials of type (a) include:

4-bromobutyltrimethylstannane;
3-chloropropyltrimethylstannane; 5-bromopentyltrimethylistannane; 6-chlorohexyltrimethylst.annane; 7-bromoheptyltrimethylstannane; 8-iodoctyltrimethylstannane;
9-chlorononyltrimethylstannane; 10-bromodecyltrimethylstannane; II-bromundecyltrimethylstannane.

Suitable starting materials of type (b) include: AIkSO ₂ R ₁

Sodium benzene sulfinate;
Sodium p-toluenesulfinate;

6 0 9 8 2 7/1022 '

Sodium g-ethylbenzenesulfinate; Sodium p-n-propylbenzenesulfinate; Sodium p-i-propylene benzene sulfinate; Sodium p 1-4 n-butylbenzenesulfinate; Sodium p _-! 3-butylbenzenesulfinate; Sodium p-t-butylbenzenesulfinate; Sodium ε-i-butylbenzenesulfinate; Sodium p-ii-amylbenzenesulfinate; Sodium g-t-amylbenzenesulfinate; Sodium p-n-hexylbenzenesulfinate; Sodium p-n-octylbenzenesulfinate; Sodium p_-n-nonylbenzenesulfinate; Natriura-p_-n-decy! Benzene su If inat; Sodium p_-n_-undecylbenzenesulfinate; Sodium p_-n-dodecylbenzenesulfinate; Sodium ^ -n-tridecylbenzenesulfinate; Sodium p_-cyclohexylbenzenesulfinate; Sodium 2,4-dimethylbenzenesulfinate; Sodium 2,5-dimethylbenzenesulfinate Sodium 2,4-diethylbenzenesulfinate; Potassium 2,5-diisopropylbenzenesulfinate; Potassium 2,4,6-triraethylbenzenesulfinate; Potassium p-methoxybenzenesulfinate; Potassium p-ethoxybenzenesulfinate; Potassium p-butoxybenzenesulfinate; Potash-2,5-dimethoxybenzenesulfinate; Potassium 3,4-dimethoxybenzenesulfinate; Potassium p-methylthiobenzenesulfinate;

6 0 9 8 2 7/1022

Potassium p-butylthiobenzenesulfinate; Potassium 5-chloro-2-methoxybenzenesulfinate; Potassium 2-bromo-4-methoxybenzene sulfinate; Potassium 5-acetamido-2-methoxyberzenesulfinate; Potassium 5-nitro-2-methoxybenzenesulfinate; Potassium 2-methyl-4-methoxybenzenesulfinate; Potassium 2-methyl 1-5 chlorobenzenesulfinate; Potassium p_-fluorobenzenesulfinate; Potassium ε-bromobenzenesulfinate; Potassium p-chlorobenzenesulfinate; Potassium 2,5-dichlorobenzene sulfinate; Potassium 2,4,5-trichlorobenzene sulfinate; Potassium trifluoromethylbenzenesulfinate; Potassium 3-nitrobenzenesulfinate; Potassium 3,5-dichloro-2-hydroxybenzenesulfinate; Potassium ε-acetamidobenzenesulfinate; Potassium ß-carboxybenzenesulfinate; Potassium - ^ - butoxycarbonylbenzenesulfinate; Potassium] 2-carbamoylbenzenesulfinate; Potassium ε -cyanobenzenesulfinate; Potassium jj-acetylbenzenesulfinate; Potassium 2-naphthalene sulfinate; Potassium phenylbenzenesulfinate; Potassium metharisulfinate; Potassium ethanesulfinate; Potassium 1-propanesulfinate; Potassium 2-propanesulfinate Potassium 2-butanesulfinate;

60982 7/1 fJ 22

Potassium 2-pentasulfinate; ■ -.- Potassium cyclohexanesulfinate ; Lithium 1-octanesulfinate ■ lithium i-dodecanesulfinate; Lithium 1-octadecanesulfinate; 1,2-ethylene bi-lithium sulfinate; 1,4-tetra-methylene bislithium sulfate,

AIkOR ₇

Nat.riunimethoxia;
Sodium ethoxide;
i \ 'atrium-n-propoxide;Sodium-t_-butoxide; Sodium n-hexoxide; sodium 2-ethylhexoxide; Natriura-n-decoxide; . Sodium n-dodecoxide;

• sodium'-n-eicosoxide; Sodium n-stearyloxide;

• sodium phenoxide;
Lithium naphthoxide; Lithium ε-ethylphenoxide; Lithiura-p_-i-propylphenoxide; Lithium ^ -n-tridecylphenoxide; Lithium-2 _i ^ -dimethylphenoxide; Lithium 2,5-dimethylphenoxide; Lithium 2,4,5 ~ trimethylphenoxide; Lithium p-methoxyphenoxide; Lithium £ -n-butoxyphenoxide;

'60 982 7/102 2

LithiumKi-3, ^ -diinethoxyphenoxide; Lithium-js-n-octoxyphenoxide; Xalium-p-chlorophenoxide; Potassium fluorine oxide; Potassium p-bronium dioxide ; Ka.ll \ iTTi-2, ^ -dichlorophenoxide; Potassium 2-methyl-5-chlorophenoxide; Potassium p-acetylphenoxide; Potassium 3-nitrophenoxide; Potassium £ -methylt.hiophe: ioxide; Xalium-5-nitro-2-methoxyphenoxide; Potassium acetylphenoxide; Potassium cyclohexoxide. AIkSR ₁ "

iiatriurnraetiiylmercaptid; Imtriuraäthy liner capt id; Sodium rn propyl mercaptide; i-i-sodium-i_-propyl mercaptide; Ilafcrium n-butylinercaptide; Katriura £ -butyl mercaptide; Sodium-fc-butyl mercaptide; Katriurn-ri-pentyl mercaptide; Sodium i ^ -pentyl mercaptide; sodium s_-pentyl mercaptide; Sodium t-pentyl mercaptide \ sodium n-hexyl mercaptide; Sodium cyclohexyl mercaptide; Sodium ¹ I -methylcyclohexyl mercaptide;

U09827 / IÜ22

iiatrium-no c ty lmer cap t id; Sodium 1-ό cty lme rc ap ti ά; liatrium benzyl mercaptide; Sodium p-chlorobenzyl mercaptide; Sodium phenyl mercaptide; Sodium p-tolylrriercaptide; Ijatrium - ^ - ethylphenylrr.ercaptiü; Sodium 1-propylphenyl acaptide; Sodium p-i-propylphenyl mercaptide; Sodium n-butylphenyl mercaptide; Sodium - ^ - i-butylphenyl mercaptide; iiatrium-p_-s_-butylphenyl liner capt ia j sodium- £ -t_-butylphenyl mercaptia; Sodium p_-ri-pentylphenylraercaptide; i-i-sodium-p_-t ^ -pentylphenylrner eaptide; Sodium p-n-hexylphenyl mercaptide; Sodium-p_-n-heptylphenylmer cap t id j / I / Sodium-pn.-octylphenylmercaptide; Sodium p-nonylphenyl mercaptide; Sodium decylphenyl mercaptide; rjatrium- ^ dodecylphenylmercaptidj sodium-p_-tr ide cylpheny lmer capt id; Sodium - ^ - cyclohexylphenyl mercaptide; Natriuni-S, ¹ ! -Dimethylphenylmer capt id; Sodium 2,5-dimethylphenyl mercaptide; Sodium 2, ^ - diethylphenyl mercaptide; Sodium 2,5-diisopropylphenyl mercaptide; Sodium 2,4-6-trimethylphenyl mercaptide;

6 0 9 8 2 7/1022

Sodium methoxyphenyl mercaptide; Nutrium £ ethoxypheny liner capt id] Sodium £ -butoxypheny liner cap t id; Potassium octoxyphenylraercaptide; Natriura-3j4-dinethoxyphenyl mercaptide; Sodium pj-methylthiophonyl mercaptide; Sodium 5-chloro-2-methoxyphenyl mercaptide;

■ sodium 2-chloro- ⁱ l-methoxyphenyliiiercaptid;

■ Sodium J-bromo - ^ - methoxyphenyl mercaptide; Sodium 2-nitro- ⁱ l-methoxyphenyl mercaptide; Sodium 2-methyl- ⁱ l-methoxyphenylraercaptide; Sodium -. ^ Fluorophenylraercaptide; l ^ atriura-pj-bromophenyl mercaptidj sodium- ^ chlorophenyl mercaptide; Sodium 2 _S 5 ~ dichlorophenyl mercaptide; Sodium ^ 3, λ-dichlorophenyl mercaptide; Sodium 2 j4, 5-trichloropljenyl mercaptide; ■ sodium trifluoromethylphenyl mercaptide; Sodium 3-nitroplienyl mercaptide; Sodium ^ acetamidophenyl mercaptide.

The specific preparative details for Compounds 90-92 are set forth below. The reaction times are in the range 'of 0.5 to 2k hours, and suitable reaction temperatures are in the range of 20 ° to 120 ⁰ C.
The catalyst can be any phase change catalyst as described by EV Dehmlow, Chem. Tech. (1975), beginning on page 210, the citation of which is hereby incorporated by reference.

609827/10 22

will be alive. . .

Example 9 (compound 9.0). -

A 125 ml single-necked round cap. which was equipped with a Teflon-coated magnetic stirrer and a reflux condenser, 4.45 g of sodium p-toluenesulfinate, 20 ml of water, 10 ml of toluene, 7 g of 75% 4-ßrombutyltrimethylstannane and U, 44 g of Tri-n -butylhexadecylphosphonium bromide charged. The mixture was refluxed for 2.5 hours with rapid stirring, the organic phase was separated off on cooling, dried over anhydrous magnesium sulfate and the solvent was stripped off on a rotary evaporator. The oil residue was distilled twice through a short distillation attachment. The second distillation gave 3 ₃ 3 g of 4- (p-tolylsulfonyl) butyltrimethylstannane, boiling point 136 to 140 ° C. (1 × 10 mm Hg). The presence of both the sulforyl and trimethyltin moieties produced strong infrared absorption bands at 1315 cm " ¹ , 1300 cm" ¹ , 11 ^ 2 cm " ¹ (-S0 ₂ ~) and 765 cm" ¹ (CIU) ^ Sn - displayed. The NMR spectroscopy showed the following:

The aromatic frotons appeared as two multiplets, each with a center at 768 Hz and 726 Hz (with 2 protons each); the protons in the alpha position to the sulfonyl group appeared as a complex multiplet with the center at 291 Uz (2 protons); the ß- and gamma-methylene protons appeared as a complex hultiplet with the center at 157 üz ( ¹ \ protons); the p_-tolylmethyl group appeared as a singlet at 244 Hz

BO9827 / 10 2 2

(3 protons); the methylene protons adjacent to the tin atom appeared as a complex multiplet with the center at 74 Hz (2 protons); the "protons of the trimethyltin group appeared as a singlet flanked on both sides by satellite bands , at -4 liz from the inner standard tetramethylsilane (9 protons)

Analysis: Calculated on- C. ^ K ^ CuSSn (percent):

C, 44.83; H,. 6.43; S, - B , 55; Sn ₅ 31.64.

Found: C, 44.89; H, 6.61; -S, 8.46; Sn, 31.65.

example 10 (connection Jl)

In a 100 ml single neck round bottom flask fitted with a Teflon coated magnetic stir bar and a reflux condenser, 7.68 g of a 1: 1 mixture of 4-iiromobutyltrimethyistannane was obtained and 4-chloro-butyltriethylstarinane, 15 ml of toluene, 5 g p _-_ t-butylthiophenol, 1.2 g sodium hydroxide, 20. ml v / water and 0.44 g of tri-n-butylhexadecylphosphonium bromide were used. the The mixture was refluxed for half an hour. When cooling, the phases were separated and the Viass layer with Toluene extracted. The organic phase was combined with the extract and washed once with water and over anhydrous Dried magnesium sulfate. The solvent was on a rotary evaporator deducted. The product was distilled over a short distillation head, leaving 7.36 g of liquid

609827/1022

.. 116 to 121 ⁰ C (Ix 10 now) -were obtained 4- (p_-t_-butylphenylthio) butyltrimethylstannan ₃ Kp "The presence of the Trimethylzinnteils was indicated by a strong infrared absorption band at 76o cm The KMR spectroscopy shows the following.:

The aromatic protons appeared as a singlet at 717 Hz (4 protons); the protons in alpha position to Thio group appeared as a cult triplet with the center at 282 Hz (2 protons)] the ß- and gamma-methylene protons appeared as a cultiplet centered at 160 Hz (4 protons); the Ethyl protons of the t_-butyl group appeared as a singlet. at 130 Hz (9 protons); the hetnylene protons in the neighboring position to the tin atom appeared as a complex multiplet with the center at -91 Hz (2 protons); -the protons of the trimethyltin group appeared as a singlet at 3 Hz (9 protons) from the tetramethylsilane (internal standard) that was on both sides was flanked by satellite gangs,

Analysis: calculated on 'C ₁₇ H, -, SSn (percent):

C ₁ 53.01; H ₃ 7.85; S ₃ b ₅ 32; Sn ₃ 30.81. Found: C, 53.26; H ₃ 8 ₃ 24j. S, ö, 28j Sn ₃ 29.89.

Example 11 (compound 92)

In the manner described for compound 91, a Mixture of 10-, 57 g of 75 iS-igem ^ -bromobutyltrimethylstannane, 10 ml toluene, 2.89 g thiophenol, 1.08 g sodium hydroxide, 20 ml

609827/1022

Water and O ₃ 4 ^ g of tri-butylhexadecylphoophoniuinbroinid heated at 40 ° C. for half an hour. The crude product was distilled through a short attachment, where 6.14 g of a liquid, _ 4- (phenylthio) butyltrir; _: Ethylstannan, bp 95 to 97 ⁰ C (0.02 mm) was obtained.. The presence of the trimethyl tin moiety was indicated by a strong infrared absorption band

- 1
displayed at 760 cm. The lJHR spectroscopy showed the following:

The aromatic protons appeared as a complex one Multiplet by the center at 713 Hz (5 protons); the protons in the alpha position to the thio group appeared as a triplet with the center at 28 * 1 Hz (2 protons); the ß- and gamma protons "appeared as a complex multiplet with the center at 160 Hz (4 protons) -; the ethylene protons in Position adjacent to the Zinnatorn appeared as a complex multiplet with the center at 89 Hz (2 protons); the protons of the trimethyltin group appeared as a singlet at 4 Hz (9 protons) dated. Tetramethylsilane (internal standard), the was flanked on both sides by satellite gangs. .

Analysis: Calculated on CL ^ m ₂ SSn (percent):

C, 47.44; H, 6.74; S _3, 9.74; Sn, 36.07. Found: C, 47.46; H, 6.77; S, 9.29; Sn, 35, ^ 3.

609827/1022

Example 12 , '

The organotin compounds of the invention were used as Insecticides and keroicides according to the following test arrangements tested: _ ■ -

A. 'Mosquito Solvent Test

The batches were prepared by dissolving 30 mg of organotin compound of the invention in 10 ml of acetone. These . Solution was then diluted to 1 ppm with water. Two 25 ml aliquots were placed in test tubes, to which 10 to 25 larvae (fourth stage of development) of the yellow fever mosquito, Aede's aegypti (Linnaeus) were added. The tubes were kept in the dark for 72 hours. At the end of this period, the percentage regulation was determined.

B. Aphid contact test

Test batches were prepared for spraying at a 1000 ppm (parts per million) concentration _} by dissolving them in a small amount of acetone and adding a suitable wetting agent. Typically 0-6 g of organotin compound dissolved (or suspended) in 10 ml of acetone, 2 drops of Triton-X100 wetting agent (octylphenoxypolyethoxyethanol with 9-10 mol-? Polyethylene oxide) were added and this was added to 300 ml of water to make a 60Q ppm suspension. An aliphatic portion was then further diluted with distilled water to a "concentration of 1000 ppm of the organotin compound.

60 9827/1022 '■ -

Eight to ten-day-old barley seeds (10 plants each 5 ^ 0 g pot) were contaminated with corn aphids Rhopalisiphum niaidis (Fitcu) two days before the lease. Two pots were treated with each batch by spraying with a spray atomizer while the plants were rotating on a turntable. After the treatment, the plants were kept in the greenhouse for 5 days. At the end of this period, the percentage wasRegu. ¹ ation of the aphids on the basis of the reduction in population density compared to untreated plants, which were used as controls, determined.

C. "tobacco caterpillar" cheese test "

The test batches were with 10QO ppm as under B, the above aphid contact test. 2/10 m.l of the diluted batches were applied to the surface of 5 g of a synthetic Food mixture pipetted into partially filled Cells in a plastic jelly dish. 5 cells were treated with each chemical dilution. The food mix was a modified Vanderzant food, those made from egg germ, soy flour, agar, sugar, salts, vitamins, Preservatives and water. The jelly shells had 50 holes per plate, each hole approximately 2.5 by 4.0 by 1.5 cm was great.

After the treatment, a larva (third or early fourth stage of development) of the tobacco caterpillar, Hello this virescens (Fabricius) was inserted into each cell. The bowls

609827/10 22

were covered with a plastic film and a plate covered in hard plastic and placed in an incubator Maintained 26.7 ° C. . '

after the end of a. Vioche examined the bowls and the percentage regulation was determined because of the natural Mortality in the PC control tests was adjusted by Abbott's formula. The shells were another v / o marriage preserved ■ and any deviation in the evolution of the survivors was recorded.

D. cotton capsule bug test

The batches were prepared at 1000 ppm as under B, the above aphid contact test. 12 to Ik-day-old grew up in 3 ^ 0 g plug baumv; ollsämlinge were used. Two pots were treated with each formulation by spraying with a sprayer while the pots were rotating on a turntable. Five adult cotton boll beetles, Anthonomous g ^ randis Boheman, were placed in each pot after treatment and confined by covering the pots with an inverted 453 g Styrofoam shell with small perforations punched in the ears. Surviving beetles were counted after five days in the greenhouse to determine the percentage regulation that Abbott's formula corrected for natural mortality in the control plants. The percentage reduction in food intake was determined by visual comparison of the damage caused by food intake of the treated plants with the con-

609827/1022

troli plants (untreated) estimated.

E. mite contact test "

The preparations used were, with 1000 ppm as below B, the above aphid contact test.

Cotton plants in the second Kauptblatt stage, grown in 340 g pots under greenhouse conditions at 21.1 ° to 23.5 ° C, were used in this test. One plant (two main leaves) in a pot was used per replicate and two replicates were made for each organotin compound tested. A 25.4 mm diameter circle of tree tanglefoot, a sticky, non-toxic preparation, was used to mark the strokes include the upper leaf surfaces. Approximately 25 adult two-spotted spider mites, Tetranyehus urticae Koch, were transferred to each test plant 24 hours prior to treatment.

■ The infested plants were taken with the dispersions Use a small spray atomizer to sprinkle the Thoroughly soak the foliage. The plants were used for Returned to the greenhouse where they were kept for 6 days. After this period, the plants were examined for adult live mites that remained on the leaves was. The percentage regulation was made on an estimate basis and compared with the number of live mites on the ... Control plants determined. -. ...

609827/1022:

b \ ! -, ilben. one day residue s t it t

The 'were i'es onnectivity tv as under L, ₃ the above sheet auskontaktt ^ est, prepares, however v; ere it to 500 ppm r.:it water diluted lances Laumwdlpf, the im. second main leaf stage in 3 ^ 0 E heads under greenhouse conditions at 21 j 1 ° - 23.9 ⁰ C - were used in this test. - ■. ■

i; ine plant (two main leaves). in a pot was used per repetition; ends * 2v. ^; One repetitions were made for each concentration of the tested organic sense compound

The plants were using the dispersions a small sprayer sprinkled around the foliage to soak thoroughly.

One day after the treatment, a circle of "tree tanglefoot" was drawn on the upper surface of the treated leaves and adult kilbes, Tetranychus urticae Koch, were transferred into this enclosure.

Six days after the mite infestation, the plants were examined for adult live mites left on the leaves. The percentage regulation was on on an estimate basis compared to the number of live mites on the control plants.

609827/1022

ü. Abbott's formula:

Adjusted percent mortality -

/ o Ieüend i _m Cont roll.-TCST - I live in behände th th st% lebend- in the control test ^{x 1o} °!

The results of the tests described above are given below Table II lists the compounds within those in Table I above.

6 0 9 8 2 7/1 ü 2 2

Table II Organotin Compounds as Insecticides

Connection % regul. % Regul. ^ Regulator,

dung mosquito aphids tobacco germ

No larvae caterpillar

ppm 1000 ppm 1000 ppm

% Regul. Cotton boll beetle 1000 ppm boll beetle
% reduction
Food intake
cotton

Mite cor.takt

1000 ppm

Mites one day residue 500ppm

2)

• loo
6ο
98

8ο

75
100

100

8ο

100

95

100

100
100
100
100
100
100
100
100

100
100
100

100
100
100
100
100
100
100
#

100
100
100
100

100

87

56 100

85

71

100

100

67

100

67

100 100

8ο

100

100
100

90
100

90
94

100

100

IOC 100 100

ice

100 100

90

100

100 % regulation, at 100 ppm; not tested at 1000 ppm. 100 % regulation, at 100 ppm; ■ not tested at 500 ppm.

Table II (continued)

Connect- '■ % regul. % Regul. % Regul.

dung mosquito aphids tobacco germ no. larvae caterpillar

ppm 1000 ppm 1000 ppm

% Regul.
cotton
pod beetle
1000 ppm Capsule beetle
% reduction
Feed
recorded
cotton Mites
Contact
1000 ppm . 100 95 . 100 100 ■ 56 70 β * 5β '' 80 " 28 50 ■ at the 5β 90 - 28 . '{0 ta « '. 67 . 90 100 100 85 95 '43 70 - 100 95

Dust mites. giger. . Residue 500ppm

•O
cd 15

Ü7 ro l8

19th
20th
21
22nd
23
24 25

100
100

15th
100

100
100
100
100
100
100
100
100

100
100
100

95

20th

30th

95

100

100

100 100 100 100 100 100 100 100 100 100 100 100 100 100

Bo

> - J

9O

40 95

0 ■ <! CD CD

Table II (continued)

• Connection % regul. % Regul. % Regul. % Regul.

dung mosquito aphids tobacco germ cotton

No larvae caterpillar pod beetle

1 ppm 1000 ppm 1000 ppm 1000 ppm

Kaps elkä; ■ «■""
% reduction
Food intake
cotton

Kilben contact

1000 ppm

One-day mite residue 500 ppm

σ> 2β

to 27

.31 32.

34 35 36 37

100 30th 100 100 95 100 100 100 57 70 100 100 100 100 100 100 100 100 90 loo 100 90 100 100 100 100 6o 100 30th 50 6o 100 100 57 90 100 100 100 100 100 100 100 100 44 70 100 * · ** 100 100 75 80 100 100 100 100 95 100 100 100 100 100

100

■ 25

100

100

100

100-3 CO CD

100 % regulation, at 100 ppm; not tested, at 500 ppm. 100 % regulation, at 0.001 ppm.

Table II (continued)

Connection % regul. % Regul. ^ Regulator,

dung mosquito aphids tobacco germ no. larvae 'caterpillar

1 ppm 1000 ppm. 1000 ppm

% Regul. Cotton boll weevil 1000 ppm

Capsule beetle
% reduction
Food intake
cotton

Mite cor.takt

10000 ppm

Mites
giger
Residue 500ppm

38 39 40 41 42

44 45 46 47 48 49

100 100 100 44 80 100 100 10 ° 75. 8o 0 100 100 50 70 100 ■ 100 loo 100 100 0 100 100 63 70 100 0 100 71 90 70 100. 100 75 80 IOC 100 100 100 ■ 100 0 100 100 22nd 70 15th 100 100 85 95 100 100 100 29 95 100 100 100 71 90

100

100

100

100 0 φ

100 ICO

10CN3 cn

Table II (continued)

Connection % regul. % Regul. % Regulator,

dung mosquito aphids tobacco

iiv. larvae caterpillar

!, ppm 1000 ppm 1000 ppm

% Regul.
Cotton
pod beetle
1000 ppm Capsule beetle
% reduction
Feed
recorded
cotton Mites
Contact
1000 ppm 100 95 85 95 100 100 - 100 90 - 57 70 - 70 - 100 ■ 95 - 89 95 _

Mites one day residue 500 ppm

100
100
100
100

100

100

100

100
100
100

100
100
100

95
100
100

100
1 '0

97

30th

20th

100

100 100 100 100 100 100 100 100 100 100 100 100 56
71
89
22nd

95
50

100

++ ■

100 % regulation, at 100 ppm; not tested at 500 ppm.

100

100

100

100

100

0 cn cn

Table II (continued)

link

No.

% Regul. % Regul. % Regul. Mosquito aphids tobacco germ larvae caterpillar
ppm 1000 ppm 1000 ppm

100

100

100
100
100
100
100

100

100
100
100

95
100

100

75
10

100
100
100
100
100

90
90

100

100 100 100 100 100 100 100 100 100 100 100

% Regul.
Cotton
pod beetle
1000 ppm Capsule beetle
% reduction ·
FoodGauf
take on
cotton 85 90 100 90 ■ 55 80 8o 100 100 - 88 100 88 100 78 ■ 95 100 100 90 50 100 50 100 95

Stroke one day residue ppm

100 100 50 100 100 100 100 100 100 100 100

ro cn cn

Table .11 (continued)

Connect % Regul. manure Mosquiuo- No. larvae 1 ppm

% Regul. % Regul. Aphids tobacco caterpillar
ppm 1000 ppm

% Regul. Cotton boll weevil 1000 ppm boll weevil % reduc. Food intake on cotton

Mites one day residue 500 ppm

74 σ
co 75 00
N>
~ * 3 76 "^.
_x 77 O
K> . 78 * »* 79 : 80 j 81 82 83

85

J. V ^ U 0 100 100 ice 95 100 8o 100 100 100 , 100 ICO 100 100, 100 100 100 100 100 100 20th 100 ICK) 93 100 QO 100 6o ICO 100 75 100 ■ 100 75 15th 100 100 75 65 97 100 100 100 95 100 100

100 100 I. 100 100 } 90 . 100 100 100 100 100 100 100 95 100 ro 100 100 cn
cn 100 ■ ioo “J 100 100 CD
CD 100 100 100 100

Table II (continued)

Connection ur .

) = Regulate. % Regul. % Regul. Mosquito aphids tobacco germ larvae. bead 1 ppm 1000 ppm 1000 ppm

% Regul. Baumwo11-capsule beetle 1000 ppm capsule beetle % reduced.
Food intake on cotton

Kilben one day residue 500 ppm

σ; 86 CD CO 87 OO ro 88 89

iUÜ 100 ioo 90 ICO 95 ICO .87 100 100 100 100 100 ■ 8o 6o 100 100 100 [ ο 100 100 100 '"• 0 Ί Λ, "ι 95 ICO

100

95

100 100 100 100 100

100 100 100 100 100 100

ro cn cn

Table II (continued)

Comparative data

Regulator % Regulate, λ-regulate. % Regulier capsule beetle mites

Mosquito larvae 1 ppm

Aphids

1000 ppm

Tobacco caterpillar
1000 ppm

Cotton % redua. One day pod beetle liahrungsauf- residue 1000 ppm would take up '. 500 ppm cotton

tribe et al. 0 3,206. 489 I!

H "), SnCH ₂ CH ₂ -G-CCH ₇ 2-thioacetoxyethyltri-n-butyltin

20th

90

80

Koopmans et al. 3.31,483 ₀ Ο

(CH,), SnOS - (θ) - CH, TrimethylsiteM-p-toluenesulfinate

100

100

100

100

The Stamm et al. , the data of which is given at the end of Table II, was made in accordance with Example 1 of U.S. Patent 3,206,489. the Compound by Koopmans et al., Whose data are similar shown was prepared as follows.

A solution of

- +
5.95 g (0.033 KoI) CH, - "_ .; -SO Ira in 50 n; I Ii ₀ O. Then 6.6 g (0.033 mol) (CK ^), SnCl in 100 ml acetone were added dropwise , a white precipitate to which was formed. the reaction mixture was heated to 60 ⁰ C for 20 minutes. 'After being stirred overnight, the Ace'ton was removed by evaporation and separated a white viscous residue. the water layer was decanted. the viscous residue was treated with 50 ml of petroleum ether. 8.1 g of a solid product with a temperature of 98 to 102 ° C. was isolated. In the Ph. D. dissertation (Peter M. Siegen, Univ. of North Carolina, 1967) is a melting point for Irimethylzinn-p-toluene 97-101 ⁰ C listed. The IR showed strong absorption bands at 955 ei "and 990 cm.

As can be seen from the results listed in Table II above, the organotin compounds according to the invention have good to excellent insecticidal activity for a wide variety of insects in particular when compared with the two connections according to the prior art.

6 0 9827/1022

In all of the following examples, the numbered links correspond to those listed in Table I above are. ■.

Example 13 - Mites One-Day Residue Test of Organotin Compounds at Different Preparation Concentrations

- In this example, test batches were prepared containing various concentrations of some representative organotin compounds of the invention included. The method used was as follows: -

Cotton plants in the .second main leaf stage., Which are in 3 ^ 0 g trays under greenhouse conditions at 21.1 to 23.9 ° C were used in this test. One plant (two main leaves) in one pot was used per replicate and ζ v / ei replicates were used per concentration of the tin compound tested is used. The test batches were prepared by adding 50 mg of tin compound in one ml Acetone dissolves, -a drop of Emulfor 719, a technical one surface-active dispersant (polyoxyethylated vegetable oil) is added and in 50 ml of water to a concentration of 1000 ppm (parts per million) suspended. Aliquots of this solution were added to concentrations further with distilled water diluted by 100, 20 and 5 ppm. The plants were mixed with the batches using a small spray atomizer sprayed to thoroughly wet the foliage. One day after the treatment, a circle of "tree tangle-

60 9827/1022

foot "was applied to the upper surfaces of the treated leaves and adult kilbes, ΐetranychus urticae Koch, were transferred into this perimeter. A count of these kilbes was made immediately after the transfer and again six days later.

Abbott's formula was made to balance out mortality control and used to maintain the adjusted percentage regulation. The results are in below Table III listed.

Table III Mites One Day Residue Test

link 100 ppm Regulator 5 ppm 100 20 ppm 63 1 100 99 49 14th 94 68 44 23 100 45 57 41 87

The above results clearly show that the selected organotin compounds according to the invention have a high degree of activity exhibit at different concentration levels.

60982771022

Example I ^ - Tobacco Sprout - Baumwo lltest

The test batches in this example were prepared in the same way, around different consentrations of representative compounds of the invention which were then tested according to the method described below:

The test batches were prepared by dissolving 50 mg of organotin compound of the invention in one ml of acetone, a drop of Emulfor 719, a technical surfactant Dispersing agent (polyoxyäthylxerteo vegetable oil) is added and in 50 ml of water to a concentration of 1000 ppm (parts per Killion). -Aliquots of the solution were further mixed with distilled water to concentrations of 100, Diluted 20 and 5 ppm.

Two week old cotton seedlings were 'used up.' These were grown in 3 × J0 g dishes with two plants per dish. The diluted batches were applied to the seedling plants with a spray atomizer and allowed to dry. Three dishes were treated with one diluted batch each. A larva (third stage of development) of the Tabalc Tcelin caterpillar, Heliothis virescens . (Fabricius), was placed in each pot and enclosed by turning a perforated 453 ^ 6 g styrofoam shell over the pot. The percentage regulation of the caterpillars was determined after two weeks in the greenhouse.

The results of this test are shown in Table IV below. 6Q9827 / 1022

Tatelle IV

"Tobacco germ on hothouse cotton

Connection no

"f. regulation 5 p 100 ppm 20 ppm 100 10ü 100 ; so ICO 100 r \
\ J CC -50 CC 100 33 O ICO 100 O 100 100 O 100 0 O If 33

1
14 ■ 23 36

45 52 56

As can be seen from the results shown in Table IV above, the organotin compounds are Invention excellent for controlling this type of insect.

' Example 3-5 ~ Aphid - soil soak test

This example is similar to Examples 12 and 13 above, by testing mixtures containing different concentrations of representative organotin compounds and then tested according to the following procedure:

The test batches were prepared by adding 10 mg of organotin compound of the invention in one ml of acetone and one drop

■ 609827/1022 ■ " ^fc

(about 30 ing) EmuIfor 119, aem the same surface-active agent, which is identified in the above example 1 <<, dissolves, and diluted with water to 100 ml of a concentrate of 100 ppm of a test organosin compound in water. - Further dilutions to 10 ppm and 1 ppm were made with V.asser.

Eight day old Barley seedlings were grown (10 Fflanzen per dish) in 340 g shells, with a total weight including the bottom of approximately ^l 4k0 g were used. The seedlings were aosicntlicn mix; Corn aphids, Fihopalosiphum πκαΐ ^ is (Fitch), infected one day before treatment. The surface of the lüpfe v / urae was soaked with 2 ml of aliphotic fractions "of the diluted batches, but not treating the contaminated parts of the plant. Two dishes were treated at each rate. The rates were in kg / ha on a weight basis of ½ hO g / pot and assuming that 0.4 ha of soil with a depth of 17.8 cm weighs 907,000 kg.

The percentage regulation was determined by observation. that was made a week after the treatment. The results are given in Table V below, where "A7A" means the calculated kg / ha.

6 0 9 8 2 7/1022

Spoilage
IJr. 11 1 100 14 ' 86 23 95 45 100 52 100 56 ICO

Table V

Barley - soil soak

/ j regulation of aphids

I ₃ 121 jr / k 0.11 ^ / A

93 8c

30th ο

Ö6. '78

99 0

80 40

97 70

This test shows that the chemicals of the invention also effective as systemic insecticides on sersten plants are by taking sufficient amounts of the organotin according to the invention Absorb compound for effective aphid control.

Example 16 - Organotin Compounds as Preemergence Herbicides

This example illustrates the use of the invention Organotin compounds as pre-emergence herbicides. 600 mg of organotin compound were in 10 ml of an organic Solvent (e.g. acetone), which was a technical emulsifier (e.g. isooctyl polyethoxyethanol, "Triton X100") was added .. The solution was diluted to 100 ml with distilled water. 20 ml of this bOCO ppm solution were further diluted to 250 ppm with distilled water.

609827/1022

- 1 Ω? -

The solution was applied at the rate of 11.12. $ / A (kg / ha) by soaking the surface of Cite Coders in 11.4 cm plastic pots with 46 ml of the 2 ^ 0 ppir. Solution. The pots had been planted with the following weeds: Crooked ruffle, Amaranthus ret roflexus L .; Vegetable Portuiack, ■ Portulaca ole '-: ^ ;! 'J - .; or common thorn apple, Dätura stramonium L .; purple bindweed, Ipomea purpurea (L.) Roth; Faden-Fingergras, Dig it aria ischaemum (Schreb '.) Muhl .; common barren grass, Echinochloa crusgalli (L.) Beauv.j millet, Setaria faberi Lord .; and round cypergrass, Gy perus rotundus L. The percentage regulation of the weeds was determined by comparison with the untreated weeds, which were used as controls, one week after the treatment. The data in Table VI. Show the effectiveness of the compounds according to the invention as pre-emergence herbicides.

609827/102 2

Table VI ■

Organotin compounds as pre-emergence herbicides

link
No.

Rate crooked vegetable port », - Purple kg / ha Fox lacquer (ρ) or funnel tail common wind thorn apple,

Thread-
finger
grass Bristles
millet Common
Ilühner-
grass . 100 100. 100 ■ 100 100 lOO ' 100 100 100 100 100 100 100 .loo. ■ 100 100 100 100 100 100 100 ■ 15 30th 2 0 100 100. · 100 100 100 100 100 100 100 100. 100 80 100 100 IC

CD
O
CD
CD
I * O

i)

5
6th

7th
8th

11

12th

13th

HJ

15th

11.2
11.2
11.2
11.2
11.2
11.2
11.2
11.2
11.2

11.2
11.2
11.2

J700 100 100 100 100 100 100 100 100 100 100 100 100

100p

100

100

100

100

100

100

100

100p

100

100p

100

100

100 x 100 100 100 100 100 100 10 100 100 100

93 100

Table vr ~ (continued)

Organotin compounds as "pre-emergence herbicides

link 16 rate crooked Vegetable porW: - Crimson ■. Thread- Bristles mean t I. No. • 17th kg / ha . Fox lack (p) or Instinct Finger- millet Bolder Η *
O 18th tail meaner winds . grass grass I. 19th Thorn apple. 20 ' 11.2 100 100 100 100 100 100 21 11.2 ' 100 100 ■ 100 100 • 100 cn 22nd 11.2 100 100 100 100 100 100 ro ο
co 23 11.2 100 100 100 100 . 100 100 cn
cn co 24 11.2 - 100 100 ■ 100 100 100 100 CD 25th 11.2 10.0. 100 95 ■ . '■ 85 60 100. · O O
(V ' 2 ⁶ 11.2 -.00 95 50 95 8o 100 to 27 11.2 100 · 50p 65 '■ 70 90 8o 28 11.2 100 100 100 100 100 100 11.2 100 100 . . 100 100 • 100. 100 11.2 ' 100 98 0 50 95 0 11.2 90 8o 90 100 100 10 11.2 0 0 0 0 0 0

'. belle VI (continued)

Organotin compounds as pre-emergence herbicides

Connection no.

e
Ha crooked,
Fox-
sc hv / an ζ Geinüseportu, -
lack (ρ) or
meaner
Thorn apple. Crimson
funnel
winds 11.2 100 100 35 11.2 100 0 • 25 11.2 ; 100 0 100 11.2 100 · 100 11.2 100 8o 11.2 100p 100 11.2 100 80 20th 11.2 100 O' '20 11.2 100
r 100 100 11.2 ^: ιοο 100 98 11.2 45 100 100 11.2 100 100 100 11.2 100 0 0 11.2 100 100 95 100 85 100

Thread-finger grass

Bristle common millet · chicken grass

29 30 31 32 33

35 36 y (. 38

40 41 42 65 0

90 100

100 90 60 100 100 100 100 80 95

98 100 I. 98, · 100 O
VJi 100 ■ 90 I. 100 ■ 100 98 100 100 100 255 100. 60 -J 60 4o CO
CD 100 100 100 100 100 100 100
0 100
0 100 100

Table VI (continued)

Organotin compounds as. Vorauflauf herbicides

link 43 rate 11.2 crooked GGirtüseportM.- Crimson 0 Thread- 0 Bristles 0 mean I. No. kg / ha 11.2 Puch3- lack (ρ) or Funnel gate , 20 finger 6o millet 60 ■ Chicken 45 11.2 scrrwanz meaner winds 35 grass 75 0 grass . I. 46 11.2 Thorn apple ■ 100. 100 • loo 47 11.2 65 0 90 95 85. 99 48 11.2 100 Bo. 0 . 100 100 6o cn 49 11.2 100 90 100 100 100 '. 98. CD
CD
location 50 11.2 lOOp 100 100 100 100 xn
cn K>
-α 51 11.2 100 80 100 100 85 CO -Λ 52 11.2 100 : loo 95 100 · 90 ■ 45 O O
N>
K> 53 11.2 100 100 '98 100 100 ' , loo 54 11.2 • 100 100 30th 100 100 100 55 11.2 100 100 100 ■ 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

Table VI (continued)

Organotin compounds as! Voraufl''aufherbiside

link
No. 56 rate
. kg / ha crooked
Fox
tail Vegetable Portu.-
lack (p) or
meaner
Thorn apple Crimson
funnel
winds' Thread-_
finger
grass Bristles
millet mean
■ chickens
grass I.
[ι Ί 57
58 . 11.2 100 loo 30th 100 100 100 C.
I. co
ο
co 59 11.2
11.2 100
100 100
100p. 100
90 100
100 100
100 - 100
100 OO
ro 61 11.2 100 100 Ίοο .100 100 100 .62 11.2 100 0 100 95 70 • 98 ο 63 11.2 100 100 85 95 85 93 to 11.2 95 85 0. 0 0 0

As from the results listed in Table VI above as can be seen are the organic compounds of the invention in general as pre-emergence herbicides for a. great variety of weeds excellently suited.

Example 17 - Organotin compounds as post-emergence herbicides

This example illustrates the effectiveness of the organotin compounds according to the invention as overrun herbicides. The OOCO pprn solution described in Example 10 above was obtained in the same way, and atomized to a drop point using a customary DoVilbiss sprayer while wetting the foliage. The weeds, which were the same species as described in Example 10 above, were treated six days after germination. Percentage ^: regulation was estimated two weeks after treatment. The "Table VIT" below shows the results using the compounds according to the invention as post-emergence herbicides.

60982 7/1022

Table VII

Organotin compounds as overrun herbicides

link

No.

rate
ppm

0982 .3 * -. '4 1022 5 7th 8th ■ 9

12th

j 13
14th

crooked vegetable pint u * -. Crimson Fox lacquer (ρ) funnel tail or common thorn apple

βοοο
βοοο
βοοο
βοοο
βοοο
βοοο
βοοο
βοοο
βοοο
βοοο
βοοο
βοοο
βοοο

100
100
100
100
100
100
100
100
98
. 100

■ loo

100

.98

10Op

.100
90

100 ·
100
100

. 15th
5

100
100

50

100.

100

100

100

100

100

100

15. 100 100 100

95

Thread-
finger
grass Bristles
millet common
Chicken-·
grass 50 . ' 90 βο 100 100 100 100 75 / '100 '100 100 100 100 100 100 100 100 '100 100 100 15th 4ο. 40 0 5. 10 100 . 100 100 100 100 100 100 100 100 15th 5 ' 30th

Table VII (continued) Organotin compounds as a follower hear biz icle

Connect
manure
No.. . rate
ppm crooked
Fox
tail ■ Vegetable port u-
lacquer (ρ)
or 'more common
Thorn apple Crimson
funnel
winds, Thread-
finger
grass ■ bristles
millet ■ mean
Chicken-
grass OTT 15th 6000 100 • 100 100 30th 35 75 ' I. 16. 6000 100 100 100 '50 95 98 17th 6ooo 100 15th . 100 .65 25th ■ 4o 18th 6ooo 75 15th 30th '5 0 ' 15th 19th 6000 20th 5 ■ 25th 15th 15th 15th 20th 6ooo 15th 20th 80 10 0 10 NJ 21 6ooo 10 0 30th 10 5 · , 0 cn
cn 22nd 6ooo 0 75 20th 10 5 co 23 6ooo 100 0 98 Ul 5 25th CD 24 6ooo 90 25- 75 ■ 15 0 10 ■ 25th f 000 ■ 100 50p 25th '5 0 90 26th 6ooo 15th Ul ■ 15 5 .0 10 27 6ooo 100 0 35 75 60 ■ 70 28 6ooo 25th 0 35 50 15th 10

; Table VII (continued) Organotin Compounds as Post-emergence Herbicides

rate
ppm crooked.
Fox ■
tail Vegetable Pcrt Uf
lacquer (p)
or meaner
Thorn apple Crimson
funnel
winds Thread-
Finger-
. grass Bristles
millet mean
Chicken- .
■ grass I. Vorbin
manure
Mr. 6ooo 100 10 98 95 35 '15 29 ' 6000 65 5 6o 25th • '5 • '5 1 30th 6ooo 0 0 0 3 0 0 31 ' 6ooo .100 ■ ίο 100 ■ 65 ^: . 35. ' 20th 6000 100 0 50 35 5 ' Ul 32 6000 100 100p 100 100 100 100 33 6ooö 95 ^ί 25th 90 60 70 6o ΓΟ 34 6ooo ' 100. 25th 95 4o . .50 60 cn
cn 6ooo 100 100 100 100 100 100 CD 35 6ooo ' 100 , 100 100 100 ■ 100 100 CD ^: 36 6ooo 100 ■ 30 ..45 35 5 15 · 37 6ooo 90 20th 4o 50 8o 8o _; 38 6ooo 100 . . 0 ■ -. 75 0 0 15th 39 6ooo 95 20th 95 50 8o 8o 40 41 42

Table VII (continued) Organotin Compounds as Post-emergence Herbicides

Connect
manure
iir. . rate
ppm kr u run er
Fox
tail G a Γ; s ep crt u-
lacquer (p.)
or meaner
Thorn apple. purple
Funnel-
winds. Thread-
finger
grass Bristles
millet gerieir.es
Chicken-
• grass . I. 43 6ooo 65 5 10 0 0 0 112 44 6ooo 95 " 0 25th 20th ■ 20 25th ¹ 45 6000 100 5 75. 25th 75 75 46 6ooo ■ 100 lÖOp 100 90 . 98 ■ 85 47 6ooo 100 50 90 50 35 70 ■
48 6ooo 100 0 20th 5 5 25th 49 6ooo 100 .100 100 100 100 100 2554 50 .6000 100 · 100 100 ■ 98 95 100 co 51 6ooo . '., 100 100 100 100 100 100 O 52
53 6ooo
6000 ' 90
100 15th
95 0
100 10
95 10
98 10
90 54 6000 100 100 98 100 90 98 55 6000 100 5 95 10 5 30th ^ f ₁ 6000 100 100 100 100 ■ 98

255A79C

rH C ri O

cd zs

O C ο ta

(ß-Ci I

• Η C) Q "C CT

κ χ: ei.

■ 1): "3 ί ·.

CU P 1)

(■; ίο U ί. O · Η

I ί-, C ί) iJ OT 13 C Kl

ti fL, ta

I 0) E-i

>, -.-> ΓΛ ϋ ZS f-,

, ^ ¹

Ί - ν

ζ- C.

40 M.

Π, Ρ <CU ί ^

ι!) ■ - 'U) co

13 .C.

i; OC ^{1 1} D

ο CiJ -ei ^>

O

S W cd

£ ΧΙ ί:

3 -J JC

U ZS

^; fc (O

rf a

1 C. • • Η 3 Ό

O O H

O O H

O O

O O

in

O

OO CO H

IO.

ο ιη ο t> -H

O H

co

O H

ι η ιη

OJ

O CO

uS in

CVI

uv ο ο

ο ο

CT \

in

ι η cn

CO

CO

O CO

in in vo

O CO

m ο

CVl

ο ο

O O O O O O O O • O O O O O O O O O O O O O VO VO VO vo VO vo VO

η cvi cn vo vo vo

60982 7/1022

The results in Table VII above show that further the organotin compounds of the invention; generally excellent as "casserole herbicides for a wide variety of Weeds are suitable.

As already pointed out at the beginning of the description, is subject to a Peterson sulfonyl linkage on exposure Air of a hydrolysis .-- The following example serves as a corroboration this conclusion.

Example 13

A. The compound exposed to humid air was a typical Peterson compound: phenylsulfonylmethyltriniethylstannane, (CH ^), SnCH S- / c \

A 19,0..1-OIaS vmrde placed on one side on a wooden support and contained a wire mesh cover to support the test samples over a mixture of 152 g (NU ₁ ,) ~ SO η in 166 g water. An excess of (NKn) ₂ SOi, in contact with a saturated aqueous solution of (KHn) ₀ SOh, gives 8 liters of 3% moisture in a closed space (Handbook of Chemistry and Physics, Chem. Rubber Pub. Co., p. 2500 (i960)). The following samples of this Peterscn compound were drawn into 4G ml OD Petri dishes (without lids) 8 mm deep and the dishes placed in the humidity chamber, and the chamber was then sealed: - ^ - '15 dish 0.2186 g; ^ k bowl 0.2006 g. Before the samples were unbalanced, a solid began to build up

609827/1022

Crust formed on the surface of the liquid eu and covered the entire liquid surface within IO rent. A odor of a volatile trimethyltin compound was noticed. Once the samples were placed in the Feuchtigkeitskandier _s the sample coated on almost the entire surface within the shells. DueA9 , υ 1 glass was on a bench

exposed to normal laboratory light conditions. The initial temperature inside the chamber was 24.5 ° C. For four days the temperature was between the initial temperature and a low temperature of l'o G. The / rl: j sample was removed after four days. Under the surface there was an oily solid. The sample was made with a; Scraped spatula into a sample vial. The remaining oily solid was washed with chloroform (about 0.5 to 1 ml) in a flask. The chloroform was removed under a stream of nitrogen. The JrJ> k fpobe was removed from the chamber after seven days. The sample was completely solid and was scraped into a vial. The HMR spectra for both samples showed that, in addition to the aromatic absorptions, there was a singlet at 307 Hz, the

is assigned,

'the CEL of the hydrolysis product, ClUS0 ^ - (o) and a broadened singlet, at 36.5 Hz for (Ch ^.), £ n, which was flanked by satellite bands ", and a broadened singlet at 191 Hz for the OH- These results show the formation of a mixture of trimethyltin hydroxide and methylphenylsulfone, leaving no unreacted starting Peterson compound.

609827/1022

B. A corresponding inventive compound, phenyl

I!

sulfonylethyltrimethylstannari, (CK-,) -SnCK ^ CluS-phenyl . was exposed to similar humidity conditions in the same equipment. The following samples of the displayed · compound v purified by Säulenchrornatographie; ar were abgev ogen in small Petri dish lid / and inserted into the chamber with 8l% moisture at a temperature of 27 ⁰ C,: .Schale f ^ - 'l5 0.2426 G; Bowl ff 3 ^ 0,202ü g. The temperature was maintained at room temperature over the test period. The.-Φ 3 K sample was removed from the chamber after four days and an infrared spectrum was run within a few minutes. This showed no additional absorption bands other than those of the starting material. The? R15?. Robe was removed from the chamber after two weeks away. The infrared spectrum of this sample was identical to the spectrum of the starting material. No additional absorption bands were present. The ΝΓ-iR spectra for both samples were identical to that of the starting material. It is thus demonstrated that the tested compound according to the invention is not subject to hydrolysis under the specified conditions.

In the following an attempt is made to the general procedure of US Patent 3 79 ¹ * 670, 2-jj for preparing a compound of the invention? -T-butylphenyl

sulfonyl] ethyltrimethylstannane, (CH) SnCH CH S- / oVc (CH)

) SnCH

use. However, the compound obtained has been found to be 1- j.p-t-Butylphenylsulfonylj äthyltrimethylstannan,

6 0 9 8 2 7/1022

CH .- ■ - ..

if? r- \
(CH ₀ ) "- Sn-CH-§- (oVc (CHo) o highlighted.

This connection suffers from the same kydrolyi deficiencies like the Peterson compound of the previous example.

Example 19

The equipment used was a 500 ml, three neck, round bottom flask fitted with a mechanical stirrer, nitrogen inlet Y-attachment, a 125 ml dropping funnel (flame-dried and nitrogen precipitated) and an EiS 'water bath; for later use: a .simple distillation attachment, a .Thermometer and an oil bath. The following substances were used:

1) l40-ml (total volume) synthetic benzene used for removal of the water azeotrope was distilled.

2) 18.5 ml (13.1 E ₃ 0.18 mol) diethylamine (dried).

3) 94.0 ml (0.15 mol) 1.6 molar n-cutyllithium in n-hexane.

¹ O- 29.8 g (0.15 koi) trimethyltin chloride. 5) 33.9 g (0.15 liters) of pt-butylphenylethylsulfone (molecular weight 226.3).

All syringes used were previously ^{dried in the oven at 110 °} C. and cooled under a stream of nitrogen. The diethylamine (via syringe) and 50 ml of benzene (via syringe) were added to the flask. The butyllithium was added to the dropping funnel (via syringe). The reaction flask was heated using: the ice water bath under mechanical.

; nd ix η s α es Eisv,

B i) 9 ^ 2 7/102

- II8 -

Stir cooled and the butyllithium was added dropwise over a period of 33 minutes. The reaction solution now turned milky white. The dropping funnel was rinsed out with 10 μl of benzene (via a syringe) and drained immediately in the reaction flask. Triinethyltin chloride was weighed into a nitrogen-flushed 125 ml Erlenmeyer flask and dissolved in 50 ml benzene (via syringe) and poured into the dropping funnel (via syringe). Another 25 .nil 'benzene was used for rinsing of the piston-and then the dropping funnel was added .. While maintaining the reaction mixture at 0-5 ⁰ C in an ice bath, the stannous chloride was added dropwise üoer a period of one hour, added. The reaction mixture was then allowed to warm to room temperature with stirring for one hour and 10 minutes. The sulfon was weighed and added immediately as a solid and dissolved slightly. The mixture was stirred for half a stand at room temperature and kept under nitrogen overnight. The reaction mixture was a slightly milky tannin.

In the morning the device was set up for distillation using an immersion thermometer, a reflux thermometer, an oil bath thermometer plus connector and condenser, and a 300 ml flat-round neck adapter
was kept under nitrogen.

300 ml flat-round single-necked template flask, with everything

609827/1022

Table VIII

ο to ro

Elapsed time

Beginning

15 minutes

22 min

25 min

35 min

46 min ·, ·

1 h 5 min

1 h. 45 min

2 · h 15 min

3 h 20 min

3 hours 55 minutes 4 hours 5 minutes

Oil bath internal reflux temperature, vessel temperature.

54 ' 37.5 . 69 · 55.0 '84' 64 86 ' 66 • 83, . 73.5 95.5 .77 100 • 83 110, 95 117 105 '. '' 123.5 ' 112 125 ' 115 ■ '125 115 125.5 • 115.5

24 (R.T.)

24

49 (distillate is transferred to the template)

61.5 ■

70 (streak effect in the template) 72 (streak effect in the template)

70 (stake decreasing)

50.5 (stopped, vessel contents cloudy; brown pulp)

60 (slowing down stirring; a few ■ drops go over)

49 (occasional drops)

. Table VIII (continued)

Elapsed time

CD 4th * 5 H 15th min σ
CD 4th H 50 min OO 5 ro -J O ro H 5 min IO H 15th min

Oil bath interior 'reflux'

temperature vessel temperature

temperature

123
123.5

124.5 115.5 123 113.

113

(Beginning of rinsing with IL through the reaction flask / sur receiver; ^{refluxed at 6O 0} C; vessel temperature to 111 ° C; '
the distillate passes over).

57.5 (occasional drops)

. ■ (occasional drops; under N. allow to cool to room temperature).

ro cn cn

■ <] CD O

The distillation apparatus was dismantled after cooling. The initial charge was kept under nitrogen with stirring and cooled to Ob ° C. in an ice bath, a thick, slightly brown paste being obtained. ¹ I ₁ G g "(3, cm- ^ ^1, 0.04 mol) of HCl were added to 200 CRRR HPO and the resulting solution was slowly added to the original. Zuerbt increased the pot temperature to 30-33 ⁰ C and sank rapidly wherein the remaining HGL solution was added the Ei3bad was removed, two phases were formed. a clear upper ILO-phase and a slightly brown viscous untei-e ülschicht 100 CRRR CHCl, for solving were the oil to the;. ; Pot added, and the whole thing was transferred to a 1 l separator; a further 100 ml of CKCl-,. Were added. Most of the organic layer was decanted. The remaining organic and Κ, Ο layers were mixed twice with , washed, and the resulting organic layers were CIiCl. decanted. the total combined organic phase was dried over anhydrous MgSO. ₂ through iiacht dried. the whole was iltriert using a l ^c j cm Buchner filter vakuunf, wherein all kept covered and an air suction through the funnel was avoided in order to avoid moisture contact. The slightly cloudy filtrate was treated with Darco C 60 at room temperature for about 1.5 hours and filtered into a tared 1 1 single-necked round bottom flask (kept covered) and the CiICl was drawn off on the Rotovac (Rotovac ventilated under K_), whereby a clear brown , slightly viscous liquid with a crude yield of 46.2 g remained.

609827/10 22

Thin layer chromatography (TLC) on silica gel (Eastman) (9/1 volume ratio cyclohexane / ethyl acetate) showed two large spots which were 25 mm and 37 nm away from the point of application. The spot with the shorter distance was the same distance as that for the starting ethyl sulfone. The spots were almost the same size and intensity when observed under short-wave UV. The oil was subjected to vacuum distillation via a short distillation attachment using a single 50 ml receiver. An oil was collected between 120-15 "4 ⁰ C at" θ, 06-0.12 nm Hg. The vessel temperature ranged between I5O ⁰ and 200 C. In this distillation head seemed no dividing points to be present. The oily distillate formed some solid which was isolated by decanting the oil and pressing the solid onto filter paper (3.86 g). The solid was recrystallized from petroleum ether, mp 43-65 ⁰ C. The DünnschichtchromatoKraphie of this substance showed the same two spots as aas crude ;. The distillate oil was redistilled over a vacuum-jacketed Xikro-Vigreaux column . Fraction tfl: boiling point 48-112.5 ° C. (2.5-3 × 10 '^' mm). Thin layer chromatography showed a large spot (starting sulfone) and a faint spot for the product. Fraction ^ 2: Kp. IO0-I36 ⁰ (2-8 χ .10 "" - ViIIi). Thin-layer chromatography showed a large spot for the starting material and a smaller spot for the product. Fraction '^ 3: bp 140-145 ° ~ (0.01 μm). Thin-layer chromatography showed a larger component for the product (faster moving component) and a smaller spot for the starting sulfone. Fractions 1 and 2

B09827 / 1022 ■. ■■

-4 * 3 -

were discarded because they had very little product. All three "fractions" were solids. Fraction # 3 weighed 5.6 g.

The solid product from fraction il 3 was introduced into sieacnden petroleum ether and filtered to remove the turbidity. The solution was concentrated to a v / a 2. x j ml and cooled in an ice-water mixture. The solid was pressure-filtered under nitrogen, 2.7 g of a white solid product (mp 76-8 ° C.) being obtained. The solid was recrystallized from petroleum ether (about 10 to 15 ml, cooled to -15 ° C.). The solid was filtered off under nitrogen pressure, giving 2.2 μg of a white crystalline solid, mp 79.5-61 , ^{Receives 5 0} C,

The nuclear magnetic spectrum showed a typical 1,4-disubstituted aromatic pattern with a relative intensity of 'k protons, which is associated with a Ba.ide with the center at 7.75 ςί , the two protons ortho to the SO ^ group, and its mirror image with the center at 7, ^ 7c / contains that

'the two protons ortho to the tertiary butyl group

heard. A quartet of bands with the center at 2.84 _u ^r , with the relative intensity of a proton, belongs to the riethin proton. The resonances of the tertiary butyl and the individual methyl

. group overlap to form a band with a relative intensity of 12 protons, the tertiary butyl resonance as a singlet with the center at 1.35 ^ and the methyl resonance appears as a doublet with the center at 1.29 c / ". A singlet at 0.37 c /. (37 Hz) with two small satellite

60982 7/1022

doublets on both sides have a relative total intensity of y protons. This band belongs to the trimethyltin group. The two sets of Satellitendubletts belong to the coupling of the three Methylgruppen'init the two isotopes of tin Sn ■ "" and Cn. "- with a core spinning of 1/2 Thus, the structure as vox irn Aböchnitt ¹ of this Example stated iot, affirmed.

■ The comparison data in the following table (Table IX) were with compound 13 of the invention, a Peterson compound (TrinethylphenyloUlfonylmethylGtannan) and the Peterson hydrolysis product j to that referred to above v; urde (trimethylisine hydroxide) ". The Peterson compound was obtained in accordance with Example 1 of Uo-Patent 3 79 ^ ß70 prepared except that an equivalent amount of trimethyltin chloride was used in place of trimethyltin bromide. The trimethyltin hydroxide was prepared using the following Prepared literary position: J. G. A. Luijten, Rec. Trav. chim. 82_, 1179 (1963).

The mite one day residue test differed from the test listed in Example 13 '; as follows. The plants were kept in a greenhouse chamber at 29 ^ ⁰ C, and they were exposed to fluorescent light with a high intensity long lh days. The recorded observations were made three days after the mites were applied.

The three-day tobacco sprout test on cotton made a difference

6 09827/1022

differ from the ^{test listed in Example I 2} I as follows. The plants used were three weeks old and were with
Gauze covered during the test. Six replicates were performed per test compound rii. With one caterpillar per plant. The recorded observations were "three tare after the ^1st
^ pretreatment done. In both tests, the solutions were prepared in milliraoi / 1, since the compounds have different Iolo-kulargev.'icnt - so that the results are exactly comparable.

609827/1022

cn ο CO 00

! • o connection

O N)

Table IX

Daytime tobacco caterpillar mites
residue ·

% reduced ','> regulation % regulation of food intake

(nl.iol / l). (mmol / lV (mftol / l)

0.6 0.3 0.15 0.6 0.3 0.15, 0.6 0.3 0.1

/ 7Λ ¹ 93 H 100 73 IOC. 83 33.9S 92 88

/ -ν 1 * 4 ■ -ik IS '66 0 '40 ^: . 90 52 73 (CH ₃ ) 3SnCH ₂ -Sh (C ₁ )

3 ^ ^{7 6G 1δ l6 8l 6} ? ^ O

The decided superiority of the invention Connection via the closest comparable pe-terson connection And its hydrolysis product is easily recognizable. -

The unsubstituted phenyl compounds were used in this Comparison test verv; ends because one has found that a alkyl-substituted phenyl-Peterson compound not prepared according to the procedure of US Pat. No. 3,79 ^ GTO could be. The following is an attempt at making it of triethyl-4- "t-buty! phenylsulfonylinethylstannane described in detail. '-

Example 1 of US Pat. No. 3,794,670 served as the working procedure. 9 ^, 0 ml (0 15 _moles}) 1,6-1-1 n-butyllithium in n-liexan v; ere added dropwise with stirring under nitrogen at 0 ° to 8 ⁰ C to a solution of "13.5 ml (0.13 mol) diethylamine in 50 ml of dry benzene was added A solution of 29.8 g (G, 15 Γ · Ίο1) ¹ trine thy 1-tin chloride in 50 ml of benzene was added to the white suspension at 0 ° to 5 ° C. over 40 minutes, the reaction mixture was stirred at room temperature for 1.5 hours, 31.8 g (0.15 mol) of 4-1-butylphenylniethylsulfone was added to the reaction mixture, after which the reaction mixture was stirred overnight at room temperature the flask was heated to remove the diethylamine and benzene by distillation and was then kept for two hours at 100 to 110 ° C. After cooling to room temperature, was

609827/1022

A solution of 'k g kenzentrierter hydrochloric acid in 200 ml of water for Keaktionsiiiischunc under rapid ": scrambled eggs: added within 2 minutes. The resulting concentration was quickly extracted in a separator with 200 nil Chioroforrr. shaken out. The lower organic phase was separated off, dried (Mp; SO ^) and. stripped from the solvent, with nan receiving 51.3 g of an amber-colored oil. Day viscous oil was subjected to vacuum distillation using a short distillation head. The following fractions were taken: '■

Fraction> 1, bp 26 ° bis'. IHb ⁰ C (5 χ ΙΟ " ³ - 0.014 mm),

; .a solid ι fraction £ 2, -Kp. l ^ b ° to 358 ^Q C (C ₅ Ol ^ - C, 03 only.), 'a

oily solid;

Fraction fr3, bp 158 ^P brs 159 ° C (G ₃ OJ up to 0.8 min), an oil. ■ The vessel residue gave a black, brittle glass on cooling and weighed 16.2 g. The fractions were analyzed by gas-liquid chromatography (GLC) using a 1.33 m long 3.12 mm diameter column packed with 10% silicone gum on silanized diatomaceous earth at a column temperature of 20 ° C. The main component of fraction ft-1 was 4-t _ -utylphenyl methyl sulfone; Fraction P 2 consisted of a mixture of mainly starting sulfone: and a higher-boiling component; Fraction ~ ip 3 consisted of the same mixture in which the higher-boiling component was concentrated. There was also a more volatile component, the amount of which increased in each successive fraction. The latter observation, the

60982 7/1022

by a gradual loss in; Vacuum is usually associated with some thermal decomposition. The fractions 2 and 2 were used for a second distillation and conversion of a vacuum. Vigreaux column ■ combined. A promotion rate of bp ^ ⁰ to 123 ⁰ C (0.016 0.023 mm) was obtained. Analysis of this solid revealed mainly the starting sulfone and little of the higher boiling component. Analysis of the vessel residue (8 g) showed an approximately 1: 1 mixture of the starting sulfone and the higher-boiling component. The Vigreaux column was replaced by a short distillation bucket and a third. Distillation, the residue vessel ir.it driven, here the folcenucn fractions were obtained: fraction ffl, bp 28 ° to 172 ⁰ C (0.002 to 0 02 ₃ ir.ni), approximately.

1 ml of a yellowish liquid; Fraction if. 2, bp 17 ° to 166 ° C (0.025-0.13 mm)

Solid, ■ 1.5 ml.

The analysis of fraction : J1 again showed a mixture of the two identical components and fraction jr 2 only showed the starting sulfone. A sample of fraction if- I was analyzed with the aid of nuclear magnetic resonance spectroscopy (IJMR). The Μ · ΪΡι spectra showed a 1: 2 molar mixture of the starting sulfone and the derived product, 4-t-butylphenylsulfonylmethyltrimethylstannane. In summary, the product could only be used as a mixture with the starting sulfone despite three distillation documents for separation the mixture can be obtained. All evidence shows the thermal instability of the product at the temperature required for distillation

609827/1022

of the starting sulfone is required. In addition, the Examination of cold traps (-70 C) To prevent contamination of the vacuum pumps) a liquid (Smell), which, when reaching room temperature volatilized, the volatile substance being a decomposition product. · -.

A second attempt to prepare and isolate triethyl-4-t-biitylphenylsulfonylmethylstannane using the general working instruction de: Example III in US Pat. No. 3,79,670 and the same starting materials listed above was unsuccessful. In this case 53j6 g. an oil isolated from the work-up. Using a vakuumümnian te It en Vigreaux column, distillation of the oil yielded only a small amount of distillate, PIp. 70 to 132 ° C (0.0.2-0.0 * 1 micron.), V.-elcne was analyzed as the starting sulfone, '. "After replacing the column with a short ■ distillation attachment, only 11.1 g of distillate were possible, . Xp 70 ° to 150 ⁰ C (0.019 - 0.27 mn), are obtained, which is attributed to a permanent Väkuumverlust, as analysis showed the distillate with the aid of GLC that the Ausgangssulfon constitutes at least 90% of the distillate..

609827/1022

Claims (11)

Claims (1. Fetrasubstituted organotin compounds, marked by the general formula R ^1. (CH,) ₃ Sn (CH ₂ ) _n -CH-X wherein: R 'is hydrogen, hydroxyl, methyl or ethoxy; X has one of the following meanings: (a) -SOpR ₁ , where R ¹ is water and where R _{1 is} a straight-chain or branched alkyl with 1 to 18 ili_.nlenstoffatomen, cyclohexyl, benzyl, phenyl or phenyl, which is substituted by one or more groups, which can be the same or different and which can be alkoxyl with 1 to 8 carbon atoms, alkylthio with 1 to 8 carbon atoms, halogen, nitro, acetyl, acetamido, carboxyl, alkoxycarbonyl, carbamoyl, cyano, hydroxy, trifluoromethyl, benzyl, naphthyl or norbornyl; Naphthyl, biphenylyl, piperidinoethylmethyl iodide, -R ₂ Sn (CH,) ,, where R _{2 is} polymethylene having 2 to 11 carbon atoms or -RhSO ₂ Rt-S, where R _{1 is} ^ ethylene, and R ₅ is defined as above ; 609827/1022 (b) -OR ₇ , where R '. Is hydrogen, and where R- 'a straight-chain or branched alkyl with 8 to 16 carbon atoms, aryl, alkoxyaryl, alkaryl, haloaryl, Ν, Ν-dialkylaminoalkyl, orter -RgSn (CH ₃ ) ₃ , where Rg is alkylene with 2'to 11 carbon atoms, a cycloaliphatic radical having 4 to 6 carbon atoms, or tetrahydro-1,1-dioxo-3-thienyl; -SR ₁₀ , where R ^{1 is} hydrogen and where R _{10 is} straight-chain or branched alkyl having 1 to 16 carbon atoms, phenyl, chlorophenyl, t-butylphenyl or -R ₂ Sn (CH ₃ ) ₃ ; (d) -COR ₁₁ , where R ^{1 is} hydrogen, and where R ₁₁ ~ ^NHR 12 ' ^{where R} i2 is ^a 9 ^straight- chain or branched alkyl having 1 to 12 carbon atoms or aryl; -NHCH ₂ OH; -NHNH ₂ ; -NHCH ₇ NHCOR ₂ Sn (CH ₃ ) ₃ ; or -OR ₁₃ , wherein R is a straight or branched chain alkyl having 8 to 15 carbon atoms; - (CH ₂ ) _m 0H, where my integer is from 2 to 4; - (CH ₂ ) ^ N (R ₁₄ ) _{? F} where ρ is an integer from 2 to 4 and R _{14 is} a straight-chain or branched alkyl * * having 1 to 5 carbon atoms; - (CH ₂ ) OCOR ₂ Sn (CH ₃ ) ,, wherein σ is defined as ρ above; or - <CH ₂ ) _S N (CH ₃ ) ₃ ^J , where s is defined as ρ above; ' 609827/1022 - ¹³³ - 255A790 (e) -NHCONH ₂ , where R ^{1 is} hydrogen; (f) -NHCSNH ₂ , where R ^{1 is} hydrogen; (g) 1-imidazolyl, where R ^{1 is} hydrogen; (h) N-2-oxopyrrolidinyl, where R ^{1 is} hydrogen; (i) -OCOR ₁₇ , where R ^{1 is} hydrogen, and where Rj7 -NHR ₁ Q, where R ₁ Q is straight or branched chain alkyl of 1 to 5 carbon atoms; 2-furyl; or -0 (CH ₂ ) _t Sn (CH ₃ ) ₃ , where t is 2 to 11; (j) -PO (OR ₂₀ J ₂ , where R ^{1 is} hydrogen or ethoxy, and where R _{30 is} straight-chain or branched alkyl having up to 5 carbon atoms; (k) tetrahydro-l, l-dioxo-2-thenyl, where R ^{1 is} hydroxyl; (1) -Si (OR ₂₁ ) ₃ , where R "is hydrogen, and where R _{31 is} straight or branched alkyl of 1 to 5 carbon atoms; (m) C-CH ₂ Sn (CH ^)
H where R ^{1 is} methyl; (n) where R ^{1 is} hydrogen; (o) 2-pyridyl; (p) 4-pyridyl; (q) 2-alkyl-5-pyridyl; and η is an integer from 1 to 10. 609827/10 2 2 2. A compound of the general formula according to claim 1, characterized in that R ^{f is} hydrogen and X is -SOpFL, where R ^ is a straight-chain or branched alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, bicyclo [2.2.11heptyl, benzyl, phenyl , Alkoxyphenyl with 1 to 3 carbon atoms in the alkoxy group, halophenyl, piperidinoethyl methiodide, -RpSn (CH,) ,, where Rp is polymethylene with 2 to 11 carbon atoms or -R ₁₁ SO ₂ R ₅ Sn (CH ₅ ), where Rh is ethylene and Rj- is defined as Rp above and η is an integer from 1 to 10. 3. Compound according to claim 1, characterized by one of the following compounds: 2,2 · -Sulfonylbisäthyltrimethylstannan, 2-dodecoxyäthyltrimethylstannan, Ν, Ν ¹ -methylenebis (2-carbamoyläthyltrimethylstannan), 3,3 '- (carbonyldioxy) bispropyltrimethylstannane, 2.2 '- (Ethylenedioxydicarbony1) bisethyltrimethylstannane, 2- (2-methyl-5-pyridyl) ethyltrimethylstannane, 2- (£ -t_-butylphenylsulfonyl) ethyltrimethylstannane and 2- (£ -tolylsulfonyl) ethyltrimethylstannane. 4. A compound according to claim 1, characterized by the compound 2- (£ -t-butylphenylsulfonyl) ethyltrimethylstannane. 5. A process for the preparation of tetrasubstituted organotin compounds of the general formula according to claim 1, especially those in which the substituents have the following meanings: 609827/1022 wherein R 'is hydrogen, hydroxyl, alkoxyl or a straight chain or is branched alkyl group having 1 to 5 carbon atoms; X has one of the following meanings: (a) -SOpTL, where u 'is hydrogen and where R _{1 is} a straight or branched alkyl having 1 to 18 carbon atoms, cyclohexyl, benzyl, phenyl or phenyl, which is substituted by one or more groups, which can be the same or different and which are linear or branched alkyl with 1 to 20 carbon atoms, a cycloaliphatic radical with 4 to 6 carbon atoms, straight-chain or branched alkenyl with 2 to 20 carbon atoms, alkoxy with 1 to 8 carbon atoms, alkylthio with 1 to 8 carbon atoms , Halogen ,. Nitro, acetyl, acetamido, carboxy, alkoxycarbonyl, carbamoyl, cyano, hydroxy, trifluoromethyl, benzyl, naphthyl or norbonyl can be; Naphthyl, biphenylyl, piperidinoethyl methiodide, -R ₃ Sn (CH ₃ ) ₃ , where R _{2 is} polymethylene having 2 to 11 carbon atoms, or -R ^ SO ₂ R ₅ Sn (CH ₃ ) ₃ ; where R 1 is ethylene and R _{5 is} as defined above for R _2; (b) -OR_, where R ^ is a straight or branched chain Alkyl with 1 to 20 carbon atoms, haloalkyl, aryl, Haloaryl, alkaryl, alkoxyaryl, epoxyalkylene, wherein the Alkylene group has 2 to 4 carbon atoms, N, N- 609827/1022 Dialkylaminoalkyl, tetrahydro-1, l-dioxo-3-thienyl, or -R ₈ Sn (CH ₃ ) ₃ , where R _{g is} alkylene with 2 to 11 carbon atoms, a cycloaliphatic radical with 4 to 6 carbon atoms or aryl ; (c) -SR ₁₀ , where R 'is hydrogen and where R _{10 is} a straight-chain or branched alkyl having 1 to 18 carbon atoms, cyclohexyl, benzyl, phenyl or phenyl _f the • is substituted with one or more groups which are identical or different can and which linear or branched alkyl with 1 to 20 carbon atoms, a cycloaliphatic? Radical with 4 to 6 carbon atoms, straight-chain or branched alkenyl with 2 to 20 carbon atoms, alkoxy with 1 to 8 carbon atoms, alkylthio with 1 to 8 carbon atoms, halogen, nitro, acetyl, acetamido, carboxy, alkoxycarbonyl, carbamoyl, cyano, Can be hydroxy, trifluoromethyl, benzyl, naphthyl or norbonyl; Naphthyl, Biphenylyl, Piperidinoäthylmethjodid, -R ₃ Sn (CH ₃ ) ₃ , where R _{3 is} Polymethyl.n with 2 to 11 carbon atoms, or -R _{4 is} SO ₃ R ₅ Sn (CH ₃ ) 3, where R _{4 is} ethylene and R _{5 is defined} as R ₂ above; (d) -COR ₁₁ , wherein R _{11 is} -NH ₃ , -NHNH ₃ , -NHCH ₂ OH, -NHR _13,. wherein R _{12 is} straight or branched alkyl having ^: 1 to 12 carbon atoms or aryl; -NHCH ₃ NHCOR ₂ Sn (CH ₃ ) ₃ or -OR ₁ J, where R ₁ ^ is a straight-chain or branched alkyl with 1 to 15 carbon atoms, - (CH ₂ ) _m OH, where- 609827/1022 rin m is an integer from 2 to 4, - (CH ₂ ) _D N (R ₁₄ ) ₂ , where ρ is an integer from 2 to 4 and R ₁ . is straight or branched alkyl of 1 to 5 carbon atoms, - (CH ₉ ) OCOR ₀ Sn (CH.,). ,, wherein q is defined as ρ above, or - (CH ₃ ) _s N (CH ₃ ) ₃ J is where s is as defined above ρ; Ce) -NHCONH ₂ ; (f) -NHCSNH ₂ ;
. (g) 2-pyridyl; (h) 4-pyridyl; (i) 2-alkyl-5-pyridyl; (j) 9-carbazolyl; (k) 1-imidazolyl; . . (1) N-2-oxopyrrolidinyl; (m) -OCOR ₁₇ , wherein R ₁₇ -NHR ₁₈ , wherein R _{18 is} straight or branched alkyl having 1 to 5 carbon atoms or aryl; 2-furyl; or -0 (CH ₂ ) _t Sn (CH ₃ ) ₃ , where t is an integer from 2 to 11; (n) -PO (OR ₂₀ ) ₂ , wherein R _{20 is} straight or branched chain alkyl of 1 to 5 carbon atoms; (o) tetrahydro-1,1-dioxo-2-thenyl; (p) -Si (OR ₂₁ J ₃ , where R _{21 is} a straight-chain or branched alkyl having 1 to 5 carbon atoms; ■ (q) <r ^H 3 ' C-CH ₂ Sn (CH ₃ ) ₃ ;
H 609827/1022 (r) cyano;
(s) OH; and η is an integer from 1 to IO, characterized in that one triraethyltin hydride with a compound which has an olefinic group and the structure R ¹ R "τ t K ₅ C = C - (CH) -X contains, wherein X has the meaning given above, R ^{1 can be} hydrogen, a straight-chain or branched alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms and R "can be hydrogen, hydroxyl or an alkyl group with 1 to 5 carbon atoms and m is a number from 0 to 9, with approximately equimolar amounts of the compound with the olefinic group mixed under an inert atmosphere in a glass reaction flask and with a mercury vapor lamp for a time of about 4 to 232 hours at a temperature of about 0 to 50 ^° C be irradiated. 609827/1022 6. The method according to claim 5, characterized in that that the reaction is carried out in the presence of a solvent. 7. A process for the preparation of tetrasubstituted organotin compounds of the general formula according to claim 1, wherein R ^{1 has} the meaning given in claim 5 and X has the meaning of (a) to (c) according to claim 5 and η is an integer from 2 to 10 or in which R ^{1 has} the meaning given in claim 1 and X has the meaning of (a) to (c) according to claim 1 and η is an integer from 2 to 10, characterized in that (1) a haloalkyltrimethylstannane of the general formula R '(CH ₃ ) ₃ Sn (CH ₂ ) _n -CH-Z where Z is chlorine, bromine or iodine, with (2) one of the compounds: AIkSOpR ₁ , AIkOR ₇ or AIkSR ^ ₀ , where Alk is sodium, potassium or lithium, in the presence of a phase ^{change catalyst at a temperature of 20 to 120 °} C for about Reacts 0.5 to 2 ¹ I hours. 8. Use of the compounds according to claims ibis h or the compounds prepared according to claims 5 to 7 for combating insects or insect diseases or for weed control, characterized in that one for the infested by insect or insect disease site or on the weed one for the insect or insect disease 609827/1022. control effective amount or a herbicidally effective amount the organotin compound of the general formula according to claim 1, in which R ', X and η are those given in claim 5 Have meaning. 9. Use according to claim 8, characterized in that that one applies compounds of the general formula according to claim, in which R 'is hydrogen, X -SOpR. means where R _{1 is} a straight-chain or branched alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, bicyclo β , 2, Ijheptyl, benzyl, phenyl or a phenyl which is substituted by one or more groups which could be the same or different and a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloaliphatic group having 4 to 6 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, halogen, piperidinoethyl methiodide, -R ₂ Sn (CIU) ,, wherein R _{2 is} polymethylene with 2 to 11 Carbon atoms or -RjjSO ₂ Rf-Sn (CH-, K, where Rj is ethylene and R ^ - is as defined for _{R 2 above; and} η is an integer from 1 to 10. 10. Use according to claim 8, characterized in that the organotin compound is 2,2'-sulfonylbisäthyltrimethyIstannan, 2-dodecoxyethyltrimethylstannane, N, N'-methylenebis (2-carbamoylethyltrimethylstannane), 2.2'- 609827/1022 (Ethylene-dioxydicarbonyDbisäthyltrimethylstannan, 2- (p_-t_- Butylphenylsulfonyl> äthyltrimethylstannan, 3,3 '- (Carbonyldioxy) bispropyltriraethyIstannanj 2- (2-Methyl-5-pyridyl) -äthyltrimethy-istannane or trimethyl-3-phenylthiopropylstannane is applied. 11. Use according to claim 8 for Eekämpfung of Ilasquitolarven _s characterized in that these larvae i4enge with effective for the control of mosquito larvae into contact of Trinietnyl-S-phenylthiopropylstannan 609827/1022