US2934558A - Nitrazaalkylnitrates - Google Patents

Nitrazaalkylnitrates Download PDF

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US2934558A
US2934558A US704227A US70422757A US2934558A US 2934558 A US2934558 A US 2934558A US 704227 A US704227 A US 704227A US 70422757 A US70422757 A US 70422757A US 2934558 A US2934558 A US 2934558A
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radical
aza
nitrazaalkylnitrates
general formula
azaalkanol
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US704227A
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Milton B Frankel
Gustave B Linden
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Aerojet Rocketdyne Inc
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Aerojet General Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/02—Preparation of esters of nitric acid
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine

Definitions

  • This invention relates to new compositions of matter and to a method for their preparation. More particularly, the invention relates to high energy nitrazaalkylnitrates of the following general formula:
  • R is a hydrogen, nitro, halogen, alkyl, nitroalkyl or halonitroalkyl radical
  • R is a hydrogen, halogen, alkyl, nitroalkyl or halonitroalkyl radical
  • A is an alkylene radical
  • the high energy nitrazaalkylnitrates of this invention contain three types of nitro groups (nitramino, aliphatic nitro, and nitrate ester) and are useful as high explosives. These compounds can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge.
  • An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949.
  • One way of using the high explosives in a device such as that disclosed in United States Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge,
  • novel high energy nitrazaalkylnitrates of our invention are prepared by reacting an azaalkanol with nitric acid in accordance with the general reaction scheme set forth below:
  • EXAMPLE H Preparation of 3-aza-3,5,5-trinitro-1-hexylnitrate This example differs from Example I in that 3-aza- 3,5,5-trinitro-1-hexanol is used as the starting alcohol instead of 3-aza-5,5-dinitro-l-hexanol to produce the same final product.
  • the azaalkanol starting materials of this invention such as 3-aza-5,5-dinitro-l-hexanol, in which the R" shown in the general reaction scheme is hydrogen, are prepared by condensing a nitroalkanol, such as 2,2-dinitropropanol with an alkanolamine, such as ethanolamine, as more fully disclosed in our copending United States patent application Serial No. 711,768, filed concurrently with the present application.
  • azaalkanol starting materials in which the R in a nitro radical, such as 3-aZa-3,5,5-trinitro-l-hexanol are obtained by the reduction at azaalkanoyl halides, such as 3-aza-3,5,5-trinitro-l-hexanoyl chloride, with sodium borohydride, as more fully disclosed in assignees copending United States patent application Serial No. 392,471, filed November 16, 1953, now abandoned.
  • Reaction temperatures are not critical in the practice of this invention and can be varied over wide ranges, the only efiect of temperature variation being a corresponding increase or decrease in reaction rate.
  • the azaalkanol starting material is of the type in which the R radical is a nitro group
  • the azaalkanol starting material is of the type in which the R" radical is a hydrogen
  • the slower controlling reaction (nitration of the NH group) requires higher temperatures to increase its rate to an optimum value
  • the controlling reaction (ester formation) is extremely rapid, and for the purposes of better control and higher yields, lower temperatures should be employed.
  • the nitration reactions of this invention can be conducted using nitric acid alone or a mixture of nitric acid and a dehydrating agent such as sulfuric acid, the purpose of the dehydrating agent being to remove the Water which forms as a product of the nitration reaction. It is more desirable to conduct the nitration reaction in the presence of a dehydrating agent in the case where the starting azaalkanol is of the type in which R" is a hydrogen radical than in the case in which the starting azaalkanol has a nitro group as the R" radical, since in the latter case the presence of water has less effect on the principal reaction.
  • nitrazaalkylnitrates within the scope of the present invention can be prepared in accordance with the method taught herein.
  • 7-aza-9-nitro-l-decanol, 7-aza-9-chloro- 9, l l-dinitro-l-undecanol and 7-aza-ll-bromo-9,1l-dinitrol-dodecanol when nitrated according to the method of our invention yield 7-aza-7,9-dinitro-l-decylnitrate, 7-aza- 9-chloro-7,9,l1-trinitro-l-undecylnitrate and 7-aza-11- bromo 7,9,11 trinitro 1 dodecylnitrate, respectively.
  • nitrazaalkylnitrates having the general formula:
  • R is a radical selected from the group consisting of hydrogen, nitro, halogen, lower alkyl, lower nitroalkyl, and lower halonitroalkyl radicals
  • R is a radical selected from the group consisting of hydrogen, halogen, lower alkyl, lower nitroalkyl, and lower halonitroalkyl radicals
  • A is a lower alkylene radical.
  • nitrazaalkylnitrates having the general formula:
  • R is a nitro radical
  • R is a lower alkyl radical
  • A is a lower alkylene radical
  • R is a halogen radical
  • R is a lower nitroalkyl radical
  • A is a lower alkylene radical
  • nitrazaalkylnitrates having the general formula:
  • R' is a lower alkyl radical and A is a lower alkylene radical.
  • R is a lower halonitroalkyl radical and A is a lower alkylene radical.
  • R is a nitro radical
  • R' is a lower alkyl radical
  • A is a lower alkylene radical
  • R is a lower alkyl radical and A is a lower alkylene radical.
  • R is a lower halonitroalkyl radical and A is a lower alkylene radical.
  • R is a nitro radical, R is a lower alkyl radical and A is a lower alkylene radical.
  • III 03 IIIO 2 RCOHrNCH2-A-OH with nitric acid wherein R is a halogen radical, R is a lower nitroalkyl radical and A is a lower alkylene radical.
  • R is a lower alkyl radical and A is a lower alkylene radical.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

United States Patent NITRAZAALKYLNITRATES Milton B. Frankel and Gustave B. Linden, Pasadena, Calif., assignors to Aerojet-General Corporation, Azusa, Calif., a corporation of Ohio No Drawing. Application December 19, 1957 Serial No. 704,227
20 Claims. (Cl. 260-467) This invention relates to new compositions of matter and to a method for their preparation. More particularly, the invention relates to high energy nitrazaalkylnitrates of the following general formula:
wherein R is a hydrogen, nitro, halogen, alkyl, nitroalkyl or halonitroalkyl radical; R is a hydrogen, halogen, alkyl, nitroalkyl or halonitroalkyl radical; and A is an alkylene radical.
The high energy nitrazaalkylnitrates of this invention contain three types of nitro groups (nitramino, aliphatic nitro, and nitrate ester) and are useful as high explosives. These compounds can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives in a device such as that disclosed in United States Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge,
and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.
The novel high energy nitrazaalkylnitrates of our invention are prepared by reacting an azaalkanol with nitric acid in accordance with the general reaction scheme set forth below:
NO: R
EXAMPLE I Preparation of 3aza-3,5,5-trinitr0-1-hexylnitrate A l-liter, 3-necked flask fitted with stirrer and thermometer was charged with 220 ml. tech. 100% nitric acid and 195 ml. conc. sulfuric acid. At 40' to 45 C., 46 g. of 3-aza-5,5-dinitro-l-hexanol was added over about minutes. The resulting yellow solution was heated at 54 to 57 C. for 35 minutes withstirring, and drowned with excess ice. The resulting beige solid was filtered, washed well with water, and recrystallized from methanol to yield 27 g. (23%) of 3-aza-3,5,5-trinitro-l-hexylnitrate product having a melting point of 108 to 111 C. Analytical results are given below.
Analysis-Calculated for C H N O percent C, 21.21; percent H, 3.20; percent N, 24.74. Found: percent C, 21.89; percent H, 3.33; percent N, 22.19.
EXAMPLE H Preparation of 3-aza-3,5,5-trinitro-1-hexylnitrate This example differs from Example I in that 3-aza- 3,5,5-trinitro-1-hexanol is used as the starting alcohol instead of 3-aza-5,5-dinitro-l-hexanol to produce the same final product.
Thirty ml. of 100% nitric acid was cooled to 5 C. and 3.0 g. (0.012 mole) of 3-aza-3,5,5-trinitro-l-hexanol was added. The solution was stirred for 15 minutes at 5 C. and poured on ice. A white solid formed which was collected, washed with water, and dried to yield 3.3 g. (92.7%) of 3-aza-3,5,5-trinitro-1-hexylnitrate product having a melting point of 98 C. Two recrystallizations from methanol raised the melting point of the product to 108-111 C. Analytical results are given below.
Analysis-Calculated for C H N O percent C, 21.21; percent H, 3.20; percent N, 24.74. Found: percent C, 21.74; percent H, 3.51; percent N, 25.31.
Cryst. dens. g. in." =1.73
Thermal stability (gas vol./ g. at l00)=1.l in 48 hours,
1.5 in 120 hours Lead block value=142 (TNT- Ballistic mortar value=146 (TNT=100) The azaalkanol starting materials of this invention, such as 3-aza-5,5-dinitro-l-hexanol, in which the R" shown in the general reaction scheme is hydrogen, are prepared by condensing a nitroalkanol, such as 2,2-dinitropropanol with an alkanolamine, such as ethanolamine, as more fully disclosed in our copending United States patent application Serial No. 711,768, filed concurrently with the present application.
The azaalkanol starting materials in which the R in a nitro radical, such as 3-aZa-3,5,5-trinitro-l-hexanol, are obtained by the reduction at azaalkanoyl halides, such as 3-aza-3,5,5-trinitro-l-hexanoyl chloride, with sodium borohydride, as more fully disclosed in assignees copending United States patent application Serial No. 392,471, filed November 16, 1953, now abandoned.
Reaction temperatures are not critical in the practice of this invention and can be varied over wide ranges, the only efiect of temperature variation being a corresponding increase or decrease in reaction rate. However, in the case where the azaalkanol starting material is of the type in which the R radical is a nitro group, in order to obtain higher yields it is preferred to conduct the nitration at a relatively low temperature, such as from about 0 to about 10 0., since better control of the reaction is thereby achieved. This reaction proceeds very rapidly at higher temperatures, thus making control more difficult at these temperatures than at lower temperatures. On the other hand, when the azaalkanol starting material is of the type in which the R" radical is a hydrogen, it is usually desirable to conduct thenitration reaction at somewhat elevated temperatures, such as from about 40 to about 60 C. Elevated temperatures are preferred for this reaction because nitration of the NH group in the azaalkanol proceeds at a much slower rate than the ester reaction which is substantially the only reaction in the nitration of the azaalkanols wherein R" radical is a nitro group. Thus, in the former case, the slower controlling reaction (nitration of the NH group) requires higher temperatures to increase its rate to an optimum value, whereas in the latter case the controlling reaction (ester formation) is extremely rapid, and for the purposes of better control and higher yields, lower temperatures should be employed.
The nitration reactions of this invention can be conducted using nitric acid alone or a mixture of nitric acid and a dehydrating agent such as sulfuric acid, the purpose of the dehydrating agent being to remove the Water which forms as a product of the nitration reaction. It is more desirable to conduct the nitration reaction in the presence of a dehydrating agent in the case where the starting azaalkanol is of the type in which R" is a hydrogen radical than in the case in which the starting azaalkanol has a nitro group as the R" radical, since in the latter case the presence of water has less effect on the principal reaction.
It will be appreciated that a wide variety of nitrazaalkylnitrates within the scope of the present invention can be prepared in accordance with the method taught herein. For example, 7-aza-9-nitro-l-decanol, 7-aza-9-chloro- 9, l l-dinitro-l-undecanol and 7-aza-ll-bromo-9,1l-dinitrol-dodecanol when nitrated according to the method of our invention yield 7-aza-7,9-dinitro-l-decylnitrate, 7-aza- 9-chloro-7,9,l1-trinitro-l-undecylnitrate and 7-aza-11- bromo 7,9,11 trinitro 1 dodecylnitrate, respectively. Likewise, 7-aza-7,9-dinitro-l-decanol, 7-aza-9-chloro- 7,9,1l-trinitro-l-undecanol and 7-aza-l1-bromo-7,9,l1- trinitro-l-dodecanol when nitrated, yield 7-aza-7,9-dinitrol-decylnitrate, 7-aza-9-chloro-7,9,1l-trinitro-l-undecylnitrate and 7-aza-11-boromo-7,9,1l-trinitro-l-dodecylnitrate, respectively. Other members of this new series of compounds can be prepared by nitrating appropriate starting materials according to the method taught herein.
We claim:
1. As new compositions of matter, nitrazaalkylnitrates having the general formula:
wherein R is a radical selected from the group consisting of hydrogen, nitro, halogen, lower alkyl, lower nitroalkyl, and lower halonitroalkyl radicals; R is a radical selected from the group consisting of hydrogen, halogen, lower alkyl, lower nitroalkyl, and lower halonitroalkyl radicals; and A is a lower alkylene radical.
2. As new compositions of matter, nitrazaalkylnitrates having the general formula:
wherein R is a nitro radical, R is a lower alkyl radical and A is a lower alkylene radical.
3. As new compositions of matter, nitrazaalkylnitrates having the general formula:
wherein R is a halogen radical, R is a lower nitroalkyl radical, and A is a lower alkylene radical.
4. As new compositions of matter, nitrazaalkylnitrates having the general formula:
wherein R' is a lower alkyl radical and A is a lower alkylene radical.
5. As new compositions of matter, nitrazaalkylnitrates having the general formula:
wherein R is a lower halonitroalkyl radical and A is a lower alkylene radical.
6. As a new composition of matter, 3-aza-3,5,5-trinitrol-hexylnitrate having the structural formula:
7. As a new composition of matter, 7-aza-7,9-dinitrol-decylnitrate having the structural formula:
8. As a new composition of matter, 7-aza-9-chloro- 7,9,1l-trinitro-l-undecy1nitrate having the structural formula:
9. As a new composition of matter, 7-aza-11-bromo- 7,9,1l-trinitro-l-dodecylnitrate having the structural formula:
10. The method of preparing nitrazaalkylnitrates having the general formula:
N0, N0: R(:JCH:-N-OH:A-ONO:
which comprises nitrating an azaalkanol having the general formula:
which comprises nitrating an azaalkanol having the general formula:
with nitric acid; wherein R is a nitro radical, R' is a lower alkyl radical and A is a lower alkylene radical.
12. The method of preparing nitrazaalkylnitrates having the general formula:
which comprises nitrating an azaalkanol having the gen eral formula:
N 0; R( JCHr-I TCHnA-OH with nitric acid; wherein R is a halogen radical, R is a lower nitroalkyl radical and A is a lower alkylene radical.
13. The method of preparing nitrazaalkylnitrates having the general formula:
NO: NO: H-'iIOHz-I ICHTA-ONO:
which comprises nitrating an azaalkanol having the general formula:
with nitric acid; wherein R is a lower alkyl radical and A is a lower alkylene radical.
14. The method of preparing nitrazaalkylnitrates having the general formula:
which comprises nitrating an azaalkanol having the general formula:
with nitric acid; wherein R is a lower halonitroalkyl radical and A is a lower alkylene radical.
15. The method of preparing nitrazaalkylnitrates having the general formula:
which comprises nitrating an azaalkanol having the general formula:
6 with nitric acid; wherein R is a nitro radical, R is a lower alkyl radical and A is a lower alkylene radical.
16. The method of preparing nitrazaalkylnitrates having the general formula:
which comprises nitrating an azaalkanol having the general formula:
III 03 IIIO 2 RCOHrNCH2-A-OH with nitric acid; wherein R is a halogen radical, R is a lower nitroalkyl radical and A is a lower alkylene radical.
17. The method of preparing nitrazaalkylnitrates having the general formula:
which comprises nitrating an azaalkanol having the general formula:
with nitric acid; wherein R is a lower alkyl radical and A is a lower alkylene radical.
18. The method of preparing nitrazaalkylnitrates having the general formula:
which comprises nitrating azaalkanols having the general formula:
No references cited.

Claims (1)

1. AS NEW COMPOSITIONS OF MATTER, NITRAZAALKYLNITRATES HAVING THE GENERAL FORMULA:
US704227A 1957-12-19 1957-12-19 Nitrazaalkylnitrates Expired - Lifetime US2934558A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248420A (en) * 1962-04-09 1966-04-26 Aerojet General Co Process for making the acetates of trinitro-aza-alkylnitrates
US5599994A (en) * 1994-07-07 1997-02-04 Pharm-Eco Laboratories, Inc. Amino acid-derived diaminopropanols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248420A (en) * 1962-04-09 1966-04-26 Aerojet General Co Process for making the acetates of trinitro-aza-alkylnitrates
US5599994A (en) * 1994-07-07 1997-02-04 Pharm-Eco Laboratories, Inc. Amino acid-derived diaminopropanols

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