CA1188709A - Benzamidosulfenyl n- acid halides methylcarbamic - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

N-(Benzamidosulfenyl)-N-methylcarbamic acid halides of the formula:

wherein R1 is C1-C10alkyl, X is halogen, and each of X1, X2 and X3 is hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyl. These compounds find use as intermediates in the preparation of carba-mates containing an

Description

This applica-tion is a divisional application from application No.
387,041 filed September 30, 1~81.
Application 3S7,041 relates to N-(benzamidosulfenyl)-N-methylcarba-mates, to the production thereof, and to the use thereof in pest control.
These N-(benzamidosulfenyl)-N-methylcarbamates have the Eormula 1 _ O R CH O SR
~ \ 1! 11 1 3 11 1 2 .- C - N - S - N - C - ON = C - R3 (I) X2 t3 Rl is C1-ClOalkyl, R2 is C1-C3 alkyl or allyl, R is methyl -CONH2 or -CON(C~l3)2, and each of Xl, X2 and X3 is hydrogen, halogen, Cl-C4alkyl or Cl-c4haloalkyl.
Halogen in the above definitions denotes fluorine, chlorine, bromine or iodine, with chlorine being preferred.
The alkyl groups suitable for Rl, R2, Xl, X2 and X3 can be straight chain or branched. Examples of such groups are: methyl, trifluoromethyl, ethyl, propyl, isopropyl, n-bu~yl, isobutyl, sec- and tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, and the isomers thereof.
Preferred for their activity are compounds of the formula I, wherein Rl is methyl, R2 is Cl-C3alkyl, R3 is methyl or -CON(CH3~2, and each of Xl, X2 and X3 is hydrogen, chlorine, methyl or trifluoromethyl.
Particularly preferred, however, are compounds of the formula I, wherein Rl is methyl, R2 is Cl-C3alkyl, R3 is methyl or -CON(CH3)2, each of Xl and X2 i.s hydrogen, chlorine, methyl or trifluoromethyl, and X3 is hydrogen.

As is disclosed in application 387,041 the compounds of formula I
are obtained as follows:

1) X~ ~ \ Rl CIH3 11 ISR2 j- C - N - S - N - C - X + HO - N ~ C - R3-E-ase ~ I
X2 .~.
3 (II) (III)

2) Xl .- C - N - SX + HN - C - ON = C - R3- base t x3 (IV) (V) In formulae II to V above, Rl, ~2~ R3 and X3 are as defined for formula I and X is a halogen atom~ in particular a fluorine or chlorine atom.

The processes are carried out at a reaction temperature in the range from -50C to +130C, preferably from -10 to +100C, under normal or slightly elevated pressure and in the presence of a solvent or diluent which is inert to the reactants.
Suitable bases for the processes are, in particular, tertiary amines such as trialkylamines, pyridines and dialkyl anilines, and also hydrox-ides~ oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, as well as alkali metal alcoholates, e.g. potassium tert-butylate and sodium methylate.

~ 81~

Examples of suitable solvents or diluents are: ethers and ethereal compounds such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofurane;
aliphatic and aromatic hydrocarbons, in particular benzene, toluene and xylenes; and ketones such as acetone, methyl ethyl ketone and cyclohexanone.
This application is directly concerned with the G~ e acid halides of formula II above, and with their method of preparation.
Thus in a first aspect this invention provides an N-(benzamidosul-fenyl)-N-methyl carb~nic acid halide of the formula.

X1 ~ CO-N-S-N-COX
X~
x3 wherein Rl is Cl-C10 alkyl, X is halogen, and each of Xl, X2, and X3 is hydrogen, Cl-C4 alkyl, Cl-C4 haloalkyl, or halogen.
In a second aspect this invention provides a process for the preparation of an N-(benzamidosulfenyl)-N-methyl carbamic acid halide of the formula Xl ~ ~ C0-N-S-N-COX
X2~

wherein Rl is Cl-C10 alkyl, X is halogen, and each of Xl, X2 and X3 is hydrogen, halogen, Cl-C4 alkyl, or Cl-C4 haloalkyl; which process comprises reacting together a compound of the formula HX together with N-methylisocyanate, and reacting the thus obtained intermediate with a benzoyl amido sulfenyl halide of the formula ~ A

~7108 Preferably, the quantity of water used is equal or greater than that required to keep the terephthalic acid dis-solved under hydrolysis conditions.
The present invention may also be defined as the continuous process for obtaining pure terephthalic acid and glycol from polyethylene terephthalate waste comprising the steps: subjecting polyethylene terephthalate waste to neutral, aqueous hydrolysis in ah~drol~sis zone at a temperature of between 200C and 300C and superatmospheric pressure of at least 15 atmospheres, said hydrolysis being conducted in the presence of decolorizing carbon in an amount of between 0.1 to 30 weight percent of said waste; removing supernatant liquid from said hydrolysis zone and filtering said liquid under conditions of high temperature and pressure to recover an aqueous solution of terephthalic acid and glycol passing said aqueous solution of terephthalic acid and glycol to a crystal-lization zone and cooling said solu'cion to a temperature of between -10C and 200C in said crystallization zone to there-by cause crystallization of terephthalic acid from said solu-tion; separating by filtering or centrifuge said terephthalicacid crystals from the liquid in said crystallization zone and washing and drying said crystals to provide pure terephthalic acid; passing the liquid from said crystallization zone to a distillation zone and distilling said liquid to provide pure glycol.

Detailed description of the invention According to the preferred method of this invention, the polyethylene terephthalate waste is supplied in the form of granules or yarns or in any other for~. suitable for handling, to the melting chamber of a screw-type extruder so that the extruder, in turn, feeds it, in a continuous manner, to a hydrolyzer. Alternately, the polymer can also be melted and r~
~, vi Compounds of formula I also have a very advantageous action against flies, e.g, Musca domestica, and against mosqui~o larvaa.
In addition, the compounds of formula I have a broad ovicidal and ovilarvicidal action, and they also have a useful action against phytopathogenic nema~odes as well as against ectoparisitic mites and tic~s e.g. of the families Ioxodidae, Argasidae and ~ermanyssidae.
In the following examples are given typical procedures for the preparation of both intermediates of formula II, and of corresponding compounds of formula I, together with some biological text data for some compounds of formula I.

Fxample a) Preparation of N'-~N-(4-methylbenzoyl)-N-methylamido]-sulfenyl-N'-methylcarbamoylfluoride 15.7 of HF are introduced at -50C into 200 ml of toluene (in a polyethylene apparatus). ~hen 46.7 ml of N-methylisocyanate are added dropwise at -50C. I~e mixture is then stirred for 2 hours at -30 to 50C and subsequently dilutcd with toluene. At -10C the dropwise addition is made firstly of 145 g of 4-methylbenzoylamidomethylsulfenyl chloride and then, over 30 minutes, of 108.5 ml of triethylamine. The reaction mi:~ture is stirred for 18 hours at 20C and for 6 hours at 50C, then cooled and filtered with suction. The filtrate is concen-trated. Recrystallisation of the crude product from methylene chloride/
he~ane (1:1) yields the compaund of the formula C~3~ C - ~ 3 S - ~ 3 COF

with a melting point of 66~67C.

The following compounds are also prepared in analogous manner:

o ca3 CH
~ C - N - S N - COF b.p.: llZ-115~C

O C~ C~
O~j ll 1 3 1 3 Cl~ C - N - S - N - COF m.p.: 88-89C

~ 1 3 C~3 o~ ~o-C - N - S - N - COF m.p.: ~3-5$C
\Cl ~ Cl o ca ca ll I 1 3 -C - N - S - N - COF

Cl Cl1 o C~3 C~3 / \ I
Cl-~ C - N - S - N - COF

Cl1 0 ca3 c~3 C - N - S N - COF

C~3 0 CH3 ~a3 .,o 11 o~ ~-C - ~ - S - N - COF

b) Preparation of N'-~N-(4-methylbenzoyl)-~-methylamido)-sulfenyl]-[(N'-methylcarbamoyl)oxylthioacetimidate 6.3 g of l-methylmercap~oacetaloxime and 15.4 g of N'-[N-(4-methyl-benzoyl)-N-methylamidosulfenyl~N'-methylcarbamoylfluoride are dissolved in 50 ml of methylene chloride. With stirring, 11.05 g of triethyl~
amine are added dropwise to this solution. The reaction mixture is stirred for 16 hours at 20C and for 2 hours at 45C. lhe solvent is distilled off and the crude product is recrystallised from a 1:1 mixture of methylene chloride and hexane, affording the compound of the formula C~ ' C~ SCH
~ \ 1 3 1 3 ~ 3 C~3-~ CO - N - S - N --COO - ~ ~ C----CH3 - .
with a melting point of 118-121~C.

The following compounds are also prepared in analogous manner:

O R C~ O SR
Xl`;X' 11 1 1 1 3 11 1 2 C - N - S - N - C - ON - C - R

~3 7~

~ _. .. .. _ 1 2 3 Rl R2 R3 Physical data ___, . ~ . __ ____ H H H CX3 3 CH3 m.p.: 98~102C
H E H ca3 C2H; 3 ~ - 1.5525 H H H CH3 C3~7(i) c~3 m.p.: 74 77C
H H H ca3 C3H7(~ CH3 m.p.: 86-90C
a H H CH3 3 -CON(C~3)2 m.p.: 145-147C
4-Cl H H CH3 CH3 CH3 m.p.: 117-120C
2-Cl H H CH3 CH3 CH3 m.p.: 136-137C
4-Cl H H CH3 C2~5 CH3 m.p.: 56-58C
2-Cl H H CH3 C2~5 CH3 m.p.: 112-114C
4-CH3 H H CH3 C2H5 CH3 m.p.: 83-85~C
4-Cl H H CH3 CH3 -CON(CH3)2 m.p.: 137-139C
2-Cl H H 3 3 -CON(CX3~2 m.p.: 138-139C
4-CH3 E H CH3 CH3 -CON(CH3)2 m.p.: 106-108C

3-Cl H H CH3 CH3 CH3 resin 3-CF3 E H CH3 CH3 CH3 resin 2-Cl 4-Cl H CH3 CH3 CH3 m.p.: 135C
2-Cl~-Cl H CH3 CH3 CH3 resin

4-CH3H H C3~7ti) CH3 CH3 m.p. 101-103C
H H H C4x9(n) CH3 CH3 resin H ~ H C6~13(n) C~3 CH3 resin 3-CF3 ~ _ C~3 3 -CON~CE3)~ resin Biological Examples Example 2: Insecticidal stomach poison a littoralis and Heliothis virescens Cotton plants are sprayed with a solution containing 50, 100, 200 or 400 ppm of the compound to be tested. After the coaCing has dried, - - ~

the plants are populated wi~.h larvae oE the species Spodoptera littoralis (L3-stage) or Helioehis virescens (L3-stage). Two plants are used for each test compound and test species. A mortality count is made after 2, 4, 24 and 48 hours. The test is carried out at 28C
and ~0% relative humidity.

Within the above concentration limits, the compounds of Example 1 effect 100% kill of larvae of the species Spodoptera littoralis and Heliothis virescensO

Example 3: Insecticidal contact action against Myzus persicae _ .
~efore the start of the test, bean plants (Vicia faba) reared in water are each populated ~ith about 200 insects of the species Myzus persi-cae. The treated plants are sprayed 3 days later dripping wet from a distance of 30 cm with a solution containing 10 or l ppm of the compound to be tested. Two plants are used for each test compound at its given concentration and a mortality count is made after a further 24 hours.

Within the above concentration limits~ the compounds of Example 1 effect 100% kill of insects of the species Myzus persicae.
.
Example 4: Systemic insecticidal action against Aphis craccivora -Bean plants which have grown roots are transplanted into pots containing 600 ccm of soil and then 50 ml of a solution containing 25 ppm, 5 ppm or 1 ppm of the compound to be tested are poured direct onto the soil.

After 24 hours the parts of the plants above the soil are populated with lice of the species Aphis craccivora and a plastic cylinder is then slipped over the plants to protect the lice from any possible contact with the tes~ substance either directly or via the gas phase.

~8~

A mortality count is made 24 and 48 hours respectively after the start of the test. Two plants, each in a separate pot, are used per concen-tration of test substance. The test is carried out at. 25C. and 70%
relative humidity.

Within the given concentration limits, the compounds of Example 1 have a 100% systemic action against insects of the species Aphis craccivora.

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An N-(benzamidosulfenyl)-N-methyl carbamic acid halide of the formula wherein R1 is C1-C10 alkyl, X is halogen, and each of X1, X2, and X3 is hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, or halogen.

2. A compound according to claim 1 in which R1 is a methyl or isopropyl group.

3. A compound according to claim 1 or claim 2 in which X1 is chosen from hydrogen, 2-chloro, 3-trifluoromethyl, 4-chloro or 4-methyl, and both X2 and X3 are hydrogen.

4. A compound according to claim 1 or claim 2 in which X1 and X2 represent 2,4-dichloro and X3 represents hydrogen.

5. A compound according to claim 1 in which X is chlorine or fluorine.

6. A process for the preparation of an N-(benzamido-sulfenyl)-N-methyl carbamic acid halide of the formula wherein R1 is C1-C10 alkyl, X is halogen, and each of X1, X2 and X3 is hydrogen, halogen, C1-C4 alkyl, or C1-C4 haloalkyl;
which process comprises reacting together a compound of the formula HX together with N-methylisocyanate, and reacting the thus obtained intermediate with a benzoyl amido sulfenyl halide of the formula wherein R1, X1, X2 and X3 are as defined above and X4 represents halogen in the presence of a base.

7 A process according to claim 6 in which the base is triethylamine.

8. A process according to claim 6 in which X is fluorine and X4 is chlorine.

9. A process according to claim 6 in which R1 is a methyl or isopropyl group.

10. A process according to claim 6 in which X1 is chosen from hydrogen, 2-chloro, 3-trifluoromethyl, 4-chloro or 4-methyl, and both X2 and X3 are hydrogen.

11. A process according to claim 6 in which X1 and X2 represent 2,4-dichloro and X3 represents hydrogen.

12. A process according to claim 6 in which X is chlorine or fluorine.