# US RE31,330 E · 1,1,1-Trihalogeno-4-methylpentenes, method of preparing the same and use of the same in the preparation of 1,1-dihalogeno-4-methyl-1,3-pentadienes

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- Number: US RE31,330 E
- Document ID: USRE31330E
- Status: Granted
- Kind: E
- Application number: 06/200,087
- Filed: 1980-10-23
- Granted: 1983-08-02
- Earliest claimed: 1975-04-14
- Assignees: Kuraray Co., Ltd.
- Inventors: Yoshiji Fujita; Yoshiaki Omura; Fumio Mori; Kazuo Itoi; Takashi Nishida; Yoshin Tamai; Sukeji Aihara; Takeo Hosogai; Fumio Wada
- Web page: https://patentgrep.com/patent/USRE31330E

## Abstract

1,1,1-Trihalogeno-4-methyl pentenes and 1,1-dihalogeno-4-methyl-1,3-pentadienes are produced. These compounds are of value as intermediates for the production of pyrethrin analogs which are of use as insecticides or agricultural chemicals.

## Claims

### Claim at position 1 (depends on 1)

[2. A 1,1,1-trihalogeno-4-methylpentene as set forth in claim 1, which has the formula:] ##STR74##

### Claim at position 2 (depends on 1)

[3. A 1,1,1-trihalogeno-4-methylpentene as set forth in claim 1, which has the formula:] ##STR75##
4. A process for producing a 1,1,1-trihalogeno-4-methylpentene of the formula ##STR76## wherein Z is a group of the formula ##STR77## or a group of the formula ##STR78## and X.sup.1, X.sup.2 and X.sup.3 are the same or different and each represents a halogen atom, which comprises removing R.sup.1 OH from a compound of the formula ##STR79## wherein R.sup.1 is a hydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl or acyl group; and X.sup.1, X.sup.2 and X.sup.3 are as defined above in the presence [of an effective amount of an acid catalyst or] of an effective amount of at least one member selected from the group consisting silica gel, aluminum silicate, kieselguhr, pumice, Fuller's earth,
activated alumina and activated carbon.

### Claim at position 3 (depends on 4)

[5. A process as set forth in claim 4 wherein the reaction is carried out at a temperature of from room temperature to about 160.degree. C. in the presence of 0.01 to 30%, based on the weight of said compound of formula III, of an acid catalyst.]

### Claim at position 4 (depends on 5)

[6. A process as set forth in claim 5 wherein the temperature is from room temperature to 120.degree. C.]

### Claim at position 5 (depends on 5, 9, 10)

[7. A process as set forth in claim 5 wherein said acid catalyst is present in an amount within the
range of 0.1 to 10%.] 8. A process as set forth in claim [5] 4 wherein the reaction is carried out at a temperature of from 80.degree. to 250.degree. C. in gaseous or liquid phase [in the presence of at least one member selected from the group consisting of silica gel, aluminum silicate, kieselguhr, pumice, Fuller's earth, activated alumina
and activated carbon.] 9. A process for producing a 1,1,1-trihalogeno-4-methyl-3-pentene, which comprises removing R.sup.1 OH from a compound of the formula ##STR80## wherein R.sup.1 is a hydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl or acyl group and X.sup.1, X.sup.2 and X.sup.3 are the same or different and each represents a halogen atom in the presence of an effective amount of an acid catalyst or of an effective amount of at least one member selected from the group consisting of silica gel, aluminum silicate, kieselguhr, pumice, Fuller's earth, activated alumina and activated carbon to obtain a mixture of a 1,1,1-trihalogeno-4-methyl-4-pentene of the formula ##STR81## wherein X.sup.1, X.sup.2 and X.sup.3 are as defined above and a 1,1,1-trihalogeno-4-methyl-3-pentene of the formula ##STR82## wherein X.sup.1, X.sup.2 and X.sup.3 are as defined above and subjecting said mixture to fractional distillation to isolate said 1,1,1-trihalogeno-4-methyl-3-pentene with a first-emerging fraction rich in said 1,1,1-trihalogeno-4-methyl-4-pentene being recycled to the
reaction system. 10. A process as set forth in claim 9 wherein the reaction is carried out at a temperature of from room temperature to about 160.degree. C. in the presence of 0.01 to 30%, based on the weight of said
compound of formula III, of an acid catalyst. 11. A process as set forth in claim 10 wherein the temperature is from room temperature to
120.degree. C. 12. A process as set forth in claim 10 wherein said acid
catalyst is present in an amount within the range of 0.1 to 10%. 13. A process as set forth in claim 9 wherein the reaction is carried out at a temperature of from 80.degree. to 250.degree. C. in gaseous or liquid phase in the presence of at least one member selected from the group consisting of silica gel, aluminum silicate, kieselguhr, pumice, Fuller's
earth, activated alumina and activated carbon. 14. A process for producing a 1,1,1-trihalogeno-4-methylpentene of the formula ##STR83## wherein X.sup.1, X.sup.2 and X.sup.3 are the same or different and each represents a halogen atom and Z is a group of the formula ##STR84## or a group of the formula ##STR85## which comprises adding a haloform to a dimethyl vinyl carbinol compound of the formula ##STR86## wherein R.sup.1 is a hydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl or acyl group under radical-reaction conditions to obtain a compound of the formula ##STR87## wherein R.sup.1, X.sup.1, X.sup.2 and X.sup.3 are as defined above and removing R.sup.1 OH from the last-mentioned compound III in the presence [of an effective amount of an acid catalyst or] of an effective amount of at least one member selected from the group consisting of silica gel, aluminum silicate, kieselguhr, pumice, Fuller's earth, activated alumina
and activated carbon.

### Claim at position 6 (depends on 14)

[15. A process as set forth in claim 14 wherein the reaction is carried out at a temperature of from room temperature to about 160.degree. C. in the presence of 0.01 to 30%, based on the weight of said compound of formula III, of an acid catalyst.]

### Claim at position 7 (depends on 15)

[16. A process as set forth in claim 15 wherein the temperature is from room temperature to 120.degree. C.]

### Claim at position 8 (depends on 14, 15, 23, 26, 27, 30, 35, 39)

[17. A process as set forth in claim 15 wherein said acid catalyst is present in an amount within the range of 0.1 to
10%.] 18. A process as set forth in claim 14 wherein the reaction is carried out at a temperature of from 80.degree. to 250.degree. C. in gaseous or liquid phase [in the presence of at least one member selected from the group consisting of silica gel, aluminum silicate, kieselguhr,
pumice, Fuller's earth, activated alumina and activated carbon.] 19. A process as set forth in claim 14 wherein R.sup.1 in formula IV is a
hydrogen atom. 20. A process as set forth in claim 14 wherein said
haloform is chloroform or bromoform. 21. A process as set forth in claim 14 wherein the reaction under said radical-reaction conditions is conducted in the presence of a radical-reaction initiator and at a
temperature in the range of 70.degree. to 180.degree. C. 22. A process as set forth in claim 14 wherein the reaction under said radical-reaction conditions is conducted under irradiation and at a temperature in the
range of room temperature to 100.degree. C. 23. A process for producing a 1,1,1-trihalogeno-4-methyl-3-pentene of the formula ##STR88## wherein X.sup.1, X.sup.2 and X.sup.3 are the same or different and each represents a halogen atom, which comprises isomerizing a 1,1,1-trihalogeno-4-methyl-4-pentene of the formula ##STR89## wherein X.sup.1, X.sup.2 and X.sup.3 are as defined above by heating at a temperature of from 80.degree. to 200.degree. C. in the presence of 0.001 to 30%, based on the weight of said 1,1,1-trihalogeno-4-methyl-4-pentene, of at least one member selected from the group consisting of a transition metal of Group 6B, Group 7B or Group 8 of the Periodic Table of the
Elements, a compound of said transition metal and an acid catalyst. 24. A process as set forth in claim 23 wherein said temperature is in the range
of 110.degree. to 170.degree. C. 25. A [processas] process as set forth in claim 23 wherein the proportion of any of said transition metals and compounds of transition metals or of said acid
catalyst is in the range of 0.1 to 10 weight percent. 26. A process for producing a 1,1-dihalogeno-4-methyl-1,3-pentadiene of the formula ##STR90## wherein X and Y are the same or different and each represents a halogen atom, which comprises treating a 1,1,1-trihalogeno-4-methyl-3-pentene of the formula ##STR91## wherein X.sup.1, X.sup.2 and X.sup.3 are the same or different and each represents a halogen atom with a basic reagent at a temperature of from
room temperature to 150.degree. C. 27. A process as set forth in claim 26 wherein said basic reagent is at least one member selected from the group consisting of an alkali or alkaline earth metal hydroxide, a metal alcoholate, an alkali metal hydride, an alkali metal amide, an amine and
an organolithium compound. 28. A process as set forth in claim 27 wherein said basic reagent is an alkali metal alcoholate, alkali metal hydride or
alkali metal hydroxide. 29. A process as set forth in claim 26 wherein
said temperature is from 50.degree. to 130.degree. C. 30. A process for producing a 1,1-dihalogeno-4-methyl-1,3-pentadiene of the formula ##STR92## wherein X and Y are the same or different and each represents a halogen atom, which comprises adding a haloform to a dimethyl vinyl carbinol compound of the formula ##STR93## wherein R.sup.1 is a hydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl or acyl group under radical-reaction conditions to obtain a compound of the formula ##STR94## wherein R.sup.1 is as defined above and X.sup.1, X.sup.2 and X.sup.3 are the same or different and each represents a halogen atom; removing R.sup.1 OH from the compound III in the presence of an effective amount of an acid catalyst or an effective amount of at least one member selected from the group consisting of silica gel, aluminum silicate, kieselguhr, pumice, Fuller's earth, activated alumina and activated carbon to obtain a mixture of a 1,1,1-trihalogeno-4-methyl-4-pentene of the formula ##STR95## wherein X.sup.1, X.sup.2 and X.sup.3 are as defined above and a 1,1,1-trihalogeno-4-methyl-3-pentene of the formula ##STR96## wherein X.sup.1, X.sup.2 and X.sup.3 are as defined above; subjecting said mixture to fractional distillation to isolate said 1,1,1-trihalogeno-4-methyl-3-pentene and treating said 1,1,1-trihalogeno-4-methyl-3-pentene with a basic reagent at a temperature
of from room temperature to 150.degree. C. 31. A process as set forth in
claim 30 wherein R.sup.1 in formula IV is a hydrogen atom. 32. A process as set forth in claim 30 wherein said haloform is chloroform or bromoform.
3. A process as set forth in claim 30 wherein the reaction under said radical-reaction conditions is conducted in the presence of a radical-reaction initiator and at a temperature in the range of 70.degree.
to 180.degree. C. 34. A process as set forth in claim 30 wherein the reaction under said radical-reaction conditions is conducted under irradiation and at a temperature in the range of room temperature to
100.degree. C. 35. A process as set forth in claim 30 wherein the removal of R.sup.1 OH is carried out at a temperature of from room temperature to about 160.degree. C. in the presence of 0.01 to 30%, based on the weight
of said compound of formula III, of an acid catalyst. 36. A process as set forth in claim 35 wherein the temperature is from room temperature to
120.degree. C. 37. A process as set forth in claim 35 wherein said acid
catalyst is present in an amount within the range of 0.1 to 10%. 38. A process as set forth in claim 30 wherein the removing of R.sup.1 OH is carried out at a temperature of from 80.degree. C. to 250.degree. C. in gaseous or liquid phase in the presence of at least one member selected from the group consisting of silica gel, aluminum silicate, kieselguhr,
pumice, Fuller's earth, activated alumina and activated carbon. 39. A process as set forth in claim 30 wherein the basic reagent is at least one member selected from the group consisting of an alkali or alkaline earth metal hydroxide, a metal alcoholate, an alkali metal hydride, an alkali
metal amide, an amine and an organolithium compound. 40. A process as set forth in claim 39 wherein said basic reagent is an alkali metal
alcoholate, alkali metal hydride or alkali metal hydroxide. 41. A process as set forth in claim 30 wherein the treatment with a basic reagent is carried out at a temperature of from 50.degree. to 130.degree. C.

### Claim 42

A process for producing a 1,1,1-trihalogeno-4-methylpenetene of the formula ##STR97## wherein Z is a group of the formula ##STR98## or a group of the formula ##STR99## and X.sup.1, X.sup.2 and X.sup.3 are the same or different and each represents a halogen atom, which comprises removing R.sup.1 OH from a compound of the formula ##STR100## wherein R.sup.1 is a hydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl or acyl group; and X.sup.1 X.sup.2 and X.sup.3 are as defined above, in the presence of an effective amount of at least one acid catalyst selected from the group consisting of sulfuric acid, phosphoric acid, p-toluenesulfonic acid, lauryl sulfonate, phosphorus pentoxide, vanadium
pentoxide and wolfram trioxide.

### Claim 43 (depends on 42)

A process as set forth in claim 42 wherein the reaction is carried out at a temperature of from room temperature to about 160.degree. C. in the presence of 0.01 to 30%, based on the weight of said compound of formula III, of said catalyst.

### Claim 44 (depends on 43)

A process as set forth in claim 43 wherein the temperature is from room temperature to 120.degree.C.

### Claim 45 (depends on 43)

A process as set forth in claim 43 wherein said catalyst is present in an amount within the range of 0.1 to 10%.

### Claim 46

A process for producing a 1,1,1-trihalogeno-4-methyl-pentene of the formula ##STR101## wherein X.sup.1, X.sup.2, and X.sup.3 are the same or different and each represents a halogen atom and Z is a group of the formula ##STR102## or a group of the formula ##STR103## which comprises adding a haloform to a dimethyl vinyl carbinol compound of the formula ##STR104## wherein R.sup.1 is a hydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl or acyl group, under radical-reaction conditions to obtain a compound of the formula ##STR105## wherein R.sup.1, X.sup.1 X.sup.2 and X.sup.3 are as defined above, and removing R.sup.1 OH from the last-mentioned compound III in the presence of an effective amount of at least one acid catalyst selected from the group consisting of sulfuric acid, phosphoric acid, p-toluene-sulfonic acid, lauryl sulfonate, phosphorus pentoxide, vanadium pentoxide and
wolfram trioxide.

### Claim 47 (depends on 46)

A process as set forth in claim 46 wherein the reaction is carried out at a temperature of from room temperature to about 160.degree. C. in the presence of 0.01 to 30%, based on the weight of said compound of formula III, of said catalyst.

### Claim 48 (depends on 47)

A process as set forth in claim 47 wherein the temperature is from room temperature to 120.degree. C.

### Claim 49 (depends on 47)

A process as set forth in claim 47 wherein said catalyst is present in an amount within the range of 0.1 to 10%.